CA2179265C - Detergent compositions inhibiting dye transfer - Google Patents
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- CA2179265C CA2179265C CA002179265A CA2179265A CA2179265C CA 2179265 C CA2179265 C CA 2179265C CA 002179265 A CA002179265 A CA 002179265A CA 2179265 A CA2179265 A CA 2179265A CA 2179265 C CA2179265 C CA 2179265C
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3792—Amine oxide containing polymers
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
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Abstract
A dye transfer inhibiting composition comprising a mixture of polyamine N-oxide polymers having a low and high oxidation degree, said polyamine N-oxide polymers containing units having structural formula (I), wherein P is a polymerisable unit, whereto the N-O group can be attached to or wherein the N-O group forms part of the polymerisable unit. A is (a), (b), (c), -O-, -S-, (d); x is 0 or 1; R are aliphatic, ethoxylated, aliphatic, aromatic, heterocyclic or alicyclic groups whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
Description
DETERGENT COMPOSITIONS INHIBITING
DYE TRANSFER
Field of the Invention The present invention relates to a composition and a process for inhibiting dye transfer between fabrics during washing.
More in particular, the present invention relates to dye transfer inhibiting compositions comprising a mixture of polyamine N-oxide polymers having a low oxidation degree and polyamine N-oxide polymers having a high oxidation degree.
Background of the=_ Invention One 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.
z 1796 One way of overcoming this problem would be to complex or adsorb the fugitive dyes washed out of dyed fabrics before they have the opportunity to become attached to other articles in the wash.
Polymers have been used within detergent compositions to inhibit dye transfer. EP-A-O 102 923 describes the use of carboxyl containing polymers within aqueous compositions. DE-A-2 814 329 discloses the use of N-vinyl-oxazolidone polymers and FR-A-2 144 721 discloses the use of 15-35~ of a copolymer of polyvinylpyrrolidone and acrylic acid nitrile or malefic anhydride within a washing powder.
EP-265 257 describes detergent compositions comprising an alkali-metal carboxy-metal carboxymethylcellulose, a vinylpyrrolidone polymer and a polycarboxylate polymer.
It has now been surprisingly found that a particular combination of polyamine N-oxide polymers having a low oxidation degree and polyamine N-oxide polymers having a high oxidation degree are very efficient in eliminating transfer of a broad range of solubilized or suspended dyes. This finding allows to formulate compositions which exhibit excellent dye transfer inhibiting properties over a broad selection of dyes.
According to another embodiment of this invention a process is also provided for laundering operations involving colored fabrics.
Summarv of the Invention The present invention relates to inhibiting dye transfer compositions comprising a mixture of polyamine N-oxide polymers having a low oxidation degree and polyamine N-oxide polymers having a high oxidation degree.
Detailed description of the invention The compositions of the present invention comprise a mixture of polyamine N-oxide polymers having a low oxidation degree ("LOPAO") and polyamine N-oxide polymers having a high oxidation degree ("HOPAO").
By "polyamine N-oxide polymers having a low oxidation degree"
as used herein, is meant polyamine N-oxide polymers wherein the ratio of amine to amine N-o~:ide is from 1000:1 to 1:1, more preferably from 100:1 to 1:1., most preferably from 10:1 to 1:1.
By "polyamine N-oxide polymers having a high oxidation degree"
as used herein, is meant polyamine N-oxide polymers wherein the ratio of amine to amine N-oxide is from 2:3 to 1:1000000, more preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000.
The amount of amine oxide groups present in said polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxidation.
The polyamine N-oxide polymers contain units having the following structure formula .
P
I
(I) Ax I
R
wherein P is a polymerisable unit, whereto the N-0 group can be attached to or wherein the N-O group forms part of the polymerisable unit or a combination of both.
n a n I
A is NC, C0, C, -O-,-S-, -N- : x is 0 or 1:
WO 95/20032 ~ PCT/US95/00626 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 wherein the nitrogen of the N-O group is part of these groups.
The N-0 group can be represented by the following general structures .
I I
(R1 ) x -N- (R2 ) y =N- (R1 ) x I
(R3) z wherein R1, R2, R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group forms part of these groups.
The N-0 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-0 group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
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 pyridine, pyrole, imidazole, pyrolidine, piperidine, quinoline, acridine and derivatives thereof.
Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-0 group is attached to the R-group.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-0 group is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.
Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrole, imidazole and derivatives thereof.
Another preferred class of pclyamine 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-0 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 polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer types is either an amine N-oxide or not . The amine oxide unit of the polyamine N-oxides has a PKa < 10, preferably PKa < 7, more preferred PKa < 6.
The polyamine oxides can be obtained in almost any degree of polymerisation. The degree of po:Lymerisation 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 1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20, 000.
WO 95!20032 ~ ~ l 9 2 6 5 pCT/US95/00626 The polyamine N-oxides of the present invention are typically present from 0.001 to 100 , more preferably from 0.01 to 2%, most preferred from 0.05 to to by weight of the dye transfer inhibiting composition.
The present compositions are conveniently used as additives to conventional detergent compositions for use in laundry operations. The present invention also encompasses dye transfer inhibiting compositions which will contain detergent ingredients and thus serve as detergent compositions.
Methods for making polyamine N-oxides .
The production of the polyamine-N-oxides may be accomplished by polymerizing the amine monomer and oxidizing the resultant polymer with a suitable oxidizing agent, or the amine oxide monomer may itself be polymerized to obtain the polyamine N-oxide.
The synthesis of polyamine N-oxide can be exemplified by the synthesis of polyvinyl-pyridine N-oxide.
Poly-4-vinylpyridine ex Polysciences (mw. 50 000, 5.0 g., 0.0475 mole) was predisolved in 50 ml acetic acid and treated with a peracetic acid solution (25 g of glacial acetic acid, 6.4 g of a 30~ vol. solution of H202, and a few drops of H2S04 give 0.0523 mols of peracetic acid) via a pipette. The mixture was stirred over 30 minutes at ambient temperature (32 C).
The mixture was then heated to 80-85 C using an oil bath for 3 hours before allowing to stand overnight. The polymer solution then obtained is mixed with 11 of acetone under agitation. The resulting yellow brown viscous syrup formed on the bottom is washed again with 11 of aceton to yield a pale crystalline solid.
The solid was filtered off by gravity, washed with acetone and then dried over P205.
The amine . amine N-oxide ratio of this polymer is 1:4.
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 surfactants, is given in US Patent 3,664,961 issued to Norris on May 23, 1972.
Mixtures of anionic surfactants are particularly suitable herein, especially mixtures of sulphonate and sulphate 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-C:18 fatty source preferably from a C16-Clg fatty source. In each instance the cation is an alkali metal, preferably sodium. Preferred sulphate 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 C14-15 alkyl sulphates. The cation in each instance is again an alkali metal cation, preferably sodium.
One class of nonionic surfactants useful in the present ~_nvention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HL:B) in the range from 8 to 17, preferably from 9.5 to 13.5, snore 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 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.
WO 95/20032 ~ ~ ~ ~ L ~ ~ PCT/US95/00626 Especially preferred nonionic surfactants of this type are the Cg-C15 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C14-C15 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 (CnH2n0)tZx wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon 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 and less than 50o 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.
Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula R2 - C - N - Z, I
wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having 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 C11-15 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 pentamethylenephosphon:ic acid. Though less preferred ' 1 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-6T"' (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si205).
Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic: acid and ether derivatives thereof as disclosed in Beigia;n Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, malefic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1.379,241, lactoxysuccinates described in Canadian Patent No. 973,771, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.
,o Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1, 1, 2. 2-ethane tetracarboxylates, 1, 1, 3, 3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxyla-tes containing su:lfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos.
1, 398, 421 and 1, 398, 422 and in LJ. S . Patent No . 3, 936, 448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1,439,000.
Alicyclic and heterocycli<: polycarboxylates include cyclopentane-cis,cis,cis-tetraca,rboxylates, cyclopentadienide pentacarboxylates, 2,3,9,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran -cis - dicarboxylates, 2,2,5,5-tetrahydrofuran - tet:racarboxylates, 1,2,3,4,5,6-hexane -hexacarboxylates and and carboxymethyl derivatives of polyhydric alcohols such as so:rbitol, mannitol and xylitol.
Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS-6), and a water-soluble carboxylate chelating agent such as citric acid.
A suitable chelant for inclusion in the detergent compositions in accordance with the invention is ethylenediamine-N, N'-disucciriic acid (EDDS) or the alkali metal, alkaline earth metal,, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Preferred EDDS
compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of ~.~~4 EDDS include Na2EDDS and Na4EDDS. Examples of such preferred magnesium salts of ED17S include MgEDDS and Mg2EDDS. The magnesium salts are the most prE:ferred for inclusion in compositions in accordance with the invention.
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 preferred unsaturated fatty acid is oleic 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 builder system for use in granular compositions the purposes of the invention include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amiono polyalkylene 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, 596, 756.
Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with malefic anhydride, such copolymers having 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.
Detergent ingredients that can be included in the detergent compositions of the present invention include bleaching agents.
,.
These bleaching agent componenr_s can include one or more oxygen bleaching agents and, depending upon the bleaching agent chosen, one cr more bleach activators. When present bleaching compounds will typically be present at levels of from about l~s to aboLt 10$, of the detergent composition. In general, bleaching compounds are: optional components in non-liquid formulations, e.g. granular detergents. If present, the amount of bleach activators will typically be from about 0.1~ to about 60$, more typically from about 0.5~ to about 40$ of the bleaching composition.
The bleaching agent compone>nt for use herein can be any of the bleaching agents useful for detergent compositions including oxygen bleaches as well as others known in the art.
In a method aspect, this invention further provides a method for cleaning fabrica, fibers, textiles. at temperatures below about 50°C. especially below about 40°C, with a detergent composition containing polyamine N-oxide containing polymers, optional auxiliary detersive surfactants. optional detersive: adjunct ingredients, and a bleaching agent.
The bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent.
One category of oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perberzoic acid. 4-nonylamino-4-oxoperoxybutyric acid and dip~eroxydodecanedioic acid. Such bleaching agents are disclosed in~U.S. Patent 4,483,781, U.S.
Patent No. 4,634,551, European Patent Application 0,133,354 and U. S . Patent 4, 412, 934 . High.ly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,,551.
Another category of bleaching agents that can be used encompasses the halogen bleaching agents. Examples of hypohalite bleaching agents, for example, include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-~chloro and N-bromo alkane sulphonamides. Such materials are normally added at 0.5-lOX
by weight of the finished product, preferably 1-5~ by weight.
Preferably, the bleaches suitable for the present invention include peroxygen bleaches. Examples of suitable water-soluble solid peroxygen bleaches include hydrogen peroxide releasing agents ~~uch as hydrogen peroxide, perborates, e.g. perborate monohydrate, perborate tetrahydrate, persulfates, percarbonates, peroxydisulfates, perphosphates and peroxyhydrates. Preferred bleaches are percarbonates and perborates.
The hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine(TAED), nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934) , 3,5,-trimethylhexanoloxybenzenesulfo;nate (ISONOBS, described in EP
120,591) or pentaacetylglucose (PAG). which are perhydrolyze_d to form a peracid as the active: bleaching species, leading to improved bleaching effect. Fvlso ,suitable activators are acylated citrate esters (ATC) such as disclosed in Canadian Application No. 2,124,787.
The hydrogen peroxide may also be present by adding an enzymatic system (i.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 537,381 published April 4, 1993.
Other peroxygen bleaches suitable for the present invention include organic peroxyacids such as percarboxylic acids.
Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent o:E particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials can be Bt -. 217926 5 deposited upca the substrate duri~g the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is, bleached. Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718. Typically, detergent compositions will contain about 0.025$ to about 1.25$, b y weight, of sulfonated zinc phthalocyanine.
Other detergent ingredients that can be included are detersive enzymes which can be included in the detergent formulations for a wide variety of purposes including removal of protein-based. carbohydrate-based, or triglyceride-based stains, for example, and prevention of refugee dye transfer.
The enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.05 mg to about 3 mg, of active enzyme per gram of the composition. .
Suitable examples of proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the trademarks Alcalase , Savinase and Esperase by Novo Industries A./S (Denmark) and Maxatase by International Hio-Synthetics, Lnc. (The Netherlands) and FN-base by Genencor, Optimase and Opticlean by MKC.
Of interest in the category of proteolytic enzymes, especially for liquid detergent compositions, are enzymes referred to herein as Protease A and Protease B. Protease A
is described in European Patent Application 130,756. Protease B is described in European Patent Application No. 251,446 published January 7, 1988. Amylases include, for example, -amylases Bt obtained from a special strain of B.licheniforms, described in more detail in British Patent. Specification No. 1,296,839 (Novo). Amylolytic proteins include, for example, Rapidase~'"', Maxamylz'"' (International Bio-Synthetics, Inc. ) and TermamylT'", (Novo Industries) .
The cellulases usable in the present invention include both bacterial or fungal cellulase. 1?referably, they will have a pH optimum of between 5 and 9~.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens.
Suitable cellulases are also disclosed in GH-A-2.075.028 ;
GB-A-2.095.275 and DE-OS-2.247.8:32.
Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var.
thermoidea), particularly the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase .extracted from the hepatopancreas of a marine mollusc (Dolabella Auricula Sola:nder).
Other suitable cellulases are cellulases originated from Humicola Insulens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids.
Especially suitable cellulase are the cellulase having color care benefits. Examples of such cellulases are cellulase described in United States Patent No. 5,520,838.
Suitable lipase enzymes for detergent usage include those produced by microorganisms of t:he Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.1.54, as disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunoligical cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade mark Lipase P "Amano." hereinafter referred to as "Amano-P".
~B1 Especially suitable Lipase are lipase such as M1 LipaseTh' (Ibis) and LipolaseT''' (Novo) .
Peroxidase enzymes are used in combination with oxygen sources, e.g, percarbonate, perborate, persulfate, hydrogen peroxide. etc. They are used for "solution bleaching", i.e.
to prevent transfer of dyes. of pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chl.oro- and bromo-peroxidase.
Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813 and in Canadian Patent Application No. 2,122,987.
In liquid formulations, an enzyme stabilization system is preferably utilized. Enzyme stabilization techniques for aqueous detergent compositions are well known in the art. For example, one technique for enzyme stabilization in aqueous solutions involves the use of free calcium ions from sources such as calcium acetate, calcium formate and calcium propionate. Calcium ions can be used in combination with short chain carboxylic acid salts, preferably formates. See, for example, U.S. patent 4,318,~g18. It has also been proposed to use polyols like glycerol and sorbitol. Alkoxy-alcohols, dialkylglycoethers, mixtures of polyvalent alcohols with polyfunctional aliphatic .amines (e.g., such as diethanolamine, triethanolamine, di-isopropanolamime, etc.), and boric acid or alkali metal. borate. Enzyme stabilization techniques are additionally disclosed and exemplified in U.S.
patent 4, 261, 868, U.S. Patent 3, 600, 319, and European Patent Application Publication No. 0 199 405. Non-boric acid and borate stabilizers are preferred. Enzyme stabilization systems are also described, for example, in U.S. Patents 4,261,868, 3,600,319 and 3,519,570.
Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending European Patent Application No. 553,607 published August 4, 1993. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
B!
Especially preferred detergent ingredients are combinations with technologies which also provide a type of color care benefit. Examples of these technologies are cellulase and/or peroxidases and/or metallo catalysts for color maintance rejuvenation.
Another optional ingredient: is a suds suppressor, exemplified by silicones, and silica-silicone mixtures.
Silicones can be generally represented by alkylated polysiloxane materials while ailica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silic;as of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent impermeable carrier. Alternatively the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
A preferred silicone suds cons=rolling agent is disclosed in Bartollota et al. U.S. Patent 3 933 672. Other particularly useful suds suppres~ors are t:he self-emulsifying silicone suds suppressors, described in ~~erman Patent Application DTOS
2 646 126 published April 28, 1977. An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. Especially preferred suds controlling agent are the suds suppressor system comprising a mixture of silicone oils and 2-alkyl-alcanols.
Suitable 2-alkyl-alcanols are: 2-butyl-octanol which are commercially available under the trade mark Isofol 12 R.
Such suds suppressor system are described in Canadian Patent Application No. 2,146,636.
Especially preferred silicone suds controlling agents are described in European Patent Application No. 573,699 published June 6, 1992.
2~~92s5 18 Said compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as AerosilR.
The suds suppressors described above are normally employed at levels of from 0 . 001 o to 2 o by weight of the composition, preferably from O.Olo to 1~ by weight.
Other components used in detergent compositions may be employed, such as soil-suspending agents soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and non-encapsulated and encapsulated perfumes.
Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo-or co-polymeric polycarboxylic acids or their salts. Polymers of this type include the polyacrylates and malefic anhydride-acrylic acid copolymers previously mentioned as builders, as well as copolymers of malefic anhydride with ethylene, methylvinyl ether or methacrylic acid, the malefic anhydride constituting at least 20 mole percent of the copolymer.
These materials are normally used at levels of from 0.5$ to 10~ by weight, more preferably from 0.75 to 8~, most preferably from 1$ to 6~ by weight of the composition.
Preferred optical brighteners are anionic in character, examples of which are disodium 4,41-bis-(2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-2:21 disulphonate, disodium 4, - 41-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:21 - disulphonate, disodium 4,41 - bis-(2,9-dianilino-s-triazin-6-ylamino)stilbene-2:21 -disulphonate, monosodium 41,411 -bis-(2,4-dianilino-s-triazin-6 ylamino)stilbene-2-sulphonate, disodium 4,41 -bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,21 - disulphonate, disodium 4,41 -bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,21 disulphonate, disodium 4,41bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-~v s-triazin-6- ylamino)stilbene-2,21disulphonate and sodium ~ ~ ~~~a _.. WO 95120032 PCTIUS95/00626 2(stilbyl-411-(naphtho-11,21:4,5)-1,2,3 - triazole-211-sulphonate.
Other useful polymeric materials are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 a.nd most preferably about 4000. These are used at levels of from 0.20$ to 5~ more preferably from 0.25$ to 2.5~ by weight. These polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.
Soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has 'the formula - (CH3(PEG)43)0.75(POH)0.25~T-PO)2.8(~r-PEG)0.4~T(PO-H)0.25((PEG)43CH3)p.75 where PEG is -(OC2H4)O-,PO is (OC3H60) and T is (pcOC6H4C0).
Also very useful are modified polyesters as random copolymers of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol. The target is to obtain a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers, herein will be end-capped by sulphobenzoate groups. However, sc>me copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist "secondarily" of such species.
The selected polyesters herein contain about 46$ by weight of dimethyl terephtalic acid, about 16$ by weight of propane -1.2 diol, about 10$ by weight ethylene glycol about 13$ by weight of dimethyl sulfobenzoid acid and about 15$ by weight of sulfoisophtalic acid, and have a molecular weight of about 3.000. The polyesters and their method of preparation are described in detail in EPA 311 342.
The detergent compositions according to the invention can be in liquid, paste, gels 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/1; in such 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 metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10$ filler salt. The liquid compositions according to the present invention can also be in "concentrated form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents. Typically, the water content of the concentrated liquid detergent is less than 30$, more preferably less than 20$, most preferably less than 10$ by weight of the detergent compositions.
The present invention also relates to a process for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.
The process comprises contacting fabrics with a laundering solution as hereinbefore described.
The process of the invention is conveniently carried out in the course of the washing process. The washing process is ,_ WO 95/20032 PCT/US95100626 preferably carried out at 5 °C to 75 °C, especially 20 to 60, but the polymers are effective at up to 95°C and higher temperatures. The pH of the treatmE~nt solution is preferably from 7 to 11, especially from 7.5 to 10.5.
The process and compositions of the invention can also be used as detergent additive products..
Such additive products are intendE:d to supplement or boost the performance of conventional detE:rgent compositions.
The detergent compositions according to the present invention include compositions which are t:o be used for cleaning substrates, such as fabrics, fibers, hard surfaces, skin etc., for example hard surface cleaning compositions (with or without abrasives), laundry detergent compositions, automatic and non automatic dishwashing compositions.
The following examples are meant to exemplify compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention, said scope being determined according to claims which follow.
A liquid detergent composition according to the present invention is prepared, having the following compositions .
$ by weight of the total detergent composition Linear alkylbenzene sulfonate 10 Alkyl sulphate 4 Fatty alcohol (C12-C15) ethoxylate 12 Fatty acid 10 Oleic acid 4 Citric acid 1 NaOH 3.4 Propanediol 1.5 Ethanol 10 Table I
The extent of dye transfer is assessed by a Hunter Colour measurement. The Hunter Colour system evaluates the colour of a fabric sample in terms of the Dc value which represents the change in the Hunter a, b values which are determined by reflecting spectofotometry. The Dc value is defined by the following equation:
Dc = ~(af -ai)2 + (bf-bi)2}1/2 where the subscripts i and f refer to the Hunter value before and after washing in the presence of the bleeding fabric, respectively. The least significant difference is 1 at 95~
confidence level.
EXAMPLE I
The extent of dye transfer from different colored fabrics was studied using a launder-o-meter test that simulates a 30 min wash cycle. The launder-o-meter beaker contains 200 ml of a detergent solution, a lOcmxlOcm piece of the colored fabric and a multifiber swatch which is used as a pick-up tracer for the bleeding dye. The bleeding dye consists of one part direct blue 90, one part direct blue 112 and one part direct violet 47. The multifiber swatch consists of cotton.
Experimental conditions:
pH =7.8 A: A detergent composition according to Table I which does not contain any dye transfer inhibition system.
B: A detergent composition according to Table I containing 10 ppm of PVNO (poly(4-vinylpyridine-N-oxide)) which has an average molecular weight of about 10,000 and an amine to amine N-oxide ratio of 1:10 (HOPAO).
C: A detergent composition according to Table I containing 10 ppm of PVNO (poly(4-vinylpyridine-N-oxide)) which has an average molecular weight of about 30,000 and an amine to amine N-oxide ratio of l:l (LOPAO).
2~ ~'~~~~'_ ._ WO 95120032 PCTIUS95/00626 D: A detergent composition according to Table I containing 5ppm of PVNO (poly(4-vinylpyridine-N-oxide)) which has an average molecular weight of about 3(),000 and an amine to amine N-oxide ratio of 1:10, and 5ppm of 1?VNO (poly(4-vinylpyridine-N-oxide)) which has an average molecular weight of about 30,000 and an amine to amine N-oxide ratio of 1:1 (HOPAO +
LOPAO).
Results: Dc values for the cotton pick-up tracer.
Bleeding fabric A B C D
color Direct Blue 90/ 10.3 4.2 4.5 3 Direct Blue 112 and Direct Violet 47 EXAMPLE II (A/B/C/D) Liquid detergent composi~ions according to the present invention are prepared, having the following compositions .
P. B C D
Linear alkylbenzene sulfonate 1.8 - 6 -C12-C15 alkyl sulfate -~ 16.0 - -C12-C15 alkyl ethoxylated sulfate -~ 11.0 4.0 25.0 C12-C14 N-methyl glucamide -~ 7.0 9.0 9.0 C12-C14 fatty alcohol ethoxylate 1.2.0 5.0 6.0 6.0 C12-C16 fatty acid 9.0 6.8 14.0 14.0 Fatty acid 1.0 10 10 10 Oleic acid 4 4 4 4 Citric acid 1 1 1 1 Diethylenetriaminepentamethylene 1.5 1.5 1.5 1.5 phosphoric acid ,.
Y ~ ~. ~ . . .
.',b f ,.., ,. , ' f : ' t , , , Propanedioi 1.5 1.5 1.5 1.5 Ethanol 10 10 10 10 Ethoxylated tetraethylene pentamine 0.7 0.7 0.7 0.7 Poly(4-vinylpyridine)-N-oxide (HOPAO) 0.3 0.3 0.3 0.3 Poly(4-vinylpyridine)-N-oxide (LOPAO) 0.3 0.3 0.3 0.3 ThermamylT"' 0.13 0.13 0.13 0.13 CarezymeT"' 0.014 0.014 0.014 0.014 EN-Base 1.8 1.8 1.8. 1.8 Lipolase 0.14 0.14 0.14 0.1 Endoglucanase A 0.53 0.53 0.53 0.53 Suds supressor (ISOFOL) 2.5 2.5 2.5 2.5 Water and Minors up to 100 NaOH and/or MEA to adjust pH '7.8 to EXAMPLE III (A/H/C/D) --Compact granular detergent compositions according to the present invention are prepared, having the following formulation:
% by weight of the total detergent compoaitioa A, B C D
Polyhydroxy fatty 'acid amide 10 Alkyl alkoxylated sulfate - 9 9 9 Alkyl sulphate 9.80 4.80 4.80 4.60 C14-15-alcohol 7 times 9.00 4.00 4.00 4.00 ethoxylate Tallow alcohol 11 times 1.8 1.80 1.8 1.8 ethoxylated Dispersant 0.07 0.07 0.07 0.07 Silicone fluid 0.80 0.80 0.80 0.80 Trisodium citrate ~ 14.00 14.00 14.00 14.00 Citric acid 3.00 3.00 3.00 3.00 Bi Zeolite 25.00 20.00 20.00 32.50 Diethylenetriamine penta- 0.6 0.6 0.6 0.6 methylene phosphonic acid Malefic acid acrylic acid 5.00 5.00 5.00 5.00 copolymer Carezyme T-granulate 0.2 0.5 0.15 0.3 Alcalase T-granulate 0.60 0.60 0.20 0.50 Lipolase T-granulate 0.20 0.10 0.25 0.40 Termamyl T-granulate 0.3 0.3 0.3 0.3 Sodium silicate 2.00 2.00 2.00 2.00 Sodium sulphate 3.50 3.50 3.50 3.50 Percarbonate - - 20 -Perborate 15 15 - -Encapsulated perfume 0.2 - - -Perfume 0.3 0.2 0.3 0.2 Poly(4-vinylpyrridine) N-oxide (HOPAO) 0.3 0.3 0.3 0.3 Poly(4-vinylpyrridine) N-oxide (LOPAO) 0.3 0.3 0.3 0.3 Minors up to 100
DYE TRANSFER
Field of the Invention The present invention relates to a composition and a process for inhibiting dye transfer between fabrics during washing.
More in particular, the present invention relates to dye transfer inhibiting compositions comprising a mixture of polyamine N-oxide polymers having a low oxidation degree and polyamine N-oxide polymers having a high oxidation degree.
Background of the=_ Invention One 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.
z 1796 One way of overcoming this problem would be to complex or adsorb the fugitive dyes washed out of dyed fabrics before they have the opportunity to become attached to other articles in the wash.
Polymers have been used within detergent compositions to inhibit dye transfer. EP-A-O 102 923 describes the use of carboxyl containing polymers within aqueous compositions. DE-A-2 814 329 discloses the use of N-vinyl-oxazolidone polymers and FR-A-2 144 721 discloses the use of 15-35~ of a copolymer of polyvinylpyrrolidone and acrylic acid nitrile or malefic anhydride within a washing powder.
EP-265 257 describes detergent compositions comprising an alkali-metal carboxy-metal carboxymethylcellulose, a vinylpyrrolidone polymer and a polycarboxylate polymer.
It has now been surprisingly found that a particular combination of polyamine N-oxide polymers having a low oxidation degree and polyamine N-oxide polymers having a high oxidation degree are very efficient in eliminating transfer of a broad range of solubilized or suspended dyes. This finding allows to formulate compositions which exhibit excellent dye transfer inhibiting properties over a broad selection of dyes.
According to another embodiment of this invention a process is also provided for laundering operations involving colored fabrics.
Summarv of the Invention The present invention relates to inhibiting dye transfer compositions comprising a mixture of polyamine N-oxide polymers having a low oxidation degree and polyamine N-oxide polymers having a high oxidation degree.
Detailed description of the invention The compositions of the present invention comprise a mixture of polyamine N-oxide polymers having a low oxidation degree ("LOPAO") and polyamine N-oxide polymers having a high oxidation degree ("HOPAO").
By "polyamine N-oxide polymers having a low oxidation degree"
as used herein, is meant polyamine N-oxide polymers wherein the ratio of amine to amine N-o~:ide is from 1000:1 to 1:1, more preferably from 100:1 to 1:1., most preferably from 10:1 to 1:1.
By "polyamine N-oxide polymers having a high oxidation degree"
as used herein, is meant polyamine N-oxide polymers wherein the ratio of amine to amine N-oxide is from 2:3 to 1:1000000, more preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000.
The amount of amine oxide groups present in said polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxidation.
The polyamine N-oxide polymers contain units having the following structure formula .
P
I
(I) Ax I
R
wherein P is a polymerisable unit, whereto the N-0 group can be attached to or wherein the N-O group forms part of the polymerisable unit or a combination of both.
n a n I
A is NC, C0, C, -O-,-S-, -N- : x is 0 or 1:
WO 95/20032 ~ PCT/US95/00626 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 wherein the nitrogen of the N-O group is part of these groups.
The N-0 group can be represented by the following general structures .
I I
(R1 ) x -N- (R2 ) y =N- (R1 ) x I
(R3) z wherein R1, R2, R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group forms part of these groups.
The N-0 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-0 group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
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 pyridine, pyrole, imidazole, pyrolidine, piperidine, quinoline, acridine and derivatives thereof.
Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-0 group is attached to the R-group.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-0 group is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.
Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrole, imidazole and derivatives thereof.
Another preferred class of pclyamine 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-0 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 polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer types is either an amine N-oxide or not . The amine oxide unit of the polyamine N-oxides has a PKa < 10, preferably PKa < 7, more preferred PKa < 6.
The polyamine oxides can be obtained in almost any degree of polymerisation. The degree of po:Lymerisation 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 1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20, 000.
WO 95!20032 ~ ~ l 9 2 6 5 pCT/US95/00626 The polyamine N-oxides of the present invention are typically present from 0.001 to 100 , more preferably from 0.01 to 2%, most preferred from 0.05 to to by weight of the dye transfer inhibiting composition.
The present compositions are conveniently used as additives to conventional detergent compositions for use in laundry operations. The present invention also encompasses dye transfer inhibiting compositions which will contain detergent ingredients and thus serve as detergent compositions.
Methods for making polyamine N-oxides .
The production of the polyamine-N-oxides may be accomplished by polymerizing the amine monomer and oxidizing the resultant polymer with a suitable oxidizing agent, or the amine oxide monomer may itself be polymerized to obtain the polyamine N-oxide.
The synthesis of polyamine N-oxide can be exemplified by the synthesis of polyvinyl-pyridine N-oxide.
Poly-4-vinylpyridine ex Polysciences (mw. 50 000, 5.0 g., 0.0475 mole) was predisolved in 50 ml acetic acid and treated with a peracetic acid solution (25 g of glacial acetic acid, 6.4 g of a 30~ vol. solution of H202, and a few drops of H2S04 give 0.0523 mols of peracetic acid) via a pipette. The mixture was stirred over 30 minutes at ambient temperature (32 C).
The mixture was then heated to 80-85 C using an oil bath for 3 hours before allowing to stand overnight. The polymer solution then obtained is mixed with 11 of acetone under agitation. The resulting yellow brown viscous syrup formed on the bottom is washed again with 11 of aceton to yield a pale crystalline solid.
The solid was filtered off by gravity, washed with acetone and then dried over P205.
The amine . amine N-oxide ratio of this polymer is 1:4.
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 surfactants, is given in US Patent 3,664,961 issued to Norris on May 23, 1972.
Mixtures of anionic surfactants are particularly suitable herein, especially mixtures of sulphonate and sulphate 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-C:18 fatty source preferably from a C16-Clg fatty source. In each instance the cation is an alkali metal, preferably sodium. Preferred sulphate 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 C14-15 alkyl sulphates. The cation in each instance is again an alkali metal cation, preferably sodium.
One class of nonionic surfactants useful in the present ~_nvention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HL:B) in the range from 8 to 17, preferably from 9.5 to 13.5, snore 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 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.
WO 95/20032 ~ ~ ~ ~ L ~ ~ PCT/US95/00626 Especially preferred nonionic surfactants of this type are the Cg-C15 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C14-C15 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 (CnH2n0)tZx wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon 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 and less than 50o 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.
Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula R2 - C - N - Z, I
wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having 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 C11-15 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 pentamethylenephosphon:ic acid. Though less preferred ' 1 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-6T"' (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si205).
Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic: acid and ether derivatives thereof as disclosed in Beigia;n Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, malefic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1.379,241, lactoxysuccinates described in Canadian Patent No. 973,771, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.
,o Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1, 1, 2. 2-ethane tetracarboxylates, 1, 1, 3, 3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxyla-tes containing su:lfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos.
1, 398, 421 and 1, 398, 422 and in LJ. S . Patent No . 3, 936, 448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1,439,000.
Alicyclic and heterocycli<: polycarboxylates include cyclopentane-cis,cis,cis-tetraca,rboxylates, cyclopentadienide pentacarboxylates, 2,3,9,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran -cis - dicarboxylates, 2,2,5,5-tetrahydrofuran - tet:racarboxylates, 1,2,3,4,5,6-hexane -hexacarboxylates and and carboxymethyl derivatives of polyhydric alcohols such as so:rbitol, mannitol and xylitol.
Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS-6), and a water-soluble carboxylate chelating agent such as citric acid.
A suitable chelant for inclusion in the detergent compositions in accordance with the invention is ethylenediamine-N, N'-disucciriic acid (EDDS) or the alkali metal, alkaline earth metal,, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Preferred EDDS
compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of ~.~~4 EDDS include Na2EDDS and Na4EDDS. Examples of such preferred magnesium salts of ED17S include MgEDDS and Mg2EDDS. The magnesium salts are the most prE:ferred for inclusion in compositions in accordance with the invention.
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 preferred unsaturated fatty acid is oleic 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 builder system for use in granular compositions the purposes of the invention include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amiono polyalkylene 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, 596, 756.
Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with malefic anhydride, such copolymers having 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.
Detergent ingredients that can be included in the detergent compositions of the present invention include bleaching agents.
,.
These bleaching agent componenr_s can include one or more oxygen bleaching agents and, depending upon the bleaching agent chosen, one cr more bleach activators. When present bleaching compounds will typically be present at levels of from about l~s to aboLt 10$, of the detergent composition. In general, bleaching compounds are: optional components in non-liquid formulations, e.g. granular detergents. If present, the amount of bleach activators will typically be from about 0.1~ to about 60$, more typically from about 0.5~ to about 40$ of the bleaching composition.
The bleaching agent compone>nt for use herein can be any of the bleaching agents useful for detergent compositions including oxygen bleaches as well as others known in the art.
In a method aspect, this invention further provides a method for cleaning fabrica, fibers, textiles. at temperatures below about 50°C. especially below about 40°C, with a detergent composition containing polyamine N-oxide containing polymers, optional auxiliary detersive surfactants. optional detersive: adjunct ingredients, and a bleaching agent.
The bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent.
One category of oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perberzoic acid. 4-nonylamino-4-oxoperoxybutyric acid and dip~eroxydodecanedioic acid. Such bleaching agents are disclosed in~U.S. Patent 4,483,781, U.S.
Patent No. 4,634,551, European Patent Application 0,133,354 and U. S . Patent 4, 412, 934 . High.ly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,,551.
Another category of bleaching agents that can be used encompasses the halogen bleaching agents. Examples of hypohalite bleaching agents, for example, include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-~chloro and N-bromo alkane sulphonamides. Such materials are normally added at 0.5-lOX
by weight of the finished product, preferably 1-5~ by weight.
Preferably, the bleaches suitable for the present invention include peroxygen bleaches. Examples of suitable water-soluble solid peroxygen bleaches include hydrogen peroxide releasing agents ~~uch as hydrogen peroxide, perborates, e.g. perborate monohydrate, perborate tetrahydrate, persulfates, percarbonates, peroxydisulfates, perphosphates and peroxyhydrates. Preferred bleaches are percarbonates and perborates.
The hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine(TAED), nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934) , 3,5,-trimethylhexanoloxybenzenesulfo;nate (ISONOBS, described in EP
120,591) or pentaacetylglucose (PAG). which are perhydrolyze_d to form a peracid as the active: bleaching species, leading to improved bleaching effect. Fvlso ,suitable activators are acylated citrate esters (ATC) such as disclosed in Canadian Application No. 2,124,787.
The hydrogen peroxide may also be present by adding an enzymatic system (i.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 537,381 published April 4, 1993.
Other peroxygen bleaches suitable for the present invention include organic peroxyacids such as percarboxylic acids.
Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent o:E particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials can be Bt -. 217926 5 deposited upca the substrate duri~g the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is, bleached. Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718. Typically, detergent compositions will contain about 0.025$ to about 1.25$, b y weight, of sulfonated zinc phthalocyanine.
Other detergent ingredients that can be included are detersive enzymes which can be included in the detergent formulations for a wide variety of purposes including removal of protein-based. carbohydrate-based, or triglyceride-based stains, for example, and prevention of refugee dye transfer.
The enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.05 mg to about 3 mg, of active enzyme per gram of the composition. .
Suitable examples of proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the trademarks Alcalase , Savinase and Esperase by Novo Industries A./S (Denmark) and Maxatase by International Hio-Synthetics, Lnc. (The Netherlands) and FN-base by Genencor, Optimase and Opticlean by MKC.
Of interest in the category of proteolytic enzymes, especially for liquid detergent compositions, are enzymes referred to herein as Protease A and Protease B. Protease A
is described in European Patent Application 130,756. Protease B is described in European Patent Application No. 251,446 published January 7, 1988. Amylases include, for example, -amylases Bt obtained from a special strain of B.licheniforms, described in more detail in British Patent. Specification No. 1,296,839 (Novo). Amylolytic proteins include, for example, Rapidase~'"', Maxamylz'"' (International Bio-Synthetics, Inc. ) and TermamylT'", (Novo Industries) .
The cellulases usable in the present invention include both bacterial or fungal cellulase. 1?referably, they will have a pH optimum of between 5 and 9~.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens.
Suitable cellulases are also disclosed in GH-A-2.075.028 ;
GB-A-2.095.275 and DE-OS-2.247.8:32.
Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var.
thermoidea), particularly the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase .extracted from the hepatopancreas of a marine mollusc (Dolabella Auricula Sola:nder).
Other suitable cellulases are cellulases originated from Humicola Insulens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids.
Especially suitable cellulase are the cellulase having color care benefits. Examples of such cellulases are cellulase described in United States Patent No. 5,520,838.
Suitable lipase enzymes for detergent usage include those produced by microorganisms of t:he Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.1.54, as disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunoligical cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade mark Lipase P "Amano." hereinafter referred to as "Amano-P".
~B1 Especially suitable Lipase are lipase such as M1 LipaseTh' (Ibis) and LipolaseT''' (Novo) .
Peroxidase enzymes are used in combination with oxygen sources, e.g, percarbonate, perborate, persulfate, hydrogen peroxide. etc. They are used for "solution bleaching", i.e.
to prevent transfer of dyes. of pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chl.oro- and bromo-peroxidase.
Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813 and in Canadian Patent Application No. 2,122,987.
In liquid formulations, an enzyme stabilization system is preferably utilized. Enzyme stabilization techniques for aqueous detergent compositions are well known in the art. For example, one technique for enzyme stabilization in aqueous solutions involves the use of free calcium ions from sources such as calcium acetate, calcium formate and calcium propionate. Calcium ions can be used in combination with short chain carboxylic acid salts, preferably formates. See, for example, U.S. patent 4,318,~g18. It has also been proposed to use polyols like glycerol and sorbitol. Alkoxy-alcohols, dialkylglycoethers, mixtures of polyvalent alcohols with polyfunctional aliphatic .amines (e.g., such as diethanolamine, triethanolamine, di-isopropanolamime, etc.), and boric acid or alkali metal. borate. Enzyme stabilization techniques are additionally disclosed and exemplified in U.S.
patent 4, 261, 868, U.S. Patent 3, 600, 319, and European Patent Application Publication No. 0 199 405. Non-boric acid and borate stabilizers are preferred. Enzyme stabilization systems are also described, for example, in U.S. Patents 4,261,868, 3,600,319 and 3,519,570.
Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending European Patent Application No. 553,607 published August 4, 1993. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
B!
Especially preferred detergent ingredients are combinations with technologies which also provide a type of color care benefit. Examples of these technologies are cellulase and/or peroxidases and/or metallo catalysts for color maintance rejuvenation.
Another optional ingredient: is a suds suppressor, exemplified by silicones, and silica-silicone mixtures.
Silicones can be generally represented by alkylated polysiloxane materials while ailica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silic;as of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent impermeable carrier. Alternatively the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
A preferred silicone suds cons=rolling agent is disclosed in Bartollota et al. U.S. Patent 3 933 672. Other particularly useful suds suppres~ors are t:he self-emulsifying silicone suds suppressors, described in ~~erman Patent Application DTOS
2 646 126 published April 28, 1977. An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. Especially preferred suds controlling agent are the suds suppressor system comprising a mixture of silicone oils and 2-alkyl-alcanols.
Suitable 2-alkyl-alcanols are: 2-butyl-octanol which are commercially available under the trade mark Isofol 12 R.
Such suds suppressor system are described in Canadian Patent Application No. 2,146,636.
Especially preferred silicone suds controlling agents are described in European Patent Application No. 573,699 published June 6, 1992.
2~~92s5 18 Said compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as AerosilR.
The suds suppressors described above are normally employed at levels of from 0 . 001 o to 2 o by weight of the composition, preferably from O.Olo to 1~ by weight.
Other components used in detergent compositions may be employed, such as soil-suspending agents soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and non-encapsulated and encapsulated perfumes.
Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo-or co-polymeric polycarboxylic acids or their salts. Polymers of this type include the polyacrylates and malefic anhydride-acrylic acid copolymers previously mentioned as builders, as well as copolymers of malefic anhydride with ethylene, methylvinyl ether or methacrylic acid, the malefic anhydride constituting at least 20 mole percent of the copolymer.
These materials are normally used at levels of from 0.5$ to 10~ by weight, more preferably from 0.75 to 8~, most preferably from 1$ to 6~ by weight of the composition.
Preferred optical brighteners are anionic in character, examples of which are disodium 4,41-bis-(2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-2:21 disulphonate, disodium 4, - 41-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:21 - disulphonate, disodium 4,41 - bis-(2,9-dianilino-s-triazin-6-ylamino)stilbene-2:21 -disulphonate, monosodium 41,411 -bis-(2,4-dianilino-s-triazin-6 ylamino)stilbene-2-sulphonate, disodium 4,41 -bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,21 - disulphonate, disodium 4,41 -bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,21 disulphonate, disodium 4,41bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-~v s-triazin-6- ylamino)stilbene-2,21disulphonate and sodium ~ ~ ~~~a _.. WO 95120032 PCTIUS95/00626 2(stilbyl-411-(naphtho-11,21:4,5)-1,2,3 - triazole-211-sulphonate.
Other useful polymeric materials are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 a.nd most preferably about 4000. These are used at levels of from 0.20$ to 5~ more preferably from 0.25$ to 2.5~ by weight. These polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.
Soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has 'the formula - (CH3(PEG)43)0.75(POH)0.25~T-PO)2.8(~r-PEG)0.4~T(PO-H)0.25((PEG)43CH3)p.75 where PEG is -(OC2H4)O-,PO is (OC3H60) and T is (pcOC6H4C0).
Also very useful are modified polyesters as random copolymers of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol. The target is to obtain a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers, herein will be end-capped by sulphobenzoate groups. However, sc>me copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist "secondarily" of such species.
The selected polyesters herein contain about 46$ by weight of dimethyl terephtalic acid, about 16$ by weight of propane -1.2 diol, about 10$ by weight ethylene glycol about 13$ by weight of dimethyl sulfobenzoid acid and about 15$ by weight of sulfoisophtalic acid, and have a molecular weight of about 3.000. The polyesters and their method of preparation are described in detail in EPA 311 342.
The detergent compositions according to the invention can be in liquid, paste, gels 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/1; in such 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 metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10$ filler salt. The liquid compositions according to the present invention can also be in "concentrated form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents. Typically, the water content of the concentrated liquid detergent is less than 30$, more preferably less than 20$, most preferably less than 10$ by weight of the detergent compositions.
The present invention also relates to a process for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.
The process comprises contacting fabrics with a laundering solution as hereinbefore described.
The process of the invention is conveniently carried out in the course of the washing process. The washing process is ,_ WO 95/20032 PCT/US95100626 preferably carried out at 5 °C to 75 °C, especially 20 to 60, but the polymers are effective at up to 95°C and higher temperatures. The pH of the treatmE~nt solution is preferably from 7 to 11, especially from 7.5 to 10.5.
The process and compositions of the invention can also be used as detergent additive products..
Such additive products are intendE:d to supplement or boost the performance of conventional detE:rgent compositions.
The detergent compositions according to the present invention include compositions which are t:o be used for cleaning substrates, such as fabrics, fibers, hard surfaces, skin etc., for example hard surface cleaning compositions (with or without abrasives), laundry detergent compositions, automatic and non automatic dishwashing compositions.
The following examples are meant to exemplify compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention, said scope being determined according to claims which follow.
A liquid detergent composition according to the present invention is prepared, having the following compositions .
$ by weight of the total detergent composition Linear alkylbenzene sulfonate 10 Alkyl sulphate 4 Fatty alcohol (C12-C15) ethoxylate 12 Fatty acid 10 Oleic acid 4 Citric acid 1 NaOH 3.4 Propanediol 1.5 Ethanol 10 Table I
The extent of dye transfer is assessed by a Hunter Colour measurement. The Hunter Colour system evaluates the colour of a fabric sample in terms of the Dc value which represents the change in the Hunter a, b values which are determined by reflecting spectofotometry. The Dc value is defined by the following equation:
Dc = ~(af -ai)2 + (bf-bi)2}1/2 where the subscripts i and f refer to the Hunter value before and after washing in the presence of the bleeding fabric, respectively. The least significant difference is 1 at 95~
confidence level.
EXAMPLE I
The extent of dye transfer from different colored fabrics was studied using a launder-o-meter test that simulates a 30 min wash cycle. The launder-o-meter beaker contains 200 ml of a detergent solution, a lOcmxlOcm piece of the colored fabric and a multifiber swatch which is used as a pick-up tracer for the bleeding dye. The bleeding dye consists of one part direct blue 90, one part direct blue 112 and one part direct violet 47. The multifiber swatch consists of cotton.
Experimental conditions:
pH =7.8 A: A detergent composition according to Table I which does not contain any dye transfer inhibition system.
B: A detergent composition according to Table I containing 10 ppm of PVNO (poly(4-vinylpyridine-N-oxide)) which has an average molecular weight of about 10,000 and an amine to amine N-oxide ratio of 1:10 (HOPAO).
C: A detergent composition according to Table I containing 10 ppm of PVNO (poly(4-vinylpyridine-N-oxide)) which has an average molecular weight of about 30,000 and an amine to amine N-oxide ratio of l:l (LOPAO).
2~ ~'~~~~'_ ._ WO 95120032 PCTIUS95/00626 D: A detergent composition according to Table I containing 5ppm of PVNO (poly(4-vinylpyridine-N-oxide)) which has an average molecular weight of about 3(),000 and an amine to amine N-oxide ratio of 1:10, and 5ppm of 1?VNO (poly(4-vinylpyridine-N-oxide)) which has an average molecular weight of about 30,000 and an amine to amine N-oxide ratio of 1:1 (HOPAO +
LOPAO).
Results: Dc values for the cotton pick-up tracer.
Bleeding fabric A B C D
color Direct Blue 90/ 10.3 4.2 4.5 3 Direct Blue 112 and Direct Violet 47 EXAMPLE II (A/B/C/D) Liquid detergent composi~ions according to the present invention are prepared, having the following compositions .
P. B C D
Linear alkylbenzene sulfonate 1.8 - 6 -C12-C15 alkyl sulfate -~ 16.0 - -C12-C15 alkyl ethoxylated sulfate -~ 11.0 4.0 25.0 C12-C14 N-methyl glucamide -~ 7.0 9.0 9.0 C12-C14 fatty alcohol ethoxylate 1.2.0 5.0 6.0 6.0 C12-C16 fatty acid 9.0 6.8 14.0 14.0 Fatty acid 1.0 10 10 10 Oleic acid 4 4 4 4 Citric acid 1 1 1 1 Diethylenetriaminepentamethylene 1.5 1.5 1.5 1.5 phosphoric acid ,.
Y ~ ~. ~ . . .
.',b f ,.., ,. , ' f : ' t , , , Propanedioi 1.5 1.5 1.5 1.5 Ethanol 10 10 10 10 Ethoxylated tetraethylene pentamine 0.7 0.7 0.7 0.7 Poly(4-vinylpyridine)-N-oxide (HOPAO) 0.3 0.3 0.3 0.3 Poly(4-vinylpyridine)-N-oxide (LOPAO) 0.3 0.3 0.3 0.3 ThermamylT"' 0.13 0.13 0.13 0.13 CarezymeT"' 0.014 0.014 0.014 0.014 EN-Base 1.8 1.8 1.8. 1.8 Lipolase 0.14 0.14 0.14 0.1 Endoglucanase A 0.53 0.53 0.53 0.53 Suds supressor (ISOFOL) 2.5 2.5 2.5 2.5 Water and Minors up to 100 NaOH and/or MEA to adjust pH '7.8 to EXAMPLE III (A/H/C/D) --Compact granular detergent compositions according to the present invention are prepared, having the following formulation:
% by weight of the total detergent compoaitioa A, B C D
Polyhydroxy fatty 'acid amide 10 Alkyl alkoxylated sulfate - 9 9 9 Alkyl sulphate 9.80 4.80 4.80 4.60 C14-15-alcohol 7 times 9.00 4.00 4.00 4.00 ethoxylate Tallow alcohol 11 times 1.8 1.80 1.8 1.8 ethoxylated Dispersant 0.07 0.07 0.07 0.07 Silicone fluid 0.80 0.80 0.80 0.80 Trisodium citrate ~ 14.00 14.00 14.00 14.00 Citric acid 3.00 3.00 3.00 3.00 Bi Zeolite 25.00 20.00 20.00 32.50 Diethylenetriamine penta- 0.6 0.6 0.6 0.6 methylene phosphonic acid Malefic acid acrylic acid 5.00 5.00 5.00 5.00 copolymer Carezyme T-granulate 0.2 0.5 0.15 0.3 Alcalase T-granulate 0.60 0.60 0.20 0.50 Lipolase T-granulate 0.20 0.10 0.25 0.40 Termamyl T-granulate 0.3 0.3 0.3 0.3 Sodium silicate 2.00 2.00 2.00 2.00 Sodium sulphate 3.50 3.50 3.50 3.50 Percarbonate - - 20 -Perborate 15 15 - -Encapsulated perfume 0.2 - - -Perfume 0.3 0.2 0.3 0.2 Poly(4-vinylpyrridine) N-oxide (HOPAO) 0.3 0.3 0.3 0.3 Poly(4-vinylpyrridine) N-oxide (LOPAO) 0.3 0.3 0.3 0.3 Minors up to 100
Claims (15)
1. A dye transfer inhibiting composition comprising a mixture of polyamine N-oxide polymers having a low and high oxidation degree, said polyamine N-oxide polymers containing units having the following structure formula :
wherein P is a polymerisable unit, whereto the N-O group can be attached to or wherein the N-O group forms part of the polymerisable unit.
A is -O-,-S-,-N- ; x is 0 or 1;
R are aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
wherein P is a polymerisable unit, whereto the N-O group can be attached to or wherein the N-O group forms part of the polymerisable unit.
A is -O-,-S-,-N- ; x is 0 or 1;
R are aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
2. A dye transfer inhibiting composition according to claim 1 wherein P is a polymerisable unit wherein the N-O group is attached to and wherein R is selected from an aromatic or heterocyclic group.
3. A dye transfer inhibiting composition according to claim 2 wherein the nitrogen of the N-O group forms part of the R-group.
4. A dye transfer inhibiting composition according to claim 3 wherein the R-group is selected from pyridine, pyrrole, quinoline, acridine, imidazole and derivatives thereof.
5. A dye transfer inhibiting composition according to claim 1 wherein the nitrogen of the N-O group is attached to the R-group.
6. A dye transfer inhibiting composition according to claim 5 wherein R is a phenyl group.
7. A dye transfer composition according to claim 1 wherein P
is a polymerisable unit, whereto the N-O group forms part of the polymerisable unit and wherein R is selected from an aromatic or heterocyclic group.
is a polymerisable unit, whereto the N-O group forms part of the polymerisable unit and wherein R is selected from an aromatic or heterocyclic group.
8. A dye transfer inhibiting composition according to claim 7 wherein the nitrogen of the N-O group forms part of the R-group.
9. A dye transfer inhibiting composition according to claim 8 wherein the R-group is selected from pyridine, pyrrole, quinoline, acridine, imidazole and derivatives thereof.
10. A dye transfer inhibiting composition according to claim 1 wherein the polymeric backbone is derived from the group of the polyvinyl polymers.
11. A dye transfer inhibiting composition according to claim 1 wherein said polyamine N-oxide polymers having a low oxidation degree has a ratio of amine to amine N-oxide from 1000:1 to 1:1.
12. A dye transfer inhibiting composition according to claim 1 wherein the polyamine N-oxide has an average molecular weight within the range of 500 to 1000,000.
13. A dye transfer inhibiting composition according to claim 1 wherein the polyamine N-oxide is present at levels from 0.001 to 10 % by weight of the composition.
14. A dye transfer inhibiting composition according to claim 1 which is a detergent additive, in the form of a non-dusting granule or a liquid.
15. A detergent composition which comprises a dye transfer inhibiting composition according to claim 1 further comprising surfactants, builders, enzymes and other detergent ingredients.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP94870007.5 | 1994-01-19 | ||
| EP19940870007 EP0664332B1 (en) | 1994-01-19 | 1994-01-19 | Detergent compositions inhibiting dye transfer |
| PCT/US1995/000626 WO1995020032A1 (en) | 1994-01-19 | 1995-01-13 | Detergent compositions inhibiting dye transfer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2179265C true CA2179265C (en) | 2000-02-22 |
Family
ID=8218613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002179265A Expired - Fee Related CA2179265C (en) | 1994-01-19 | 1995-01-13 | Detergent compositions inhibiting dye transfer |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0664332B1 (en) |
| JP (1) | JPH09508164A (en) |
| CN (1) | CN1066192C (en) |
| CA (1) | CA2179265C (en) |
| DE (1) | DE69419715T2 (en) |
| WO (1) | WO1995020032A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19605578C2 (en) * | 1996-02-15 | 2001-03-29 | Dystar Textilfarben Gmbh & Co | Process for producing an anionic textile dye printed textile material |
| BR9707836A (en) * | 1996-03-06 | 1999-07-27 | Novo Nordisk | Processes to inhibit microorganisms present in washing clothes and microbial growth on a hard surface and to exterminate microbial cells present in the skin of humans or animals in the mucous membranes in the teeth in bruises or eye injuries or to inhibit their growth |
| US6794355B1 (en) * | 1998-11-02 | 2004-09-21 | The Procter & Gamble Company | Fabric care composition having reduced fabric abrasion |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3159611A (en) * | 1961-04-03 | 1964-12-01 | Union Carbide Corp | Preparation of polymers which contain the nu-oxide function |
| DE1253411B (en) * | 1965-09-09 | 1967-11-02 | Bayer Ag | Process for obtaining a therapeutically useful, easily soluble poly-2-vinylpyridine-N-oxide preparation |
| 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 |
| US5009980A (en) * | 1988-12-30 | 1991-04-23 | E. I. Du Pont De Nemours And Company | Aromatic nitrogen-containing compounds as adjuvants for electrostatic liquid developers |
| DE69321778T2 (en) * | 1992-07-15 | 1999-06-10 | Procter & Gamble | Detergent compositions to prevent dye transfer |
-
1994
- 1994-01-19 DE DE1994619715 patent/DE69419715T2/en not_active Expired - Fee Related
- 1994-01-19 EP EP19940870007 patent/EP0664332B1/en not_active Expired - Lifetime
-
1995
- 1995-01-13 CA CA002179265A patent/CA2179265C/en not_active Expired - Fee Related
- 1995-01-13 JP JP7519622A patent/JPH09508164A/en not_active Ceased
- 1995-01-13 CN CN95191288A patent/CN1066192C/en not_active Expired - Fee Related
- 1995-01-13 WO PCT/US1995/000626 patent/WO1995020032A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO1995020032A1 (en) | 1995-07-27 |
| JPH09508164A (en) | 1997-08-19 |
| EP0664332B1 (en) | 1999-07-28 |
| EP0664332A1 (en) | 1995-07-26 |
| CN1066192C (en) | 2001-05-23 |
| DE69419715T2 (en) | 2000-05-31 |
| DE69419715D1 (en) | 1999-09-02 |
| CN1138875A (en) | 1996-12-25 |
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