CN1047619C - Detergent comositions inhibiting dye transfer - Google Patents
Detergent comositions inhibiting dye transfer Download PDFInfo
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- CN1047619C CN1047619C CN93120225A CN93120225A CN1047619C CN 1047619 C CN1047619 C CN 1047619C CN 93120225 A CN93120225 A CN 93120225A CN 93120225 A CN93120225 A CN 93120225A CN 1047619 C CN1047619 C CN 1047619C
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/75—Amino oxides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3792—Amine oxide containing polymers
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Polyesters Or Polycarbonates (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to inhibiting dye transfer compositions comprising polyamine N-oxide containing polymers and terephthalate-based polymers.
Description
Dye for fabrics transfer compositions and method when the present invention relates to eliminate washing.
In the modern fabrics washing process, at most and one of problem of trouble is that some colored fabrics can discharge some dyestuffs in washings, and dyestuff will be transferred to other fabric that together washs and gets on then.
A method that addresses this problem be when washing the dyestuff of stripping attached to other article on before with regard to complexing or adsorb the dyestuff that these discharge from colored fabric.Some polymkeric substance often are used in the detergent composition so that eliminate dye transfer, for example referring to EP-A-0, and 102,923, DE-A-2,814,329, FR-A-2,144,721 and EP-265,257.
Unsettled european patent application 92202168.8 has been described the elimination dye transfer compositions, and it is formed by containing the polymeric amine n-oxide.
Except the dyestuff combination, prevent that colored fabric released dye in washings from also being important.Have now found that in the time of in adding polymeric amine n-oxide dye transfer composition for eliminating, terephthalic acid ester group dirt release agent polymkeric substance can improve the effect of whole elimination dye transfer.
This discovery has caused highly effective detergent composition prescription aspect the dye transfer that prevents bleeding and elimination dissolved or suspension.
According to another embodiment of the invention, it also provides a kind of washing methods that includes yarn dyed fabric.
Terephthalic acid ester group dirt release agent polymkeric substance also has description in the prior art, for example referring to, GB 2,137,221, US 4,116,885, US, 132,680, EP185,427 EP 199,403, EP241,985 and EP 241,984.
The present invention relates to eliminate dye transfer compositions, it comprises:
A) polymeric amine n-oxide.
B) terephthalate based polyalcohol.
Composition of the present invention is made up of polymeric amine n-oxide (A) and terephthalate based polyalcohol (B) as basic component.
(A) polymeric amine n-oxide
The polymeric amine n-oxide contains the unit of following structural:
Wherein, P is polymerisable unit, and it can be connected with the N-O group, perhaps a wherein part or its two combination of N-O group formation polymerizable unit.A is
-O-.-S-,
X is 0 or 1;
R is aliphatic, ethoxylation aliphatic, fragrance, heterocyclic, the group of alicyclic ring (family) or its any combination, it can be connected with the N-of N-O group or the N of N-O group is the part of these groups.
This N-O group can be represented with following general formula:
R wherein
1, R
2, R
3Be fat (fat) family group, aromatic group, heterocyclic group, or alicyclic ring (family) group or their combination, x or/and Y or/and z is 0 or 1, and wherein the N of N-O group can connect, or wherein the N of N-O group constitutes the part of these groups.
The N-O group can be that the part of polymerizable unit (p) maybe can be connected on the main polymer chain or the two combination.
Suitable polymeric amine n-oxide (wherein the N-O group forms the part of polymerizable unit) comprises the polymeric amine n-oxide that R selects from fat (fat) family, fragrance (family), alicyclic ring (family) or heterocyclic group.
Said polymeric amine n-oxide, one class comprise the wherein polymeric amine n-oxide of the N formation R group part of N-O group.Preferred polymeric amine n-oxide be those wherein R be heterocyclic group for example, pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and their derivative.Another kind of said polymeric amine n-oxide comprises that the N of N-O group wherein is connected the polymeric amine n-oxide on the R group.
Other suitable polymeric amine n-oxide is that the N-O group is connected the polymeric amine n-oxide on the polymerizable unit.A preferred class is the polymeric amine n-oxide with general formula 1 in these polymeric amine n-oxides, and wherein R is aromatic, heterocycle family, the group of alicyclic ring (family), wherein the N in the N-O functional group is the part of said R group.The example of these classes is that wherein R is the polymeric amine n-oxide of heterogeneous ring compound such as pyridine, pyrroles, imidazoles and derivative thereof.
Another kind of preferred polymeric amine n-oxide is the polymeric amine n-oxide with general formula 1, and wherein R is aromatic, and heterocycle be family or alicyclic ring (family) group, and wherein the N in the N-O functional group is connected on the said R group.The example of these classes is that wherein the R group can be the polymeric amine n-oxide of for example phenyl of fragrance.
Any main polymer chain all can adopt, as long as formed amine oxide polymkeric substance is water miscible and has the effect of eliminating dye transfer.The example of suitable polymers main chain is polyvinyls, poly-inferior hydrocarbon compound, polyester, polyethers, polymeric amide, polyimide, polyacrylate and their mixture.
Amine n-oxide polymkeric substance of the present invention, wherein the ratio of amine and amine n-oxide is 10: 1 to 1: 1000000 typically.Yet the quantity of the amine oxide group that exists in the polymeric amine n-oxide can change by the N-oxidation of suitable copolymerization and suitable degree.The ratio of this amine and amine n-oxide is preferably from 3: 1 to 1: 1000000.In fact multipolymer of the present invention comprises random or segmented copolymer, and one of them haplotype is an amine n-oxide, and another haplotype is N-oxide compound or other.
The amine oxide unit of polymeric amine n-oxide, its Pka＜10, preferably Pka＜7 more preferably are Pka＜6.
The polymeric amine n-oxide almost can obtain with the polymerization of any degree.Have only this material to have desired water-soluble and dye suspension power, the copolymerization degree is not crucial.
Molecular weight is typically at 500-1000, in 000 the scope; More preferably 1000 to 500,000; Most preferably 5000 to 100,000.
Polymeric amine n-oxide of the present invention typical amount in eliminating dye transfer compositions weight is 0.01 to 10%, 0.05-1% more preferably, most preferably 0.05 to 0.5%.
(B) terephthalic acid fat base dirt release agent polymkeric substance
Be surprised to find that now that by adding the dirt release agent polymkeric substance total efficiency of the elimination dye transfer of the detergent composition of being made up of the polymeric amine n-oxide will improve.
Confirmed that the polymeric amine n-oxide has improved the adsorptive power of terephthalic acid fat base dirt release agent polymkeric substance to fabric.Its result, the dirt release agent polymkeric substance is adsorbed on the fabric face that is immersed in the washings preferably.Confirm that also end group produces frees the performance of dirt, the absorption on fabric is important and backbone structure is for polymkeric substance.The polyester that is adsorbed then forms the film that prevents the fabric bleeding on fabric.Said terephthalate based polyalcohol and the combination that contains the polymeric amine n-oxide can be formed on us and prevent bleeding and eliminate dyestuff generation transfer aspect lysed or that suspend and more effectively eliminate dye transfer compositions.
Composition of the present invention comprises the terephthalic acid ester group dirt release agent polymkeric substance that accounts for elimination dye transfer composition total weight 0.01 to 10%.Preferably 0.05% to 5%.Such dirt release polymer is extensively described in the prior art, US.4 for example, and 116,885, US4,132,680, EP185 427, and EP 199 403, EP 241,985 and EP 241,984.
The polymkeric substance that comprises following general formula at this polymkeric substance that is suitable for: X-
(OCH
2CH (Y)) n (OR
5) m
A-R
1-A-R
2) u (A-R
3-A-R
2) v
-A-R
4-A
(R
5O) m (CH (Y) CH
2O) n
X in following formula, [(A-R
1-A-R
2) u (A-R
3-A-R
2) v] A-R
4-A partly forms the main chain of this compound oligopolymer or polymkeric substance.Connecting the A part mainly is
Or
Part, compound promptly of the present invention is a polyester." the A part mainly is in that this is said
Or
Part " refer to A part fully by
Or
Part is formed or part for example is connected part
Or
(acid amides) and
Or
The compound that (urethane fat) replaces.The degree of carrying out the part replacement with these connection portions should make the performance of freeing dirt can not be subjected to too big baneful influence.Preferred connection portion A is fully by (100% forms)
Or
Part is formed, i.e. each A or be
Be
R
1Part mainly is the 1.4-phenylen moiety.When this uses, term " R
1Part mainly is 1, the 4-phenylen moiety " refer to R
1Part is fully by 1, and is that the 4-phenylen moiety is formed or with other arylidene or alkarylene part, alkylene moiety, and the chain alkenylene is partly or the compound that partly replaces of their mixture.Be used for 1, arylidene or alkylene moiety that the part of 4-phenylene replaces comprise 1,3-phenylene, 1,2-phenylene, 1,8 naphthylidene, 1,4-naphthylidene, 2,2-biphenylene, 4-4 '-biphenylene and their mixture.The alkylidene group and the chain alkenylene that can partly be replaced comprise ethylene, propylene, and tetramethylene, pentamethylene, hexamethylene, 1, the inferior heptyl of 7-, 1-8-is octylene, and 1,4-cyclohexylene, and their mixture.
For R
1Part, with removing 1, the intensity that the part beyond the 4-phenylene is carried out the part replacement should make the performance of freeing dirt of compound can not be subjected to too big baneful influence.General endurable part replacement degree depends on the length of compound main chain, and promptly main chain is long more, and the degree that partly replaces the 1-4 phenylene just can be big more.Usually, R
1By about 50 to 100% 1, the compound that the 4-phenylen moiety is formed (0-50% removes 1, the part beyond the 4-phenylene) has the suitable performance of freeing dirt.For example according to polyester of the present invention, it is that 40: 60 m-phthalic acid (1, the 3-phenylene) makes with terephthalic acid (1, the 4-phenylene) by molar ratio, and it just has the suitable performance of freeing dirt.Yet the polyester that is used for the overwhelming majority of fiber manufacturing is made up of terephthalic acid ethyl unit, and therefore, in order to obtain the best performance of freeing dirt, people always expect will be except that 1, and the 4-phenylene reduces to minimum with the part replacement degree of outside part.Preferably, R
1Part is fully by (100% forms) 1, and the 4-phenylen moiety is formed, each R
1Part all is 1, the 4-phenylene.
The R2 part mainly is the ethylene part or has C
1-C
4The replacement of alkyl or alkoxy substituent the ethylene part.At this said term " R
2Part mainly is, ethylene part or have C
1-C
4The replacement that alkyl or alkoxyl group replace the ethylene part ", refer to some compound of the present invention, wherein R like this
2Part partly is made up of ethylene or substituted ethylene fully, or is made up of the part that is replaced by other compatible part.The example of these other parts comprises C
3-C
6The straight-chain alkyl-sub-part, trimethylene for example, tetramethylene, pentamethylene, or hexamethylene, 1,2-encircles alkylene moiety, as 1,2-cyclohexylene, 1,4-encircles alkylene moiety, as 1, and 4-cyclohexylene and 1,4-dimethylene cyclohexylene, 1 of polyoxyalkylated, 2-hydroxyl alkylidene group, as
With the oxyalkylene group part, as-CH
2CH
2OCH
2CH
2OCH
2CH
2-or-CH
2CH
2OCH
2CH
2-
For R
2Part, the degree of carrying out the part replacement with these other parts should make the performance of freeing dirt of compound can not be subjected to too big baneful influence.General admissible part replacement degree is decided by the length of compound main chain, and main chain is long more, and part replacement degree is big more usually.Usually, R
2The compound that 1.2-ethylidene by about 20% to 100% ethylene or replacement is partly formed (but other receiving part is divided into 0 to about 80%) has the suitable performance of freeing dirt.For example, polyester of the present invention, it is 75: 25 diethylidene glycol (CH by mol ratio
2CH
2OCH
2CH
2-) and 1,2 ethylene glycol (ethylene) make, it has the suitable performance of freeing dirt.Yet for obtaining the best performance of freeing dirt, part replaces, and particularly wishes to reduce to minimum with the part replacement of oxyalkylene group.In the preparation process according to polyester of the present invention, have a small amount of (as two aklylene glycols) in these alkylidene oxide parts are formed from glycol by side reaction typically, are introduced in the polyester then.Preferably, R
2By about 80-100%1.2-ethylidene, but or the 1.2-ethylidene that replaces part or from 0 to about 20% other receiving part be grouped into.
For R
2Part, the suitable 1.2-ethylidene or the 1.2-ethylidene of replacement partly comprise the 1.2-ethylidene, 1.2-propylidene, 1.2-butylidene, 1.2-hexylidene, 3-methoxyl group-1.2 propylidene and their mixture.R preferably
2Part mainly is a 1.2-ethylidene part, 1.2-propylidene part or their mixture.Confirmed that the content of 1.2-ethylidene part is high more and improved the performance that compound is freed dirt.The high-content that is surprised to find that 1.2-propylidene part can improve the water-soluble of compound.
For R
3Part, the C of suitable replacement
2-C
18Inferior hydroxylic moiety can comprise the C of replacement
2-C
12Alkylidene group, chain alkenylene, arylidene, alkarylene, and similar part.The alkylidene group of these replacements or chain alkenylene part can be straight chains, ramose or ring-like.R
3Part also can be whole identical (as the arylidene of whole replacements), or a kind of mixture (the alkylidene group mixture of the arylidene of replacement and replacement).Preferred R
3Part is the 1.3-phenylen moiety of which replacement.The R of this replacement
3Part preferably has only-individual SO
3M ,-COOM ,-O
(R
5O) m (CH (Y) CH
2O) n
X or-A
(R
2-A-R
4-A)
w
(R
5O) m (CH (Y) (H
2O) n
The X substituting group.But M H or any compatible water-soluble cationic.Suitable water-soluble cationic comprises water miscible basic metal, such as, potassium (K
4) and sodium (Na particularly
+), and ammonium (NH
4 +).Other suitable ion is the ammonium ion with replacement of following general formula:
In the formula, R
1And R
2Each is C naturally
1-C
20Alkyl (as, alkyl, hydroxyalkyl) or form jointly the ring of 4-6 carbon atom or heterocycle (as, piperidines, morpholine); R
3Be C
1-C
20Alkyl; R
4Be H (ammonium) or C
1-C
20Alkyl, (quaternary amine).The typical ammonium cation group that replaces is such group, wherein R
4Be H/ (ammonium) or C
1-C
4Alkyl, particularly methyl (quaternary amine); R
1Be C
10-C
18Alkyl, particularly C
12-C
14Alkyl; And R
2And R
3Each is C naturally
1-C
4Alkyl, particularly methyl have-A
(R
2-A-R
4A)
w
(R
5O) m (CH (Y) CH
2O) n
The substituent R of X
3Part provides the branch backbone compounds.Has A
(R
2-A-R
4-A)
W R
2The R of-A part
3Part provides crosslinked backbone compounds.In fact, the building-up reactions that is used for preparing the branch backbone compounds typically provides some crosslinked backbone compounds at least.
(R
5O) m (CH (Y) CH
2O) n
With
(OCH (Y) CH
2) n (OR
5) m
In the part-(R
5O)-part and-(CH (Y) CH
2O)-part can be mixed in together, or formation-(R preferably
5O)-and-(CH (Y) CH
2O)-block partly.Preferably-(R
5O)-block is near the compound main chain.Work as R
5Be-R
2-A-R
6During-part, m is 1, and ,-R
2-A-R
6-part is preferably near the main chain of compound, for R
5, preferred C
3-C
4Alkylidene group is C
3H
6(1.2-propylidene); Work as R
3Be C
3-C
4During alkylidene group, m preferably 0 to about 5 and O most preferably.R
6Preferably methylene radical or 1.4-phenylene.-(CH (Y) CH
2O)-partly preferably by about at least 75% (wt)
(R
5O) m (CH (Y) CH
2n
Part, most preferably 100% forms (m is o).
Each
(R
5O) m (CH (Y) CH
2) n
The Y substituting group of part can be-CH
2(OCH
2CH
2) the pO-X ether moiety, or be typically the miscellany of this ether moiety and H more; P can be between 0 to 100, but is typically O.When the Y substituting group is mixture ,-(CH (Y) CH
2O) n-can use with the lower section and represent:
N wherein
1At least be 1, and n
1+ n
2Total amount be n.Typically, n
1Mean value be approximately 1 to 10.Part
With
Can be mixed in together, but form block typically with the lower section
With
Part
X can be H, C
1-C
4Alkyl or
, R in the formula
7Be C
1-C
4Alkyl.X is methyl or ethyl preferably, but methyl most preferably.It is about 6 that the numerical value of each n is at least, but preferably be 10 approximately at least.The numerical value of each n is usually greatly between 12 to 113.Typically, the n value is greatly between 12 to 43.
Main chain part A-R
1-A-R
2 and A-R
3-A-R
2 can mix, and also can form A-R
1-A-R
2 and A-R
3-A-R
2 part block.The numerical value of having found u+V approximately is at least 3 so that make compound of the present invention have the suitable performance of freeing dirt.The maximum value of u+V is usually by the method decision for preparing compound, but can reach 25, that is to say that compound of the present invention is oligopolymer or low-molecular-weight polymkeric substance.Comparatively speaking, the polyester that is used for fiber production typically has much higher molecular weight, and about 50 to 250 terephthalic acid ethyl unit are for example arranged.For compound of the present invention, the total amount of u+V is typically greatly between 3 to 10.
Ordinary u+V value is big more, and the solubility property of compound is more little, particularly works as R
3The part do not have substituting group-COOM or-SO
3In the time of M.The n value increases in addition, and u+V value also should increase so that can be deposited on the fabric better when compound is washed.Work as R
3Part has limit Dai Ji-A-
(R
2-A-R
4-A)
w
(R
5O) m (CH (Y) CH
2O) n
X (branch backbone compounds) or-A-
(R
2-A-R
4-A)
WR
2During-A-(crosslinked backbone compounds), V typically is at least 1 and by the decision of the manufacture method of compound.For these branches or crosslinked backbone compounds, the value of u+V+W is greatly between 3 to 25.
In this base polymer, preferred compound is the block polymer with following general formula,
Wherein, R
1Part is the 1.4-phenylen moiety entirely; R
2Part mainly is a 1.2-ethylidene part, 1.2-propylidene part or their mixture; R
3Part is potassium or sodium 5-sulfo group-1.3-phenylen moiety or 5 have the following substituent 1.3-phenylen moiety that has replaced in the position preferably entirely,
R
4Part is R
1Or R
3Part, or their mixture, X is ethyl or methyl preferably; Each n
1Be 1 to about 5; n
1+ n
2Total amount approximately be between 12 to 43; When W was 0, u+V approximately was between 3 to 10; When W was 1 at least, u+V+W approximately was between 3 to 10.
Particularly preferred block polymer is that those V are straight chain block polymers of 0.For these most preferred straight chain block polymers, u is typically greatly between 3-8.In these straight chain block polymers, water-soluble best be the u polymkeric substance between 3 to 5 greatly.
The polymkeric substance that comprises following general formula in this other used suitable polymers:
X
(OCH
2CH(Y))
n(OR
4)
m 
(A-R
1-A-R
2)
u(A-R
1-A-R
3)
v
-A-R
1-A-
(R
4O)
m(CH (Y) CH
2O)
n 
X in this general formula,
(A-R
1-A-R
2) u (A-R
1-A-R
3) v
A-R
1-A partly forms this compound oligopolymer or main polymer chain.X-
(OCH
2CH (Y)) n (OR
4) m
With
(R
4O) m (CH (Y) CH
2O) n
The X group generally is connected the end of this oligomer/polymer main chain.
Connecting the A part mainly is
Or
Part, compound promptly of the present invention is a polyester." the A part mainly is term when this uses
Or
Part " refer to like this some compounds, this moment the A part be fully by
Or
Form, or part by such as
And
Or
The connection portion of (urethane) replaces.The degree that is replaced by these connection portions parts should make that the performance of freeing dirt is unlikely to be subjected to too big baneful influence.Preferably part connection portion A is fully by (100% forms)
Or
Part is formed, and each A is
Or
R
1Part mainly is the 1.4-phenylen moiety.At this illustrated term " R
1Part mainly is a 1.4-phenylene portion " refer to wherein R of such Xing's thing
1Part forms by the 1.4-phenylen moiety fully or part by other arylidene, alkarylene, alkylidene group, chain alkenylene partly and their mixture replace.The arylidene or the alkarylene that are used for the replacement of 1.4-phenylen moiety partly comprise the 1.3-phenylene, the 1.2-phenylene, and the 1.8-naphthylidene, the 1.4-naphthylidene, the 2.2-biphenylene, 4.4 '-biphenylene and their mixture.Alkylidene group that can partly replace and chain alkenylene partly comprise the 1.2-ethylidene, the 1.2-propylidene, and the 1.4-butylidene, the 1.5-pentylidene, the 1.6-hexylidene, the inferior heptyl of 1.7-, 1.8-is octylene, 1.4-cyclohexylene and their mixture.
These other arylidene, alkylidene group, chain alkenylene part can be substituted or have at least one-SO
3M ,-COOM-or-A-R
7-
A-R
1-A-R
7-O
WX-substituting group or very rare one-A-R
7 
A-R
1-A-R
7 WA-part and another R
1Partial cross-linked, R wherein
7Be R
2Or R
3Part; W is 0 or is 1 at least.Preferably, the R of these replacements
1Part has only one-SO
3M ,-COOM-or-A-R
7 A-R
1-A-R
7-O
W X substituting group.M can be H or any compatible water-soluble cationic.Suitable water-soluble cationic comprises water miscible basic metal, for example potassium (K
+), particularly preferably be sodium (Na
+) and ammonium (NH
4 +).And suitable substituted ammonium ion has following general formula:
In the formula, R
1And R
2Each is C naturally
1-C
20Hydrocarbyl group (as alkyl or hydrocarbon alkyl), or their common ring or heterocycles (as piperidines, morpholine) that forms 4-6 carbon atom; R
3Be C
1-C
20Hydrocarbyl group; R
4Be H (ammonium) or C
1-C
20Alkyl (quaternary ammonium), the typical ammonium cation group that replaces is such group, wherein R
4Be H (ammonium) or C
1-C
4Alkyl, preferably methyl (quaternary ammonium); R
1Be C
10-C
18Alkyl, particularly C
12-C
14Alkyl; R
3And R
2Each is C naturally
1-C
4Alkyl, particularly methyl.
Contain-A-R
7 
A-R
1-A-R
7-O
The substituent R of w
1Part provides the branch backbone compounds.Have-A-R
7-
A-R
1-A-R
7 The R of wA-part
1Crosslinked backbone compounds is provided.In fact the building-up reactions that is used to prepare the branch backbone compounds typically provides some crosslinked backbone compounds at least.
For R
1Part, the degree of carrying out the part replacement with the part except that the 1.4-phenylene should make the performance of freeing dirt of compound be unlikely to be subjected to too big baneful influence.Usually, the part replacement degree that can allow depends on the backbone length of compound, and promptly main chain is long more, and the degree of the replacement of 1.4-phenylen moiety is also just big more.Usually work as R in the compound
1When containing about 50-100%1.4-phenylen moiety (removing the 1.4-phenylen moiety from 0-50%), this compound has the appropriate performance of freeing dirt.Yet, comprise terephthalic acid ethyl unit owing to be used for most of polyester of fiber manufacturing, in order to obtain the best performance of freeing dirt, carry out the degree of part replacement with the part except that the 1.4-phenylene and always wish to reduce to minimum.R preferably
1Part is made up of (promptly 100% forms) 1.4-phenylene fully, i.e. each R
1Part all is the 1.4-phenylene.
R
2Part mainly is to contain C
1-C
4The replacement of alkyl or alkoxy substituent 1,2.-ethylidene part.At this said term " R
2Part mainly is to contain C
1-C
4The replacement of alkyl or alkoxy substituent 1.2-ethylidene part " refer to like this some compounds of the present invention, this moment R
2Part is fully partly formed or is partly replaced by other compatible part by the 1.2-ethylidene that has replaced.The example of these other parts comprises straight chain C
2-C
6Alkylene moiety, as the 1.2-ethylidene, 1.3-propylidene, 1.4-butylidene, 1.5-pentylidene or 1.6-hexylidene, 1.2-ring alkylene part is as the 1.2-cyclohexylene, 1.4-the ring alkylene moiety is as 1.4-cyclohexylene and 1.4-dimethylene one ring inferior hexyl, the 1.2-hydroxyl alkylidene group of polyoxyalkylated
With such as-CH
2CH
2OCH
2-the oxyalkylene group part.
For R
2Part, the degree that the part of these other parts replaces should make the performance of freeing dirt of compound and the water soluble characteristic of compound be unlikely to be subjected to too big baneful influence.Usually, admissible part replaces degree will depend on desirable dirt and the solubility property of freeing, and (promptly long main chain generally can have the type that bigger part replaces and relate to part to the backbone length of this compound.For example, the degree of partly carrying out the part replacement with the 1.2-hexylidene is big more, and usually, solvability is just more little).Usually, if in the compound, R
2So, this compound just has the suitable performance of freeing dirt to contain about 20 to the 100% 1.2-ethylidene parts (containing other compatible part of 0 to about 80%) that replace.Yet, to render a service in order to obtain best freeing dirt and dissolve, such part replaces always wishes to reduce to minimum.(according to the present invention, in the preparation of polyester, small amounts alkylene moiety (two aklylene glycols can be formed to introduce the polyester then by glycol and go from side reaction).Preferably, R
2The 1.2-ethylidene part that contains the replacement that is approximately 80-100%.But and contain 0 to about 20% other receiving part branch.For R
2Part, the 1.2-ethylidene of suitable replacement partly comprises, 1.2-propylidene, 1.2-butylidene, 3-methoxyl group-1.2-propylidene, and their mixture, preferred R
2Part mainly is a 1.2-propylidene part.
R
3Part mainly is polyoxyethylene base section-(CH
2CH
2O) q-CH
2CH
2-.At this said " R
3Part mainly is polyoxyethylene part-(CH
2CH
2O) z-H
2CH
2-" refer to like this some compound of the present invention, wherein R
3Part partly is made up of the polyoxy ethyl fully, but or also comprises other receiving part branch.These other example comprises C
2-C
6Oxy alkylene part, for example oxygen propylidene and oxygen butylidene; The poly (oxyalkylene) base section for example, polyoxy propylidene and polyoxy butylidene; The hydroxyl alkylene oxide of polyoxy alkanisation, for example
The degree that contains these other parts should make the performance of freeing dirt of this compound be unlikely to be subjected to too big baneful influence.Usually in compound of the present invention, this polyoxyethylene base section comprises about R of 50 to 100%
3Part.Preferably this polyoxyethylene partly comprises the R of 90-100%
3Partly (in polyester manufacture, minute quantity oxygen alkylene part can be connected on the polyoxyethylene base section in side reaction according to the present invention, and introduces R
3In the part).
For the polyoxyethylene base section, the q value is approximately 9 at least, and preferably approximately is at least 12.Between 12-180, typical q value should be between about 12 to about 90 usually for the q value.
Each
(R
5O) m (CH (Y) CH
2O) n
The Y substituting group be H ,-CH
2(OCH
2CH
2) the pO-X ether moiety, or the miscellany of ether moiety and H; P can be between 0 to 100, but is typically O.Typical Y substituting group is H entirely.When the Y substituting group is the miscellany of this ether moiety and H ,-(CH (Y) CH
2O) the n-part is available represents with the lower section:
N wherein
1At least be 1, n
1+ n
2Total amount be the n value, typical n
1, its mean value is greatly between 1 to 10.With the lower section
With-(CH
2CH
2O) n
2-can mix, but typically form block with the lower section,
With-(CH
2CH
2O) n
2
X can be H, C
1-C
4Alkyl or
R in the formula
7Be C
1-C
4Alkyl.X is methyl or ethyl preferably, and methyl most preferably, and each n value is 6 approximately at least, but preferably is 10 approximately at least, and each n value is usually greatly between 12 to 113.Typical each n value is between about 12 to 45.
Main chain part (A-R
1-A-R
2) and (A-R
1-A-R
3) can form (A-R
1-A-R
2) and (A-R
1-A-R
3) part block, but more typical be arbitrarily to be blended in one.For these main chain parts, the mean value of u is between about 2 to 50; The mean value of V is greatly between 1 and 20; Between 3 and 70, u, the mean value of v and u+v are usually by the method decision for preparing compound greatly for the mean value of u+V.Generally, between 5 to 20, between 1 and 10, the mean value of u+V is greatly between 6 and 30 greatly for the mean value of V greatly for the mean value of the big more or u+V of the mean value of V.Usually the ratio of u and V is 1 approximately at least, typically between 1 and 6.
In this base polymer, preferred compound is the polyester with following general formula, X-(OCH
2CH
2)
n 
(CH
2CH
2O)
n-X
Wherein, R
1It is the 1.4-phenylen moiety; R
2It mainly is 1.2-propylidene part; R
3Mainly be the polyoxyethylene base section ,-(CH
2CH
2O) q-CH
2CH
2-; Each X is an ethyl, preferably methyl; N is between about 12-45; Q is between 12 and 90; The mean value of u is about between 5 to 20; The mean value of V is between 1 to 10; The mean value of u+V is between 6 to 30; The ratio of u and V is approximately between 1 to 6.
Have the following formula of opening at a little used more preferably polymkeric substance:
XO(CH
2CH
2n
R
1Part mainly is the 1.4-phenylen moiety, at this said term " R
1Mainly be the 1.4-phenylen moiety " refer to some compounds like this, wherein, R
1Part all is made up of the 1.4-phenylen moiety, or part is used other arylidene, alkarylene part, alkylene moiety, chain alkenylene part and the replacement of their miscellany.Arylidene and alkarylene part that part replaces the 1.4-phenylene can comprise the 1.3-phenylene, the 1.2-phenylene, and the 1.8-naphthylidene, the 1.4-naphthylidene, the 2.2-biphenylene, 4.4 '-biphenylene and their miscellany thereof.The alkylidene group that can partly replace, the chain alkenylene comprises the 1.2-ethylidene, the 1.2-propylidene, the 1.4-butylidene, the 1.5-pentylidene, the 1.6-hexylidene, the inferior heptyl of 1.7-, 1.8-is octylene, 1.4-cyclohexylene and their miscellany.
For R
1Part, the other parts except that the 1.4-phenylene are carried out the performance that degree that part replaces should make compound free dirt and are unlikely to be subjected to too big baneful influence.Usually, admissible part replacement degree depends on the backbone length of compound, and promptly main chain is long more, and the degree that partly replaces the 1.4-phenylen moiety just can be big more.Generally, R in compound
1When comprising the 1.4-phenylen moiety of about 50%-100% (part except that the 1.4-phenylene of 0-50%), this compound has the performance of freeing dirt preferably.For example, adopt m-phthalic acid (1.3-phenylene) and terephthalic acid 1.4-phenylene according to the present invention) mol ratio be the polyester of preparation in 40: 60 o'clock, it has the suitable performance of freeing dirt.Yet comprise the terephthalic acid ethyl owing to be used for the polyester overwhelming majority of fiber manufacturing, thereby in order to obtain the best performance of freeing dirt, the part except that the 1.4-phenylene replaces degree and always wishes to reduce to minimum.R preferably
1Part (i.e. 100% composition) fully is made of each R the 1.4-phenylen moiety
1Part all is the 1.4-phenylene.
To R
2Part, suitable 1.2-ethylidene or the 1.2-ethylidene that has replaced partly comprise: 1.2-ethylidene, 1.2-propylidene, 1.2-butylidene, 3-methoxyl group-1.2-propylidene and miscellany thereof.R preferably
2Part mainly is a 1.2-ethylidene part, or, preferably 1.2-propylidene part or their miscellany.Although the percentage composition of 1.2-ethylidene part is to be subjected to water miscible restriction.Be unexpectedly, the degree of 1.2-propylidene part is higher to improve the water-soluble of compound, and then, improve the ability that forms isotropic water soluble detergent composition and can serious harm not free the performance of dirt.
For the present invention, application 1.2-propylidene part or similar branch equivalent are vital for the composition of freeing dirt of farthest introducing basic content in the heavy duty liquid laundry detergent composition.Preferably, the 1.2-propylidene should account for R greatly
2The 75%-100% of part weight, what be more preferably should account for 90% to 100%.
Usually, the composition that dissolved is freed dirt in cold (15 ℃) ethanol also is applicable to composition of the present invention.
The mean value of n is at least about 10, but the fluctuation to some extent of n value.Between 10 and 50, the mean value of preferred n is between 10 and 25 usually for each n value.
The preferred method that the composition of detergency is separated in preparation comprises such step, at low temperature as being about 10 ℃ to 15 ℃, when being preferably lower than 13 ℃, the polymkeric substance that has a kind of exemplary distribution with anhydrous basically alcohol extraction, wherein, essential part is equal to or greater than 6 material by u and forms.Basically do not had long polymkeric substance also to introduce at an easy rate in isotropic heavy-filth liquid by the part of dissolve with ethanol and go, particularly introducing has in the liquid of more auxiliary agent.Although u approximately less than 3 polymkeric substance for providing the effect of freeing dirt essentially no value, they are compared with going in the easier introducing liquid of the polymkeric substance of high u value.
The preferred method of preparation dirt composition is directly synthetic.
For freeing composition of dirt and preparation method thereof, it is more fully described can be at debatable U.S. Patent application, and ordinal number is to find in 684,511, this application is that Eugene.PGosselink proposed in 1984.12 months 21 days, and the document is hereby incorporated by.
Meet following general formula at this used most preferred polymkeric substance:
X OCH
2CH
2 n
CH
2CH
2O
n?X
X is a methyl in the formula, and n is 16, R
1Be the 1.4-phenylen moiety, R
2Be 1.2-propylidene part, u is basically between 3 and 5.
Detergent builder
This composition can be easily as the additive of washing with conventional washing agent composition.Thereby the present invention also comprises and contains the washing composition composition as the elimination dye transfer compositions of detergent composition.
There is the kinds of surface promoting agent to can be used in the detergent composition.Norris has provided negatively charged ion in the U.S. Pat 3,664,961 of being applied on May 23rd, 1972, nonionic, the exemplary and the kind of amphoteric and these tensio-active agents of amphoteric ion type.
The mixture of anion surfactant is specially adapted to this, and particularly weight ratio is 5: 1 to 1: 2, and being preferably 3: 1 to 2: 3 more preferably is 3: 1 to 1: 1 the sulfonate and the mixture of sulfate surfactant.Preferred sulfonate comprises the alkylbenzene sulfonate (having 9 to 15 in this alkyl, preferably 11 to 13 carbon atoms) and the fatty acid methyl ester of α-sulfonic acid salinization, and (wherein this fatty acid source is in C
12-C
18Fat source is preferably from C
15-C
18Fat source).Positively charged ion all is alkalimetal ion, preferably sodium under each situation.Preferred sulfate surfactant is in the alkyl, the alkyl-sulphate of 12 to 18 carbon atoms is arranged, and optionally with in the alkyl have 10 to 20, and preferably 10 to 16 carbon atoms and average degree of ethoxylation are that 1 to 6 ethoxy sulfate is mixed.At this preferred alkyl-sulphate be fatization alkyl-sulphate, coconut alkyl-sulphate and C
14-C
15Alkyl-sulphate.Positively charged ion under each situation or alkalimetal ion, preferably sodium.
Thereby used in the present invention nonionogenic tenside is the condensation product of oxyethane and hydrophobic part provides that to have average hydrophile-lipophile balance value (HLB) be 8 to 17, is preferably 9.5 to 13.5, more preferably 10 to 12.5 tensio-active agent.This hydrophobic (oleophylic) part is fat (fat) family, aromatics, and and the length of the spissated polyoxyethylene group of special hydrophobic grouping be artificially to regulate the water-soluble cpds that has suitable balanced degree between hydrophilic segment and the hydrophobic ingredient to be created in.
This type of particularly preferred nonionogenic tenside is C
9-C
15The primary alconol ethoxy compound, it contains every mol of alcohol 3-8 moles of ethylene oxide, particularly C
14-C
15Primary alconol, its epoxy second that contains every mol of alcohol 6-8 mole is burnt, and C
12-C
14Primary alconol, it contains every mol of alcohol 3-5 moles of ethylene oxide.
Another kind of ionic surfactant pack is drawn together the alkyl poly glucoside compound, and it has following general formula.
RO (CnH
2NO) Z is the part that derives from glucose in the tZx formula, and R is the saturated hydrophobic alkyl group that contains 12 to 18 carbon atoms; T is between 0 to 10, and n is 2 or 3; X is between 1.3 to 4, and this compound comprises and is less than 10% unreacted Fatty Alcohol(C12-C14 and C12-C18) and is less than 50% and the short-chain alkyl poly glucoside.This compounds and in detergent application at EP-B0070, the existing description in 077,0075996 and 0094,118.
What be fit in addition to make nonionogenic tenside is polyhydroxy fatty acid amide surfactant, and it has following general formula,
Wherein, R
1Be H or R
1Be the C1-4 alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R
2Be C
5-31Alkyl; And Z is poly-hydroxyl alkyl, and it has at least 3 hydroxyls and directly is connected in hydrocarbyl chain on the chain or its oxyalkylated derivative.R preferably
1Be methyl, R
2Be line style C
11-15Alkyl or alkenyl chain, as the coconut alkyl, or their mixture, and Z derive from the reductive amination reaction such as glucose, fructose, maltose, the reducing sugar of lactose.
Composition of the present invention also can comprise builder system.Any traditional washing assistant all is suitable at this, comprises aluminosilicate material, silicate, and polycarboxylate (ester) and fatty acid material are such as tetraacethyl 1.2-quadrol; Metal ion chelation agent, as amino polyphosphonates, particularly tetramethyl-phosphonic acids 1.2-quadrol and pentamethylene phosphonic acids ethylidene triamine.Even not too preferred but phosphoric acid washing assistant also can be used at this for environmental consideration significantly.
Suitable washing assistant can be an inorganic ion exchange material, common inorganic hydrous alumino silicates material, and particularly aqueous permutite is as aqueous zeolite A, X, B or HS.
Another kind of suitable, inorganic builders material is a layered silicate.As SKS-6 (Hoechst).SKS-6 contains water glass (Na
2Si
2O
5) the crystalline state layered silicate.
Comprise citric acid at this used suitable polycarboxylate (fat) washing assistant, the preferably form of water-soluble salt, and general formula is R-CH (COOH) CH
2The derivative of the succsinic acid of COOH, R is C in the formula
12-15Alkyl or alkenyl, C preferably
12-16, perhaps wherein R can be by hydroxyl, and sulfo group sulfoxylic acid base or sulfuryl substituting group replace.Special example comprises the succsinic acid lauryl, succsinic acid tetradecane ester, succsinic acid n-Hexadecane ester, succsinic acid 2-+=alkane ester, succsinic acid 2 one tetradecanoic acids.The succinate washing assistant preferably with their water-soluble salt form usefulness, comprises sodium, potassium, ammonia, and alkanol ammonium salts.
Other suitable polycarboxylate (ester) is the mixture of oxosuccinic acid salt (ester) and monosuccinic acid tartrate and disuccinic acid tartrate, and they are at US 4,663, and oneself has description in 071.
At this,, be saturated or undersaturated C at this lipid acid washing assistant that is suitable for particularly for fluid operated
10-18Lipid acid, and corresponding soap class.Preferred saturated kind has 12-16 carbon atom in alkyl chain, preferred unsaturated fatty acids is an oleic acid.The builder system that preferably is used for the particle shape composition comprises such as the water-soluble plumbous silicate-like builder of zeolite A and mixture such as water-soluble carboxylate (ester) sequestrant of citric acid.
The washing assistant material of the part of other the builder system that can be formed for particulate composition (being used for the object of the invention) comprises such as the inorganic materials of alkaline carbonate, supercarbonate, silicate with such as organic phosphonate (ester); The organic materials of hydrogen base polyphosphonic acid alkylene ester and aminopolycarboxylic salt (fat).
Other suitable water-soluble organic salt is homology or co-polymeric acids or their salt, and wherein, this poly carboxylic acid comprises two carboxyls at least, and these two carboxyls are opened by no more than 2 carbon atoms separate each other.
This type of polymkeric substance is at GB-A-1, and oneself has description in 596,756, the example of this salt is the multipolymer of the polyacrylate (ester) of MW 2000-5000 and they and maleic anhydride, and the molecular weight of this multipolymer is 20,000-70, between 000, particularly about 40,000.
Salt as decontamination lotion promoter accounts for 10% to 80% of composition weight, preferably 20%-70% usually.30%-60% most preferably.
In detergent composition, also can adopt other component, such as SYNTHETIC OPTICAL WHITNER, foam promotes or inhibitor, enzyme, stablizer, or activator, dirt suspension agent, dirt release agent, optical brightener, anti-wear agent, sterilant, loss of gloss remover, tinting material and spices.
Particularly preferably be with the technology that the color protection can be provided and combine.The example of these technology is to have used polyvinyl pyrrolidone polymers and had other polymkeric substance of eliminating the dye transfer characteristic.Another example of said technology is the cellulase that is used for color protection/recovery.
But detergent composition liquid of the present invention, slurry, or granular.It is that they have higher relatively density promptly between the 550-950 grams per liter than traditional granulated detergent that granular composition of the present invention also can be " closely knit form, "; In the case, granular detergent composition of the present invention contains more a spot of " mineral filler salt "; (comparing) with traditional granulated detergent.Typical filling salt is the vitriol and the muriate of alkali ± metal, typically sodium sulfate; " closely knit " washing composition typically comprises no more than 10% filling salt.Liquid composition of the present invention also has closely knit form, and in the case, liquid detergent composition of the present invention is compared with traditional liquid detergent composition and contained more a spot of water.
The present invention relates in the washing relevant, eliminate dissolving and the dyestuff that suspends is transferred to method on another part fabric from a fabric with colored fabric.
Present method comprises with above said washings contact fabric.
Method of the present invention can be implemented in washing process easily.The washing preferably between 5 ℃ to 75 ℃, carry out, particularly 20 to 60 times, but this polymkeric substance until 95 ℃ still effective, the pH value of treatment soln is preferably between 7 to 11.2, particularly between 7.5 to 10.5.
The compositions and methods of the invention also can be as additive when washing.
Following example is the composition that the present invention demonstrates, and not necessarily scope of the present invention is limited or limits, and said scope is determined by appended claims.
Embodiment 1:
Prepared liquid detergent composition of the present invention has following composition: linear alkyl benzene sulphonic acid ester (salt) 10 alkylsulfonates (ester) 4 Fatty Alcohol(C12-C14 and C12-C18) (C
12-C
15) poly-(the 4-vinylpyridine)-N-oxide of ethoxylate 12 aliphatic acid 10 oleic acid 4 citric acids 1 NaoH 3.4 propane diols 1.5 ethanol 10 0.3 terephthalic acids fat based polyalcohol 0.4 other add to 100
Embodiment 2:
The closely knit powder detergent composition of made the present invention has following proportioning: straight chain type alkylsulfonate 11.40 tallow alkyl sodium sulfate esters 1.80 sulfuric acid C
45The C of 3.007 ethoxylations of alkyl ester
45Other adds to 100 poly-(the 4-vinylpyridine)-N-oxide of tallow alcohol 1.8 dispersants 0.07 siloxanes fluids 0.80 trisodium citrate 14.00 citric acids 3.00 zeolites 32.50 maleic acid actylic acid copolymer 5.00DETMPA 1.00 cellulases (activated protein) 0.03Alk alase/BAN 0.60 lipase 0.36 sodium metasilicate 2.00 sodium sulphate 3.50 glucose 10.00 of 4.0011 ethoxylations of alcohol 0.3 terephthalic acids fat based polyalcohol 0.4
Embodiment 3-6:
Composition of the present invention is described further by following examples, and following liquid detergent composition is by making with listed ratio (weight ratio) mixed composition.
These compositions comprise the pH-fluctuation system that is made up of polyhydroxy fatty acid amide, borate and/or propylene glycol.Said composition is being lower than 7, is preferably under 6.5 the pH value condition to form.Can form pH value at least after the dilution of these title complexs and be 7.4 washings, this pH value fluctuates the unsettled composition in some pH values can be formed under lower pH value condition.The example of this based composition is the composition that contains polymkeric substance that has better polymer stabilizing under low pH value.In addition, the advantage of this pH fluctuation system comprises that also it can improve the ability of removing and the low preparation cost of changeable colour dyestuff through pre-treatment, only needs this moment less neutralization reagent just can obtain high pH value.
345 6C
12-C
15Alkyl sodium sulfate ester-19.0 21.0-C
12-C
15Alkyl sodium sulfate ester 23.0 4.0 4.0 25.0C of ethoxylation
12-C
14N-methyl glucoside acid amides 9.0 9.0 9.0 9.0C
12-C
14Fatty alcohol ethoxylate 6.0 6.0 6.0 6.0C
12-C
16Poly-(4-vinylpyridine)-N-oxide 0.5 0.5 boric acid, 2.4 2.4 2.8 2.82-butyl octanol 2.0 2.0 2.0 2.0DC 3421K (1) 0.3 0.4 0.3 0.4FF 400R (2) water of aliphatic acid 9.0 6.8 14.0 14.0 anhydrous citric acids 6.0 4.5 3.5 3.5 diethylenetriamines pentylidene phosphonic acids 1.0 1.0 2.0 2.0 MEAs 13.2 12.7 12.8 11.0 propane diols 12.7 14.5 13.1 10.0 enzymes 2.4 2.4 2.0 2.0 ethanol 1.8 1.8 4.7 5.4 terephthalic acids fat based polyalcohols 0.5 0.5 0.5 0.5 polyvinyl pyridine alkane ketone 1.0 1.0--and other add to 100%
(1) DC 3421 is the silicone oil that is purchased that comes from DOW Corning,
(2) be from DOW Corning and the silanol emulsifying agent that comes.
Claims (6)
1. elimination dye transfer compositions comprises
(a) 0.01% to 10% polyvinyl pyridine N-oxide;
(b) 0.01% to 10% terephthalate based polyalcohol; With
(c) the traditional detergent ingredients of other of surplus.
2. according to the elimination dye transfer compositions of claim 1, wherein, said terephthalate based polyalcohol has following general formula: x (OCH
2CH
2)
n 
(CH
2CH
2O)
nX
3. according to the composition of claim 1, the average molecular weight range of wherein said polyvinyl pyridine N-oxide is 500 to 1,000,000.
4. according to the composition of claim 3, the average molecular weight range of wherein said polyvinyl pyridine N-oxide is 5,000 to 100,000.
5. each the application method of elimination dye transfer compositions of claim 1-4, it is as a kind of detergent additives, with dustless particle or liquid form.
6. detergent composition, it comprises the elimination dye transfer compositions of claim 1, also comprises tensio-active agent, washing assistant, enzyme and other traditional washing composition composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92203287A EP0594893B1 (en) | 1992-10-27 | 1992-10-27 | Detergent compositions inhibiting dye transfer |
| EP92203287.5 | 1992-10-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1089645A CN1089645A (en) | 1994-07-20 |
| CN1047619C true CN1047619C (en) | 1999-12-22 |
Family
ID=8210998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93120225A Expired - Fee Related CN1047619C (en) | 1992-10-27 | 1993-10-27 | Detergent comositions inhibiting dye transfer |
Country Status (19)
| Country | Link |
|---|---|
| EP (1) | EP0594893B1 (en) |
| JP (1) | JPH08502547A (en) |
| KR (1) | KR100329878B1 (en) |
| CN (1) | CN1047619C (en) |
| AT (1) | ATE163036T1 (en) |
| AU (1) | AU669029B2 (en) |
| BR (1) | BR9307320A (en) |
| CA (1) | CA2148005C (en) |
| CZ (1) | CZ288208B6 (en) |
| DE (1) | DE69224385T2 (en) |
| DK (1) | DK0594893T3 (en) |
| ES (1) | ES2111607T3 (en) |
| GR (1) | GR3026078T3 (en) |
| HU (1) | HU217365B (en) |
| MX (1) | MX9306674A (en) |
| PH (1) | PH31042A (en) |
| PL (1) | PL175437B1 (en) |
| TW (1) | TW276269B (en) |
| WO (1) | WO1994010277A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO108522B1 (en) * | 1987-04-23 | 1994-06-30 | Fmc Corp | Derivates of di(aryl)-cyclopropyl, its substitutes and intermediaries thereof |
| US5783548A (en) * | 1992-11-06 | 1998-07-21 | The Procter & Gamble Company | Stable liquid detergent compositions inhibiting dye transfer |
| AU678838B2 (en) * | 1993-09-07 | 1997-06-12 | Colgate-Palmolive Company, The | Laundry detergent compositions containing lipase and soil release polymer |
| US5451341A (en) * | 1993-09-10 | 1995-09-19 | The Procter & Gamble Company | Soil release polymer in detergent compositions containing dye transfer inhibiting agents to improve cleaning performance |
| EP0786517B1 (en) | 1996-01-25 | 2001-09-19 | Unilever N.V. | Detergent composition |
| US5876625A (en) * | 1996-07-22 | 1999-03-02 | Carnegie Mellon University | Metal ligand containing bleaching compositions |
| DE102004018051A1 (en) * | 2004-04-08 | 2005-11-10 | Clariant Gmbh | Detergents and cleaning agents containing dye fixing agents and soil release polymers |
| US20210095229A1 (en) * | 2019-09-30 | 2021-04-01 | The Procter & Gamble Company | Fabric care compositions that include a copolymer and related methods |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0199403A2 (en) * | 1985-04-15 | 1986-10-29 | The Procter & Gamble Company | Stable liquid detergent compositions |
| EP0241985A2 (en) * | 1986-04-15 | 1987-10-21 | The Procter & Gamble Company | Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3637682A (en) * | 1967-10-24 | 1972-01-25 | Colgate Palmolive Co | N-2-hydroxy alkyl morpholine oxides |
| US4394305A (en) * | 1981-03-17 | 1983-07-19 | The Procter & Gamble Company | Alpha-oxyalkylene amine oxide compounds useful in detergents |
| SE459972B (en) * | 1983-03-29 | 1989-08-28 | Colgate Palmolive Co | DIRTY REFERENCE PARTICULAR DETERGENT COMPOSITION CONTAINING A DIRT-REFERENCE POLYMER, PROCEDURE FOR ITS PREPARATION AND ITS USE OF WASHING OF SYNTHETIC ORGANIC POLYMER FIBERIAL |
| US4548744A (en) * | 1983-07-22 | 1985-10-22 | Connor Daniel S | Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions |
| EP0185427B1 (en) * | 1984-12-21 | 1992-03-04 | The Procter & Gamble Company | Block polyesters and like compounds useful as soil release agents in detergent compositions |
| US4713194A (en) * | 1986-04-15 | 1987-12-15 | The Procter & Gamble Company | Block polyester and like compounds having branched hydrophilic capping groups useful as soil release agents in detergent compositions |
| EP0508034B1 (en) * | 1991-04-12 | 1996-02-28 | The Procter & Gamble Company | Compact detergent composition containing polyvinylpyrrolidone |
-
1992
- 1992-10-27 EP EP92203287A patent/EP0594893B1/en not_active Expired - Lifetime
- 1992-10-27 ES ES92203287T patent/ES2111607T3/en not_active Expired - Lifetime
- 1992-10-27 DE DE69224385T patent/DE69224385T2/en not_active Expired - Lifetime
- 1992-10-27 DK DK92203287.5T patent/DK0594893T3/en active
- 1992-10-27 AT AT92203287T patent/ATE163036T1/en not_active IP Right Cessation
-
1993
- 1993-10-15 CZ CZ19951058A patent/CZ288208B6/en not_active IP Right Cessation
- 1993-10-15 WO PCT/US1993/009936 patent/WO1994010277A1/en active IP Right Grant
- 1993-10-15 CA CA002148005A patent/CA2148005C/en not_active Expired - Fee Related
- 1993-10-15 BR BR9307320A patent/BR9307320A/en not_active IP Right Cessation
- 1993-10-15 KR KR1019950701582A patent/KR100329878B1/en not_active IP Right Cessation
- 1993-10-15 AU AU53632/94A patent/AU669029B2/en not_active Ceased
- 1993-10-15 PL PL93308544A patent/PL175437B1/en unknown
- 1993-10-15 HU HU9501189A patent/HU217365B/en not_active IP Right Cessation
- 1993-10-15 JP JP6511120A patent/JPH08502547A/en active Pending
- 1993-10-26 PH PH47714693A patent/PH31042A/en unknown
- 1993-10-26 MX MX9306674A patent/MX9306674A/en unknown
- 1993-10-27 CN CN93120225A patent/CN1047619C/en not_active Expired - Fee Related
- 1993-12-13 TW TW082110535A patent/TW276269B/zh active
-
1998
- 1998-02-05 GR GR980400212T patent/GR3026078T3/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0199403A2 (en) * | 1985-04-15 | 1986-10-29 | The Procter & Gamble Company | Stable liquid detergent compositions |
| EP0241985A2 (en) * | 1986-04-15 | 1987-10-21 | The Procter & Gamble Company | Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents |
Also Published As
| Publication number | Publication date |
|---|---|
| PH31042A (en) | 1997-12-29 |
| KR950704463A (en) | 1995-11-20 |
| CZ288208B6 (en) | 2001-05-16 |
| ES2111607T3 (en) | 1998-03-16 |
| AU669029B2 (en) | 1996-05-23 |
| PL308544A1 (en) | 1995-08-21 |
| CZ105895A3 (en) | 1995-12-13 |
| HUT71958A (en) | 1996-02-28 |
| CA2148005A1 (en) | 1994-05-11 |
| AU5363294A (en) | 1994-05-24 |
| HU217365B (en) | 2000-01-28 |
| CA2148005C (en) | 1999-04-13 |
| HU9501189D0 (en) | 1995-06-28 |
| KR100329878B1 (en) | 2002-08-08 |
| DE69224385D1 (en) | 1998-03-12 |
| BR9307320A (en) | 1999-06-01 |
| CN1089645A (en) | 1994-07-20 |
| PL175437B1 (en) | 1998-12-31 |
| EP0594893B1 (en) | 1998-02-04 |
| DK0594893T3 (en) | 1998-03-02 |
| JPH08502547A (en) | 1996-03-19 |
| ATE163036T1 (en) | 1998-02-15 |
| WO1994010277A1 (en) | 1994-05-11 |
| MX9306674A (en) | 1994-04-29 |
| TW276269B (en) | 1996-05-21 |
| EP0594893A1 (en) | 1994-05-04 |
| DE69224385T2 (en) | 1998-08-20 |
| GR3026078T3 (en) | 1998-05-29 |
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