CN100415861C - Soft compound and use thereof - Google Patents
Soft compound and use thereof Download PDFInfo
- Publication number
- CN100415861C CN100415861C CNB2005101370187A CN200510137018A CN100415861C CN 100415861 C CN100415861 C CN 100415861C CN B2005101370187 A CNB2005101370187 A CN B2005101370187A CN 200510137018 A CN200510137018 A CN 200510137018A CN 100415861 C CN100415861 C CN 100415861C
- Authority
- CN
- China
- Prior art keywords
- composition
- amine
- amino
- methyl
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to soft composition, which comprises soft chemical compound of 1 to 80 weight percent, first and/or secondary amine chemical compound, and reacting product selected from the active components of ketone, aldehyde and the mixture. The soft composition is characterized in that the odor intensity index of the amine chemical compound is lower than the odor intensity index of 1 percent solution of amino benzene methyl formate in dipropylene glycol, and the composition has a pH value of 2.0 to 5; the composition is prefabricated before being diluted into an integrally prepared composition. The invention also relates to a method for supplying residual scent on a surface.
Description
The application be that July 12, application number in 1999 are 99808506.5 the applying date, denomination of invention divides an application for the application for a patent for invention of " amine reaction compounds that comprises one or more activeconstituentss ".
Invention field
The present invention relates to amine and active constituent, particularly active aldehydes or ketones, the more preferably reaction product of aldehydes or ketones spices.More specifically, the present invention relates to be used for this reaction product of soft compound.
Background of invention
Adding incense products is that prior art is known.Yet the human consumer is not only determined by the performance that these products obtain this acceptability that adds incense products such as flexible products, but also is determined by related with it aesthetic beauty.Therefore the spices component is an importance of successfully preparing this commerical prod.
The human consumer wishes that also the fabric of handling keeps long pleasant fragrance.In fact, spice additive makes this composition make the human consumer happier aesthetically, and in some cases, spices is given pleasant fragrance with the fabric of its processing.Yet, from laundry take out of the water-bath to deposit to amount of flavorants on the fabric normally a spot of and can not be lasting on fabric.In addition, spices is very expensive usually, and they can not be used effectively in laundry and cleaning combination and can not supply with fabric effectively, and this causes bringing very high cost to human consumer and laundry and cleaning manufacturers.Therefore, the more effective fragrance donor that is used for doing washing with cleaning products, the persistent fragrance of fabric of particularly improving supply are sought in industrial urgent continuation.
The carrier mechanism that a kind of way is to use spices to transmit is for example passed through encapsulate.This has instruction in the prior art and is described in the United States Patent (USP) 5188753.
Also having another kind of way is the preparation compound, and it is than using spices itself can postpone to discharge spices for more time.The disclosure of this compound is found in WO95/04809, WO 95/08976 and autre action pendante application EP95303762.9.
Yet,, still need a kind of providing to postpone to discharge active constituent, the particularly compound of spices component though prior art makes progress.
This need be for the spices component that is feature with clear bright odor type, i.e. aldehyde and ketone spices component even stronger.In fact, though these spices provide clean-fresh odor, these spices are also very volatile and low affinity arranged on surface to be processed such as fabric.
Therefore, a present invention also purpose provides a kind of soft compound, and it comprises the spices component that clean-fresh odor is provided and the surface of handling is had affinity.
The inventor now finds the specific reaction product of amine compound and active aldehydes or ketones, and for example group with imine moiety also provides and postpones to discharge actives, for example spices.
Under the Schiff's base title, group with imine moiety is known in the prior art, and it is the condenses of aldehyde spices component and Aminobenzoate.General description is found in the United States Patent (USP) 4853369.Rely on this compound, making aldehyde spices become fabric is affinity.Yet the problem that these Schiff's base run into is that the Methyl anthranilate compound also shows strong smell, and the result produces mixed flavor, reduces thus or even has suppressed the fragrance sense of aldehyde and/or ketone.
In order to obtain to have the clear bright odor type of aldehydes or ketones of comparability, this flavor compositions that also has satisfied fabric affinity simultaneously, the spices teacher has prepared composition roughly. and for example, this odor type is adopted carrier or cover material, for example use cyclodextrin, zeolite or starch.
Yet also have another kind of way to be to use the glycosamine of describing among the JP09040687., find that this compound has low-down stability in washing process.As a result, find that these glycosamine compounds have insufficient spices residual on the fabric of handling.There is not to disclose its application in soft compound.
Other way is described in chemistry and discharges control (Chemical release control), Kamogawa etc., J.Poly.Sci.Polym.Chem.Ed. the 20th roll up, 3121 (1982), the amino-benzene vinyl compound that it has described use and the condensation of aldehyde spices relies on the copolymerization of this compound or acidifying to cause release spices thus.Yet do not mention its application.
The applicant finds that now the reaction product between specific uncle and/or secondary amine and active constituent has also satisfied this needs.
Another advantage of The compounds of this invention is their easy preparations, causes their application the most desirable.
Summary of the invention
The present invention relates to uncle and/or secondary amine compound and be selected from reaction product between the active constituent of ketone, aldehyde and its mixture, be characterised in that the odor strength index of described amine compound is lower than the odor strength index of 1% solution of Methyl anthranilate in dipropylene glycol, the smell index of doing the surface is greater than 5; Condition is that described amine compound is not an amino-benzene ethene.
Another aspect of the present invention, a kind of soft compound is provided, the active constituent that it comprises uncle and/or secondary amine compound and is selected from ketone, aldehyde and its mixture is characterised in that the odor strength index of described amine compound is lower than the odor strength index of 1% solution of Methyl anthranilate in dipropylene glycol.
Another aspect of the present invention, a kind of method of transmitting remained on surface fragrance is provided, comprise described surface is contacted with The compounds of this invention or composition that the fabric that will handle contacts with a kind of material afterwards, so that actives discharges from the reaction product of amine and actives.
Detailed Description Of The Invention
Necessary component of the present invention is the reaction product between uncle and/or secondary amine compound and the active constituent that is selected from ketone, aldehyde and its mixture, be characterised in that the odor strength index of described amine compound is lower than the odor strength index of 1% solution of Methyl anthranilate in dipropylene glycol, the smell index of doing the surface is greater than 5; Condition is that described amine compound is not an amino-benzene ethene.
In the time of in mixing soft compound, amine reaction product is the reaction product between uncle and/or secondary amine compound and the active constituent that is selected from ketone, aldehyde and its mixture, is characterised in that the odor strength index of described amine compound is lower than the odor strength index of 1% solution of Methyl anthranilate in dipropylene glycol.
Preferably, the smell index on the dried surface of this compound is greater than 5.
1-contains uncle and/or the compound of secondary amine functional groups and the reaction product between the spices component
Necessary component of the present invention is to contain uncle and/or the compound of secondary amine functional groups and the reaction product between the spices component, hereinafter so-called " amine reaction product ".
A-uncle and/or secondary amine
" uncle and/or secondary amine " meaning is the compound that has at least one uncle and/or secondary amine and/or amide functional group.
Uncle and/or secondary amine compound feature are that also the odor strength index is lower than the odor strength index of 1% solution of Methyl anthranilate in dipropylene glycol.
The odor strength index method
To be the dilution of pure chemical be 1% solution of the solvent dipropylene glycol of the no stink that uses in the perfume industry for odor strength index, the meaning.This percentage ratio has more the representativeness of usage quantity.To smell bar, or so-called " blotting paper " floods and submits to the member of panel of experts who judges.The assessed member of the member of panel of experts is with regard to smell grading training at least 6 months, examines the accuracy of their grading and based on existing, the reproducibility of relative reference.For each amine compound, submit to two blotting paper of group member: a reference (Methyl anthranilate, group member's the unknown) and a sample.Please the group member smell bar for these two kinds by 0-5 odor strength grade separation, the 0th, do not detect stink, the 5th, there is very strong stink.
The result
Below expression is applicable to the odor strength index of amine compound of the present invention according to above-mentioned steps.In each case, numerical value is 5 members' of panel of experts arithmetical av, and the result has the notable difference on the statistics under 95% degree of confidence:
Methyl anthranilate 1% (reference) 3.4
4-subcutin (EAB) 1% 0.9
The general structure of primary amine of the present invention is as follows:
B-(NH
2)
n
Wherein B is a solid support material, and n is the index of numerical value at least 1.
The compound that contains secondary amine group has structure similar to the above, and just this compound comprises one or more-NH-group replacement-NH
2In addition, the structure of this compound also has one or more NH
2With-the NH-group.
Preferred B carrier is inorganic or organic carrier.
" inorganic carrier ", the meaning are the carriers that does not have or do not have basically based on carbon skeleton.
In inorganic carrier, preferred inorganic carrier is monomer or the polymkeric substance or the organic-Organosiliconcopolymere of amino deutero-organosilane, siloxanes, silazane, alumane, siloxanes aluminium or aluminium silicate compounds.The representative instance of this carrier is to have at least one primary amine part as Diaminoalkyl siloxanes [H
2NCH
2(CH
3)
2Si] O or organic amino base silane (C
6H
5)
3SiNH
2Organo-siloxane, it is described in polysiloxane chemistry and the technology (Chemistry and Technologyof Silicone), W.Noll, Academic Press Inc.1998, London, the 209th, 106 page.
The monomer or polymkeric substance or the organic-Organosiliconcopolymere that also preferably contain one or more Organosilyl hydrazine parts.The representative instance of this class solid support material is N, N '-two (trimethyl silyl) hydrazine (Me
3Si)
2NNH
2, it is described in the symposial of organosilicon chemistry second itternational, pure and mild applied chemistry (Pure and Applied Chemistry), the 19th volume, 3-4 number (1969).
Below also be preferred monomer or polymeric silazane, it is exemplified as 1,1,1,3,3,3-hexamethyl-2-phenyl diamino silyl disilazane [(CH
3)
3Si]
2NSi ((C
6H
5) NH
2)
2, it is described in silicoorganic compound, and 1965, V.Bazant and al.Academic Press).Other preferred embodiments of polymer siloxane derivative are ring-types 1,1,5,5,7,7,7,11, two [2-(2-aminoethylamino) ethyls]-1,5 of 11-prestox-3-9-, 7,11-four silas-3,9-diaza-6,12-Er Evil cyclododecane and six oxyethyl group diamino cyclotetrasiloxane (C
6H
5) (NH
2)
2Si
4O
4, the 2nd volume, part 2, the 474th, 454 page.
The inorganic polymeric carrier that is used for the preferred aminofunctional of the present invention is poly-aminoalkyl group polysiloxane.General disclosure is found in JP79131096 and EP058493.Be applicable to the polydialkysiloxane that other inorganic polymeric carriers of the present invention are the aminofunctionals described in EP150867, it has general formula:
R=C wherein
1-6, preferred C
1-4Alkyl; N is the integer of 0-16, preferred 1-6, R '=zero, O, C=O, COO, NC=O, C=O-NR, NR, SO
m, m=2,3.
Organic carrier, the meaning are the carriers that mainly has the carbon bond skeleton.Typical amines with organic carrier comprise the amine of aminoaryl derivative, polyamine, amino acid and derivative, replacement and acid amides, glycosamine, dendrimers (dendrimer) and amino replace single, two, oligomeric, polysaccharide.
Certainly, amine compound can be connected base or Mierocrystalline cellulose affine base interval or replace.The general formula of this amine compound can be expressed as follows:
NH2
n-L
m-B-L
m-R
m *
Wherein as mentioned above, each m is that numerical value is the index of O or at least 1, and n is the index of numerical value at least 1.By above as can be seen, aminoly be connected with the carrier molecule of type definition hereinafter described.Uncle and/or secondary amino group can directly be connected with carrier group or pass through the basic L of connection is connected with carrier.Carrier also can be replaced R by the R* substituting group
*Can directly or by connecting basic L be connected with carrier.Certainly, R
*Also can contain the branching group, for example tertiary amine and amide group.
For the object of the invention importantly amine compound comprise with spices aldehyde and/or reactive ketone formation reaction product at least one uncle and/or secondary amine group.Certainly, amine compound is not limited to only have an amine functional group.In fact, more preferably amine compound comprises more than an amine functional group, can make amine compound and several aldehyde and/or reactive ketone thus.Therefore, can obtain having the reaction product of blended aldehyde and/or ketone, cause mixing this spices of release thus.
The typical base that connects comprises:
Adjacent,, replace in the contraposition
L can also be following combination:
For example:
If this group directly is not connected with N, L also can contain-O-,
H for example
2N-CH
2-CH
2O-
Hereinafter the most compounds of describing in the amine compound class contains and classifies as R
*At least one substituting group.
R
*Main chain contain 1-22 carbon atom and randomly can be alkyl, alkenyl or alkylbenzene chain.It also can contain alicyclic ring, aromatics, heteroaromatic or heterocyclic system, and they are inserted in the main chain or are used to replace the H atom of main chain.In addition, as indicated above, R
*Can be connected with carrier B or be connected with carrier B by connecting basic L.In this case, L can also be-O-.
Main chain can contain 1 to 15 R
*Group.
Typical R
*The insertion group comprises::
*Arrow is illustrated in 3 replacements of as many as on 2,3,4.
R
*Also can contain several insertion groups that link together, for example:
In addition, R
*Can have the end functional groups E that other surperficial affinity can be provided.The typical organic group of this end group E comprises:
E can also be aromatics, alicyclic ring, heteroaromatic or heterocyclic radical, comprises list, two, oligomeric, polysaccharide:
In addition, R
*Base also can be modified by the one or more H atoms that replace in the main chain.Substituting group can be E defined above or insert group, wherein insert cardinal extremity and take over what H, E or R
*
R
*Can also be the group that is made of oxyethyl group or epoxy group(ing), n be 1-15, comprises such as following group:
-(CH
2CH
2O)
nH
-(C
3H
6O)
n·H -(O-C
3H
6)
n-OH
As indicated above, the amine that preferably contains the organic carrier substance B can be selected from the amine of aminoaryl derivative, polyamine, amino acid and derivative, replacement and acid amides, glycosamine, amino replace single, two, oligomeric, polysaccharide, dendrimers and/or its mixture.
1-aminoaryl derivative
In this compounds, amino preferably is connected with phenyl ring.Phenyl ring to and/or a position by above-mentioned R
*Further replace.R
*Can be connected with phenyl ring by connecting basic L.Phenyl ring can be replaced by other aromatic ring systems, comprises naphthalene, indoles, benzoglyoxaline, pyrimidine, purine and its mixture.
Preferred R
*Contraposition at phenyl ring is attached thereto.
Typical aminophenyl derivative has following formula:
Preferred aminophenyl derivative has following formula:
Preferred aminophenyl derivative is a 4-benzaminic acid alkyl ester compound, is preferably selected from 4-subcutin, 4-benzaminic acid phenethyl ester, 4-aminobenzoic acid phenenyl ester, 4-amino-N '-(3-aminopropyl) benzamide and its mixture.
The 2-polyamine
Polyamine of the present invention requires to have at least one, preferably more than free and a unmodified uncle and/or a secondary amine with active aldehydes or reactive ketone.In polyamine, H can be by R
*Replace, randomly by connecting basic L.In addition, uncle and/or secondary amine can be connected with the polymkeric substance end by connecting basic L.
Be applicable to that polyamino compound of the present invention is water-soluble or dispersible polyamine.Generally, be used for the molecular weight of polyamine of the present invention in 150-2 * 10
6Between, preferably at 400-10
6, most preferably at 5000-10
6Between.It can be straight chain or cyclic main chain that these polyamine comprise.This polyamine main chain also can comprise big or than the polyamine side chain of low degree, preferably, polyamine main chain described herein is to be modified by this way: at least one in this polyamine chain, preferably each nitrogen is the unit of hereinafter retouching reach substituted, quaternized, oxidation or its array mode.
For the object of the invention, the term " modification " that relates to the chemical structure of polyamine be defined as by R ' unit (substituting group) replace on the main chain-nitrogen on the hydrogen atom of NH, the nitrogen (quaternised) on the quaternized main chain or the oxidation main chain becomes N-oxide compound (oxidation).Term " modification " and " replacement " can be used alternatingly when relating to when using R ' unit to replace to be connected the process of the hydrogen atom on the main chain nitrogen.Quaternized or oxygenizement can occur in the equivalent environment that does not have to replace, but preferred the replacement followed oxidation that at least one main chain nitrogen takes place or quaternized.
The straight chain or the acyclic polyamine main chain that constitute polyamine have following general formula:
The cyclic polyamines main chain that constitutes polyamine has following general formula:
Above main chain is optional, but before preferred subsequently the modification, comprise by the connection of R " connections " unit primary, the second month in a season and tertiary amine nitrogen.
For the object of the invention, this main chain or the side chain that contain primary amine nitrogen ought be modified, and then are defined as V or Z " end " unit.For example, the primary amine part that has following structure when the end that is positioned at polyamine main framing or side chain:
H
2N-[R]-
When being modified according to the present invention, it is defined as V " end " unit or simple V unit hereinafter.
But for the object of the invention, some or all of primary amine parts can keep not being modified after through the restriction that hereinafter further describes.These unmodified primary amine parts are owing to their residing positions on main chain remain " end " unit.Equally, when being positioned at the primary amine part that polyamine main framing end has following structure:
-NH
2
When being modified according to the present invention, it is defined as Z " end " unit hereinafter or is called for short the Z unit.This unit can keep not being modified after through the restriction that hereinafter further describes.
In a similar fashion, contain this main chain of secondary amine nitrogen or side chain when being modified, then be defined as W " main chain " unit.For example, when secondary amine part with following structure, the main component part of main chain promptly of the present invention and side chain:
When being modified according to the present invention, it is defined as W " main chain " unit hereinafter, or is called for short the W unit.But for the object of the invention, some or all of secondary amine parts can keep not being modified.These unmodified secondary amine parts are owing to their residing positions on main chain remain " main chain " unit.
In addition in a similar fashion, in a single day this main chain or the side chain that contain tertiary amine nitrogen are modified, and also are called as Y " side chain " unit.For example, when the tertiary amine part with following formula structure of the side chain position that is in polyamine main chain or other side chain or ring:
When being modified according to the present invention, it is defined as Y " side chain " unit hereinafter, or is called for short the Y unit.But for the object of the invention, some or all of tertiary amine parts can keep not being modified.These unmodified tertiary amine parts are owing to their residing positions on main chain remain " side chain " unit.Working the R unit relevant with Y unit nitrogen with V, W that connects the effect of polyamine nitrogen is described hereinafter.
Therefore, the structure of the polyamine of the present invention that finally is modified, can represent by following general formula for straight-chain polyamine:
V
(n+1)W
mY
nZ
With represent cyclic polyamines by following general formula:
V
(n-k+1)W
mY
nY’
kZ
For the polyamine situation that comprises ring, the Y ' unit of following formula:
Side chain as a main chain or a chain link.For each Y ' unit, there is Y unit with following formula:
It will constitute the tie point of ring and main polymer chain or side chain.Main chain be a complete ring in particular cases, this polyamine main chain has following formula:
Therefore it does not comprise the Z end unit, and has following formula:
V
n-kW
mY
nY’
k
Wherein k is the number that constitutes the unitary ring of side chain.Preferably, polyamine main chain of the present invention does not comprise ring.
Under acyclic polyamine situation, the ratio of subscript n and subscript m relates to the relative extent of branching.Straight-chain polyamine according to the modification of complete non-branching of the present invention has following formula:
VW
mZ
That is, n equals 0.N value big more (ratio of m and n is lower), the degree of branching is big more in molecule.Generally, the scope of m value is from minimum value 2 to 700, and is preferred 4 to 400, still, and bigger m value is particularly very low or also be preferred near 0 the time when the numerical value of subscript n.
Every kind of polyamine nitrogen no matter be primary, the second month in a season or uncle's nitrogen, in a single day is modified according to the present invention, and it further is defined as a kind of in the following threeway class: simply substituted, seasonization or oxidation.Those polyamine nitrogen unit that are not modified according to they whether be primary, the second month in a season or uncle's nitrogen is classified into V, W, Y, Y ' or Z unit.That is, for the object of the invention, the primary amine nitrogen that is not modified is V or Z unit, and the secondary amine nitrogen that is not modified is W unit or Y ' unit, and the tertiary amine nitrogen that is not modified is the Y unit.
The primary amine of modification partly is defined as V " end " unit, and it has a kind of in following three kinds of structures:
A) have the unit of the simple replacement of following structure:
B) have the quaternized unit of following structure:
Wherein X provides the counterion that is fit to of charge balance; With
C) have the oxidation unit of following structure:
The secondary amine of modification partly is defined as W " main chain " unit, and it has a kind of in following three kinds of structures:
A) have the unit of the simple replacement of following structure:
B) have the quaternized unit of following structure:
Wherein X provides the counterion that is fit to of charge balance; With
C) have the oxidation unit of following structure:
The secondary amine of other modification partly is defined as Y ' unit, and it has a kind of in following three kinds of structures:
A) have the unit of the simple replacement of following structure:
B) have the quaternized unit of following structure:
Wherein X provides the counterion that is fit to of charge balance; With
C) have the oxidation unit of following structure:
The tertiary amine of modification partly is defined as Y " side chain " unit, and it has a kind of in following three kinds of structures:
A) have the unmodified unit of following structure:
B) have the quaternized unit of following structure:
Wherein X provides the counterion that is fit to of charge balance; With
C) have the oxidation unit of following structure:
The primary amine of some modification partly is defined as Z " end " unit, and it has a kind of in following three kinds of structures:
A) have the unit of the simple replacement of following structure:
B) have the quaternized unit of following structure:
Wherein X provides the counterion that is fit to of charge balance; With
C) have the oxidation unit of following structure:
When any position on the nitrogen is not substituted or is not modified, be to be understood that hydrogen will be used for replacing R '.For example, comprising the unitary primary amine of the R ' with a hydroxyethyl form unit is to have formula: (HOCH
2CH
2) the V end unit of HN-.
For the object of the invention, two class end units are arranged, i.e. V and Z unit.Z " end " unit is by having structure-NH
2The end primary amino partly obtain.Acyclic polyamine main chain according to the present invention only comprises a Z unit, and cyclic polyamines can not comprise the Z unit.Z " end " unit except when be modified forms outside the N-oxide compound, and any R ' unit that further describes below available replaces.Be oxidized under the situation of N-oxide compound at Z unit nitrogen, nitrogen must be modified, so R ' can not be a hydrogen.
Polyamine of the present invention has comprised main chain R " connection " unit that connects the nitrogen-atoms effect on the main chain.The R unit comprises, for the object of the invention, is called as " alkyl R " unit and " oxo R " unitary unit." alkyl R " unit is C
2-C
12Alkylidene group, C
4-C
12Alkylene group, C
3-C
12The hydroxyl alkylidene group, wherein hydroxylic moiety can be substituted in any position on the R cellular chain, except with carbon atom that polyamine main chain nitrogen directly links to each other; C
4-C
12Alkyl sub-dihydroxy, wherein hydroxylic moiety can occupy any two carbon atoms on the R cellular chain, except with those carbon atoms that polyamine main chain nitrogen directly links to each other; For the object of the invention, C
8-C
12The dialkyl group arylidene is the arylidene part that has as two alkyl substituents of the part of connection chain.For example, the dialkyl group arylene units has formula:
Or
Although this unit needs not to be 1,4-replaces, and can be 1,2 or 1,3 C that replaces
2-C
12Alkylidene group, preferred ethylidene, propylene and its mixture, more preferably ethylidene." oxo " R unit comprises-(R
1O)
rR
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 its mixture.Preferred R unit is selected from C
2-C
12Alkylidene group, C
3-C
12Hydroxyl alkylidene group, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-(R
1O)
xR
1-,-CH
2CH (OR
2) CH
2-,-(CH
2CH (OH) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OH) CH
2)
w-,-(R
1O)
xR
5(OR
1)
x-, preferred R unit is C
2-C
12Alkylidene group, C
3-C
12Hydroxyl alkylidene group, C
4-C
12Alkyl sub-dihydroxy ,-(R
1O)
xR
1,-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OH) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OH) CH
2)
w-and its mixture, even preferred R unit is C
2-C
12Alkylidene group, C
3Hydroxyl alkylidene group and its mixture, most preferably C
2-C
6Alkylidene group.The most preferred main chain of the present invention comprises at least 50% and is the R unit of ethylidene.
R
1The unit is C
2-C
6Alkylidene group and its mixture, preferred ethylidene.
R
2Be hydrogen and-(R
1O)
xB, preferred hydrogen.
R
3Be C
1-C
18Alkyl, C
7-C
12Aryl alkylene, C
7-C
12The aryl that alkyl replaces, C
6-C
12Aryl and its mixture, preferred C
1-C
12Alkyl, C
7-C
12Aryl alkylene, more preferably C
1-C
12Alkyl, most preferable.R
3The unit is as the unitary part of R ' described below.
R
4Be C
1-C
12Alkylidene group, C
4-C
12Alkylene group, C
8-C
12Aryl alkylene, C
6-C
10Arylidene, preferred C
1-C
10Alkylidene group, C
8-C
12Aryl alkylene, more preferably C
2-C
8Alkylidene group, most preferably ethylidene or butylidene.
R
5Be C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-C (O) (R
4)
rC (O)-,-R
1(OR
1)-,-CH
2CH (OH) CH
2O (R
1O)
yR
1-OCH
2CH (OH) CH
2-,-C (O) (R
4)
rC (O)-,-CH
2CH (OH) CH
2-, R
5Ethylidene preferably ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O)
yR
1-OCH
2CH (OH) CH
2-, more preferably-CH
2CH (OH) CH
2-.
R
6Be C
2-C
12Alkylidene group or C
6-C
12Arylidene.
Preferably " oxo " R unit advances-goes on foot according to R
1, R
2And R
5The unit definition.Preferably " oxo " R unit comprises preferred R
1, R
2And R
5The unit.Preferred polyamine of the present invention comprises at least 50% and is the R of ethylidene
1The unit.Preferred R
1, R
2And R
5The unit combines in the following manner with " oxo " R unit and obtains preferred " oxo " R unit:
I) with preferred R
5Replace to go into-(CH
2CH
2O)
xR
5(OCH
2CH
2)
x-in obtain-(CH
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)
w-in obtain-(CH
2CH (O) CH
2O)
z(CH
2CH
2O)
yCH
2CH
2O (CH
2CH (OH) CH
2)
w-.
Iii) with preferred R
2Replace to go into-CH
2CH (OR
2) CH
2-in obtain-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, preferred hydrogen, C
2-C
22Hydroxy alkylidene, benzyl, C
1-C
22Alkylidene group ,-(R
1O)
mB ,-C (O) R
3,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M-, more preferably C
1-C
22Alkylidene group ,-(R
1O)
xB ,-C (O) R
3,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M-, most preferably C
1-C
22Alkylidene group ,-(R
1O)
xB and-C (O) R
3When nitrogen not carried out modification or replacing, then hydrogen atom will keep as the part of representing R '.Most preferred R ' unit is (R
1O)
xB.
When V, W or Z unit were oxidized, when promptly nitrogen-atoms was the N-oxide compound, R ' unit did not comprise hydrogen atom.For example, main chain or side chain do not comprise following structural unit:
In addition, when V, W or Z unit were oxidized, when promptly nitrogen-atoms was the N-oxide compound, R ' unit did not comprise the carbonyl moiety of Direct Bonding on nitrogen-atoms.According to the present invention, R ' unit-C (O) R
3Part is not bonded on the nitrogen-atoms of modification of N-oxide compound,, does not have the N-oxide compound acid amides of following structure or its combination that is:
B is hydrogen, C
1-C
6Alkyl ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSO
2M) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M, preferred hydrogen ,-(CH
2)
qSO
3M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q(CHSO
2M) CH
2SO
3M, more preferably hydrogen or-(CH
2)
qSO
3M.
M is hydrogen or water-soluble cationic, and its quantity is enough to satisfy charge balance.For example, sodium cation is of equal value satisfies-(CH
2)
pCO
2M and-(CH
2)
qSO
3M obtains-(CH thus
2)
pCO
2Na and-(CH
2)
qSO
3The Na part.Can satisfy desired chemical charge balance in conjunction with monovalent cation (sodium, potassium etc.) more than one.But, can obtain charge balance with divalent cation more than an anionic group, maybe may satisfy the electric charge needs of polyanionic group more than a monovalent cation.For example, with sodium atom replace-(CH
2)
pPO
3M partly has formula-(CH
2)
pPO
3Na
3Divalent cation is calcium (Ca for example
2+) or magnesium (Mg
2+) can be used to replace other monovalence water-soluble cationic that is fit to or combination with it.Preferred cation is sodium and potassium, is more preferably sodium.
X is a water soluble anion, for example chlorine (Cl
-), bromine (Br
-) and iodine (I
-), or X can be any negative charge group, for example sulfate radical (SO
4 2-) and methyl-sulfuric acid root (CH
3SO
3 -).
The subscript of this formula has the numerical value that following numerical value: p is 1-6; Q is the numerical value of 0-6; R is 0 or 1; W is 0 or 1; X is the numerical value of 1-100; Y is the numerical value of 0-100; Z is 0 or 1; The m value is 2-700, preferred 4-400, and the n value is 0-350, preferred 0-200; M+n is at least 5 numerical value.
Preferred x value is in the 1-20 scope, preferably 1-10.
Preferred polyamine of the present invention comprises the polyamine main chain, wherein is less than 50% R group and comprises " oxo " R group, preferably is less than 20%, and more preferably less than 5%, most preferably the R unit does not comprise " oxo " R unit.
Do not comprise the unitary most preferred polyamine of " oxo " R and comprise the polyamine main chain, wherein be less than 50% R group and comprise more than 3 carbon atoms.For example, ethylidene, propylene and trimethylene comprise 3 or carbon atom still less, and they are preferred " alkyl " R unit.Promptly the R unit when main chain is C
2-C
12During alkylidene group, C preferably
2-C
3Alkylidene group most preferably is an ethylidene.
Polyamine of the present invention comprises the homogeneous of modification and the polyamine main chain of non-homogeneous, wherein 100% or still less-the NH unit is modified.For the object of the invention, term " the polyamine main chain of homogeneous " is defined as the having identical R unit polyamine main chain of (promptly all being ethylidene).But the polyamine of the main polymer chain that comprises the extra cell that contains other (owing to the artefact of selected chemical synthesis process exists) is not got rid of in the definition of this identity.For example, the known thanomin of those skilled in the art can be used as synthetic polyethylene imine based " initiator ", and the polyethylene imine based product that therefore comprises the hydroxyethyl part that " initiator " by polymerization obtain is considered to constitute the homogeneous polyamine main chain of the object of the invention.Comprise all is that unitary wherein not have the unitary polyamine main chain of branching Y be the homogeneous main chain to ethylidene R.Comprising all is that the unitary polyamine main chain of ethylidene R is the homogeneous main chain, does not consider the number of existing degree of branching or ring side chain.
For the object of the invention, term " non-homogeneous main polymer chain " is meant the polyamine main chain of being made up of various chain length R unit and all kinds R unit.For example, the main chain of non-homogeneous is included as the R unit of ethylidene and the unitary mixture of propylene.For the object of the invention, it is necessary that the unitary mixture of " alkyl " and " oxo " R does not provide non-homogeneous main chain.
Preferred polyamine of the present invention comprises homogeneous polyamine main chain, its all or part of by polyoxyethylene partly replace, it is all or part of by the amine of seasonization, all or part of N-of the being oxidized to oxide compound of nitrogen and its mixture.But the nitrogen-atoms of not every main chain amine must be modified by identical mode, for the selection of the modification particular requirement decision by the prescription teacher.Ethoxylation degree is also determined by prescription teacher's particular requirement.
The preferred polyamine that comprises the main chain of The compounds of this invention generally is polyalkyleneimine (PAI ' s), preferably polyethylene imine based (PEI ' s), or connects the PEI ' s with R unitary part longer than parent PAI ' s or PEI ' s.
Be included as C
2That the unitary preferred amine polymer main chain of the unitary R of alkylidene group (ethylidene) is also referred to as is polyethylene imine based (PEI ' s).Preferred PEI ' s has the branching of moderate at least, and promptly the ratio of m and n is lower than 4: 1, and the ratio that still has m and n is that 2: 1 PEI ' s is most preferred.Preferred main chain before modification has general formula:
Wherein R ', m and n are with above definition.Preferred PEI ' s has molecular weight greater than 200 dalton.
In the polyamine main chain primary, the second month in a season and the unitary relative proportion of tertiary amine, particularly under the situation of PEI ' s, will change according to preparation method.Each hydrogen atom that is connected with each nitrogen-atoms on the polyamine main chain is represented the possible position of follow-up replacement, quaternized or oxidation.
These polyamine can by for example in the presence of catalyzer the polymerization ethylene imine prepare, catalyzer is carbonic acid gas, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetate etc. for example.The concrete grammar for preparing these polyamine main chains is disclosed in the US2182306 of the Ulrich that authorizes December 5 nineteen thirty-nine etc.; The US3033746 of the Mayle that on May 8th, 1962 authorized etc.; The US2208095 of the Esselmann that on July 16th, 1940 authorized etc.; The US2806839 of the Crowther that authorize September 17 nineteen fifty-seven; US2553696 with the Wilson that authorizes May 21 nineteen fifty-one; All these documents are quoted for referencial use at this paper.
Preferred polyamine be can by following trade(brand)name be purchased polyethylene imine based: Lupasol is such as Lupasol FG (MW800), G20wfv (MW1300), PR8515 (MW2000), WF (MW25000), FC (MW800), G20 (MW1300), G35 (MW1200), G100 (MW2000), HF (MW25000), P (MW750000), PS (MW750000), SK (MW2000000), SNA (MW1000000).
Be applicable to that other polyamine of the present invention are poly-[oxo (methyl isophthalic acid, 2-second two bases)], α-(2-aminomethylethyl)-ω-(2-amino methyl-oxyethyl group)-(=C.A.S. 9046-10-0); Poly-[oxo (methyl isophthalic acid, 2-second two bases)], α-hydrogen-ω-(2-amino methyl oxyethyl group)-, 2-ethyl-2-(methylol)-1, the ether of ammediol (=C.A.S. 39423-51-3); Can be by trade(brand)name Jeffamines T-403, D-230, D-400, D-2000 is purchased; 2,2 ', 2 "-the triamino triethylamine; 2,2 '-diamino diethylamide; 3,3 '-diamino-dipropylamine, can from Mitsibushi be purchased 1,3-diamino ethyl hexanaphthene and the C12 tail amine that can be purchased from Clariant, as C12 tail amine (inferior propylamine), n=3/4 and its mixture.
3-amino acid and derivative
Being used for other compounds that are fit to of the present invention is amino acid and its derivative, particularly ester and amide derivatives.Preferred compound is owing to their constitutional features makes those that surperficial affinity increases.In order to clarify, term amino acid and derivative do not comprise polymerizable compound.
The amino acid that is fit to has the following formula functionality:
R wherein
1=H, R
*Or (L)-R
*, R is an amino acid side group, is commonly referred to as " R yl ", for example described in " biochemical theory ", and Lehninger etc., 1997, second edition, Worth, 114-116 page or leaf.
Be used for preferred amino acids of the present invention and be selected from tyrosine, tryptophane, Methionin, L-glutamic acid, glutamine, aspartic acid, arginine, l-asparagine, phenylalanine, proline(Pro), glycine, Serine, Histidine, Threonine, methionine(Met) and its mixture, most preferably be selected from tyrosine, tryptophane and its mixture.
Other also preferred compounds are amino acid derivative, are selected from tyrosine ethyl ester, glycine methyl ester, tryptophane ethyl ester and its mixture.
Amine and acid amides that 4-replaces
In order to clarify, amine and acid amides that term replaces do not comprise polymerizable compound.The amine and the amide compound that are applicable to replacement of the present invention have following general formula:
NH
2-L-R
*, wherein under the situation of acid amides, L is-CO-.
Other optional connection bases can be as R
*The following definition.
R
*R as mentioned
*The following definition, condition be its contain at least 6 carbon atoms and/or N atom and/or cyclohexyl-, piperidines, piperazine and other heterocyclic groups, as:
Randomly, the H among the NH can be by R
*Replace.
Be used for that the present invention preferably replaces amine and acid amides is selected from piperidyl urea, N-cocoyl-1,3-propylene diamine; N-oil base-1, the 3-propylene diamine; N-(tallow alkyl)-1, the 3-propylene diamine; 1, the 4-diamino-cyclohexane; 1, the 2-diamino-cyclohexane; 1,12-diamino dodecane and its mixture.
The 5-glycosamine
The glucose amine that an also preferred amine compound is following formula:
NH
2-CH
2-(CH (OH))
x-CH
2OH wherein preferably uses-OR
*Replace one or several OH functional group and wherein x be 3 or 4 integer.Described under L as mentioned, R
*Can directly or by connecting basic unit be connected with the OH group.
In order to clarify, the term glycosamine does not comprise polymerizable compound.
The preferred compound of this class is selected from 2,3,4,5,6-pentamethoxyl glycosamine; 6-acetyl glucosamine, glycosamine and its mixture.
The 6-dendrimers
Another kind of amine compound is the dendrimers class.The dendrimers that is fit to has the free uncle and/or stretches amine groups in the periphery of spherical molecule, it can generate amine reaction product (spices component) required for the present invention with the reaction of (spices) aldehydes or ketones.
Dendrimers is understood that molecule is made of core element, as WO96/02588 and synthetic (Synthesis), and in February, 1978,155-158 page or leaf or polymkeric substance science and technology and technology encyclopedia (Encyclopedia of Polyer Science; Enginerring), the 2nd edition, Hedstrand etc. are particularly described in the 46-91 page or leaf.Core generally is connected with multifunctional component, constitutes " modified version ".For the object of the invention, the character of internal modifications is not crucial.They are based on polyamidoamines amine for example, polyamidoamines alcohol, polyethers, polymeric amide, polyethylene imine based etc.For the object of the invention, importantly outside the improvement contained come-at-able uncle and/or secondary amino group functional group.
That also be fit to is ethylene glycol dendrimers (glyco dendrimers), as Nachrichten aus Chemie 11 (1996), described in 1073-1079 page or leaf and the WO97/48711, condition is to have free uncle and/or secondary amine group on the surface of these molecules.
Preferred compound is polyethylene imine based and polytrimethylene imines dendrimers, and is commercially available
Polyamidoamines amine (PAMAM) dendrimers, the modified version G0-G10 and the dendrimers that obtain from Dendritech
, from the modified version 1-5 that DSM obtains, it is diaminobutane polyamine DAB (PA)
X, x=2
n* 4, n is generally O-4.
The list of 7-amino-replacement-, two-, oligomeric-, polysaccharide
Also be suitable for the present invention seeks to the list that specific amino replaces-, two-, oligomeric-, polysaccharide.
About the monose that amino of the present invention replaces, necessary is that half acetal and/or hemiketal functional group are protected by the substituting group that is fit to, and provides enough stability to the application of expecting.As indicated above, glycosamine is not the amine that is fit to.Yet, if the OH functional group of half acetal is by R
*Replace, then described monose becomes and is suitable for the object of the invention.Amino can be on 2-5 or 6, and this depends on the type of monose, preferably in C2, C5 or C6 position.The monose that the amino that is fit to replaces is:
-C5 aldose/ketose: ribose, pectinose, wood sugar, lyxose, ribulose, xylulose;
-C6 aldose/ketose: allose, altrose, glucose, seminose, gulose, idose, semi-lactosi, talose, fructose, sorbose, tagatose, psicose.
About the disaccharides that the amino that has unsubstituted aldose or ketose group replaces, free OH group need be by R
*Replace, for example in the situation of lactose and maltose, and in the situation of sucrose, do not have free aldehyde/ketone OH group.Randomly, available R
*Replacement is more than an OH group.The disaccharides that the amino that is fit to replaces is amino lactose, maltose, sucrose, cellobiose and the trehalose that replaces.
That the amino that is fit to replaces is oligomeric-, polysaccharide is the amino starch that replaces, cyclodextrin, dextran, glycogen, Mierocrystalline cellulose, mannosans, gueran, Polylevulosan, alternately glucose, seminose, semi-lactosi, fructose, lactose, maltose, sucrose, cellobiose, cyclodextrin, chitosan and/or its mixture.These molecules need have at least 1, preferred 3 amino.Chitosan does not need other amino to replace.
Also be suitable for coupling contain carboxyl or aldehyde compound be the following Carbomer of being available commercially from company functionalized oligomeric-, polysaccharide and glycan.Ask for an interview the Ref. No. of the Carbomer in the bracket:
Amino alginates (500002), diamino alginates (500003), hexanediamine alginates (500004-500006-500008), dodecane diamines alginates (500005-500007-500009), 6-amino-6-deoxycellulose (500020), O-ethamine Mierocrystalline cellulose (500022), O-methylamine Mierocrystalline cellulose (500023), 3-amino-3-deoxycellulose (500024), 2-amino-2-deoxycellulose (500025), 2,3-diamino-2,3-dideoxy Mierocrystalline cellulose (500026), 6-[N-(1, the 6-hexanediamine)]-6-deoxycellulose (500027), 6-[N-(1,12-dodecane diamines)]-6-deoxycellulose (500028), O-[methyl-(N-1, the 6-hexanediamine)] Mierocrystalline cellulose (500029), O-[methyl-(N-1,12-dodecane diamines)] Mierocrystalline cellulose (500030), 2,3-two-[N-(1,12-dodecane diamines)] Mierocrystalline cellulose (500031), 2,3-diamino-2,3-deoxidation a-cyclodextrin (500050), 2,3-diamino-2,3-deoxidation beta-cyclodextrin (500051), 2,3-diamino-2,3-deoxidation γ-Huan Hujing (500052), 6-amino-6-deoxidation a-cyclodextrin (500053), 6-amino-6-deoxidation beta-cyclodextrin (500054), O-ethylamino beta-cyclodextrin (500055), 6[N-(1, the 6-hexanediamine)-6-deoxidation a-cyclodextrin (500056), 6[N-(1, the 6-hexanediamine)-6-deoxidation beta-cyclodextrin (500057), amino dextran (500060), N-[two-(1, the 6-hexanediamine)] dextran (500061), N-[two-(1,12-dodecane diamines)] dextran (500062), 6-amino-6-deoxidation-a-D-galactosyl-polygalactomannan (500070), O-ethylamino polygalactomannan (500071), diamino polygalactomannan (500072), 6-amino-6-deoxidation starch (500080), O-ethylamino starch (500081), 2,3-diamines-2,3-dideoxy starch (500082), N-[6-(1, the 6-hexanediamine)]-6-deoxidation starch (500083), N-[6-(1,12-dodecane diamines)]-6-deoxidation starch (500084) and 2,3-two-[N (1, the 6-hexanediamine)] 3-dideoxy starch (500085)-2.
In addition, comprise more than using under some compounds of at least one uncle and/or secondary amine group, such as polyamine, the amine reaction product that obtains can advantageously provide the appearance of fabrics effect, particularly color nursing and prevent fabric abrasion.In fact, fabric for example the outward appearance of clothes, bed clothes, family expenses fabric such as tablecloth be one of zone of being concerned about of human consumer.In fact, use when the human consumer is general that fabric is for example worn, when washing, rinse and/or roll-drying fabric, the outward appearance of observing fabric has loss, this at least partly cause be that color naturalness and color sharpness have loss.The problem of this colour loss is after wash(ing)cycle repeatedly even more serious.Find that the present composition provides appearance of fabrics and the anti-fabric abrasion of improving and given the fabric of washing, particularly after wash(ing)cycle repeatedly, provide the color of improving nursing.
Therefore, the present composition can provide fabric nursing and persistent spices effect simultaneously.
Active ketone of B-and/or aldehyde
Preferably, about above-mentioned compound, the active ketone or the active aldehydes meaning are to have to contain at least 1 carbon atom, any chain of preferred at least 5 carbon atoms.
Preferred active ketone or active aldehydes are selected from fragrance ketone or aldehyde component, medicinal ketone or aldehyde component, biological control ketone or aldehyde reagent, spices ketone or aldehyde component, nice and cool ketone or aldehyde reagent and its mixture respectively.
Flavor component comprises spices, promotes the sweetener of total fragrance sense.
The medical active thing comprises medicine.
Biocontrol agent comprises biocide, antiseptic-germicide, sterilant, mycocide, algicide, mould inhibitor, sterilizing agent, sanitas, sterilant, wormer, plant growth hormones.
Biocontrol agent comprises biocide, antiseptic-germicide, sterilant, mycocide, algicide, mould inhibitor, sterilizing agent, sanitising agent such as SYNTHETIC OPTICAL WHITNER, sanitas, sterilant, insect and/or moth protective agent, wormer, plant growth hormones.
Typical antiseptic-germicide comprises glutaraldehyde, phenylacrolein and its mixture.Typical insect and/or moth protective agent are the spices components, for example geranial, citral, N, N-n,N-diethyl meta-toluamide, Rotundial, 8-acetoxyl group carvotanacetone and its mixture.Other examples that are used for insect of the present invention and/or moth protective agent are disclosed in United States Patent (USP) 4449987,4693890,4696676,4933371,5030660,5196200 and " fragrance and perfume molecules are to the symptom activity of various insects ", B.D.Mookherjee etc. are published in
Biology from plant Active volatile compound(Bioactive Volatile Compounds from Plants), ASC collection of thesis book series 525, R.Teranishi, R.G.Buttery and H.Sugisawa, 1993, the 35-48 pages or leaves.
The generality that tradition is used for the ketone that is fit to of perfumery and/or aldehyde discloses can be referring to " spices and aromachemicals ", I and II, S.Arctander, Allured Publishing, 1994, ISBN0-931710-35-5.
Spices ketone component comprises the component with fragrance character.
Preferably, for above-mentioned compound, spices ketone is selected from the buccoxime of scent of feature; Isojasmone; Methyl β naphthyl ketone; Moschus indone, tonalide/Moschus; The a-damascone; β-damascone; δ-damascone; different damascone; trans-Damascenone; damarose; methyl dihydrojasmonate; piperitone; Karvon; camphor; fenchone; the a-ionone; β-ionone; so-called γ-methyl ionone; alismone; Dihydrojasmone; cis-jasmone; different-E-Super; methyl-cypress ketenes or vertofix coeur (cedrylone); methyl phenyl ketone; methyl acetophenone; p-methoxy-acetophenone; methyl-betanaphthyl ketone; benzyl acetone; benzophenone; the p-hydroxybenzene butanone; apione or livescone; different sec.-propyl ten dihydros of 6--2-naphthalenone; the dimethyl-octa ketenes; freskomenthe; 4-(1-vinyl ethyl ether base)-3; 3; 5; 5;-tetramethyl--pimelinketone; Sulcatone; 2-(2-(4-methyl-3-tetrahydrobenzene-1-yl) propyl group cyclopentanone; 1-(Foxlene-6 (2)-yl)-1-acetone; 4-(4-hydroxy 3-methoxybenzene base)-2-butanone; 2-ethanoyl-3; 3-dimethyl-norbornane; 6; 7-dihydro-1; 1; 2; 3; 3-pentamethyl--4 (5H)-indone; 4-damascol; piperonylacetone or 3; 4-methylenedioxy benzyl acetone; gelsone; the allyl jononeionone; iso-cyclenone E; methyl ring lemon; methyl lavender ketone; orivone; to tertiary butyl pimelinketone; verdone; delphone; muskone; new methylene acetone; plicatone; veloutone; 2; 4; 4; 7-tetramethyl--oct-6-ene-3-ketone, tetrameran.
About above-claimed cpd, preferred ketone be selected from a-damascone, δ-damascone, different damascone, Karvon, γ-methyl ionone, different-E-Super, 2,4,4,7-tetramethyl--oct-6-ene-3-ketone, benzyl acetone, β-damascone, trans-Damascenone, methyl dihydrojasmonate, vertofix coeur and its mixture.
Spices aldehyde component comprises the component with adour properties.
About above-claimed cpd, preferred spices aldehyde is selected from the adoxal of scent of feature; Anisyl aldehyde; Cymal; Vanillal; Florhydral; The piperonyl propionic aldehyde; Piperonylaldehyde; Laurine; Koavone; Lauryl aldehyde; LYRAL; Methyl nonyl acetaldehyde, P.T. are to the tertiary butyl-a-hydrogenated methyl phenylacrolein; Phenyl acetaldehyde; Undecenal; Vanillin; 2,6,10-trimethylammonium-9-undecenal, 3-dodecylene-1-aldehyde, a-n-pentyl phenylacrolein, the 4-methoxybenzaldehyde, phenyl aldehyde, 3-(4-tert-butyl-phenyl) propionic aldehyde, 2-methyl-3-(p-methoxyphenyl propionic aldehyde, 2-methyl-4-(2,6,6-trimethylammonium-2 (1) tetrahydrobenzene-1-yl) butyraldehyde, 3-phenyl-2-propenal, cis/trans-3,7-dimethyl-2,6-octadiene-1-aldehyde, 3,7-dimethyl-6-octene-1-aldehyde, [(3,7-dimethyl-6-octene) oxygen base] acetaldehyde, 4-isopropyl benzene formaldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-tetrahydrobenzene-1-formaldehyde, 2-methyl-3-(isopropyl phenyl) propionic aldehyde, the 1-capraldehyde; Capraldehyde, 2,6-dimethyl-5-heptenal, ([5.2.1.0 (2 for three rings for 4-, 6)]-decylidene-8)-butyraldehyde, octahydro-4,7-methylene radical-1H-indenes formaldehyde, vanirom, to ethyl-a, a-dimethyl hydrogenation phenylacrolein, a-methyl-3,4-(methylene radical dioxy base) hydrocinnamic aldehyde, 3,4-methylenedioxyphenyl formaldehyde, a-n-hexyl phenylacrolein, between isopropyl benzene-7-formaldehyde, a-aminomethyl phenyl formaldehyde, 7-hydroxyl-3,7-dimethyl octanal, undecenal, 2,4,6-trimethylammonium-3-tetrahydrobenzene-1-formaldehyde, 4-(3) (4-methyl-3-pentenyl)-3-tetrahydrobenzene formaldehyde, the 1-lauric aldehyde, 2, the 4-triplal, 4-(4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-formaldehyde, 7-methoxyl group-3,7-dimethyl-octa-1-aldehyde, the 2-methyl undecyl aldehyde, 2-methyl capraldehyde, the 1-aldehyde C-9, the 1-octanal, 2,6,10-trimethylammonium-5, the 9-undecadienal, 2-methyl-3-(the 4-tertiary butyl) propionic aldehyde, dihydro cinnamon aldehyde, 1-methyl-4-(4-methyl-3-pentenyl)-3-tetrahydrobenzene-1-formaldehyde, 5 or 6 methoxyl group six hydrogen-4,7-methylene radical 1,2 indane-1 or 2 formaldehyde, 3,7-dimethyl-octa-1-aldehyde, the 1-undecyl aldehyde, 10-undecene-1-aldehyde, 4-hydroxy 3-methoxybenzene formaldehyde, 1-methyl-3-(4-methyl amyl)-3-tetrahydrobenzene formaldehyde, 7-hydroxyl-3,7-dimethyl octanal, trans-the 4-decenal, 2, the 6-nonadienal, p-methylphenyl acetaldehyde, 4-aminomethyl phenyl acetaldehyde, 2-methyl-4-(2,6,6-trimethylammonium-1-tetrahydrobenzene-1-yl)-crotonic aldehyde, positive methoxycinnamic aldehyde, 3,5,6-trimethylammonium-3-tetrahydrobenzene formaldehyde, 3,7-dimethyl-2-methylene radical-6-octenal, phenoxy acetaldehyde, 5,9-dimethyl-4, the 8-decadienal, Chinese herbaceous peony aldehyde, (6,10-dimethyl-3-oxa--5,9-11 carbon diene-1-aldehyde), six hydrogen-4,7-methylene radical 1,2-indane-1-formaldehyde, 2 methyl octylaldehyde, a-methyl-4-(1-methylethyl) phenylacetic aldehyde, 6, firpene-2-propionic aldehyde falls in 6-dimethyl-2-, to the methylenedioxy phenoxy ethylhexanal, 2-methyl-3-phenyl-2-propylene-1-aldehyde, 3,5,5,-trimethylammonium hexanal, six hydrogen-8,8-dimethyl-2-naphthaldehyde, 3-propyl group-dicyclo [2.2.1]-heptan-5-alkene-2-formaldehyde, the 9-decenal, 3-methyl-5-phenyl-1-valeral, methyl nonyl acetaldehyde, hexanal, trans-the 2-hexenoic aldehyde, 1-is right-Meng alkene menthene-q-formaldehyde and its mixture.
Most preferred aldehyde is selected from 1-capraldehyde, phenyl aldehyde, florhydral, 2,4-dimethyl-3-tetrahydrobenzene-1-formaldehyde, cis/trans-3,7-dimethyl-2,6-octadiene-1-aldehyde, piperonylaldehyde, 2,4,6-trimethylammonium-3-tetrahydrobenzene-1-formaldehyde, 2,6-nonadienal, a-n-pentyl phenylacrolein, a-n-hexyl phenylacrolein, P.T. are to the tertiary butyl-a-hydrogenated methyl phenylacrolein, LYRAL, cymal, methyl nonyl acetaldehyde, hexanal, trans-2-hexenoic aldehyde and its mixture.
In the above listed spices component, some are to well known to a person skilled in the art conventional trade(brand)name, and also comprise isomer.This isomer also is applicable to the present invention.
In another embodiment, what be particularly suitable for the object of the invention is flavor compounds, and preferred spices ketone or active aldehydes are characterised in that to have low odor detection threshold values.This odor detection threshold values (ODT) should be less than or equal to 1ppm, preferably is less than or equal to 10ppb, by for example measuring under controlled gas-chromatography (GC) condition hereinafter described.This parameter is classified as the conventional numerical value that uses of field of perfumery, and it is the minimum concentration of the more existing odoring substances when taking place obviously to discover.For example please refer to " smell and sense of taste threshold values data compilations (ASTM DS 48A) " (Compilation of Odor and Taste Threshold Value data (ASTM DS48A) "; by F.A.Fazzalari; International BusinessMachines; Hopwell Junction; NY edits and at spices, practice and the principle (Perfumery; Practice and Principles) of Calkin etc., John Willey; Sons, the 243rd page of Inc. and the example in (1994) hereinafter thereof.For the object of the invention, the odor detection threshold values is measured according to following method:
Gas-chromatography is characterised in that the accurate volume that can measure the material that is injected by syringe, accurate splitting ratio and use the standard concentration known and the hydrocarbon sensitivity of chain length distribution hydrocarbon.Accurately measure air velocity, suppose that the time length that human body sucks reaches 0.02 minute, the calculating sample volume.Because at any time, the accurate concentration in the detector is known, and the per unit volume soakage is known, so material concentration also is known.In order to measure the ODT of fragrance material, solution is delivered to suction opening with the concentration of subsequent calculations.Member of panel of experts smells the GC air-flow and the residence time when determining to perceive smell.Determine perceptible threshold values by all members' of panel of experts mean value.The requirement of analyzer is injected post, on detector, obtain definite concentration, for example 10ppb.The typical gas-chromatography parameter of measuring the odor detection threshold values is as follows: GC: the 5890 serial II that have fid detector
7673 self-actuated samplers
Post: J ﹠amp; W Scientific DB-1
30 meters of length, ID0.25mm, 1 micron of thickness
Method:
Shunting injection: 17/1 splitting ratio
Self-actuated sampler: 1.13 microlitre/injections
Column flow rate: 1.10 ml/min
Air velocity: 345 ml/min
Temperature in: 245 ℃
Detector temperature: 285 ℃
Temperature information
Starting temperature; 50 ℃
Speed: 5 ℃/minute
Outlet temperature: 280 ℃
Final time: 6 minutes
Main prerequisite: the GC air 0.02 minute that at every turn sucks diluted sample
The example of this preferred spices component is to be selected from following those: 2-methyl-2-(p-isopropyl phenyl) propionic aldehyde, 1-(2,6,6-trimethylammonium-2-hexamethylene-1-yl)-2-butylene ketone and/or to methoxy acetone.Even more preferably measure as stated above, the following compound of ODT≤10ppb: undecenal, γ undecalactone, piperonylaldehyde, γ dodecanoic acid lactone, p-anisaldehyde, p-hydroxybenzene butanone, cymal, benzyl acetone, a-ionone, P.T. are to the tertiary butyl-a-hydrogenated methyl phenylacrolein, trans-Damascenone, β ionone and methyl nonyl ketone.
Generally, the content of actives is 10%-90%, preferred 30%-85%, more preferably 45%-80% weight amine reaction product.
Preferred amine reaction product is to react those that obtain by polyethylene imine based polymkeric substance such as Lupasol polymkeric substance and one or more following compounds: a-damascone, δ-damascone, Karvon, methyl dihydrojasmonate, florhydral, Ling Lanquan, piperonylaldehyde, γ methyl ionone and 2,4-dimethyl-3-tetrahydrobenzene-1-formaldehyde.Other also preferred amine reaction products be obtain by the reaction of Astramol dendrimers and Karvon those and by 4-subcutin and 2, those that 4-dimethyl-3-tetrahydrobenzene-1-formaldehyde reaction obtains.
Most preferred amine reaction product is by Lupasol HF and δ-damascone; LupasolG35 and a-damascone; LupasolG100 and 2,4-dimethyl-3-tetrahydrobenzene-1-formaldehyde; 4-subcutin and 2, those that 4-dimethyl-3-tetrahydrobenzene-1-formaldehyde reaction obtains.
Method
Prepare component by following synthetic embodiment.Generally, to be called azomethine, Schiff's base or preferred title be imines to the nitrogen analogs of ketone and aldehyde.These imines can be easily by primary amine and carbonyl compound condensation, and removing anhydrates prepares.
General response situation is as follows:
Alpha, beta-unsaturated ketone not only forms imines with the amine condensation, but also experiences 1 of competition, and the 4-addition reaction forms beta-amino ketones:
By this simple method, the compound of making and contain described compound compositions and can reach and postpone to discharge active constituent.
As observable, the content of general spices component is and mol such as amine-functionalized compound, so that make reaction that amine reaction product can take place and obtain.Certainly, do not get rid of higher amount, even more preferably amine compound comprises more than an amine functional group.When amine compound has more than a free uncle and/or secondary amine functional groups, several different perfume bases can be connected on the amine compound.
Releasing mechanism
By the present invention, obtained postponing the spices component of release, i.e. ketone or aldehyde.Without being limited by theory, believe that this release is to take place by following mechanism:
For group with imine moiety, the release of spices component is through the breaking of imine linkage, and causes discharging spices component and primary amine.This can decompose by hydrolysis, photochemistry decomposition, oxygenolysis or enzyme realizes.
For the beta-amino ketones compound, can successfully discharge spices component and amine compound with damp atmosphere and/or water treatment.Yet, do not get rid of other delivery modes such as hydrolysis, photochemistry decomposition, oxygenolysis or enzyme and urge decomposition.
Other modes that discharge imines and beta-amino ketones compound can think for example to press steaming step, roll-drying and/or the dress of handling fabric.
The set of applications compound
Set of applications compound of the present invention comprises that needs postpone to discharge the composition of active ketone or aldehyde.This comprises the composition soft compound for example that is used for rinse, and individual clean-out system is shower glue, reodorant, bar, shampoo for example; Independently composition is as the composition of deodorizing, agrochemical.
Those compositions that preferably cause The compounds of this invention to contact with fabric.The present composition is applicable to any step of home treated, and it is pre-treatment and/or post-treatment composition, as detergent additive, as the composition that is applicable to rinse process.Obviously, multiple application can be arranged, for example handle fabric, afterwards with the compositions-treated that is applicable to rinse process and/or drying process with pretreatment compositions of the present invention.
Be applicable to the composition of rinse process, these are the composition that comprises such as following by understanding: the fabric softener composition that adds when the rinse of softness and/or antistatic effect can be provided and be added to composition (for example sheet) and rinse additive in the moisture eliminator.
Those compositions that preferably cause The compounds of this invention to contact with fabric.These are the composition that comprises such as following by understanding: the fabric softener composition that adds when the rinse of softness and/or antistatic effect can be provided and be added to composition (for example sheet) in the moisture eliminator.
Preferably, the amine reaction product that is incorporated in this composition has desiccated surface smell index greater than 5, and preferably at least 10.
Desiccated surface smell index, the meaning be the δ of amine reaction product greater than 5, wherein δ is smell index poor of the desiccated surface only handled with perfume base of the smell exponential sum of the desiccated surface handled with amine reaction product.
The desiccated surface smell exponential measuring method of fabric face
Product preparation:
Amine reaction product is added in the product base of perfuming not.
The product base of perfuming is not as follows, wherein abbreviation such as among the embodiment hereinafter definition:
Selection amine reaction product content makes that can obtain oder levels on dry fabric is at least 20.Under the situation of liquid,, under the powder situation, use scraper, behind the careful mixing prod, allow and placed 24 hours by vibration container.
Washing methods:
The product that obtains is suitable in the divider of this type by being metered into the washing machine neutralization.This amount is equivalent to the suggestion usage quantity of respective market product: for detergent powder or liquid, by common metering outfit such as granulette or ariellette, generally between 70-150g, for liquid fabric softener, generally between 25-40ml.This tote is made of 4 bath towels (170g), uses Miele W830 washing machine, and under 40 minutes short loop cycle, the water of input: 15 ° of hardness, temperature are 10-18 ℃, and rotating speed is 1200rpm fully.
Same method is applicable to the corresponding free spice component of being considered and is used as reference.The consumption of this reference and sample, the fabric of loading and be wash(ing)cycle identical.
Drying means
In 2 hours after finishing wash(ing)cycle, use the smell of that following scale evaluation rotates through but still moist fabric.Afterwards, half pieces of fabric is hung on the line away from any possible pollutent dry 24 hours.Except as otherwise noted, this drying is carried out indoor.Room temperature condition is 18-25 ℃, and atmospheric moisture is at 50-80%.Other half pieces of fabric is put in the rotatory drier and experiences the loop cycle of " very dried " fully, and promptly at Miele, among the Novotronic T430, the program of setting is ultrawhite drying (a fully loop cycle).Also evaluate the fabric of Rotary drying in next day.Then fabric is left in the indoor uncovered aluminium bag of odorlessness in evaluation again after 7 days.
The smell evaluation
Carefully smell fabric by the member of panel of experts and evaluate smell.Total fabric oder levels uses the 0-100 scale.Grade scale is as follows:
The fragrance scent that 100=is extremely strong
The fragrance scent that 75=is very strong
The strong smell of 50=
40=moderate fragrance scent
30=fragrance scent slightly
20=mild spices smell
The very weak fragrance scent of 10=
0=does not have smell.
After 1 day and/or 7 days, it is significant on the statistics differing by more than 5 grades between amine reaction product and perfume base.After 1 day and/or 7 days, differ 10 grades or more multilist show that step changes.In other words, when all observing between amine reaction product and perfume base rank difference after 1 day or 7 days or after 1 day and 7 days greater than 5, preferably at least 10 the time, deducibility goes out amine reaction product and is applicable to the present invention, and condition is that amine compound satisfies the odor strength index.
Amine reaction product defined above generally accounts for the 0.0001%-10% of composition weight, preferred 0.001%-5%, more preferably 0.01%-2%.The present invention also can use the mixture of compound.
In the present composition, mix amine reaction product,, can suit to carry out,, for example described in the GB146616, do interpolation or use the cyclodextrin encapsulate for example by sprinkling, encapsulate such as starch encapsulate with the routine method of mixing as if needing.Preferably, the preprocess amine reaction product mixes in the present composition then.In other words, spices component and amine compound at first one react, and obtain the amine reaction product of the present invention's definition and formation in a single day, only mix in the present composition.Mix after prefabricated in the complete composition prepared, obtained good control prepared compound.Therefore, avoided and interaction that is present in the flavor compositions in the complete composition prepared and contingent side reaction.In addition, by this method of mixing, controlled the yield and the purity of compound effectively.
Most preferably, when the present composition comprised spices, amine reaction product and spices mixed in the composition separately.By this method, amine reaction product and its follow-up spices discharge and are controlled better.
Generally, the present composition comprises tensio-active agent component for example fabric softener or the tensio-active agent as optional components hereinafter described.
When said composition comprised softening agent, the composition that obtains was a soft compound.
Fabric softener
The fabric softener component provides softness and anti-static function for the fabric of handling.When using, the general amount that exists of fabric softener component is enough to provide softness and anti-static function
Described fabric sofetening component can be selected from positively charged ion, nonionic, both sexes or negatively charged ion fabric sofetening component.
The soft component of typical positively charged ion is quaternary ammonium compound or its amine precursor that hereinafter defines.
A)-the soft active compound of quaternary ammonium fabric
(1) the soft active compound of preferred quaternary ammonium fabric has formula
Or formula:
Wherein Q is the carbonyl unit with following formula:
Each R unit is hydrogen independently, C
1-C
6Alkyl, C
1-C
6Hydroxyalkyl and their mixture, preferable methyl or hydroxyalkyl; Each R
1The unit is straight or branched C independently
11-C
22Alkyl, straight or branched C
11-C
22Alkenyl and their mixture; R
2Be hydrogen, C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl and their mixture; X is and fabric softener active matter and the compatible negatively charged ion of binder component; Subscript m is 1-4, preferred 2; Subscript n is 1-4, preferred 2.
The example of preferred fabric softener active matter is the mixture with quaternary ammonium of following formula:
Wherein R is preferably methyl; R
1Be to contain at least 11 carbon atoms, the straight or branched alkyl or the alkenyl chain of preferred at least 15 carbon atoms.In above-mentioned fabrics softening agent example, unit-O
2CR
1Expression derives from the fatty acyl group unit in triglyceride level source usually.The triglyceride level source preferably derives from butter, partially hydrogenated butter, lard, partially hydrogenated lard, vegetables oil and/or partially hydrogenated vegetables oil, Tower rape oil for example, Thistle oil, peanut oil, Trisun Oil R 80, Semen Maydis oil, soybean oil, Yatall MA, rice bran wet goods and these oily mixtures.
The preferred fabric sofetening actives of the present invention is diester and/or diamide quaternary ammonium compound (DEQA), and this diester class and diamide have following formula:
R wherein, R
1, X, with the above-mentioned formula of n and this paper (1) and (2) middle define identical, Q has following formula:
The formation of these preferred fabric sofetening activess is by amine and fatty acyl group unit process, forms the amine intermediate with following formula:
Wherein R is preferably methyl, and Q and R ' are with above definition; The final softening agent actives of quaternized then formation.
The limiting examples that is used for forming the preferred amines of DEQA fabric sofetening actives according to the present invention comprises two (2-hydroxyethyl) amine of the methyl with following formula:
Two (2-hydroxypropyl) amine of methyl with following formula:
Methyl (3-aminopropyl) (2-hydroxyethyl) amine with following formula:
Two (2-amino-ethyl) amine of methyl with following formula:
Trolamine with following formula:
Two (2-amino-ethyl) thanomin with following formula:
Above-mentioned counterion X
(1)Can be arbitrarily with the compatible negatively charged ion of softening agent, the preferred negatively charged ion of strong acid, chlorion for example, bromide anion, methylsulfate, ethyl sulphate, sulfate radical, nitrate radical etc., more preferably chlorion or methylsulfate.Negatively charged ion can also but not too preferably have double charge, X in this case
(1)Represent group half.
Butter and Tower rape oil are convenient and the cheap unitary source of fatty acyl group, and it is suitable among the present invention as R
1The unit.It below is the limiting examples that is suitable for the quaternary ammonium compound in the present composition.Used term below this paper " butter acyl group " expression R
1The unit derives from butter triglyceride level source, and is the unitary mixture of fatty acyl group.Equally, use term canola oleoyl to refer to the unitary mixture of the fatty acyl group that derives from Tower rape oil.
Table II
Fabric softener active matter
N, N-two (butter acyloxy-ethyl)-N, N-alkyl dimethyl ammonium chloride;
N, N-two (Tower rape oil acyloxy-ethyl)-N, N-alkyl dimethyl ammonium chloride;
N, N-two (butter acyloxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride;
N, N-two (Tower rape oil acyloxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride;
N, N-two (2-butter acyloxy-2-oxo-ethyl)-N, N-alkyl dimethyl ammonium chloride;
N, N-two (2-Tower rape oil acyloxy-2-oxo-ethyl)-N, N-alkyl dimethyl ammonium chloride;
N, N-two (2-butter acyloxy ethyl oxy carbonyl ethyl)-N, N-alkyl dimethyl ammonium chloride;
N, N-two (2-Tower rape oil acyloxy ethyl oxy carbonyl ethyl)-N, N-alkyl dimethyl ammonium chloride;
N-(2-butter acyloxy-2-ethyl)-N-(2-butter acyloxy-2-oxo-ethyl)-N, the N-alkyl dimethyl ammonium chloride;
N-(2-Tower rape oil acyloxy-2-ethyl)-N-(2-Tower rape oil acyloxy-2-oxo-ethyl)-N, the N-alkyl dimethyl ammonium chloride;
N, N, N-three (butter acyloxy-ethyl)-N-ammonio methacrylate;
N, N, N-three (Tower rape oil acyloxy-ethyl)-N-ammonio methacrylate;
N-(2-butter acyloxy-2-oxoethyl)-N-(butter acyl group)-N, the N-alkyl dimethyl ammonium chloride;
N-(2-Tower rape oil acyloxy-2-oxoethyl)-N-(canola oleoyl)-N, the N-alkyl dimethyl ammonium chloride;
1,2-two butter acyloxy-3-N, N, N-trimethyl ammonium propane chloride; With
1,2-two Tower rape oil acyloxy-3-N, N, N-trimethyl ammonium propane chloride;
And the mixture of above-mentioned actives.
Other example of quaternary ammonium softening compound thing is two (butter amido ethyl) (2-hydroxyethyl) ammonium methyl sulfates of methyl and two (h-tallow amido ethyl) (2-hydroxyethyl) ammonium methyl sulfates of methyl; These materials can be buied from Witco chemical company, and trade(brand)name respectively is
222 Hes
110.
Particularly preferably be N, N-two (Tower rape oil acyloxy-ethyl)-N, the N-alkyl dimethyl ammonium chloride, wherein the butter chain is undersaturated to small part.
Can measure the degree of unsaturation that is included in butter, Tower rape oil or other fatty acyl group cellular chain by the iodine number (IV) of corresponding lipid acid; should be preferably within the 5-100 scope under the situation of the present invention its, be distinguished into have iodine number less than or greater than 25 two compounds.
In fact, to having the compound that derives from tallow fatty acid of following formula:
When iodine number is 5-25, during preferred 15-20, the weight ratio of having found suitable/trans isomer is preferably greater than 50/50 greater than 30/70, has best condensability more preferably greater than 70/30.
Concerning this type of by iodine number greater than the compound of 25 tallow fatty acid preparation, found that the ratio of cis-trans-isomer is not too strict, unless need very high concentration.
The example of the fabric softener active matter that other is fit to derives from the fatty acyl base class; term in the wherein above-mentioned example " butter acyl group " and " canola oleoyl " available term " cocoyl; palmityl (palmyl); lauryl; oil base, castor oil-base, stearyl; palmityl " replace, and it is corresponding to obtaining the unitary triglyceride level of fatty acyl group source.These interchangeable fatty acyl group sources can be contained fully saturated, perhaps preferably to the undersaturated chain of small part.
Above-mentioned as this paper, the R unit is methyl preferably, yet the fabric softener active matter that is fit to is described to replace term " methyl " in the above Table II example with " ethyl, oxyethyl group, propyl group, propoxy-, sec.-propyl, butyl, isobutyl-and the tertiary butyl " unit.
Counterion X in the Table II example can use bromide anion, methylsulfate, formate, sulfate radical, nitrate radical and their mixture to replace aptly.In fact, negatively charged ion X only is the counterion existence as positively charged quaternary ammonium compound.Do not think that scope of the present invention is limited to any specific negatively charged ion.
For above-mentioned ester fabric softener, the pH value of the present composition is an important parameter of the present invention.In fact, it can influence the stability of quaternary ammonium compound or amine precursor compound, is being under the condition that prolongs the shelf lives especially.
The pH value of definition is to measure in 20 ℃ pure composition in the scope of the invention.Though it is exactly feasible that these compositions are lower than at 6.0 o'clock in the pH value, for obtaining the optimum hydrolysis stability of these compositions, the pure pH value of Ce Dinging preferably must be in the 2.0-5 scope under these conditions, preferably in the 2.5-4.5 scope, and preferred 2.5-3.5.The pH value of these compositions can be regulated by adding a kind of protonic acid herein.
The example of suitable acid comprises mineral acid, carboxylic acid, particularly lower molecular weight (C1-C5) carboxylic acid, and alkylsulphonic acid.Suitable mineral acid comprises HCl, H
2SO
4, HNO
3And H
3PO
4Suitable organic acid comprises formic acid, acetate, citric acid, methylsulfonic acid and ethyl sulfonic acid.Preferred acid is citric acid, hydrochloric acid, phosphoric acid, formic acid, methylsulfonic acid, and phenylformic acid.
As described herein, when mentioning diester, it comprises the monoesters that exists usually in the production.For soft purpose, do not having/be loaded with under the laundry situation of low amount washing composition, the percentage composition of monoesters should be low as far as possible, and preferred no more than 2.5%.Yet, under the condition that is loaded with a large amount washing composition, preferably have some monoesters.The overall proportion of diester and monoesters is 100: 1-2: 1, preferred 50: 1-5: 1, more preferably 13: 1-8: 1.Under the condition that is loaded with a large amount washing composition, diester/monoesters was than preferred 11: 1.In the production of softener compound, can control the amount of monoesters.
Also can preparation formula (1) and the mixture of formula (2) actives.
2)-and other suitable quaternary ammonium fabric softening compound things of being used for herein are the nitrogenous salts of positively charged ion, this salt has two or more long-chains and does not have cyclic aliphatic C
8-C
22Alkyl or have a described group and an aralkyl, it can use separately or use as the part of mixture, is selected from:
(i) have the acyclic quaternary ammonium salt of following formula:
R wherein
4Be no cyclic aliphatic C
8-C
22Alkyl, R
5Be C
1-C
4Saturated alkyl or hydroxyalkyl, R
8Be selected from R
4And R
5Base, A
-It is negatively charged ion defined above;
The diamino alkoxy quaternary ammonium salt that (ii) has following formula:
Wherein n equals 1-5, R
1, R
2, R
5And A
-As top defined;
(iii) their mixture.
The example of the nitrogenous salt of the above-mentioned type positively charged ion is well-known dialkyl dimethyl ammonium salt, as two butter alkyl dimethyl ammonium chlorides, two butter dimethyl methyl ammonium sulfate, two (h-tallow) alkyl dimethyl ammonium chloride, VARISOFT TA100, two mountain Yu base alkyl dimethyl ammonium chloride.Two (h-tallow) alkyl dimethyl ammonium chlorides and two butter alkyl dimethyl ammonium chlorides are preferred.The example that is used for commercially available dialkyl dimethyl ammonium salt class of the present invention is two (h-tallow) alkyl dimethyl ammonium chloride (trade(brand)name
442), two butter alkyl dimethyl ammonium chloride (trade(brand)names
470,
3445), VARISOFT TA100 (trade(brand)name
TA-100), all available from Witco chemical company.Two mountain Yu base alkyl dimethyl ammonium chloride is to be sold by the Humko chemistry branch of Witco chemical company with trade(brand)name Kemamine Q-2802C.
Dimethyl stearyl benzyl ammonium chloride is by trade(brand)name by Witco chemical company
SDC and press by Onyx chemical company
490 sell.
B)-amine fabric sofetening active compound
Be used for the suitable amine fabric soft compound of this paper, it can be the form or the cationic form of amine, is selected from:
(i)-and the reaction product of higher fatty acid and polyamine, this polyamine is selected from hydroxyalkyl Alkylenediamine and two alkylene triamine and its mixture.In view of the polyfunctional structure of polyamine, these reaction product are mixtures of some kinds of compounds.
Preferred ingredients (i) is the nitrogenous compound that is selected from some selected components in mixed reaction product or the mixture.
A kind of preferred ingredients (i) is the imidazolinium compounds that is selected from the replacement with following formula:
R wherein
7Be no cyclic aliphatic C
16-C
21Alkyl, R
8Be divalence C
1-C
3Alkylidene group.
Component (i) material is commercially available to be sold in: Mazer Chemicals
6, or Sandoz Colors ﹠amp; Chemicals sells
HC; By AlkarilChemicals, Inc. is with trade(brand)name
ST or by ScherChemicals, Inc. is with trade(brand)name
The stearic hydroxyethyl imidazole quinoline that S sells; N, N " two butter alkyloyl diethylenetriamine; 1-butter amido ethyl-2-butter tetrahydroglyoxaline (R in aforementioned structure wherein
1Be aliphatic C
15-C
17Alkyl, R
8Be the divalence ethylidene).
Some component (i) also can at first be dispersed in the pKa value and be not more than in 4 the protonic acid dispersing auxiliary; Condition is that the pH of final composition is not more than 6.Some preferred dispersing auxiliaries are hydrochloric acid, phosphoric acid, or methylsulphonic acid.
N; N " the two is the reaction product of tallow fatty acid and diethylenetriamine two butter alkyloyl diethylenetriamine and 1-butter (amido ethyl)-2-butter tetrahydroglyoxaline; and be the precursor (referring to " as the cats product of fabric softener "; R.R.Egan; U.S. oiling association will (Journal of American Oil Chemicals ' Society); in January, 1978,118-121 page or leaf) of cationic fabric softener methyl isophthalic acid-butter amido ethyl-2-butter tetrahydroglyoxaline Methylsulfate.N, " two butter alkyloyl diethylenetriamine and 1-butter amido ethyl-2-butter tetrahydroglyoxaline can obtain with chemical as experiment from Witco chemical company N.Methyl isophthalic acid-butter amido ethyl-2-butter tetrahydroglyoxaline Methylsulfate by Witco chemical company with trade(brand)name
475 sell.
(ii)-have a softening agent of following formula:
Each R wherein
2Be C
1-6Alkylidene group, preferred ethylidene; G be Sauerstoffatom or-the NR-base; Each R, R
1, R
2And R
5Has the definition that provides above, A
-Has the X that provides above
-Definition.
A compound example (ii) is 1-oil base amido ethyl-2-oil-based imidazoline muriate, wherein R
1Be no cyclic aliphatic C
15-C
17Alkyl, R
2Be ethylidene, G is the NH base, R
5Be methyl and A
-It is cl anion.
(iii)-have a softening agent of following formula:
R wherein, R
1, R
2And A
-Definition the same.
A compound example (iii) is the compound with following formula:
R wherein
1Derive from oleic acid.
Except cationic fabric softener or as the substituting of cationic fabric softener, can use other fabric sofetening materials.These can be selected from nonionic, both sexes or negatively charged ion fabric sofetening material.The disclosure of these materials can be referring to U.S. Pat 4327133; US4421792; US4426299; US4460485; US3644203; US4661269; US4439335; US3861870; US4308151; US3886075; US4233164; US4401578; US3974076; US4237016 and EP472178.
Generally, it is 2 to 9 that this nonionic fabric softener material has the HLB value, is more typically 3 to 7.This nonionic fabric softener material itself or when they and other material example single-long-chain alkyl cats product as will be detailed later mixed, their are inclined to was easy dispersive.Can by use longer single-long-chain alkyl cats product, its with the mixture of other material of description, use hotter water and/or more stirring to improve dispersiveness.Generally, selecteed material should be crystal relatively, have higher fusing point (for example＞40 ℃) with relative be water-insoluble.
Preferred NON IONIC SOFTNER is the partial fatty acid ester of polyvalent alcohol or their acid anhydrides, and wherein alcohol or acid anhydride contain 2 to 18, preferred 2 to 8 carbon atoms, and each fatty acid part contains 12-30, preferred 16-20 carbon atom.Typically, this softening agent per molecule contains 1-3, preferred 2 fatty acid-based.
The polyol moiety of this ester can be ethylene glycol, glycerine, poly-(for example two, three, four, five and/or six) glycerine, Xylitol, sucrose, tetrahydroxybutane, tetramethylolmethane, Sorbitol Powder or sorbitan.Sorbitan ester and poly-glyceryl monostearate are particularly preferred.
Generally by having 12 to 30, the lipid acid of preferred 16 to 20 carbon atoms obtains the fatty acid part of this ester, and the representative instance of said lipid acid is lauric acid, tetradecanoic acid, palmitinic acid, stearic acid and mountain Yu acid.
Being used for highly preferred optional NON IONIC SOFTNER of the present invention is sorbitan ester and glyceryl ester, and said sorbitan ester is the dewatered product of Sorbitol Powder esterification.
The sorbitan monostearate that the merchant sells is the material that is fit to.Have stearate/cetylate weight ratio at the stearic acid sorbitan ester of 10: 1 to 1: 10 scopes and the mixture and 1 of palmitinic acid sorbitan ester, the 5-sorbitan ester also is fit to.
Glycerine and polyglycerol ester, particularly glycerine, two glycerine, triglycerin and Polyglycerine list and/or diester, preferred monoesters is the present invention's preferred (poly-glyceryl monostearate that for example has commodity Radiasurf7248 by name).
Useful glycerine and polyglycerol ester comprise stearic acid, oleic acid, palmitinic acid, lauric acid, Unimac 5680, tetradecanoic acid and/or mountain Yu acid monoester and stearic acid, oleic acid, palmitinic acid, lauric acid, Unimac 5680, mountain Yu acid and/or tetradecanoic acid diester.Be to be understood that general monoesters contains some two and three esters etc.
" glyceryl ester " also comprises polyglycerol ester, for example two glycerine to eight glyceryl ester.The many alcohol of these Polyglycerine are by with glycerine or Epicholorohydrin condensation together, connect by ehter bond that the glycerine part forms.The lists of the many alcohol of this Polyglycerine and/or diester are preferred, those that the fatty acyl group part is above described in sorbitan and the glyceryl ester typically.
Be applicable to that in addition fabric sofetening component of the present invention is a mild clay, for example be described in a kind of of low ion-exchange capacity among the EP-A-0150531.
Certainly, term " soft actives " also can comprise the soft promoting agent of blended.
In the disclosed softener compound type in this paper front, the soft active compound (DEQA) of diester or diamide quaternary ammonium fabric preferably.
The content of fabric softener compound of the present invention is the 1%-80% of the present composition, this depends on the composition of enforcement, it can dilute, preferred active matter content is 5%-15%, or it is spissated, preferred active matter content is 15%-50%, most preferably is the 15%-35% of composition weight.
The soft compound of complete preparation preferably also contains one or more following components except containing the above-mentioned component of this paper.
(A)
Whitening agent
The wetting ability white dyes that also can randomly comprise about some type of 0.005%-5% weight in the present composition, they also work to suppress dye transfer.If use, the present composition preferably includes this white dyes of 0.001%-1% weight.
Be used for wetting ability white dyes of the present invention and be following those of structural formula:
R wherein
1Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R
2Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morphine base, chlorine and amino; M is salt-forming cation such as sodium or potassium.
R in following formula
1Be anilino, R
2Be N-2-two-hydroxyethyl, and M is when being positively charged ion such as sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-sym-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.This special brightener species by Ciba-Geigy company with trade(brand)name Tinopal-UNPA-
Sell.Tinopal-UNPA-GX is the preferred wetting ability white dyes of composition that adds when being used for the rinsing of this paper.
R in following formula
1Be anilino, R
2Be N-2-hydroxyethyl-N-2-methylamino-, and M is when being positively charged ion such as sodium, then whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-sym-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid disodium salt.This special brightener species by Ciba-Geigy company with trade(brand)name Tinopal 5BM-
Sell.
R in following formula
1Be anilino, R
2Be the morphine base, and M is when being positively charged ion such as sodium, then whitening agent is 4,4 '-two [(4-anilino-6-morphine base-sym-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid, sodium salt.This special brightener species by Ciba-Geigy company with trade(brand)name TinopalAMS-
Sell.
(B)
Dispersing auxiliary
Can be prepared into stable contain saturated and unsaturated diester quat than concentrated composition, and needn't add concentrated assistant.But the present composition may need organic and/or inorganic concentrated assistant to reach higher concentration and/or to satisfy higher stability criterion, and this depends on other components.These concentrated assistants may be that need or preferred, under extreme conditions stability when guaranteeing the softening agent actives when the use certain content, and these concentrated assistants are generally viscosity modifier.The tensio-active agent concentrated assistant is selected from (1) single-long-chain alkyl cats product usually; (2) nonionogenic tenside; (3) amine oxide class; (4) fatty acid; (5) their mixture.These auxiliary agents are described among the WO94/20597, specifically are the 14th page 12 and walk to the 20th page of 12 row, and this patent is quoted as a reference at this paper.
When having described dispersing auxiliary, its total content is the 2%-25% of composition weight, preferred 3%-17%, more preferably 4%-15%, most preferably 5%-13%.These materials or add as the part of REACTIVE SOFTNER raw material (I), for example, foregoing single-long-chain alkyl cats product and/or be used for forms the lipid acid of the reactant of biodegradable fabric softener active matter, or adds as independent component.The total content of dispersing auxiliary comprises any amount that may exist as the part of component (I).
(1)
The monoalkyl cationic quaternary ammonium compound
When having the monoalkyl cationic quaternary ammonium compound, its content is generally the 2%-25% of composition weight, preferred 3%-17%, and more preferably 4%-15%, 5%-13% most preferably, total monoalkyl cationic quaternary ammonium compound is significant quantity at least.
Be used for the preferably following quaternary ammonium salt of general formula of this monoalkyl cationic quaternary ammonium compound of the present invention:
[R
4N
+(R
5)
3]X
-
R wherein
4Be C
8-C
22Alkyl or alkenyl, preferred C
10-C
18Alkyl or alkenyl; More preferably C
10-C
14Or C
16-C
18Alkyl or alkenyl;
Each R
5Be C
1-6The alkyl of alkyl or replacement (as hydroxyalkyl), preferred C
1-C
3Alkyl, as methyl (most preferably), ethyl, propyl group etc., benzyl, hydrogen has 2-20 oxygen ethylene unit, preferred 2.5-13 oxygen ethylene unit, the more preferably polyethoxylated chain of 3-10 oxygen ethylene unit, and their mixture; With
X
-With front identical to formula (I) definition.
Particularly preferred dispersing auxiliary is can be from Witco with trade(brand)name
412 Hes
471 single lauryl trimethyl ammonium chlorides of having bought and single tallow trimethyl ammonium chloride can be from Witco with trade(brand)names
417 single oil bases of having bought or single canola oil base trimethyl ammonium chloride can be from Witco with trade(brand)names
461 single cocoyl trimethyl ammonium chlorides of having bought and can be from Witco with trade(brand)name
The soybean oil based trimethyl ammonium chloride of 415 lists of having bought.
R
4Base also can be connected with azonia by the group that contains linking groups such as one or more esters, acid amides, ether, amine, and this linking group is an ideal for the concentrated power of raising component (1) etc.These linking groups are preferably in 1-3 carbon atom of nitrogen-atoms.
The monoalkyl cationic quaternary ammonium compound also comprises C
8-C
22The alkyl cholinesterase.This type of preferred dispersing auxiliary has following chemical formula:
R
1C(O)-O-CH
2CH
2N
+(R)
3X
-
R wherein
1, R and X
-Definition the same.
Highly preferred dispersing auxiliary comprises C
12-C
14Cocounut oil cholinesterase and C
16-C
18The butter cholinesterase.
Described the suitable biodegradable single-long-chain alkyl dispersing auxiliary that contains ester bond in long-chain in U.S. Pat 4840738, this patent is hereby incorporated by.
When dispersing auxiliary comprises the alkyl cholinesterase, preferably also contain in the composition a spot of, preferably account for the organic acid of composition weight 2%-5%.Organic acid is described among the EP404471, and this patent is hereby incorporated by.Organic acid is preferably selected from oxyacetic acid, acetate, citric acid and composition thereof.
The ethoxylation quaternary ammonium compound that can be used as the dispersing auxiliary use comprises two (polyethoxyethanols) alkylammonium sulfovinates of the ethyl with 17 moles of ethylene oxide, and it is with trade(brand)name
66 available from Witco company; With trade(brand)name
0/25 polyoxyethylene glycol (15) oil base ammonium chloride available from Akzo; With with trade(brand)name
C/25 is available from polyoxyethylene glycol (15) the cocoyl ammonium chloride of Akzo.
Have only the quaternary ammonium compound of a single-long-chain alkyl can protect cationic softener not interact with anion surfactant and/or the washing auxiliary detergent brought into from washings the rinsing liquid.
(2)
Nonionogenic tenside (alcoxylates)
Draw together the adduct of oxyethane and optional propylene oxide and Fatty Alcohol(C12-C14 and C12-C18), lipid acid, aliphatic amide etc. as the suitable ionic surfactant pack of viscosity/dispersion force conditioning agent.They are referred to herein as ethoxylized fatty alcohol, ethoxylated fatty acid and ethoxylated fatty amine.The alcoxylates of any hereinafter described particular type all can be used as nonionogenic tenside and uses.In general, nonionogenic tenside herein is when using separately, and the content in liquid composition is 0%-5%, preferred 0.1%-5%, more preferably 0.2%-3%.Suitable compounds is the water miscible basically tensio-active agent with following general formula:
R
2-Y-(C
2H
4O)
Z-C
2H
4OH
For solid and liquid composition, wherein R
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; And primary, the phenol alkyl that replaces of the second month in a season and branched-chain alkyl and alkenyl; It is 8-20 that described alkyl has the alkyl chain length, preferred 10-18 carbon atom.More preferably for liquid composition, the alkyl chain length is a 16-18 carbon atom, and for solids composition, the alkyl chain length is a 10-14 carbon atom.In the ethoxylated non-ionic surface active agent general formula of this paper, Y is generally-O-,-C (O) O-,-C (O) N (R) or-C (O) N (R) R-, preferred-O-, and R wherein
2With R when existing, have the meaning that preamble provides, and/or R can be hydrogen, Z is 8 at least, preferably 10-11 at least.When having few oxyethyl group, the performance of softener composition and stability can reduce usually.
The nonionogenic tenside of this paper is characterised in that HLB (hydrophile-lipophile balance value) is 7-20, preferred 8-15.Certainly, by limiting R
2With the ethoxy radix, the HLB value of tensio-active agent is general just have been determined.But, should be understood that nonionic ethoxylated surfactant used herein, for spissated liquid composition, comprise the R of relative long-chain
2Base and relative high ethoxylation degree.Can have desired HLB value though have the tensio-active agent of the shorter alkyl chain of short oxyethyl group, they are not effective in this article.
For the composition of higher flavour content, more preferred than other conditioning agents disclosed herein as the nonionogenic tenside of viscosity/dispersion force conditioning agent.
It below is the example of nonionogenic tenside.Nonionogenic tenside of the present invention is not limited to these embodiment.In an embodiment, integer has defined the number of oxyethyl group (E0) in the molecule.
(3)
Amine oxide
Suitable amine oxide comprises having a 8-22 carbon atom, preferred 10-18 carbon atom, more preferably the alkyl of 8-14 carbon atom or hydroxyalkyl are partly and those amine oxides that are selected from two moieties of alkyl with 1-3 carbon atom and hydroxyalkyl.
Example comprises dimethyl octyl group amine oxide, diethyl decyl amine oxide compound, two-(2-hydroxyethyl) dodecyl amine oxide, dimethyl dodecyl amine oxide, dipropyl tetradecyl amine oxide, methylethyl hexadecyl amine oxide, dimethyl-2-hydroxyl octadecyl amine oxide and coconut oil fat alkyl dimethyl amine oxide.
(C)
Stablizer
In the present composition, can there be stablizer.Terminology used here " stablizer " comprises antioxidant and reductive agent.The amount of these reagent is 0%-2%, and preferred 0.01%-0.2% is for more preferably 0.035%-0.1% of antioxidant, for more preferably 0.01%-0.2% of reductive agent.This has guaranteed the good odor stable under the standing storage condition.Antioxidant and reductive agent stablizer are for product perfuming or low fragrance (do not have or seldom spices) particularly important.
The example that can be added to the antioxidant in the present composition comprises the Products available from EastmanChemical, and the Inc. commodity are by name
PG and
The mixture of the xitix of S-1, Quicifal and tangerine propyl propionate; Available from Eastman ChemicalProducts, the Inc. commodity are by name
The mixture of-6 BHT (Yoshinox BHT), BHA (butylated hydroxyanisol), lattice propyl propionate and citric acid; By name available from UOP ProcessDivision commodity
The Yoshinox BHT of BHT; Available from EastmanChemical Products, the Inc. commodity are by name
The tertiary butylated hydroquinone of TBHQ; Available from Eastman Chemical Products, the Inc. commodity are by name
The natural tocopherol of GT-1/GT-2; And available from Eastman Chemical Products, the butylated hydroxyanisol of Inc. commodity BHA by name; Long-chain (the C of tangerine acid
8-C
22) ester, for example dodecyl lattice acid esters;
1010;
1035;
B1171:
1425;
3114;
3125; With their mixture; Preferably
3125,
1425,
3114 and composition thereof; More preferably independent
3125 or with citric acid and/or other sequestrant such as citric acid isopropyl ester blended; Available from the Monsanto chemical name is 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid (Etidronic Acid)
2010; Be 4 available from the Kodak chemical name, Phenylsulfonic acid/sodium salt between the 5-dihydroxyl
And be diethylene triaminepentaacetic acid(DTPA) available from the Aldrich chemical name
(D) dirt release agent
In the present invention, can add optional dirt release agent.Generally in said composition, mix 0%-10%, preferred 0.2%-5% dirt release agent.Preferred this dirt release agent is a polymkeric substance.
Dirt release agent is suitable in the fabric sofetening composition of the present invention.Any polymerization dirt release agent well known by persons skilled in the art can randomly be used for the present composition.The polymerization dirt release agent is characterised in that to have the hydrophilic segment that makes hydrophobic fiber such as polyester and nylon surface hydrophilic, with the hydrophobic part that is deposited on the hydrophobic fiber and keeps being attached thereto in whole washing and rinse cycle, so it is as the fixture of hydrophilic segment.This can be so that spot easier being cleaned in washing process afterwards that produces subsequently of handling with dirt release agent.
If you are using, dirt release agent generally accounts for about 0.01%-10.0% of detergent composition weight of the present invention, generally about 0.1%-5%, preferably about 0.2%-3.0%.
Following document description be applicable to dirt release agent polymkeric substance of the present invention, these documents all are included in for referencial use herein: the US3959230 of the Hays that authorized on May 25th, 1976; The US3893929 of the Basadur that on July 8th, 1975 authorized; The US4000093 of the Nicol that on December 28th, 1976 authorized etc.; The US4702857 of the Gosselink that on October 27th, 1987 authorized; The US4968451 of the Scheibel that November 6 authorized etc.; The US4702857 of the Gosselink that on October 27th, 1987 authorized; The US4711730 of the Gosselink that on December 8th, 1987 authorized etc.; The US4721580 of the Gosselink that on January 26th, 1988 authorized; The US4877896 such as Maldonado that on October 31st, 1989 authorized; The US4956447 of the Gosselink that authorize September 11 nineteen ninety etc.; The US5415807 of the Gosselink that authorize May 16 nineteen ninety-five etc.; April in 1987 disclosed Kud on the 22nd etc. european patent application 0219048.
The dirt release agent of Shi Heing is described in the US4201824 of Violland etc. in addition; The US4240918 of Lagasse etc.; The US4525524 of Tung etc.; The US4579681 of Ruppert etc.; US4240918; US4787989; US4525524; The EP279134A of Rhone-Poulenc Chemie in 1988; (1991) EP457205 of BASF; With the DE2335044 of Unilever N.V. in 1974, all these documents are quoted for referencial use at this paper.
Commercially available dirt release agent comprises METOLOSE SM100, the METOLOSE SM200 that is produced by Shin-etsu Kagaku Kogyo K.K, the SOKALAN section bar material of buying from BASF (Germany), for example SOKALAN HP-22, ZELCON 5126 (buying) and MILEASET (buying) from ICI from Dupont.
(E)-the soap scum dispersion agent
In the present invention, pre-composition can with soap scum dispersant a kind of optional adding, that be different from dirt release agent, and be heated to each component fusing point or be higher than the temperature of its fusing point.
Preferred herein soap scum dispersion agent is that the lyophobic dust by the height ethoxylation forms.These lyophobic dusts can be Fatty Alcohol(C12-C14 and C12-C18), lipid acid, aliphatic amide, fatty amide, amine oxide, quaternary ammonium compound, or are used for forming the hydrophobic parts of dirt release agent polymkeric substance.Preferred soap scum dispersion agent is the height ethoxylation, for example every mole on average have greater than 17, be preferably greater than 25, more preferably greater than 40 moles of ethylene oxide, polyoxyethylene partly accounts for the 76%-97% of total molecule weight, preferred 81%-94%.
The content of soap scum dispersion agent is enough to make under working conditions soap scum to remain on acceptable, the unnoticed degree preferably of human consumer, but is not enough to that softnessization is had disadvantageous effect.Because preferably there is not soap scum in some purpose.Amount according to negatively charged ion that in the washing stage of typical laundry processes, uses or nonionic detergent etc., the efficient of the rinse stage before adding this paper composition, and water hardness, the amount of negatively charged ion of carrying secretly in fabric (clothes) or nonionic detergent tensio-active agent and washing assistant (especially phosphoric acid salt and zeolite) can change.Usually, should use the soap scum dispersion agent of minimum to avoid disadvantageous effect to softness.Generally, the requirement of soap scum dispersion agent is at least 2% of a softening agent active matter content, preferably is at least 4% (for farthest avoiding soap scum, at least 6%, preferably at least 10%).But under 10% (with respect to softening agent material) or higher content, the softness effect of product has the danger of reduction, especially contains under the situation of a high proportion of nonionogenic tenside that absorbs during the washing operation in fabric.
Preferred soap scum dispersion agent is:
Varonic U-
Genapol T-
Genapol T-
Plurafac A-
With Neodo 125-
(F)
Sterilant
The example of the sterilant that uses in the present composition comprises glutaraldehyde, formaldehyde, and 2-bromo-2-nitro the third-1, (sold by the Inolex Chemicals company that is positioned at Philadelphia, Binzhou, commodity are by name for the 3-glycol
), and the mixture of 5-chloro-2-methyl-4-isothiazoline-3-ketone and 2-methyl-4-isothiazoline-3-ketone (sold by Rohm and Hass company, commodity are called Kathon), consumption is 1-1000ppm.
(G)
Spices
The present invention can comprise any and the compatible spices of softening agent.Suitable spices is disclosed in the U.S. Pat 5500138, and this patent is hereby incorporated by.
The spices that is used for this paper comprises the mixture of aromatoising substance or aromatoising substance, comprising natural (promptly obtaining with plant by extracting flower, grass, leaf, root, bark, timber, flowers), synthetical (being the mixture of different natural oils or oily composition) and synthetic (i.e. synthetic preparation) aromatoising substance.These materials usually are attended by auxiliary substance, for example fixative, extender, stablizer and solvent.These auxiliarys are also included within the intended scope of this paper said " spices ".Usually, spices is the complex mixture of a lot of organic compound.
The example of spices component that is used for the spices of the present composition includes but not limited to: hexyl cinnamic aldehyde; Amyl cinnamic aldehyde; Orchidae; N-Hexyl salicylate; Terpinol; 3,7-dimethyl-suitable-2,6-octadiene-1-alcohol; 2,6-dimethyl-sec-n-octyl alcohol; 2,6-dimethyl-7-octen-2-ol; 3,7-dimethyl-3-octanol; 3,7-dimethyl-anti--2,6-octadiene-1-alcohol; 3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol; 2-methyl-3-(right-tert-butyl-phenyl)-propionic aldehyde; 4-(4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-formaldehyde; The tricyclic decenyl propionic ester; The tricyclo decene yl acetate; Aubepine; 2-methyl-2-(right-isopropyl phenyl)-propionic aldehyde; Ethyl-3-methyl-3-phenyl glycidyl acid esters; 4-(right-hydroxy phenyl)-Ding-2-ketone; 1-(2,6,6-trimethylammonium-2-tetrahydrobenzene-1-yl)-2-butylene-1-ketone; Right-methoxyacetophenone; Right-methoxyl group-α-the phenyl propylene; Methyl-2-n-hexyl-3-oxo-Cyclopentane carboxylic acid ester; Peach aldehyde.
Other example of aromatoising substance includes but not limited to: orange oil; Lemon oil; Oil of grapefruit; Oils, bergamot peel; Clove(bud)oil; γ-dodecylic acid lactone; Methyl-2-(2-amyl group-3-oxo-cyclopentyl) acetic ester; β-Nai Jiami; Methyl-β-naphthalenone; Tonka bean camphor; Capraldehyde; Phenyl aldehyde; 4-tert-butylcyclohexyl acetic ester; α, alpha-alpha-dimethyl styroyl acetic ester; The methyl phenyl carbinol acetic ester; The Schiff's base of 4-(4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-formaldehyde and methyl o-aminobenzoate; The ring ethylene glycol diester of undecane dicarboxylic acid; 3,7-dimethyl-2,6-octadiene-1-nitrile; γ-methyl ionone; α-Zi Luotong; β-ionone; Petitgrain oil; Vertofix coeur; 7-ethanoyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; The methyl ionone; Methyl isophthalic acid, 6,10-trimethylammonium-2,5,9-cyclododecatriene-1-base ketone; 7-ethanoyl-1,1,3,4,4,6-hexamethyl 1,2,3,4-tetralin; 4-ethanoyl-6-the tertiary butyl-1,1-dimethyl 1,2-indane; Benzophenone; 6-ethanoyl-1,1,2,3,3,5-hexamethyl 1,2-indane; 5-ethanoyl-3-sec.-propyl-1,1,2,6-tetramethyl-1,2-indane; The 1-dodecanal; 7-hydroxyl-3,7-dimethyl octanal; 10-hendecene-1-aldehyde; Dissident's thiazolinyl hexahydrobenzaldehyde; The formyl radical tristane; The cyclopentadecane acid lactide; 16-hydroxyl-9-hexadecanoic acid lactone;
1,3,4,6,7,8-six hydrogen-4,6,6,7,8,8-hexamethyl cyclopenta-γ-2-chromene; Artemisiifolia alkane (ambroxane); Ten dihydros-3a, 6,6,9a-tetramethyl-naphtho--[2,1b] furans; Cypress camphor; 5-(2,2,3-front three basic ring penta-3-thiazolinyl)-3-methylpent-2-alcohol; 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes-1-yl)-2-butylene-1-alcohol; Caryophyllenol; Cedryl acetate; Right-the tert-butylcyclohexyl acetic ester; Wrinkled Gianthyssop Herb; The frankincense resinoid; Cistus creticus; Vetiveria zizanoides; Cuba's fat; Canada turpentine; And the condensation product of following material: laurine and methyl o-aminobenzoate; Laurine and indoles; Phenylacetic aldehyde and indoles; 4-(4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-formaldehyde and methyl o-aminobenzoate.
Other examples of spices component have: Geraniol; Meraneine; Phantol; Phanteine; Tetrahydrolinalool; Geraniol; Citronellyl acetate; Dihydromyrcenol; Acetate dihydromyrcene ester; Tetrahydromyrcenol; Tirpinyl acetate; Nopol; Nopyl acetate; The 2-phenylethyl alcohol; Acetate 2-phenyl chlorocarbonate; Phenylcarbinol; Jasmal; Benzyl salicylate; Peruscabin; Phenylethyl ethanoate; Dimethylbenzylcarbinol; Trichloromethyl phenyl methyl alcohol methyl phenyl carbinol acetic ester; Vanoris; Vetiveryl acetate; Vetiverol; 2-methyl-3-(right-tert-butyl-phenyl)-propionic aldehyde; 2-methyl-3-(right-isopropyl phenyl)-propionic aldehyde; 3-(right-tert-butyl-phenyl)-propionic aldehyde; 4-(4-methyl-3-pentenyl)-3-tetrahydrobenzene formaldehyde; 4-acetoxy-3-amyl group tetrahydropyrans; Methyl dihydrojasmonate; 2-n-heptyl cyclopentanone; 3-methyl-2-amyl group cyclopentanone; N-capric aldehyde; N-dodecane aldehyde; 9-decenol-1; Phenoxy group ethyl isobutyrate; Phenylacetaldehyde dimethyl acetal; Phenyl acetaldehyde diethyl acetal; Geranonitrile; Citronellyl nitrile; The cypress acetal; The 3-Santalex; Cypress base methyl ether; The different ketone that comes into leaves; The aubepine nitrile; Aubepine; Heliotropine; Oxymethoxyallylbenzene; Vanillin food grade,1000.000000ine mesh; Phenylbenzene oxidation thing; The laurine ionone; The methyl ionone; Different methyl ionone; Irone; Suitable-3-hexenol and ester thereof; 1,2-indane musk odorant; The 1,2,3,4-tetralin musk odorant; Isochroman musk spices; Macrocyclic ketone; Big lactone musk odorant; The brazilic acid vinyl acetate.
The spices that is used for the present composition is not halide matter and nitro musk basically.
The The suitable solvent, the diluent or carrier that are used for above-mentioned spices component are: for example, and ethanol, Virahol, Diethylene Glycol, single ethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate etc.These solvents, the diluent or carrier add-on in spices preferably remains provides even spice solution needed minimum quantity.
The amount of spices can be the 0%-10% of final product composition having weight, preferred 0.1%-5%, more preferably 0.2%-3%.Fabric softener composition of the present invention has improved the spices deposition of fabric.
(H)
Sequestrant
The present composition and method can randomly be used one or more copper and/or nickel sequestrant.This water-soluble chelator can be selected from aminocarboxylate, amino phosphonates do, and aromatic chelating agent of multifunctional replacement and composition thereof, all sequestrants are as definition hereinafter.By the effect of this sequestrant, improve basically or recovered the whiteness and/or the brightness of fabric and improved the stability of material in composition.Do not accept the restriction of opinion, the agency part that it is believed that these materials is that they remove the ability free from worldly cares of de-iron and mn ion by forming the soluble chelating thing from washing soln.
Aminocarboxylate as optional sequestrant comprises edetate, the N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their an alkali metal salt, ammonium salt and substituted ammonium salt and their mixture.
When allowing to have low at least total phosphorous in detergent composition, amino phosphonates do also is suitable as the sequestrant of the present composition, comprising: ethylenediamine tetraacetic (methylene phosphonic acid salt) is called DEQUEST.These amino phosphonates do preferably do not contain alkyl or the alkenyl that surpasses about 6 carbon atoms.
In the present composition, can also use the aromatic chelating agent of multifunctional replacement.Referring to people's U.S. Pat 3812044 such as Connor of authorizing on May 21st, 1974.The compound of preferred this class acid form be the dihydroxyl disulfobenzene as 1,2-dihydroxyl-3,5-disulfobenzene.
Being used for the preferred biodegradable cheating agent of the present invention is ethylenediamine disuccinate (" EDDS "), especially its [S, the S] isomer as describing in the U.S. Pat 4704233 of authorizing Hartman and Perkins on November 3rd, 1987.
The present composition also can contain water miscible methylglycine oxalic acid (MGDA) salt (or sour form) as sequestrant, or as the auxiliary washing assistant that uses with for example insoluble washing assistant such as zeolite, layered silicate etc.
Preferred sequestrant comprises DETMP, DETPA, NTA, EDDS and its mixture.
If the use sequestrant, then its consumption is generally about 0.1%-15% of Fabrid care composition weight of the present invention.If the use sequestrant, more preferably its consumption is about 0.1%-3.0% of said composition weight.
(1)
The crystal growth inhibitor component
The present composition also can contain the crystal growth inhibitor component, preferred organic diphosphonic acid component, and by the weight of said composition, preferably its content is 0.01%-5%, more preferably 0.1%-2%.
Organic diphosphonic acid, here the meaning is the organic diphosphonic acid that does not contain as the nitrogen of the part of its chemical structure.Therefore, organic amino phosphonates do has been got rid of in this definition, yet it can be included in the present composition as the heavy metal ion chelating agent component.
Organic diphosphonic acid is C preferably
1-C
4Di 2 ethylhexyl phosphonic acid, more preferably C
2Di 2 ethylhexyl phosphonic acid, for example ethylidene diphosphonic acid or most preferably ethane 1-hydroxyl-1,1-di 2 ethylhexyl phosphonic acid (HEDP), it can partially or completely Ionized form exist, and particularly exists as salt or title complex.
The present invention also as crystal growth inhibitor be organic mono phosphonic acid.Organic mono phosphonic acid or its a kind of salt or title complex also are suitable for the present invention, are called CGl.
Here organic mono phosphonic acid meaning is not contain organic mono phosphonic acid of nitrogen as its chemical structure part.Therefore, organic amino phosphonates do has been got rid of in this definition, yet it can be included in the present composition as heavy metal ion chelating agent.
Organic mono phosphonic acid component can sour form or its a kind of salt form or exist with the complex form of suitable balance cation.Preferably, any salt/title complex is water miscible, and basic metal and alkaline earth salt/title complex are particularly preferred.
Preferred organic mono phosphonic acid is a 2-phosphine butyl-1,2, and the 4-tricarboxylic acid can be purchased by trade(brand)name Bayhibit from Bayer.
(J)
Enzyme
The present composition and method can randomly be used one or more enzymes for example lipase, proteolytic enzyme, cellulase, amylase and peroxidase.Preferred enzyme used herein is a cellulase.In fact, this fermentoid is returned processed fabric color-protecting function is provided.Can be used for cellulase of the present invention and comprise two kinds of bacteria type and mould bacterial types, preferably having optimal ph is 5-9.5.The suitable plain enzyme of mould fiber type by unusual humicola lanuginosa (Humicolainsolens) or 1800 generations of humicola lanuginosa (Humicola) strain DSM is disclosed in the U.S. Pat 4435307, or belong to the cellulase 212 of generation mould of Aeromonas and the cellulase that extracts from the hepatopancreas of a kind of sea mollusk Dolabella Auricula Solander.The cellulase that is fit to also is disclosed in GB-A-2075028; GB-A-2095275; In DE-OS-2247832.
With
(Novo) be useful especially.Other cellulases that are fit to also are disclosed in the WO91/17243 of Novo, and WO96/34092 is among WO96/34945 and the EP-A-0739982.In the enforcement of present commodity preparation, general consumption be the organized enzyme that has of every gram detergent composition up to 5mg weight, be more generally 0.01mg-3mg.In other words, the present composition generally comprises 0.001%-5%, the commercial enzyme preparation of preferred 0.01%-1% weight.The activity of zymin can define in addition in particular cases for example with the cellulase definition, corresponding activity unit is preferred (for example CEVU or cellulase equivalent viscosity unit).For example, the composition of the present invention amount that can comprise cellulase is equivalent to the activity of every gram composition 0.5-1000CEVU.The cellulase preparation that uses for preparation present composition purpose generally has active 1000-10000CEVU/ gram when liquid form, when solid form, generally have active about 1000CEVU/ and restrain.
(K)
Liquid vehicle
Another kind is chosen wantonly, but preferred ingredients is a liquid vehicle.The liquid vehicle that uses in the present composition preferably at least mainly is a water, this be since its cost low, can get relatively, safety and and environmentally compatible.The content of water in the liquid vehicle, by the weight of this carrier, preferably at least 50%, most preferably at least 60%.The mixture of water and lower molecular weight organic solvent for example＜200 is suitable as liquid vehicle, and described organic solvent is lower alcohol such as ethanol, propyl alcohol, Virahol or butanols for example.Low-molecular-weight alcohol comprises monohydroxy-alcohol, dibasic alcohol (ethylene glycol etc.), trivalent alcohol (glycerine etc.) and higher polyol.
(L)
Other optional components
The present invention can be included in the textile treatment composition the conventional optional components of using, tinting material for example, sanitas, tensio-active agent, sanforzing agent, fabric stiffener, spotting agent, sterilant, mycocide, antioxidant such as Yoshinox BHT, sanitas, enzyme stabilizers, effectively suppress dyestuff is transferred to another kind of fabric from a kind of fabric in cleaning process material (being dye transfer inhibitor), hydrotropic agent, processing aid, dyestuff or pigment etc.
The present invention also can comprise other compatible components, is included in those disclosed among WO96/02625, WO96/21714 and the WO96/21715.
The form of composition
The present composition can be taked various physical form, comprises liquid, gel, foams, particle and the sheet of water base or non-water base form.
When being liquid form, said composition is the available allocation device also, and for example spray sprinker or aerosol spray device and distribute.
The spraying sprinker
The invention still further relates to and add this composition of making a kind of goods in the spraying sprinker, this goods can help described compositions-treated fabric and/or the surface of containing amine reaction product and other components (example is cyclodextrin, polysaccharide, polymkeric substance, tensio-active agent, spices, softening agent) with significant quantity, and can not recognize when in surface drying.This spraying sprinker comprises the spraying plant of manual triggering and non-hand drive (operation) and contains the container of treatment compositions.The generality of this spraying sprinker discloses can be referring to-22 page of the 27th row of the 19th page of 21 row of WO96/04940.These goods preferably with working instructions, are used enough composition components to guarantee the human consumer, to obtain required effect.The general composition that sprays from atomizer, the weight by using composition contains the 0.01%-5% that has an appointment, preferably about 0.05%-2%, more preferably from about 0.1%-1% amine reaction product.
Using method
The present invention also provides a kind of method that can postpone to discharge active ketone or aldehyde, it comprises the step that the surface that will handle contacts with The compounds of this invention or composition, afterwards surface treated is contacted a kind of material, preferably water base medium such as moisture content or stand from amine reaction product, to discharge any other means of actives.
" surface ", but the meaning is any surface of deposited compound.The general example of this material is that fabric, crust such as tableware, floor, bathroom, water closet, kitchen, skin and other need postpone to discharge the surface of active ketone or aldehyde, and for example rubbish is such as the place of animal rubbish.Preferably, this surface is a fabric.
" postponing to discharge " meaning is than using actives (for example spices) itself, discharging active constituent (for example spices) through the longer time.
Embodiment
That uses in following present composition embodiment writes a Chinese character in simplified form
In composition embodiment, the component symbol of abbreviation has following implication:
DEQA: two (butter acyloxy ethyl) alkyl dimethyl ammonium chloride
DTDMAC: ditallow dimethyl ammonium chloride
DEQA (2): methylsulfuric acidization two (soft tallow acyloxy ethyl) hydroxyethyl ammonium methyl
DTDMAMS: ditallow dimethyl methyl ammonium sulfate
SDASA: 1: 2 stearyl dimethyl amine: triple pressed stearic acid
The stearic acid of lipid acid: IV=0
Ionogen: calcium chloride
PEG: Macrogol 4000
Neodol 45-13: by the C14-C15 straight chain primary alcohol ethoxylation of Shell chemical company sale
Thing
Cellulase: by Novo Nordisk A/S with trade(brand)name Carezyme, Celluzyme and/
Or the cellulolytic enzyme of Endolase sale
Polysiloxane disappears: the polydimethylsiloxane foam control agent with as the siloxanes-oxidation of dispersion agent
The mixture of infusion alkene copolymer, the ratio of described foam control agent and described dispersion agent
Be 10: 1-100: 1
PEI: polyethylene imine based, molecular-weight average is 1800, the average ethoxylation of each nitrogen
Degree is 7 oxyethyl group residues
HEDP: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid
ARP1: by the 4-subcutin and 2 of synthetic embodiment 1 preparation, the 4-dimethyl-
The amine reaction product of 3-tetrahydrobenzene-1-formaldehyde
ARP2: according to the benzaminic acid and 2 of synthetic embodiment 1 preparation, 4-dimethyl-3-ring
The amine reaction product of hexene-1-formaldehyde
ARP3: by the Lupasol P of synthetic EXAMPLE III preparation and the amine of α-damascone
Reaction product
ARP4: by the D-glycosamine of synthetic example II preparation and the amine reaction product of geranial
ARP5: by the Lupasol HF of synthetic EXAMPLE III preparation and δ-damascone
Amine reaction product
Polymkeric substance: the Polyvinylpyrolidone (PVP) of buying from BASF by trade(brand)name Luviskol K90
K90
Dye-fixing agent: the dye-fixing agent that is purchased from Clariant trade(brand)name Cartafix CB
Polyamine: 1,4-pair-(3-aminopropyl) piperazine
Bayhibit AM: from the 2-phosphine butane-1,2 that Bayer is purchased, 4-tricarboxylic acid
Fabric softener activity: methylsulfuric acidization two (Tower rape oil acyloxy ethyl) hydroxyethyl ammonium methyl thing
HPBDC: hydroxypropyl
RAMEB: the random beta-cyclodextrin that methylates
Bardac2050: Quaternium 24,50% solution
Bardac22250: Timbercote 2000,50% solution
Genamin C100: the cocounut oil fat of the usefulness 10 moles of ethylene oxide ethoxylations that are purchased from Clariant
Fat amine
Genapol V4463: the lauric alcohol of the usefulness 10 moles of ethylene oxide ethoxylations that are purchased from Clariant
Silwet 7604: can be from Osi Specialties, and Inc., Danbury, Connecticut is purchased
MW be 4000 formula R-(CH
3)
2SiO-[(CH
3)
2SiO]
a-
[(CH
3) (R) SiO]
b-Si (CH
3)
2The polyoxyalkylene polysiloxane of-R, wherein,
The mean value of a+b is 21.
Silwet 7600: can be from Osi Specialties, and Inc., Danbury, Connecticut is purchased
MW be 4000 formula R-(CH
3)
2SiO-[(CH
3)
2SiO]
a-
[(CH
3) (R) SiO]
b-Si (CH
3)
2The polyoxyalkylene polysiloxane of-R, wherein,
The mean value of a+b is 11.
Below be synthetic embodiment according to compound of the present invention:
Synthesizing of I-4-subcutin and 2.4-dimethyl-3-tetrahydrobenzene-1-formaldehyde is anti-
Should
To the 10g in 35ml EtOH 2, the ice-cold stirred solution of 4-dimethyl-3-tetrahydrobenzene-1-formaldehyde (0.07 mole) and molecular sieve (
20g), add 1 equivalent amine by feed hopper.Stirred reaction mixture and avoid illumination under nitrogen atmosphere.After 6 days, filtering mixt also removes and desolvates.The yield that forms imines is about 90%.
Replace 2 with bourgeonal or trans-2-nonenal, 4-dimethyl-3-tetrahydrobenzene-1-formaldehyde obtains similar results.In addition, obtain similar results with 4-aminobenzoic acid substitution 4-subcutin.
II-
D-glycosamine and 2, the building-up reactions of 4-dimethyl-3-tetrahydrobenzene-1-formaldehyde
To the ice-cold solution of the 1mmol of about 30ml EtOH D-glycosamine and molecular sieve (
5g), add 1 equivalent 2,4-dimethyl-3-tetrahydrobenzene-1-formaldehyde.Stirring reaction and avoid illumination under nitrogen atmosphere.After 3-4 days, remove molecular sieve and solvent with evaporation after filtration respectively.The yield that obtains the solid imines is 85%-90%.
Replace 2 with geranial, trans-2-nonenal or capraldehyde, 4-dimethyl-3-tetrahydrobenzene-1-formaldehyde obtains similar results.
III-
The building-up reactions of Lupasol and damascone
Use any of these three kinds of different methods as described below to prepare beta-amino ketones by Lupasol G100 (be purchased by BASF, contain 50% water, 50%Lupasol G100 (Mw5000)) and a-damascone:
1. the Lupasol G100 that uses following method drying to be purchased: with 20g Lupasol solution on rotatory evaporator dry several hours.The residue that obtains still contains the 4.5gH that has an appointment
2O uses the methylbenzene azeotropic distillation on rotatory evaporator.Then residue is placed in 60 ℃ of following exsiccant moisture eliminators and (uses P
2O
5As water-absorbing material).According to the weight that obtains, we derive this oil body contains and is lower than 10%H
2O.According to NMR-spectrum, we may be lower than 5% at the water outlet of deriving.In the preparation of beta-amino ketones, use this dry sample then.
1.38g exsiccant Lupasol G100 is dissolved in the 7ml ethanol.Leniently stir this solution several minutes with magnetic stirring bar, add 2gNa then
2SO
4(anhydrous).Behind the restir several minutes, added 2.21g a-damascone through 1 minute.After reaction 2 days, filter this mixture through kieselguhr filter (seeing above), with the thorough wash residual thing of ethanol.Obtain the slightly filtrate of foaming of about 180ml.Use rotatory evaporator to concentrate this filtrate, until drying, and under room temperature the P in the moisture eliminator
2O
5Dry.Obtain the colourless oil body of about 3.5g.
2. 4.3g Lupasol G100 solution (not having drying) is dissolved in the 10ml ethanol.Stir this solution several minutes with magnetic stirring bar, added 3.47g a-damascone then through 1.5 minutes.After at room temperature reacting 2 days, filter this reaction mixture and with the thorough wash residual thing of ethanol through diatomite (seeing above).In vaporizer, concentrate this filtrate (200ml, slightly foaming) and moisture eliminator (P at room temperature
2O
5As siccative) middle dry.Obtain the colourless oil body of about 6.0g.
3. in about 3.0g Lupasol G100 solution (by using like this), add 2.41g a-damascone.Do not using this mixture of stirring under the solvent.After stirring 4 days, the oil body that obtains is dissolved among the 100mlTHF, use MgSO
4Drying, filtration also concentrate this filtrate on rotatory evaporator.Dehumidizier (P at room temperature
2O
5) in after the drying, obtain the colourless oil body of about 4.1g.This oil body still contains 13% (w/w) THF that has an appointment, even after long-term dry (3 days).
The product that is obtained by these three kinds of methods has identical NMR-spectrum.
Use method as described below to prepare beta-amino ketones by Lupasol P and a-damascone:
Will about 1.8g Lupasol P solution (50%H
2O, 50%Lupasol Mw.750000 obtains from BASF) be dissolved in the 7ml ethanol.Stir this solution several minutes with magnetic stirring bar, add 1.44g a-damascone then.After 3 days, filter this reaction mixture and with the thorough wash residual thing of ethanol through kieselguhr filter (seeing above).Concentrated filtrate and moisture eliminator (P at room temperature
2O
5) in behind the oil body that obtains of drying, obtain the about 3g reaction product between Lupasol and the a-damascone.
In following formulation Example, unless otherwise indicated, all content are that the % by composition weight represents, by dried mixed (d), described in GB-1464616, with starch encapsulate (es), or with cyclodextrin (ec) encapsulate, (hereinafter referred to as " ARP ") mixes in the composition of complete formula with amine reaction product, or it is with composition forms as herein described.The parenthetic term of ARP in formulation Example refers to the meaning of mixing.When not indicating, mix by actual.No matter the given content of ARP be that handle or untreated, refers to the content of actual ARP, rather than refer to the ARP content handled.
Embodiment 1
Following fabric sofetening composition is according to composition of the present invention:
Embodiment 2
The fabric softener composition that adds during following rinse produced according to the present invention:
| A | B | C | D | E | |
| DEQA(2) | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 |
| ARP 1 | 0.5 | - | - | - | - |
| ARP 2 | - | 0.3 | - | - | 0.04 |
| ARP 3 | - | 0.1 | 0.1 | - | - |
| ARP 4 | - | - | - | 0.1 | 0.1 |
| Mierocrystalline cellulose | 0.001 | 0.001 | 0.001 | 0.001 | 0.001 |
| HCL | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 |
| Polysiloxane defoamers | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 |
| Blue dyestuff | 25ppm | 25ppm | 25ppm | 25ppm | 25ppm |
| Ionogen | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 |
Embodiment 3
Following fabric softener composition produced according to the present invention:
| A | B | C | D | E | F | G | H | |
| DEQA | 2.6 | 2.6 | 2.6 | 2.6 | 19.0 | 19.0 | 19.0 | 19.0 |
| Lipid acid | 0.3 | 0.3 | 0.3 | 0.3 | - | - | - | - |
| Hydrochloric acid | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 |
| ARP 1 | 0.02 | - | - | - | - | 0.1 | 0.23 | 0.2 |
| ARP 5 | - | 0.2 | 0.2 | - | - | - | - | 0.1 |
| ARP 3 | - | - | 0.2 | 0.05 | 0.3 | 0.2 | - | 0.2 |
| Spices | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| PEI | - | 0.5 | 0.3 | 0.3 | - | 2.0 | 1.5 | 1.5 |
| HEDP | - | - | 0.05 | 0.05 | - | - | 0.3 | 0.3 |
| Polysiloxane defoamers | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 |
| Ionogen | - | - | - | - | 0.1 | 0.1 | 0.1 | 0.1 |
| Dyestuff | 10 ppm | 10 ppm | 10 ppm | 10 ppm | 25 ppm | 25 ppm | 25 ppm | 25 ppm |
| Water and subsidiary | 100％ | 100％ | 100％ | 100％ | 100％ | 100％ | 100％ | 100％ |
Embodiment 4
The following fabric conditioner composition that adds in the moisture eliminator produced according to the present invention:
| A | B | C | D | E | F | G | |
| DEQA(2) | - | - | - | - | 51.8 | 51.8 | 51.8 |
| DTMAMS | - | - | 26.0 | 26.0 | - | - | - |
| SDASA | 70.0 | 70.0 | 42.0 | 42.0 | 40.2 | 40.2 | 40.2 |
| Neodol 45-13 | 13.0 | 13.0 | - | - | - | - | - |
| Ethanol | 1.0 | 1.0 | - | - | - | - | - |
| A | B | C | D | E | F | G | |
| ARP 1(es) | 0.1 | - | - | 0.1 | 0.2 | - | - |
| ARP 2(ec) | - | 0.1 | - | - | - | - | - |
| ARP 3(es) | - | - | 0.05 | - | - | 0.2 | - |
| ARP 5(d) | - | - | - | - | - | - | 0.3 |
| Spices | 0.75 | 0.75 | 1.0 | 1.0 | 1.5 | 1.5 | 1.5 |
| Glycoperse S-20 | - | - | - | - | 15.4 | 15.4 | 15.4 |
| Glyceryl monostearate | - | - | 26.0 | 26.0 | - | - | - |
| The succsinic acid geraniol ester | 0.38 | 0.38 | - | - | - | - | - |
| Clay | - | - | 3.0 | 3.0 | - | - | - |
| Dyestuff | 0.01 | 0.01 | - | - | - | - | - |
Embodiment 5
Below be the unrestricted embodiment according to pre-soaking fabric-conditioning of the present invention and/or fabric gain combination thing, it is applicable to doing washing the rinse stage:
| Component | A | B | C | D | E | F |
| Polymkeric substance | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 |
| Dye-fixing agent | 2.3 | 2.3 | 2.4 | 2.4 | 2.5 | 2.5 |
| Polyamine | 15.0 | 15.0 | 17.5 | 17.5 | 20.0 | 20.0 |
| Bayhibit AM | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Chlorination C 12-C 14The dimethyl ethoxyl quaternary ammonium salt | - | 5.0 | 5.0 | - | - | - |
| Fabric softener active matter | - | - | 2.5 | 2.5 | - | - |
| Genamin C100 | 0.33 | - | 0.33 | 0.33 | 0.33 | - |
| Genapol V4463 | 0.2 | - | 0.2 | 0.2 | 0.2 | - |
| ARP1 | 1.0 | 2.0 | 0.1 | 0.5 | 0.05 | 0.08 |
| Water and subsidiary | Equal amount | Equal amount | Equal amount | Equal amount | Equal amount | Equal amount |
Embodiment 6
Below be the unrestricted embodiment of composition that is suitable for the absorption stink of spray application:
| Embodiment | A | B | C | D | E |
| Component | Wt.％ | Wt.％ | Wt.％ | Wt.％ | Wt.％ |
| HPBCD | 1.0 | - | 1.0 | - | 1.2 |
| RAMEB | - | 1.0 | - | 0.8 | - |
| Tetronic 901 | - | - | 0.1 | - | - |
| Silwet L-7604 | - | - | - | 0.1 | - |
| Silwet L-7600 | 0.1 | - | - | - | 0.1 |
| Bardac 2050 | - | - | - | 0.03 | - |
| Bardac 2250 | - | 0.2 | - | - | 0.1 |
| Diethylene Glycol | - | 1.0 | - | - | 0.2 |
| Triethylene glycol | - | - | 0.1 | - | - |
| Ethanol | - | - | - | - | 2.5 |
| Spices 1 | 0.1 | - | - | - | - |
| Spices 2 | - | 0.05 | - | 0.1 | - |
| Spices 3 | - | - | 0.1 | - | 0.1 |
| Kathon | 3ppm | 3ppm | 3ppm | 3ppm | - |
| HCl | to pH 4.5 | to pH 4.5 | to pH 3.5 | to pH 3.5 | to pH 3.5 |
| ARP1 | 5.0 | 1.0 | - | - | - |
| ARP3 | - | - | 0.5 | 0.1 | 0.08 |
| Distilled water | Equal amount | Equal amount | Equal amount | Equal amount | Equal amount |
Spices 1,2 and 3 has following composition:
| Spices | 1 | 2 | 3 |
| The spices component | Wt.％ | Wt.％ | Wt.％ |
| Aubepine | - | - | 2 |
| Benzophenone | 3 | 5 | - |
| Jasmal | 10 | 15 | 5 |
| Benzyl salicylate | 5 | 20 | 5 |
| Cypress camphor | 2 | - | - |
| Geraniol | 10 | - | 5 |
| Tonka bean camphor | - | - | 5 |
| Cymal | - | - | 3 |
| Dihydromyrcenol | 10 | - | 5 |
| Flor acetate | 5 | - | 5 |
| Galaxolide | 10 | - | - |
| Ling Lanquan | 10 | 15 | 20 |
| Nopyl acetate | 4 | - | 5 |
| Phantol | 6 | 15 | 5 |
| Methyl dihydrojasmonate | 3 | 10 | 5 |
| Phenylethyl ethanoate | 2 | 5 | 1 |
| Phenylethyl alcohol | 15 | 15 | 20 |
| The a-Terpineol 350 | 5 | - | 8 |
| Vanillin food grade,1000.000000ine mesh | - | - | 1 |
| Amount to | 100 | 100 | 100 |
Claims (18)
1. soft compound, comprise 1%-80% weight softening compound thing, and uncle and/or secondary amine compound and be selected from reaction product between the active constituent of spices ketone, spices aldehyde and its mixture, it is characterized in that the odor strength index of described amine compound is lower than the odor strength index of 1% solution of Methyl anthranilate in dipropylene glycol, its feature is that also described composition has 2.0 to 5 pH value; And its feature is that also described reaction product mixes in the complete composition prepared after prefabricated; Wherein said amine reaction product has the surperficial smell index of doing greater than 5; Described amine compound has and is selected from following empirical formula:
B-(NH
2)
nB-(NH-)
nAnd B-(NH-)
n-(NH
2)
n
Wherein B is a solid support material, and each n is the index of numerical value at least 1 independently;
The content of described reaction product, the weight by composition is 0.001%-10%.
2. according to the composition of claim 1, wherein said solid support material is selected from inorganic or organic carrier.
3. according to the composition of claim 2, wherein inorganic carrier is the polydialkysiloxane of aminofunctional.
4. according to the composition of claim 2, the wherein said amine that contains organic support material B be selected from the amine of aminoaryl derivative, polyamine, amino acid, replacement and acid amides, glycosamine, dendrimers (dendrimer) and amino replace single, two, oligomeric, polysaccharide and/or its mixture.
5. according to the composition of claim 4, wherein said aminoaryl derivative is an aminophenyl derivative.
6. according to the composition of claim 4, wherein said polyamine is polyethylene imine based, 2,2 '; 2 "-triamino triethylamine, 2,2 '-diamino diethylamide, 3,3 '-diamino-dipropylamine, 1,3-diamino ethyl hexanaphthene, poly-[oxo (methyl isophthalic acid, 2-second two bases)], α-(2-aminomethylethyl)-ω-(2-amino methyl-oxyethyl group)-, poly-[oxo (methyl isophthalic acid, 2-second two bases)], α-hydrogen-ω-(2-amino methyl oxyethyl group)-, 2-ethyl-2-(methylol)-1, the ether of ammediol, C12 tail amine and its mixture.
7. according to the composition of claim 4, wherein said amine compound is an amino acid.
8. according to the composition of claim 4, wherein said amine compound is amine and the acid amides that replaces.
9. according to the composition of claim 4, wherein said amine compound is formula H
2N-CH
2-(CH (OH))
x-CH
2The glucose amine of OH, one of them or several OH functional group be substituted or do not replace and wherein x be 3 or 4 integer.
10. according to the composition of claim 4, wherein said amine compound is selected from polyamidoamines amine dendrimers, polyethylene imine based and/or polytrimethylene imines dendrimers and diaminobutane polyamine DAB (PA)
xDendrimers, x=2
n* 4, n is 0-4, and/or its mixture.
11. according to the composition of claim 4, wherein said amine compound is selected from the amino monose that replaces, it is the acetal or the ketone acetal form of glucose, seminose, semi-lactosi and/or fructose; The amino disaccharides that replaces, it is the acetal or the ketone acetal form of lactose, maltose, sucrose and/or cellobiose; Oligose that the amino of cyclodextrin, chitosan, Mierocrystalline cellulose, starch, gueran, mannosans and/or dextran replaces and/or the amino polysaccharide that replaces; And/or its mixture.
12. composition according to claim 11, wherein said amino replace oligomeric-, polysaccharide is selected from amino alginates, the diamino alginates, hexanediamine alginates, dodecane diamines alginates, 6-amino-6-deoxycellulose, O-ethamine Mierocrystalline cellulose, O-methylamine Mierocrystalline cellulose, 3-amino-3-deoxycellulose, 2-amino-2-deoxycellulose, 2,3-diamino-2,3-dideoxy Mierocrystalline cellulose, 6-[N-(1, the 6-hexanediamine)]-and the 6-deoxycellulose, 6-[N-(1,12-dodecane diamines)]-the 6-deoxycellulose, O-[methyl-(N-1, the 6-hexanediamine)] Mierocrystalline cellulose, O-[methyl-(N-1,12-dodecane diamines)] Mierocrystalline cellulose, 2,3-two-[N-(1,12-dodecane diamines)] Mierocrystalline cellulose, 2,3-diamino-2,3-deoxidation a-cyclodextrin, 2,3-diamino-2,3-deoxidation beta-cyclodextrin, 2,3-diamino-2,3-deoxidation γ-Huan Hujing, 6-amino-6-deoxidation a-cyclodextrin, 6-amino-6-deoxidation beta-cyclodextrin, O-ethylamino beta-cyclodextrin, 6[N-(1, the 6-hexanediamine)-6-deoxidation a-cyclodextrin, 6[N-(1, the 6-hexanediamine)-6-deoxidation beta-cyclodextrin, amino dextran, N-[two-(1, the 6-hexanediamine)] dextran, N-[two-(1,12-dodecane diamines)] dextran, 6-amino-6-deoxidation-a-D-galactosyl-polygalactomannan, O-ethylamino polygalactomannan, the diamino polygalactomannan, 6-amino-6-deoxidation starch, O-ethylamino starch, 2,3-diamines-2,3-dideoxy starch, N-[6-(1, the 6-hexanediamine)]-6-deoxidation starch, N-[6-(1,12-dodecane diamines)]-6-deoxidation starch and 2,3-two-[N (1, the 6-hexanediamine)]-2,3-dideoxy starch and/or its mixture.
13. composition according to claim 1, wherein said active constituent is a spices aldehyde, be selected from 1-capraldehyde, phenyl aldehyde, florhydra l, 2,4-dimethyl-3-tetrahydrobenzene-1-formaldehyde, cis/trans-3,7-dimethyl-2,6-octadiene-1-aldehyde, piperonylaldehyde, 2,4,6-trimethylammonium-3-tetrahydrobenzene-1-formaldehyde, 2,6-nonadienal, a-n-pentyl phenylacrolein, a-n-hexyl phenylacrolein, P.T. are to the tertiary butyl-a-hydrogenated methyl phenylacrolein, LYRAL, cymal, methyl nonyl acetaldehyde, hexanal, trans-2-hexenoic aldehyde and its mixture.
14. composition according to claim 1, wherein said active constituent is a spices ketone, be selected from a-damascone, δ-damascone, different damascone, Karvon, γ-methyl ionone, different-E-Super, 2,4,4,7-tetramethyl--oct-6-ene-3-ketone, benzyl acetone, β-damascone, trans-Damascenone, methyl dihydrojasmonate, vertofix coeur and its mixture.
15. according to the composition of claim 1, the odor detection threshold values of wherein said spices is less than or equal to 1ppm.
16. according to the composition of claim 15, wherein said spices is selected from undecenal, γ undecalactone, piperonylaldehyde, γ dodecanoic acid lactone, p-anisaldehyde, p-hydroxybenzene butanone, cymal, benzyl acetone, a-ionone, P.T. to the tertiary butyl-a-hydrogenated methyl phenylacrolein, trans-Damascenone, β ionone and methyl nonyl ketone and/or its mixture.
17. a method of supplying with remained on surface fragrance comprises that the composition that described surface and claim 1-19 are defined in each contacts, and afterwards surface treated is contacted with a kind of material, so that actives discharges from amine reaction product.
18. according to the method for claim 17, wherein said material is a water.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98870156 | 1998-07-10 | ||
| EP98870156.1 | 1998-07-10 | ||
| EP98870227.0 | 1998-10-28 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998085065A Division CN100384974C (en) | 1998-07-10 | 1999-07-12 | Amine reaction compounds comprising one or more active ingredient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1789399A CN1789399A (en) | 2006-06-21 |
| CN100415861C true CN100415861C (en) | 2008-09-03 |
Family
ID=36787525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101370187A Expired - Lifetime CN100415861C (en) | 1998-07-10 | 1999-07-12 | Soft compound and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100415861C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2399942T3 (en) * | 2007-06-05 | 2013-04-04 | The Procter & Gamble Company | Perfume systems |
| CN103554493B (en) * | 2013-09-30 | 2015-12-02 | 上海维凯光电新材料有限公司 | Imidazolidine-type high-molecular spice precursor and synthesis thereof, purposes |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3625710A (en) * | 1969-06-25 | 1971-12-07 | Procter & Gamble | Aldimines as chocolate-like flavors |
| EP0175871A1 (en) * | 1984-09-12 | 1986-04-02 | Firmenich Sa | Process for improving or modifying the taste and aroma of citrus fruit compositions |
| US4853369A (en) * | 1987-12-18 | 1989-08-01 | International Flavors & Fragrances Inc. | Schiff base reaction product of ethyl vanillin and methyl anthranilate and organoleptic uses thereof |
| EP0392619A2 (en) * | 1989-04-12 | 1990-10-17 | Quest International B.V. | Malodors reduction |
| WO1995004809A1 (en) * | 1993-08-09 | 1995-02-16 | Firmenich S.A. | Fabric scenting method |
-
1999
- 1999-07-12 CN CNB2005101370187A patent/CN100415861C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3625710A (en) * | 1969-06-25 | 1971-12-07 | Procter & Gamble | Aldimines as chocolate-like flavors |
| EP0175871A1 (en) * | 1984-09-12 | 1986-04-02 | Firmenich Sa | Process for improving or modifying the taste and aroma of citrus fruit compositions |
| US4853369A (en) * | 1987-12-18 | 1989-08-01 | International Flavors & Fragrances Inc. | Schiff base reaction product of ethyl vanillin and methyl anthranilate and organoleptic uses thereof |
| EP0392619A2 (en) * | 1989-04-12 | 1990-10-17 | Quest International B.V. | Malodors reduction |
| WO1995004809A1 (en) * | 1993-08-09 | 1995-02-16 | Firmenich S.A. | Fabric scenting method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1789399A (en) | 2006-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100384974C (en) | Amine reaction compounds comprising one or more active ingredient | |
| US6413920B1 (en) | Amine reaction compounds comprising one or more active ingredient | |
| CN100523161C (en) | Benefit agent delivery systems | |
| JP5289651B2 (en) | Laundry and cleaning composition | |
| CN1328365C (en) | Laundry and cleaning and/or fabric care compositions | |
| DE69923351T2 (en) | AMINATION PRODUCTS CONTAINING ONE OR MORE ACTIVE SUBSTANCES | |
| US6790815B1 (en) | Amine reaction compounds comprising one or more active ingredient | |
| CA2606626A1 (en) | Fabric care composition comprising polymer encapsulated fabric or skin beneficiating ingredient | |
| ES2385996T3 (en) | Perfume precursor compositions used in cleaning or tissue treatment products | |
| JP2003504353A (en) | Preparation of amine compounds | |
| CN100415861C (en) | Soft compound and use thereof | |
| CN100441671C (en) | Process for making detergent product | |
| MXPA01000365A (en) | Amine reaction compounds comprising one or more active ingredient | |
| MXPA01000291A (en) | Amine reaction compounds comprising one or more active ingredient |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20080903 |