CN1255158A - Fabric care compositions - Google Patents
Fabric care compositions Download PDFInfo
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- CN1255158A CN1255158A CN 98804979 CN98804979A CN1255158A CN 1255158 A CN1255158 A CN 1255158A CN 98804979 CN98804979 CN 98804979 CN 98804979 A CN98804979 A CN 98804979A CN 1255158 A CN1255158 A CN 1255158A
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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
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/507—Compounds releasing perfumes by thermal or chemical activation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3792—Amine oxide containing polymers
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Cosmetics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A fabric care composition is provided comprising a pro-fragrance and an amino-functional polymer, resulting in improved pro-fragrance deposition and/or substantivity on treated fabrics.
Description
Invention field
The present invention relates to a kind of Fabrid care composition that effective fragrance sends that on fabric, has.
Background of invention
Fabric with fresh scent is one of field of being concerned about of human consumer.For addressing this need, essence is added in the composition that home treated uses, for example in common laundry processes, in the composition that uses in pre-treatment, laundry cycles, rinse cycle, drum dried process and their combination.Yet the problem that conventional essence ran into is, though they provide scentetd fabric, they do not provide long-acting fragrance, and is promptly a kind of than using conventional longer fragrance of essence time length.In fact, the fabric of handling with conventional essence usually at first shows a kind of fragrance of outburst on new processed fabric, but along with time fragrance will be reduced to attractive hardly degree.
Therefore, the purpose of this invention is to provide a kind of composition that on fabric, has effective long-acting fragrance.
Long-acting fragrance refers to a kind of fragrance on the fabric of handling, and its fragrance promptly is preferably and was longer than 3 days than using essence itself to continue the longer time in composition, more preferably is longer than 6 days.
Fragrance precursors is known in satisfying the prior art of these type of needs, described at WO96/02625.The term here " fragrance precursor " refers to a kind of like this compound, itself can be fragrant or may be not fragrant, but along with the hydrolysis meeting produces the desirable fragrance that is feature with its one or more hydrolysates.Certainly, the mixture of fragrance precursors also can be considered to a kind of fragrance precursor.
Though satisfactory, the fragrance precursor component can lose, reduce the effectiveness of these compounds on the fabric of handling thus in treating processes.
Therefore, also need a kind of composition that on the fabric of handling, has the long-acting fragrance of improvement.
A terms of settlement of this problem is to make the fragrance precursor component encapsulated.Typical disclosure can find in EP0601074 that wherein the encapsulated of sensitive ingredients makes by sealing with cyclodextrin.Yet,, also increased the complicacy of expense and prescription though this provides a kind of method that overcomes the above-mentioned shortcoming of mentioning.
The applicant now is surprisingly found out that, uses the amino-functional polymkeric substance to address this need in the composition that comprises the fragrance precursor component.In fact, deposition and/or the affinity of having found spices precursor component on the fabric of handling have improved.
Therefore, an advantage of the invention is a kind of composition that has the long-acting aroma characteristic of improvement on fabric is provided.
Another one advantage of the present invention provide a kind of have improve the composition that fabric protects look.In fact,, on the fabric of handling, not only observe the long-acting fragrance of improvement, also observe the look that protects of improvement by using the amino-functional polymkeric substance.
Summary of the invention
The present invention relates to a kind of Fabrid care composition that comprises fragrance precursor and amino-functional polymkeric substance, it is characterized in that described fragrance precursor is selected from:
A)-a kind of nonionic or anionic ester with allyl alcohol spices of following formula:
Wherein R is selected from that nonionic or negatively charged ion replace or unsubstituted C1-C30 straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; Each R ', R " and R " ' be selected from hydrogen respectively, nonionic or negatively charged ion replace or unsubstituted C1-C25 straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl, or aryl; And n is 1 or greater than 1 integer;
B)-a kind of nonionic or anionic ester with non-allylic alcohol spices of following formula:
Wherein R is selected from that nonionic or negatively charged ion replace or unsubstituted C1-C30 straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; Each R ', R " and R " ' be selected from hydrogen respectively, nonionic or anionic replacement or unsubstituted C1-C25 straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; And n is 1 or greater than 1 integer;
C)-and a kind of ester of perfume alcohol, comprise at least one free carboxy, have following formula:
Wherein R is selected from and replaces or unsubstituted C1-C30 straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; R ' be under 760mmHg boiling point less than about 300 ℃ perfume alcohol; And n and m each naturally 1 or greater than 1 integer; With
D)-their mixture.
Another aspect of the present invention is, provide to have the method for protecting look and essence deposition and/or affinity on a kind of processed fabric in home treated, this method comprises the step that contacts with fabric with a kind of composition that contains fragrance precursor and amino-functional polymkeric substance.This contact procedure can be in water-bearing media as carrying out in rinse cycle, the preprocessing process, or in water-bearing media not as in the drum dried process, carry out.
Detailed Description Of The Invention
The amino-functional polymkeric substance
A necessary component of the present invention is the amino-functional polymkeric substance.Really, by this component, deposition and/or the affinity of fragrance precursor on the fabric of handling improved.The another one advantage of amino-functional polymkeric substance is that they provide care benefits to fabric color.
Amino-functional polymkeric substance of the present invention is water miscible or the dispersible polyamine of water.Typically, to have molecular weight be 200-10 for used here amino-functional polymkeric substance
6, preferred 600-20000, more preferably 1000-10000.These polyamine comprise straight chain or cyclic main chain.The polyamine main chain is also largely or comprise the polyamine side chain on the less degree.Polyamine main chain as described herein preferably is modified by this way, to such an extent as at least one of polyamine chain, be preferably each nitrogen-atoms after this all according to replacing, quaternised, oxidation, or the unit of its combination is described.
For the present invention, term " modification " refers to the hydrogen atom of using among R ' replacement unit main chain-NH (replacement) when it relates to the chemical structure of polyamine, and quaternized main chain nitrogen-atoms (quaternized) or oxidation main chain nitrogen-atoms form N-oxide compound (oxidation).When referring to use R ' replacement unit to be connected this process of hydrogen atom on the main chain nitrogen, term " modification " and " replacement " are used interchangeably.Quaternized or oxidation can take place in some cases and not replace, but replaces the oxidation that preferably is accompanied by at least one main chain nitrogen-atoms or quaternized.
The straight chain or the acyclic polyamine main chain that comprise the amino-functional polymkeric substance have following general formula:
The cyclic polyamine main chain that comprises the amino-functional polymkeric substance has following general formula:
By optional but before preferably being carried out substituting modification, above-mentioned main chain, comprise by R " connection " unit connect the primary, the second month in a season, tertiary amine nitrogen atom.
For the present invention, comprise that the main chain after the modification or the primary amine nitrogen-atoms of side chain are defined as V or Z " end " unit.For example, when the primary amine that is positioned at a polyamine main chain or a chain end partly has structure be
H
2N-[R]-
When carrying out modification according to the present invention, after this it is defined as V " end " unit, or abbreviates the V unit as.Yet for the present invention, some or all primary amine part can keep being subjected to hereinafter further specifying the unmodified state of restriction.These unmodified primary amine partly are because its position in main chain still is in the event in " end " unit.Equally, when the primary amine part-structure that is positioned at polyamine main chain end be
-NH
2
When carrying out modification according to the present invention, after this it is defined as Z " end " unit, or abbreviates the Z unit as.This element still keeps being subjected to hereinafter further specifying the unmodified state of restriction.
In a similar fashion, comprise that main chain or side chain secondary amine nitrogen atom after the modification are defined as W " main chain " unit.For example, when the chief component secondary amine of main chain of the present invention and side chain part, structure is
When carrying out modification, after this be defined as W " main chain " unit surely, or abbreviate the W unit as according to the present invention.Yet for the present invention, some or all secondary amine part still can keep unmodified state.These unmodified secondary amine partly are because its position in main chain still is in the event in " main chain " unit.
With alternative similar fashion, comprise that the main chain after changing or the tertiary amine nitrogen atom of side chain are called as Y " branching " unit.For example, when the structure as the tertiary amine part of the chain fulcrum of polyamine main chain or other side chain or ring is,
When carrying out modification according to the present invention, after this it is defined as Y " branching " unit, or abbreviates the Y unit as.Yet for the present invention, some or all tertiary amine part still can keep unmodified state.These unmodified tertiary amines partly are because its position in main chain still keeps the event in " branching " unit.Link to each other with V, W and Y unit nitrogen-atoms, work the R unit that is connected the effect of polyamine nitrogen-atoms and will be described below.
Therefore the final modified structure of polyamine of the present invention can be used following general formula:
V
(n+1)W
mY
nZ
With regard to the amino-functional polymkeric substance of straight chain, its general formula is:
V
(n-k+1)W
mY
nY’
kZ
With regard to the cyclic amino functional polymer.For the situation of the polyamine that comprises ring, formula:
Y ' unit play the branch point effect of main chain or supporting ring.For each Y ' unit, there is one and has following formula
, the Y unit that main polymer chain or straight chain formed the tie point of ring.At main chain is under the unique situation of unbroken loop, and the polyamine main chain has following formula
Therefore do not comprise the Z terminal units and have following formula
V
n-kW
mY
nY’
k
Wherein k forms the unitary number of rings of side chain.Polyamine main chain of the present invention does not preferably contain ring.
With regard to the non-annularity polyamine, the ratio of subscript n and subscript m relates to corresponding degree of branching.Modified polyamine according to a kind of complete unbranched straight chain of the present invention has following formula
VWmZ
That is, n equals 0.The value of n big more (m is more little to the ratio of n), the degree of branching is just high more in the molecule.Generally, the m value is preferably 4-400 within the scope of minimum value 2 to 700, yet, bigger m value is particularly very low or also be preferred near 0 the time as subscript n.
According to each polyamine nitrogen-atoms through modification of the present invention no matter be primary, the second month in a season or tertiary N atom, further be defined as a kind of of three kinds of common types: the simple replacement, quaternized or oxidation.Those unmodified polyamine nitrogen unit are classified into V, W, Y, Y ' or Z unit, and this depends on, and they are primary, the second month in a season or tertiary N atom.That is, for the present invention, unmodified primary amine nitrogen-atoms is V or Z unit, and unmodified secondary amine nitrogen atom is that W or Y ' unit and unmodified tertiary amine nitrogen atom are the Y unit.
The primary amine of modification partly is defined as V " end " unit, and it has one of following three kinds of forms:
A) simply replace the unit, its structure is
B) quaternized unit, its structure is
Wherein X provides the suitable gegenion of charge balance; With
C) oxidation unit, its structure is
The secondary amine of modification partly is defined as W " main chain " unit, and it has one of following three kinds of forms:
A) simply replace the unit, its structure is
B) quaternized unit, its structure is
Wherein X provides the suitable gegenion of charge balance; With
C) oxidation unit, its structure is
The secondary amine of other modification partly is defined as Y ' unit, and it has one of following three kinds of forms:
A) simply replace the unit, its structure is
B) quaternized unit, its structure is
Wherein X provides the suitable gegenion of charge balance; With
C) oxidation unit, its structure is
The tertiary amine of modification partly is defined as Y " branching " unit, and it has one of following three kinds of forms:
A) unmodified unit, its structure is
B) quaternized unit, its structure is
Wherein X provides the suitable gegenion of charge balance; With
C) oxidation unit, its structure is
The primary amine of some modification partly is defined as Z " end " unit, and it has one of following three kinds of forms:
A) simply replace the unit, its structure is
B) quaternized unit, its structure is
Wherein X provides the suitable gegenion of charge balance; With
C) oxidation unit, its structure is
When the optional position of nitrogen-atoms is in the not replacement state that is not modified, should be understood to replace R ' with hydrogen.For example, comprising a form is that the hydroxyethyl unitary primary amine of R ' unit partly is for having formula (HOCH
2CH
2) the V terminal units of HN-.
For the present invention, two types chain termination unit is arranged, V and Z unit.Z " end " unit derives from structure and is the amino part of the terminal primary of-NH2.Only comprise a Z unit according to non-annularity polyamine main chain of the present invention, and cyclic polyamines can not comprise the Z unit.Can replace Z " end " unit with any R ' unit that hereinafter further describes, unless be modified and form a kind of N oxide compound when the Z unit.Nitrogen in the Z unit is oxidized under a kind of situation of oxynitride, and nitrogen-atoms must be modified, and therefore R ' can not be a hydrogen.
Polyamine of the present invention comprises main chain R " connection " unit, and its effect is the nitrogen-atoms that connects on the main chain.For the present invention, the R unit comprises and is called as " alkyl R " unit and " oxygen base R " unitary unit." alkyl R " unit is C
2-C
12Alkylidene group; C
4-C
12Alkenylene; C
3-C
12The hydroxyl alkylidene group, wherein hydroxylic moiety can occupy on the R cellular chain except that with carbon atom that polyamine main chain nitrogen directly links to each other the optional position; C
4-C
12The dihydroxy alkylidene group, wherein hydroxylic moiety can occupy the R cellular chain except those with carbon atom that polyamine main chain nitrogen directly links to each other any two carbon atoms; C
8-C
12The dialkyl group arylidene, it is to have the arylidene part of two alkyl substituents as the part connection chain for the present invention.For example, the dialkyl group arylene units has general formula
Though this unit must not be 1,4-replaces, and can also be 1,2 or 1,3 C that replaces
2-C
12Alkylidene group, be preferably ethylene, propylene, and composition thereof, ethylene more preferably." 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 composition thereof.Preferred R unit is selected from C
2-C
12Alkylidene group, C
3-C
12Hydroxyl alkylidene group, C
4-C
12Dihydroxy alkylidene group, 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-, preferred R unit is C
2-C
12Alkylidene group, C
3-C
12Hydroxyl alkylidene group, C
4-C
12The dihydroxy alkylidene group ,-(R
1O) xR
1-,-(R
1O)
xR
5(OR
1)
x-, (CH
2CH (OH) CH
2O) z (R
1O) yR
1(OCH
2CH-(OH) CH
2) w-, and composition thereof, also preferred R unit is C
2-C
12Alkylidene group, C
3The hydroxyl alkylidene group, and composition thereof, C most preferably
2-C
6Alkylidene group.The most preferred main chain of the present invention comprises the R unit of at least 50% ethylene.
R
1The unit is C
2-C
6Alkylidene group, and composition thereof, be preferably ethylene.
R
2Be hydrogen and-(R
1O) xB, preferably hydrogen.
R
3Be C
1-C
18Alkyl, C
7-C
12Aryl alkylene, C
7-C
12Aryl, C that alkyl replaces
6-C
12Aryl, and composition thereof, be preferably C
1-C
12Alkyl, C
7-C
12Aryl alkylene, more preferably C
1-C
12Alkyl most preferably is methyl.R
3The unit is as the unitary part of hereinafter describing of R '.
R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkenylene, C
8-C
12Aryl alkylene, C
6-C
10Arylidene is preferably C
1-C
10Alkylidene group, C
8-C
12Aryl alkylene, more preferably C
2-C
8Alkylidene group most preferably is ethylene or butylidene.
R
5Be C
1-C
12Alkylidene group, C
3-C
12Hydroxyl alkylidene group, C
4-C
12Dihydroxy alkylidene group, 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 ethylene ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O) yR
1OCH
2CH (OH) CH
2-, more preferably-CH
2CH (OH) CH
2-.
R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene.
Preferably " oxygen base " R unit is further according to R
1, R
2, and R
5The unit defines.Preferably " oxygen base " R unit comprises preferred R
1, R
2, and R
5The unit.The preferred cotton goods stain remover of the present invention comprises the R of at least 50% ethylene
1The unit.Preferred R
1, R
2, and R
5The unit with " the oxygen base " R combines, and produces " oxygen base " R unit of preferred following manner.
I) with preferred R
5Replace to go into-(CH
2CH
2O) xR
5(OCH
2CH
2) generation-(CH among the x-
2CH
2O) xCH
2CHOHCH
2(OCH
2CH
2) x-.
Ii) with preferred R
1And R
2Replace to go into-(CH
2CH (OR
2) CH
2O) z-(R
1O) yR
1O (CH
2CH (OR
2) CH
2) generation-(CH among the w-
2CH (OH) CH
2O) z-(CH
2CH
2O) yCH
2CH
2O (CH
2CH (OH) CH
3) w-.
Iii) with preferred R
2Replace to go into-CH
2CH (OR
2) CH
3-middle generation-CH
2CH (OH) CH
2-.
R ' unit is selected from hydrogen, C
1-C
22Alkyl, C
3-C
22Alkenyl, 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, preferably hydrogen, C
2-C
22Hydroxyl alkylidene group, 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 is 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 is C
1-C
22Alkylidene group ,-(R
1O) xB and-C (O) R
3When not having modification or replace generation on nitrogen-atoms, then hydrogen atom will keep as the part of representing R '.Most preferred R ' unit is (R
1O) xB.
Oxidized when V, W or Z unit, when promptly nitrogen became oxynitride, R ' unit did not contain hydrogen atom.For example, main chain or side chain do not contain the unit of array structure down:
In addition, oxidized when V, W or Z unit, when promptly nitrogen became oxynitride, R ' unit did not contain the carbonyl moiety that directly links to each other with nitrogen-atoms.According to the present invention, R ' unit-C (O) R
3Part is free of attachment on the nitrogen-atoms of N oxide modifying, does not promptly have structure to be
Oxynitride acid amides or its mixture.
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, be preferably hydrogen ,-(CH
2) qSOxM ,-(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 the water-soluble cationic of hydrogen or the q.s that satisfies charge balance.For example, the Na positively charged ion can satisfy-(CH comparably
2) pCO
2M and-(CH
2) qSO
3M, generation-(CH thus
2) pCO
2Na and-(CH
2) qSO
3The Na part.Can be in conjunction with not only a kind of monovalent cation (sodium, potassium etc.), to satisfy needed chemical charge balance.Yet not only a kind of anionic group can be reached charge balance by divalent cation, or not only a kind of monovalent cation is that to satisfy the charge balance of polyanionic group necessary.For example, with sodium atom replace-(CH
2) pPO
3M partly has formula-(CH
2) pPO
3Na
3Can use divalent cation such as calcium (Ca
2+) or magnesium (Mg
2+) replace or combine with other suitable monovalence water-soluble cationic.Preferred cation is sodium and potassium, is more preferably sodium.
X is water soluble anion such as chlorine (Cl
-), bromine (Br
-) and iodine (I
-) or X can be any electronegativity group such as sulfate radical (SO
4 2-) and methylsulfate (CH
3SO
3 -).
Target value is as follows under the structural formula: the p value is 1-6, and the q value is 0-6; The r value is 0-1; The w value is 0 or 1, and the x value is 1-100; The y value is 0-100; The z value is 0 or 1; The m value is 2-700, be preferably 4-400, and the n value is 0-350, be preferably 0-200; The value of m+n is 5 at least.
Preferred x value is between the 1-20, is preferably 1-10.
The preferred property of the present invention amino-functional polymkeric substance contains the polyamine main chain, and wherein the R base of less than 50% contains " oxygen base " R unit, is preferably less than 20%, more preferably less than 5%, most preferred R unit do not contain " oxygen base " R unit.
The most preferred unitary amino-functional polymkeric substance of " oxygen base " R that do not contain comprises the polyamine main chain, and wherein the R base of less than 50% contains more than 3 carbon atoms.For example, ethylene, propylene and trimethylene are preferred " alkyl " R unit.Promptly working as main chain R unit is C
2-C
12During alkylidene group, quilt is C preferably
2-C
3Alkylidene group, most preferably ethylene.
Amino-functional polymkeric substance of the present invention comprises the homogeneous of modification or the polyamine main chain of non-homogeneous, wherein 100% or be lower than 100%-the NH unit is modified.For the present invention, term " the polyamine main chain of homogeneous " is defined as having the polyamine main chain of identical R unit (that is, being ethylene).Yet the definition of this identity is not got rid of and is comprised other and add unitary polyamine, and this adds the unit can comprise the main polymer chain that the artifact owing to selected chemical synthesis process exists.For example, those skilled in the art know that thanomin can be used as " initiator " when the synthesizing polyethylene imines, therefore, for the present invention, comprise an example that comes from the hydroxyethyl polymine partly of polymerization " initiator ", will be considered to comprise the polyamine main chain of homogeneous.The main chain that comprising all is the R unit of ethylene, wherein not have the unitary polyamine main chain of Y of branching be homogeneous.Comprising all is that the unitary polyamine main chain of R of ethylene is a kind of homogeneous main chain, the degree of it and branching or exist the number of ring-type side chain irrelevant.
For the present invention, term " main polymer chain of non-homogeneous " refers to the polyamine main chain of the combination of different R element lengths and R cell type.For example, a kind of main chain of non-homogeneous comprises the R unit of ethylene unit and the unitary mixture of propylene.For the present invention, " alkyl " and the unitary mixture of " oxygen base " R are not essential when forming the main chain of non-homogeneous.
The preferred amino-functional polymkeric substance of the present invention comprises the homogeneous polyamine main chain amino-functional polymkeric substance that all or part of quaternised, all or part of nitrogen oxide that partly replaced by polyethoxye, all or part of forms oxynitride, or their mixture.Yet not every main chain amine nitrogen atom must be modified in the same way, and the selection of modification is to decide on prescription teacher's concrete needs.The degree of ethoxylation also depends on the teacher's that fills a prescription specific requirement and decides.
The preferred polyamine that comprises the The compounds of this invention main chain generally is polyalkyleneimine (PAI ' s), by polymine preferably (PEI ' s), or by having the PEI ' s that the R cell mesh of being longer than parent PAI ' s or PEI ' s links to each other.
Preferred amine polymer main chain comprises C
2The unitary R of alkylidene group (ethylene) unit is also referred to as polymine (PEI ' s).Preferred PEI ' s has and is at least the medium degree of branching, and promptly the ratio of m and n is less than 4: 1, yet the ratio with m and n is that 2: 1 PEI ' s is most preferred.Before modification, preferred main chain has following general formula:
R ' wherein, m is identical with definition above with n.The molecular weight of preferred PEI ' s is greater than 200 dalton.
In the polyamine main chain primary, the relative proportion of the second month in a season and tertiary amine is different, especially under the situation of PEI ' s, this depends on the method for preparation.Concerning subsequently replacement, quaternized or oxygenizement, each hydrogen atom that links to each other with each nitrogen-atoms on the polyamine main chain is represented a kind of potential position.
These polyamine can pass through, and for example, the polymerising ethylene imines prepares in the presence of catalyzer, described catalyzer such as carbonic acid gas, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid etc.The concrete grammar for preparing these polyamine main chains is disclosed in the people's such as Ulrich that authorize December 5 nineteen thirty-nine U.S. Pat 2182306; The people's such as Mayle that on May 8th, 1962 authorized U.S. Pat 3033746; The people's such as Esselmann that on July 16th, 1940 authorized U.S. Pat 2208095; The U.S. Pat 2806839 of the Crowther that authorize September 17 nineteen fifty-seven; In the U.S. Pat 2553696 of the Wilson that authorize May 21 nineteen fifty-one; All documents are hereby incorporated by.
The example that comprises the amino-functional polymkeric substance of PEI ' s is illustrated by following formula I-IV:
Formula I has described a kind of amino-functional polymkeric substance of the PEI of comprising main chain, and wherein all commutable nitrogen are by using polyoxy alkylidene oxygen unit-(CH
2CH
2O) H replacement hydrogen comes modification, and it has following formula
Formula I
This is by the example of the amino-functional polymkeric substance of the complete modification of a class group.
Formula II has described a kind of amino-functional polymkeric substance of the PEI of comprising main chain, and wherein all commutable primary amine nitrogen are by using polyoxy alkylidene oxygen unit-(CH
2CH
2O)
2The H replacement comes modification for hydrogen, and this molecule comes modification by subsequently all oxidable primary and secondary nitrogen-atoms oxidations being formed N oxide compounds then, and this polymkeric substance has following formula
Formula II
Formula III has been described a kind of amino-functional polymkeric substance of the PEI of comprising main chain, and wherein all main chain hydrogen atoms all are substituted, and some main chain amine units are by quaternized.Substituting group is polyoxy alkylidene oxygen unit-(CH
2CH
2O)
7H or methyl.The PEI of modification has following formula
Formula III
Formula IV has described a kind of amino-functional polymkeric substance of the PEI of comprising main chain, and wherein main chain nitrogen (promptly passes through-(CH by replacing
2CH
2O)
3H or methyl substituted), quaternized, be oxidized to N oxide compound or its combination and be modified.The polymkeric substance that generates has following formula
Formula IV
In above-mentioned example, be not that all nitrogen-atoms of a kind of unit class all comprise identical modification mode.The present invention allows teacher of the prescription with the ethoxylation of part secondary amine nitrogen, and other secondary amine nitrogen is oxidized to the N oxide compound.This also is applicable to primary amine nitrogen because oxidation or quaternized before, the prescription teacher can be with all or part of primary amine nitrogen of one or more substituting groups selection modifications.The combination of any possible R ' group all can be substituted on primary amine and secondary amine nitrogen, except restriction described above.
Be fit to commercially available amino-functional polymkeric substance used herein and be to have MW and be 1200 polymine, the MW that Polysciences company sells is 2000 hydroxyethylation polymine and Aldrich company 80% hydroxyethylated polymine.
The general quantity that is used for the amino-functional polymkeric substance of the present composition is preferably up to 90% weight, and with composition weight meter, actives is preferably 0.01%-50% actives weight, more preferably 0.1%-20% weight and 0.5%-15% most preferably.
Fragrance precursor
The necessary component of another kind of the present invention is the fragrance precursor component.
A class fragrance precursor component that is suitable among the present invention is nonionic or the anionic ester as a kind of allyl alcohol spices of describing in WO96/02625.This fragrance precursor has following formula:
Wherein R is selected from nonionic or anionic replacement or unsubstituted C
1-C
30Straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; Each R ', R " and R " ' be selected from hydrogen respectively, or a kind of nonionic or anionic replacement or unsubstituted C
1-C
25Straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; And n is 1 or greater than 1 integer.
Preferred R is selected from nonionic or anionic replacement or unsubstituted C
1-C
20Straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; The R ' of at least one is a hydrogen; R " be hydrogen; A R " ' be hydrogen, methyl or ethyl, other R " ' be straight chain, side chain or cyclic, nonionic or anionic replacement or unsubstituted C
1-C
20Alkyl, thiazolinyl or alkaryl; And substituting group is selected from halogen, nitro, carboxyl, carbonyl, sulfate radical, sulfonate radical, hydroxyl and alkoxyl group and its mixture.
Preferred fragrance precursor is a kind of nonionic or anionic ester of allyl alcohol spices in this type of, and has following formula:
Wherein R is selected from nonionic or anionic replacement or unsubstituted C
1-C
30Straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; And n is 1 or greater than 1 integer.
In this type of preferred fragrance precursor component be those wherein the ester of allyl alcohol spices be selected from succsinic acid two geraniol esters, succsinic acid two flores aurantii esters, succsinic acid spiceleaf-flores aurantii ester, geranyl phenylacetate, neryl phenylacetate, lauric acid geraniol ester, lauric acid flores aurantii ester, and composition thereof.
Be adapted at nonionic or anionic ester that a class fragrance precursor component in addition used herein is a kind of non-allylic alcohol spices, described in U.S. Pat 5531910, and have following formula:
Wherein R is selected from nonionic or anionic replacement or unsubstituted C
1-C
30Straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; Each R ', R " and R " ' be selected from hydrogen respectively, or a kind of nonionic or anionic replacement or unsubstituted C
1-C
25Straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; And n is 1 or greater than 1 integer.
Preferably at least one R ' is a hydrogen; A R " ' be hydrogen or straight chain, side chain or cyclic C
1-C
20Alkyl or alkenyl.R more preferably " ' be hydrogen, methyl, ethyl or thiazolinyl and another R " ' be straight chain, side chain or cyclic C
1-C
20Alkyl, thiazolinyl or alkaryl.
Preferred ester comprises the ester of following spices alcohols in this type of: phenoxy group alcohol, fragrance of a flower alcohol, β-geraniol, nonyl alcohol (nonadyl alcohol), cyclohexyl ethyl alcohol, phenylethyl alcohol, iso-borneol, fenchyl alcohol, different cyclogeraniol, 2-phenyl-1-propyl alcohol and/or 3,7-dimethyl-1-octanol.
This type of most preferred ester used herein is: two-β-toxilic acid citronellyl acrylate, dinonyl maleate, toxilic acid hexichol oxygen ester, succsinic acid two (3,7-dimethyl-1-octyl group) ester, toxilic acid two (cyclohexyl ethyl) ester, succsinic acid two (floral base) ester and hexanodioic acid two (styroyl) ester.
Being adapted at another kind of fragrance precursor component used herein is the compound with ester of a kind of perfume alcohol, described in U.S. Pat 5562847.Described ester contains at least one free carboxyl, and has following formula
Wherein R is selected from and replaces or unsubstituted C
1-C
30Straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; R ' is that fusing point is lower than about 300 ℃ perfume alcohol under 760mmHg; And n and m each naturally 1 or greater than 1 integer.
Preferred R is selected from and replaces or unsubstituted C
1-C
20Straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl, aryl or contain a heteroatomic ring.Most preferred ester is the maleic acid ester of alcohols spices, succinate, pyromellitic ester, trimellitate, citrate, phthalic ester or adipic acid ester.As can be seen, formula (I) comprises at least one free carboxy.
R ' is that fusing point is lower than about 300 ℃ perfume alcohol under 760mmHg.Be lower than under all spendable situation of about 300 ℃ most of any perfume alcohol at fusing point, preferred alcohols comprises Geraniol, vernol, benzene oxygen alcohol, fragrance of a flower alcohol, β-geraniol, nonyl alcohol (nonadol), cyclohexyl ethyl alcohol, phenylethyl alcohol, Phenoxyethanol, iso-borneol, fenchyl alcohol, different cyclogeraniol, 2-phenyl-1-propyl alcohol, 3,7-dimethyl-1-octanol, anisy alcohol, styryl carbinol, the last of the ten Heavenly stems-9-alkene-1-alcohol, 3-methyl-5-phenyl-1-amylalcohol, 7-is right-first-1-alcohol, 2,6-dimethyl-octa-7-alkene-2-alcohol, (Z)-and oneself-3-alkene-1-alcohol, 1-hexanol, 2-hexanol, 5-ethyl-2-aldehyde C-9, the ninth of the ten Heavenly Stems-2,6-diene-1-alcohol, borneol, suffering-1-alkene-3-alcohol, 4-cyclohexyl-2-methyl-2-butanols, 2-methyl-4-phenyl-2-butanols, 2-methyl isophthalic acid-phenyl-2-propyl alcohol, the cyclohexyl methyl geraniol, decyl alcohol, p-Propylguaiacol, 8-is right-the Meng alkanol, 3,7-dimethyl-1-octanol, 2,6-dimethyl-2-enanthol, dodecanol, eucalyptol, oxymethoxyallylbenzene, tetrahydrochysene-2-isobutyl--4-methyl-4 (2H)-pyrans alcohol, isoeugenol, phantol, 2-methoxyl group-4-propyl group-1-hexalin, Terpineol 350, tetrahydromuguol, 3,7-dimethyl-3-octanol, 3-and 4-(4-hydroxy-4-methyl amyl group) hexamethylene-3-alkene-1-formaldehyde and their combination.
Most preferred alcohols (R ' base) be selected from Geraniol, vernol, benzene oxygen alcohol, fragrance of a flower alcohol, β-geraniol, nonyl alcohol (nonadol), cyclohexyl ethyl alcohol, phenylethyl alcohol, Phenoxyethanol, iso-borneol, fenchyl alcohol, different cyclogeraniol, 2-phenyl-1-propyl alcohol, 3,7-dimethyl-1-octanol, with their combination, and ester is preferably selected from the maleic acid ester of perfume alcohol, succinate, adipic acid ester, phthalic ester, citrate or pyromellitic ester.
Therefore, the preferred ester class of the present invention comprises the succsinic acid geraniol ester, succsinic acid flores aurantii ester, toxilic acid (β-citronellyl) ester, toxilic acid ester in the ninth of the ten Heavenly Stems (nonadyl maleate), toxilic acid benzene oxygen ester, succsinic acid (3,7-dimethyl-1-octyl group) ester, toxilic acid (cyclohexyl ethyl) ester, phthalic acid (β-citronellyl) ester, succsinic acid fragrance of a flower ester and hexanodioic acid phenethyl ester.Certainly, those of ordinary skills know that other ester class that satisfies general formula (I) also can be used among the present invention, as citric acid list geraniol ester, and the isomer of pyromellitic acid two (β-citronellyl) ester and citric acid two (cyclohexyl ethyl) ester and all such compounds.
Certainly, also can use the mixture of fragrance precursors herein, so that a kind of more graceful fragrance to be provided.
In above-mentioned disclosed fragrance precursor type, nonionic or anionic ester that a preferred class is an allyl alcohol spices.
During use, the consumption of optional fragrance precursor component is generally 0.01%-10% weight, is preferably 0.05%-5%, more preferably 0.1%-2%, with composition weight meter.
The dyestuff sticking agent
A kind of optional components of the present invention is the dyestuff sticking agent.Dyestuff sticking agent or " laking agent " are well-known commercially available materials, its objective is with since washing and be reduced to from the dyestuff that fabric loses minimum, thereby improve the outward appearance be colored fabric.Do not comprise the amino-functional polymkeric substance that those are hereinafter described as component or those of fabric softener within this range of definition.
Many dyestuff sticking agents are cationic, and are based on various quaternised or other positively charged organic nitrogen compounds.Cationic fixing agent can the extensive stock name be buied from manufacturer of a few family.Representative example comprises: available from CROSCOLOR PMF (in the July, 1981 of Crosfield company, Code No.7894) and CROSCOLOR NOFF (in January, 1988, CodeNo.8544), available from INDOSOL E-50 (on February 27th, 1984, the reference number 6008.35.84 of Sandoz company; Polyethylene amido cationic fixing agent); Also be the SANDOFIX TPS available from Sandoz company, it is a kind of preferred polycation laking agent used herein; With the SANDOFIX SWE (resin cation (R.C.) type compound) available from CHT-Beitlich GMBH company, REWIN SRF, REWIN SRF-O and REWIN DWR; Tinofix ECO, Tinofix FRD and Solfin available from Ciba-Geigy company.
Other cationic dyestuff sticking agent has been described in " improving the aftertreatment of dyestuff fastness on the fabric fibre " (Aftertreatments for improving the fastness of dyes ontextile fibres) of Christopher C.Cook (REV.PROG.COLORATION Vol.12,1982) literary composition.The cationic dyestuff sticking agent that is suitable among the present invention is ammonium compound such as lipid acid-diamines condenses, the for example hydrochloride of oil base diethylamino buserelin, acetate, Methylsulfate and benzyl ester hydrochloride, oil base methyl diethylenediamine Methylsulfate, the oxidation products of amino trimethyl ammonium Methylsulfate of single stearyl ethylene and tertiary amine; The derivative of alkyl diamine polymkeric substance, polyamine-cyanuryl chloride condenses and amination DCH.
The general quantity that is used for the dyestuff sticking agent of the present composition is preferably up to 90% weight, is preferably up to 50% weight, and 0.001%-10% weight more preferably, 0.5%-5% actives most preferably is with composition weight meter.
Polyolefin dispersion
Polyolefin dispersion can randomly be used for composition of the present invention, in order that the water-absorbent benefit of crease resistance and improvement is provided to fabric.Polyolefine is polyethylene preferably, polypropylene or its mixture.Polyolefine can be modified at least in part so that comprise various functional groups, as carboxyl, and carbonyl, ester group, ether, alkylamidoalkyl, sulfonic group or amide group.The polyolefine that more preferably is used for the present invention for to small part with carboxy-modified, or in other words, be oxidized.Polyethylene oxidation or carboxy-modified is particularly preferred in the composition of the present invention.
For being easy to preparation, preferably with polyethylene as a kind of suspension or a kind ofly add with emulsifying agent dispersive polyethylene emulsion.Polyethylene suspension or emulsion be preferably 1-50%, more preferably 10-35% weight, most preferably be 15-30% weight, in the polyethylene weight in emulsion.It is 1000-15000,4000-10000 more preferably that preferably polyethylene has molecular weight.
When using emulsion, emulsifying agent can be any suitable emulsification or suspension agent.Preferred solvent is positively charged ion, nonionic, zwitter-ion or anion surfactant or its mixture.Most preferred, be that any suitable positively charged ion, nonionic or anion surfactant all can be used as emulsifying agent.Preferred solvent is the aliphatic amide tensio-active agent of cats product such as aliphatic amide tensio-active agent, particularly ethoxylation.Particularly, cats product is preferred as emulsifying agent among the present invention.With the ratio of emulsifying agent or suspension agent dispersible polyolefin is emulsifying agent and the ratio of polyolefine is 1: 10-3: 1.Preferably, in polyolefin emulsion, comprise 0.1-50%, 1-20% and most preferably be the emulsifying agent of 2.5-10% weight more preferably.Be applicable to polyethylene emulsion of the present invention and suspension can trade(brand)name VELUSTROL available from the HOECHST Aktiengesellschaft of Frankfurtam Main of Germany.Particularly, with trade(brand)name VELUSTROL PKS, VELUSTROL KPA, or the polyethylene emulsion that VELUSTROL P-40 sells can be used in the composition of the present invention.
When it exists, composition of the present invention will comprise the dispersible polyolefin of 0.01%-8% weight, and 0.1%-5% weight more preferably most preferably is the polyolefine of 0.1%-3% weight.When polyolefine was added in the composition of the present invention as emulsion or suspension, the addition of emulsion or suspension should enough provide the content of dispersible polyolefin in the composition above-mentioned.
Non-polymeric chlorine scavenger
Non-polymeric chlorine scavenger is an another kind of optional components of the present invention.
The appropriate level of chlorine scavenger can be preferably 0.02%-10% in the present composition within the 0.01%-15% scope, most preferably is 0.25%-5%, in the gross weight of composition.If the positively charged ion of scavenging agent and negatively charged ion all react with chlorine, that is desirable, then can regulate dosage to the chlorine with the equivalent existence and react.
The chlorine scavenger of Shi Yonging is selected from non-polymeric ammonium salt herein.The non-polymeric ammonium salt that is adapted at herein using has following general formula:
[R
2N+R
3]X
-
R wherein
2Base is C
1-C
9Alkyl or replacement (for example hydroxylation) alkyl or hydrogen, be preferably hydrogen.
Each R is C
1-C
4Alkyl or replacement (for example hydroxylation) alkyl or hydrogen, be preferably methyl or hydrogen, hydrogen more preferably, and gegenion X
-Be compatible negatively charged ion, for example muriate, bromide, Citrate trianion, vitriol etc. are preferably muriate.
The example of most preferred non-polymeric ammonium salt be selected from ammonium chloride, ammonium sulfate, and composition thereof.Ammonium chloride is a kind of preferred cheap chlorine scavenger used herein.
The fabric softener component
Randomly, the fabric softener component also can suitably be used for composition of the present invention, so that flexibility and antistatic property are provided for processed fabric.When it used, the general amount of fabric softener component should enough provide flexibility and antistatic property.General content is the amount that those routines are used for fabric sofetening composition, i.e. the 1%-99% of composition weight.This depends on the preparation situation of composition, promptly be liquid or solid, for liquid composition, it is 1%-5% weight (rare composition) that composition preferably includes the fabric sofetening components contents, or 5%-80%, more preferably 10%-50%, most preferably be 15%-35% weight (concentrated composition).Under the situation that contains nonionic fabric softener component, the NON IONIC SOFTNER components contents is generally 0.1%-10% in the composition, is preferably 1%-5% weight.
Be used at the composition that comprises the softening agent component under the situation of substrate such as dried cloth, the preferred content of fabric softener component will be preferably 20%-99%, more preferably 30%-90% weight even 35%-85% weight more preferably.
Described fabric sofetening component can be selected from positively charged ion, nonionic, both sexes or anionic fabric sofetening component.
The soft component of preferred typical cationic fabric comprises the soft actives of water-insoluble quaternary ammonium fabric, and the most frequently used is two long alkyl chain ammonium chloride or Methylsulfate.
The preferred cation softening agent comprises following material in these materials:
1) ditallow dimethyl ammonium chloride (DTDMAC);
2) dihydro tallow alkyl dimethyl ammonium chloride;
3) dihydro tallow dimethyl methyl ammonium sulfate;
4) distearyl acyl group alkyl dimethyl ammonium chloride;
5) two oil base alkyl dimethyl ammonium chlorides;
6) two palmityl hydroxyethyl ammonio methacrylates;
7) stearyl-benzyl dimethyl ammonium chloride;
8) h-tallow base trimethyl ammonium chloride;
9) C
12-18Alkyl dihydroxy ethyl ammonio methacrylate;
10) ditallow tetrahydroglyoxaline Methylsulfate;
11) 1-(2-tallow amido-ethyl)-2-tallow tetrahydroglyoxaline Methylsulfate.
Yet, in recent years, the demand of the more compatible material of environment was risen, but the two long alkyl chain ammonium chloride that the quaternary ammonium compound that has occurred fast degraded biologically uses as tradition and the surrogate of Methylsulfate.Described material has been disclosed among many publications such as EP-A-0040562 and the EP-A-0239910 with the fabric sofetening component that comprises them.
Quaternary ammonium compound herein and amine precursor have following formula (I) or (II):
Wherein Q be selected from-O-C (O)-,-C (O)-O-,-O-C (O)-O-, NR
4-C (O)-,-C (O)-NR
4-;
R
1Be (CH
2) n-Q-T
2Or T
3
R
2Be (CH
2) m-Q-T
4Or T
5Or R
3
R
3Be C
1-C
4Alkyl or C
1-C
4Hydroxyalkyl or H;
R
4Be H or C
1-C
4Alkyl or C
1-C
4Hydroxyalkyl;
T
1, T
2, T
3, T
4, T
5Be respectively C
6-C
22Alkyl or alkenyl;
N and m are the integers of 1-4; With
X
-Be the negatively charged ion compatible with softening agent.
The anionic non-limiting instance compatible with softening agent comprises muriate or Methylsulfate.
Alkyl or alkenyl, chain T
1, T
2, T
3, T
4, T
5Must comprise 6 carbon atoms at least, be preferably at least 11 carbon atoms, more preferably at least 16 carbon atoms.Chain can be a straight or branched.
Butter are a kind of convenience and cheap raw materials of chain alkyl and alkenyl material.T wherein
1, T
2, T
3, T
4, T
5Representative generally as the compound of the mixture of the long-chain material of butter especially by preferably.
The specific examples that is suitable for the quaternary ammonium compound in the aqueous fabric soft compound comprises:
1) N, N-two (butter acyloxy ethyl)-N, N-alkyl dimethyl ammonium chloride;
2) N, N-two (butter acyloxy ethyl)-N-methyl, N-(2-hydroxyethyl) methylsulfuric acid ammonium;
3) N, N-two (tallow-oxygen base-2-oxo-ethyl)-N, N-alkyl dimethyl ammonium chloride;
4) N, N-two (tallow-oxygen base-ethyl carbonyl-oxygen base-ethyl)-N, N-alkyl dimethyl ammonium chloride;
5) N-(butter acyloxy-2-ethyl)-N-(tallow-oxygen base-2-oxo-ethyl)-N, the N-alkyl dimethyl ammonium chloride;
6) N, N, N-three (butter acyloxy ethyl)-N-ammonio methacrylate;
7) N-(tallow-oxygen base-2-oxo-ethyl)-N-tallow-N, the N-alkyl dimethyl ammonium chloride; With
8) 1,2-two butter acyloxy-3-trimethyl ammonium propane chloride;
9) two (stearoyl keto ethyl) alkyl dimethyl ammonium chlorides (DSOEDMAC);
Mixture with above-mentioned any material.
In the middle of these, compound 1-7 is formula (I) examples for compounds; Compound 8 is compounds of formula (II).
Particularly preferably be N, N-two (butter acyloxy ethyl)-N, the N-alkyl dimethyl ammonium chloride, wherein butter chain to small part is undersaturated.
The unsaturated tolerance of aliphatic chain can be determined by the iodine number (IV) of corresponding lipid acid, and it is should be preferably within the 5-200 scope under the situation of the present invention, is preferably 5-150,5-100 more preferably, and think iodine number less than or distinguish two compounds greater than 25.
In fact, for being 5-25 by iodine number, being preferably formula (I) compound that the tallow fatty acid of 15-20 is made, the weight ratio of having found suitable/trans isomer for greater than 30/70, be preferably more than 50/50, more preferably can provide best concentrated property greater than 70/30.
For the formula of being made greater than 25 tallow fatty acid by iodine number (I) compound, the ratio of having found cis-trans-isomer is not too important, unless need very high concentration.
The example of other suitable formula (I) and quaternary ammonium salt (II) can be obtained by following mode, for example:
-in above-claimed cpd, wait to replace " butter " with for example Oleum Cocois, plam oil, lauryl, oil base, castor oil-base, stearyl, palmityl, described fatty acyl chain or fully saturated, or preferably be that part is undersaturated at least;
-in above-claimed cpd, replace " methyl " with ethyl, oxyethyl group, propyl group, propoxy-, sec.-propyl, butyl, isobutyl-or the tertiary butyl;
-in above-claimed cpd, wait to replace " muriate " with bromide, Methylsulfate, formate, vitriol, nitrate.
In fact, negatively charged ion is the gegenion existence as the quaternary ammonium compound of positively charged.The character of gegenion is for unimportant in all practices of the present invention.Scope of the present invention is not thought and is limited to any special negatively charged ion.
" its amine precursor " refers to secondary amine and the tertiary amine corresponding to above-mentioned quaternary ammonium compound, at the amine described in the present composition because pH value and basically by protonated.
Other fabric sofetening material also can be used or with its surrogate as cationic fabric softener in addition.These fabric sofetening materials can be selected from nonionic, both sexes or anionic fabric sofetening material.Found that these materials are disclosed: US4327133 in following document; US4421792; US4426299; US4460485; US3644203; US4661269; U.S4439335; U.S3861870; US4308151; US3886075; US4233164; US4401578; US3974076; US4237016 and EP472178.
These nonionic fabric softener materials typically have the HLB value for 2-9, more be typically 3-7.Such nonionic fabric softener material is tending towards by itself, or combines as the alkyl cats product of the single long-chain that hereinafter will describe in detail with other material and disperseed apace by them.Dispersed improvement can mix with other material that hereinafter proposes mutually by using the alkyl cats product of more single long-chain, uses the water of heat, and/or stronger stirring.In general, selected material should be relative crystallization, more dystectic (for example＞40 ℃) and more water-insoluble.
Preferred NON IONIC SOFTNER is the fatty acid partial ester of polyvalent alcohol or its acid anhydrides, and wherein alcohol or acid anhydrides comprise 2-18, are preferably 2-8 carbon atom, and each fatty acid part comprises 12-30, is preferably 16-20 carbon atom.Such softening agent per molecule generally comprises 1-3, is preferably 2 for fatty acid-based.
The polyol moiety of ester can be ethylene glycol, glycerine, poly-(for example two, three, four, five, and/or six) glycerine, Xylitol, sucrose, tetrahydroxybutane, tetramethylolmethane, sorbyl alcohol or anhydro sorbitol.Isosorbide Dinitrate and Polyglycerine monostearate are particularly preferred.
The fatty acid part of ester derives from the lipid acid that has 12-30, is preferably 16-20 carbon atom usually, and the representative instance of described lipid acid is lauric acid, tetradecanoic acid, palmitinic acid, stearic acid He docosoic.
The NON IONIC SOFTNER that is used for very preferred optional of the present invention is an Isosorbide Dinitrate, and it is the esterification dewatered product of sorbyl alcohol, and glyceryl ester.
The commodity Arlacel-60 is a kind of suitable material.Having stearate/cetylate weight ratio is 10: 1-1: 10 sorbitan monostearate and the mixture of Span 40 and 1, the 5-Isosorbide Dinitrate also is suitable for.
Glycerine and polyglycerol ester, particularly glycerine, two glycerine, triglycerin and Polyglycerine list and/or diester, preferably monoesters is here by preferred (for example Polyglycerine monostearate of commodity Radiasurf 7248 by name).
The monoesters that glycerine that is suitable for and polyglycerol ester comprise stearic acid, oleic acid, palmitinic acid, lauric acid, Unimac 5680, tetradecanoic acid and/or docosoic and the diester of stearic acid, oleic acid, palmitinic acid, lauric acid, Unimac 5680, docosoic and/or tetradecanoic acid.Should be appreciated that general monoesters comprises some two-or three-esters etc.
" glyceryl ester " also comprise polyglycerol ester for example two glycerine until the ester of eight glycerine.The Polyglycerine polyvalent alcohol is by glycerine or Epicholorohydrin condensation together, forms through ehter bond connection glycerine part.The list of Polyglycerine polyvalent alcohol-and/or diester be preferred, fatty acyl group generally be above describe be used for those of anhydro sorbitol and glyceryl ester.
For the above-mentioned fabrics softening agent, particularly biodegradable fabric softener, the pH value of liquid composition is a call parameter of the present invention herein.In fact, it can influence the stability of quaternary ammonium compound or amine precursor compound, particularly under situation about extending shelf life.Ding Yi pH value is to measure in the composition pure in the time of 20 ℃ herein.For obtaining the stability to hydrolysis of these composition the bests, above-mentioned mention the pure state pH value of measuring under the condition must be within the 2.0-4.5 scope.Best, when liquid fabric softening composition of the present invention was conc forms, the pH value of pure state composition was within the 2.0-3.5 scope, and when it was dilute form, the pH value of pure state composition was within the 2.0-3.0 scope.The pH value of these compositions can be regulated by adding protonic acid herein.
The example of the acid that is fit to comprises inorganic mineral acid, carboxylic acid, particularly lower molecular weight (C
1-C
5) carboxylic acid and alkylsulphonic acid.The mineral acid that is fit to comprises HCl, H
2SO
4, HNO
3And H
3PO
4The organic acid that is fit to comprises formic acid, acetate, citric acid, methylsulphonic acid and ethylsulfonic acid.Preferred acid is citric acid, hydrochloric acid, phosphoric acid, formic acid, methylsulphonic acid and phenylformic acid.
Except that previously described component, the fabric sofetening composition of complete formula also preferably comprises one or more following components.
Concentrate composition of the present invention may need organic and/or inorganic concentrated assistant to reach higher concentration and/or to satisfy higher stability criterion, and this also depends on other component.The tensio-active agent concentrated assistant generally is selected from single-long-chain alkyl cats product, nonionogenic tenside, amine oxide, lipid acid or its mixture, and general usage quantity is the 0-15% of composition.
The ionic surfactant pack that is used for being fit to is herein drawn together the adduct of oxyethane and optional propylene oxide and Fatty Alcohol(C12-C14 and C12-C18), lipid acid and aliphatic amide.
The compound that is fit to is the water miscible basically tensio-active agent with following general formula:
R
2-Y-(C
2H
4O)
z-C
2H
4OH
R wherein
2Be selected from primary, the second month in a season and branched-chain alkyl and/or acyl group alkyl; The primary, the second month in a season and branched alkenyl alkyl; With the primary, the phenol alkyl that the second month in a season and branched-chain alkyl and alkenyl replace; Described alkyl has up to 20, be preferably the hydrocarbyl chain length of 10-18 carbon atom.
Y generally is-O-,-C (O) O-,-C (O) N (R)-or-C (O) N (R) R-, wherein ought there be R
2During with R, it has the above implication of defined, and/or R can be hydrogen, and z is 5-50, is preferably 1-30.
The HLB value (hydrophile-lipophile balance value) that is characterised in that of nonionogenic tenside herein is 7-20, preferred 8-15.
Particularly suitable ionic surfactant pack is drawn together:
-straight chain primary alcohol alcoxylates such as tallow alcohol-EO (11), tallow alcohol-EO (18) and tallow alcohol-EO (25);
-linear secondary alcoxylates such as 2-C
16EO (11), 2-C
20EO (11) and 2-C
16EO (14);
-alkyl phenolic alkoxy thing is as right-tridecyl phenol EO (11) and right-pentadecyl phenol EO (18); And
-olefinic alcoxylates and branched alkoxylates side chain primary and secondary alcohol as obtaining by well-known " OXO " method.
Also the inorganic viscosity control agent of useful as surfactants concentrated assistant or enhancing tensio-active agent concentrated assistant effectiveness comprises water miscible ionogenic salt (also can randomly join in the composition of the present invention).Many ionogenic salts all can be used.The example that is fit to salt is the halogenide of IA and IIA family metal in the periodic table of elements, for example calcium chloride, magnesium chloride, sodium-chlor, Potassium Bromide and lithium chloride.Ionizable salt forms in the process of this paper composition mixing each component, and is useful especially to the desirable viscosity of later acquisition.The usage quantity of ionizable salt depends on the amount of the active ingredient of using in the composition, and can regulate according to prescription teacher's hope.The salt amount that generally is used for control combination thing viscosity is 1,000,000/20-20000 (ppm), is preferably 20-11000ppm, with composition weight meter.
The poly-ammonium salt of alkylidene group can join in the composition so that viscosity controller to be provided in addition, or replaces above-mentioned water-soluble, ionogenic salt.In addition, these reagent can be used as scavenging agent, and form ion pair from main washing process, in the rinsing and at the anionic detergent that fabric is transferred, and can improve softness.Compare with inorganic electrolyte, these reagent can be within a wide temperature range stable viscosity, particularly at low temperatures.
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.
Optional perfume composition
The product here also can comprise 0.0001%-about 10%, more preferably about 0.001%-5%, the conventional perfume composition of more preferably about 0.01%-1% composition weight also.
Can use a large amount of known perfume compositions natural or synthetic source to prepare the flavor compositions of complete formula.The scope of natural matter material not only can comprise volatile component, but also comprise medium volatilization and little evaporable component, synthetic can comprise the representative in the aromatoising substance of all categories in fact, this will be obvious in following exemplary compilation: natural product class such as tree moss absolute, basil oil, both citrus fruit oil are (as Oils, bergamot peel, the orange wet goods), the Pistacia lentiscus absolute oil, Myrtus communis oil, rusa oil, patchouli oil, Paraguay's petitgrain oil, wormwood oil; Alcohols such as farnesol, Geraniol, phantol, vernol, phenylethyl alcohol, rhodinol, styryl carbinol; Aldehydes such as citral, Helional
TM, α-hexyl-phenylacrolein, laurine, Ling Lanquan [merchant] (right-tertiary butyl-Alpha-Methyl dihydro cinnamon aldehyde), methyl nonyl acetaldehyde; Ketone such as allyl ionone, α-Zi Luolantong, alpha, beta-lonone, isoraldeine (different methyl-α-Zi Luolantong), methylionone; Ester class such as Allyl Phenoxyacetate, benzyl salicylate, propionic acid cinnamyl ester, acetate citronellyl ester, ethoxy acid citronellyl ester, decyl acetate, acetate (dimethylbenzyl ylmethyl) ester (dimethylbenzylcarbinylacetate), butyric acid (dimethylbenzyl ylmethyl) ester (dimethylbenzylcarbinylbutyrate), methyl aceto acetate, methyl aceto acetate, isopropylformic acid hexenyl ester, phanteine, methyl dihydrojasmonate, styroyl acetate (styrallylacetate), vetiveryl acetate etc.; Lactone such as peach aldehyde; Be usually used in various components in the spices such as musk ketone, indoles, right-Meng alkane-8-mercaptan-3-ketone, and methyleugenol.Equally, also can add some conventional aromaticity acetal as known in the art or ketals in the composition of the present invention, as the optional components (c) of routine preparation essence.These conventional aromaticity acetals and ketal comprise well-known methyl and ethyl acetals and ketal, and based on the acetal or the ketal of phenyl aldehyde, the acetal and the ketal that contain the styroyl part, or the specialty chemicals of exploitation recently are called those acetals and ketal in the United States Patent (USP) of authorizing, transfer Givaudan company in " oxo-1; 2,3,4-tetraline and oxo-1; acetal of 2-indane and ketal ", on January 28th, 1992 as being described in name, referring to US5084440.Certainly, the essence combination that is used for Fabrid care composition of the present invention also can comprise other recent synthetic specialty chemicals.These chemical comprise oxo-1,2,3,4-tetralin and the oxo-1 that replaces as the alkyl described in the U.S. Pat 5332725 of authorizing, transfer Givaudan company on July 26th, 1994, the enol ester of 2-indane; Or as authorize, transfer Schiff's base described in the U.S. Pat 5264615 of Givaudan company on October 9th, 1991.
Another kind of optional but be liquid vehicle by preferred ingredients.The liquid vehicle that uses in the present composition preferably at least mainly is a water because its low cost, be easy to obtain relatively, safety and with the consistency of environment.The content of water is 50%, most preferably at least 60% at least preferably in the liquid vehicle, in vehicle weight.Water and lower molecular weight also are suitable for as liquid vehicle as＜200 the organic solvent such as the mixture of lower alcohols such as ethanol, propyl alcohol, Virahol or butanols.The lower molecular weight alcohols comprises monobasic, binary (glycol etc.), ternary (glycerine etc.) and higher polynary (polyvalent alcohol) alcohols.
Also having other optional component is soil release polymer, sterilant, tinting material, essence, sanitas, white dyes, anti-ionizer, defoamer etc.
It is various that other is optional, be that conventional binder component also can here use to the detergent formulation teacher of laundry or cleaning products.
The description of following component is in order to provide convenience for the prescription teacher, but does not plan to be confined to these components.
The decontamination component
The decontamination component also can be used in the composition of the present invention.The decontamination component that is fit to is that those detergent formulation teachers for laundry and cleaning products are conventional components.General these conventional decontamination components comprise decontamination tensio-active agent, washing assistant, bleaching compounds, and composition thereof.
The tensio-active agent of decontamination
The general content of Shi Yonging is that the limiting examples of the tensio-active agent of 1%-55% weight comprises conventional C herein
11-C
18Alkylbenzene sulfonate (" LAS ") and main chain, side chain and random C
10-C
20Alkyl-sulphate (" AS "); General formula is CH
3(CH
2) x (CHOSO
3 -M
+) CH
3And CH
3(CH
2) y (CHOSO
3 -M
+) CH
2CH
3C
10-C
18Secondary (2,3) alkyl-sulphate, wherein x and (y+1) be at least 7 integer, preferably be 9 at least, and M is water-soluble cationic, particularly sodium; Unsaturated vitriol such as oleyl sulfate; C
10-C
18Alkyl alkoxy sulfate (" AExS "; Particularly x is up to the ethoxy sulfate of 7 EO); C
10-C
18Alkyl alkoxy carboxylate salt (particularly EO is the ethoxy carboxylate of 1-5); C
10-C
18Glyceryl ether; C
10-C
18Alkyl polyglycoside and corresponding sulfation alkyl polyglycoside thereof; And C
12-C
18α-sulfonated fatty acid ester.If desired, also can contain conventional nonionic and amphoterics such as C in the whole composition
12-C
18Alkylethoxylate (" AE ") comprises so-called narrow peak alkylethoxylate and C
6-C
12Alkylphenol ethoxylate (particularly ethoxylate and blended oxyethyl group/propoxylated glycerine), C
12-C
18Trimethyl-glycine and sultaine, C
10-C
18Amine oxide, cats product etc.Also can use C
10-C
18N-alkyl polyhydroxy fatty acid amide.Typical example comprises C
12-C
18The N-methyl glucose amide.Referring to WO9206154.Other comprises N-alkoxyl group polyhydroxy fatty acid amide by sugared deutero-tensio-active agent, as C
10-C
18N-(3-methoxy-propyl) glucamide.Can use the C of N-propyl group during low the foaming until the N-hexyl
12-C
18Glucamide.Also can use C
10-C
20Conventional soap class.If want high the foaming, can use side chain C
10-C
16The soap class.The mixture of negatively charged ion and nonionogenic tenside is a particularly suitable.Other conventional tensio-active agent that is suitable for is listed in the standard textbook.
Washing assistant
Can randomly comprise washing auxiliary detergent in the composition herein, to help the control hardness of minerals.Can use inorganic and organic washing-assisting detergent.Washing assistant generally is used for fabric cleaning composition, to help removing the particulate state dirt.
The content of washing assistant can change in wide region, and this depends on the end-use and the desirable physical aspect thereof of composition.When described washing assistant existed, composition generally comprised at least 1% washing assistant, is preferably 1%-80%.Liquid formulations generally comprises 5%-50%, is more generally the detergent builder of 5%-30% weight.The particulate state prescription generally comprises 1%-80%, the more general detergent builder that comprise 5%-50% weight.Yet this does not also mean that the washing assistant of the lower or high level of eliminating.
Inorganic or contain the P detergent builder and comprise, but be not limited to, the basic metal of poly-phosphate, ammonium and alkanolamine salt (tri-polyphosphate for example, pyrophosphate salt and glass polymer metaphosphate), phosphonate, phytinic acid, silicate, carbonate (comprising two carbonate and sesquicarbonate), vitriol and aluminosilicate.Yet, need nonphosphate builders in some occasion.Importantly, the composition of this paper even in the presence of what is called " weak " washing assistant (comparing with phosphoric acid salt) such as Citrate trianion perhaps exists under what is called " low-builder " situation of zeolite or layered silicate washing assistant, also function well astoundingly.
The example of silicate-like builder is alkalimetal silicate, particularly has a SiO
2: Na
2The ratio of O is 1.0: 1-3.2: those alkalimetal silicates of 1, and layered silicate, as be described in lamina sodium silicate among the US4664839.NaSKS-6 is by the trade name of the commercially available crystalline layered silicate of Hoechst company (being abbreviated as " SKS-6 " herein usually).Be different from zeolite builders, the NaSKS-6 silicate-like builder does not contain aluminium.NaSKS-6 has δ-Na
2SiO
5The layered silicate of morphology form.Its preparation method can be as being described in those methods among German patent DE-A-3417649 and the DE-A-3742043.SKS-6 is the very preferred layered silicate that is used for herein, but also can use other such layered silicate herein, as has general formula NaMSi
xO
2x+1YH
2O (wherein M is sodium or hydrogen, x be 1.9-4 number, be preferably 2, y be 0-20 number, be preferably 0) those layered silicates.Various other layered silicates that Hoechst company sells comprise as α, the form NaSKS-5 of beta, gamma, NaSKS-7 and NaSKS-11. as mentioned above, δ-Na
2SiO
5(NaSKS-6 form) be used for most preferred herein.Other silicate also can be for example Magnesium Silicate q-agent that is suitable for, its in particulate state prescription as a kind of crisp dose, in oxygen bleaching agent as stablizer with as a kind of component of the suds hierarchy of control.
The example of carbonate builders is alkaline-earth metal and alkaline carbonate, as is described in disclosed German patent application DE2321001 on November 15th, 1973 those.
The aluminosilicate washing assistant is suitable in the present invention.The aluminosilicate washing assistant is very important in the at present commercially available dirty granular detergent composition of weight of great majority, and also can be as a kind of effective builder component in liquid detergent formula.The aluminosilicate washing assistant comprises those with following empirical formula:
M
z/n[(AlO
2)
z(SiO
2)
y]·xH
2O
Wherein z and y are for usually being 6 integer at least, and the mol ratio of z and y is 1.0-0, and x is the integer of 0-264, and M is IA and IIA family element, Na for example, and K, Mg, Ca, its valency are n.
The aluminosilicate ion exchange material that is suitable for is can buy on the market.These aluminosilicates can be crystallization or unbodied structure, and can be the aluminosilicates in naturally occurring aluminosilicate or synthetic source.A kind of method for preparing the aluminosilicate ion exchange material is disclosed in the U.S. Pat 3985669 that authorize on October 12nd, 1976, people such as Krummel.The preferred synthesising crystal aluminium silicate ion exchange material of Shi Yonging can be buied with trade mark zeolite A, zeolite P (B), zeolite MAP and X zeolite herein.In particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has general formula:
Na
12[(AlO
2)
12(SiO
2)
12]·xH
2O
Wherein x is 20-30, particularly 27.This material is called as zeolite A.Here also can use dehydration zeolite (x=0-10).The granular size of aluminosilicate is preferably diameter 0.1-10 micron.
The organic detergent auxiliary agent that is fit to the object of the invention comprises, but is not to limit various polycarboxylic acid salt compounds.Here " polycarboxylate " of Shi Yonging refers to the compound with a plurality of carboxyls, preferably is at least 3 carboxyls.The polycarboxylate washing assistant generally is added in the composition with the form of acid, but the form of the salt after also can neutralizing adds.When its form with salt is used, basic metal such as sodium, potassium, and lithium, or alkanolamine salt is preferred.
Comprise various types of other useful material in the polycarboxylate washing assistant.A kind of polycarboxylate washing assistant of important class comprises the ether polycarboxylate, comprise the oxidation disuccinate, be disclosed in the U.S. Pat 3635830 of authorizing in 18 days January in 1972 of people such as the U.S. Pat 3128287 of authorizing in 7 days April in 1964 of Berg and Lamberti.Also referring to " TMS/TDS " washing assistant in the U.S. Pat 4663071 of authorizing people such as Bush on May 5th, 1987.The ether polycarboxylate who is suitable for also comprises ring compound, particularly alicyclic compound, as is described in U.S. Pat 3923679; 3835163; 4158635; 4120847; With 4102903 in those compounds.
Other washing assistant that is suitable for comprises the ether hydroxy-polycarboxylate, the multipolymer of maleic anhydride and ethene or ethene methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyl oxygen base succsinic acid, the basic metal of various poly-acetate, ammonium and substituted ammonium salt such as ethylenediamine tetraacetic acid (EDTA) and nitrilo acetic acid, and polycarboxylate such as mellitic acid, 1,2,4,5-pyromellitic acid, succsinic acid, oxidation disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxy methoxy-succinic acid and their soluble salt.
The Citrate trianion washing assistant, for example citric acid and water-soluble salt thereof (particularly sodium salt) they are the polycarboxylate washing assistants of particularly important in the heavy duty liquid laundry detergent prescription, reason is that they can be obtained and their biological degradability by renewable resource.Citrate trianion also can be used in the granular composition, especially is used in combination with zeolite and/or layered silicate washing assistant.The oxidation disuccinate also is useful especially in these compositions and mixture.
Also be applicable to be disclosed 3 in the U.S. Pat 4566984 of the Bush that authorizes on January 28th, 1986 in the present composition, 3-dicarboxyl-4-oxa--1,6-adipate and relevant compound.Useful succsinic acid washing assistant comprises C
5-C
20Alkyl and alkenyl succinic and salt thereof.In this type, be the dodecenyl succinic succsinic acid by preferred compound especially.The object lesson of succinate washing assistant comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The lauryl succinate is a preferred washing assistant in this group, and is described in the European patent EP 0200263.
Other polycarboxylate that is suitable for is disclosed among U.S. Pat 4144226 and the US3308067.Also referring to US3723322.
Lipid acid, for example C
12-C
18Monocarboxylic acid such as oleic acid and/or its salt also can join in the composition separately, or combine with aforesaid washing assistant, especially Citrate trianion and/or succinate washing assistant and to join in the composition, so that additional washing assistant activity to be provided.So use lipid acid generally can cause reducing whipability, this prescription teacher should consider.
Under situation about can use, especially, can use various alkali metal phosphates tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate as everyone knows at the prescription of the detergent bar that is used for hand-washing operation based on the washing assistant of phosphorus.Phosphate builders such as ethane-1-hydroxyl-1,1-diphosphate and other known phosphate (referring to, for example U.S. Pat 3159581; US3213030; US3422021; US3400148 and US3422137) also can use.
Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach activator
Composition can randomly comprise SYNTHETIC OPTICAL WHITNER or contain SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more bleach activators herein.When having SYNTHETIC OPTICAL WHITNER, its amount is generally detergent composition, in particular for the 1%-30% of the detergent composition of laundering of textile fabrics, be more generally 5%-20%.If there is bleach activator, its amount is generally the 0.1%-60% that contains SYNTHETIC OPTICAL WHITNER and add the bleaching composition of bleach activator, is more generally 0.5%-40%.
The SYNTHETIC OPTICAL WHITNER of Shi Yonging is to show the known any SYNTHETIC OPTICAL WHITNER useful to detergent composition in the known cleaning use that maybe will become in fabric cleaning or other herein.These SYNTHETIC OPTICAL WHITNER comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Can use perborate bleach herein, for example Sodium peroxoborate (for example its monohydrate or tetrahydrate).
The another kind of SYNTHETIC OPTICAL WHITNER that can use without restriction comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The example that this class SYNTHETIC OPTICAL WHITNER is suitable comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid and diperoxy dodecanedioic acid.These SYNTHETIC OPTICAL WHITNER are disclosed among US4483781, US740446, EP0133354 and the US4412934.Most preferred SYNTHETIC OPTICAL WHITNER comprises also in the U.S. Pat 4634551 that 6-amino in the ninth of the ten Heavenly Stems-6-oxo of describing crosses oxy hexanoic acid.
Also can use peroxygen bleach.The peroxy bleaching agent compound that is fit to comprises yellow soda ash peroxyhydrate and suitable " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example OXONE is produced on a large scale by DuPont).
Preferred percarbonate bleach comprises that median size is 500 microns-1000 microns a dried particle, and the described particle that is no more than 10% weight is less than 200 microns, and the described particulate that is no more than 10% weight is greater than 1250 microns.Percarbonate can randomly apply with silicate, borate or water soluble surfactant active.Percarbonate can be from various commercially available sources as from FMC, Solvay and Tokai Denka obtain.
Also can use the mixture of SYNTHETIC OPTICAL WHITNER.
Peroxygen bleach, perborate, percarbonate etc. preferably are used in combination with bleach activator, and this causes producing on the spot the peroxy acid that is equivalent to bleach activator in the aqueous solution (promptly at washing process).The various limiting examples of promoting agent are disclosed among U.S. Pat 4915854 and the US4412934.Nonanoyl hydroxy benzene sulfonate (NOBS), 3,5,5-trimethyl acetyl base hydroxy benzene sulfonate (ISONOBS) and tetra acetyl ethylene diamine (TAED) promoting agent are normally used, and also can use their mixture.Typical SYNTHETIC OPTICAL WHITNER of useful herein other and promoting agent are also referring to the references to U.S. patent US4634551 of this paper.
Most preferred bleach activator derived from amido comprises (6-decoyl amino-caproyl) phenolsulfonate; (6-nonanoyl amino-caproyl) hydroxy benzene sulfonate; (6-caprinoyl amino-caproyl) hydroxy benzene sulfonate; and composition thereof, they are described in the U.S. Pat 4634551 that is hereby incorporated by.
Another kind of bleach activator comprises that people such as Hodge are disclosed in the benzo oxazinyl promoting agent in the U.S. Pat 4966723.Also have another kind of preferred bleach activator to comprise the acyl lactam activator.Most preferred lactan activator comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5; 5-trimethyl acetyl base caprolactam, nonanoyl hexanolactam, decanoyl hexanolactam, undecylene acyl caprolactam, benzoyl Valerolactim, capryloyl Valerolactim, decanoyl Valerolactim, undecylene acyl group Valerolactim, nonanoyl Valerolactim, 3; 5,5-trimethyl acetyl base Valerolactim and their mixture.Also the U.S. Pat 4545784 of authorizing Sanderson referring on October 8th, 1985 is incorporated herein this patent as a reference, this patent disclosure comprise the acyl lactam of benzoyl caprolactam, it is attracted in the Sodium peroxoborate.
Those SYNTHETIC OPTICAL WHITNER of non-oxygen type SYNTHETIC OPTICAL WHITNER also are as known in the art and can here use.The non-oxygen type of class SYNTHETIC OPTICAL WHITNER with special benefit comprises the SYNTHETIC OPTICAL WHITNER of photoactivation, as sulfonation phthalocyanine phthalocyanine zinc and/or aluminium.Referring to the U.S. Pat 4033718 of authorizing people such as Holcombe on July 5th, 1977.If be used, detergent composition generally contains this SYNTHETIC OPTICAL WHITNER, particularly sulfonation phthalocyanine phthalocyanine zinc of 0.025%-1.25% weight.
If desired, can come the catalytically bleaching compound by manganic compound.Such compound is well-known in the art, comprises for example disclosed manganese-based catalyst in US5246621, US5244594, US5194416, US5114606 and EP549271A1,549272A1,544440A2 and 544490A1.
In fact and without restriction, can adjust herein composition and method, be approximately 1/10,000,000 active bleaching catalyst class so that provide in aqueous cleaning solution, the catalyzer class in washings is preferably 0.1ppm-700ppm, more preferably 1ppm-500ppm.
Other preferred optional component comprises enzyme, for example lipase, proteolytic enzyme, cellulase, amylase and peroxidase.Preferred enzyme used herein is a cellulase.In fact, this fermentoid has the benefit to the color and luster nursing of processed fabric in addition.The available cellulase comprises bacteria type and the plain enzyme of mould fiber type herein, and preferably having optimal ph is 5-9.5.Authorized on March 6th, 1984 and disclose the plain enzyme of the mould fiber type that is suitable for that produces by unusual detritus enzyme (Humicola insolens) or detritus enzyme (Humicola) strain DSM 1800 in people's such as Barbesgoard the U.S. Pat 4435307, or belong to the cellulase 212 of generation mould of Aeromonas and the cellulase that extracts from a kind of hepatopancreas of Dolabella Auricula Solanderd sea mollusk.The cellulase that is fit to also is disclosed GB-A-2075028; GB-A-2095275; In DE-OS-2247832.CAREZYME and CELLUZYME (Novo) are useful especially.Other cellulase that is fit to also is disclosed the WO91/17243 of Novo, and WO96/34092 is among WO96/34945 and the EP-A-0739982.
What be adapted at using is comprised enzyme stabilizers by the preferred optional component herein in addition in addition, the polymerization stain remover, to in cleaning process, stoping dyestuff to be transferred to another kind of fabric effective substance (being dye transfer inhibitor) from a kind of fabric, polymeric dispersant, suds suppressor, white dyes or other increase gorgeous or whitening agent, sequestrant, the fabric sofetening clay, static inhibitor, other active ingredient, carrier, hydrotropic agent, processing material, dyestuff or pigment, the solvent of liquid formulations and for the solid packing of bar compositions.
When being formulated into liquid detergent composition, composition comprises water and other solvent as carrier.Low-molecular-weight primary alconol or secondary alcohol for example methyl alcohol, ethanol, propyl alcohol and Virahol are fit to.For solubilizing surfactant, monohydroxy-alcohol is preferred, but for example also can use those polyvalent alcohols that contain 2-6 carbon atom and 2-6 hydroxyl (for example 1, ammediol, ethylene glycol, glycerol and 1,2-propylene glycol).Composition can comprise 5%-90%, is generally this carrier of 10%-50%.
When being formulated into granular detergent composition, detergent composition can prepare by for example spraying drying (the finished product density 520g/l) or agglomeration (the finished product density is greater than 600g/l) base-material particle.Then the dried component of remainder is for example admixed with the base-material particle in the rotation tempering tank mutually with granular or powder-form, and liquid ingredient (for example anion surfactant and essence) can spray into.
The detergent composition of this paper preferably is mixed with such form, and when consequently using in moisture cleaning operation, washing water have the pH value and are 6.5-11, are preferably 7.5-10.5.Laundry product pH value is generally 9-11.Technology in the use range of suggestion that the pH value is controlled at comprises uses damping fluid, alkali, acid etc., and this is known to those skilled in the art.
Method
A kind of deposition of protecting look and fragrance precursor and/or method of affinity of providing on the fabric of home treated is provided another aspect of the present invention.Use composition according to the present invention is compared with using the composition that does not contain poly-amino-functional polymkeric substance, observes the fragrance precursor deposition of improvement on processed fabric, reaches fragrance lasting and that improve thus on processed fabric.Use composition of the present invention to compare with using the composition that does not contain poly-amino-functional polymkeric substance, the fabric of also observing raising protects look.
Home treated comprises water-bearing media and the contacted step of fabric with the composition that contains the preamble definition.The preferred temperature of described water-bearing media is 2-40 ℃, more preferably 5-25 ℃.
Also having another kind of home treated is that composition of the present invention is applied to substrate, on a kind of cloth of doing.Therefore, the present invention also provides a kind of the have deposition of protecting look and fragrance precursor and/or the method for affinity on the fabric of home treated, this method comprises the contacted step of composition with fabric and preamble definition, wherein said composition is applied in substrate, is preferably on a kind of cloth of doing.Be applied at composition of the present invention under the situation of more dried cloth, preferably in the drum dried process, use described composition.
" fragrance precursor deposition and/or the affinity improved on fabric " refers to, compare with the composition that comprises fragrance precursor but do not comprise the amino-functional polymkeric substance, be presented at spices deposition and/or affinity better or identical on the fabric with the contacted fabric of composition of the present invention.
The deposition of evaluation fragrance precursor on the fabric of handling and/or the benefit of affinity are that fabric by evaluation hang airing and drum dried discharges spices from the fragrance precursor component after last 6 day intensity is estimated.This method is undertaken by one 6 people's expert judging group.These experts are through using sensory evaluation's training.In this case, the expert is defined as and trained at least 6 months, and existing evidence proves the people with olfactory sensitivity.To use data that blending gas strength grade obtains in addition average then, and obtain homogeneity value as the aroma strength of awaring.
The aroma strength grade is as follows:
0-does not have fragrance,
The slight fragrance of 25-,
The medium fragrance of 50-,
The fragrance that 75-is very strong and
The fragrance that 100-is extremely strong.
" protecting look " refers to, contact with the composition of the present invention of preamble definition, and after contact and/or before and/or simultaneously with the fabric of detergent composition cleaning, and do not compare with the contacted fabric of said composition, the former demonstrates better fabric color outward appearance.
Can estimate the benefit of protecting look by range estimation or by measuring so-called δ-E value.
When using visual assessment, expert's level group is according to the expert that set up the organizational level of marking, by range estimation come relatively with and the fabric need not compositions-treated of the present invention crossed.Positive PSU value shows to have protects the look performance preferably.(the PSU rank: 0=is as broad as long, and it is distinguishing that 1=I think, and I know and have any different that I know that very big difference is arranged 3=2=, and I know that great difference is arranged 4=).
Evaluation is to measure so-called δ-E value to the another kind of method of protecting the look benefit of fabric.δ-E value for example is defined among the ASTM D2244.δ-E value as defined in ASTM D2244 be the aberration that calculates, promptly be defined as tristimulus values, or on two psychophysics of tristimulus coordinates and luminance factor chromaticness in the difference of size and Orientation, it be by one the cover specific colour difference formula calculate into, this formula is defined as the anti-color space (opponent-color space) among CIE 1976 CIELAB, the anti-color space of Hunter, Friele-MacAdam-Chickering color space or any identical color space.
Use
Composition of the present invention is applicable to any home treated step, promptly can be used as pretreatment compositions, and laundry additive is applicable to the composition in the rinse cycle of laundry cycles, or is applied on the dried cloth.Obviously, for the present invention, can realize multiple application,, can also be applicable to composition of the present invention in the rinse cycle thereafter and/or be used for dried cloth as handling fabric with pretreatment compositions of the present invention.Composition of the present invention can also spraying, foam or aerocolloidal form for example are applicable to flatiron or be applied to the surface of rotary drum dryer.
With following non-limiting examples the present invention is described, outside the person, wherein all per-cent is all in actives weight unless otherwise stated.
In an embodiment, the component symbol of abbreviation has following meaning: DEQA: two-(tallow-oxygen base-ethyl) alkyl dimethyl ammonium chloride DOEQA: two-(oil base oxygen base ethyl) dimethyl methyl ammonium sulfate DTDMAC: ditallow dimethyl ammonium chloride DHEQA: two-(soft tallow base-oxygen base-ethyl) hydroxyethyl methyl
Methylsulfuric acid ammonium lipid acid: tallow fatty acid IV=18 ionogen: calcium chloride DTDMAMS: ditallow dimethyl methyl ammonium sulfate SDASA: ratio is 1: 2 a stearyl dimethyl amine: three press tristearin
Acid Glycosperse S-20: available from the sorbitan monostearate clay of Lonza: calcium bentonite clay, wilkinite L, by Southern
Clay Products sells TAE25: have the butter that every mol of alcohol is 25 moles of ethylene oxide
Alcohol ethoxylate PEG: Macrogol 4000 PEI 1800 E1: ethoxylation polymine (MW 1800,50% activity
Thing), synthetic PEI 1800 E3 in synthetic embodiment 1: ethoxylation polymine (MW 1800,50% activity
Thing), according to synthetic embodiment 1 synthetic PEI 1800 E7 AO: the amine oxide (MW of ethoxylation polymine
1800,50% activess), close according to synthetic embodiment 4
Become PEI 1200 E1: the ethoxylation polymine (MW 1200, in water
50% actives), synthetic PEI 1200 E2 in synthetic embodiment 5: the ethoxylation polymine (MW 1200, in water
50% actives), synthesize PEI 1200 E7 according to synthetic embodiment 5: the ethoxylation polymine (MW 1200, in water
50% actives), according to synthetic embodiment 5 synthetic PEI 1200 E7 AO: the amine oxide (MW of ethoxylation polymine
1200,50% actives), according to synthetic embodiment 5
With 4 synthetic Dye Fix 1: available from the commodity of Ciba-Geigy Tinofix by name
The cationic dyestuff sticking agent of Eco (50% actives) Dye Fix 2: available from the commodity of CHT-Beitlich Rewin by name
(30% lives the emulsification cationic dyestuff sticking agent of SRF-O
The property thing) NH4Cl: ammonium chloride succsinic acid two geraniol esters: 1, the 4-Succinic Acid (3,7-dimethyl-2-6-octadiene
Base) ester lauric acid geraniol ester: dodecylic acid (3,7-dimethyl-2-6-octadienyl)
Ester succsinic acid spiceleaf/flores aurantii ester: 1, the 4-Succinic Acid, (3,7-dimethyl-2-6-octadiene
Base) ester toxilic acid two (cyclohexyl ethyl) ester: 1,4-Succinic Acid (2-cyclohexyl-ethyl) ester LAS: straight chain C
12Sodium alkyl benzene sulfonate TAS: tallow alcohol sodium sulfate C25AS:C
12-C
15Straight-chain alkyl sulfate CxyEzS: with the C of z moles of ethylene oxide condensation
1x-C
1yBranched alkane
Base sodium sulfate C45E7: with the C of average 7 moles of ethylene oxide condensations
14-15Straight chain
Be main primary alconol C25E3: with the C of average 3 moles of ethylene oxide condensations
12-15Side chain
Primary alconol cationic ester: C
12/ C
14The mixture soap of cholinesterase: derive from 80/20 butter and coconut oil blend
Straight-chain alkyl carboxylic acid's sodium TFAA:C
16-C
18Alkyl N-methyl glucose amide TPKFA:C
12-C
14The full cut lipid acid of topping zeolite A: molecular formula is Na
12(AlO
2SiO
2)
1227H
2The hydration of O
Sodium aluminium silicate, main size range 0.1-10 micron citric acid: Citric Acid, usp, Anhydrous Powder carbonate: anhydrous sodium carbonate, granularity are 200-900 μ m silicate: amorphous sodium silicate (SiO
2: Na
2O is 2.0) vitriol: the anhydrous slufuric acid na citrate: activity is 86.4% citrate trisodium dihydrate, grain
Degree is distributed as 425-850 μ mMA/AA:1: toxilic acid/acrylic copolymer of 4, mean molecule
Measure approximately 70,000CMC: Xylo-Mucine Savinase: activity is the proteolytic enzyme Carezyme of 4KNPU/g: actively be the cellulase Termamyl of 1000CEVU/g: actively be the amylase Lipolase of 60KNU/g: activity is the lipase of 100KLU/g
All these enzymes are sold by NOVO Industries A/S, and have above-mentioned active PB4 except that other has the stipulator: general formula is NaBO
23H
2OH
2O
2Sodium perborate tetrahydrate PB1: general formula is NaBO
2H
2O
2Anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER TAED: tetraacetyl ethylene diamine DTPMP: two Asias of the commodity Dequest 2060 by name that sells by Monsanto
Ethyl triamine five (methylene phosphonic acid) photoactivation SYNTHETIC OPTICAL WHITNER: the sulfonation phthalocyanine phthalocyanine zinc whitening agent of sealing with the dextrin soluble polymer: 4,4 '-two (4-anilino-6-morpholino-1,3,5-triazines-2-yl) ammonia
Base) stilbene-2:2 '-disulfonic acid disodium silicone suds suppressor: polydimethylsiloxane Foam Control
(Polydimethyl diloxane) with as the oxidation Asia of dispersion agent
The multipolymer of alkylsiloxane, described control agent and described dispersion agent
Ratio is 10: 1-100: 1
The preparation of synthetic embodiment 1-PEI 1800 E1
Steps A)-and in the stainless steel autoclave that one 2 gallons bands stir, carrying out ethoxylation, described autoclave is furnished with that temperature survey and control, pressure survey, vacuum and rare gas element wash that still purifies, sampling and device that oxyethane is added as liquid.Prepare an oxyethane steel cylinder (ARC) that net weight is about 20 pounds, will send in the autoclave as the oxyethane of liquid by pump, steel cylinder is placed on the scale pan to monitor the changes in weight of steel cylinder.
The polymine (PEI) of a 750g (originate from the Epomin SP-018 of Nippon Shokubai, the sequence average molecular weight is 1800, be equivalent to 0.417 moles of polymer and 17.4 mole of nitrogen effects) is joined in the autoclave.Then autoclave is sealed side by side net air (be evacuated to negative 28 " Hg, then be forced into 250psia, be vented to normal atmosphere then) with nitrogen.The content of autoclave is heated to 130 ℃ to vacuumize simultaneously.After about 1 hour, autoclave fills nitrogen and cools off extremely about 105 ℃ of autoclaves simultaneously to about 250psia.Then oxyethane is incrementally joined in time the flow velocity of pressure, temperature and the oxyethane of careful simultaneously control autoclave in the autoclave.Turn off the oxyethane pump, and the enforcement cooling is to limit any temperature rising that is produced by the reaction heat radiation.Temperature is maintained at 100-110 ℃ of while and in reaction process total pressure is raise gradually.In total amount is (roughly being equivalent to each PEI nitrogen and 1 moles of ethylene oxide works) after the oxyethane of 750 grams fill into autoclave, temperature is risen to 110 ℃, to the other restir of autoclave 1 hour.At this moment, open vacuum to remove any residual unreacted oxyethane.
Step B)-then to the reaction mixture deodorization, make about 100 cubic feet rare gas element (argon or nitrogen),, stir simultaneously and heated mixt to 130 ℃ again by reaction mixture by a kind of gas dispersion frit.
Final reacting product is cooled off a little and be collected in the Glass Containers of crossing with purging with nitrogen gas.
In another kind of preparation method, in reactor, finish neutralization and deodorization before the discharging.
If want PEI 1800 E7, between steps A and B, also comprise the step of following adding catalyzer.
Continue to open vacuum, simultaneously autoclave is cooled to about 50 ℃, add the methanol solution (1.74 moles) of the sodium methylate of 376g 25% simultaneously to reach 10% catalyst weight based on the effect of PEI nitrogen.Under vacuum, methylate solution is drawn in the autoclave, rises to 130 ℃ with the set-point of the temperature regulator that is about to autoclave.Use a kind of device to control the used up power of agitator.Monitor the power of agitator with temperature and pressure.Along with methyl alcohol is discharged from autoclave, agitator power and temperature value raise gradually, and mixture viscosity increases, and stablizes about 1 hour, and this shows that most of methyl alcohol is discharged from.Then mixture is further heated, and under vacuum, stirred in addition again 30 minutes.
Remove vacuum and autoclave is cooled to 105 ℃, charge into nitrogen therein to 250psia simultaneously, be vented to ambient pressure then.Autoclave is charged into the nitrogen of 200psia.Again oxyethane is joined in the autoclave gradually as the front with increasing, the flow velocity of simultaneously careful monitoring autoclave pressure, temperature and oxyethane, holding temperature is at 100-110 ℃ simultaneously, and limits any because the temperature rising that the reaction heat radiation causes.When the add-on of oxyethane after several hours reaches 4500g when (causing every mole of PEI nitrogen and 7 moles of ethylene oxide effects altogether), temperature is risen to 110 ℃, and mixture was stirred 1 hour more in addition.
Then reaction mixture is collected in the container that purging with nitrogen gas crosses, transfers at last in the three neck round-bottomed bottles that heating and whipping appts are housed of a 22L.By adding in the 167g methylsulfonic acid (1.74 moles) and alkali catalyst.
The available aforesaid method of other preferred examples such as PEI 1800 E2, PEI 1800 E3, PEI 1800 E15 and PEI 1800 E20, the relative quantity by the oxyethane that uses in adjusting reaction time and the reaction prepares.
Synthetic quaternised PEI 1800 E7 of embodiment 2-4.7%
In a 500ml Erlenmeyer flask that magnetic stirring bar is housed, add MW and be 1800, ethoxylation degree is 7 polymine (224g, 0.637mol nitrogen is as synthetic embodiment 1 preparation) and acetonitrile (Baker, 150g, 3.65mol).(Aldrich, 3.8g 0.030mol) once join in the solution of quick stirring entirely, then its jam-pack and stirring are at room temperature spent the night with methyl-sulfate.Boiling off acetonitrile on the rotatory evaporator under～60 ℃, obtaining at～80 ℃～desired material of 220g by Kugelrohr device (Adrich) subsequently, this material is the brownish black thick liquid.
13C-NMR (D
2O) spectrum shows and does not exist～peak corresponding to methyl-sulfate of 58ppm.
1H-NMR (D
2O) spectrum shows at 2.5ppm (methylene radical that is connected with not quaternised nitrogen) the skew of part peak to～3.0ppm place.
The oxidation of synthetic quaternized PEI 1800 E7 of embodiment 3-4.7%
In a 500ml Erlenmeyer flask that magnetic stirring bar is housed, add MW and be 1800, ethoxylation degree be 7 and reach～4.7% quaternised polymine (121.7g with methyl-sulfate, the oxidable nitrogen of～0.32mol, as preparation in synthetic embodiment 2), hydrogen peroxide (Adrich, the aqueous solution of 50% weight of 40g, 0.588mol), and water (109.4g).With the Erlenmeyer flask jam-pack, after the initial heat release, at room temperature stirred solution spends the night.
1H-NMR (D
2O) the spectrum total offset that shows the ethylidene peak at 2.5-3.0ppm to～3.5ppm place.The 0.5%Pd of adding～5g on alumina particle in the solution, make solution leave standstill at room temperature state～3 days.There is not remaining superoxide in the superoxide spike paper demonstration system.This product stores with 46.5% the aqueous solution.
The formation of the amine oxide of synthetic embodiment 4-PEI 1800 E7
In a 500ml Erlenmeyer flask that magnetic stirring bar is housed, add molecular weight and be 1800, (PEI 1800 for the polymine of about 7 oxyethyl groups of each nitrogen for ethoxylation degree, E7) (209g, 0.595mol nitrogen, as preparation in synthetic embodiment 1), and hydrogen peroxide (aqueous solution of 30% weight of 120g, 1.06mol).With the Erlenmeyer flask jam-pack, after initial heat release, at room temperature stirred solution spends the night.Obtain by sample of reaction mixture
1H-NMR (D
2O) spectrum shows conversion fully.Owing near the not resonance of the methene proton of nitrogen oxide atom, be displaced to～3.5ppm from the zero position of～2.5ppm.Add the 0.5%Pd on alumina particle of about 5g in the reaction solution, solution is kept at room temperature left standstill about 3 days.Do not find superoxide with spike paper test soln.The product that obtains is fit to store with the aqueous solution of 51.1% actives.
The preparation of synthetic embodiment 5-PEI 1200 E1
Steps A)-and in the stainless steel autoclave that one 2 gallons bands stir, carrying out ethoxylation, described autoclave is furnished with that temperature survey and control, pressure survey, vacuum and rare gas element wash that still purifies, sampling and device that oxyethane is added as liquid.Prepare an oxyethane steel cylinder (ARC) that net weight is about 20 pounds, will send in the autoclave as the oxyethane of liquid by pump, steel cylinder is placed on the scale pan to monitor the changes in weight of steel cylinder.
The polymine (PEI) of a 750g (have the sequence average molecular weight be 1200, be equivalent to about 0.625 mole polymkeric substance and 17.4 mole of nitrogen effects) is joined in the autoclave.Then autoclave is sealed side by side net air (be evacuated to negative 28 " Hg, then be forced into 250psia, be vented to normal atmosphere then) with nitrogen.The content of autoclave is heated to 130 ℃ to vacuumize simultaneously.After about 1 hour, autoclave is filled nitrogen and is cooled off extremely about 105 ℃ of autoclaves simultaneously to about 250psia.Then oxyethane is incrementally joined in time the careful simultaneously flow velocity that monitors pressure, temperature and the oxyethane of autoclave in the autoclave.Turn off the oxyethane pump, and the enforcement cooling is to limit any temperature rising that is produced by the reaction heat radiation.Temperature remains on 100-110 ℃ of while and in reaction process total pressure is raise gradually.In total amount is (roughly being equivalent to each PEI nitrogen and 1 moles of ethylene oxide effect) after 750 oxyethane that restrain fill into autoclave, temperature is risen to 110 ℃, to the other restir l of autoclave hour.At this moment, open vacuum to remove any residual unreacted oxyethane.
Step B)-then to the reaction mixture deodorization, make about 100 cubic feet rare gas element (argon or nitrogen),, stir simultaneously and heated mixt to 130 ℃ again by reaction mixture by a kind of gas dispersion frit.
Final reacting product is cooled off a little and be collected in the Glass Containers of crossing with purging with nitrogen gas.
In another kind of preparation method, in reactor, finish neutralization and deodorization before the discharging.
If want PEI 1200 E7, between steps A and B, also comprise the step of following adding catalyzer.
Continue to open vacuum, simultaneously autoclave is cooled to about 50 ℃, add the methanol solution (1.74 moles) of the sodium methylate of 376g25% simultaneously to reach 10% catalyst weight based on the effect of PEI nitrogen.Under vacuum, methylate solution is drawn in the autoclave, rises to 130 ℃ with the set-point of the temperature regulator that is about to autoclave.Use a kind of device to control the used up power of agitator.Monitor the power of agitator with temperature and pressure.Along with methyl alcohol is discharged from autoclave, agitator power and temperature value raise gradually, and mixture viscosity increases, and stablizes about 1 hour, and this shows that most of methyl alcohol is discharged from.Then mixture is further heated, and under vacuum, stirred in addition again 30 minutes.
Remove vacuum and autoclave is cooled to 105 ℃, charge into nitrogen therein to 250psia simultaneously, be vented to ambient pressure then.Autoclave is charged into the nitrogen of 200psia.Again oxyethane is joined in the autoclave gradually as the front with increasing, the flow velocity of simultaneously careful monitoring autoclave pressure, temperature and oxyethane, holding temperature is at 100-110 ℃ simultaneously, and limits any because the temperature rising that the reaction heat radiation causes.When the add-on of oxyethane after several hours reaches 4500g (every mole of PEI official's energy nitrogen produces 7 moles of ethylene oxide altogether), temperature is risen to 110 ℃, and mixture was stirred 1 hour more in addition.
Then reaction mixture is collected in the container that purging with nitrogen gas crosses, transfers at last in the three neck round-bottomed bottles that heating and whipping appts are housed of a 22L.By adding in the 167g methylsulfonic acid (1.74 moles) and alkali catalyst.
The available aforesaid method of other preferred examples such as PEI 1200 E2, PEI 1200 E3, PEI 1200 E15 and PEI 1200 E20, the relative quantity by the oxyethane that uses in adjusting reaction time and the reaction prepares.
The corresponding amine oxide of above-mentioned ethoxylation PEI also can prepare according to synthetic embodiment 4.
Synthetic quaternised PEI 1200 E7 of embodiment 6-9.7%
In a 500ml Erlenmeyer flask that magnetic stirring bar is housed, add MW and be 1200, ethoxylation degree is 7 polymine (248.4g, 0.707mol nitrogen is as synthetic embodiment 5 preparations) and acetonitrile (Baker, 200mL).(Aldrich, 8.48g 0.067mol) once join in the solution of quick stirring entirely, then its jam-pack and stirring are at room temperature spent the night with methyl-sulfate.Boiling off acetonitrile on the rotatory evaporator under～60 ℃, obtaining at～80 ℃～desired material of 220g by Kugelrohr device (Adrich) subsequently, this material is the brownish black thick liquid.
13C-NMR (D
2O) spectrum shows and does not exist～peak corresponding to methyl-sulfate of 58ppm.
1H-NMR (D
2O) spectrum shows at 2.5ppm (methylene radical that is connected with not quaternised nitrogen) the skew of part peak to～3.0ppm place.
4.7% oxidation of synthetic quaternized PEI 1200 E7 of embodiment 7-9.5%
In a 500ml Erlenmeyer flask that magnetic stirring bar is housed, add MW and be 1200, ethoxylation degree be 7 and reach～9.5% quaternised polymine (144g with methyl-sulfate, the oxidable nitrogen of～0.37mol, as preparation in embodiment 6), hydrogen peroxide (Adrich, 35.4g the aqueous solution of 50% weight, 0.52mol), and water (100g).With the Erlenmeyer flask jam-pack, after initial heat release, at room temperature stirred solution spends the night.
1H-NMR (D
2O) the spectrum total offset that shows the ethylidene peak at 2.5-3.0ppm to～3.5ppm place.In solution, add just 40% aqueous solution of sodium bisulfite of enough amounts, make residual peroxide level reduce to 1-5ppm.The sodium sulfate that forms causes aqueous phase separation, and described water comprises salt, but does not almost have or do not contain organism.Remove aqueous salt face, obtain needed oxidic polyethylene imine derivative and store with 52% the aqueous solution.Embodiment 1 is except composition 1 and 2, and following composition is according to of the present invention.
| Component | ????A | ????B | ?C | ?D | ?E | ?F |
| DEQA | ????2.6 | ????2.9 | ?18.0 | ?19.0 | ?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 | ?0.02 |
| PEG | ????- | ????- | ?0.6 | ?0.6 | ?0.6 | ?0.6 |
| Succsinic acid two geraniol esters | ????0.6 | ????- | ?- | ?- | ?0.8 | ?- |
| The lauric acid geraniol ester | ????- | ????- | ?0.6 | ?- | ?- | ?- |
| Toxilic acid two (cyclohexyl ethyl) ester | ????- | ????0.5 | ?- | ?- | ?- | ?0.8 |
| Succsinic acid spiceleaf/flores aurantii ester | ????- | ????- | ?- | ?0.6 | ?- | ?- |
| Spices | ????0.5 | ????0.7 | ?1.0 | ?1.5 | ?0.7 | ?0.5 |
| Carezyme (Cevu/g) | ????- | ????- | ?- | ?12 | ?- | ?- |
| Silicone suds suppressor | ????0.01 | ????0.01 | ?0.01 | ?0.01 | ?0.01 | ?0.01 |
| PEI?1200?E1 | ????3 | ????3 | ?3 | ?3 | ?3 | ?- |
| PEI?1200?E2 | ????- | ????- | ?- | ?- | ?- | ?3 |
| Laking agent 1 | ????- | ????1 | ?1 | ?1 | ?1 | ?- |
| Laking agent 2 | ????- | ????2 | ?2 | ?2 | ?2 | ?- |
| Ionogen (ppm) | ????- | ????- | 600 | ?600 | ?600 | ?1200 |
| Dyestuff (ppm) | ????10 | ????10 | 50 | ?50 | ?50 | ?50 |
| NH4Cl | ????- | ????- | - | ?- | ?0.5 | ?- |
| Surplus is water and minor component to 100 | ||||||
| Component | ????G | ????H | ????I | ????J |
| DEQA | ?????- | ????- | ????- | ????- |
| TAE25 | ?????- | ????- | ????- | ????- |
| Lipid acid | ?????- | ????- | ????- | ????- |
| Hydrochloric acid | ?????- | ????- | ????- | ????- |
| PEG | ?????- | ????- | ????- | ????- |
| Succsinic acid two geraniol esters | ?????0.1 | ????- | ????- | ????- |
| The lauric acid geraniol ester | ?????- | ????0.1 | ????0.3 | ????- |
| Toxilic acid two (cyclohexyl ethyl) ester | ?????- | ????- | ????- | ????0.5 |
| Succsinic acid spiceleaf/flores aurantii ester | ?????- | ????- | ????- | ????- |
| Spices | ?????0.1 | ????0.2 | ????- | ????0.1 |
| Carezyme (Cevu/g) | ?????12 | ????- | ????- | ????- |
| Silicone suds suppressor | ?????- | ????- | ????- | ????- |
| PEI?1200?E1 | ?????15 | ????15 | ????- | ????10 |
| PEI?1200?E2 | ?????- | ????- | ????10 | ????- |
| Laking agent 1 | ?????- | ????- | ????10 | ????- |
| Laking agent 2 | ?????- | ????- | ????- | ????- |
| Ionogen (ppm) | ?????- | ????- | ????- | ????- |
| Dyestuff (ppm) | ?????- | ????- | ????- | ????- |
| NH4Cl | ?????- | ????1.0 | ????- | ????- |
| Surplus is water and minor component to 100 |
| Component | ????K | ?L | ?M | ?N | ?O |
| DTDMAC | ????- | ?- | ?- | ?- | ?- |
| DEQA | ????2.6 | ?2.9 | ?18.0 | ?19.0 | ?19.0 |
| TAE25 | ????0.3 | ?- | ?1.0 | ?- | ?0.1 |
| 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 |
| Succsinic acid two geraniol esters | ????0.5 | ?- | ?- | ?- | ?1.0 |
| The lauric acid geraniol ester | ????- | ?0.5 | ?- | ?- | ?- |
| Toxilic acid two (cyclohexyl ethyl) ester | ????- | ?- | ?0.8 | ?- | ?- |
| Succsinic acid geraniol ester/succsinic acid flores aurantii ester | ????- | ?- | ?- | ?0.8 | ?- |
| Spices | ????0.5 | ?1.0 | ?- | ?1.0 | ?0.5 |
| Silicone suds suppressor | ????0.01 | ?0.01 | ?0.01 | ?0.01 | ?0.01 |
| PEI?1800?E1 | ????3 | ?- | ?- | ?3 | ?- |
| PEI?1200?E1 | ????- | ?3 | ?3 | ?- | ?3 |
| Laking agent 1 | ????1 | ?- | ?1 | ?1 | ?3 |
| Laking agent 2 | ????2 | ?- | ?2 | ?2 | ?- |
| Ionogen (ppm) | ????- | ?- | 600 | ?600 | ?1200 |
| Dyestuff (ppm) | ????10 | ????10 | ?50 | ?50 | ?50 |
| Surplus is water and minor component to 100 | |||||
| Component | P | ????Q | ?????R | ?S | ????1 | ????2 * |
| DTDMAC | - | ???- | ????4.5 | ??15 | ????- | ???- |
| DEQA | - | ???- | ????- | ??- | ????2.6 | ???19 |
| TAE25 | - | ???- | ????- | ??- | ????0.3 | ???- |
| Lipid acid | - | ???- | ????- | ??- | ????0.3 | ???- |
| Hydrochloric acid | - | ???- | ????0.02 | ??0.02 | ????0.02 | ???0.02 |
| PEG | - | ???- | ????- | ??0.6 | ????- | ???0.6 |
| Succsinic acid two geraniol esters | - | ???- | ????1.0 | ??- | ????- | ???- |
| The lauric acid geraniol ester | 0.8 | ???- | ????- | ??- | ????- | ???- |
| Toxilic acid two (cyclohexyl ethyl) ester | - | ???0.5 | ????- | ??- | ????- | ???- |
| Succsinic acid geraniol ester/succsinic acid flores aurantii ester | - | ???- | ????- | ??0.5 | ????- | ??- |
| Spices | 0.5 | ???0.5 | ????0.8 | ??0.5 | ????1.0 | ??2.0 |
| Silicone suds suppressor | - | ???- | ????0.01 | ??0.01 | ????0.01 | ??0.01 |
| PEI?1800?E1 | 10 | ???- | ????- | ??3 | ????3 | ??- |
| PEI?1200?E1 | - | ???15 | ????3 | ??- | ????- | ??3 |
| Laking agent 1 | 10 | ???5 | ????1 | ??1 | ????1 | ??1 |
| Laking agent 2 | - | ???- | ????2 | ??2 | ????2 | ??2 |
| Ionogen (ppm) | - | ???- | ????- | ??600 | ????- | ??- |
| Dyestuff (ppm) | - | ???- | ????10 | ??50 | ????10 | ??50 |
| Surplus is water and minor component to 100 | ||||||
(*) spices that uses in the composition 2 is a kind of hydrophobicity flavor compositions, and it is 3 or littler component that the spices that promptly wherein is lower than 25% weight comprises Clog P, as definition in the U.S. Pat 5460736.
The following composition that embodiment 2 is used to add the drying machine cloth is according to composition of the present invention.
| ????T | ????U | ????V | ????W | ????X | ????Y | |
| DOEQA | ????40 | ????25 | ????- | ????- | ???- | ????- |
| DHEQA | ????- | ????- | ????20 | ????- | ???- | ????- |
| DTDMAMS | ????- | ????- | ????- | ????20 | ???12 | ????60 |
| SDASA | ????30 | ????30 | ????20 | ????30 | ???20 | ????- |
| Glycosperse?S- 20 | ????- | ????- | ????10 | ????- | ???- | ????- |
| Zerol | ????- | ????- | ????- | ????20 | ???10 | ????- |
| Clay | ????4 | ????4 | ????3 | ????4 | ????4 | ????- |
| Succsinic acid two geraniol esters | ????- | ????1.0 | ????- | ????- | ????- | ????0.5 |
| The lauric acid geraniol ester | ????- | ????- | ????0.5 | ????- | ????- | ????- |
| Toxilic acid two (cyclohexyl ethyl) ester | ????- | ????- | ????- | ????0.8 | ????- | ????- |
| Succsinic acid geraniol ester/succsinic acid flores aurantii ester | ????0.5 | ????- | ????- | ????- | ????0.2 | ????- |
| Spices | ????0.5 | ????0.5 | ????0.5 | ????0.8 | ????0.8 | ????1.0 |
| PEI?1800?E1 | ????- | ????5 | ????- | ????- | ????- | ????- |
| PEI?1200?E1 | ????- | ????- | ????4 | ????2.2 | ????- | ????- |
| PEI?1800?E3 | ????2 | ????- | ????- | ????- | ????5 | ????7.0 |
| Laking agent 1 | ????2 | ????5 | ????4 | ????2.2 | ????5 | ????3 |
| Surplus is a stearic acid | ||||||
Embodiment 3
Following detergent formulations X and Y are according to detergent formulations of the present invention.
| Z | ?AA |
| Zeolite A | ????24.0 | ?23.0 |
| Vitriol | ????9.0 | ?- |
| ????MA/AA | ????4.0 | ?4.0 |
| ????LAS | ????8.0 | ?8.0 |
| ????TAS | ????- | ?2.0 |
| Silicate | ????3.0 | ?3.0 |
| ????CMC | ????1.0 | ?0.4 |
| Whitening agent | ????0.2 | ?- |
| Soap | ????1.0 | ?- |
| ????DTPMP | ????0.4 | ?0.4 |
| ????C45E7 | ????2.5 | ?2.0 |
| ????C25E3 | ????2.5 | ?2.0 |
| Silicone suds suppressor | ????0.3 | ?5.0 |
| Toxilic acid two (cyclohexyl ethyl) ester | ????1.0 | ?1.0 |
| Spices | ????0.3 | ?0.3 |
| Carbonate | ????13.0 | ?16.0 |
| Citrate trianion | ????- | ?5.0 |
| ????PB4 | ????18.0 | ?- |
| ????PB1 | ????4.0 | ?14.0 |
| ????TAED | ????3.0 | ?6.0 |
| The photoactivation SYNTHETIC OPTICAL WHITNER | ????0.02％ | ?- |
| ????Savinase | ????1.0 | ?1.0 |
| ????Lipolase | ????0.4 | ?0.4 |
| ????Termamyl | ????0.30 | ?0.6 |
| ????Carezyme | ????- | ?0.6 |
| ????PEI?1800?E7?AO | ????1.0 | ?- |
| ????PEI?1200?E7?AO | ????- | ?1.0 |
| Surplus (moisture content and assorted component) is to 100 | ||
Embodiment 4
Following liquid detergent preparation produced according to the present invention.
| ????AB |
| ?C25AS | ????13 |
| ?C25E3S | ????2 |
| ?TFAA | ????6 |
| ?C 12-14The alkyl dimethyl hydroxyethyl ammonium chloride | ????1 |
| Cationic ester | ????1.5 |
| ?TPKFA | ????15 |
| Citric acid | ????1 |
| Ethanol | ????2 |
| 1, the 2-propylene glycol | ????8 |
| NaOH to pH | ????7.5 |
| ?DTPMP | ????1.2 |
| ?Savinase | ????0.5 |
| ?Termamyl(300KNU/g) | ????0.15 |
| Boric acid | ????1.5 |
| The bentonite type mild clay | ????4 |
| Suspended clay SD3 | ????0.3 |
| ?PEI?1200?E7 | ????1 |
| Succsinic acid geraniol ester/succsinic acid flores aurantii ester | ????0.5 |
| Spices | ????0.5 |
| Surplus (moisture and assorted component) | ????100 |
Claims (16)
1. Fabrid care composition that comprises fragrance precursor and amino-functional polymkeric substance is characterized in that described fragrance precursor is selected from:
A)-a kind of nonionic or anionic ester with allyl alcohol spices of following formula:
Wherein R is selected from that nonionic or negatively charged ion replace or unsubstituted C1-C30 straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; Each R ', R " and R " ' be selected from hydrogen respectively, nonionic or negatively charged ion replace or unsubstituted C1-C25 straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; And n is 1 or greater than 1 integer;
B)-a kind of nonionic or anionic ester with non-allylic alcohol spices of following formula:
Wherein R is selected from that nonionic or negatively charged ion replace or unsubstituted C1-C30 straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; Each R ', R " and R " ' be selected from hydrogen respectively, nonionic or negatively charged ion replace or unsubstituted C1-C25 straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; And n is 1 or greater than 1 integer;
C)-and a kind of ester of perfume alcohol, comprise at least one free carboxy, have following formula:
Wherein R is selected from and replaces or unsubstituted C
1-C
30Straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl or aryl; R ' be under 760mmHg boiling point less than about 300 ℃ perfume alcohol; And n and m each naturally 1 or greater than 1 integer; With
D)-their mixture.
2. according to the composition of claim 1, wherein said amino-functional polymkeric substance comprises the polyamine main chain corresponding to following formula:
Its polyamine general formula is V
(n+)W
mY
nZ, or corresponding to the polyamine main chain of following formula:
Its polyamine general formula is V
(n-k+1)W
mY
nY '
kZ, wherein k is for being less than or equal to n, and described polyamine main chain has molecular weight greater than 200 dalton, wherein
I) the V unit is the terminal units with following formula:
Ii) the W unit is the backbone units with following formula:
Iii) the Y unit is the chain unit with following formula:
With
Iv) Y ' unit is the branch point of main chain or supporting ring, has following formula:
V) the Z unit is the terminal units with following formula:
The R unit that wherein connects main chain is selected from C
2-C
12Alkylidene group, C
4-C
12Alkenylene, C
3-C
12Hydroxyl alkylidene group, C
4-C
12Dihydroxy alkylidene group, 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 composition thereof; R wherein
1Be selected from C
2-C
6Alkylidene group and its mixture; R
2Be selected from hydrogen ,-(R
1O) xB, and composition thereof; R
4Be selected from C
1-C
12Alkylidene group, C
4-C
12Alkenylene, C
8-C
12Aryl alkylene, C
6-C
10Arylidene, and composition thereof; R
5Be selected from C
1-C
12Alkylidene group, C
3-C
12Hydroxyl alkylidene group, C
4-C
12Dihydroxy alkylidene group, C
8-C
12The dialkyl group arylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-C (O) (R
4) rC (O)-,-CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O) yR
1OCH
2CH (OH) CH
2-, and composition thereof; 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
22Alkenyl, 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
3, and composition thereof; 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 composition thereof; R
3Be selected from C
1-C
18Alkyl, C
7-C
12Arylalkyl, C
7-C
12Aryl, C that alkyl replaces
6-C
12Aryl, and composition thereof; M is the water-soluble cationic of hydrogen or the q.s that satisfies charge balance; X is a water soluble anion; The m value is 2-700; The n value is 0-350; The p value is 1-6, and the q value is 0-6; The r value is 0 or 1; The w value is 0 or 1; The x value is 1-100; The y value is 0-100; The z value is 0 or 1.
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 composition thereof, R ' unit is preferably selected from hydrogen, C
1-C
22Alkyl ,-(R
1O) xB ,-C (O) R
3, and composition thereof, preferred R ' unit is-(R
1O) xB.
4. according to any one composition in claim 2 or 3, wherein the x value is preferably 1-10 within the 1-20 scope.
5. according to the composition of arbitrary claim among the claim 1-4, wherein fragrance precursor is a kind of nonionic or anionic ester of allyl alcohol spices, has following formula:
Wherein R is selected from nonionic or negatively charged ion replacement or unsubstituted C
1-C
30Straight chain, side chain or cyclic alkyl, thiazolinyl, alkynyl, alkaryl, or aryl; And n is 1 or greater than 1 integer.
6. according to the composition of claim 5, wherein the ester of allyl alcohol spices is selected from succsinic acid two geraniol esters, succsinic acid two flores aurantii esters, succsinic acid spiceleaf-flores aurantii ester, geranyl phenylacetate, neryl phenylacetate, lauric acid geraniol ester, lauric acid flores aurantii ester and their mixture.
7. according to the composition of arbitrary claim among the claim 1-6, wherein said composition further comprises the dyestuff sticking agent, is preferably the cationic dyestuff sticking agent, more preferably polycation dyestuff sticking agent.
8. according to the composition of arbitrary claim among the claim 1-7, wherein said composition further comprises a kind of dispersible polyolefin.
9. according to the composition of arbitrary claim among the claim 1-8, wherein said composition further comprises fabric softener, is preferably cationic fabric softener, biodegradable cationic fabric softener more preferably, and it is selected from have following formula (I) or quaternary ammonium compound (II) and amine precursor:
Wherein Q be selected from-O-C (O)-,-C (O)-O-,-O-C (O)-O-, NR
4-C (O)-,-C (O)-NR
4-;
R
1Be (CH
2) n-Q-T
2Or T
3
R
2Be (CH
2) m-Q-T
4Or T
5Or R
3
R
3Be C
1-C
4Alkyl or C
1-C
4Hydroxyalkyl or H;
R
4Be H or C
1-C
4Alkyl or C
1-C
4Hydroxyalkyl;
T
1, T
2, T
3, T
4, T
5Be respectively C
6-C
22Alkyl or alkenyl;
N and m are the integers of 1-4; With
X
-Be the negatively charged ion compatible with softening agent.
10. according to the composition or the purposes of arbitrary claim among the claim 1-9, wherein said composition further comprises one or more decontamination components.
11. according to the composition or the purposes of arbitrary claim among the claim 1-10, wherein said composition is in liquid form.
12. according to the composition or the purposes of arbitrary claim among the claim 1-10, wherein said composition is applied on the substrate, on preferred a kind of dried cloth.
13. the purposes of amino-functional polymkeric substance in flavor compositions is used for providing the deposition and/or the affinity of protecting look and fragrance precursor on the fabric of home treated.
14. one kind provides the method for protecting look and spices deposition and/or affinity on the fabric of home treated, it comprises that with fabric and the contacted step of a kind of water-bearing media, this water-bearing media comprises the defined composition of arbitrary claim among the claim 1-11.
15. according to the method for claim 13, wherein said water-bearing media temperature is 2-40 ℃, is preferably 5-25 ℃.
16. one kind provides the method for protecting look and spices deposition and/or affinity on the fabric of home treated, it comprises fabric and the contacted step of the defined composition of claim 12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97200777A EP0864642A1 (en) | 1997-03-14 | 1997-03-14 | Fabric care compositions |
| EP97200777.7 | 1997-03-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1255158A true CN1255158A (en) | 2000-05-31 |
Family
ID=8228108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98804979 Pending CN1255158A (en) | 1997-03-14 | 1998-03-16 | Fabric care compositions |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0864642A1 (en) |
| JP (1) | JP2001515547A (en) |
| CN (1) | CN1255158A (en) |
| AR (1) | AR012840A1 (en) |
| BR (1) | BR9808015A (en) |
| CA (1) | CA2282566A1 (en) |
| WO (1) | WO1998041605A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001521059A (en) * | 1997-10-29 | 2001-11-06 | ザ、プロクター、エンド、ギャンブル、カンパニー | Laundry composition with reduced odor and method for producing the same |
| JP2002527575A (en) * | 1998-10-13 | 2002-08-27 | ザ、プロクター、エンド、ギャンブル、カンパニー | Laundry detergent composition having cationically charged dye-retaining polymer |
| US6753307B1 (en) | 1998-10-13 | 2004-06-22 | The Procter & Gamble Company | Laundry detergent compositions with a cationically charged dye maintenance polymer |
| US6187727B1 (en) * | 1999-07-12 | 2001-02-13 | Bush Boake Allen, Inc. | Fragrance materials |
| EP1111034A1 (en) | 1999-12-22 | 2001-06-27 | The Procter & Gamble Company | Laundry and cleaning and/or fabric care compositions |
| ATE343627T1 (en) * | 1999-12-22 | 2006-11-15 | Procter & Gamble | FRAGRANCE COMPOSITIONS WITH INCREASED VISCOSITY AND METHOD FOR THE PRODUCTION THEREOF |
| US20030158079A1 (en) * | 2001-10-19 | 2003-08-21 | The Procter & Gamble Company | Controlled benefit agent delivery system |
| CN102037112A (en) * | 2008-05-28 | 2011-04-27 | 宝洁公司 | Fabric softening laundry detergents with good stability |
| JP6607686B2 (en) * | 2015-03-26 | 2019-11-20 | ライオン株式会社 | Liquid detergent for textile products |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3165042D1 (en) * | 1980-06-17 | 1984-08-30 | Procter & Gamble | Detergent composition containing low level of substituted polyamines |
| US4597898A (en) * | 1982-12-23 | 1986-07-01 | The Proctor & Gamble Company | Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties |
| US4891160A (en) * | 1982-12-23 | 1990-01-02 | The Proctor & Gamble Company | Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties |
| DE4125752A1 (en) * | 1991-08-03 | 1993-02-04 | Basf Ag | POLYMERISATES FROM ETHYLENICALLY UNSATURATED, N-CONTAINING COMPOUNDS, POLYMERIZED IN THE PRESENCE OF MONOSACCHARIDES, OLIGOSACCHARIDES, POLYSACCHARIDES OR THEIR DERIVATIVES |
| US5500154A (en) * | 1994-10-20 | 1996-03-19 | The Procter & Gamble Company | Detergent compositions containing enduring perfume |
| US5559088A (en) * | 1995-07-07 | 1996-09-24 | The Proctor & Gamble Company | Dryer-activated fabric conditioning and antistatic compositions with improved perfume longevity |
| US5531910A (en) * | 1995-07-07 | 1996-07-02 | The Procter & Gamble Company | Biodegradable fabric softener compositions with improved perfume longevity |
| ATE321574T1 (en) * | 1995-08-31 | 2006-04-15 | Procter & Gamble | USE OF ALLYL ALCOHOL AS AN AGENT TO REDUCE BAD SMELLS |
| US5562847A (en) * | 1995-11-03 | 1996-10-08 | The Procter & Gamble Company | Dryer-activated fabric conditioning and antistatic compositions with improved perfume longevity |
-
1997
- 1997-03-14 EP EP97200777A patent/EP0864642A1/en not_active Withdrawn
-
1998
- 1998-03-13 AR ARP980101156 patent/AR012840A1/en unknown
- 1998-03-16 WO PCT/IB1998/000373 patent/WO1998041605A1/en not_active Ceased
- 1998-03-16 BR BR9808015-6A patent/BR9808015A/en not_active IP Right Cessation
- 1998-03-16 JP JP54027698A patent/JP2001515547A/en active Pending
- 1998-03-16 CN CN 98804979 patent/CN1255158A/en active Pending
- 1998-03-16 CA CA002282566A patent/CA2282566A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998041605A1 (en) | 1998-09-24 |
| CA2282566A1 (en) | 1998-09-24 |
| JP2001515547A (en) | 2001-09-18 |
| BR9808015A (en) | 2000-03-08 |
| AR012840A1 (en) | 2000-11-22 |
| EP0864642A1 (en) | 1998-09-16 |
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