CN1314937A - Fabric care compositions - Google Patents
Fabric care compositions Download PDFInfo
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- CN1314937A CN1314937A CN 98814179 CN98814179A CN1314937A CN 1314937 A CN1314937 A CN 1314937A CN 98814179 CN98814179 CN 98814179 CN 98814179 A CN98814179 A CN 98814179A CN 1314937 A CN1314937 A CN 1314937A
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Abstract
The present invention is a fabric care composition comprising a nitrogen containing compound selected from a polyamino-functional polymer, a dye fixing agent, and mixtures thereof, and a scum reducing agent selected from a water-soluble cationic surface active agent; a polyoxyalkylene alkyl amine surface active agent, and mixtures thereof, whereby the composition exhibit reduced or even no scum formation on fabric and/or washing machine parts compared to compositions which do not comprise the scum reducing agent.
Description
Invention field
The present invention relates to a kind of Fabrid care composition, relate more specifically to a kind of method and composition, said composition is presented on fabric and/or the washing machine parts and reduces or even do not form insoluble precipitate, and the fabric of returning simultaneously with its processing provides the color nursing.
Background of invention
The colored fabric for example outward appearance of clothes, bed clothes, domestic fabric such as tablecloth is one of zone of being concerned about of human consumer.In fact, fabric uses through human consumer's generality and for example dresses, washing, rinse and/or roll-drying fabric, and the outward appearance of observing fabric has loss, and this incurs loss in part because of color fidelity and sharpness at least.This problem of colour loss is after wash(ing)cycle repeatedly even more serious.
Therefore the object of the invention provides a kind of composition, and color nursing that it provide improvement can for the fabric of washing is particularly after wash(ing)cycle repeatedly.
Component as the fixed dye described in EP462806 is the component that this purpose is fit to.In fact, these components are by helping that the nursing that provides on the fabric fabric color is provided lax dyestuff.
Also have a class novel material, promptly the amino-functional polymkeric substance also can use.In fact, recent findings has increased the use of these materials in handling fabric, so that the nursing to fabric color is provided.
Yet, the relevant composition that comprises this laking agent and/or amino-functional polymkeric substance, the problem that now runs into is to have formed insoluble precipitate on fabric of handling and/or washing machine parts.
Without being limited by theory, the formation of believing insoluble precipitate is by nitrogenous this compound, be amino-functional polymkeric substance and/or laking agent and from washing composition, particularly interacting as anion surfactant through the anionic species that repeatedly carries wash(ing)cycle produces.This interaction causes forming throw out insoluble, viscosity on fabric and/or washing machine parts.
Therefore, the prescription teacher of Fabrid care composition is faced with and will prepares the composition that show to reduce or even do not form insoluble precipitate, and the color to the fabric handled does not have the destructive double challenge simultaneously.
The insoluble precipitate that the applicant now finds to be selected from water-soluble cationic tensio-active agent, polyoxyalkylene alkylamine surfactant and its mixture surprisingly reduces agent and supplies with the composition that comprises the nitrogenous compound that is selected from amino-functional polymkeric substance, laking agent and its mixture and overcome this problem.
Summary of the invention
The present invention relates to a kind of Fabrid care composition, it comprises:
ⅰ) nitrogenous compound, its be selected from poly-amino-functional polymkeric substance, laking agent and its mixture and
ⅱ) insoluble precipitate reduces agent, and it is selected from water-soluble cationic tensio-active agent, polyoxyalkylene alkylamine surfactant and its mixture; Condition is that the content of this polymkeric substance is greater than 1% weight when unique nitrogenous compound is poly-amino-functional polymkeric substance.
Another aspect of the present invention, provide tensio-active agent in the composition that comprises the nitrogenous compound that is selected from poly-amino-functional polymkeric substance, laking agent and its mixture, to be used to reduce be suppressed at the fabric that contact with said composition or the washing machine parts on the purposes of formation insoluble precipitate.
Detailed Description Of The Invention
According to an aspect of the present invention, providing a kind of has effectively and lasting Fabrid care composition of nursing color property.
Necessary component of the present invention is the nitrogenous compound that is selected from amino-functional polymkeric substance, laking agent and its mixture.The amino-functional polymkeric substance
The amino-functional polymkeric substance has advantageously provided the nursing to fabric color.
Amino-functional polymkeric substance of the present invention is water-soluble or dispersible polyamine.Generally, the molecular weight that is used for amino-functional polymkeric substance of the present invention is between 200-106, preferably at 600-20000, most preferably between 1000-10000.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 nitrogen in this polyamine chain, preferably each nitrogen is the unit of substituted, quaternized, oxidation described below or its array mode.
For the object of the invention, the term " modification " that relates to the chemical structure of polyamine is defined as becoming N-oxide compound (oxidation) by hydrogen atom, quaternized skeleton nitrogen (quaternised) or the oxidation skeleton nitrogen of R ＇ unit (substituting group) replacement skeleton-NH.Term " modification " and " replacement " replace when being connected the process of the hydrogen atom on the skeleton nitrogen when relating to R ＇ unit, can be used alternatingly.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 skeleton nitrogen takes place or quaternized.
The straight chain or the acyclic polyamine main chain that constitute the amino-functional polymkeric substance have following general formula:
The cyclic polyamines main chain that constitutes the amino-functional polymkeric substance has following general formula:
Above main chain is optional, but before the preferred follow-up 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, in a single day the main chain or the side chain that contain primary amine nitrogen are modified, and then are defined as V or Z " end " unit.For example, when the primary amine part that is positioned at a polyamine main chain or a chain end with following structure:
H
2N-[R]-when being modified according to the present invention, it is defined as V " end " unit hereinafter or is called for short the V unit.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 the primary amine part that is positioned at polyamine main chain end with following structure:
-NH
2When 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, in a single day the main chain or the side chain that contain secondary amine nitrogen are modified, and then are 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 the 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 chains 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.
For straight chain amino-functional polymkeric substance, the available thus following general formula of the structure of the polyamine of the present invention that finally is modified is represented:
V
(n+1)W
mY
nZ and represent ring-type amino-functional polymkeric substance with following general formula:
V
(n-k+1)W
mY
nY ＇
kZ is for the polyamine situation that comprises ring, the Y ＇ unit of following formula:
Fulcrum as main chain or branching ring.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 ＇
kWherein k is the number that forms the ring of branching unit.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 promptly, 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.
Each polyamine nitrogen, no matter be primary, the second month in a season or uncle's nitrogen, when being modified according to the present invention, it further is defined as a kind of in following three kinds of universal classes: simply substituted, quaternised 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 counter ion that are fit to of charge balance; With
C) have the oxidation unit of following structure:
The secondary amine of modification partly is defined as W " skeleton " 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 counter ion that are fit to of charge balance; With
C) have the oxidation unit of following structure:
The secondary amine of other modifications 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 counter ion that are fit to of charge balance; With
C) have the oxidation unit of following structure:
The tertiary amine of modification partly is defined as Y " branching " 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 counter ion that are 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 counter ion that are 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 a R ＇ unit with the hydroxyethyl form 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 structure-NH
2The end primary amino partly derive and 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 skeleton 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 also 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)
xR
5(OR
1)
x-,-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OR
2) CH
2)
w-,-CH
2CH (OR
2) CH
2-, (R
1O)
xR
1-and 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 is further according to R
1, R
2And R
5The unit definition.Preferably " oxo " R unit comprises preferred R
1, R
2And R
5The unit.The preferred cotton goods dirt release agent 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:
Or
Or
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:
Or
Or
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 satisfies-(CH equally
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 base 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 cationics that are 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 (Bf
-) 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 0 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.
The preferred amino-functional polymkeric substance 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 amino-functional polymkeric substance 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 working as skeleton R unit is C
2-C
12During alkylidene group, C preferably
2-C
3Alkylidene group most preferably is an ethylidene.
Amino-functional polymkeric substance 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 this conforming definition.For example, the known thanomin of those skilled in the art can be used as " initiator " of synthesizing polyethylene imines, and the polyethyleneimine: amine 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.
The preferred amino-functional polymkeric substance of the present invention comprises homogeneous polyamine main chain, its all or part of by poly-inferior ethoxyl partly replace, it is all or part of by quaternised amine, 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 imines (PEI ＇ s), or connect PEI ＇ s with R cell mesh longer than parent PAI ＇ s or PEI ＇ s.
Be included as C
2The unitary preferred amine polymer main chain of the unitary R of alkylidene group (ethylidene) is also referred to as polymine (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 polymerising ethylene imines prepare, catalyzer for example is carbonic acid gas, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetate etc.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.
The example that comprises the amino-functional polymkeric substance of PEI ＇ s is illustrated in formula I-IV:
The formula I has been described the amino-functional polymkeric substance that comprises the PEI main chain, and wherein all commutable nitrogen are by using polyoxy alkylidene oxygen unit ,-(CH
2CH
2O) H replaces hydrogen and is modified, and it has following formula:
The formula I
This is fully by the example of the amino-functional polymkeric substance of one type residue modification.
The formula II has been described the amino-functional polymkeric substance that comprises the PEI main chain, and wherein all commutable primary amine nitrogen are by using polyoxy alkylidene oxygen unit ,-(CH
2CH
2O)
2H replaces hydrogen and is modified, and this molecule is modified by oxidation then, and all oxidable primary and secondary nitrogen are oxidized to the N-oxide compound, and said polymkeric substance has following formula:
The formula II
The formula III has been described the amino-functional polymkeric substance that comprises the PEI main chain, and wherein the hydrogen atom of all main chains is substituted amine unit with some main chains by quaternized.Substituting group is polyoxy alkylidene oxygen unit ,-(CH
2CH
2O)
7H or methyl.The PEI of this modification has formula:
The formula III
The formula IV has been described the amino-functional polymkeric substance that comprises the PEI main chain, and wherein the nitrogen of main chain is by being substituted (i.e. quilt-(CH
2CH
2O)
3H or methyl substituted), quaternized, be oxidized to N-oxide compound or its array mode and be modified.The polymkeric substance that obtains has formula:
The formula IV
In above embodiment, not every nitrogen comprises same modification in the class unit.The present invention allows teacher of the prescription to make the ethoxylation of part secondary amine nitrogen, and other secondary amine nitrogen are oxidized to the N-oxide compound simultaneously.This also is applicable to primary amine nitrogen, promptly oxidation or quaternized before, the prescription teacher can select with one or more substituting group modification all or part primary amine nitrogen.Except the above-mentioned restriction of this paper, any possible combination of R1 group can be substituted on the primary and secondary amine nitrogen.
Be applicable to that commercially available amino-functional polymkeric substance of the present invention is poly-(ethyleneimine) of molecular weight 1200, the molecular weight that derives from Polysciences is 2000 hydroxyethoxylation poly-(ethyleneimine) and 80% hydroxyethoxylation poly-(ethyleneimine) that derives from Aldrich.
The amino-functional polymkeric substance that in the present composition, uses, when as unique nitrogenous compound, general its content, account for the weight of composition by actives,, be preferably up to 50% greater than 1%, more preferably greater than 1% to 25%, most preferably greater than 1% to 10%.Laking agent
Laking agent or " fixing agent " are known commercially available materials, and it improves the outward appearance of colored fabric by the loss that reduces the dye for fabrics that causes owing to washing.In this definition, do not comprise it being fabric softener or following those components as the amino-functional polymkeric substance.
Many laking agent be cationic and based on various quaternized or other the band cationic charges organic nitrogen compound.Cationic fixative obtains from a plurality of suppliers with different trade names.Representative example comprises: the Cartafix CB that obtains from Clariant, the CROSCOLOR PMF (in July, 1981, code No.7894) and the CROSCOLORNOFF (in January, 1988, code No.8544) that are obtained by Crosfield; The INDOSOL E-50 (on February 27th, 1984, the reference number 6008.35.84 that obtain by Sandoz; Based on poly-inferior ethamine); SANDOFIXTPS, it also obtains from Sandoz, this is the SANDOFIX SWE (resin cation (R.C.) compound) that is used for preferred polycation type fixing agent of the present invention and is obtained by CHT-Beitlich GMBH, REWIN SRF, REWIN SRF-O and REWIN DWR, the Tinofix that buys from Ciba-Geigy
_ECO, Tinofix
_FRD and Solfin
_
Other cationic fixing agents are being described in " improving the aftertreatment of dyestuff firmness on the fabric fibre " among the Christopher C.Cook (dyeing Overview of Progress (REV.PROG.COLORATION), the 12nd volume, 1982).Be applicable to that laking agent of the present invention is an ammonium compound, lipid acid-diamines condenses for example, for example oxidation products of the hydrochloride of oil base diethyl amino yl acetamide, acetate, metilsulfate and benzyl hydrochloride, oil base methyl-two quadrol Methylsulfate, the amino trimethyl ammonium Methylsulfate of single stearyl-ethylene and tertiary amine; The derivative of polymerization alkyl diamine, polyamine-cyanuryl chloride condenses and amination glycerin dichlorohydrin.
Preferred laking agent is the laking agent of cellulolytic activity.
" laking agent of cellulolytic activity " meaning is when heat treated, and this reagent can react with cellulosic fibre.Be applicable to that this reagent of the present invention can be definite by following experimental technique, promptly so-called cellulolytic activity measuring.The cellulolytic activity measuring
The fabric (for example using directly red 80 painted 10 * 10cm knitted cottons) of two bleeding was soaked 20 minutes in the laking agent sampling aqueous solution of the cellulolytic activity of 1% (w/w).The pH of this solution is the pH that obtains under this concentration.
Dry then cloth specimen.With an exsiccant cloth specimen and unsoaked cloth specimen (contrast 1) 10 flatirons through the flatiron wheel press on the linen pad, settled.
Also use contrast 2 cloth specimens in this test experiments, it is the cloth specimen that does not soak with non-flatiron.
4 cloth specimens are washed under general condition the bottle formula detergency test instrument respectively, the washing composition that uses the merchant to sell, by the usage quantity 60 ℃ of suggestions in following 1/2 hour, abundant rinse 4 times in 200ml cold water dries then then.
Then, measure the fastness to washing of cloth specimen by so-called δ-E value of measuring the new relatively untreated cloth specimen of cloth specimen.δ-E value for example is defined among the ASTM D2244.δ-E is the aberration that calculates by definition among the ASTMD2244, be that it is by tristimulus values or by the measuring and indicating of the difference between two kinds of psychophysics colour stimulus of chromaticity coordinates and luminance factor definition, as by CIE1976 CIELAB relatively-color space, Hunter (Hunter) be relative-color difference equation of the set of regulations that defines in the color space, Fu Lier-MacAdam-Chickering (Friele-Mac Adam-Chickering) color space or any color space that is equal to calculates.
Therefore, the cloth specimen that δ-E value is new relatively is low more, and fastness to washing is improved just good more.
If the improvement of the fastness to washing of the cloth specimen that press-soaked is better and also than two separately contrasts 1 and 2 good, then this sampling is the laking agent that is used for the cellulolytic activity of the object of the invention than the cloth specimen that does not press immersion.
The laking agent of typical cellulolytic activity is the product that contains the active group of reactive dyestuffs class, and it is selected from halo triazine product, vinyl sulphone compound, epichlorohydrin derived thing, hydroxy ethylene urea derivatives, formaldehyde condensation products, multi-carboxylate, oxalic dialdehyde and glutaraldehyde derivative and its mixture.
Other functional groups to cellulolytic activity are found in textile treatment and character, the Elsevier of Tyrone L.Vigo (1997), and the 120-121 page or leaf provides and has used the specific electrophilic group that has cellulose affinity.
Preferred hydroxy ethylene urea derivatives comprises dihydroxyl ethylene methyl alcohol, urea and dimethyl urea oxalic dialdehyde.
Preferred formaldehyde condensation products comprises by formaldehyde and the group deutero-condensation product that is selected from amino, imino-, phenylol, urea groups, amino cyano group and aryl.Commercially available compound is the Sandofix WE56 that derives from Clariant in such, derives from the Zetex E and the Levogen BF that derives from Bayer of Zeneca.
Preferred multi-carboxylate's derivative comprises butane tetracarboxylic acid derivative, citric acid derivant, polyacrylate and its derivative.
The laking agent of most preferred cellulolytic activity is a kind of in the hydroxy ethylene urea derivatives type, and it is purchased from Clariant by trade(brand)name Indosol CR.The laking agent of other most preferred cellulolytic activities is purchased from CHT R.Beitlich by trade(brand)name Rewin DWR and Rewin WBS.
In disclosed laking agent, it is cationic being used for the preferred reagent of the present invention, particularly the polycation laking agent.
The laking agent that is used for the present composition, general its content accounts for the weight of composition by actives, and is preferred 1% to 50%, and more preferably 1% to 25%, most preferably 1.5% to 10%.
When using laking agent and poly-amino-functional polymkeric substance, the total amount of these components accounts for composition weight meter by actives, and is general high to 90%, is preferably up to 50%, more preferably 1%-25%, most preferably 1%-10%.The water-soluble cationic tensio-active agent
" water-soluble wetting agent " meaning is a wetting agent when dissolving 0.2% weight in 25 ℃ of water, the isotropic aqueous solution of formation substantial transparent.
Can use the water-soluble cationic tensio-active agent of any kind, to give the character that reduces insoluble precipitate.Yet some water-soluble cationic tensio-active agents and its mixture are preferred.Therefore, the preferred cationic tensio-active agent is to have hydrophobic tail chain of straight or branched and the positively charged basic surface active molecules of hydrophilic head, more preferably is used for the quaternary ammonium salt that cats product of the present invention is a following formula:
[R
1N
+R
3] X
-R wherein
1Be C
10-C
22Alkyl, preferred C
12-C
18There are short alkylidene group (C in alkyl, or corresponding ester bond group at interval between ester bond and N
1-C
4) group and similar alkyl, for example fatty acid ester of choline, preferably C
12-C
14(coconut) cholinesterase and/or C
16-C
18The butter cholinesterase.This alkyl can be by other group such as COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO at interval.Each R is C
1-C
4(for example hydroxyl) alkyl of alkyl or replacement, or hydrogen, preferable methyl and counter ion X-are the compatible negatively charged ion of softening agent, for example chlorion, bromide anion, methylsulfate etc.
The long-chain base R1 of single-long-chain alkyl tensio-active agent generally contains 10-22 carbon atom, preferred about 16 carbon atoms of 12-, the more preferably alkylidene group of 12-18 carbon atom.The R1 base can be by containing one or more esters, acid amides, ether, amine etc., and the group of the connection base of preferred ester is connected with cationic nitrogen, and this connection base is an ideal for improving hydrophilic power, biodegradability etc.It is preferred in about 3 carbon atoms of nitrogen-atoms that these connect base.This type of preferred cationic surfactants is N, N dimethyl-N-(2-hydroxyethyl)-N-dodecyl/Tetradecylammonium bromide.
If use corresponding on-quaternised amine, can add any acid (preferred inorganic or poly carboxylic acid) and keep ester group stable, it is protonated that it also makes amine remain in composition.
These of general disclosure are applicable to that cats product of the present invention is the cholinesterase tensio-active agent of following formula:
R wherein
1Be C
10-C
22Straight or branched alkyl, alkenyl or alkaryl chain, or M
-N
+(R
6R
7R
8) (CH
2)
sX and Y are independently selected from COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO, and wherein at least one X or Y are COO, OCO, OCOO, OCONH or NHCOO group; R
2, R
3, R
4, R
6, R
7And R
8Be independently selected from alkyl, alkenyl, hydroxyalkyl and hydroxyl alkenyl with 1-4 carbon atom, and alkaryl; And R
5Be H or C independently
1-C
3Alkyl; Wherein m, n, s and t value are 0-8 independently, and the b value is in the 0-20 scope, and a, u and v value are 0 or 1 independently, and precondition is that at least one u or v must be 1; Wherein M is a counter anion.
Preferred M is selected from halogen ion, methylsulfate, sulfate radical and nitrate radical, more preferably methylsulfate, chlorine, bromine or iodine.
Highly preferred water-soluble cholinesterase tensio-active agent is the ester with following formula:
Wherein m is 1-4, preferred 2 or 3 and R wherein
1Be C
11-C
19The straight or branched alkyl chain.
Particularly preferred this cholinomimetic ester comprises stearyl-cholinesterase quaternary ammonium methyl halogenide (R
1=C
17Alkyl), palmitoyl cholinesterase quaternary ammonium methyl halogenide (R
1=C
15Alkyl), myristoyl cholinesterase quaternary ammonium methyl halogenide (R
1=C
13Alkyl), lauroyl cholinesterase ammonium methyl halogenide (R
1=C
11Alkyl), cocoyl cholinesterase quaternary ammonium methyl halogenide (R
1=C
11-C
13Alkyl), butter acyl group cholinesterase quaternary ammonium methyl halogenide (R
1=C
15-C
17Alkyl) and its any mixture.
This type of the most particularly preferred cholinesterase is selected from myristoyl cholinesterase quaternary ammonium methyl halogenide, lauroyl cholinesterase ammonium methyl halogenide, cocoyl cholinesterase quaternary ammonium methyl halogenide and its any mixture.
The particularly preferred cholinesterase that more than provides can be by under acid catalyst, and the lipid acid and the dimethylaminoethanol direct esterification that will have required chain length prepare.Reaction product uses methyl halogenide quaternized then, preferably solvent for example ethanol, water, propylene glycol or preferred fat alcohol ethoxylate for example every mole have the C that ethoxylation degree is the 3-50 oxyethyl group
10-C
18Fatty alcohol ethoxylate exists down, forms required cationic substance.Also can be by in the presence of the acid catalyst material, the longer chain fatty acid and the direct esterification of 2-ethylene halohydrin that will have required chain length prepare them, and this reaction product and Trimethylamine are quaternized then, form required cationic substance.The polyoxyalkylene alkylamine surfactant
The polyoxyalkylene alkylamine surfactant also is the another kind of necessary component of the present composition.In fact, because the effect of this component, reduce or even suppressed the formation of insoluble precipitate.
Preferably, be applicable to that polyoxyalkylene alkylamine nonionogenic tenside of the present invention has following formula:
Wherein R is selected from C
7-C
21Straight chained alkyl, C
7-C
21Branched-chain alkyl, C
7-C
21Straight alkenyl, C
7-C
21Branched alkenyl and its mixture.This nonionogenic tenside of the present invention is to be derived by the raw material of synthetic or natural generation to obtain, and preferably the raw material by natural generation obtains, and therefore, described ionic surfactant pack is drawn together the acyl group unit with following formula:
Wherein said acyl group unit is derived from the triglyceride level source, and this triglyceride level is selected from butter; partially hydrogenated butter; lard; Oleum Cocois; partially hydrogenated Oleum Cocois; palm-kernel oil; hydrogenant palm-kernel oil; Tower rape oil; partially hydrogenated Tower rape oil; Thistle oil; partially hydrogenated Thistle oil; peanut oil; partially hydrogenated peanut oil; Oleum Helianthi; partially hydrogenated Oleum Helianthi; Semen Maydis oil; partially hydrogenated Semen Maydis oil; soybean oil; partially hydrogenated soybean oil; Yatall MA; partially hydrogenated Yatall MA; Rice pollard oil; partially hydrogenated Rice pollard oil and its mixture.The unitary in addition preferred triglyceride level source of acyl group is the synthetic triglyceride feedstock, for example the non-triglyceride level derived from natural matter for preparing by chemical reaction or additive method.The unitary preferred raw material of described acyl group is butter, partially hydrogenated butter, Oleum Cocois, partially hydrogenated Oleum Cocois, Tower rape oil, hydrogenant Tower rape oil, synthetic glycerine three esters and its mixture.Preferred triglyceride level source is three oleic acid base glycerols, three esters.
R
1It is ethylidene; R
2Be selected from C
3-C
4Straight chained alkyl, C
3-C
4Branched-chain alkyl and its mixture; Preferred R
2It is propylene.Comprise R
1And R
2The nonionogenic tenside of mixed cell preferably includes about 12 ethylidene unit of about 4-and about 4 the unitary combinations of propylene of about 1-.These unit can alternate or combine with any array mode that is suitable for teacher of the prescription.Preferably, R
1Unit and R
2Unitary ratio is about 4: 1-8: 1.Preferred R
2Unit (being propylene) is connected on the nitrogen-atoms, connects afterwards and comprises 4-8 the unitary balancing chain of ethylidene.
R
3Be selected from hydrogen, C
1-C
4Straight chained alkyl, C
3-C
4Branched-chain alkyl and its mixture; Preferred hydrogen or methyl, more preferably hydrogen.
R
4Be selected from hydrogen, C
1-C
4Straight chained alkyl, C
3-C
4Branched-chain alkyl and its mixture; Preferred hydrogen.When subscript m equaled 2, subscript n must equal 0 and R
4The unit does not exist, and with-[(R
1O)
x(R
2O)
yR
3] unit substitutes.
A is:
R
5Be selected from-[(R
1O)
x(R
2O)
y] unit, C
1-C
16Straight chained alkyl, C
1-C
16Branched-chain alkyl, C
1-C
16Straight alkenyl, C
1-C
16Branched alkenyl and its mixture are preferably selected from C
3Straight chained alkyl, C
3Branched-chain alkyl, C
3Straight alkenyl, C
3Branched alkenyl and its mixture.
Subscript m is 1 or 2, and subscript n is 0 or 1, and condition is when m equals 1, and n equals 1; With when m is 2, n is 0; Preferred m equals 2, and n equals 0, causes existing two-[(R
1O)
x(R
2O)
yR
3] unit and do not have R
4Subscript x is that 0-is about 50, and preferably about 1-is about 25, and more preferably from about 3-about 10.Subscript y is that 0-is about 10, and is preferred 0, yet when subscript y was not equal to 0, y was 1-about 4.Preferred all alkylidene group oxygen unit are ethyleneoxy group unit.The technician in ethoxylation polyoxyalkylene alkylamine surfactant field will appreciate that the numerical value of subscript x and y is mean value, and real numerical value may be in several numerical ranges, and this depends on the employed method of this amine of alkoxylate.
Subscript q is 0 or 1.
The polyoxyalkylene alkylamine can be buied from several suppliers by the extensive stock name.Representational example comprises the Ethomeen available from Akzo Chemicals, Ethoduomeen, and/or the Secomine that buys from Stepan.
By the weight of composition, the general content of polyoxyalkylene alkylamine surfactant is 0.001%-20%, preferred 0.5%-12%, more preferably 1%-8%.
Reduce in the agent preferably water-soluble cationic tensio-active agent at insoluble precipitate as herein described.
Performance for the minimizing insoluble precipitate that further improves composition, when above-mentioned poly-amino-functional polymkeric substance is unique nitrogenous compound, also find preferably, insoluble precipitate reduces agent and polymkeric substance with weight ratio 0.02: 1-2: 1, preferred 0.05: 1-1.5: 1, most preferably 0.1: 1-0.8: 1 exists.
When laking agent is unique nitrogenous compound, in order to obtain reducing the optimum performance of insoluble precipitate, find that the weight ratio that insoluble precipitate preferably reduces agent and laking agent is 0.05: 1-5: 1, more preferably 0.1: 1-2.5: 1, most preferably 0.5: 1-1: 1.
When using the mixture of poly-amino-functional polymkeric substance and laking agent, in order to obtain reducing the performance of improving of insoluble precipitate, the weight ratio that preferred insoluble precipitate reduces agent and poly-amino-functional polymkeric substance and laking agent summation is 0.05: 1-2: 1, preferred 0.1: 1-1: 1.
Except above-mentioned insoluble precipitate reduces agent, find to use the water-insoluble cats product that is commonly referred to fabric soft compound also to provide at the beneficial effect that reduces the insoluble precipitate aspect of performance.Fabric soft compound
In said composition, the general add-on of softening compound thing is the 1%-80% weight of composition weight, preferred 5%-75%, more preferably 15%-70%, even more preferably 19%-65%.
The soft component of typical positively charged ion is quaternary ammonium compound or the amine precursor as hereinafter definition.A)-the soft active compound of quaternary ammonium fabric
(1) the soft active compound of preferred quaternary ammonium fabric has formula
(1) or likes:
(2) 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 amines 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:
Or
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 counter ion X (-) 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, half group of X (-) expression in this case.
Butter and Tower rape oil are the unitary suitable and cheap sources 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 be meant the unitary mixture of the fatty acyl group that derives from Tower rape oil.
The 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 examples of quaternary ammonium softening compound thing are 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 Varisoft
_222 and Varisoft
_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 chains 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 other iodine number of phase region 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 greater than about 30/70, is preferably greater than approximately 50/50, provides best condensability more preferably greater than about 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 are 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 equivalent to obtain 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 obtain with the term " methyl " in the above-mentioned table II example of " ethyl, oxyethyl group, propyl group, propoxy-, sec.-propyl, butyl, isobutyl-and the tertiary butyl " replacement.
Counter ion 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 counter ion existence as positively charged quaternary ammonium compound.Should 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 situation about prolonging 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 about 6.0 o'clock in the pH value, for these compositions have optimum hydrolysis stability, the pure pH value of Ce Dinging preferably must be in about 2.0-5 scope under these conditions, in the preferred 2.5-4.5 scope, and preferably about 2.5-3.5.The pH value of these compositions can be regulated by adding a kind of Bronsted acid (protonic acid) herein.
The example of suitable acid comprises mineral acid, carboxylic acid, particularly lower molecular weight (C
1-C
5) 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, not or 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 about 2.5%.Yet under the condition that is loaded with a large amount washing composition, some monoesters are preferred.The overall proportion of diester and monoesters is about 100: 1-2: 1, preferred about 50: 1-5: 1, more preferably from about 13: 1-8: 1.Under the condition that is loaded with a large amount washing composition, diester/monoesters was than preferred about 11: 1.In the production of softener compound, can control the content of monoesters.
Also can preparation formula (1) and the mixture of formula (2) actives.
2)-and other also 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, and it 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;
(ⅱ) have the diamino alkoxy quaternary ammonium salt of following formula:
Wherein to equal 1-about 5 for n, R
1, R
2, R
5And A
-As top definition;
(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 ditallow dimethyl ammonium chloride, ditallow dimethyl methyl ammonium sulfate, two (h-tallow base) alkyl dimethyl ammonium chloride, VARISOFT TA100, two mountain Yu base alkyl dimethyl ammonium chloride.Two (h-tallow base) alkyl dimethyl ammonium chlorides and ditallow dimethyl ammonium chloride are preferred.The example that is used for commercially available dialkyl dimethyl ammonium salt class of the present invention is two (h-tallow base) alkyl dimethyl ammonium chloride (trade(brand)name Adogen
_442), ditallow dimethyl ammonium chloride (trade(brand)name Adogen
_470, Praepagen
_3445), VARISOFT TA100 (trade(brand)name Arosurf
_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 Varisoft by Witco chemical company
_SDC and press Ammonyx 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 amine form or cationic form, 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
15-C
21Alkyl, R
8Be divalence C
1-C
3Alkylidene group.
The commercially available Mazamide that sells in: Mazer Chemicals of component (ⅰ) material
_6, or Sandoz Colors﹠amp; The Ceranine that Chemicals sells
_HC; By AlkarilChemicals, Inc. is with trade(brand)name Alkazine
_ST or by Scher Chemicals, Inc. is with trade(brand)name Schercozoline
_The imidazoline-based stearyl hydroxyethyl that S sells; N, N 〃-ditallow alkyloyl diethylenetriamine; 1-tallow amido ethyl-2-tallow 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 about 4 the protonic acid dispersing auxiliary; Condition is that the pH of final composition is not more than about 6.Some preferred dispersing auxiliaries are hydrochloric acid, phosphoric acid, or methylsulphonic acid.
N; the two is the reaction product of tallow fatty acid and diethylenetriamine N 〃-ditallow alkyloyl diethylenetriamine and 1-tallow (amido ethyl)-2-tallow tetrahydroglyoxaline; and the precursor that is cationic fabric softener methyl isophthalic acid-tallow amido ethyl-2-tallow tetrahydroglyoxaline metilsulfate is (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, the 118-121 page or leaf).N, N 〃-ditallow alkyloyl diethylenetriamine and 1-tallow amido ethyl-2-tallow tetrahydroglyoxaline can obtain with chemical as experiment from Witco chemical company.Methyl isophthalic acid-tallow amido ethyl-2-tallow tetrahydroglyoxaline metilsulfate by Witco chemical company with trade(brand)name Varisoft
_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
-The definition that definition provides with top X.
An example of compound (ⅱ) is 1-oil base amido ethyl-2-oil-based imidazoline muriate, wherein R
1Be no cyclic aliphatic C
15-C
17Alkyl, R
2Be ethylidene, G is the NH 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.
An example of compound (ⅲ) is the compound with following formula:
R wherein
1Derive from oleic acid.
Be used for other fabric softener herein and be described in that to authorize name on April 28th, 1987 be Toan Trinh, Errol H.Wahl is in the U.S. Pat 4661269 of Donald M.Swartley and Ronald L.Hemingway; Authorized the U.S. Pat 4439335 of Burns on March 27th, 1984; And the U.S. Pat 3861870 of Edwards and Diehl; The US4308151 of Cambre; The US3886075 of Bernardino; The US4233164 of Davis; The US4401578 of Verbruggen; The US3974076 of Wiersema and Rieke; Rudkin, the US4237016 of Clint and Young; And people's such as Yamamura European patent application publication No. EP472178, all above-mentioned documents are hereby incorporated by.
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 Fabrid care composition of complete formula also can contain one or more following components except containing the above-mentioned component of this paper.Optional component (A) 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 because its low cost, can get relatively, safety and and environmentally compatible.The content of water in liquid vehicle is by the weight of this carrier, preferably at least about 50%, most preferably at least about 60%.Water and lower molecular weight for example are suitable as liquid vehicle less than the mixture of about 200 organic solvent, 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.(B) additional solvent
The present composition can comprise one or more solvents that can increase the preparation easiness.Making preparation be easy to these solvents all is disclosed among the WO97/03169.The situation when obtaining liq, transparent fabric sofetening composition particularly.When using, make preparation be easy to solvent system and preferably account for composition weight and be less than approximately 40%, preferably about 10%-is about 35%, and more preferably from about 12%-is about 25%, even 14%-about 20% more preferably from about.Make preparation be easy to this choice of Solvent and will make its solvent odor minimum that in composition, produces, and make final composition have low viscosity.For example, Virahol is not very effective and the intensive smell is arranged.N-propyl alcohol is comparatively effective, but tangible smell is also arranged.Several butanols are scent of also, but because effectively the transparency/stability is so can use, especially when as making the part use of preparing easy solvent system when reducing its smell.Also to select to have best low-temperature stability to alcohols, promptly, still to form under about 40 °F (about 4.4 ℃) be the composition of liquid being low to moderate for they, said composition has acceptable low viscosity and translucent, preferably transparent, and after being low to moderate about 20 (about 6.7 ℃) following storage, can restore.
For preparation have desired stability liquid state of the present invention, concentrate, the fabric softener composition of preferably transparent, the suitability that makes preparation be easy to any solvent all is optionally astoundingly.Suitable solvent can be according to selecting as their the octanol/water partition ratio (P) that defines among the WO97/03169.
The selected ClogP that makes preparation be easy to solvent of the present invention is about 0.15-about 0.64, preferred about 0.25-about 0.62, more preferably from about 0.40-about 0.60, it is described that to make preparation be easy to solvent preferably be asymmetric to a certain degree at least, and preferably its fusing point that has or solidification point make it room temperature or near under the room temperature for liquid.For some reason, lower molecular weight and biodegradable solvent also need.As if more asymmetric solvent is very desirable, and highly symmetric solvent is as 1,7-heptanediol or 1, two (methylol) hexanaphthenes of 4-, they have symmetry centre, show the composition that can not form substantial transparent when using separately, though its Clog P value is in the preferred range.
The most preferred easy solvent of preparation that makes can differentiate that this is to arrive with the cryogenic freezing electron microscopy observation after composition is diluted to the concentration of using in the rinse by the appearance of softening agent vesica.It is the dispersion of fabric softener that these dilute compositions show, and its fabric softener composition than routine has more the unilamellar vesicle outward appearance.As if outward appearance is more near the individual layer system, and the performance of composition is good more.These compositions are compared with the analogous composition for preparing with same fabric softener active matter in the usual way, and good fabric sofetening effect is provided astoundingly.
The spendable of ClogP value scope with the requirement of dropping on makes preparation be easy to solvent openly side by side hereinafter.These comprise monohydroxy-alcohol, C6 dibasic alcohol, C7 dibasic alcohol, ethohexadiol isomer, butyleneglycol derivative, neopentyl glycol isomer, ethyl-methyl pentanediol isomer, propyl group pentanediol isomer, dimethyl hexylene glycol isomer, Rutgers 612 isomer, methyl heptanediol isomer, ethohexadiol isomer, nonanediol isomer, alkyl glycerylether, two (hydroxyalkyl) ether and Arylglycerine ether, aromatics glyceryl ether, alicyclic diol and its derivative, C
3-C
7Glycol alkoxy derivative, aromatic diol and unsaturated diol.Particularly preferredly make preparation be easy to solvent to comprise hexylene glycol for example 1 2-hexylene glycol and 2-ethyl-1,3-hexylene glycol and pentanediol for example 2,2,4-trimethylammonium-1,3-pentanediol.(C) dispersing auxiliary
The denseer composition that contains saturated and unsaturated diester quat can be prepared into stabilising system and needn't add concentrated assistant.But composition of the present invention may need organic and/or inorganic concentrated assistant to reach higher concentrating and/or satisfied higher stability criterion, and this depends on other components.These concentrated assistants that generally are viscosity modifier may need, or preferred, in order that stability when guaranteeing softening agent actives when the use certain content under extreme conditions.The tensio-active agent concentrated assistant is selected from (1) single-long-chain alkyl cats product usually; (2) nonionogenic tenside; (3) oxidation amine; (4) fatty acid; (5) their mixture.These auxiliary agents are described in WO94/20597, specifically are to walk to the 20th page of 12 row at the 14th page 12, 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) add for example as the lipid acid of the reactant of the above-mentioned biodegradable fabric softener active matter of preparation, or as independent component.The total content of dispersing auxiliary comprises any amount that may exist as the part of component (I).
Can also play inorganic viscosity/dispersity control agent similar or effect of increase tensio-active agent concentrated assistant and comprise water-soluble ionogenic salt, they also can randomly add in the present composition.Can use various ionogenic salt.The example of the salt that is fit to is the halogenide of I A and II A family metal in the periodic table of elements, for example calcium chloride, magnesium chloride, sodium-chlor, Potassium Bromide and lithium chloride.Blending ingredients prepare in the process of the present composition and the follow-up process that will obtain required viscosity in, ionogenic salt is useful especially.The amount of employed ionogenic salt depends on the amount of the active ingredient of using in composition, it can be mediated according to prescription teacher's requirement.The amount of the general employed salt of control combination thing viscosity is counted each 1,000,000 parts about 20 to about 20,000 parts (ppm) by the weight of composition, and preferred about 20 to about 11,000ppm.
The poly-ammonium salt of alkylidene group can add in the composition to obtain subcontrol or the above water-soluble ionogenic salt of replacement to viscosity.In addition, these reagent can be used as scavenging agent, form ion pair with the anionic detergent that carries with fabric that carries from main washing, rinse, and can improve softness.These reagent are compared with inorganic electrolyte, can be in wide temperature range stable viscosity, particularly under cryogenic situation.
The specific examples of the poly-ammonium salt of alkylidene group comprises 1-Methionin one hydrochloride and 1,5-two ammonium 2-methylpentane dihydrochlorides.(D) stablizer
In the present composition, can there be stablizer.Terminology used here " stablizer " comprises antioxidant and reductive agent.The content of these reagent is about 2% for about 0-, and preferably about 0.01%-is about 0.2%, and more preferably from about 0.035%-is about 0.1% for antioxidant, for reductive agent 0.01%-about 0.2% more preferably from about.This has guaranteed that composition and the compound deposited with the fusion form have good odor stable under the standing storage condition.The use of antioxidant and reductive agent stablizer is for product (seldom spices) particularly important of low fragrance.
The example that can be added to the antioxidant in the present composition comprises EastmanChemical Product, and Inc is with trade name Tenox
_The mixture of xitix, ascorbyl palmitate and propyl gallate that PG and Tenox S-1 sell; Can be by EastmanChemical Product, the trade name that Inc. obtains is the mixture of BHT (Yoshinox BHT), BHA (butylated hydroxyanisol), propyl gallate and the citric acid of Tenox-6; The trade name that can be obtained by UOP Process Division is Sustane
_The Yoshinox BHT of BHT; Eastman Chemical Products, the trade name of Inc. is the tertiary butylated hydroquinone of Tenox TBHQ; Eastman Chemical Products, the natural tocopherol that Inc. sells with the trade name of Tenox GT-1/GT-2; And Eastman Chemical Products, the butylated hydroxyanisol of the trade name BHA of Inc.; Long-chain (the C of gallate
8-C
22) ester, for example gallate dodecyl ester; Irganox
_1010; Irganox
_1035; Irganox
_B 1171; Irganox
_1425; Irganox
_3114; Irganox
_3125; And their mixture; Preferred Irganox
_3125; Irganox
_1425; Irganox
_3114 and composition thereof; More preferably Irganox
_3125 itself or with citric acid and/or other sequestrants mixture of citric acid isopropyl ester for example; The chemical name that can be obtained by Monsanto is a 1-hydroxy ethylene-1, the Dequest of 1-di 2 ethylhexyl phosphonic acid (Etidronic Acid)
_2010, the chemical name that can be obtained by Kodak company is 4, the Tiron of Phenylsulfonic acid/sodium salt between the 5-dihydroxyl (EDDS)
_, and the chemical name that can be obtained by Aldrich is the DTPA of diethylene triaminepentaacetic acid(DTPA)
_More than the chemical name of some stablizers and CAS number column in the following table II.
The change of using in the code of table II antioxidant GAS numbering the United States Federal regulation
Formal name used at school claims Irganox
_1010 6683-19-8 four (methylene radical (3,5-di-t-butyl-4-hydroxyl
The base hydrogenated cinnamate)) methane Irganox
_1035 41484-35-9 sulfo-diethylidenes two (3, the 5-di-t-butyl-
4-hydroxyl hydrogenated cinnamate) Irganox
_1098 23128-74-7 N, and N '-hexa-methylene two (3, the 5-di-t-butyl
-4-hydroxyl hydrocinnamamide) Irganox
_B1171 31570-04-4 Irganox
_1098 and Irgafos
_168
1: 1 mixture Irganox of 23128-74-7
_1425 65140-91-2 two (single ethyl (3,5-two-tert-butyl-4-
Acrinyl) phosphonic acid ester calcium Irganox
_3114 65140-91-2 two (single ethyl (3,5--tert-butyl-4-
Acrinyl) calcium Irganox phosphonic acid ester)
_3125 34137-09-2 3,5-two-tert-butyl-4-hydroxyl-hydroxylation meat
Cinnamic acid and 1,3,5-three (2-hydroxyethyl)-all
-triazine-2,4,6-(1H, 3H, 5H) triketone
Three ester Irgafos
_168 31570-4--4 three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester
The example of reductive agent comprises sodium borohydride, Hypophosporous Acid, 50, Irgafos
_168 and their mixture.(E) dirt release agent
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 make with spot easier being cleaned in washing process afterwards that produces subsequently of dirt release agent processing.
If you are using, it is about 10.0% that dirt release agent generally accounts for about 0.01%-of detergent composition weight of the present invention, and generally about 0.1%-is about 5%, preferably about 0.2%-about 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.(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 called Bronopol to the 3-glycol
_), and by the sale of Rohm and Hass company, the 5-chloro-2-methyl-4-isothiazoline-3-ketone of commodity Kathon by name and the mixture of 2-methyl-4-isothiazoline-3-ketone, its reagent dosage is 1-1000ppm.(G)-spices
The present invention can comprise any spices.Suitable spices is disclosed in the U.S. Pat 5500138, and this patent is hereby incorporated by.
Be used for the mixture that spices of the present invention comprises aromatoising substance or aromatoising substance, comprising natural (promptly obtaining with plant), synthetical (being the mixture of different natural oils or oily composition) and synthetic (i.e. synthetic preparation) aromatoising substance by extracting flower, grass, leaf, root, bark, timber, flowers.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 perfume composition 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-trans-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 examples of aromatoising substance include 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 perfume composition 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; Styroyl acetate; 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 the homogeneous 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.
Perfume composition is also suitable to add as releasable spices, for example describe in the U.S. Pat 5652205 of the Hartman that authorizes on July 29th, 1997 etc. as fragrant-inner agent, this patent is quoted for referencial use at this paper.(H)-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, its preferred best pH value 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.CAREZYME
_And CELLUZYME
_(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.Activity in zymin can define in particular cases in addition, and 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 the active 1000-10000CEVU/ of being gram when liquid form, be approximately 1000 CEVU/ and restrain when solid form.
(1) crystal growth inhibitor component
The present composition also can contain the crystal growth inhibitor component, preferred organic diphosphonic acid component, and/or organic mono phosphonic acid, 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 not contain the organic diphosphonic acid of nitrogen as 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 CG1.
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 counter 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 butane-1,2, and the 4-tricarboxylic acid can be purchased by trade(brand)name Bayhibit from Bayer.Other optional components
The present invention can be included in the textile treatment composition the conventional optional components of using, for example whitening agent, tinting material, tensio-active agent, sanforzing agent, the fabric stiffener, spotting agent, sterilant, mycocide, antioxidant such as Yoshinox BHT, sanitas, defoamer etc.
The present invention also can comprise other compatible components, is included among WO96/02625, WO96/21714 and the WO96/21715 those disclosed and disclosed dispersible polyolefin Velustrol for example in autre action pendante application PCT/US97/01644
_Deng.The present invention also can contain for example quadrol-N of optional sequestrant, and N '-disuccinic acid is (S, S) isomer (EDDS) and crystal growth inhibitor oxyacetic acid and/or 1 for example, the 1-hydroxyl ethane di 2 ethylhexyl phosphonic acid (HEDP) of sodium-salt form.The form of composition
Fabrid care composition can be taked various physical form, comprises for example solid particulate form of for example aqueous or non-water base composition of liquid and solid form.
This composition can be applied on the substrate flaked product that moisture eliminator is for example used, the product that adds during as rinsing or as sprays or froth product.
Therefore, another aspect of the present invention, tensio-active agent is provided, and the above-mentioned insoluble precipitate of preferred this paper reduces the purposes of formation insoluble precipitate on agent is used to reduce or inhibition contacts with said composition fabric or the washing machine parts in the composition that comprises the nitrogenous compound that is selected from poly-amino-functional polymkeric substance, laking agent and its mixture.In other words, comprise the nitrogenous compound of preamble definition, do not compare with the present composition but do not contain the composition that insoluble precipitate reduces agent, the insoluble precipitate of generation increases.Method
Fabric sofetening composition can suit to prepare according to technician's known method.Exemplary open giving in EP-A-0668902.
The present invention illustrates that with following non-restrictive example except as otherwise noted, wherein all percentage ratios are based on the weight meter.
In an embodiment, the component symbol of abbreviation has following implication: DEQA: two (butter acyloxy ethyl) alkyl dimethyl ammonium chloride DOEQA: two (oily acyloxy ethyl) dimethyl methyl ammonium sulfate DTDMAC: ditallow dimethyl ammonium chloride DHEQA: two (soft tallow acyloxy ethyl) hydroxyethyl methyl methyl-sulfuric acid
Ammonium lipid acid: the tallow fatty acid ionogen of IV=18: calcium chloride DTDMAMS: tallow dimethyl methyl ammonium sulfate SDASA: 1: 2 stearyl dimethyl amine: triple pressed stearic acid Glycosperse S-20: the polyethoxylated anhydro sorbitol list that obtains from Lonza
Stearate clay: swollen by the calcium that Southern Clay Products sells
Profit soil, wilkinite LTAE 25: every mol of alcohol is with 25 moles of ethylene oxide ethoxylations
Tallow alcohol PEG: Macrogol 4000 PEI 1800E1: by synthetic embodiment 1 synthetic ethoxylation polyethyleneimine:
Amine (MW1800,50% actives) PEI 1800E3: by synthetic embodiment 1 synthetic ethoxylation polyethyleneimine:
Amine (MW1800,50% actives) PEI 1800E7A0: by synthetic embodiment 4 synthetic ethoxylation polyethyleneimine :s
The amine oxide PEI 1200E1 of amine (MW1800,50% actives): by synthetic embodiment 5 synthetic ethoxylation polyethyleneimine :s
Amine (MW1200,50% actives) PEI 1200E2: by synthetic embodiment 5 synthetic ethoxylation polyethyleneimine :s
Amine (MW1200,50% actives) PEI 1200E7: by synthetic embodiment 5 synthetic ethoxylation polyethyleneimine :s
Amine (MW1200,50% actives) PEI 1200E7AO: by synthetic embodiment 5 and the poly-second of 4 synthetic ethoxylations
The amine oxide laking agent 1 of alkene imines (MW1200,50% actives): purchase from Ciba-Geigy trade(brand)name Tinofix FRD
The laking agent laking agent 2 of cellulolytic activity: from CHT R.Beitlich with trade(brand)name Rewin DWR
The laking agent insoluble precipitate of the cellulolytic activity of buying reduces agent 1:N, N dimethyl-N-(2-hydroxyethyl)-N-dodecyl/
The Tetradecylammonium bromide insoluble precipitate reduces agent 2:C12/C14 cholinesterase insoluble precipitate and reduces agent 3: can be from the commodity that Akzo is purchased Ethomeen T/15 by name
Polyoxyalkylene alkylamine insoluble precipitate reduce agent 4: can be from the commodity that Stepan is purchased Secomine TA by name
15 polyoxyalkylene alkylamine insoluble precipitate reduces agent 5: can be from the commodity that Akzo is purchased Ethoduomeen by name
The polyoxyalkylene alkylamine LAS of T/20: straight chain C
12Sodium alkyl benzene sulfonate TAS: tallow alcohol sodium sulfate C25AS: C
12-C
15Straight-chain alkyl sulfate C
XyE
zS: with the C of Z moles of ethylene oxide condensation
1x-C
1yBranched-chain alkyl
Sodium sulfate C45E7: with the straight chain that is mainly of average 7 moles of ethylene oxide condensations
C
14-15Primary alconol C25E3: with the C of average 3 moles of ethylene oxide condensations
12-15Side chain primary
The alcohol soap: by 80/20 mixture of butter and Oleum Cocois obtain straight
Alkyl group carboxylic acid sodium TFAA: C
16-C
18Alkyl N-methyl glucose amide TPKFA: C
12-C
14The full cut lipid acid of topping zeolite A: formula Na
12(AlO
2SiO
2)
12.27H
2The hydration silicoaluminate of O
Sodium, primary particle size are 0.1-10 micron citric acid: Citric Acid, usp, Anhydrous Powder carbonate: granularity is the Carbon Dioxide sodium silicate of 200-900 micron: amorphous sodium silicate (SiO
2: Na
2The O ratio is 2.0) sodium sulfate: anhydrous slufuric acid na citrate: citrate trisodium dihydrate, activity 86.4%, granularity
Be distributed in 425-850 micron MA/AA: 1: 4 toxilic acid/acrylic copolymer, molecular-weight average are approximately
70000CMC: Xylo-Mucine
Savinase: activity is the proteolytic ferment of 4KNPU/g
Carezyme: activity is the cellulolytic enzyme of 100CEVU/g
Termamyl: the active amylase of separating for 60kNU/g
Lipolase: activity is the lipolytic enzyme of 100KLU/g
All these enzymes are all by NOVO Industries A/S
Sale also has above-mentioned activity, PB4 unless otherwise indicated: standard type NaBO
2.3H
2O.H
2O
2Sodium peroxoborate four hydrations
Thing PBl: standard type NaBO
2.H
2O
2Anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER TAED: tetra acetyl ethylene diamine DTPMP: diethylenetriamine five (methylene phosphonic acid), by Meng Shandou
Sell the photosensitization SYNTHETIC OPTICAL WHITNER with trade(brand)name Dequest 2060: the sulfonation phthalocyanine phthalocyanine zinc whitening agent of using the cyclodextrin poly compound encapsulate of solubility: 4,4 '-two (4-phenylaminos-6-morpholino-1,3,5-triazines
-2-yl) amino) stilbene-2: 2 '-disulfonic acid disodium polysiloxane defoamers: the polydimethylsiloxane foam control agent with as the silicon of dispersion agent
Oxygen alkane-oxyalkylene copolymers, described foam control agent and described branch
The ratio of powder is 10: 1-100: 1HEDP: 1, and 1-hydroxyl ethane di 2 ethylhexyl phosphonic acid Bayhibit AM: from the 2-phosphine butane-1,2 that Bayer is purchased, 4-tricarboxylic acid TPTA: from the N that Aldrich is purchased, N ＇-two (3-amino third
Base)-1, the 3-propylene diamine synthesizes embodiment 1-PEI 1800E
1Preparation
Steps A)-and in the stainless steel autoclave of 2 gallons of stirrings, carrying out ethoxylation, this autoclave is equipped with temperature survey and function unit, pressure measurement unit, decompression member and inert gas purge parts, sampling parts and is used to be incorporated as the parts of the oxyethane of liquid.Lay the oxyethane steel cylinder (ARC) of about 20 pounds of net weight, carry in autoclave by pump to be the oxyethane of liquid, this steel cylinder is placed on the scale amount dish, so that can monitor the changes in weight of steel cylinder.
In autoclave, add 750g polymine (PEI) (Nippon Shokubai, Epomin SP-018 have 1800 listed molecular-weight average, equal 0.417 moles of polymer and 17.4 mole of nitrogen functional groups).Sealing autoclave then, (" decompression of Hg is then with nitrogen pressure to 250 pound/inch by providing-28 to purge out air
2, connect normal atmosphere then).Material to 130 when decompression is provided in the heating high-pressure still ℃.After about 1 hour, autoclave is charged into nitrogen to about 250 pounds/inch
2, cool off autoclave simultaneously to about 105 ℃.Oxyethane is added in the autoclave through for some time in the mode that increases progressively then, monitor the flow velocity of pressure, temperature and the oxyethane of autoclave simultaneously closely.Closing ring oxidative ethane pump, cooling is risen because of the temperature that any exothermic heat of reaction causes with restriction.Temperature is maintained between 100-110 ℃, allows simultaneously that total pressure rises gradually in reaction process.After amounting to 750 gram oxyethane to be added into autoclave (equal every mole of PEI nitrogen functional group roughly 1 moles of ethylene oxide is arranged), temperature increases to 110 ℃, makes the autoclave restir 1 hour.At this moment, provide decompression to remove any residual unreacted oxyethane.
Step B)-then by the gas dispersion screen plate, feed about 100 cubic feet of rare gas elementes (argon gas or nitrogen) and, make the reaction mixture deodorization, stir simultaneously and heated mixt to 130 ℃ by reaction mixture.
Final reacting product is slightly cooled off and is collected in the Glass Containers of crossing with nitrogen purging.
In other preparation, neutralization and deodorization are to finish in reactor before the product discharging.
PEI 1800E if desired
7, between steps A and B, add following catalyzer and add step.
Decompression is provided continuously, and autoclave is cooled to about 50 ℃ simultaneously, is added in 25% sodium methylate (1.74 moles have 10% catalyst loading based on the PEI nitrogen functional group) of the 376g in the methanol solution simultaneously.Under reduced pressure, methylate solution is aspirated in the autoclave, improve temperature to 130 that the autoclave temp controller sets ℃ then.Use a kind of equipment to monitor the power that agitator consumes.The power of monitoring agitator, and temperature and pressure.Along with methyl alcohol is removed from autoclave, agitator power and temperature value rise gradually, and the viscosity of mixture increases and stablized about 1 hour, shows that most of methyl alcohol are removed.Mixture is reheat and stirring 30 minutes under reduced pressure.
Remove decompression, autoclave is cooled to 105 ℃, charges into nitrogen to 250 pound/inch simultaneously
2, connect environmental stress then.Autoclave charges into nitrogen to 200 pound/inch
2In autoclave, add oxyethane in the mode that increases progressively again, monitor the flow velocity of pressure, temperature and the oxyethane of autoclave then closely, maintain the temperature at simultaneously between 100-110 ℃, and restriction is because any temperature rising that exothermic heat of reaction causes.Through several hours, add 4500g oxyethane after (obtain every mole of PEI nitrogen functional group 7 moles of ethylene oxide of total arranged), temperature rises to 110 ℃, restir mixture 1 hour.
Reaction mixture is collected in the container that nitrogen purging crosses then, is transferred to 22L at last and is equipped with in the three neck round-bottomed flasks of heating and mixing component.Add in the 167g methylsulfonic acid (1.74 moles) and alkali catalyst.
Can prepare other preferred examples for example PEI 1800 E2, PEI 1800 E3, PEI1800 E15 and PEI 1800 E20 by the relative quantity of above method by the oxyethane adjusting the reaction times and in reaction, use.4.7% quaterisation of synthetic embodiment 2-PEI 1800 E7
The adding ethoxylation degree is 7 poly-(ethyleneimine) in the 500ml erlenmeyer flask that magnetic stirring bar is housed, MW1800 (224g, 0.637 mole of nitrogen is by synthetic embodiment 1 preparation) and acetonitrile (Baker, 150g, 3.65 moles).Immediately all methyl-sulfates (Aldrich, 3.8g, 0.030 mole) are added in this solution that stirs fast, stopper and stirring are at room temperature spent the night beyond the Great Wall then.Under～60 ℃, on rotatory evaporator, evaporate acetonitrile, under～80 ℃, obtain～the required material of 220g then through Kugelrohr apparatus (Aldrich), be the chocolate thick liquid.
13C-NMR (D
2O) spectrum be presented at～there is not the peak corresponding to methyl-sulfate in the 58ppm place.
1H-NMR (D
2O) spectrum peak (methylene radical that is connected with the not quaternized nitrogen-atoms) partial dislocation that is presented at the 2.5ppm place is to～3.0ppm.The oxidizing reaction of synthetic quaternised PEI 1800 E7 of embodiment 3-4.7%
In the 500ml erlenmeyer flask that magnetic stirring bar is housed, add ethoxylation degree and be 7 and with methyl-sulfate～4.7% quaternised gather (ethyleneimine), MW1800 (121.7g,～0.32 mole of oxidable nitrogen, by synthetic embodiment 2 preparations), hydrogen peroxide (Aldrich, 50% weightaqueous solution of 40g, 0.588 mole) and water (109.4g).With this flask stopper beyond the Great Wall, after initial exotherm, at room temperature stirred solution spends the night.
1H-NMR (D
2O) the spectrum methylene peak that is presented at the 2.5-3.0ppm place all is moved to～3.5ppm.The 0.5%Pd/Al grain of adding～5g in this solution, make solution at room temperature place～3 days.The superoxide test paper is presented in this system and does not stay superoxide.This material stores by 46.5% aqueous solution.Synthetic embodiment 4-PEI 1800 E
7The formation of amine oxide
In the 500ml erlenmeyer flask that magnetic stirring bar is housed, add molecular weight and be 1800 and each nitrogen ethoxylation degree to poly-(ethyleneimine) (PEI-1800 of about 7 oxyethyl groups, E7) (209g, 0.595mol nitrogen, by synthetic embodiment 1 preparation) and hydrogen peroxide (30% weightaqueous solution of 120g, 1.06 moles).With this flask stopper beyond the Great Wall, after initial exotherm, at room temperature stirred solution spends the night.Obtain by the reaction mixture sample
1H-NMR (D
2O) spectrum shows conversion fully.The response of the methene proton adjacent with unoxidized nitrogen is moved to～3.5ppm from～2.5ppm original position.In this solution, add the 0.5%Pd/Al grain of about 5g, solution was at room temperature placed about 3 days.Test soln also finds to show to superoxide it is negative by indication paper.Resulting material is suitable to be stored by 51.1% active water solution.Synthetic embodiment 5-PEI 1200 E
1Preparation
Steps A)-and in the stainless steel autoclave of 2 gallons of stirrings, carrying out ethoxylation, this autoclave is equipped with temperature survey and function unit, pressure measurement unit, decompression member and inert gas purge parts, sampling parts and is used to be incorporated as the parts of the oxyethane of liquid.Lay the oxyethane steel cylinder (ARC) of about 20 pounds of net weight, carry in autoclave by pump to be the oxyethane of liquid, this steel cylinder is placed on the scale amount dish, so that can monitor the changes in weight of steel cylinder.
In autoclave, add 750g polymine (PEI) (have 1200 listed molecular-weight average, equal about 0.625 moles of polymer and 17.4 mole of nitrogen functional groups).Sealing autoclave then, purge out air (by providing-28 " decompression of Hg, then with nitrogen pressure to 250 pound/inch
2, connect normal atmosphere then).Material to 130 when decompression is provided in the heating high-pressure still ℃.After about 1 hour, autoclave is charged into nitrogen to about 250 pounds/inch
2, cool off autoclave simultaneously to about 105 ℃.Oxyethane is added in the autoclave through for some time in the mode that increases progressively then, monitor the flow velocity of pressure, temperature and the oxyethane of autoclave simultaneously closely.Closing ring oxidative ethane pump, cooling is risen because of the temperature that any exothermic heat of reaction causes with restriction.Temperature is maintained between 100-110 ℃, allows simultaneously that total pressure rises gradually in reaction process.After amounting to 750 gram oxyethane to be added into autoclave (equal every mole of PEI nitrogen functional group roughly 1 moles of ethylene oxide is arranged), temperature increases to 110 ℃, makes the autoclave restir 1 hour.At this moment, provide decompression to remove any residual unreacted oxyethane.
Step B)-then by the gas dispersion screen plate, feed about 100 cubic feet of rare gas elementes (argon gas or nitrogen) and, make the reaction mixture deodorization, stir simultaneously and heated mixt to 130 ℃ by reaction mixture.
Final reacting product is slightly cooled off and is collected in the Glass Containers of crossing with nitrogen purging.
In other preparation, neutralization and deodorization are to finish in reactor before the product discharging.
PEI 1200E if desired
7, between steps A and B, add following catalyzer and add step.
Decompression is provided continuously, and autoclave is cooled to about 50 ℃ simultaneously, is added in 25% sodium methylate (1.74 moles have 10% catalyst loading based on the PEI nitrogen functional group) of the 376g in the methanol solution simultaneously.Under reduced pressure, methylate solution is aspirated in the autoclave, improve the design temperature to 130 ℃ of autoclave temp controller then.Use a kind of equipment to monitor the power that agitator consumes.The power of monitoring agitator, and temperature and pressure.Along with methyl alcohol is removed from autoclave, agitator power and temperature value rise gradually, and the viscosity of mixture increases and stablized about 1 hour, shows that most of methyl alcohol are removed.Mixture is reheat and stirring 30 minutes under reduced pressure.
Remove decompression, autoclave is cooled to 105 ℃, charges into nitrogen to 250 pound/inch simultaneously
2, connect environmental stress then.Autoclave charges into nitrogen to 200 pound/inch
2In autoclave, add oxyethane in the mode that increases progressively again, monitor the flow velocity of pressure, temperature and the oxyethane of autoclave then closely, maintain the temperature at simultaneously between 100-110 ℃, and restriction is because any temperature rising that exothermic heat of reaction causes.Through several hours, add 4500g oxyethane after (obtain every mole of PEI nitrogen functional group 7 moles of ethylene oxide of total arranged), temperature rises to 110 ℃, restir mixture 1 hour.
Reaction mixture is collected in the container that nitrogen purging crosses then, is transferred to 22L at last and is equipped with in the three neck round-bottomed flasks of heating and mixing component.Add in the 167g methylsulfonic acid (1.74 moles) and alkali catalyst.
Can prepare other preferred examples for example PEI 1200 E2, PEI 1200 E3, PEI1200 E15 and PEI 1200 E20 by the relative quantity of above method by the oxyethane adjusting the reaction times and in reaction, use.
The corresponding oxidation amine of above ethoxylation PEI also can prepare according to synthetic embodiment 4.9.7% quaterisation of synthetic embodiment 6-PEI 1200 E7
The adding ethoxylation degree is 7 poly-(ethyleneimine) in the 500ml erlenmeyer flask that magnetic stirring bar is housed, and MW1200 (248.4g, 0.707 mole of nitrogen is by synthetic embodiment 5 preparations) and acetonitrile (Baker, 200ml).Immediately all methyl-sulfates (Aldrich, 8.48g, 0.067 mole) are added in this solution that stirs fast, stopper and stirring are at room temperature spent the night beyond the Great Wall then.Under～60 ℃, on rotatory evaporator, evaporate acetonitrile, under～80 ℃, obtain～the required material of 220g then through Kugelrohr apparatus (Aldrich), be the chocolate thick liquid.
13C-NMR (D
2O) spectrum be presented at～there is not the peak corresponding to methyl-sulfate in the 58ppm place.
1H-NMR (D
2O) spectrum peak (methylene radical that is connected with the not quaternized nitrogen-atoms) partial dislocation that is presented at the 2.5ppm place is to～3.0ppm.4.7% oxidizing reaction of synthetic quaternised PEI 1200 E7 of embodiment 7-9.5%
In the 500ml erlenmeyer flask that magnetic stirring bar is housed, add ethoxylation degree and be 7 and with quaternised gather (ethyleneimine) of methyl-sulfate～9.5%, MW1200 (144g,～0.37 mole of oxidable nitrogen, press embodiment 6 preparations), hydrogen peroxide (Aldrich, 35.4g 50% weightaqueous solution, 0.52 mole) and water (100g).With this flask stopper beyond the Great Wall, after initial exotherm, at room temperature stirred solution spends the night.
1H-NMR (D
2O) the spectrum methylene peak that is presented at the 2.5-3.0ppm place all is moved to～3.5ppm.What adding was enough just in this solution is the sodium bisulfite of 40% aqueous solution, makes residual amount of peroxides reduce to 1-5ppm.The sodium sulfate that forms causes aqueous phase separation, and it contains salt, but seldom or do not have an organism.Remove aqueous salt phase, obtain the polyethylenimine derivates of required oxidation, and store by 52% aqueous solution.
Embodiment 1
Following composition is according to composition of the present invention
Embodiment 2
| Actives (content %) | ????Ⅰ | ????Ⅱ | ????Ⅲ | ????Ⅳ | ????Ⅴ |
| ?Dye?Fix1 | ????5.0 | ????5.0 | ????5.0 | ????5.0 | ????10.0 |
| ?PEI?1200?E1 | ????- | ????10.0 | ????20.0 | ????5.0 | ????20.0 |
| ?DEQA | ????- | ????- | ?????- | ????- | ?????- |
| ?Bayhibit?AM | ????1.0 | ????0.2 | ????1.0 | ????1.0 | ????1.0 |
| ?NH 4Cl | ????- | ????- | ????0.2 | ????0.2 | ????0.5 |
| ?SRP2 | ????- | ????- | ?????- | ????0.5 | ????1.0 |
| ?MgCl 2 | ????- | ????- | ?????- | ????- | ????4.0 |
| Whitening agent 1 | ????- | ????- | ?????- | ????- | ????0.2 |
| Insoluble precipitate reduces agent 3 | ????5 | ????10 | ????10 | ????5 | ????10 |
| Water and submember surplus to 100 |
Following composition is according to composition of the present invention
| Component | Ⅰ | ?Ⅱ | Ⅲ | Ⅳ | ?Ⅴ |
| Insoluble precipitate reduces agent 1 | ??1.0 | ???- | ?- | ?5.0 | ???5.0 |
| Insoluble precipitate reduces agent 2 | ??- | ???- | ?- | ?2.5 | ???2.5 |
| Insoluble precipitate reduces agent 5 | ??- | ???2.0 | ?2.0 | ??- | ????- |
| DEQA | ??2.6 | ???18.0 | ?19.0 | ??- | ????- |
| TAE25 | ??- | ???1.0 | ?- | ??- | ????- |
| Lipid acid | ??0.3 | ???1.0 | ?- | ??- | ????- |
| Hydrochloric acid | ??0.02 | ???0.02 | ?0.02 | ??- | ????- |
| PEG | ??- | ???0.6 | ?0.6 | ??- | ????- |
| Spices | ??1.0 | ???1.0 | ?1.0 | ?0.1 | ???0.1 |
| Polysiloxane defoamers | ??0.01 | ???0.01 | ?0.01 | ??- | ????- |
| PEI?1200?E4 | ??3 | ???3 | ?- | ?15 | ????- |
| TPTA | ??- | ???- | ?5 | ??- | ???10 |
| Laking agent 1 | ??1.0 | ???- | ?5.0 | ??- | ???10 |
| Laking agent 2 | ??- | ???3 | ?- | ?5.0 | ????- |
| HEDP | ??0.2 | ???- | ?- | ?0.4 | ????- |
| Ionogen (ppm) | ??- | ???600 | ?1200 | ??- | ????- |
| Dyestuff (ppm) | ??10 | ???50 | ?50 | ??- | ????- |
| Water and submember surplus to 100 | |||||
| Component | Ⅵ | ?Ⅶ | ?Ⅷ | ?Ⅸ |
| Insoluble precipitate reduces agent 4 | ?2.5 | ??5.0 | ?10.0 | ?1.0 |
| DTDMAC | ?- | ??- | ??- | ?15 |
| DEQA | ?2.6 | ?19.0 | ??- | ?- |
| TAE25 | ?0.3 | ??- | ??- | ?- |
| Lipid acid | ?0.3 | ??- | ??- | ?- |
| Hydrochloric acid | ?0.02 | ?0.02 | ??- | ?0.02 |
| PEG | ?- | ?0.6 | ??- | ?0.6 |
| Spices | ?1.0 | ?1.0 | ?0.1 | ?1.0 |
| Polysiloxane defoamers | ?0.01 | ?0.01 | ??- | ?0.01 |
| PEI?1800?E4 | ?3 | ?3 | ?10 | ?3 |
| Laking agent 1 | ?1 | ?3.0 | ?10 | ?1 |
| Laking agent 2 | ?2 | ??- | ??- | ?2 |
| Ionogen (ppm) | ?- | ?600 | ??- | ?600 |
| Dyestuff (ppm) | ?10 | ?50 | ??- | ?50 |
| Water and submember surplus to 100 | ||||
Be according to composition of the present invention below as the composition that adds the tablet in the moisture eliminator to
| Ⅰ | ?Ⅱ | Ⅲ | Ⅳ | ?Ⅴ | ?Ⅵ | |
| Insoluble precipitate reduces agent 3 | ?10.0 | ?5.0 | ?2.5 | ?1.0 | ?5.0 | ?0.1 |
| DOEQA | ?40 | ?25 | ?- | ??- | ??- | ?- |
| DHEQA | ?- | ??- | ?20 | ??- | ??- | ?- |
| DTDMAMS | ?- | ??- | ??- | ?20 | ?12 | ?60 |
| SDASA | ?30 | ?30 | ?20 | ?30 | ?20 | ?- |
| Glycosperse?S-20 | ?- | ??- | ?10 | ?- | ??- | ?- |
| Zerol | ?- | ??- | ??- | ?20 | ?10 | ?- |
| Clay | ?4 | ?4 | ??3 | ?4 | ?4 | ?- |
| Spices | ?0.7 | ?1.1 | ?0.7 | ?1.6 | ?2.6 | ?1.4 |
| PEI?1800?E1 | ??- | ?5 | ?- | ?- | ?- | ?- |
| PEI?1200?E4 | ??- | ?- | ?4 | ?2.2 | ?- | ?- |
| PEI?1800?E4 | ?2 | ?- | ?- | ?- | ?5 | ?7.0 |
| Laking agent 1 | ?2 | ?5 | ?4 | ?2.2 | ?5 | ?3 |
| HEDP | ?0.2 | ?- | ?0.5 | ?- | ?- | ?0.7 |
| Oxyacetic acid | ??- | ?0.2 | ?- | ?0.2 | ?- | ??- |
| Poly carboxylic acid | ??- | ?0.2 | ?- | ?- | ?0.4 | ??- |
| Stearic acid is a surplus | ||||||
Following detergent formulation S and T are according to prescription of the present invention
Embodiment 5
| ?S | ?T | |
| Zeolite A | ?24.0 | ?23.0 |
| Vitriol | ?9.0 | ??- |
| MA/AA | ?4.0 | ?4.0 |
| LAS | ?8.0 | ?8.0 |
| TAS | ?- | ?2.0 |
| Silicate | ?3.0 | ?3.0 |
| CMC | ?1.0 | ?0.4 |
| Whitening agent | ?0.2 | ??- |
| Soap | ?1.0 | ??- |
| DTPMP | ?0.4 | ?0.4 |
| C45E7 | ?2.5 | ?2.0 |
| C25E3 | ?2.5 | ?2.0 |
| Polysiloxane defoamers | ?0.3 | ?5.0 |
| Spices | ?0.3 | ?0.3 |
| Carbonate | ?13.0 | ?16.0 |
| Citrate trianion | ?- | ?5.0 |
| PB4 | ?18.0 | ??- |
| PB1 | ?4.0 | ?14.0 |
| TAED | ?3.0 | ?6.0 |
| Photoactivated SYNTHETIC OPTICAL WHITNER | ?0.02％ | ??- |
| Savinase | ?1.0 | ?1.0 |
| Lipolase | ?0.4 | ?0.4 |
| Termamyl | ?0.30 | ?0.6 |
| Carezyme | ?- | ?0.6 |
| PEI?1800?E7AO | ?1.0 | ??- |
| PEI?1200?E7AO | ?- | ?1.0 |
| Laking agent 1 | ?2.0 | ?1.0 |
| Insoluble precipitate reduces agent 4 | ?0.5 | ?0.5 |
| HEDP | ?0.2 | ??- |
| Oxyacetic acid | ?- | ?0.2 |
| Poly carboxylic acid | ?- | ?0.2 |
| Surplus (water and other) is to 100 | ||
Preparation is according to following liquid detergent formula of the present invention.
| ?U | |
| C25AS | ?13 |
| C25E3S | ?2 |
| TFAA | ?6 |
| C12-14 alkyl dimethyl hydroxyethyl ammonium chloride | ?1 |
| Cationic ester | ?1.5 |
| TPKFA | ?15 |
| Citric acid | ?1 |
| Ethanol | ?2 |
| 1,2 propylene glycol | ?8 |
| NaOH transfers to pH | ?7.5 |
| DTPMP | ?1.2 |
| Savinase | ?0.5 |
| Termamyl(300?KNU/g) | ?0.15 |
| Boric acid | ?1.5 |
| The mild clay of bentonite type | ?4 |
| The clay SD3 of suspension effect | ?0.3 |
| PEl?1200?E7 | ?1 |
| Laking agent 2 | ?1 |
| Insoluble precipitate reduces agent 5 | ?0.2 |
| Surplus (water and other) | ?100 |
Claims (11)
1. Fabrid care composition, it comprises:
ⅰ) nitrogenous compound, its be selected from poly-amino-functional polymkeric substance, laking agent and its mixture and
ⅱ) insoluble precipitate reduces agent, and it is selected from the water-soluble cationic tensio-active agent; Polyoxyalkylene alkylamine surfactant and its mixture; Condition is that the content of this polymkeric substance is greater than 1% weight when unique nitrogenous compound is poly-amino-functional polymkeric substance.
2. according to the composition of claim 1, wherein said water-soluble cationic tensio-active agent has formula:
[R
1N
+R
3] X R wherein
1Be C
10-C
22There are C in alkyl, or corresponding ester bond group at interval between ester bond and N
1-C
4Alkylidene group, each R is C
1-C
4The alkyl of alkyl or replacement, or hydrogen and counter ion X-are the compatible negatively charged ion of softening agent.
3. according to the composition of claim 2; wherein the water-soluble cationic tensio-active agent is selected from N; N dimethyl-N-(2-hydroxyethyl)-N-dodecyl/Tetradecylammonium bromide, myristoyl cholinesterase quaternary ammonium methyl halogenide, lauroyl cholinesterase ammonium methyl halogenide, cocoyl cholinesterase quaternary ammonium methyl halogenide and its mixture.
4. the composition arbitrary according to claim 1-3, wherein the polyoxyalkylene alkylamine surfactant has formula:
Wherein R is selected from C
7-C
21Straight chained alkyl, C
7-C
21Branched-chain alkyl, C
7-C
21Straight alkenyl, C
7-C
21Branched alkenyl and its mixture; R
1It is ethylidene; R
2Be selected from C
3-C
4Straight chained alkyl, C
3-C
4Branched-chain alkyl and its mixture; R
3Be selected from hydrogen, C
1-C
4Straight chained alkyl, C
3-C
4Branched-chain alkyl and its mixture; R
4Be selected from hydrogen, C
1-C
4Straight chained alkyl, C
3-C
4Branched-chain alkyl and its mixture; A is:
R
5Be selected from-[(R
1O)
x(R
2O)
y] unit, C
1-C
16Straight chained alkyl, C
1-C
16Branched-chain alkyl, C
1-C
16Straight alkenyl, C
1-C
16Branched alkenyl and its mixture;
Wherein subscript m is 1 or 2, and subscript n is 0 or 1, and condition is when m equals 1, and n equals 1; With when m is 2, n is 0;
Wherein subscript x is that 0-is about 50, preferred 1-25,
Wherein subscript y is 0-about 10;
Wherein subscript q is 0 or 1.
5. according to the composition of claim 4, wherein said subscript x is 1-25.
6. according to claim 4 or 5 arbitrary compositions, wherein said subscript m equals 2, and n equals 0.
7. the composition arbitrary according to claim 1-6, wherein said polymkeric substance comprise and have polyamine formula V
(n+l)W
mY
nThe polyamine main chain of Z corresponding to following formula:
Or has a polyamine formula V
(n-k+1)W
mY
nY ＇
kThe polyamine main chain of Z corresponding to following formula:
, wherein k is less than or equal to n, and the molecular weight of described polyamine main chain is greater than 200 dalton, wherein
ⅰ) the V unit is the end unit with following formula:
Or
Or
ⅱ) the W unit is the backbone units with following formula:
Or
Or
ⅲ) the Y unit is the branching unit with following formula:
Or
Or
With
ⅳ) Y ＇ unit is the branch point of main chain or branching ring, and it has following formula:
Or
Or
ⅴ) the Z unit is the end unit with following formula:
Or
Or
The R unit that wherein connects main chain is selected from C
2-C
12Alkylidene group, C
4-C
12Alkylene group, C
3-C
12Hydroxyl alkylidene group, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-(R
1O)
xR
1-,-(R
1O)
xR
5(OR
1)
x-,-(CH
2CH (OR
2) CH
2O)
z(R
1O)
yR
1(OCH
2CH (OR
2) CH
2)
w-,-C (O) (R
4)
rC (O)-,-CH
2CH (OR
2) CH
2-and its mixture; R wherein
1Be selected from C
2-C
6Alkylidene group and its mixture; R
2Be selected from hydrogen ,-(R
1O)
xB and its mixture; R
4Be selected from C
1-C
12Alkylidene group, C
4-C
12Alkylene group, C
8-C
12Aryl alkylene, C
6-C
10Arylidene and its mixture; R
5Be selected from C
1-C
12Alkylidene group, C
3-C
12Hydroxy alkylidene, C
4-C
12Alkyl sub-dihydroxy, C
8-C
12The dialkyl group arylidene ,-C (O)-,-C (O) NHR
6NHC (O)-,-R
1(OR
1)-,-C (O) (R
4)
rC (O)-,-CH
2CH (OH) CH
2-,-CH
2CH (OH) CH
2O (R
1O)
yR
1OCH
2CH (OH) CH
2-and its mixture; R
6Be selected from C
2-C
12Alkylidene group or C
6-C
12Arylidene; R ＇ unit is selected from hydrogen, C
1-C
22Alkyl, C
3-C
22Alkenyl, C
7-C
22Arylalkyl, C
2-C
22Hydroxyalkyl ,-(CH
2)
pCO
2M ,-(CH
2)
qSO
3M ,-CH (CH
2CO
2M) CO
2M ,-(CH
2)
pPO
3M ,-(R
1O)
xB ,-C (O) R
3With its mixture; B is selected from hydrogen, C
1-C
6Alkyl ,-(CH
2)
qSO
3M ,-(CH
2)
pCO
2M ,-(CH
2)
q(CHSO
3M) CH
2SO
3M ,-(CH
2)
q-(CHSO
2M) CH
2SO
3M ,-(CH
2)
pPO
3M ,-PO
3M and its mixture; R
3Be selected from C
1-C
18Alkyl, C
7-C
12Arylalkyl, C
7-C
12Aryl, C that alkyl replaces
6-C
12Aryl and its mixture; M is hydrogen or water-soluble cationic, and its quantity is enough to satisfy charge balance; X is a water soluble anion; The m value is 2-700; The n value is O-350; The p value is 1-6, and the q value is 0-6; The r value is 0 or 1; The w value is 0 or 1; The x value is 1-100; The y value is 0-100; The z value is 0 or 1.
8. the composition arbitrary according to claim 1-7, wherein said laking agent are the laking agent of cellulolytic activity.
9. the composition arbitrary according to claim 1-8, nitrogenous compound wherein accounts for the weight of composition by actives, is 1%-25%, most preferably 1%-10%.
10. tensio-active agent is used to reduce or is suppressed at the purposes of formation insoluble precipitate on the fabric that contact with said composition or the washing machine parts in the composition that comprises the nitrogenous compound that is selected from poly-amino-functional polymkeric substance, laking agent and its mixture.
11. according to the purposes of claim 9, wherein said tensio-active agent is selected from the water-soluble cationic tensio-active agent; Polyoxyalkylene alkylamine surfactant, water-insoluble softening compound thing and its mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98814179 CN1314937A (en) | 1998-07-31 | 1998-07-31 | Fabric care compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98814179 CN1314937A (en) | 1998-07-31 | 1998-07-31 | Fabric care compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1314937A true CN1314937A (en) | 2001-09-26 |
Family
ID=34170449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98814179 Pending CN1314937A (en) | 1998-07-31 | 1998-07-31 | Fabric care compositions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1314937A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736580B (en) * | 2009-12-21 | 2013-08-14 | 北京绿泽宇和科技有限公司 | Fabric maintenance softener |
| CN106590580A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Salinity resistant foam scrubbing agent composition used for drainage gas recovery and preparation method and application thereof |
-
1998
- 1998-07-31 CN CN 98814179 patent/CN1314937A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736580B (en) * | 2009-12-21 | 2013-08-14 | 北京绿泽宇和科技有限公司 | Fabric maintenance softener |
| CN106590580A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Salinity resistant foam scrubbing agent composition used for drainage gas recovery and preparation method and application thereof |
| CN106590580B (en) * | 2015-10-20 | 2019-07-09 | 中国石油化工股份有限公司 | Anti- salinity water pumping gas production foam discharging agent composition and the preparation method and application thereof |
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