CA2148811A1 - Dye transfer inhibiting compositions containing a metallocatalyst, a bleach and polyamine n-oxide polymer - Google Patents
Dye transfer inhibiting compositions containing a metallocatalyst, a bleach and polyamine n-oxide polymerInfo
- Publication number
- CA2148811A1 CA2148811A1 CA 2148811 CA2148811A CA2148811A1 CA 2148811 A1 CA2148811 A1 CA 2148811A1 CA 2148811 CA2148811 CA 2148811 CA 2148811 A CA2148811 A CA 2148811A CA 2148811 A1 CA2148811 A1 CA 2148811A1
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- Prior art keywords
- dye transfer
- transfer inhibiting
- composition according
- water
- inhibiting composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
-
- 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
- C11D3/3723—Polyamines or polyalkyleneimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
2148811 9411477 PCTABScor01 A) A metallocatalyst selected from: a) metalloporphin and water-soluble or water-dispersable derivatives thereof; b) metalloporphyrin and water-soluble or water-dispersable derivatives thereof;
c) metallophthalocyanine and water-soluble or water-dispersable derivatives thereof; B) a polyamine N-oxide containing polymers; C) an efficient amount of a bleaching agent.
c) metallophthalocyanine and water-soluble or water-dispersable derivatives thereof; B) a polyamine N-oxide containing polymers; C) an efficient amount of a bleaching agent.
Description
~: W094/1]477 2 1 ~ 8 8 1 1 PCT/US93tlO543 ,3 1 .
DYE TRANSFER INHIBITING COMPOSITIONS CONTAINING A METALL~
CATALYST, A BLEACH & PO~YAMINE N-OXIDE POLYMER
**~*~***********
i Field of the Invention The present invention relates to a composition and a process for inhibiting dye transfer between fabrics during washing.
Ba _ground of the Invention , Qne of the most persistent and troublesome problems arising during modern fabric laundering operations is the tendency of some colored fabrics` to release dye into the laundering solutions. The dye is then transferred onto other fabrics being washed therewith. ~-One way of overcoming this problem would be to complex or adsorb the fugitive dyes~washed out of dyed fabrics before they h~ve the opportunity to become attached to other articles in the wash.
:; : ' .-:"
1`WO 94/11477 PCr/US93/10~43 :~
DYE TRANSFER INHIBITING COMPOSITIONS CONTAINING A METALL~
CATALYST, A BLEACH & PO~YAMINE N-OXIDE POLYMER
**~*~***********
i Field of the Invention The present invention relates to a composition and a process for inhibiting dye transfer between fabrics during washing.
Ba _ground of the Invention , Qne of the most persistent and troublesome problems arising during modern fabric laundering operations is the tendency of some colored fabrics` to release dye into the laundering solutions. The dye is then transferred onto other fabrics being washed therewith. ~-One way of overcoming this problem would be to complex or adsorb the fugitive dyes~washed out of dyed fabrics before they h~ve the opportunity to become attached to other articles in the wash.
:; : ' .-:"
1`WO 94/11477 PCr/US93/10~43 :~
2 ~
Polymers have been used within detergent compositions to inhibit dye transfer, such as disclosed in EP-A-102 923, DE-A-2 814 329, FR-A-2 144 721 and EP-265 257.
Copending EP Patent Application 92202168.8 describes dye transfer inhibiting compostions comprising polyamine N-oxides containing polymers.
Another way of overcoming the problem of dye transfer would be to bleach the fugitive dyes washed out of dyed fabrics before they have the opportunity to become attached to other articles in the wash.
Suspended or solubilized dyes can to some degree be oxidized in solution by employing known bleaching agents.
GB 2 101 167 describes a stable liquid bleaching composition containing a hydrogen peroxide precursor which is activated to yield hydrogen peroxide on dilution.
However it is important at the same time not to bleach the dyes actually remaining on the fabrics, that is, not to cause color damage.
U.S. Patent 4,077,768 describes a process for inhibiting dye transfer by the use of an oxidizing bleaching agent together with a catalytic compound such as iron porphins.
, Copending EP Patent Application 91202655.6 filed October 9, 1991, relates to dye transfer inhibiting compositions comprising an enzymatic system capable of generating hydro~en peroxide and porphin catalysts.
It has now been surprisingly found that polyamine N-oxicle ~ `
polymers and metallo-catalysts provide superior and synergistic dye transfer inhibiting propertles compared to the catalyst- or polymers-system taken alone. This finding allows to formulate compositions which exhibit excellent dye transfer inhibiting properties with low level of catalysts, which in turn, reduces the problem of catalyst deposition onto fabrics. .
According to anokher embodiment of this invention a process 1 1 is also provided for laundering operations involving colored - i fabrics.
i~
"
, 1.
, !WO 94/11477 PCT/US93/10543 :' ~ 3 2I~8811 j`~`
Summary of the Invention '.
The present invention relates to inhibiting dye transfer ~ compositions comprising polyamine N-oxide containing polymers ~, and metallo catalysts and an efficlent amount of bleaching 1 agent.
'' .~ Detailed description of the invention ~j ~ Polyamine N-oxide contalning polymers ,, ;~ The compositions of the present invention comprise as an 1 essential element polyamine N oxide polymers which contain . units having the following structure formula :
P
;~ Ax i. R
l herein P is a polymerisable unit, whereto the R-N-O group ,, can be attached to or wherein ~.he R-N-O group forms part of the polymerisable unit or a combination of both.
' ' 11 R 1l ~ ' A is NC, CO, C, -O-,-S-, -N- ; x is or O or l;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wh~erein the nitrogen of the N-O group is part of these groups.
~ W~ 94/1 1477 2 1 4 S ~ 1 ~ PCT/US93/10543 ~-i , ~ .
The N-O group can be represented by the following general ~1 structures :
;~
O O '~
j(Rl)x -N- ~R2)y =N- (Rl~x ,~ I
(~3) z wherein Rl, R2, R3 are ~liphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or l and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O
group forms part of these groups.
The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part I of the pol~merisable unit comprise polyamine N-oxides wherein j R is selected from aliphatic, aromatic, alicyclic or ~ heterocyclic groups.
I One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
.
Another class of said polyamine N-oxldes comprises the group ,.
of polyamine N-oxides wherein the nitrogen of the N-O group is attached to the R-group.~ I
Other suitable polyamine N-oxides are the polyamine oxides 1-whereto the N-O group is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula tI) wherein R is an aromatic, heterocycllc or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.
l .
W094~11477 21~ PCT/US93/1~43 : 1.
! Examples of these classes are polyamine oxides wherein R
is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
.~
Another preferred class o~ polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is attached to said R
groups.
Examples of these classes are polyamine oxides wherein R
groups can be aromatic such as phenyl.
Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
The amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of lO : 1 to l: lQOOOOO. However the amount of amine oxide groups present in the polyamine oxide polymer can be ~aried by appropriate copolymerization or by appropriate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 3:l to l:lOOOOOO. The polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide or not. ~-The amine oxide unit of the polyamine N-oxides has a pKa < 7-lO, preferably pKa < 7, more preferred pKa < 6.
The polyamine-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
Typically, the average molecular weight is within the range of 500 to lOOO,OOO ; more preferred lOOO to 500,000 ; most preferred 5000 to 1~0,000.
WO94/1l477 PCT/US93/10543 ~
21~811 6 ` ~
~; The polyamine N-oxides of the present invention are typically present from 0.01 to 10% , more preferably from 0.05 to 1~, most preferred from 0.05 to 0.5 ~ by weight of the dye transfer inhibiting composition.
`,j ~3 Metallo catalyst , l The preferred usage range of the catalyst in the wash is 3 10-8 molar to 10-3 molar, more preferred 10-6 - 10-4 molar.
The esserltial metallo porphin structure may be visualized as indlcated in Formula I in the accompanying drawings. In Formula I the atom positions of the porphin structure are numbered conventionally and the double bonds are put in conventionally. In other formula, the double bonds have been omitted in the drawings, but are actually present as in I.
,, 'i Preferred metallo porphin structures are those substituted at one or more of the 5, 10, 15 and 20 carbon positions of Formula I (Meso positions), with a phenyl or pyridyl substituent selected from the group consisting of .1 ~
1, ~ (~)n~(A)m ~ ~+~(~)n~(A) m .~ .
wherein n and m may be 0 or 1; A is selected f-om water-solubilizing group, e.g., sulfate, sulfonate, phosphate or carboxylate groups; and B is selected from the group consisting of Cl-C1o alkyl, C1-C1o polyethoxy alkyl and C~-C1o hydroxy alkyl.
Preferred molecules are those in which the substituents on the phenyl or pyridyl groups are selected from the group consisting of -CH3, -C2H5~ -~H2CH2CH2SO3-, -CH2--~ and -cH2cH(oH)cH
-SO3.
/ W~94/11477 PCT/US93/10543 2~8Sl ~
. , .
A particularly preferred metallo phorphin is one in which the molecule is substituted at the 5, 10 15, and 20 carbon positions with the substituent ~ SD3 ijj This preferred compound is known as metallo tetrasulfonated tetraphenylporphin. The symbol Xl is (--CY-) wherein each Y, independently, is hydrogen, chlorine, bromine, fluorine or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or ~ heteroaryl.
.~ ~
i The symbol x2 of Formula I represents an anion, preferably OH- or Cl-. The compound of Formula I may be substituted at one or more of the remaining carbon positions with C1-Clo alkyl, hydroxyalkyl or oxyalkyl groups.
tI) Porphin derivatives also include chlorophyls, chlorines, i.e. isobacterio chlorines and bacteriochlorines.
Metallo porphyrin and water-soluble or water-dispersable`
derivatives thereof have a structure given in formula II. ~, ! ~ I
X X
~1 X~ X
~ X ~ tII) , 1~ :
, WO9~ 77 PCT~US93/10~43 `;j ,, 2 ~ 4 y) 8 ~
j where X can be al~yl, alkyl carboxy, alkyl hydroxyl, vinyl, alkenyl, alkyl sulfate, alkylsulfonate, sulfate, sulfonate, aryl.
~, The symbol x2 of Formula II represents an anion, preferably 1 o~~ or Cl-.
The symbol X can be alkyl, alkylcarboxy, alkylhydroxyl, vinyl, alkenyl, alkylsulfate, alkylsulfonate, sulfate, sulfonate.
Metallo phthalocyanine and derivatives have the structure indicated in Formula III, wherein the atom positions of the phthalocyanine structure are numbered conventionally. The I anionic groups in the above structures contain cations selected from the ~roup consisting of sodium and potassium i cations or other non-interfering cations which leave the structures water-soluble. Preferred phthalocyanine 1 derivatives are metallo phthalocyanine trisulfonate and ¦ metallo phthalocyanine tetrasulfonate.
~ 2 ~ ~ 4 ¦ 20 N ~e 6 ~III) Another form of substitution possible for the present invention is substitution of the central metal by Fe, Mn, Co Rh, Cr, Ru, Mo or othex transition metals.
Still a number of considerations are significant in selecting variants of or substituents in the basic porphin or azaporphin structure. In the first place, one would choose compounds which are available or can be readily synthesized.
~WO94/1~477 21 ~ 8811 PCTtUS93/10~43 L' ;, 9 Beyond this, the choice of the substituent groups can be used to control the solubility of the catalyst in water or in detergent solutions. Yet again, especially where it is desired to avoid attacking dyes attached to solid surfaces, the substituents can control the affinity of the catalyst compoun~ for the surface. Thus, strongly negatively charged substituted compounds, for instance the tetrasulfonated porphin, may be repelled by negatively charged stained surfaces and are thexefore most likely not to cause attack on fixed dyes, whereas the cationic or zwitterionic compounds may be attracted to, or at least not repelled by such stained surfaces.
An efficient amount of bleaching agent The dye transfer inhibiting compositions according to the present invention comprise an efficient amount of bleaching agent.
According to the present invention, an efficient amount of bleach is by definition the necessary amount of bleach which combined with a bleach catalyst leads to a level of dye oxidation which is between 40~ to 100%, preferably 40% to 60%, more preferred 60~ to 80~, most pre~erred 80%-100% of the maximum (Z) per cent of dye oxidation that can be achieved under the most optimaL conditions ~etermined by those skilled in the art.
The bleaches suitable for the present invention can be activated or non-activated bleaches.
Preferably, the bleaches suitable for the present inventlon include peroxygen bleaches. Examples of suitable water-soluble solid peroxygen bleaches incIude hydrogen peroxide releasing agents such as hydrogen peroxide, perborates, e.g. perborate monohydrate, perborate tetrahydrate, persulfates, percarbonates, peroxydisulfates, perphosphates and W094/l1477 P~CT/US93/10543 ~, peroxyhydrates. Preferred bleaches are percarbonates and perborates.
~ '.
The hydrogen peroxide releasing agents can be used in con~ination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934),3,5,5-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP
j 120,591), or pentaacetylglucose (PAG), which are perhydrolyzed ¦ to form a peracid as the active bleaching species, leading to improved bleaching effect.
The hydrogen peroxide may also be present by adding an enzymatic system 5i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.
Other peroxygen bleaches suitable for the present invention include organic peroxyacids such as percarboxylic acids.
Test MQth~ds:
For a given catalyst concentration, temperature and pH, the following two test methods can be u_~d to estimate the optimum bleach level that gives the maximum level of dye oxidation, i.e. Z.
(a) In solution dye bleachin~:
, : .
In a detergent solution, fix the initial concentration of dye (e.g. 40 ppm) and catalyst. Record the absorbance spectrum of this solution using a W-Vis spectrophotometer according to procedures known to those skilled in the art.
Add a given concentxation of bleach (H202, oxone, percarbonate, perborate, activated bleach, etc..) and stir the solution containing the dye and catalyst. After stirring for .
, WOU4/11477 - ~ ,, 8 8 1 1 ~
`. 1 1 , 30 min, record again the absorbance spectrum of the solution.
The amount of dye oxidation can then be determined from the change in the absorbance maximum for the dye. Keeping the experimental conditions the same, vary the amount of bleach so ~l as to achieve the maximu-n dye oxidation.
~;1 :'3 ~b, ~b) Reduction of dye txansfer from fabric to another fabric In either a washing machine or launderometer, add a known bleeding fabric and a known uncolored pick-up tracer (e.g.
cotton~ to the wash load. After simulating a wash cycle, determine the amount of dye that has been picked up by the tracer according to methods known to those skilled in the art.
Now to separate washing machines, add the same amount of bleeding fabric and pick-up tracer, a fixed amount of catalyst and vary the bleach level. Determine the level of dye transfer onto the pick-up tracers and vary the amount of bleach as to minimize dye transfer. In this way the most optimal bleach concentration can be determined.
I
DETERGENT ADJUNCTS
A wide range of surfactants can be used in the detergent compositions. A typical listing of anionic, nonionic, !~ ampholytic and zwitterionic classes, and species of these 'l surfactants, is given in US Patent ~,664,961 issued to Norris ! on May 23, 1972.
! Mixtures of anionic surfactants are particularly suitable ~, ~ herein, especially mixtures of sulphonate and sulphate 3 surfactants in a weight ratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferably from 3:1 to 1:1. Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C12-Clg fatty source preferably from a l6-C18 fatty source. In each instance ~he catlon is an alkali metal, preferably sodium. Preferred sulphate ~ WO94/11477 ~ PCr/US93/10;43 ;~
; 214~811 ;i surfactants are alkyl sulphates having from 12 to 18 carbon atoms in the alkyl radical, optionally in admixture with ethoxy sulphates having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6. Examples of preferred alkyl sulphates herein are tallow alkyl sulphate, coconut alkyl sulphate, and C~ s alkyl sulphates. The cation in each instance is again an alkali metal cation, preferably sodium.
One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provi.de a surfactant having an average hydrophilic-lipophilic balance ~HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is I condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
I Especially preferred nonionic surfactants of this type are the Cg-C1s primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C14-C1s primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol and the C12 C14 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol.
.
Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO (CnH2nO)tzx wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon ~ r.
atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10~ unreacted fatty alcohol i;
and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent are disclosed in EP-B
0 070 077, 0 075 996 and 0 094 118.
.
W~ 477 PCT/US93/10543 Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula .' I R2 - C - N - Z, O
wherein R1 is H, or Rl is C1_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is Cs_31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl haviny a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
Preferably, R1 is methyl, R2 is a straight C~ s alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z
is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
The compositions according to the present invention may further comprise a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid. Though less preferred for obvious environmental reasons, phosphate builders can also be used herein.
Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.;
Another suitable inorganic builder material is layered silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2Os).
Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble saltt derivatives of succinic acid of the formula R-CH~CoOHjCH2(COOH) whereln R is C10-20 alkyl or alkenyl, i ' ~ WO94/11477 ` 21~881~ PCT/~593/1054~ :
` :
preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents. Specific examples include lauryl succinate , myristyl succinate, palmityl succinate2-dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ~ ammonium and alkanolammonium salts.
¦ Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
Especially for the liquid execution herein, suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well as well as the corresponding soaps.
Preferred saturated species have from 12 to 16 carbon atoms , in the alkyl chain. The prefe~red unsatur~ated fatty acid ls j ole.ic acid.
Preferred builder systems for use in granular compositions include a mixture of a water-insoluble aluminosilicate builder ¦ such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid.
' Other builder materials that can form part of the buildex i system for use in granular compositions the purposes of the ¦ invention include inorganic materials such as alkali metal i carbonates, bicarbonates, silicates, and organic materials ~ such as the organic phosphonates, amiono polyalkylene I phosphonates and amino polycarboxylates.
Other suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,5g6,756.
Examples of such salts axe polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having 1 a molecular weight of from 20,000 to 70,000, especially about 40,000.
Detergency builder salts are normally included in amounts of from 10~ to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight.
Other components used in detergent compositions may be employed, such as bleaches, suds boosting or depressing agents, enzymes and stabilizers or activators therefor, soil-suspending agents soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and perfumes.
Especially preferred are combinations with technologies which also provide a type of color care benefit. Examples of these technologies are polyvinylpyrrolidone polymers and other polymers which have dye transfer inhibiting properties.
Another example of said technologies are cellulase for color maintenance/ rejuvenation.
Other examples are polymers disclosed in EP 92870017.8 filed January 31, 1992 and enzyme oxidation scavengers dis~losed in ~P 92870018.6 filed January 31, 1992. also particularly suitable are amine base catalyst stabilizers disclosed in EP
92870019.4 filed January 31, 1992.
The detergent compositions according to the invention can be in liquid, paste or granular forms. Granular compositions according to the present invention can also be in "compact form", i.e. they may have a relatively higher density than conventional granular detergents, i.e. from 550 to 950 g/l; in suc~ case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth m~tal salts of sulphates and chlorides, typically sodium sulphate;
"compact" detergents typically comprise not more than 10%
filler salt. The liqùid compositions according to the present invention can also be in "compact form", in such case, the liquid detergent compositions according to the present t invention will contain ~a lower amount of water,compared to conventional liquid detergents.
The present in~ention also relates to a process for inhibiting dye transfer from one fabric to another of ~WO94~11477 PCTtUS93/]OS43 ~
21~8811 i-;`;`
- ` 16 solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.
IThe process comprises contacting fabrics with a laundering jsolution as hereinbefore described.
The process of the invention is conveniently carried out in the course of the washing process. The washing process is preferably carried out at 5 C to 75 C, especially 20 ~o 60, but the pol~mers are effecti~e at up to 95 C. The pH of the treatment solution ls preferably from 7 to 11, especially from 7.5 to 10.5.
The process and compositions of the invention can also be used as additive during laundry operations.
,The following examples are meant to exemplify compositions ¦of the present invention , but are not necessarily meant to Ilimit or otherwise define the scope of the invention, said scope being determined according to claims which follow.
Example I
The extent of dye transfer from different colored fabrics was studied using a launder-o-meter test which simulates a 30 min wash cycle. The launder-o-meter beaker contains 200 ml of a detergent solution (pH 7.5- 10.5), a l~xlO cm piece of the colored fabric and a multi-fiber swatch which is used as a pick-up tracer for the bleeding d~e. The multifiber swatch consists of 6 strips (1.5cmx1.5cm each~ made of different materials (polyacetate, cotton, polyamide, polyester, wool and orlon) which were sewn together.
The extent of dye transfer is reported in terms of the c value which represents the change in the Hunter a, b values and is defined by the following equation:
~ C - {(af ~ai)2 + (bf-bi)2}l/2 where the subscripts i and f refer to the Hunter value before and after washing in the presence of the bleeding fa~ric, respectively.
WO94/11477 17 ,?l PCI/US93/10543 ~`
Exarnple I ~a): poly(4-vinylpyridine-N-oxide) and FeTPPS
'~ I
The experimental conditions are:
A:detergent solution without any dye transfer inhibition system.
`I B:detergent solution containing 10 ppm of Iron-J tetrasulfonated phenylporphyrin ~FeTPPS) and the optimum ! level of bleach as determined from the test method above.
C:deter~ent solution containing 10 ppm of poly(4-vinylpyridine-N-oxide)(PVNO).
D:detergent solution containing 10 ppm of FeTPPS and 10 ppm of poly(4-vinylpyridine~N-oxide).
) i ~ C value on cotton Fabric A B ~ C D
~ ~, ~
blue sweater 15.2 14.7 8.2 4.8 purple trousexs-1 19.3 7.0 17.8 2.8 green sweater 8.7 8.4 6.6 4.5 purple ~ogging 12.7 12.2 7.6 5.7 purple trousers 14.5 13.1 6.4 4,3 blue trousers 18.7 13.9 22.2 10.8 The higher the ~ C value, the more dye transferred onto the pick-up swatch.
Conclusion: The dye transfex inhibition benefits from the combined PVNO and FeTPPS are in all cases better than benefits provided by either the catalyst or polymer alone. In addition, not only additive effects are observed but these results show true synergism between the catalyst and poly~4-vinylpyridine~N-oxidel.
'-'21~8811 ~xample I(b): poly(4-vinylpyridine-N-oxide) and MnPc The experimental conditions are:
A:detergent solution without any dye transfer inhibition system.
B:detergent solution containing 10 ppm of Mn-Phthalocyanine tetrasulfonated ~MnPC) and the optimum level of bleach as determined from the test method above.
C:detergent solution containing 10 ppm of poly(4-vinylpyxidine-N-oxide). (PVNO) D:detergent solution containing 10 ppm of MnPc ~nd 10 ppm of poly(4-vinylpyridine-N-oxide).
~C values on cotton _ __ Fabric A B C D
blue sweater 15.214.7 8.2 4.8 green sweater 8.7 8.4 6.6 4.5 purple jogging 12.712.2 7.6 5.7 purple trousers 14.513.1 6.4 4.3 Concluslon: The dye transfer inhibition benefits from the combined PVNO and MnPC are in all cases better than benefits provided by either the catalyst or polymer alone. In addition, these results show true synergism between the catalyst and poly(4-vinylpyridine-N-oxide).
. ~ ." ,, , . .... ..... ... ... .. . -~ WO94/11477 PCT/US93/10~43 ,21~`8811 ~I
`~ EXAMPLE II (A/B/C/D) .
, A liquid dye transfer inhibiting composition according to the present invention is prepared, having the following '~ compositions :
~i!
., - ~inear alkyl benzene sulfonate 10 - Sodium C12_15 alkyl sulfate 3 - C14_1s alkyl 2.5 times ethoxylated sulfate 0 - C12 glucose amide 0 - C12_1s alcohol 7 times ethoxylated 11.6 - Oleic acid 2.5 - Citric acid - C12_14 alkenyl substituted succinic acid 0 - Sodium Hydroxide 3.5 - Ethanol 6 - Monoethanolamine 0 - Triethanolamine 6.4 - 1,2-propane diol 1.5 - Glycerol o - Boric acid o - Diethylene triamine penta 0.8 (methylene phosphonic acid) - CaC12 - Soil release polymers 0.5 - Fatty acids 12 - Enzymes 0.65 Water and minors - - - - Balance to 100% - - -The above composition was supplemented with the catalyst, p~lymer and bleach accordlng to table I
WO94/11477 PCT/US93/10~3 ~
2~8811 20 Table I
A B C D
..
- Catalyst l: Mn-tetrasulfonated 0 0.05 0 0 tetraphenylporphine - Catalyst 2: Cr-tetrasulfonated 0 0 O.lO0 0 tetraphenylporphine - Catalyst 3: Fe tetrasulfonated 0 0 0 0.2 tetraphenylporphine - Catalyst 4: Mn-Phthalocyanine 0.15 0.0 0 0 tetrasulfonated ~ H22 0.3-0~5 0 0 0 - Perborate 0 0 1-5 0.5 - Percarbonate , 0 0.4 0 O.lO0-Pc~ly(4-vinylpyridine-N-oxide) O.l 0.30.05 0.2 Example III ~A/B/C/D):
A compact granular dye transfer inhibiting composition according to the present invention is prepared, having the followir1g formulation:
%
Linear alkyl benzene sulphonate ll.40 Tallow alkyl sulphate l.80 C4s alkyl sulphate 3.00 C~s alcohol 7 times ethoxylated 4.00 Tallow alcohol ll times ethoxylated l.80 Dispersant ` ~ 0.07 Silicone fluid 0.80 Trisodium citrate 14.00 Citric acid 3.00 Zeolite 32.50 Maleic acid actylic acid copolymer 5.00 DETMPA : l.00 Cellulase (active protein) 0.03 W094/11477 PCT/US93/l0543 Alkalase/BAN 0.60 Lipase 0.36 Sodi.um silicate 2.00 Sodium sulphate 3.50 Minors up to 100 The above composition was supplemented with the catalyst, polymer and bleach according to table II
Table II
A B C D
- Catalyst 1: Mn-tetrasulfonated 0 0.05 0 0 tetraphenylporphine - Catalyst 2: Cr-tetrasulfonated 0 0 0.100 0 tetraphenylporphine - Catalyst 3: Fe-tetrasulfonated 0 0 0 0.2 tetraphenylporphine - Catalyst 4: Mn-Phthalocyanine 0.15 0.0 0 0 tetrasulfonated ~ H22 0.3-0.5 0 0 0 Perborate 0 0 1-5 2.5 - Percarb,onate 0 0.4 0 0 - Poly(4-vinylpyridine-N-oxide) 0.050.1 0.15 0~2-0.4 - TAED 0 0 0.5 1.0 .
Polymers have been used within detergent compositions to inhibit dye transfer, such as disclosed in EP-A-102 923, DE-A-2 814 329, FR-A-2 144 721 and EP-265 257.
Copending EP Patent Application 92202168.8 describes dye transfer inhibiting compostions comprising polyamine N-oxides containing polymers.
Another way of overcoming the problem of dye transfer would be to bleach the fugitive dyes washed out of dyed fabrics before they have the opportunity to become attached to other articles in the wash.
Suspended or solubilized dyes can to some degree be oxidized in solution by employing known bleaching agents.
GB 2 101 167 describes a stable liquid bleaching composition containing a hydrogen peroxide precursor which is activated to yield hydrogen peroxide on dilution.
However it is important at the same time not to bleach the dyes actually remaining on the fabrics, that is, not to cause color damage.
U.S. Patent 4,077,768 describes a process for inhibiting dye transfer by the use of an oxidizing bleaching agent together with a catalytic compound such as iron porphins.
, Copending EP Patent Application 91202655.6 filed October 9, 1991, relates to dye transfer inhibiting compositions comprising an enzymatic system capable of generating hydro~en peroxide and porphin catalysts.
It has now been surprisingly found that polyamine N-oxicle ~ `
polymers and metallo-catalysts provide superior and synergistic dye transfer inhibiting propertles compared to the catalyst- or polymers-system taken alone. This finding allows to formulate compositions which exhibit excellent dye transfer inhibiting properties with low level of catalysts, which in turn, reduces the problem of catalyst deposition onto fabrics. .
According to anokher embodiment of this invention a process 1 1 is also provided for laundering operations involving colored - i fabrics.
i~
"
, 1.
, !WO 94/11477 PCT/US93/10543 :' ~ 3 2I~8811 j`~`
Summary of the Invention '.
The present invention relates to inhibiting dye transfer ~ compositions comprising polyamine N-oxide containing polymers ~, and metallo catalysts and an efficlent amount of bleaching 1 agent.
'' .~ Detailed description of the invention ~j ~ Polyamine N-oxide contalning polymers ,, ;~ The compositions of the present invention comprise as an 1 essential element polyamine N oxide polymers which contain . units having the following structure formula :
P
;~ Ax i. R
l herein P is a polymerisable unit, whereto the R-N-O group ,, can be attached to or wherein ~.he R-N-O group forms part of the polymerisable unit or a combination of both.
' ' 11 R 1l ~ ' A is NC, CO, C, -O-,-S-, -N- ; x is or O or l;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wh~erein the nitrogen of the N-O group is part of these groups.
~ W~ 94/1 1477 2 1 4 S ~ 1 ~ PCT/US93/10543 ~-i , ~ .
The N-O group can be represented by the following general ~1 structures :
;~
O O '~
j(Rl)x -N- ~R2)y =N- (Rl~x ,~ I
(~3) z wherein Rl, R2, R3 are ~liphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or l and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O
group forms part of these groups.
The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part I of the pol~merisable unit comprise polyamine N-oxides wherein j R is selected from aliphatic, aromatic, alicyclic or ~ heterocyclic groups.
I One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
.
Another class of said polyamine N-oxldes comprises the group ,.
of polyamine N-oxides wherein the nitrogen of the N-O group is attached to the R-group.~ I
Other suitable polyamine N-oxides are the polyamine oxides 1-whereto the N-O group is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula tI) wherein R is an aromatic, heterocycllc or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.
l .
W094~11477 21~ PCT/US93/1~43 : 1.
! Examples of these classes are polyamine oxides wherein R
is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
.~
Another preferred class o~ polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is attached to said R
groups.
Examples of these classes are polyamine oxides wherein R
groups can be aromatic such as phenyl.
Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
The amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of lO : 1 to l: lQOOOOO. However the amount of amine oxide groups present in the polyamine oxide polymer can be ~aried by appropriate copolymerization or by appropriate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 3:l to l:lOOOOOO. The polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide or not. ~-The amine oxide unit of the polyamine N-oxides has a pKa < 7-lO, preferably pKa < 7, more preferred pKa < 6.
The polyamine-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
Typically, the average molecular weight is within the range of 500 to lOOO,OOO ; more preferred lOOO to 500,000 ; most preferred 5000 to 1~0,000.
WO94/1l477 PCT/US93/10543 ~
21~811 6 ` ~
~; The polyamine N-oxides of the present invention are typically present from 0.01 to 10% , more preferably from 0.05 to 1~, most preferred from 0.05 to 0.5 ~ by weight of the dye transfer inhibiting composition.
`,j ~3 Metallo catalyst , l The preferred usage range of the catalyst in the wash is 3 10-8 molar to 10-3 molar, more preferred 10-6 - 10-4 molar.
The esserltial metallo porphin structure may be visualized as indlcated in Formula I in the accompanying drawings. In Formula I the atom positions of the porphin structure are numbered conventionally and the double bonds are put in conventionally. In other formula, the double bonds have been omitted in the drawings, but are actually present as in I.
,, 'i Preferred metallo porphin structures are those substituted at one or more of the 5, 10, 15 and 20 carbon positions of Formula I (Meso positions), with a phenyl or pyridyl substituent selected from the group consisting of .1 ~
1, ~ (~)n~(A)m ~ ~+~(~)n~(A) m .~ .
wherein n and m may be 0 or 1; A is selected f-om water-solubilizing group, e.g., sulfate, sulfonate, phosphate or carboxylate groups; and B is selected from the group consisting of Cl-C1o alkyl, C1-C1o polyethoxy alkyl and C~-C1o hydroxy alkyl.
Preferred molecules are those in which the substituents on the phenyl or pyridyl groups are selected from the group consisting of -CH3, -C2H5~ -~H2CH2CH2SO3-, -CH2--~ and -cH2cH(oH)cH
-SO3.
/ W~94/11477 PCT/US93/10543 2~8Sl ~
. , .
A particularly preferred metallo phorphin is one in which the molecule is substituted at the 5, 10 15, and 20 carbon positions with the substituent ~ SD3 ijj This preferred compound is known as metallo tetrasulfonated tetraphenylporphin. The symbol Xl is (--CY-) wherein each Y, independently, is hydrogen, chlorine, bromine, fluorine or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or ~ heteroaryl.
.~ ~
i The symbol x2 of Formula I represents an anion, preferably OH- or Cl-. The compound of Formula I may be substituted at one or more of the remaining carbon positions with C1-Clo alkyl, hydroxyalkyl or oxyalkyl groups.
tI) Porphin derivatives also include chlorophyls, chlorines, i.e. isobacterio chlorines and bacteriochlorines.
Metallo porphyrin and water-soluble or water-dispersable`
derivatives thereof have a structure given in formula II. ~, ! ~ I
X X
~1 X~ X
~ X ~ tII) , 1~ :
, WO9~ 77 PCT~US93/10~43 `;j ,, 2 ~ 4 y) 8 ~
j where X can be al~yl, alkyl carboxy, alkyl hydroxyl, vinyl, alkenyl, alkyl sulfate, alkylsulfonate, sulfate, sulfonate, aryl.
~, The symbol x2 of Formula II represents an anion, preferably 1 o~~ or Cl-.
The symbol X can be alkyl, alkylcarboxy, alkylhydroxyl, vinyl, alkenyl, alkylsulfate, alkylsulfonate, sulfate, sulfonate.
Metallo phthalocyanine and derivatives have the structure indicated in Formula III, wherein the atom positions of the phthalocyanine structure are numbered conventionally. The I anionic groups in the above structures contain cations selected from the ~roup consisting of sodium and potassium i cations or other non-interfering cations which leave the structures water-soluble. Preferred phthalocyanine 1 derivatives are metallo phthalocyanine trisulfonate and ¦ metallo phthalocyanine tetrasulfonate.
~ 2 ~ ~ 4 ¦ 20 N ~e 6 ~III) Another form of substitution possible for the present invention is substitution of the central metal by Fe, Mn, Co Rh, Cr, Ru, Mo or othex transition metals.
Still a number of considerations are significant in selecting variants of or substituents in the basic porphin or azaporphin structure. In the first place, one would choose compounds which are available or can be readily synthesized.
~WO94/1~477 21 ~ 8811 PCTtUS93/10~43 L' ;, 9 Beyond this, the choice of the substituent groups can be used to control the solubility of the catalyst in water or in detergent solutions. Yet again, especially where it is desired to avoid attacking dyes attached to solid surfaces, the substituents can control the affinity of the catalyst compoun~ for the surface. Thus, strongly negatively charged substituted compounds, for instance the tetrasulfonated porphin, may be repelled by negatively charged stained surfaces and are thexefore most likely not to cause attack on fixed dyes, whereas the cationic or zwitterionic compounds may be attracted to, or at least not repelled by such stained surfaces.
An efficient amount of bleaching agent The dye transfer inhibiting compositions according to the present invention comprise an efficient amount of bleaching agent.
According to the present invention, an efficient amount of bleach is by definition the necessary amount of bleach which combined with a bleach catalyst leads to a level of dye oxidation which is between 40~ to 100%, preferably 40% to 60%, more preferred 60~ to 80~, most pre~erred 80%-100% of the maximum (Z) per cent of dye oxidation that can be achieved under the most optimaL conditions ~etermined by those skilled in the art.
The bleaches suitable for the present invention can be activated or non-activated bleaches.
Preferably, the bleaches suitable for the present inventlon include peroxygen bleaches. Examples of suitable water-soluble solid peroxygen bleaches incIude hydrogen peroxide releasing agents such as hydrogen peroxide, perborates, e.g. perborate monohydrate, perborate tetrahydrate, persulfates, percarbonates, peroxydisulfates, perphosphates and W094/l1477 P~CT/US93/10543 ~, peroxyhydrates. Preferred bleaches are percarbonates and perborates.
~ '.
The hydrogen peroxide releasing agents can be used in con~ination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934),3,5,5-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP
j 120,591), or pentaacetylglucose (PAG), which are perhydrolyzed ¦ to form a peracid as the active bleaching species, leading to improved bleaching effect.
The hydrogen peroxide may also be present by adding an enzymatic system 5i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.
Other peroxygen bleaches suitable for the present invention include organic peroxyacids such as percarboxylic acids.
Test MQth~ds:
For a given catalyst concentration, temperature and pH, the following two test methods can be u_~d to estimate the optimum bleach level that gives the maximum level of dye oxidation, i.e. Z.
(a) In solution dye bleachin~:
, : .
In a detergent solution, fix the initial concentration of dye (e.g. 40 ppm) and catalyst. Record the absorbance spectrum of this solution using a W-Vis spectrophotometer according to procedures known to those skilled in the art.
Add a given concentxation of bleach (H202, oxone, percarbonate, perborate, activated bleach, etc..) and stir the solution containing the dye and catalyst. After stirring for .
, WOU4/11477 - ~ ,, 8 8 1 1 ~
`. 1 1 , 30 min, record again the absorbance spectrum of the solution.
The amount of dye oxidation can then be determined from the change in the absorbance maximum for the dye. Keeping the experimental conditions the same, vary the amount of bleach so ~l as to achieve the maximu-n dye oxidation.
~;1 :'3 ~b, ~b) Reduction of dye txansfer from fabric to another fabric In either a washing machine or launderometer, add a known bleeding fabric and a known uncolored pick-up tracer (e.g.
cotton~ to the wash load. After simulating a wash cycle, determine the amount of dye that has been picked up by the tracer according to methods known to those skilled in the art.
Now to separate washing machines, add the same amount of bleeding fabric and pick-up tracer, a fixed amount of catalyst and vary the bleach level. Determine the level of dye transfer onto the pick-up tracers and vary the amount of bleach as to minimize dye transfer. In this way the most optimal bleach concentration can be determined.
I
DETERGENT ADJUNCTS
A wide range of surfactants can be used in the detergent compositions. A typical listing of anionic, nonionic, !~ ampholytic and zwitterionic classes, and species of these 'l surfactants, is given in US Patent ~,664,961 issued to Norris ! on May 23, 1972.
! Mixtures of anionic surfactants are particularly suitable ~, ~ herein, especially mixtures of sulphonate and sulphate 3 surfactants in a weight ratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferably from 3:1 to 1:1. Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C12-Clg fatty source preferably from a l6-C18 fatty source. In each instance ~he catlon is an alkali metal, preferably sodium. Preferred sulphate ~ WO94/11477 ~ PCr/US93/10;43 ;~
; 214~811 ;i surfactants are alkyl sulphates having from 12 to 18 carbon atoms in the alkyl radical, optionally in admixture with ethoxy sulphates having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6. Examples of preferred alkyl sulphates herein are tallow alkyl sulphate, coconut alkyl sulphate, and C~ s alkyl sulphates. The cation in each instance is again an alkali metal cation, preferably sodium.
One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provi.de a surfactant having an average hydrophilic-lipophilic balance ~HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is I condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
I Especially preferred nonionic surfactants of this type are the Cg-C1s primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C14-C1s primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol and the C12 C14 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol.
.
Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO (CnH2nO)tzx wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon ~ r.
atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10~ unreacted fatty alcohol i;
and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent are disclosed in EP-B
0 070 077, 0 075 996 and 0 094 118.
.
W~ 477 PCT/US93/10543 Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula .' I R2 - C - N - Z, O
wherein R1 is H, or Rl is C1_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is Cs_31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl haviny a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
Preferably, R1 is methyl, R2 is a straight C~ s alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z
is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
The compositions according to the present invention may further comprise a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid. Though less preferred for obvious environmental reasons, phosphate builders can also be used herein.
Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.;
Another suitable inorganic builder material is layered silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2Os).
Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble saltt derivatives of succinic acid of the formula R-CH~CoOHjCH2(COOH) whereln R is C10-20 alkyl or alkenyl, i ' ~ WO94/11477 ` 21~881~ PCT/~593/1054~ :
` :
preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents. Specific examples include lauryl succinate , myristyl succinate, palmityl succinate2-dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ~ ammonium and alkanolammonium salts.
¦ Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
Especially for the liquid execution herein, suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well as well as the corresponding soaps.
Preferred saturated species have from 12 to 16 carbon atoms , in the alkyl chain. The prefe~red unsatur~ated fatty acid ls j ole.ic acid.
Preferred builder systems for use in granular compositions include a mixture of a water-insoluble aluminosilicate builder ¦ such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid.
' Other builder materials that can form part of the buildex i system for use in granular compositions the purposes of the ¦ invention include inorganic materials such as alkali metal i carbonates, bicarbonates, silicates, and organic materials ~ such as the organic phosphonates, amiono polyalkylene I phosphonates and amino polycarboxylates.
Other suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,5g6,756.
Examples of such salts axe polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having 1 a molecular weight of from 20,000 to 70,000, especially about 40,000.
Detergency builder salts are normally included in amounts of from 10~ to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight.
Other components used in detergent compositions may be employed, such as bleaches, suds boosting or depressing agents, enzymes and stabilizers or activators therefor, soil-suspending agents soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and perfumes.
Especially preferred are combinations with technologies which also provide a type of color care benefit. Examples of these technologies are polyvinylpyrrolidone polymers and other polymers which have dye transfer inhibiting properties.
Another example of said technologies are cellulase for color maintenance/ rejuvenation.
Other examples are polymers disclosed in EP 92870017.8 filed January 31, 1992 and enzyme oxidation scavengers dis~losed in ~P 92870018.6 filed January 31, 1992. also particularly suitable are amine base catalyst stabilizers disclosed in EP
92870019.4 filed January 31, 1992.
The detergent compositions according to the invention can be in liquid, paste or granular forms. Granular compositions according to the present invention can also be in "compact form", i.e. they may have a relatively higher density than conventional granular detergents, i.e. from 550 to 950 g/l; in suc~ case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth m~tal salts of sulphates and chlorides, typically sodium sulphate;
"compact" detergents typically comprise not more than 10%
filler salt. The liqùid compositions according to the present invention can also be in "compact form", in such case, the liquid detergent compositions according to the present t invention will contain ~a lower amount of water,compared to conventional liquid detergents.
The present in~ention also relates to a process for inhibiting dye transfer from one fabric to another of ~WO94~11477 PCTtUS93/]OS43 ~
21~8811 i-;`;`
- ` 16 solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.
IThe process comprises contacting fabrics with a laundering jsolution as hereinbefore described.
The process of the invention is conveniently carried out in the course of the washing process. The washing process is preferably carried out at 5 C to 75 C, especially 20 ~o 60, but the pol~mers are effecti~e at up to 95 C. The pH of the treatment solution ls preferably from 7 to 11, especially from 7.5 to 10.5.
The process and compositions of the invention can also be used as additive during laundry operations.
,The following examples are meant to exemplify compositions ¦of the present invention , but are not necessarily meant to Ilimit or otherwise define the scope of the invention, said scope being determined according to claims which follow.
Example I
The extent of dye transfer from different colored fabrics was studied using a launder-o-meter test which simulates a 30 min wash cycle. The launder-o-meter beaker contains 200 ml of a detergent solution (pH 7.5- 10.5), a l~xlO cm piece of the colored fabric and a multi-fiber swatch which is used as a pick-up tracer for the bleeding d~e. The multifiber swatch consists of 6 strips (1.5cmx1.5cm each~ made of different materials (polyacetate, cotton, polyamide, polyester, wool and orlon) which were sewn together.
The extent of dye transfer is reported in terms of the c value which represents the change in the Hunter a, b values and is defined by the following equation:
~ C - {(af ~ai)2 + (bf-bi)2}l/2 where the subscripts i and f refer to the Hunter value before and after washing in the presence of the bleeding fa~ric, respectively.
WO94/11477 17 ,?l PCI/US93/10543 ~`
Exarnple I ~a): poly(4-vinylpyridine-N-oxide) and FeTPPS
'~ I
The experimental conditions are:
A:detergent solution without any dye transfer inhibition system.
`I B:detergent solution containing 10 ppm of Iron-J tetrasulfonated phenylporphyrin ~FeTPPS) and the optimum ! level of bleach as determined from the test method above.
C:deter~ent solution containing 10 ppm of poly(4-vinylpyridine-N-oxide)(PVNO).
D:detergent solution containing 10 ppm of FeTPPS and 10 ppm of poly(4-vinylpyridine~N-oxide).
) i ~ C value on cotton Fabric A B ~ C D
~ ~, ~
blue sweater 15.2 14.7 8.2 4.8 purple trousexs-1 19.3 7.0 17.8 2.8 green sweater 8.7 8.4 6.6 4.5 purple ~ogging 12.7 12.2 7.6 5.7 purple trousers 14.5 13.1 6.4 4,3 blue trousers 18.7 13.9 22.2 10.8 The higher the ~ C value, the more dye transferred onto the pick-up swatch.
Conclusion: The dye transfex inhibition benefits from the combined PVNO and FeTPPS are in all cases better than benefits provided by either the catalyst or polymer alone. In addition, not only additive effects are observed but these results show true synergism between the catalyst and poly~4-vinylpyridine~N-oxidel.
'-'21~8811 ~xample I(b): poly(4-vinylpyridine-N-oxide) and MnPc The experimental conditions are:
A:detergent solution without any dye transfer inhibition system.
B:detergent solution containing 10 ppm of Mn-Phthalocyanine tetrasulfonated ~MnPC) and the optimum level of bleach as determined from the test method above.
C:detergent solution containing 10 ppm of poly(4-vinylpyxidine-N-oxide). (PVNO) D:detergent solution containing 10 ppm of MnPc ~nd 10 ppm of poly(4-vinylpyridine-N-oxide).
~C values on cotton _ __ Fabric A B C D
blue sweater 15.214.7 8.2 4.8 green sweater 8.7 8.4 6.6 4.5 purple jogging 12.712.2 7.6 5.7 purple trousers 14.513.1 6.4 4.3 Concluslon: The dye transfer inhibition benefits from the combined PVNO and MnPC are in all cases better than benefits provided by either the catalyst or polymer alone. In addition, these results show true synergism between the catalyst and poly(4-vinylpyridine-N-oxide).
. ~ ." ,, , . .... ..... ... ... .. . -~ WO94/11477 PCT/US93/10~43 ,21~`8811 ~I
`~ EXAMPLE II (A/B/C/D) .
, A liquid dye transfer inhibiting composition according to the present invention is prepared, having the following '~ compositions :
~i!
., - ~inear alkyl benzene sulfonate 10 - Sodium C12_15 alkyl sulfate 3 - C14_1s alkyl 2.5 times ethoxylated sulfate 0 - C12 glucose amide 0 - C12_1s alcohol 7 times ethoxylated 11.6 - Oleic acid 2.5 - Citric acid - C12_14 alkenyl substituted succinic acid 0 - Sodium Hydroxide 3.5 - Ethanol 6 - Monoethanolamine 0 - Triethanolamine 6.4 - 1,2-propane diol 1.5 - Glycerol o - Boric acid o - Diethylene triamine penta 0.8 (methylene phosphonic acid) - CaC12 - Soil release polymers 0.5 - Fatty acids 12 - Enzymes 0.65 Water and minors - - - - Balance to 100% - - -The above composition was supplemented with the catalyst, p~lymer and bleach accordlng to table I
WO94/11477 PCT/US93/10~3 ~
2~8811 20 Table I
A B C D
..
- Catalyst l: Mn-tetrasulfonated 0 0.05 0 0 tetraphenylporphine - Catalyst 2: Cr-tetrasulfonated 0 0 O.lO0 0 tetraphenylporphine - Catalyst 3: Fe tetrasulfonated 0 0 0 0.2 tetraphenylporphine - Catalyst 4: Mn-Phthalocyanine 0.15 0.0 0 0 tetrasulfonated ~ H22 0.3-0~5 0 0 0 - Perborate 0 0 1-5 0.5 - Percarbonate , 0 0.4 0 O.lO0-Pc~ly(4-vinylpyridine-N-oxide) O.l 0.30.05 0.2 Example III ~A/B/C/D):
A compact granular dye transfer inhibiting composition according to the present invention is prepared, having the followir1g formulation:
%
Linear alkyl benzene sulphonate ll.40 Tallow alkyl sulphate l.80 C4s alkyl sulphate 3.00 C~s alcohol 7 times ethoxylated 4.00 Tallow alcohol ll times ethoxylated l.80 Dispersant ` ~ 0.07 Silicone fluid 0.80 Trisodium citrate 14.00 Citric acid 3.00 Zeolite 32.50 Maleic acid actylic acid copolymer 5.00 DETMPA : l.00 Cellulase (active protein) 0.03 W094/11477 PCT/US93/l0543 Alkalase/BAN 0.60 Lipase 0.36 Sodi.um silicate 2.00 Sodium sulphate 3.50 Minors up to 100 The above composition was supplemented with the catalyst, polymer and bleach according to table II
Table II
A B C D
- Catalyst 1: Mn-tetrasulfonated 0 0.05 0 0 tetraphenylporphine - Catalyst 2: Cr-tetrasulfonated 0 0 0.100 0 tetraphenylporphine - Catalyst 3: Fe-tetrasulfonated 0 0 0 0.2 tetraphenylporphine - Catalyst 4: Mn-Phthalocyanine 0.15 0.0 0 0 tetrasulfonated ~ H22 0.3-0.5 0 0 0 Perborate 0 0 1-5 2.5 - Percarb,onate 0 0.4 0 0 - Poly(4-vinylpyridine-N-oxide) 0.050.1 0.15 0~2-0.4 - TAED 0 0 0.5 1.0 .
Claims (11)
1. A dye transfer inhibiting composition comprising:
A. a metallo catalyst selected from a) metallo porphin and water-soluble or water-dispersable derivatives thereof;
b) metallo porphyrin and water-soluble or water-dispersable derivatives thereof;
c) metallo phthalocyanine and water-soluble or water-dispersable derivatives thereof;
B. polyamine N-oxide containing polymers C. an efficient amount of a bleaching agent.
A. a metallo catalyst selected from a) metallo porphin and water-soluble or water-dispersable derivatives thereof;
b) metallo porphyrin and water-soluble or water-dispersable derivatives thereof;
c) metallo phthalocyanine and water-soluble or water-dispersable derivatives thereof;
B. polyamine N-oxide containing polymers C. an efficient amount of a bleaching agent.
2. A dye transfer inhibiting composition according to claim 1 containing a metallo porphin derivative, wherein said porphin is substituted on at least one of its meso positions with a phenyl or pyridyl substituent selected from the group consisting of wherein n and m may be 0 or 1, A is selected from the water-solubilizing group, e.g., sulfate, sulfonate, phosphate, and carboxylate groups, and B is selected from the group consisting of C1-C10 alkyl, C1-C10 polyethoxyalkyl and C1-C10 hydroxyalkyl.
3. A dye transfer inhibiting composition according to claim 2 wherein the substituents on the phenyl or pyridyl groups are selected from the group consisitng of -CH3, -C2H5, CH2CH2CH2SO3-, -CH2COO-, -CH2C-H(OH)CH2SO3-, and -SO3.
4. A dye transfer inhibiting composition according to claims 1-3, containing a metallo porphin derivative, wherein said metallo porphin is substituted on at least one of its meso positions with a phenyl substituent selected from the group consisting of wherein X1 is (=CY-) wherein each Y, independently, is hydrogen, chlorine, bromine or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl.
5. A dye transfer inhibiting composition according to claim 1 wherein the central atom is selected from Fe, Mn, Co, Rh, Cr, Ru, Mo or other transition metals.
6. A dye transfer inhibiting composition according to claim 1 wherein the wash concentration of metallo catalyst is from 10-8 to 10-3 molar, preferably from 10-6 to 10-4 molar.
7. A dye transfer inhibiting composition according to claims 1-6 wherein the polyamine N-oxide is polyvinylpyridine N-oxide
8. A dye transfer inhibiting composition according to claim 1 wherein the bleaching agent is selected from an activated or a non-activated bleach.
9. A dye transfer inhibiting composition according to claims 1-8 which is a detergent additive, in the form of a non-dusting granule or a liquid.
10. A detergent composition which comprises a dye transfer inhibiting composition according to any of the preceding claims further comprising enzymes, surfactants, builders, and other conventional detergent ingredients.
11. A detergent composition which comprises a dye transfer inhibiting composition according to any of the preceding claims further comprising a cellulase.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92870181.2 | 1992-11-06 | ||
| EP19920870181 EP0596184B1 (en) | 1992-11-06 | 1992-11-06 | Detergent compositions inhibiting dye transfer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2148811A1 true CA2148811A1 (en) | 1994-05-26 |
Family
ID=8212281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2148811 Abandoned CA2148811A1 (en) | 1992-11-06 | 1993-11-03 | Dye transfer inhibiting compositions containing a metallocatalyst, a bleach and polyamine n-oxide polymer |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0596184B1 (en) |
| JP (1) | JP3856817B2 (en) |
| CN (1) | CN1088253A (en) |
| AU (1) | AU5590594A (en) |
| CA (1) | CA2148811A1 (en) |
| MX (1) | MX195191B (en) |
| WO (1) | WO1994011477A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2189747A1 (en) * | 1994-05-11 | 1995-11-23 | Regine Labeque | Dye transfer inhibiting compositions with specifically selected metallo catalysts |
| US5908821A (en) * | 1994-05-11 | 1999-06-01 | Procter & Gamble Company | Dye transfer inhibiting compositions with specifically selected metallo catalysts |
| GB0118936D0 (en) * | 2001-08-02 | 2001-09-26 | Unilever Plc | Improvements relating to colour-safe fabric treatment compositions |
| KR100502955B1 (en) * | 2002-10-11 | 2005-07-21 | 씨제이라이온 주식회사 | Granulate composition for detergent to prevent from spotting on clothes |
| CA2575589C (en) * | 2004-09-23 | 2013-11-12 | Unilever Plc | Laundry treatment compositions comprising hydrophobic dyes |
| CN101922111B (en) * | 2010-09-14 | 2012-05-09 | 东华大学 | Low-temperature activation bleaching method using water-soluble metalloporphyrin |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1408144A (en) * | 1972-06-02 | 1975-10-01 | Procter & Gamble Ltd | Bleaching process |
| BE785653A (en) * | 1971-07-02 | 1973-01-02 | Procter & Gamble Europ | |
| GB1541576A (en) * | 1975-06-20 | 1979-03-07 | Procter & Gamble Ltd | Inhibiting dye ltransfer in washing |
| CA1104451A (en) * | 1978-02-28 | 1981-07-07 | Manuel Juan De Luque | Detergent bleach composition and process |
| DE2814329A1 (en) * | 1978-04-03 | 1979-10-11 | Henkel Kgaa | Washing agents contg. N-vinyl-oxazolidone polymers - inhibiting transfer of dyes from coloured textiles onto white textiles |
| US4545919A (en) * | 1982-08-31 | 1985-10-08 | Ciba-Geigy Corporation | Detergent composition for washing off dyeings obtained with fibre-reactive dyes and washing process comprising the use thereof |
| 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 |
| GB8625475D0 (en) * | 1986-10-24 | 1986-11-26 | Unilever Plc | Detergent composition |
| US5082585A (en) * | 1989-02-02 | 1992-01-21 | Lever Brothers Company, Division Of Conopco, Inc. | Enzymatic liquid detergent compositions containing nonionic copolymeric stabilizing agents for included lipolytic enzymes |
| EP0384503B1 (en) * | 1989-02-22 | 1995-06-28 | Unilever N.V. | Metallo-porphyrins for use as bleach catalyst |
| DE69117490T2 (en) * | 1991-04-12 | 1996-09-26 | Procter & Gamble | Compact detergent containing polyvinylpyrrolidone |
| ES2114536T3 (en) * | 1991-10-14 | 1998-06-01 | Procter & Gamble | DETERGENT COMPOSITIONS THAT INHIBIT THE TRANSFER OF DYES IN THE WASH. |
-
1992
- 1992-11-06 EP EP19920870181 patent/EP0596184B1/en not_active Expired - Lifetime
-
1993
- 1993-11-03 CA CA 2148811 patent/CA2148811A1/en not_active Abandoned
- 1993-11-03 WO PCT/US1993/010543 patent/WO1994011477A1/en active Application Filing
- 1993-11-03 JP JP51217394A patent/JP3856817B2/en not_active Expired - Lifetime
- 1993-11-03 AU AU55905/94A patent/AU5590594A/en not_active Abandoned
- 1993-11-06 CN CN 93112694 patent/CN1088253A/en active Pending
- 1993-11-08 MX MX9306967A patent/MX195191B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| MX9306967A (en) | 1995-01-31 |
| JPH08505162A (en) | 1996-06-04 |
| MX195191B (en) | 2000-02-04 |
| EP0596184A1 (en) | 1994-05-11 |
| EP0596184B1 (en) | 1998-04-15 |
| AU5590594A (en) | 1994-06-08 |
| WO1994011477A1 (en) | 1994-05-26 |
| JP3856817B2 (en) | 2006-12-13 |
| CN1088253A (en) | 1994-06-22 |
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