CA2195835A1 - A detergent composition comprising an amphiphilic carboxy containing polymer and an uncharged polymer - Google Patents
A detergent composition comprising an amphiphilic carboxy containing polymer and an uncharged polymerInfo
- Publication number
- CA2195835A1 CA2195835A1 CA002195835A CA2195835A CA2195835A1 CA 2195835 A1 CA2195835 A1 CA 2195835A1 CA 002195835 A CA002195835 A CA 002195835A CA 2195835 A CA2195835 A CA 2195835A CA 2195835 A1 CA2195835 A1 CA 2195835A1
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- Prior art keywords
- polymer
- alkyl
- weight
- polymers
- composition
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
-
- 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
Detergent composition comprising surfactant material, an amphiphilic carboxy containing polymers and an uncharged polymer.
Description
,C 6330 (V) . ~
21 9~8~5 r~TF~.R~.~NT ('t)MposITIoN
T~hn; cs3 1 Field 5 The present inventio~ relates to polymer t ~nti~;n;n~
detergent compo9ition9, process of preparing detergent compositions and washing methods using polymer material.
Back~roi,n~l 10 Various types of polymers have been described in the art, e.g. U.S. Patent No. 5,147,576 to Montague et al. describes decoupling polymers in structured liquids.
NO 95/13354 (P&G) discloses composition comprising active, 15 builder, fluorescent and polymer 3elected from PVPNO and N-vinyl pyrrolidone/N-vinylimidazole copolymers.
WO 94/10277 P&G discloses a compo9ition comprising polyamine N-oxide polymer and terf~rht~ e polymer.
WO 95/07336 P&G discloses granular products with active, builder, PVP-N-oxide polymer, specific PVP-VI polymer and specific sulphonated end-cappèd SRP.
"
EP 635,563, EP 635,565; WO 94/02576, WO 94/02580, WO
94/02581, WO 94/11473, WO 94/10277, WO 95/03390 and WO
95/33026 disclose compositions compriging N-c-~n~A;n;n3 polymers. Polycarboxylates are mentioned as optional ingredients .
EP 581,753 discloses N-c~nt~in;n~ compounds with polymeric polycarboxylate dispersing agents.
Polymers have been suggested for various purposes in the washing process. Anti-redeposition polymers are used to complex material in 801ution and prevent it from depositing on fabric. A special class of anti-redeposition agent are ~C 633~(V) the dye transfer inhibiting polymers which complex dye molecules in solution and thus prevents deposition of colours on fabric.
oily soil and partieulate soil release polymers are polymers which change the characteristics of fabric. In order to be effective, they have to be deposited on the fabric surface before the fabric is stained.
We have however found a way to improve stain removal of detergent compositions, in particular the removal of particulate stains, and especially when embedded in an oily or fat matrix, by using a special polymer combination which provides synergistic stain removal benef its on these stains. ~3xamples of sueh stains are make-up, lipstiek and shoe pol i sh .
In additional, we have found that the eombination of the polymer combination can be stably incor ?orated into aqueous isotropic liquid detergent eompositions.
Stat ---t of th~ Tnvl~n~ion Consequently, the invention is direeted to detergent eompositions eomprising surfaetant material, an h;~h;l;c earboxylate c~n~;n;n~ polymer and an uneharged polymer.
The present invention is further direeted to aqueous liquids eomprising the partieular polymer eombination of an h;ph;l;e earboxylate er~n~;l;ning polymer and an uneharged polymer .
The present invention is further direeted to a method of preparing a liquid detergent eomposition eomprising the polymer eombination of the invention by mixing the ingredients .
C 633~(V) 3 21 q5835 The present invention is further directed to a method of washing f abrics by adding the polymer combination of the present invention to the wash liquor.
7~ h;I.hlliC c;~rhoxy Cont~;n;nSI pol~, -r Preferably, the ~h;rh;liC carboxy c~ntA;n;ns polymers comprise ~ ~ comprising a carboxy group, said monomers being preferably selected from carboxylated sugar units, 10 carboxylated unsaturated units (like acrylate, methacrylate, itaconate, maleate and mixtures) and mixtures thereof. The amphiphilic carboxy ,-~,ntiq;n;ng polymer preferably also contains monomer units which are uncharged Preferably, these uncharged monomers are selected from 15 vinylacetate, vinylpyrrolidone, vinylpyridine, vinyl ;m;~ 70l / styrene, alkyl-esters of the above carboxylate monomers (e.g. 1-20 alk(en)yl, preferably C5-16 alkyl ) and mixtures thereof .
20 More preferably, the amphiphilic carboxy ,-"nt~;n;ng polymers are of the following type: polyacrylate, styrene-acrylate copolymer, acrylate-alkylmethacrylate copolymers, ethoxylated methacrylate-acrylate copolymer, methacrylate-vinylacetate copolymer or it~c- niqt~-vinylacetate 25 copolymers. Examples of such polymers are Narlex ~D55, Narlex H100, Narlex ~I1200 and Narlex DC1 (ex National Starch) .
Additionally, the ,h;rh;lic carboxy ~ nt~;n;n~ polymers 3 0 may pref erably be copolymers of ethoxylated maleate and dodecene-1. An example thereof is Dapral GE 202.
Optionally, the i ,h;rh;l;c carboxy r~ntfl;n;ng polymer is partly ethoxylated, e.g. with a PEG 350 side chain.
35 Most preferably, the i ,~h;rh;lic carboxy r~nti~;n;ng polymers are selected from copolymers of acrylic acid and styrene. Examples are Narlex H100 and Narlex ~1200 (ex C 6330` (V) . ~
21 9~8~5 r~TF~.R~.~NT ('t)MposITIoN
T~hn; cs3 1 Field 5 The present inventio~ relates to polymer t ~nti~;n;n~
detergent compo9ition9, process of preparing detergent compositions and washing methods using polymer material.
Back~roi,n~l 10 Various types of polymers have been described in the art, e.g. U.S. Patent No. 5,147,576 to Montague et al. describes decoupling polymers in structured liquids.
NO 95/13354 (P&G) discloses composition comprising active, 15 builder, fluorescent and polymer 3elected from PVPNO and N-vinyl pyrrolidone/N-vinylimidazole copolymers.
WO 94/10277 P&G discloses a compo9ition comprising polyamine N-oxide polymer and terf~rht~ e polymer.
WO 95/07336 P&G discloses granular products with active, builder, PVP-N-oxide polymer, specific PVP-VI polymer and specific sulphonated end-cappèd SRP.
"
EP 635,563, EP 635,565; WO 94/02576, WO 94/02580, WO
94/02581, WO 94/11473, WO 94/10277, WO 95/03390 and WO
95/33026 disclose compositions compriging N-c-~n~A;n;n3 polymers. Polycarboxylates are mentioned as optional ingredients .
EP 581,753 discloses N-c~nt~in;n~ compounds with polymeric polycarboxylate dispersing agents.
Polymers have been suggested for various purposes in the washing process. Anti-redeposition polymers are used to complex material in 801ution and prevent it from depositing on fabric. A special class of anti-redeposition agent are ~C 633~(V) the dye transfer inhibiting polymers which complex dye molecules in solution and thus prevents deposition of colours on fabric.
oily soil and partieulate soil release polymers are polymers which change the characteristics of fabric. In order to be effective, they have to be deposited on the fabric surface before the fabric is stained.
We have however found a way to improve stain removal of detergent compositions, in particular the removal of particulate stains, and especially when embedded in an oily or fat matrix, by using a special polymer combination which provides synergistic stain removal benef its on these stains. ~3xamples of sueh stains are make-up, lipstiek and shoe pol i sh .
In additional, we have found that the eombination of the polymer combination can be stably incor ?orated into aqueous isotropic liquid detergent eompositions.
Stat ---t of th~ Tnvl~n~ion Consequently, the invention is direeted to detergent eompositions eomprising surfaetant material, an h;~h;l;c earboxylate c~n~;n;n~ polymer and an uneharged polymer.
The present invention is further direeted to aqueous liquids eomprising the partieular polymer eombination of an h;ph;l;e earboxylate er~n~;l;ning polymer and an uneharged polymer .
The present invention is further direeted to a method of preparing a liquid detergent eomposition eomprising the polymer eombination of the invention by mixing the ingredients .
C 633~(V) 3 21 q5835 The present invention is further directed to a method of washing f abrics by adding the polymer combination of the present invention to the wash liquor.
7~ h;I.hlliC c;~rhoxy Cont~;n;nSI pol~, -r Preferably, the ~h;rh;liC carboxy c~ntA;n;ns polymers comprise ~ ~ comprising a carboxy group, said monomers being preferably selected from carboxylated sugar units, 10 carboxylated unsaturated units (like acrylate, methacrylate, itaconate, maleate and mixtures) and mixtures thereof. The amphiphilic carboxy ,-~,ntiq;n;ng polymer preferably also contains monomer units which are uncharged Preferably, these uncharged monomers are selected from 15 vinylacetate, vinylpyrrolidone, vinylpyridine, vinyl ;m;~ 70l / styrene, alkyl-esters of the above carboxylate monomers (e.g. 1-20 alk(en)yl, preferably C5-16 alkyl ) and mixtures thereof .
20 More preferably, the amphiphilic carboxy ,-"nt~;n;ng polymers are of the following type: polyacrylate, styrene-acrylate copolymer, acrylate-alkylmethacrylate copolymers, ethoxylated methacrylate-acrylate copolymer, methacrylate-vinylacetate copolymer or it~c- niqt~-vinylacetate 25 copolymers. Examples of such polymers are Narlex ~D55, Narlex H100, Narlex ~I1200 and Narlex DC1 (ex National Starch) .
Additionally, the ,h;rh;lic carboxy ~ nt~;n;n~ polymers 3 0 may pref erably be copolymers of ethoxylated maleate and dodecene-1. An example thereof is Dapral GE 202.
Optionally, the i ,h;rh;l;c carboxy r~ntfl;n;ng polymer is partly ethoxylated, e.g. with a PEG 350 side chain.
35 Most preferably, the i ,~h;rh;lic carboxy r~nti~;n;ng polymers are selected from copolymers of acrylic acid and styrene. Examples are Narlex H100 and Narlex ~1200 (ex C 6330` (V) . ~
4 2 ~ 95835 National Starch).
Preferably, the amphiphilic carboxy containing polymer i8 present at a level of from 0 . 05 to 5% by weight of the 5 composition, more preferably from 0.1 to 2, most preferably from 0.2 to 1.5, for instance at a level of 0.59~ by weight of the composition.
The ratio of carboxy ~nnt~;n;n~ hydrophilic momomers to 10 uncharged monomers can varry in a broad range e.g. from 100:1 to 0.5:1, preferably from 50:1 to 1:1. For copolymers of acrylic acid and styrene this ratio is preferably between 10:1 and 0.5:1, most preferred from 6:1 to 1:1.
15 ~n~-h~rged pol~
Preferably, the uncharged polymer material is selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimiidazole, polyvinylpyrrolidone, polyvinyloxazolidone, 20 polyvinylimidazole and mixtures thereof.
a. Poly~m;nf~ N--33~ olyr~s Polyamine N-oxide polymers suitable for use contain units having the following structure formula: R-Ax-P, wherein P
25 is a polymerisable unit, whereto the R-N-O group can be attached to or wherein the R-N-O group forms part of the polymerisable unit or a combination of both. A is NC (O), C(O)O, -O-, -S-, -N; x is 0 or 1; R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic 3 o group 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-O group can be represented by the following general 35 quaternary N-structure: (R1)x-N(-O) (R3)z(R2)y and =N(O) (R1)x, wherein R1, R, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations C 633~(~T) thereof, x and/or y and/or z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitroge~ of the N-O group forms part of these groups.
5 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 10 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.
15 Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, ~l;n~)l ;n~, acridine and derivatives thereof.
20 Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O
group is attached to the R-group.
Other suitable polyamine N-oxides are the polyamine oxides 25 whereto the N-O group is attached to the polymerisable unit .
Preferred class of these polyalmine N-oxides are the polyamine N-oxides having the general formula (I) wherein R
30 is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O group is part of said R group.
~xamplea of the3e classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R
C 6330~(V) ~ 2 1 95835 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. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes polyesters, polyethers, polyamide, polyimides, 10 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 10:1 to 1:1,000,000. However the amount of amine oxide 15 groups present in the polyamine oxidew polymer can be varied by appropriate copolymerization or by d~~ r iate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2:3 to 1:1,000,000. More preferably from 1:4, most preferably from 1:7 up to 1,000,000. The 20 polymers of the present invention actually f~n~ 8 random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not. The amine oxide unit of the olyamine N-oxides has a pKa<10, preferably pKa~7, more preferably 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 .
Typically, the average molecular weight is within the range of 500 to 100,000; preferably from 1,000 to 50,000, more preferably from 2, 000 to 30, 000, most preferably from 3, 000 to 20,000.
~. Co~ol rg of No-vir~ylpyrroli~lf)n~D an~ N-vinylim; ~ 7ole The N-vinylimidazole N-vinylpyrrolidone polymers which may C 633~v) 7 2~ 95835 be used in the present invention have an average molecular weight range from 5, 000 to l, 000, 000, preferably from 20, 000 to 200, 000 . Highly preferred polymer for use in detergent compositions according to the present invention 5 comprise a polymer selected from N-vinylimidazole N-vinylpyrrolidone copolymers wherein said pol~ymer has an average molecular weight range from 5, 000 to 50, 000 more preferably from 8, 000 to 30, 000, most preferably from 10, 000 to 20, 000 .
The average molecular weight range was determined by light scattering as described in Barth H.G. and Mays J.W.
Chemical Analysis VOl 113, "Modern methods of polymer characterization " .
Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight range from 5,000 to 50,000, more preferably from 8,000 to 30,000, most preferably from lO,000 to 20,000.
The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinyl;m;~7Ole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0 . 3, most pref erably f rom 0 . 6 to 0 . 4 .
c. Polyvir~ylpyrroli~ ne Detergent compositions of the present invention may also utilize polyvinylpyrrolidone (~PVP~) having an average molecular weight of from 2,500 to 400,000, preferably from 30 5,000 to 200,000, more preferably from 5,000 to 50,000 and most preferably from 5, 000 to 15, 000 . Suitable polyvinylpyrrolidone~ are commercially available from ISP
Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 35 10,000), PVP K-30 (average molecular weight of 40,000), PVP
K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360, 000) . PVP K-15 is also Ç 633~(V) available from ISP Corporation. Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
Polyvinylpyrrolidones will be known to persons skilled in 5 the detergent field; see for example EP-A-262,897 and EP-A-256, 696.
d. Polyvinyl-~7olidone Detergent compositions of the present invention may also 10 comprise polyvinyloxazolidone. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000, preferably to 200, 000, more preferably to 50, 000 and most preferably to 15, 000 .
15 e . Polyvinylim; ~l~701e Detergent compositions of the present invention may also comprise polyvinylimidazole. Said polyvinylimidazoles have an average molecular weight range from 2,500 to 400,000, preferably to 200, OO0, more preferably to 5O, OO0, and most 20 preferably to 15, 000 .
Preferably, the uncharged polymers are selected from ethoxylated ethylene-amine polymers, vinylpyrrolidone polymers, 2-vinylpyridine N-oxide c~nt~;n;n~ polymers, 25 vinylpyrrolidone-vinylacetate copolymers, vinylpyrrolidone-styrene co-polymers and vinylpyrrolidone-vinyl imidazole copolymers. Examples of such polymers are ethoxylated tetraethyl.on~r.-nt~m;n~, polyvinylpyrrolidone K15, polyvinylpyrrolidone vinylacetate (PVP/VA S-630), 30 polyvinylpyridine N-oxide, polyvinylpyrrolidone-styrene (Antara 430) and polyvinylpyrrolidone-vinylimidazole (Sokalan ~IP56). Most preferably, the uncharged polymers are selected from vinylpyrrolidone (PVP), polyvinylpyridine N-oxide and copolymers of vinylpyrrolidone and vinylimidazole 35 (PVP-PVI) . An example is Sokalan EIP 56 (ex BASF) .
Preferably, the level of the uncharged polymer is from 0.1 C 6330 (v) to 396, more preferably from 0.25 to 1.5%, for instance 0.5%
by weight of the composition.
Deter~rPnt co~osition 5 Preferably, the detergent composition comprises surfactant material. Preferably, liquids according to the present invention comprise anionic surfactants at a ievel of 5% by weight of the composition or higher.
10 In a preferred embodiment of the invention, the surfactant comprises one or more of the aurfactants selected from alkyl benzene sulphonate and 3ugar based surfactants. Sugar based surfactants are preferred. We have found that the use of these surfactants further improves the stain removal of 15 the particulated stains in a fatty or oily matrix.
L; ~ ; d rlpters~pnt c~ ositi on Preferably, the polymer com.bination is included in liquids, more preferably aqueou8 liquids. We have found that the 20 polymers can in particular be useful in isotropic liquids as the liquid remains clear after addition of the polymer.
Another preferred Pmhorl;r~nt of the invention relates to the use of the polymers in structured liquid detergent compositions, for example containing a structure of 25 1~---llAr droplets of detergent active material.
Therefor, a particular ~-~o~l;r~ t of the invention relates to isotropic liquids comprise a liquid system which comprises surfactant material, electrolyte, hydrotrope, 3 0 water and optionally monoethanolamine and/or trieth~n~ m;nP. We have found that the polymer combination of the present invention is soluble in such liquids, in particular when the ingredients are present at the levels at specif ied hereunder .
Therefor another particular embodiment of the invention relate to a structured liquid detergent composition C 6330~V) comprising surfactant material and the polymer combination of the invention.
S-lrfact;ln~ ~teri;~1 5 Compositions of the invention may also comprise surfactant materials, preferably at a level of at least 5~6 by weight of the composition, more preferred at least 10~ by weight, most preferred at least 209~ by weight and in particular at least 2596 by weight of the composition; and preferably at a 10 level of at most 60~ by weight, more preferably at most 50 and most preferably at most 4596 by weight of the composition .
In the widest definition the surfactant material in 15 general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof. For example, they may be chosen from any of the classes, sub-classes and specific materials 20 described in ' Surface Active Agents ' Vol . I, by Schwartz &
Perry, Interscience 1949 and 'Surface Active Agents~ Vol.
by Schwartz, Perry & Berch (Interscience 1958), in the current edition of "McCutcheon's Emulsifiers & Detergents"
published by the McCutcheon division of Manufacturing 25 Confectioners Company or in 'Tensid-Taschenbuch~, H.Stache, 2nd Edn., Carl E~anser Verlag, Mhnchen & Wien, 1981.
Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group 30 and a reactive llydL~y~ atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkyl oxides, ~ p,or;~lly ethylene oxide, either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C6-C1~) primary or secondary linear or branched alcohols with 35 ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene-di-amine. Other so-called nonionic C 6330 (V) detergent compounds include long chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides .
5 Preferably, the composition then comprises at most 259~, more preferably at most 2096, most preferably at most 1595, in particular at most lOg6 by weight of the total ethoxylated nonionic surfactants of long chain E0 (ethylene oxide) nonionic surfactants. Long chain E0 nonionic lO surfactants are defined as comprising 15 or more E0 groups, preferably lO or more E0 groups, more preferably 8 or more .
E0 groups per nonionic molecule. It is noted that commercially available ethoxylated nonionics always represent a nonionic mixture.
Preferably the level of nonionic surfactant materials is from l to 40~ by weight of the composition, more preferred from 2 to 20~.
20 Compositions of the present invention may contain synthetic anionic ~urf actant ingredients, which are pref erably present in combination with the above mentioned nonionic materials. Suitable anionic surfactants are usually water-soluble alkali metal salt~ of organic sulphates and 25 sulphonates having alkyl radicals c~nt~n1ng from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic surf actant compounds are sodium and potassium alkyl sulphates, especially those 30 obtained by sulphating higher (C~-C1~) alcohols produced, for example, from tallow or coconut oil, sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C1o-C~s) benzene sulphonates;
~3odium alkyl glycerol ether sulphates, especially those 35 ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohol~ derived from petroleum;
sodium coconut oil fatty monoglyceride sulphates and C 6330~V) 12 2 ~ 95835 sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C8-C18) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty 5 acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts~ of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (C8-~0) with sodium bisulphite and those derived from reacting paraffins with 10 S02 and C1~ and then hydrolysing with a base to produce a random sulphonate; and olefin sulphonates, which term is used to describe the material made by reacting olef ins, particularly C10-C~O alpha-olefins, with S03 and then neutralizing and hydrolysing the reaction product. The 15 preferred anionic surfactant compound8 are 80dium (Cl~-C1s) alkyl benzene sulphonates and sodium (C16-C13) alkyl sulphates .
Generally the level of the above mentioned non-soap anionic 20 surfactant materials is from 1-40 9~ by weight of the composition, more preferred from 2 to 255~.
It is also possible, and sometimes preferred, to include an alkali metal soap of a mono- or di-carboxylic acid, 25 especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, alk(en)yl succinate for example dodecyl succinate, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof. The sodium 3 0 or potassium soaps of these acids can be used .
Preferably the level of soap in compositions of the invention is from 1-35~ by weight of the composition, more pre f erred f rom 5 - 2 5 ~ .
Surprisingly, we have found that inclusion of sugar based surfactants (preferably alkylpolyglycosides and/or C 6330 (V) 2 ~ 95835 polyhydroxy fatty acid amide surfactants) and/or alkyl benzene sulphonate (as described above) further improve the particulate stain removal characteristics of the polymer combination of the present invention. Suitable nonionlcs 5 include aldobionamides such as are taught in U. S . Patent No. 5,296,588 to Au et al. and polyhydroxyam~ides such as are taught in U.S. Patent No. 5,312,954 to l.etton et al., both of which are incorporated by reference into the _=
subject application.
Preferably, the level of the sugar based surfactants is from 0 to 20%, more preferably up to 1596, mo3t preferably up to 10~6 and more preferably higher than 19~, most preferably higher than 3~ by weight of the composition.
Alkylpolysaccharides have been disclosed US 4,565,647 and have a hydrophobic group (-~)nti~;nlng from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group 20 r~nti~;n;n~ from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7 saccharide units. Any reducing saccharide ~r~nti~;n;ng 5 or 6 carbon atoms can be used, e.g.
glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the 25 hydrophobic group is attached at the 2-, 3-, 4-, etc.
positions thus giving a glucose or galactose a~ opposed to a glucoside or galactoside). The intersaccharide bonds can be, e.g. between the one poHition of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on 30 the preceding saccharide units.
Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched c~-nti~;n;n~
from 8 to 18 preferably from 10 to 16 carbon atoms.
35 Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to 3 hydroxy groups. Suitable alkylpolysaccharides are octyl, C 6330 (V) 14 2 1 95835 ::~
nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or 5 galactoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-penta-, and hexaglucosides.
Preferred alkylpolyglycosides have the formula:
10 R20 (CnH2nO) t (glycosyl) x, wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, lly<l~ u~y~lkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14 carbon atoms; n is 2 or 3, preferably 2; t is from O to 10, 15 preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose.
EIighly preferred nonionic surfactants are polyhydroxy fatty 20 acid amide surfactants of the formula: R2-C(O)-N(R1)-Z
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 polyh~d~ ~yllydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly 25 c~-nn,~-~ted to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight C11-15 thereof, and Z is derived f rom a reducing sugar such as glucose, f ructose, maltose, lactose, in a reductive amination reaction.
E1 ectrolyte r~t--ri ~l Compositions according to the invention preferably comprise electrolyte material, some or all of which may be builder material. Preferably the total level of electrolyte is from 35 1 to 60~ by weight of the composition, more preferred 1 to 30~6, most preferred 1 to 10~6.
C 6330~v) 15 2~ ~5835 Preferably, electrolyte material comprises material selected from citrate, borate, sulphate, carbonate, bi-carbonate, propionate, formate, chloride, phosphate, silicate and mixtures thereof.
It is preferred that compositions according to the present invention include detergency builder material, some or all of which may be electrolyte. In this context it should be noted that some surfactant materials such as for example 10 soaps, also have builder properties.
Examples of phosphorous cnnt~;n;ng inorganic detergency builders include the water-soluble salts, especially alkali metalpyrophosphates, orthophosphates, polyphosphates and 15 phosphonates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant builders may also be used. It may however be preferred to minimise the amount of phosphate builders.
Examples of non-phosphorus-containing inorganic detergency builders, when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include 25 sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites .
Examples of organic detergency builders, when present, 30 include the ~lk~l;nP metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates.
Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of 35 ethyl~n~ qm; n~tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids, CMOS, tartrate mono succinate, tartrate di succinate C 6330~1V) 16 2 1 95~35 and citric acid. Citric acids or salts thereof are preferred builder materials for use in compositions of the invention .
5 EIy~lrotro};~e ~ter; ~1 Preferably isotropic compositions according to the invention comprise hydrotrope material.
Preferably the hydrotrope material is selected from lower 10 alifatic alcohols, ethers of diethylene glycol and lower monoaliphatic monoalcohols. Specifically, ethanol, n-propanol, iso-propanol, butanol, polyethylene glycol, propyleneglycol, dipropylene glycol, hexylene glycol, methoxyethanol, ethoxyethanol, butoxyethanol, 15 ethyldiglycolether, benzylalcohol, butoxypropanol, butu~y~Lu~ yt:thanol, butoxypropu~y~, u~anol, 1, 2 propanediol, sorbitol and glycerol . Pref erably the solvent system comprises propyleneglycol and/or ethanol.
20 Preferably the level of the hydrotrope material is isotropic systems is from 5 to 25%, more preferably from 7 to 20~ by weight of the composition. Structured liquid compositions according to the invention preferably comprise no or only low levels of hydrotrope material, eg. 0 to 5 25 wt96.
Preferably, the liquid compositions of the present invention are r~nr.sntrated Therefore, the water level in 30 the liquid detergent compositions according to the present invention is preferably at most 70%, more preferably at most 60, most preferably at most 559~ by weight of the composition. Preferably, the liquid system comprises at least 10%, more preferably at least 15%, most preferably at 35 least 209~ by weight of the composition.
C 633~(V) Monoeth~n~ m; n~ n~l Trieth~n~-] Am; n,~
The liquid system of the compoeitions according to the invention optionally contain one or more compounds selected f rom monoethanolamine and/or triethanolamine at a level of 5 from 0 to 10~ by weight of the composition.
O~tion~l ; n~red; ents Apart from the ingredients already mentioned, a number of optional ingredients may also be present, for example 10 lather boosters such as alkanolamides, particularly the monoethanolamides derived f rom palm kernel f atty acids and coconut fatty acids, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing 15 bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, f luorescent agents, perfumes, enzymes such as proteases, amylases and lipases (including I-ipolase (Trade Mark) ex Novo), enzyme 20 stabilizers, anti-redeposition agents, germicides and colorants. obviously in selecting the materials other than the polymer for use in compositions of the invention, also biodegradable materials are preferred for envil ti:ll reasons .
Prodl 1 ct f orm A8 has been indicated, liquids which are isotropic or structured are well-known in the art.
30 I.iquid compositions of the invention preferably have a viscosity of less than 2,500 mPas at 21 8-1, more preferred less than 1,500 mPas, most preferred less than 1,000 mPas and preferably higher than 100 mPas at 21 8-1.
35 Liquid compositions according to the invention are physically stable. In the context of the present invention, physical stability for these systems can be defined in C 633 V) o~ 2 1 95835 terms of the maximum separation compatible with most manufacturing and retail requirements. That is, the ~ stable ' compositions will yield no more than 10 96, preferably no more than 5 96, most preferred no more than 2 5 by volume phase separation as evidenced by appearance of 2 or more separate phases when stored at 25C for 21 days f rom the time of preparation .
Preferably, the liquid compositions according to the 10 invention have a product pH of at least 6, more preferably at least 6.5, most preferably at least 7 and preferably at most 14, more preferably at most 12, most preferably at most 10.
15 Preferably the pH, as provided to the wash liquor, is at least 6, more preferably at least 7.5, most preferably at least 8. Preferably the pH is at most 12, more preferably at most 10, most preferably at most 9.
20 Ml~thnd of ~re~rati--n Liquid compositions of the invention may be prepared by any convPnt;~-n~l method for the preparation of liquid detergent compositions. A preferred process of preparation is illustrated in the examples. Such processes lead to 25 preparation of clear isotropic liquids.
The invention will be illustrated by way of the following non-limiting Examples.
C 6330~V) r ~les E le 1 The following formulation was prepared by adding the ingredients in the order listed to ~ome water:
Composition 10 Inçrr~ ntFI A
Na-citrate (37 . 5~) 13 13 Propyleneglycol 6 6 Premix of 1096 water/
7096 sorbitol/borax 19 . 5 19 . 5 - -15 NaOH (50g6) 1. 6 1. 6 Alkyl Benzene Sulphonate 7 . 8 7 . 8 Nonionic (Neodol ) 8 8 (wait until temperature i9 lower than 32C) 20 Alkyl Ether Sulphate (59~6) 23.8 23.8 Minors 1. 5 1. 5 (adjust pH to 7 with NaOH) Water up to 100 up to 100 Polymer Narlex H1200 - o . 25 25 Polymer PVP/PVI (Sokalan HP 56) - 0.5 Tests cloth~ with particulate stains (e.g. mascara, curry, make-up, shoe polish and clay) were washed with the above compositions. The composition according to the invention 3 0 showed better stain removal as evidenced by the higher Delta R ref lectance .
Narlex H100 and Alco 2~99 both have silimar effects when included in the above composition instead of Narlex EI1200 35 and replacing PVP-PVI with PVP also leads to similar result~ .
C 6330 (V) 20 2 1 95~35 E le 2 The following formulation was prepared:
Irlqred;~nt~ 2 (% by w~;Srht) 5 Na-citrate (37.5~) 10.7 Propyleneglycol 7 . 5 Premix of water/
sorbitol/borax 19 . 5 MEA o . 5 10Cocofatty acid 1. 7 (mix for 15 minutes) NaOH (50~) 2.2 Alkyl Benzene Sulphonate 10 . 3 Nonionic (Neodol) 6 . 3 15(wait until temperature is lower than 32C) Alkyl Ether Sulphate (5996) 12 . 9 Minors 1. 3 (adjust pH to 7 with NaOH) 20Water up to 100 Polymer Narlex H100 0.25 Polymer PVP K15 0 . 5 The polymer was added on top. The resulting li~uid i8 clear 25 and is stable upon storage.
C 6330~V) 21 2 ~ 95835 E le 3 The following formulation was prepared:
TnSJre~ ~nt~ 3 5 Borate 3 Propylene glycol 8 NaOH/ KOH ( 5 0 ~ ) 9 . 2 Cocof atty acid 14 ~ .
(mix for 15 minutes) 10 Premix of I.AS and Neodol 18 . 2 (mix during 5 minute~) Minors Water up to 100 Polymer Narlex H100 0.25 15 Polymer PVP K15 0 . 5 pH: about 8 . 8 The polymer was added on top. The resulting liguid is clear 20 and is stable upon storage.
F le 4 25 The formulation of Example 1 was prepared with two other polymers, ie. with Narlex II100 and PVP K15. The resulting liquid was clear and stable upon ~torage.
Preferably, the amphiphilic carboxy containing polymer i8 present at a level of from 0 . 05 to 5% by weight of the 5 composition, more preferably from 0.1 to 2, most preferably from 0.2 to 1.5, for instance at a level of 0.59~ by weight of the composition.
The ratio of carboxy ~nnt~;n;n~ hydrophilic momomers to 10 uncharged monomers can varry in a broad range e.g. from 100:1 to 0.5:1, preferably from 50:1 to 1:1. For copolymers of acrylic acid and styrene this ratio is preferably between 10:1 and 0.5:1, most preferred from 6:1 to 1:1.
15 ~n~-h~rged pol~
Preferably, the uncharged polymer material is selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimiidazole, polyvinylpyrrolidone, polyvinyloxazolidone, 20 polyvinylimidazole and mixtures thereof.
a. Poly~m;nf~ N--33~ olyr~s Polyamine N-oxide polymers suitable for use contain units having the following structure formula: R-Ax-P, wherein P
25 is a polymerisable unit, whereto the R-N-O group can be attached to or wherein the R-N-O group forms part of the polymerisable unit or a combination of both. A is NC (O), C(O)O, -O-, -S-, -N; x is 0 or 1; R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic 3 o group 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-O group can be represented by the following general 35 quaternary N-structure: (R1)x-N(-O) (R3)z(R2)y and =N(O) (R1)x, wherein R1, R, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations C 633~(~T) thereof, x and/or y and/or z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitroge~ of the N-O group forms part of these groups.
5 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 10 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.
15 Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, ~l;n~)l ;n~, acridine and derivatives thereof.
20 Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O
group is attached to the R-group.
Other suitable polyamine N-oxides are the polyamine oxides 25 whereto the N-O group is attached to the polymerisable unit .
Preferred class of these polyalmine N-oxides are the polyamine N-oxides having the general formula (I) wherein R
30 is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O group is part of said R group.
~xamplea of the3e classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R
C 6330~(V) ~ 2 1 95835 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. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes polyesters, polyethers, polyamide, polyimides, 10 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 10:1 to 1:1,000,000. However the amount of amine oxide 15 groups present in the polyamine oxidew polymer can be varied by appropriate copolymerization or by d~~ r iate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2:3 to 1:1,000,000. More preferably from 1:4, most preferably from 1:7 up to 1,000,000. The 20 polymers of the present invention actually f~n~ 8 random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not. The amine oxide unit of the olyamine N-oxides has a pKa<10, preferably pKa~7, more preferably 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 .
Typically, the average molecular weight is within the range of 500 to 100,000; preferably from 1,000 to 50,000, more preferably from 2, 000 to 30, 000, most preferably from 3, 000 to 20,000.
~. Co~ol rg of No-vir~ylpyrroli~lf)n~D an~ N-vinylim; ~ 7ole The N-vinylimidazole N-vinylpyrrolidone polymers which may C 633~v) 7 2~ 95835 be used in the present invention have an average molecular weight range from 5, 000 to l, 000, 000, preferably from 20, 000 to 200, 000 . Highly preferred polymer for use in detergent compositions according to the present invention 5 comprise a polymer selected from N-vinylimidazole N-vinylpyrrolidone copolymers wherein said pol~ymer has an average molecular weight range from 5, 000 to 50, 000 more preferably from 8, 000 to 30, 000, most preferably from 10, 000 to 20, 000 .
The average molecular weight range was determined by light scattering as described in Barth H.G. and Mays J.W.
Chemical Analysis VOl 113, "Modern methods of polymer characterization " .
Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight range from 5,000 to 50,000, more preferably from 8,000 to 30,000, most preferably from lO,000 to 20,000.
The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinyl;m;~7Ole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0 . 3, most pref erably f rom 0 . 6 to 0 . 4 .
c. Polyvir~ylpyrroli~ ne Detergent compositions of the present invention may also utilize polyvinylpyrrolidone (~PVP~) having an average molecular weight of from 2,500 to 400,000, preferably from 30 5,000 to 200,000, more preferably from 5,000 to 50,000 and most preferably from 5, 000 to 15, 000 . Suitable polyvinylpyrrolidone~ are commercially available from ISP
Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 35 10,000), PVP K-30 (average molecular weight of 40,000), PVP
K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360, 000) . PVP K-15 is also Ç 633~(V) available from ISP Corporation. Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
Polyvinylpyrrolidones will be known to persons skilled in 5 the detergent field; see for example EP-A-262,897 and EP-A-256, 696.
d. Polyvinyl-~7olidone Detergent compositions of the present invention may also 10 comprise polyvinyloxazolidone. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000, preferably to 200, 000, more preferably to 50, 000 and most preferably to 15, 000 .
15 e . Polyvinylim; ~l~701e Detergent compositions of the present invention may also comprise polyvinylimidazole. Said polyvinylimidazoles have an average molecular weight range from 2,500 to 400,000, preferably to 200, OO0, more preferably to 5O, OO0, and most 20 preferably to 15, 000 .
Preferably, the uncharged polymers are selected from ethoxylated ethylene-amine polymers, vinylpyrrolidone polymers, 2-vinylpyridine N-oxide c~nt~;n;n~ polymers, 25 vinylpyrrolidone-vinylacetate copolymers, vinylpyrrolidone-styrene co-polymers and vinylpyrrolidone-vinyl imidazole copolymers. Examples of such polymers are ethoxylated tetraethyl.on~r.-nt~m;n~, polyvinylpyrrolidone K15, polyvinylpyrrolidone vinylacetate (PVP/VA S-630), 30 polyvinylpyridine N-oxide, polyvinylpyrrolidone-styrene (Antara 430) and polyvinylpyrrolidone-vinylimidazole (Sokalan ~IP56). Most preferably, the uncharged polymers are selected from vinylpyrrolidone (PVP), polyvinylpyridine N-oxide and copolymers of vinylpyrrolidone and vinylimidazole 35 (PVP-PVI) . An example is Sokalan EIP 56 (ex BASF) .
Preferably, the level of the uncharged polymer is from 0.1 C 6330 (v) to 396, more preferably from 0.25 to 1.5%, for instance 0.5%
by weight of the composition.
Deter~rPnt co~osition 5 Preferably, the detergent composition comprises surfactant material. Preferably, liquids according to the present invention comprise anionic surfactants at a ievel of 5% by weight of the composition or higher.
10 In a preferred embodiment of the invention, the surfactant comprises one or more of the aurfactants selected from alkyl benzene sulphonate and 3ugar based surfactants. Sugar based surfactants are preferred. We have found that the use of these surfactants further improves the stain removal of 15 the particulated stains in a fatty or oily matrix.
L; ~ ; d rlpters~pnt c~ ositi on Preferably, the polymer com.bination is included in liquids, more preferably aqueou8 liquids. We have found that the 20 polymers can in particular be useful in isotropic liquids as the liquid remains clear after addition of the polymer.
Another preferred Pmhorl;r~nt of the invention relates to the use of the polymers in structured liquid detergent compositions, for example containing a structure of 25 1~---llAr droplets of detergent active material.
Therefor, a particular ~-~o~l;r~ t of the invention relates to isotropic liquids comprise a liquid system which comprises surfactant material, electrolyte, hydrotrope, 3 0 water and optionally monoethanolamine and/or trieth~n~ m;nP. We have found that the polymer combination of the present invention is soluble in such liquids, in particular when the ingredients are present at the levels at specif ied hereunder .
Therefor another particular embodiment of the invention relate to a structured liquid detergent composition C 6330~V) comprising surfactant material and the polymer combination of the invention.
S-lrfact;ln~ ~teri;~1 5 Compositions of the invention may also comprise surfactant materials, preferably at a level of at least 5~6 by weight of the composition, more preferred at least 10~ by weight, most preferred at least 209~ by weight and in particular at least 2596 by weight of the composition; and preferably at a 10 level of at most 60~ by weight, more preferably at most 50 and most preferably at most 4596 by weight of the composition .
In the widest definition the surfactant material in 15 general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof. For example, they may be chosen from any of the classes, sub-classes and specific materials 20 described in ' Surface Active Agents ' Vol . I, by Schwartz &
Perry, Interscience 1949 and 'Surface Active Agents~ Vol.
by Schwartz, Perry & Berch (Interscience 1958), in the current edition of "McCutcheon's Emulsifiers & Detergents"
published by the McCutcheon division of Manufacturing 25 Confectioners Company or in 'Tensid-Taschenbuch~, H.Stache, 2nd Edn., Carl E~anser Verlag, Mhnchen & Wien, 1981.
Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group 30 and a reactive llydL~y~ atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkyl oxides, ~ p,or;~lly ethylene oxide, either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C6-C1~) primary or secondary linear or branched alcohols with 35 ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene-di-amine. Other so-called nonionic C 6330 (V) detergent compounds include long chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides .
5 Preferably, the composition then comprises at most 259~, more preferably at most 2096, most preferably at most 1595, in particular at most lOg6 by weight of the total ethoxylated nonionic surfactants of long chain E0 (ethylene oxide) nonionic surfactants. Long chain E0 nonionic lO surfactants are defined as comprising 15 or more E0 groups, preferably lO or more E0 groups, more preferably 8 or more .
E0 groups per nonionic molecule. It is noted that commercially available ethoxylated nonionics always represent a nonionic mixture.
Preferably the level of nonionic surfactant materials is from l to 40~ by weight of the composition, more preferred from 2 to 20~.
20 Compositions of the present invention may contain synthetic anionic ~urf actant ingredients, which are pref erably present in combination with the above mentioned nonionic materials. Suitable anionic surfactants are usually water-soluble alkali metal salt~ of organic sulphates and 25 sulphonates having alkyl radicals c~nt~n1ng from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic surf actant compounds are sodium and potassium alkyl sulphates, especially those 30 obtained by sulphating higher (C~-C1~) alcohols produced, for example, from tallow or coconut oil, sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C1o-C~s) benzene sulphonates;
~3odium alkyl glycerol ether sulphates, especially those 35 ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohol~ derived from petroleum;
sodium coconut oil fatty monoglyceride sulphates and C 6330~V) 12 2 ~ 95835 sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C8-C18) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty 5 acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts~ of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (C8-~0) with sodium bisulphite and those derived from reacting paraffins with 10 S02 and C1~ and then hydrolysing with a base to produce a random sulphonate; and olefin sulphonates, which term is used to describe the material made by reacting olef ins, particularly C10-C~O alpha-olefins, with S03 and then neutralizing and hydrolysing the reaction product. The 15 preferred anionic surfactant compound8 are 80dium (Cl~-C1s) alkyl benzene sulphonates and sodium (C16-C13) alkyl sulphates .
Generally the level of the above mentioned non-soap anionic 20 surfactant materials is from 1-40 9~ by weight of the composition, more preferred from 2 to 255~.
It is also possible, and sometimes preferred, to include an alkali metal soap of a mono- or di-carboxylic acid, 25 especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, alk(en)yl succinate for example dodecyl succinate, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof. The sodium 3 0 or potassium soaps of these acids can be used .
Preferably the level of soap in compositions of the invention is from 1-35~ by weight of the composition, more pre f erred f rom 5 - 2 5 ~ .
Surprisingly, we have found that inclusion of sugar based surfactants (preferably alkylpolyglycosides and/or C 6330 (V) 2 ~ 95835 polyhydroxy fatty acid amide surfactants) and/or alkyl benzene sulphonate (as described above) further improve the particulate stain removal characteristics of the polymer combination of the present invention. Suitable nonionlcs 5 include aldobionamides such as are taught in U. S . Patent No. 5,296,588 to Au et al. and polyhydroxyam~ides such as are taught in U.S. Patent No. 5,312,954 to l.etton et al., both of which are incorporated by reference into the _=
subject application.
Preferably, the level of the sugar based surfactants is from 0 to 20%, more preferably up to 1596, mo3t preferably up to 10~6 and more preferably higher than 19~, most preferably higher than 3~ by weight of the composition.
Alkylpolysaccharides have been disclosed US 4,565,647 and have a hydrophobic group (-~)nti~;nlng from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group 20 r~nti~;n;n~ from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7 saccharide units. Any reducing saccharide ~r~nti~;n;ng 5 or 6 carbon atoms can be used, e.g.
glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the 25 hydrophobic group is attached at the 2-, 3-, 4-, etc.
positions thus giving a glucose or galactose a~ opposed to a glucoside or galactoside). The intersaccharide bonds can be, e.g. between the one poHition of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on 30 the preceding saccharide units.
Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched c~-nti~;n;n~
from 8 to 18 preferably from 10 to 16 carbon atoms.
35 Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to 3 hydroxy groups. Suitable alkylpolysaccharides are octyl, C 6330 (V) 14 2 1 95835 ::~
nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or 5 galactoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-penta-, and hexaglucosides.
Preferred alkylpolyglycosides have the formula:
10 R20 (CnH2nO) t (glycosyl) x, wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, lly<l~ u~y~lkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14 carbon atoms; n is 2 or 3, preferably 2; t is from O to 10, 15 preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose.
EIighly preferred nonionic surfactants are polyhydroxy fatty 20 acid amide surfactants of the formula: R2-C(O)-N(R1)-Z
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 polyh~d~ ~yllydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly 25 c~-nn,~-~ted to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight C11-15 thereof, and Z is derived f rom a reducing sugar such as glucose, f ructose, maltose, lactose, in a reductive amination reaction.
E1 ectrolyte r~t--ri ~l Compositions according to the invention preferably comprise electrolyte material, some or all of which may be builder material. Preferably the total level of electrolyte is from 35 1 to 60~ by weight of the composition, more preferred 1 to 30~6, most preferred 1 to 10~6.
C 6330~v) 15 2~ ~5835 Preferably, electrolyte material comprises material selected from citrate, borate, sulphate, carbonate, bi-carbonate, propionate, formate, chloride, phosphate, silicate and mixtures thereof.
It is preferred that compositions according to the present invention include detergency builder material, some or all of which may be electrolyte. In this context it should be noted that some surfactant materials such as for example 10 soaps, also have builder properties.
Examples of phosphorous cnnt~;n;ng inorganic detergency builders include the water-soluble salts, especially alkali metalpyrophosphates, orthophosphates, polyphosphates and 15 phosphonates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant builders may also be used. It may however be preferred to minimise the amount of phosphate builders.
Examples of non-phosphorus-containing inorganic detergency builders, when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include 25 sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites .
Examples of organic detergency builders, when present, 30 include the ~lk~l;nP metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates.
Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of 35 ethyl~n~ qm; n~tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids, CMOS, tartrate mono succinate, tartrate di succinate C 6330~1V) 16 2 1 95~35 and citric acid. Citric acids or salts thereof are preferred builder materials for use in compositions of the invention .
5 EIy~lrotro};~e ~ter; ~1 Preferably isotropic compositions according to the invention comprise hydrotrope material.
Preferably the hydrotrope material is selected from lower 10 alifatic alcohols, ethers of diethylene glycol and lower monoaliphatic monoalcohols. Specifically, ethanol, n-propanol, iso-propanol, butanol, polyethylene glycol, propyleneglycol, dipropylene glycol, hexylene glycol, methoxyethanol, ethoxyethanol, butoxyethanol, 15 ethyldiglycolether, benzylalcohol, butoxypropanol, butu~y~Lu~ yt:thanol, butoxypropu~y~, u~anol, 1, 2 propanediol, sorbitol and glycerol . Pref erably the solvent system comprises propyleneglycol and/or ethanol.
20 Preferably the level of the hydrotrope material is isotropic systems is from 5 to 25%, more preferably from 7 to 20~ by weight of the composition. Structured liquid compositions according to the invention preferably comprise no or only low levels of hydrotrope material, eg. 0 to 5 25 wt96.
Preferably, the liquid compositions of the present invention are r~nr.sntrated Therefore, the water level in 30 the liquid detergent compositions according to the present invention is preferably at most 70%, more preferably at most 60, most preferably at most 559~ by weight of the composition. Preferably, the liquid system comprises at least 10%, more preferably at least 15%, most preferably at 35 least 209~ by weight of the composition.
C 633~(V) Monoeth~n~ m; n~ n~l Trieth~n~-] Am; n,~
The liquid system of the compoeitions according to the invention optionally contain one or more compounds selected f rom monoethanolamine and/or triethanolamine at a level of 5 from 0 to 10~ by weight of the composition.
O~tion~l ; n~red; ents Apart from the ingredients already mentioned, a number of optional ingredients may also be present, for example 10 lather boosters such as alkanolamides, particularly the monoethanolamides derived f rom palm kernel f atty acids and coconut fatty acids, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing 15 bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, f luorescent agents, perfumes, enzymes such as proteases, amylases and lipases (including I-ipolase (Trade Mark) ex Novo), enzyme 20 stabilizers, anti-redeposition agents, germicides and colorants. obviously in selecting the materials other than the polymer for use in compositions of the invention, also biodegradable materials are preferred for envil ti:ll reasons .
Prodl 1 ct f orm A8 has been indicated, liquids which are isotropic or structured are well-known in the art.
30 I.iquid compositions of the invention preferably have a viscosity of less than 2,500 mPas at 21 8-1, more preferred less than 1,500 mPas, most preferred less than 1,000 mPas and preferably higher than 100 mPas at 21 8-1.
35 Liquid compositions according to the invention are physically stable. In the context of the present invention, physical stability for these systems can be defined in C 633 V) o~ 2 1 95835 terms of the maximum separation compatible with most manufacturing and retail requirements. That is, the ~ stable ' compositions will yield no more than 10 96, preferably no more than 5 96, most preferred no more than 2 5 by volume phase separation as evidenced by appearance of 2 or more separate phases when stored at 25C for 21 days f rom the time of preparation .
Preferably, the liquid compositions according to the 10 invention have a product pH of at least 6, more preferably at least 6.5, most preferably at least 7 and preferably at most 14, more preferably at most 12, most preferably at most 10.
15 Preferably the pH, as provided to the wash liquor, is at least 6, more preferably at least 7.5, most preferably at least 8. Preferably the pH is at most 12, more preferably at most 10, most preferably at most 9.
20 Ml~thnd of ~re~rati--n Liquid compositions of the invention may be prepared by any convPnt;~-n~l method for the preparation of liquid detergent compositions. A preferred process of preparation is illustrated in the examples. Such processes lead to 25 preparation of clear isotropic liquids.
The invention will be illustrated by way of the following non-limiting Examples.
C 6330~V) r ~les E le 1 The following formulation was prepared by adding the ingredients in the order listed to ~ome water:
Composition 10 Inçrr~ ntFI A
Na-citrate (37 . 5~) 13 13 Propyleneglycol 6 6 Premix of 1096 water/
7096 sorbitol/borax 19 . 5 19 . 5 - -15 NaOH (50g6) 1. 6 1. 6 Alkyl Benzene Sulphonate 7 . 8 7 . 8 Nonionic (Neodol ) 8 8 (wait until temperature i9 lower than 32C) 20 Alkyl Ether Sulphate (59~6) 23.8 23.8 Minors 1. 5 1. 5 (adjust pH to 7 with NaOH) Water up to 100 up to 100 Polymer Narlex H1200 - o . 25 25 Polymer PVP/PVI (Sokalan HP 56) - 0.5 Tests cloth~ with particulate stains (e.g. mascara, curry, make-up, shoe polish and clay) were washed with the above compositions. The composition according to the invention 3 0 showed better stain removal as evidenced by the higher Delta R ref lectance .
Narlex H100 and Alco 2~99 both have silimar effects when included in the above composition instead of Narlex EI1200 35 and replacing PVP-PVI with PVP also leads to similar result~ .
C 6330 (V) 20 2 1 95~35 E le 2 The following formulation was prepared:
Irlqred;~nt~ 2 (% by w~;Srht) 5 Na-citrate (37.5~) 10.7 Propyleneglycol 7 . 5 Premix of water/
sorbitol/borax 19 . 5 MEA o . 5 10Cocofatty acid 1. 7 (mix for 15 minutes) NaOH (50~) 2.2 Alkyl Benzene Sulphonate 10 . 3 Nonionic (Neodol) 6 . 3 15(wait until temperature is lower than 32C) Alkyl Ether Sulphate (5996) 12 . 9 Minors 1. 3 (adjust pH to 7 with NaOH) 20Water up to 100 Polymer Narlex H100 0.25 Polymer PVP K15 0 . 5 The polymer was added on top. The resulting li~uid i8 clear 25 and is stable upon storage.
C 6330~V) 21 2 ~ 95835 E le 3 The following formulation was prepared:
TnSJre~ ~nt~ 3 5 Borate 3 Propylene glycol 8 NaOH/ KOH ( 5 0 ~ ) 9 . 2 Cocof atty acid 14 ~ .
(mix for 15 minutes) 10 Premix of I.AS and Neodol 18 . 2 (mix during 5 minute~) Minors Water up to 100 Polymer Narlex H100 0.25 15 Polymer PVP K15 0 . 5 pH: about 8 . 8 The polymer was added on top. The resulting liguid is clear 20 and is stable upon storage.
F le 4 25 The formulation of Example 1 was prepared with two other polymers, ie. with Narlex II100 and PVP K15. The resulting liquid was clear and stable upon ~torage.
Claims (9)
1. Detergent composition comprising surfactant material, an amphiphilic carboxy containing polymers and an uncharged polymer.
2. Composition according to claim 1, wherein the amphiphilic carboxy containing polymer comprises uncharged monomers selected from:
vinylacetate, vinylpyrrolidone, vinylpyridine, vinylimidazol, styrene, alkyl-esters of acrylate, alkyl-esters of methacrylate, alkyl-esters of itaconate, alkyl-esters of maleate and mixtures thereof.
vinylacetate, vinylpyrrolidone, vinylpyridine, vinylimidazol, styrene, alkyl-esters of acrylate, alkyl-esters of methacrylate, alkyl-esters of itaconate, alkyl-esters of maleate and mixtures thereof.
3. Composition according to claim 1, wherein the amphiphilic carboxy containing polymer comprises hydrophilic momomas selected from acrylate, methacrylate, itaconate, maleate and mixtures thereof.
4. Composition according to claim 1, wherein the uncharged polymer is selected from is selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimiidazole, polyvinylpyrrolidone, polyvinyloxazolidone, polyvinylimidazole and mixtures thereof.
5. Composition according to claim 1, wherein the composition comprises a liquid system.
6. Composition according to claim 5, comprising from 5-60%
by weight of surfactant, 1-60% by weight of electrolyte, 10-70% by weight of water and optionally 0-10% by weight of one or more compounds selected from monoethanolamine and triethanolamine.
by weight of surfactant, 1-60% by weight of electrolyte, 10-70% by weight of water and optionally 0-10% by weight of one or more compounds selected from monoethanolamine and triethanolamine.
7. Method of preparing a liquid detergent composition according to claim 5 by mixing the ingredients.
8. Method of washing fabrics by adding the detergent composition of claim 1 to the wash liquor.
9. The detergent composition as claimed in claim 1 and substantially as described herein.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US59105996A | 1996-01-25 | 1996-01-25 | |
US08/591,059 | 1996-01-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2195835A1 true CA2195835A1 (en) | 1997-07-26 |
Family
ID=24364882
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002195835A Abandoned CA2195835A1 (en) | 1996-01-25 | 1997-01-23 | A detergent composition comprising an amphiphilic carboxy containing polymer and an uncharged polymer |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0786517B1 (en) |
AR (1) | AR005546A1 (en) |
BR (1) | BR9700773A (en) |
CA (1) | CA2195835A1 (en) |
DE (1) | DE69706715T2 (en) |
ES (1) | ES2163091T3 (en) |
ZA (1) | ZA97484B (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0229147D0 (en) | 2002-12-13 | 2003-01-15 | Unilever Plc | Polymers and laundry detergent compositions containing them |
GB0229146D0 (en) | 2002-12-13 | 2003-01-15 | Unilever Plc | Polymers and laundry detergent compositions containing them |
US7012054B2 (en) | 2003-12-03 | 2006-03-14 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Softening laundry detergent |
BR112014004115A2 (en) | 2011-08-31 | 2017-03-01 | Akzo Nobel Chemicals Int Bv | detergent composition, dirt release agent for detergent compositions and textile treatment method for improved dirt release |
JP6800562B2 (en) * | 2015-03-23 | 2020-12-16 | 株式会社日本触媒 | Detergent composition |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8618635D0 (en) | 1986-07-30 | 1986-09-10 | Unilever Plc | Detergent composition |
US4954292A (en) | 1986-10-01 | 1990-09-04 | Lever Brothers Co. | Detergent composition containing PVP and process of using same |
GB8813978D0 (en) | 1988-06-13 | 1988-07-20 | Unilever Plc | Liquid detergents |
AU624634B2 (en) * | 1989-08-18 | 1992-06-18 | Colgate-Palmolive Company, The | Non-aqueous, nonionic heavy duty laundry detergent |
IL91362A0 (en) | 1989-08-20 | 1990-03-19 | Yissum Res Dev Co | Bisphosphonates,process for preparing them and pharmaceutical compositions containing them |
JP2796535B2 (en) * | 1990-06-01 | 1998-09-10 | ライオン株式会社 | Zeolite-containing liquid detergent composition |
US5409629A (en) * | 1991-07-19 | 1995-04-25 | Rohm And Haas Company | Use of acrylic acid/ethyl acrylate copolymers for enhanced clay soil removal in liquid laundry detergents |
US5296588A (en) | 1991-12-31 | 1994-03-22 | Lever Brothers Company, Division Of Conopco, Inc. | Process of preparing N-substituted aldonamides |
WO1994002581A1 (en) | 1992-07-15 | 1994-02-03 | The Procter & Gamble Company | Dye transfer inhibiting compositions comprising bleaching agents |
EP0596185A1 (en) | 1992-11-06 | 1994-05-11 | The Procter & Gamble Company | Stable liquid detergent compositions inhibiting dye transfer |
JPH08512332A (en) | 1992-07-15 | 1996-12-24 | ザ、プロクター、エンド、ギャンブル、カンパニー | Dye transfer inhibiting composition with builder |
EP0581753B1 (en) | 1992-07-15 | 1998-12-09 | The Procter & Gamble Company | Dye transfer inhibiting compositions comprising polymeric dispersing agents |
AU4545693A (en) | 1992-07-15 | 1994-02-14 | Procter & Gamble Company, The | Surfactant-containing dye transfer inhibiting compositions |
ES2111607T3 (en) | 1992-10-27 | 1998-03-16 | Procter & Gamble | DETERGENT COMPOSITIONS TO INHIBIT DYE TRANSFER. |
US5409639A (en) * | 1993-06-25 | 1995-04-25 | Verona Inc. | Hardwood floor cleaner composition |
EP0710275A1 (en) | 1993-07-19 | 1996-05-08 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer in washing |
EP0635563A1 (en) | 1993-07-22 | 1995-01-25 | The Procter & Gamble Company | Dye-transfer-inhibiting compositions containing fabric-softening agent |
ES2109471T3 (en) | 1993-07-23 | 1998-01-16 | Procter & Gamble | DETERGENT COMPOSITIONS THAT INHIBIT THE TRANSFER OF DYES. |
US5451341A (en) | 1993-09-10 | 1995-09-19 | The Procter & Gamble Company | Soil release polymer in detergent compositions containing dye transfer inhibiting agents to improve cleaning performance |
US5466802A (en) | 1993-11-10 | 1995-11-14 | The Procter & Gamble Company | Detergent compositions which provide dye transfer inhibition benefits |
EP0763084A1 (en) | 1994-06-01 | 1997-03-19 | The Procter & Gamble Company | Dye transfer inhibiting compositions containing oleoyl sarcosinate |
-
1997
- 1997-01-16 DE DE69706715T patent/DE69706715T2/en not_active Expired - Fee Related
- 1997-01-16 ES ES97200107T patent/ES2163091T3/en not_active Expired - Lifetime
- 1997-01-16 EP EP97200107A patent/EP0786517B1/en not_active Expired - Lifetime
- 1997-01-21 ZA ZA97484A patent/ZA97484B/en unknown
- 1997-01-23 CA CA002195835A patent/CA2195835A1/en not_active Abandoned
- 1997-01-24 AR ARP970100294A patent/AR005546A1/en unknown
- 1997-01-24 BR BR9700773A patent/BR9700773A/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
EP0786517B1 (en) | 2001-09-19 |
DE69706715T2 (en) | 2002-05-29 |
DE69706715D1 (en) | 2001-10-25 |
AR005546A1 (en) | 1999-06-23 |
BR9700773A (en) | 1998-10-06 |
EP0786517A1 (en) | 1997-07-30 |
ZA97484B (en) | 1998-07-21 |
ES2163091T3 (en) | 2002-01-16 |
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