CA2386553C - Fabric care composition - Google Patents
Fabric care composition Download PDFInfo
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- CA2386553C CA2386553C CA2386553A CA2386553A CA2386553C CA 2386553 C CA2386553 C CA 2386553C CA 2386553 A CA2386553 A CA 2386553A CA 2386553 A CA2386553 A CA 2386553A CA 2386553 C CA2386553 C CA 2386553C
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- fabric
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- polymeric material
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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
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
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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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
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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
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
Abstract
A fabric care composition comprises a polymeric material which is capable of self cross-linking and/or of reacting with cellulose together with one or more textile compatible carriers, wherein the polymeric material comprises one or more poly(oxyalkylene) groups having an end group which comprises one or more amino groups or derivatives of said amino groups.
The compositions may be used to treat fabric as part of a laundering process and improve the surface colour definition of the fabric following multiple washings.
The compositions may be used to treat fabric as part of a laundering process and improve the surface colour definition of the fabric following multiple washings.
Description
FABRIC CARE COMPOSITION
Technical Field This invention relates to fabric care compositions and to methods of treating fabric using the compositions or the pol-ymeric materials they contain.
Background and Prior Art The laundry process generally has several benefits for fabric, the most common being to remove dirt and stains from the fabric during the wash cycle and to soften the fabric during the rinse cycle. However, there are numerous disadvantages associated with repeated use of conventional laundry treatment compositions and/or the actual laundry process; one of these being a fairly harsh treatment of fabric in the laundry process.
Fabrics can be damaged in several ways as a result of repeated laundering and/or wear. Fabric pilling and loss of fabric surface appearance e.g. fuzzing, shrinkage (or expansion), loss of colour from the fabric or running of colour on the fabric (usually termed dye transfer) are some of the common problems associated with repeated laundering.
These problems may occur merely from repeated hand washing as well as the more vigorous machine washing process.
Furthermore, problems relating to damage of fabric over time through normal use, such as loss of shape and increased likelihood of wrinkling are also significant.
The present invention is directed towards alleviating one or more of the problems referred to hereinabove.
The principal advantage of the present invention relates to improving the surface colour definition of a fabric after multiple washings and/or to imparting pill and/or fuzz resistance to fabric during laundering. The invention can have further advantages in the treatment of fabric. For example, other aspects of the overall appearance of the fabric can be improved, such as a reduction in the tendency of the fabric to become creased and/or wrinkled.
Laundry detergent compositions containing polyamide-polyamine fabric treatment agents are described in WO
98/29530. The compositions are claimed to impart improved overall appearance to fabrics laundered using the detergent compositions, in terms of surface appearance properties such as pill/fuzz reduction and antifading. Laundry compositions containing polyamide-polyamine treatment agents of similar types are taught in WO 97/42287.
Laundry compositions containing polyamide-polyamine fabric treatment agents can exhibit increased dye pick-up (ie, increased dye transfer) and poor stain removal properties compared to other conventional laundry compositions.
US 5571286 (Connell et al) discloses certain polymers and prepolymers derived from polyoxyalkyleneamines and their use in a process for shrink-proofing wool. The treated wool may also have a softer handle than untreated wool. This document does not mention the treatment of cellulosic fabrics or the problems of loss of fabric surface appearance that they can experience following laundering. Furthermore, it deals entirely with treatment of wool on an industrial scale and does not mention the application of the compositions to fabric in the context of laundering processes.
The present invention is based on the surprising finding that certain polymeric materials, including those described in US 5571286, can impart improved surface appearance to cellulosic fabrics. The polymeric materials can have the further advantage of reduced adverse side-effects, in terms of increased dye transfer and poor stain removal, for example, compared to certain compositions containing polyamide-polyamine fabric treatment agents.
Definition of the Invention According to the present invention, there is provided a fabric care composition comprising a polymeric material which is capable of self cross-linking and/or of reacting with cellulose together with one or more textile compatible carriers, in which when the textile compatible carrier is water a further additive suitable for use in laundry compositions is present, wherein the polymeric material comprises one or more poly(oxyalkylene) groups having an end group which comprises one or more amino groups or derivatives of said amino groups.
The invention also provides a method of treating fabric, as part of a laundering process, which comprises applying to the fabric a fabric care composition of the invention or a polymeric material which is a component of the fabric care composition of the invention.
Further provided by the invention in another aspect is the use of a fabric care composition of the invention or a polymeric material which is a component of the fabric care composition of the invention to improve the surface colour definition of a fabric after multiple washings.
In another aspect, the invention provides the use of a fabric care composition of the invention or a polymeric material which is a component of the fabric care composition of the invention to impart pill and/or fuzz resistance to fabric during laundering. In addition, the invention can impart other beneficial properties to the fabric, such as reduced creasing and/or wrinkling of the fabric during laundering.
Detailed Description of the Invention The compositions of the present invention comprise a polymeric material which is capable of self cross-linking and/or of reacting with cellulose together with one or more textile compatible carriers, wherein the polymeric material comprises one or more poly(oxyalkylene) groups having an end group which comprises one or more amino groups or derivatives of said amino groups.
C395G (C) - ~ - -The compositions of the invention have tlae surprising advantage of imparting wear reaistance to fabrics, and thereby -causing improved surface colour definition of the fabric after laundering, particularly after multiple washings. Furthermore, the pol.yineric materia7.s contained in the composit.ions need noG cause unacceptable dye transfer and/or stain remova3 problems.
The polymeric material which carn be used in the present inventi.on can be any of the polymers or prepolymere derived from polyoxyalkyleneami.nee that are described in US 5571266.
Methods.for preparing the polymeric materials are described in US 5571286. Hence the polymex"ic material can be, for example, the reaction product of a diamine or triamine polyoxyalkylene polymer having a polymerisation degree of from 4 to 50 or a mixture thereof with epichlorohydrx.n in a ratio of epichlarohyr3,rin to ami.no nitrogen of from 1:1 to The aminio groups in the polymeric material used in the invention may wholly or partly in the form of der'i-vatives of amino gxoups. Derivatives include, for exarnple, adducts formed by alkylation or hydroxyalkylation at the nitrogen atom or yby the formation of an amide group at the nitrogen atom. The derivatives may be formed by the reaction of the amino groups with a bifunctional bridging agent or with a cross-linking agent.
Preferably, the polymeric material is obtainable by the reaction, of a polymer of formula H(R)n, wherein n is from 1 ~
AMFNT?Fi),qHFFT
J/ 11 V 1 1 O.VI r tLd u i u~ v i ~. v E..i ~ .+=+~ ~ ~ , -++== ---C3959 (C) 6 ..
to 20, B is a backbone group to which each R is covalently bonded and R is a group comprising a pQly(oxyalkylene) chain, which chain comprises an amino end group, the polymer being optionally reacted with a bridging compound, with a 5cross-lznking,agenty It will thus be appreciated that the polyrneric material of the invention is a relatively complex mixture,comprising a number of different compounds, some or all of which may be cross-linked.
The poly(oxyalkylene) chain which forme a part of the R
group may be, for example, a pol.y(oxyethylene), pol y( oxy'butyl ene ) or poly ( oxyprcap - l, 2-ylene ) chain. The length of the chain can vary from 2 to IoO repeat units.
Convenieintly,n is 2 or 3. it will be appreciated that n may not be a whole number where the polymeric material, of the invention comprises a mixture of different polymers of formula B(R) n .
In som.e of the polymeric materials which may be used in the=
inventa.on, 8 is -O-CH2 - (CH) m-CI32 -0--O
(a.e, B is the residue of glycerol when m is 1) and rn is equal to, n-2.
However,,B can also represent other values such as , for example, the reeidue of other triols or the residue of a di-, tetra-, penta- or hexa- hydroxy compound. Alternatively, B can rerresent the rea iduqp of a di-, t.ri- or poly- amine.
AMENDED SHEET
-,..~.. . ...,. __. _ 0-11-2001 GB000369' C3959 (C) ~ 7 -Preferably, at least one R group has the formula -(CHZCH tR' )(CH2 ) a0) p-A-NHR' t, wherein.: R, is H or CH3; a is o, 1 dr,2; p is an integer from 5 to 30; A is an alkylene group; and R'' is H or alkyl, More preferably, p is from 10 to 25.
The term "alkyl" as used herein, includes C, to C,5 alkyl, optionaYly substituted on the alkyl chain, which may be branched or unbranched and, fQr C3 to Cg alkyl, may be cycZic.; The term "alkylene" is defined similarly but refers - to a divalent radical.
It willbe appreciated that the term i'end group" refers to the group at or near to the end of the poly(oxyalkylene) chain, which end, when the polymer is of formula B(R)n, is at the other end of the polymer chain from the end which is attached to B.
Suitable polymers of formula B(R)n include those having the following structure:
H2C-0 (CH2CH (R' ) O) p-A-1QH2 HC-0 (CH2CH (R' ) 0) q-A-NH2 H2C-0 (CH2CH (R' ) 0) r-A-NH2 wherein R' is as defined herein before, p, q and r are integers which may be the same or different and may be from 5 to 30 and A is branched or unbranched lower alkylene.
AMENDED SHEET
C3959(C) _ g .-Other suitable polymers of formula 8(R.)nõ in which n is equal to 2, include those having the following formula:
H2N- (CH2) b- (O (CHz ) 4) CI-b (CH2) cU ((CH2) 40) d 2 - (CHz) b-N:E-IZ
wherein; b is an integer from 1 to 6, preferably 3; c is an integer from 1 to 6, preferably 4; and d and d2 are the same or different and are integers from i0 to 15.
The cross-linking agent which is used to form the polymeric material used in the invention by reaction with the polymer, or the polymer after prior reaction with the bridging _ compound, preferably comprises an epihalohydrin.
Epichlorohydrin is a suitable epihalohydrin.
Preferably the molar ratio of cross-linking agent to polymer of formula B(R) n is from d. 5: l to 4 a 1. Other amounts of cross-linking agent may be present in the polymeric material used in,the invention.
Suitable bridging compounds comprise two epoxide or carboxylic acid groups. The epoxide or carboxylic acid groups may be linked by a linker comprising alkylene, arylene, poly(oxyalkylene) or sx].oxane groups or combinations thereof. Vxainples of bridging compounds therefore include benzene-I,A-di.carboxxylic acid, hexane=1, 6-dicarboxy3ic acid and poiy(oxyethylene) compounds terminated at both ends of the molecule by an epoxide group. Other suitable bridging compounds are disclosed in U'S 5571286.
The composition used in the a.nvention can.contain the polymeric material, optionally together with other polymeric material6. The compositioxis may further comprise a silicone _ AMENDED SHEET
which is capable of reacting with the polymeric material.
Suitable reactive silicones include those having amino or hydroxyl groups which are well-known to those skilled in the art.
Preferably, the polymeric material is capable of increasing the wet strength of paper by at least 200% compared to untreated paper when applied to paper having a weight of 80 g/m2 at a level of 1% solids by weight based on weight of paper, according to the test method described hereinafter.
Polymeric materials which are suitable for use in the present invention are available from Precision Processes Textiles (Ambergate, Derbyshire, UK) under the trade marks POLYMER AM" and POLYMER MRSM". The polymeric materials of the invention are preferably in the form of aqueous solutions.
Polymer AM is a polymer having the following structure:
N O O N
POLYMER AM
Polymer MRSM has the same structures as polymer AM but has silicone added to the polymer mixture.
The nature of the textile compatible carrier will be dictated to a large extent by the stage at which the composition of the invention is used in a laundering process, the compositions being capable of being used, in principle, at any stage of the process. For example, where the compositions are for use as main wash detergent compositions, the one or more textile compatible carriers comprise a detergent active compound. Where the compositions are for use in the rinsing step of a laundering process, the one or more textile compatible carriers may comprise a fabric softening and/or conditioning compound.
The compositions of the invention preferably comprise a perfume, such as of the type which is conventionally used in fabric care compositions. The compositions may be packaged and labelled for use in a domestic laundering process.
The polymeric material is preferably present in the product in a sufficient quantity to give an amount of 0.0005% to 5%
by weight on the fabric based on the weight of the fabric, more preferably 0.001% to 2% by weight on fabric. The amount of the polymeric material in the composition required to achieve the above % by weight on fabric will typically be in the range 0.01% to 35% by weight, preferably 0.1 to 13.5%
by weight.
The compositions of the invention, when applied to a fabric, can impart benefits to the fabric when uncured. However, they may be cured by a domestic curing step including ironing and/or domestic tumble drying, preferably tumble drying. The curing is preferably carried out at a temperature in the range of from 50 to 100 C, more preferably from 80 to 100 C.
In the context of the present invention the term "textile compatible carrier" is a component which can assist in the interaction of the first component with the fabric. The carrier can also provide benefits in addition to those provided by the first component e.g. softening, cleaning etc. The carrier may be water, in which case the composition of the invention will contain another additive, suitable for use in laundry compositions such as perfume, for example, or the carrier may be a detergent-active compound or a fabric softener or conditioning compound or other suitable detergent or fabric treatment agent.
If the composition of the invention is to be used in a laundry process as part of a conventional fabric treatment product, such as a detergent composition, the textile-compatible carrier will typically be a detergent-active compound. Whereas, if the fabric treatment product is a rinse conditioner, the textile-compatible carrier will be a fabric softening and/or conditioning compound.
If the composition of the invention is to be used before, or after, the laundry process it may be in the form of a spray or foaming product.
The fabrics which may be treated in the present invention include those which comprise cellulosic fibres, preferably from 1% to 100% cellulosic fibres (more preferably 5% to 100% cellulosic fibres, most preferably 40% to 1000). The fabric may be in the form of a garment, in which case the method of the invention may represent a method of laundering a garment. When the fabric contains less than 100%
cellulosic fibres, the balance comprises other fibres or blends of fibres suitable for use in garments such as polyester, for example. Preferably, the cellulosic fibres are of cotton or regenerated cellulose such as viscose.
The laundering processes of the present invention include the large scale and small scale (eg domestic) cleaning of fabrics. Preferably, the processes are domestic.
In the invention, the polymeric material or the composition of the invention may be used at any stage of the laundering process. Preferably, the composition or the polymeric material is used to treat the fabric in the rinse cycle of a laundering process. The rinse cycle preferably follows the treatment of the fabric with a detergent composition.
Detergent Active Compounds If the composition of the present invention is in the form of a detergent composition, the textile-compatible carrier may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof.
Many suitable detergent active compounds are available and are fully described in the literature, for example, in "'Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
The preferred textile-compatible carriers that can be used are soaps and synthetic non-soap anionic and nonionic compounds.
Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C8-C15; primary and secondary alkylsulphates, particularly Ce-C15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates;
dialkyl sulphosuccinates; and fatty acid ester sulphonates.
Sodium salts are generally preferred.
Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the Clo-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
Cationic surfactants that may be used include quaternary ammonium salts of the general formula R1R2R3R4N+ X- wherein the R groups are independently hydrocarbyl chains of C1-C22 length, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilising cation (for example, compounds in which R1 is a C8-C22 alkyl group, preferably a C8-C10 or C12-C14 alkyl group, R2 is a methyl group, and R3 and R4, which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters) and pyridinium salts.
The total quantity of detergent surfactant in the composition is suitably from 0.1 to 60 wt% e.g. 0.5-55 wt%, such as 5-50wt%.
Preferably, the quantity of anionic surfactant (when present) is in the range of from 1 to 50% by weight of the total composition. More preferably, the quantity of anionic surfactant is in the range of from 3 to 35% by weight, e.g.
5 to 30% by weight.
Preferably, the quantity of nonionic surfactant when present is in the range of from 2 to 25% by weight, more preferably from 5 to 20% by weight.
Amphoteric surfactants may also be used, for example amine oxides or betaines.
The compositions may suitably contain from 10 to 70%, preferably from 15 to 70% by weight, of detergency builder.
Preferably, the quantity of builder is in the range of from to 50% by weight.
The detergent composition may contain as builder a 10 crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate.
The aluminosilicate may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably 15 from 25 to 50%. Aluminosilicates are materials having the general formula:
0.8-1.5 M20. A1203. 0.8-6 Si02 where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
The preferred sodium aluminosilicates contain 1.5-3.5 Si02 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
Fabric Softening and/or Conditioner Compounds If the composition of the present invention is in the form of a fabric conditioner composition, the textile-compatible carrier will be a fabric softening and/or conditioning compound (hereinafter referred to as "fabric softening compound"), which may be a cationic or nonionic compound.
The softening and/or conditioning compounds may be water insoluble quaternary ammonium compounds. The compounds may be present in amounts of up to 8% by weight (based on the total amount of the composition) in which case the compositions are considered dilute, or at levels from 8% to about 50% by weight, in which case the compositions are considered concentrates.
Compositions suitable for delivery during the rinse cycle may also be delivered to the fabric in the tumble dryer if used in a suitable form. Thus, another product form is a composition (for example, a paste) suitable for coating onto, and delivery from, a substrate e.g. a flexible sheet or sponge or a suitable dispenser during a tumble dryer cycle.
Suitable cationic fabric softening compounds are substantially water-insoluble quaternary ammonium materials comprising a single alkyl or alkenyl long chain having an average chain length greater than or equal to C20 or, more preferably, compounds comprising a polar head group and two alkyl or alkenyl chains having an average chain length greater than or equal to C19. Preferably the fabric softening compounds have two long chain alkyl or alkenyl chains each having an average chain length greater than or equal to C16. Most preferably at least 50% of the long chain alkyl or alkenyl groups have a chain length of C18 or above.
It is preferred if the long chain alkyl or alkenyl groups of the fabric softening compound are predominantly linear.
Quaternary ammonium compounds having two long-chain aliphatic groups, for example, distearyldimethyl ammonium chloride and di(hardened tallow alkyl) dimethyl ammonium chloride, are widely used in commercially available rinse conditioner compositions. Other examples of these cationic compounds are to be found in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
Any of the conventional types of such compounds may be used in the compositions of the present invention.
The fabric softening compounds are preferably compounds that provide excellent softening, and are characterised by a chain melting Lp to La transition temperature greater than C, preferably greater than 35 C, most preferably greater than 45 C. This L(3 to La transition can be measured by DSC
as defined in "Handbook of Lipid Bilayers", D Marsh, CRC
20 Press, Boca Raton, Florida, 1990 (pages 137 and 337).
Substantially water-insoluble fabric softening compounds are defined as fabric softening compounds having a solubility of less than 1 x 10-3 wt % in demineralised water at 20 C.
Preferably the fabric softening compounds have a solubility 25 of less than 1 x 10-4 wt o, more preferably less than 1 x 10-8 to 1 x 10-6 wt%.
Especially preferred are cationic fabric softening compounds that are water-insoluble quaternary ammonium materials having two C12-Z2 alkyl or alkenyl groups connected to the molecule via at least one ester link, preferably two ester links. An especially preferred ester-linked quaternary ammonium material can be represented by the formula II:
R1 + R3-T-R2 ( I I) I
( CH2 ) P-T-R2 wherein each R1 group is independently selected from C1-9 alkyl or hydroxyalkyl groups or C2-4 alkenyl groups; each R2 group is independently selected from C8-28 alkyl or alkenyl groups; and wherein R3 is a linear or branched alkylene group of 1 to 5 carbon atoms, T is -0-C- or -C-O-;
and p is 0 or is an integer from 1 to 5.
Di(tallowoxyloxyethyl) dimethyl ammonium chloride and/or its hardened tallow analogue is especially preferred of the compounds of formula (II).
A second preferred type of quaternary ammonium material can be represented by the formula (III):
( Ri ) 3N+- ( CH2 ) P H ( I I I) wherein R1r p and R2 are as defined above.
It is advantageous if the quaternary ammonium material is biologically biodegradable.
Preferred materials of this class such as 1,2-bis(hardened tallowoyloxy)-3-trimethylammonium propane chloride and their methods of preparation are, for example, described in US 4 137 180 (Lever Brothers Co). Preferably these materials comprise small amounts of the corresponding monoester as described in US 4 137 180, for example, 1-hardened tallowoyloxy-2-hydroxy-3-trimethylammonium propane chloride.
Other useful cationic softening agents are alkyl pyridinium salts and substituted imidazoline species. Also useful are primary, secondary and tertiary amines and the condensation products of fatty acids with alkylpolyamines.
The compositions may alternatively or additionally contain water-soluble cationic fabric softeners, as described in GB 2 039 556B (Unilever).
The compositions may comprise a cationic fabric softening compound and an oil, for example as disclosed in EP-A-0829531.
The compositions may alternatively or additionally contain nonionic fabric softening agents such as lanolin and derivatives thereof.
Lecithins are also suitable softening compounds.
Nonionic softeners include L(3 phase forming sugar esters (as described in M Hato et al Langmuir 12, 1659, 1666, (1996)) and related materials such as glycerol monostearate or sorbitan esters. Often these materials are used in conjunction with cationic materials to assist deposition (see, for example, GB 2 202 244). Silicones are used in a similar way as a co-softener with a cationic softener in rinse treatments (see, for example, GB 1 549 180).
The compositions may also suitably contain a nonionic stabilising agent. Suitable nonionic stabilising agents are linear C8 to C22 alcohols alkoxylated with 10 to 20 moles of alkylene oxide, C10 to C20 alcohols, or mixtures thereof.
Advantageously the nonionic stabilising agent is a linear C8 to C22 alcohol alkoxylated with 10 to 20 moles of alkylene oxide. Preferably, the level of nonionic stabiliser is within the range from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight, most preferably from 1 to 4% by weight. The mole ratio of the quaternary ammonium compound and/or other cationic softening agent to the nonionic stabilising agent is suitably within the range from 40:1 to about 1:1, preferably within the range from 18:1 to about 3:1.
The composition can also contain fatty acids, for example C8 to C24 alkyl or alkenyl monocarboxylic acids or polymers thereof. Preferably saturated fatty acids are used, in particular, hardened tallow C16 to C1B fatty acids.
Preferably the fatty acid is non-saponified, more preferably the fatty acid is free, for example oleic acid, lauric acid or tallow fatty acid. The level of fatty acid material is preferably more than 0.1% by weight, more preferably more than 0.2% by weight. Concentrated compositions may comprise from 0.5 to 20% by weight of fatty acid, more preferably 1%
to 10% by weight. The weight ratio of quaternary ammonium material or other cationic softening agent to fatty acid material is preferably from 10:1 to 1:10.
The fabric conditioning compositions may include silicones, such as predominately linear polydialkylsiloxanes, e.g.
polydimethylsiloxanes or aminosilicones containing amine-functionalised side chains; soil release polymers such as block copolymers of polyethylene oxide and terephthalate;
amphoteric surfactants; smectite type inorganic clays;
zwitterionic quaternary ammonium compounds; and nonionic surfactants.
The fabric conditioning compositions may also include an agent which produces a pearlescent appearance, e.g. an organic pearlising compound such as ethylene glycol distearate, or inorganic pearlising pigments such as microfine mica or titanium dioxide (Ti02) coated mica.
The fabric conditioning compositions may be in the form of emulsions or emulsion precursors thereof.
Other optional ingredients include emulsifiers, electrolytes (for example, sodium chloride or calcium chloride) preferably in the range from 0.01 to 5% by weight, pH
buffering agents, and perfumes (preferably from 0.1 to 5% by weight).
Further optional ingredients include non-aqueous solvents, perfume carriers, fluorescers, colourants, hydrotropes, antifoaming agents, antiredeposition agents, enzymes, optical brightening agents, opacifiers, dye transfer inhibitors, anti-shrinking agents, anti-wrinkle agents, anti-spotting agents, germicides, fungicides, anti-oxidants, UV absorbers (sunscreens), heavy metal sequestrants, chlorine scavengers, dye fixatives, anti-corrosion agents, drape imparting agents, antistatic agents and ironing aids.
This list is not intended to be exhaustive.
Fabric Treatment Products The composition of the invention may be in the form of a liquid, solid (e.g. powder or tablet), a gel or paste, spray, stick or a foam or mousse. Examples including a soaking product, a rinse treatment (e.g. conditioner or finisher) or a mainwash product. The composition may also be applied to a substrate e.g. a flexible sheet or used in a dispenser which can be used in the wash cycle, rinse cycle or during the dryer cycle.
The invention will now be described by way of example only and with reference to the following non-limiting examples.
EXAMPLES
POLYMER AM (trade mark) and POLYMER MRSM (trade mark) are polymeric materials according to the invention and were obtained from Precision Processes Textiles of Ambergate, Derbyshire, UK.
Test method for assessing wet-strength resins on paper by tensile strength The test procedure used was as follows:
Paper selected = 80 gsm White Copier Bond, 210 x 297 mm, Universal Office Supplies ref UCOP80. Dry weight of one A4 sheet = 4.91 g. Weight after 30 minute soak and removal of excess water = 7.30 g. Pick-up therefore set as 50%.
For the untreated standard, the paper was soaked in deionised water for 10 minutes in a shallow tray. After this time, sheets were removed and the excess water removed by gently patting with paper towels until all surface water had been removed. The paper was then dried at 110 C for 10 minutes in a fan-assisted oven.
For the treated sample, a solution of Polymer AM or Polymer MRSM (trade mark) with water was prepared along with 2 g/l of sodium bicarbonate to provide an application level by pick-up of 1% o.w.f.
As with the reference, the treated samples are soaked for 10 minutes in the solution, the excess water removed and then dried/cured as above.
The paper is then allowed to stand for at least 24 hours (as the tensile strength measurements are carried out on saturated paper, it is not necessary to condition the paper at 65% RH).
The samples are cut using a guillotine to 270 mm by 67 mm, and lines are drawn parallel to the smaller length 35 mm in to act as a guide when clamping the sample into the Testometric jaws.
The samples are then soaked in deionised water for 30 minutes.
After this time, the majority of the water is drained away to leave the paper saturated while measurements are made.
Prior to the test being performed, the excess water is removed as before.
Testometric set-up - 25 kgf load cell, 100 mm/min speed, pre-tension 0.1 kgf, sample length 200 mm, sample width 67 mm.
The results of the tests were as follows:
Sample treatment Wet strength (kgf) Untreated paper 1.069 Polymer AM," 4.920 Polymer MRSM'm 4.017 Example 1 Dye transfer inhibition Five applications of 0.2% Kenores 1440 (trade mark) polyamine-epichlorohydrin (PAE) resin (Akzo Nobel) as disclosed in WO 97/42287 (a polymer outside the scope of this invention) were made via a domestic washing machine (Zanussi (trade mark) automatic washing machine, 40 C cotton wash cycle, Persil (trade mark) applied during the wash cycle) to white woven cotton sheeting, a theoretical maximum application of 1.0% by weight PAE on weight of fabric (owf).
A similar process was carried out using 0.2% Polymer AM
(trade mark) and 0.2% Polymer MRSM (trade mark). The treated fabrics were then washed with Direct Red 80 dyed fabric which is known to lose dye. The resulting fabrics were then measured on a Spectroflash (trade mark) spectrometer to determine the degree of dye transfer. A
blank fabric sample was used as reference.
OL DE
0. 2 o KenoresTM 1440 -3.47 6.20 0.1% KenoresTM 1440 -1.05 2.32 Polymer AMIK 0.93 2.21 Polymer MRSM" 0.28 1.47 AL = change in lightness DE = change in colour Thus, there is less change in colour for the fabric treated with a polymer according to the invention and, therefore, less dye transfer.
Example 2 Garment Care Properties Spectroflash (trade mark) measurements on a standard test fabric having black and red regions show that the fabrics treated with Polymer AM (trade mark) and Polymer MRSM (trade mark) according to Example 1 display reduced damage.
Black area:
AL AE
Untreated 9.94 10.07 Polymer AMTN 1.81 1.95 Polymer MRSM" 3.00 3.09 Red area:
dL AE
Untreated 3.30 12.62 Polymer AM" 1.20 5.39 Polymer MRSM" 1=19 4.84 In both cases, the treated areas show less change in shade than the untreated sample, indicated by the smaller AL and DE values.
Example 3 Stain removal 1 ml of red wine was applied to treated cotton according to the procedure set out in Example 1 (5 rinse applications of 0.2% per wash). The stain was measured on a Spectroflash (trade mark) spectrophotometer prior to washing and after washing at 40 C usir.g Persil Performance Biological (trade mark) powder. The change in depth of colour on the stains relative to the sample before washing was:
dL DE
Untreated -17.93 22.10 Polymer AM" -20.26 23.98 Polymer MRSM" -23.36 26.37 Kenores" 1440 -=9.38 22.37 After washing, the colour measurements were:
OL AE
Untreated -3.97 5.94 Polymer AMT" -3.65 5.10 Polymer,MRSMT" -5.70 7.98 TM
Kenores 1440 -8.42 10.45 Polymer AM (trade mark) shows almost identical stain release properties to untreated fabric, whereas Polymer MRSM (trade mark) falls between.Polymer Am (trade mark) and Kenores 1440 (trade mark).
The background area of the fabric was also measured to provide an indication of any tendency of the treatments to cause soil redeposition. The smaller the spectrometer reading, the less the change in colour and the less soil redeposition.
OL
Untreated -0.20 Polymer AM" -0.02 Polymer MRSM" -0.19 Kenores7'1440 -0 = 27 Standard rinse conditioner* -0.05 *Comfort (trade mark) (Unilever plc, UK) Although the differences are small, there are still indications that these polymers do not increase the soil redeposition properties of the fabric to the same extent that PAE-type polymers do. In the case of Polymer AM (trade mark), there is less redeposition than with the rinse conditioner.
Example 4 Fabric Conditioner Formulation Fabric conditioner formulations were made by preparing a standard fabric conditioner composition containing components 2 to 8 below and adding component 1 to it, with stirring. Compositions were prepared in both dilute and concentrated forms.
The formulations were as follows:
Dilute Concentrate 1= Polymer AM" 15.1% 48.7%
2. Water 80.04% 35.86%
3. Antifoam 0.01% 0.03%
4= Genapol" 0.25% 0.75%
5. HEQ 4.20% 13.5%
Technical Field This invention relates to fabric care compositions and to methods of treating fabric using the compositions or the pol-ymeric materials they contain.
Background and Prior Art The laundry process generally has several benefits for fabric, the most common being to remove dirt and stains from the fabric during the wash cycle and to soften the fabric during the rinse cycle. However, there are numerous disadvantages associated with repeated use of conventional laundry treatment compositions and/or the actual laundry process; one of these being a fairly harsh treatment of fabric in the laundry process.
Fabrics can be damaged in several ways as a result of repeated laundering and/or wear. Fabric pilling and loss of fabric surface appearance e.g. fuzzing, shrinkage (or expansion), loss of colour from the fabric or running of colour on the fabric (usually termed dye transfer) are some of the common problems associated with repeated laundering.
These problems may occur merely from repeated hand washing as well as the more vigorous machine washing process.
Furthermore, problems relating to damage of fabric over time through normal use, such as loss of shape and increased likelihood of wrinkling are also significant.
The present invention is directed towards alleviating one or more of the problems referred to hereinabove.
The principal advantage of the present invention relates to improving the surface colour definition of a fabric after multiple washings and/or to imparting pill and/or fuzz resistance to fabric during laundering. The invention can have further advantages in the treatment of fabric. For example, other aspects of the overall appearance of the fabric can be improved, such as a reduction in the tendency of the fabric to become creased and/or wrinkled.
Laundry detergent compositions containing polyamide-polyamine fabric treatment agents are described in WO
98/29530. The compositions are claimed to impart improved overall appearance to fabrics laundered using the detergent compositions, in terms of surface appearance properties such as pill/fuzz reduction and antifading. Laundry compositions containing polyamide-polyamine treatment agents of similar types are taught in WO 97/42287.
Laundry compositions containing polyamide-polyamine fabric treatment agents can exhibit increased dye pick-up (ie, increased dye transfer) and poor stain removal properties compared to other conventional laundry compositions.
US 5571286 (Connell et al) discloses certain polymers and prepolymers derived from polyoxyalkyleneamines and their use in a process for shrink-proofing wool. The treated wool may also have a softer handle than untreated wool. This document does not mention the treatment of cellulosic fabrics or the problems of loss of fabric surface appearance that they can experience following laundering. Furthermore, it deals entirely with treatment of wool on an industrial scale and does not mention the application of the compositions to fabric in the context of laundering processes.
The present invention is based on the surprising finding that certain polymeric materials, including those described in US 5571286, can impart improved surface appearance to cellulosic fabrics. The polymeric materials can have the further advantage of reduced adverse side-effects, in terms of increased dye transfer and poor stain removal, for example, compared to certain compositions containing polyamide-polyamine fabric treatment agents.
Definition of the Invention According to the present invention, there is provided a fabric care composition comprising a polymeric material which is capable of self cross-linking and/or of reacting with cellulose together with one or more textile compatible carriers, in which when the textile compatible carrier is water a further additive suitable for use in laundry compositions is present, wherein the polymeric material comprises one or more poly(oxyalkylene) groups having an end group which comprises one or more amino groups or derivatives of said amino groups.
The invention also provides a method of treating fabric, as part of a laundering process, which comprises applying to the fabric a fabric care composition of the invention or a polymeric material which is a component of the fabric care composition of the invention.
Further provided by the invention in another aspect is the use of a fabric care composition of the invention or a polymeric material which is a component of the fabric care composition of the invention to improve the surface colour definition of a fabric after multiple washings.
In another aspect, the invention provides the use of a fabric care composition of the invention or a polymeric material which is a component of the fabric care composition of the invention to impart pill and/or fuzz resistance to fabric during laundering. In addition, the invention can impart other beneficial properties to the fabric, such as reduced creasing and/or wrinkling of the fabric during laundering.
Detailed Description of the Invention The compositions of the present invention comprise a polymeric material which is capable of self cross-linking and/or of reacting with cellulose together with one or more textile compatible carriers, wherein the polymeric material comprises one or more poly(oxyalkylene) groups having an end group which comprises one or more amino groups or derivatives of said amino groups.
C395G (C) - ~ - -The compositions of the invention have tlae surprising advantage of imparting wear reaistance to fabrics, and thereby -causing improved surface colour definition of the fabric after laundering, particularly after multiple washings. Furthermore, the pol.yineric materia7.s contained in the composit.ions need noG cause unacceptable dye transfer and/or stain remova3 problems.
The polymeric material which carn be used in the present inventi.on can be any of the polymers or prepolymere derived from polyoxyalkyleneami.nee that are described in US 5571266.
Methods.for preparing the polymeric materials are described in US 5571286. Hence the polymex"ic material can be, for example, the reaction product of a diamine or triamine polyoxyalkylene polymer having a polymerisation degree of from 4 to 50 or a mixture thereof with epichlorohydrx.n in a ratio of epichlarohyr3,rin to ami.no nitrogen of from 1:1 to The aminio groups in the polymeric material used in the invention may wholly or partly in the form of der'i-vatives of amino gxoups. Derivatives include, for exarnple, adducts formed by alkylation or hydroxyalkylation at the nitrogen atom or yby the formation of an amide group at the nitrogen atom. The derivatives may be formed by the reaction of the amino groups with a bifunctional bridging agent or with a cross-linking agent.
Preferably, the polymeric material is obtainable by the reaction, of a polymer of formula H(R)n, wherein n is from 1 ~
AMFNT?Fi),qHFFT
J/ 11 V 1 1 O.VI r tLd u i u~ v i ~. v E..i ~ .+=+~ ~ ~ , -++== ---C3959 (C) 6 ..
to 20, B is a backbone group to which each R is covalently bonded and R is a group comprising a pQly(oxyalkylene) chain, which chain comprises an amino end group, the polymer being optionally reacted with a bridging compound, with a 5cross-lznking,agenty It will thus be appreciated that the polyrneric material of the invention is a relatively complex mixture,comprising a number of different compounds, some or all of which may be cross-linked.
The poly(oxyalkylene) chain which forme a part of the R
group may be, for example, a pol.y(oxyethylene), pol y( oxy'butyl ene ) or poly ( oxyprcap - l, 2-ylene ) chain. The length of the chain can vary from 2 to IoO repeat units.
Convenieintly,n is 2 or 3. it will be appreciated that n may not be a whole number where the polymeric material, of the invention comprises a mixture of different polymers of formula B(R) n .
In som.e of the polymeric materials which may be used in the=
inventa.on, 8 is -O-CH2 - (CH) m-CI32 -0--O
(a.e, B is the residue of glycerol when m is 1) and rn is equal to, n-2.
However,,B can also represent other values such as , for example, the reeidue of other triols or the residue of a di-, tetra-, penta- or hexa- hydroxy compound. Alternatively, B can rerresent the rea iduqp of a di-, t.ri- or poly- amine.
AMENDED SHEET
-,..~.. . ...,. __. _ 0-11-2001 GB000369' C3959 (C) ~ 7 -Preferably, at least one R group has the formula -(CHZCH tR' )(CH2 ) a0) p-A-NHR' t, wherein.: R, is H or CH3; a is o, 1 dr,2; p is an integer from 5 to 30; A is an alkylene group; and R'' is H or alkyl, More preferably, p is from 10 to 25.
The term "alkyl" as used herein, includes C, to C,5 alkyl, optionaYly substituted on the alkyl chain, which may be branched or unbranched and, fQr C3 to Cg alkyl, may be cycZic.; The term "alkylene" is defined similarly but refers - to a divalent radical.
It willbe appreciated that the term i'end group" refers to the group at or near to the end of the poly(oxyalkylene) chain, which end, when the polymer is of formula B(R)n, is at the other end of the polymer chain from the end which is attached to B.
Suitable polymers of formula B(R)n include those having the following structure:
H2C-0 (CH2CH (R' ) O) p-A-1QH2 HC-0 (CH2CH (R' ) 0) q-A-NH2 H2C-0 (CH2CH (R' ) 0) r-A-NH2 wherein R' is as defined herein before, p, q and r are integers which may be the same or different and may be from 5 to 30 and A is branched or unbranched lower alkylene.
AMENDED SHEET
C3959(C) _ g .-Other suitable polymers of formula 8(R.)nõ in which n is equal to 2, include those having the following formula:
H2N- (CH2) b- (O (CHz ) 4) CI-b (CH2) cU ((CH2) 40) d 2 - (CHz) b-N:E-IZ
wherein; b is an integer from 1 to 6, preferably 3; c is an integer from 1 to 6, preferably 4; and d and d2 are the same or different and are integers from i0 to 15.
The cross-linking agent which is used to form the polymeric material used in the invention by reaction with the polymer, or the polymer after prior reaction with the bridging _ compound, preferably comprises an epihalohydrin.
Epichlorohydrin is a suitable epihalohydrin.
Preferably the molar ratio of cross-linking agent to polymer of formula B(R) n is from d. 5: l to 4 a 1. Other amounts of cross-linking agent may be present in the polymeric material used in,the invention.
Suitable bridging compounds comprise two epoxide or carboxylic acid groups. The epoxide or carboxylic acid groups may be linked by a linker comprising alkylene, arylene, poly(oxyalkylene) or sx].oxane groups or combinations thereof. Vxainples of bridging compounds therefore include benzene-I,A-di.carboxxylic acid, hexane=1, 6-dicarboxy3ic acid and poiy(oxyethylene) compounds terminated at both ends of the molecule by an epoxide group. Other suitable bridging compounds are disclosed in U'S 5571286.
The composition used in the a.nvention can.contain the polymeric material, optionally together with other polymeric material6. The compositioxis may further comprise a silicone _ AMENDED SHEET
which is capable of reacting with the polymeric material.
Suitable reactive silicones include those having amino or hydroxyl groups which are well-known to those skilled in the art.
Preferably, the polymeric material is capable of increasing the wet strength of paper by at least 200% compared to untreated paper when applied to paper having a weight of 80 g/m2 at a level of 1% solids by weight based on weight of paper, according to the test method described hereinafter.
Polymeric materials which are suitable for use in the present invention are available from Precision Processes Textiles (Ambergate, Derbyshire, UK) under the trade marks POLYMER AM" and POLYMER MRSM". The polymeric materials of the invention are preferably in the form of aqueous solutions.
Polymer AM is a polymer having the following structure:
N O O N
POLYMER AM
Polymer MRSM has the same structures as polymer AM but has silicone added to the polymer mixture.
The nature of the textile compatible carrier will be dictated to a large extent by the stage at which the composition of the invention is used in a laundering process, the compositions being capable of being used, in principle, at any stage of the process. For example, where the compositions are for use as main wash detergent compositions, the one or more textile compatible carriers comprise a detergent active compound. Where the compositions are for use in the rinsing step of a laundering process, the one or more textile compatible carriers may comprise a fabric softening and/or conditioning compound.
The compositions of the invention preferably comprise a perfume, such as of the type which is conventionally used in fabric care compositions. The compositions may be packaged and labelled for use in a domestic laundering process.
The polymeric material is preferably present in the product in a sufficient quantity to give an amount of 0.0005% to 5%
by weight on the fabric based on the weight of the fabric, more preferably 0.001% to 2% by weight on fabric. The amount of the polymeric material in the composition required to achieve the above % by weight on fabric will typically be in the range 0.01% to 35% by weight, preferably 0.1 to 13.5%
by weight.
The compositions of the invention, when applied to a fabric, can impart benefits to the fabric when uncured. However, they may be cured by a domestic curing step including ironing and/or domestic tumble drying, preferably tumble drying. The curing is preferably carried out at a temperature in the range of from 50 to 100 C, more preferably from 80 to 100 C.
In the context of the present invention the term "textile compatible carrier" is a component which can assist in the interaction of the first component with the fabric. The carrier can also provide benefits in addition to those provided by the first component e.g. softening, cleaning etc. The carrier may be water, in which case the composition of the invention will contain another additive, suitable for use in laundry compositions such as perfume, for example, or the carrier may be a detergent-active compound or a fabric softener or conditioning compound or other suitable detergent or fabric treatment agent.
If the composition of the invention is to be used in a laundry process as part of a conventional fabric treatment product, such as a detergent composition, the textile-compatible carrier will typically be a detergent-active compound. Whereas, if the fabric treatment product is a rinse conditioner, the textile-compatible carrier will be a fabric softening and/or conditioning compound.
If the composition of the invention is to be used before, or after, the laundry process it may be in the form of a spray or foaming product.
The fabrics which may be treated in the present invention include those which comprise cellulosic fibres, preferably from 1% to 100% cellulosic fibres (more preferably 5% to 100% cellulosic fibres, most preferably 40% to 1000). The fabric may be in the form of a garment, in which case the method of the invention may represent a method of laundering a garment. When the fabric contains less than 100%
cellulosic fibres, the balance comprises other fibres or blends of fibres suitable for use in garments such as polyester, for example. Preferably, the cellulosic fibres are of cotton or regenerated cellulose such as viscose.
The laundering processes of the present invention include the large scale and small scale (eg domestic) cleaning of fabrics. Preferably, the processes are domestic.
In the invention, the polymeric material or the composition of the invention may be used at any stage of the laundering process. Preferably, the composition or the polymeric material is used to treat the fabric in the rinse cycle of a laundering process. The rinse cycle preferably follows the treatment of the fabric with a detergent composition.
Detergent Active Compounds If the composition of the present invention is in the form of a detergent composition, the textile-compatible carrier may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof.
Many suitable detergent active compounds are available and are fully described in the literature, for example, in "'Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
The preferred textile-compatible carriers that can be used are soaps and synthetic non-soap anionic and nonionic compounds.
Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C8-C15; primary and secondary alkylsulphates, particularly Ce-C15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates;
dialkyl sulphosuccinates; and fatty acid ester sulphonates.
Sodium salts are generally preferred.
Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the Clo-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
Cationic surfactants that may be used include quaternary ammonium salts of the general formula R1R2R3R4N+ X- wherein the R groups are independently hydrocarbyl chains of C1-C22 length, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilising cation (for example, compounds in which R1 is a C8-C22 alkyl group, preferably a C8-C10 or C12-C14 alkyl group, R2 is a methyl group, and R3 and R4, which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters) and pyridinium salts.
The total quantity of detergent surfactant in the composition is suitably from 0.1 to 60 wt% e.g. 0.5-55 wt%, such as 5-50wt%.
Preferably, the quantity of anionic surfactant (when present) is in the range of from 1 to 50% by weight of the total composition. More preferably, the quantity of anionic surfactant is in the range of from 3 to 35% by weight, e.g.
5 to 30% by weight.
Preferably, the quantity of nonionic surfactant when present is in the range of from 2 to 25% by weight, more preferably from 5 to 20% by weight.
Amphoteric surfactants may also be used, for example amine oxides or betaines.
The compositions may suitably contain from 10 to 70%, preferably from 15 to 70% by weight, of detergency builder.
Preferably, the quantity of builder is in the range of from to 50% by weight.
The detergent composition may contain as builder a 10 crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate.
The aluminosilicate may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably 15 from 25 to 50%. Aluminosilicates are materials having the general formula:
0.8-1.5 M20. A1203. 0.8-6 Si02 where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
The preferred sodium aluminosilicates contain 1.5-3.5 Si02 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
Fabric Softening and/or Conditioner Compounds If the composition of the present invention is in the form of a fabric conditioner composition, the textile-compatible carrier will be a fabric softening and/or conditioning compound (hereinafter referred to as "fabric softening compound"), which may be a cationic or nonionic compound.
The softening and/or conditioning compounds may be water insoluble quaternary ammonium compounds. The compounds may be present in amounts of up to 8% by weight (based on the total amount of the composition) in which case the compositions are considered dilute, or at levels from 8% to about 50% by weight, in which case the compositions are considered concentrates.
Compositions suitable for delivery during the rinse cycle may also be delivered to the fabric in the tumble dryer if used in a suitable form. Thus, another product form is a composition (for example, a paste) suitable for coating onto, and delivery from, a substrate e.g. a flexible sheet or sponge or a suitable dispenser during a tumble dryer cycle.
Suitable cationic fabric softening compounds are substantially water-insoluble quaternary ammonium materials comprising a single alkyl or alkenyl long chain having an average chain length greater than or equal to C20 or, more preferably, compounds comprising a polar head group and two alkyl or alkenyl chains having an average chain length greater than or equal to C19. Preferably the fabric softening compounds have two long chain alkyl or alkenyl chains each having an average chain length greater than or equal to C16. Most preferably at least 50% of the long chain alkyl or alkenyl groups have a chain length of C18 or above.
It is preferred if the long chain alkyl or alkenyl groups of the fabric softening compound are predominantly linear.
Quaternary ammonium compounds having two long-chain aliphatic groups, for example, distearyldimethyl ammonium chloride and di(hardened tallow alkyl) dimethyl ammonium chloride, are widely used in commercially available rinse conditioner compositions. Other examples of these cationic compounds are to be found in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
Any of the conventional types of such compounds may be used in the compositions of the present invention.
The fabric softening compounds are preferably compounds that provide excellent softening, and are characterised by a chain melting Lp to La transition temperature greater than C, preferably greater than 35 C, most preferably greater than 45 C. This L(3 to La transition can be measured by DSC
as defined in "Handbook of Lipid Bilayers", D Marsh, CRC
20 Press, Boca Raton, Florida, 1990 (pages 137 and 337).
Substantially water-insoluble fabric softening compounds are defined as fabric softening compounds having a solubility of less than 1 x 10-3 wt % in demineralised water at 20 C.
Preferably the fabric softening compounds have a solubility 25 of less than 1 x 10-4 wt o, more preferably less than 1 x 10-8 to 1 x 10-6 wt%.
Especially preferred are cationic fabric softening compounds that are water-insoluble quaternary ammonium materials having two C12-Z2 alkyl or alkenyl groups connected to the molecule via at least one ester link, preferably two ester links. An especially preferred ester-linked quaternary ammonium material can be represented by the formula II:
R1 + R3-T-R2 ( I I) I
( CH2 ) P-T-R2 wherein each R1 group is independently selected from C1-9 alkyl or hydroxyalkyl groups or C2-4 alkenyl groups; each R2 group is independently selected from C8-28 alkyl or alkenyl groups; and wherein R3 is a linear or branched alkylene group of 1 to 5 carbon atoms, T is -0-C- or -C-O-;
and p is 0 or is an integer from 1 to 5.
Di(tallowoxyloxyethyl) dimethyl ammonium chloride and/or its hardened tallow analogue is especially preferred of the compounds of formula (II).
A second preferred type of quaternary ammonium material can be represented by the formula (III):
( Ri ) 3N+- ( CH2 ) P H ( I I I) wherein R1r p and R2 are as defined above.
It is advantageous if the quaternary ammonium material is biologically biodegradable.
Preferred materials of this class such as 1,2-bis(hardened tallowoyloxy)-3-trimethylammonium propane chloride and their methods of preparation are, for example, described in US 4 137 180 (Lever Brothers Co). Preferably these materials comprise small amounts of the corresponding monoester as described in US 4 137 180, for example, 1-hardened tallowoyloxy-2-hydroxy-3-trimethylammonium propane chloride.
Other useful cationic softening agents are alkyl pyridinium salts and substituted imidazoline species. Also useful are primary, secondary and tertiary amines and the condensation products of fatty acids with alkylpolyamines.
The compositions may alternatively or additionally contain water-soluble cationic fabric softeners, as described in GB 2 039 556B (Unilever).
The compositions may comprise a cationic fabric softening compound and an oil, for example as disclosed in EP-A-0829531.
The compositions may alternatively or additionally contain nonionic fabric softening agents such as lanolin and derivatives thereof.
Lecithins are also suitable softening compounds.
Nonionic softeners include L(3 phase forming sugar esters (as described in M Hato et al Langmuir 12, 1659, 1666, (1996)) and related materials such as glycerol monostearate or sorbitan esters. Often these materials are used in conjunction with cationic materials to assist deposition (see, for example, GB 2 202 244). Silicones are used in a similar way as a co-softener with a cationic softener in rinse treatments (see, for example, GB 1 549 180).
The compositions may also suitably contain a nonionic stabilising agent. Suitable nonionic stabilising agents are linear C8 to C22 alcohols alkoxylated with 10 to 20 moles of alkylene oxide, C10 to C20 alcohols, or mixtures thereof.
Advantageously the nonionic stabilising agent is a linear C8 to C22 alcohol alkoxylated with 10 to 20 moles of alkylene oxide. Preferably, the level of nonionic stabiliser is within the range from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight, most preferably from 1 to 4% by weight. The mole ratio of the quaternary ammonium compound and/or other cationic softening agent to the nonionic stabilising agent is suitably within the range from 40:1 to about 1:1, preferably within the range from 18:1 to about 3:1.
The composition can also contain fatty acids, for example C8 to C24 alkyl or alkenyl monocarboxylic acids or polymers thereof. Preferably saturated fatty acids are used, in particular, hardened tallow C16 to C1B fatty acids.
Preferably the fatty acid is non-saponified, more preferably the fatty acid is free, for example oleic acid, lauric acid or tallow fatty acid. The level of fatty acid material is preferably more than 0.1% by weight, more preferably more than 0.2% by weight. Concentrated compositions may comprise from 0.5 to 20% by weight of fatty acid, more preferably 1%
to 10% by weight. The weight ratio of quaternary ammonium material or other cationic softening agent to fatty acid material is preferably from 10:1 to 1:10.
The fabric conditioning compositions may include silicones, such as predominately linear polydialkylsiloxanes, e.g.
polydimethylsiloxanes or aminosilicones containing amine-functionalised side chains; soil release polymers such as block copolymers of polyethylene oxide and terephthalate;
amphoteric surfactants; smectite type inorganic clays;
zwitterionic quaternary ammonium compounds; and nonionic surfactants.
The fabric conditioning compositions may also include an agent which produces a pearlescent appearance, e.g. an organic pearlising compound such as ethylene glycol distearate, or inorganic pearlising pigments such as microfine mica or titanium dioxide (Ti02) coated mica.
The fabric conditioning compositions may be in the form of emulsions or emulsion precursors thereof.
Other optional ingredients include emulsifiers, electrolytes (for example, sodium chloride or calcium chloride) preferably in the range from 0.01 to 5% by weight, pH
buffering agents, and perfumes (preferably from 0.1 to 5% by weight).
Further optional ingredients include non-aqueous solvents, perfume carriers, fluorescers, colourants, hydrotropes, antifoaming agents, antiredeposition agents, enzymes, optical brightening agents, opacifiers, dye transfer inhibitors, anti-shrinking agents, anti-wrinkle agents, anti-spotting agents, germicides, fungicides, anti-oxidants, UV absorbers (sunscreens), heavy metal sequestrants, chlorine scavengers, dye fixatives, anti-corrosion agents, drape imparting agents, antistatic agents and ironing aids.
This list is not intended to be exhaustive.
Fabric Treatment Products The composition of the invention may be in the form of a liquid, solid (e.g. powder or tablet), a gel or paste, spray, stick or a foam or mousse. Examples including a soaking product, a rinse treatment (e.g. conditioner or finisher) or a mainwash product. The composition may also be applied to a substrate e.g. a flexible sheet or used in a dispenser which can be used in the wash cycle, rinse cycle or during the dryer cycle.
The invention will now be described by way of example only and with reference to the following non-limiting examples.
EXAMPLES
POLYMER AM (trade mark) and POLYMER MRSM (trade mark) are polymeric materials according to the invention and were obtained from Precision Processes Textiles of Ambergate, Derbyshire, UK.
Test method for assessing wet-strength resins on paper by tensile strength The test procedure used was as follows:
Paper selected = 80 gsm White Copier Bond, 210 x 297 mm, Universal Office Supplies ref UCOP80. Dry weight of one A4 sheet = 4.91 g. Weight after 30 minute soak and removal of excess water = 7.30 g. Pick-up therefore set as 50%.
For the untreated standard, the paper was soaked in deionised water for 10 minutes in a shallow tray. After this time, sheets were removed and the excess water removed by gently patting with paper towels until all surface water had been removed. The paper was then dried at 110 C for 10 minutes in a fan-assisted oven.
For the treated sample, a solution of Polymer AM or Polymer MRSM (trade mark) with water was prepared along with 2 g/l of sodium bicarbonate to provide an application level by pick-up of 1% o.w.f.
As with the reference, the treated samples are soaked for 10 minutes in the solution, the excess water removed and then dried/cured as above.
The paper is then allowed to stand for at least 24 hours (as the tensile strength measurements are carried out on saturated paper, it is not necessary to condition the paper at 65% RH).
The samples are cut using a guillotine to 270 mm by 67 mm, and lines are drawn parallel to the smaller length 35 mm in to act as a guide when clamping the sample into the Testometric jaws.
The samples are then soaked in deionised water for 30 minutes.
After this time, the majority of the water is drained away to leave the paper saturated while measurements are made.
Prior to the test being performed, the excess water is removed as before.
Testometric set-up - 25 kgf load cell, 100 mm/min speed, pre-tension 0.1 kgf, sample length 200 mm, sample width 67 mm.
The results of the tests were as follows:
Sample treatment Wet strength (kgf) Untreated paper 1.069 Polymer AM," 4.920 Polymer MRSM'm 4.017 Example 1 Dye transfer inhibition Five applications of 0.2% Kenores 1440 (trade mark) polyamine-epichlorohydrin (PAE) resin (Akzo Nobel) as disclosed in WO 97/42287 (a polymer outside the scope of this invention) were made via a domestic washing machine (Zanussi (trade mark) automatic washing machine, 40 C cotton wash cycle, Persil (trade mark) applied during the wash cycle) to white woven cotton sheeting, a theoretical maximum application of 1.0% by weight PAE on weight of fabric (owf).
A similar process was carried out using 0.2% Polymer AM
(trade mark) and 0.2% Polymer MRSM (trade mark). The treated fabrics were then washed with Direct Red 80 dyed fabric which is known to lose dye. The resulting fabrics were then measured on a Spectroflash (trade mark) spectrometer to determine the degree of dye transfer. A
blank fabric sample was used as reference.
OL DE
0. 2 o KenoresTM 1440 -3.47 6.20 0.1% KenoresTM 1440 -1.05 2.32 Polymer AMIK 0.93 2.21 Polymer MRSM" 0.28 1.47 AL = change in lightness DE = change in colour Thus, there is less change in colour for the fabric treated with a polymer according to the invention and, therefore, less dye transfer.
Example 2 Garment Care Properties Spectroflash (trade mark) measurements on a standard test fabric having black and red regions show that the fabrics treated with Polymer AM (trade mark) and Polymer MRSM (trade mark) according to Example 1 display reduced damage.
Black area:
AL AE
Untreated 9.94 10.07 Polymer AMTN 1.81 1.95 Polymer MRSM" 3.00 3.09 Red area:
dL AE
Untreated 3.30 12.62 Polymer AM" 1.20 5.39 Polymer MRSM" 1=19 4.84 In both cases, the treated areas show less change in shade than the untreated sample, indicated by the smaller AL and DE values.
Example 3 Stain removal 1 ml of red wine was applied to treated cotton according to the procedure set out in Example 1 (5 rinse applications of 0.2% per wash). The stain was measured on a Spectroflash (trade mark) spectrophotometer prior to washing and after washing at 40 C usir.g Persil Performance Biological (trade mark) powder. The change in depth of colour on the stains relative to the sample before washing was:
dL DE
Untreated -17.93 22.10 Polymer AM" -20.26 23.98 Polymer MRSM" -23.36 26.37 Kenores" 1440 -=9.38 22.37 After washing, the colour measurements were:
OL AE
Untreated -3.97 5.94 Polymer AMT" -3.65 5.10 Polymer,MRSMT" -5.70 7.98 TM
Kenores 1440 -8.42 10.45 Polymer AM (trade mark) shows almost identical stain release properties to untreated fabric, whereas Polymer MRSM (trade mark) falls between.Polymer Am (trade mark) and Kenores 1440 (trade mark).
The background area of the fabric was also measured to provide an indication of any tendency of the treatments to cause soil redeposition. The smaller the spectrometer reading, the less the change in colour and the less soil redeposition.
OL
Untreated -0.20 Polymer AM" -0.02 Polymer MRSM" -0.19 Kenores7'1440 -0 = 27 Standard rinse conditioner* -0.05 *Comfort (trade mark) (Unilever plc, UK) Although the differences are small, there are still indications that these polymers do not increase the soil redeposition properties of the fabric to the same extent that PAE-type polymers do. In the case of Polymer AM (trade mark), there is less redeposition than with the rinse conditioner.
Example 4 Fabric Conditioner Formulation Fabric conditioner formulations were made by preparing a standard fabric conditioner composition containing components 2 to 8 below and adding component 1 to it, with stirring. Compositions were prepared in both dilute and concentrated forms.
The formulations were as follows:
Dilute Concentrate 1= Polymer AM" 15.1% 48.7%
2. Water 80.04% 35.86%
3. Antifoam 0.01% 0.03%
4= Genapol" 0.25% 0.75%
5. HEQ 4.20% 13.5%
6. Preservative 0.03% 0.06%
7. Dye 0.07% 0.15%
8. Perfume 0.30% 0.95%
*a C12 primary alcohol ethoxylated with 20 moles of ethylene oxide Example 5 Polymer ANI" was pad applied to 2% resinated cotton poplin monitors (40x40cm) to give a pick-up lever of 0.5% owf on the fabric. The monitors were then tumble dried. This was carried our four times to give a total level of 2% owf. A
similar procedure was carried out for Polymer MRSMTY and KenoresTY 1440. The monitors were wetted, scrunched (to simulate creasing in the wash process) then placed in a domestic tumble drier (MieleTM) with wetted cotton sheeting ballast (1 Kg when dry). The load was then dried until the anti-crease setting on the drier was attained. The monitors were then panelled against AATCC smoothness standards to determine the level of creasing. The monitors were then ironed and the crease process repeated Polymer 0.5% owf 0.5% owf 2% owf 2% owf (before (after (before (after ironing) ironing) ironing) ironing) Untreated control 1.4 1.38 1.64 1.54 PAE 1.3 1.44 2.26 1.94 KenoresTM
1440 2.28 2.06 2.3 2.52 Polymer TY
MRSM 2.1 2.34 2.38 2.8 Polymer AM" and Polymer MRSM" are considerably less creased than the untreated control. Polymer MRSMTM treated monitors become even less creased if an ironing step is included.
Polymer AMTY and Polymer MRSMri are considerably less creased than Kenores- 1440 especially at the 0.5% owf level.
*a C12 primary alcohol ethoxylated with 20 moles of ethylene oxide Example 5 Polymer ANI" was pad applied to 2% resinated cotton poplin monitors (40x40cm) to give a pick-up lever of 0.5% owf on the fabric. The monitors were then tumble dried. This was carried our four times to give a total level of 2% owf. A
similar procedure was carried out for Polymer MRSMTY and KenoresTY 1440. The monitors were wetted, scrunched (to simulate creasing in the wash process) then placed in a domestic tumble drier (MieleTM) with wetted cotton sheeting ballast (1 Kg when dry). The load was then dried until the anti-crease setting on the drier was attained. The monitors were then panelled against AATCC smoothness standards to determine the level of creasing. The monitors were then ironed and the crease process repeated Polymer 0.5% owf 0.5% owf 2% owf 2% owf (before (after (before (after ironing) ironing) ironing) ironing) Untreated control 1.4 1.38 1.64 1.54 PAE 1.3 1.44 2.26 1.94 KenoresTM
1440 2.28 2.06 2.3 2.52 Polymer TY
MRSM 2.1 2.34 2.38 2.8 Polymer AM" and Polymer MRSM" are considerably less creased than the untreated control. Polymer MRSMTM treated monitors become even less creased if an ironing step is included.
Polymer AMTY and Polymer MRSMri are considerably less creased than Kenores- 1440 especially at the 0.5% owf level.
Claims (20)
1. Use of a fabric care composition to improve the surface colour definition of a fabric comprising cellulosic fibers after multiple washings of the fabric and/or to impart pill and/or fuzz resistance to fabric during laundering; wherein the composition comprises a polymeric material which is self cross-linkable and/or reactive with cellulose together with one or more textile compatible carriers, wherein the polymeric material comprises one or more poly(oxyalkylene) groups having an end group which comprises one or more amino groups or derivatives of said amino groups, and wherein when the textile compatible carrier is water a further additive for use in laundry compositions is present.
2. Use as claimed in Claim 1, wherein the polymeric material is obtained by the reaction of (i) a polymer of formula B(R)n, wherein n an integer is from 1 to 20, B is a backbone group to which each R is covalently bonded and R is a group comprising a poly(oxyalkylene) chain, which chain comprises an amino end group, with (ii) a cross-linking agent, the polymer being optionally reacted with a bridging compound prior to reaction with the cross-linking agent.
3. Use as claimed in Claim 2, wherein n is 2 or 3.
4. Use as claimed in Claim 2 or. Claim 3, wherein B is and m is an integer equal to n-2 and n is at least 2.
5. Use as claimed in any one of Claims 2 to 4, wherein at least one R group has the formula -(CH2CH(R')(CH2)a O)p-A-NHR", wherein: R' is H or CH3; a is 0, 1 or 2; p is an integer from to 30; A is an alkylene group; and R" is H or alkyl.
6. Use as claimed in Claim 5, wherein p is from 10 to 25.
7. Use as claimed in any one of Claims 2 to 6, wherein the polymer of formula B(R)n is wherein p, q and r are integers which may be the same or different and are from 5 to 30 and A is branched or unbranched lower alkylene, and wherein R' is H or CH3.
8. Use as claimed in claim 2 or 3, wherein the polymer of formula B(R)n is H2N-(CH2)b-(O(CH2)4)d-O(CH2)c-(O-((CH2)4O)d2-(CH2)b-NH2 wherein: b is an integer from 1 to 6; c is an integer from 1 to 6; and d and d2 are the same or different and are integers from 10 to 15.
9. Use as claimed in Claim 8, wherein b is 3 and/or c is 4.
10. Use as claimed in any one of Claims 2 to 9, wherein the cross-linking agent comprises an epihalohydrin.
11. Use as claimed in any one of Claims 2 to 10 wherein the molar ratio of cross-linking agent to polymer of formula B(R)n is from 0.5:1 to 4:1.
12. Use as claimed in any one of Claims 2 to 11, wherein the bridging compound comprises two epoxide or carboxylic acid groups.
13. Use as claimed in any one of Claims 1 to 12, wherein the fabric care composition further comprises a silicone which is reactive with the polymeric material.
14. Use as claimed in any one of Claims 1 to 13, wherein the polymeric material increases the wet strength of paper by at least 200% compared to untreated paper when applied to paper having a weight of 80 g/m2 at a level of 1% solids by weight based on weight of paper.
15. Use as claimed in any one of Claims 1 to 14, wherein the one or more textile compatible carriers comprise a detergent active compound.
16. Use as claimed in any one of Claims 1 to 14, wherein the one or more textile compatibles carriers comprise a fabric softening and/or conditioning compound.
17. Use as claimed in any one of Claims 1 to 16, wherein the fabric care composition further comprises a perfume.
18. A method of treating fabric, as part of a laundering process, in order to improve the surface colour definition of the fabric after multiple washings and/or to impart pill and/or fuzz resistance to the fabric during laundering which comprises applying to the fabric a fabric care composition and/or a polymeric material as defined in any one of Claims 1 to 17.
19. A method as claimed in Claim 18 wherein the composition is applied to the fabric during a wash cycle.
20. A method as claimed in Claim 18, wherein the composition is applied to the fabric during a rinse cycle.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9923921.2 | 1999-10-08 | ||
| GBGB9923921.2A GB9923921D0 (en) | 1999-10-08 | 1999-10-08 | Fabric care composition |
| PCT/GB2000/003695 WO2001027232A1 (en) | 1999-10-08 | 2000-09-26 | Fabric care composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2386553A1 CA2386553A1 (en) | 2001-04-19 |
| CA2386553C true CA2386553C (en) | 2010-02-16 |
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ID=10862432
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2386553A Expired - Fee Related CA2386553C (en) | 1999-10-08 | 2000-09-26 | Fabric care composition |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP1218477B1 (en) |
| CN (1) | CN100457881C (en) |
| AR (1) | AR025970A1 (en) |
| AT (1) | ATE301703T1 (en) |
| AU (1) | AU7305000A (en) |
| BR (1) | BR0014560B1 (en) |
| CA (1) | CA2386553C (en) |
| CZ (1) | CZ20021239A3 (en) |
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| ES (1) | ES2245647T3 (en) |
| GB (1) | GB9923921D0 (en) |
| HU (1) | HUP0203581A2 (en) |
| PL (1) | PL354930A1 (en) |
| TR (1) | TR200200925T2 (en) |
| WO (1) | WO2001027232A1 (en) |
| ZA (1) | ZA200202685B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2431936C (en) | 2001-05-17 | 2010-02-09 | Unilever Plc | Laundry composition |
| GB2378960A (en) * | 2001-08-22 | 2003-02-26 | Unilever Plc | Fabric care composition |
| GB0122825D0 (en) * | 2001-09-21 | 2001-11-14 | Unilever Plc | Fabric care composition |
| GB0201165D0 (en) | 2002-01-18 | 2002-03-06 | Unilever Plc | Azetidinium modidfied poymers and fabric treatment composition |
| AU2003222772A1 (en) | 2002-03-20 | 2003-09-29 | Ge Bayer Silicones Gmbh And Co. Kg | Branched polyorganosiloxane polymers |
| DE10316662A1 (en) | 2003-04-11 | 2004-11-11 | Ge Bayer Silicones Gmbh & Co. Kg | Reactive amino and / or ammonium polysiloxane compounds |
| WO2013032479A1 (en) | 2011-09-01 | 2013-03-07 | Colgate-Palmolive Company | Method for providing fast dry to fabric |
| WO2013032480A1 (en) | 2011-09-01 | 2013-03-07 | Colgate-Palmolive Company | Method for ease of ironing |
| WO2013032481A1 (en) * | 2011-09-01 | 2013-03-07 | Colgate-Palmolive Company | Method for increased fragrance release during ironing |
| US9758927B2 (en) | 2011-09-01 | 2017-09-12 | Colgate-Palmolive Company | Method for ease of ironing |
| US9193939B2 (en) | 2013-03-28 | 2015-11-24 | The Procter & Gamble Company | Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose |
| BR112016002081B1 (en) | 2013-08-26 | 2022-01-25 | Basf Se | Cleaning compositions containing a polyether amine |
| JP6262365B2 (en) | 2014-03-27 | 2018-01-17 | ザ プロクター アンド ギャンブル カンパニー | Cleaning composition containing polyetheramine |
| US9719052B2 (en) | 2014-03-27 | 2017-08-01 | The Procter & Gamble Company | Cleaning compositions containing a polyetheramine |
| BR112017002772A2 (en) * | 2014-08-18 | 2018-07-17 | Colgate Palmolive Co | hair products containing polyetheramine |
| US9617502B2 (en) | 2014-09-15 | 2017-04-11 | The Procter & Gamble Company | Detergent compositions containing salts of polyetheramines and polymeric acid |
| US9752101B2 (en) | 2014-09-25 | 2017-09-05 | The Procter & Gamble Company | Liquid laundry detergent composition |
| WO2016049388A1 (en) | 2014-09-25 | 2016-03-31 | The Procter & Gamble Company | Fabric care compositions containing a polyetheramine |
| US9631163B2 (en) | 2014-09-25 | 2017-04-25 | The Procter & Gamble Company | Liquid laundry detergent composition |
| BR112017005767A2 (en) | 2014-09-25 | 2017-12-12 | Procter & Gamble | cleaning compositions containing a polyetheramine |
| US9388368B2 (en) | 2014-09-26 | 2016-07-12 | The Procter & Gamble Company | Cleaning compositions containing a polyetheramine |
| US20170275565A1 (en) | 2016-03-24 | 2017-09-28 | The Procter & Gamble Company | Compositions containing an etheramine |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH541595A (en) * | 1970-06-05 | 1973-09-15 | Sandoz Ag | Process for the production of new polyether amines |
| GB8916906D0 (en) * | 1989-07-24 | 1989-09-06 | Precision Proc Textiles Ltd | New prepolymers and their use in a method for the treatment of wool |
| US5858023A (en) * | 1990-10-15 | 1999-01-12 | Precision Processes Textiles | Softening agents |
| GB9022305D0 (en) * | 1990-10-15 | 1990-11-28 | Precision Proc Textiles Ltd | Softening agents |
| GB9626572D0 (en) * | 1996-12-20 | 1997-02-05 | Lucas Ind Plc | Control system |
| EP0960186A2 (en) * | 1996-12-31 | 1999-12-01 | The Procter & Gamble Company | Laundry detergent compositions with polyamide-polyamines to provide appearance benefits to fabrics laundered therewith |
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1999
- 1999-10-08 GB GBGB9923921.2A patent/GB9923921D0/en not_active Ceased
-
2000
- 2000-09-26 PL PL00354930A patent/PL354930A1/en unknown
- 2000-09-26 DE DE60021903T patent/DE60021903T2/en not_active Expired - Lifetime
- 2000-09-26 WO PCT/GB2000/003695 patent/WO2001027232A1/en active IP Right Grant
- 2000-09-26 ES ES00960893T patent/ES2245647T3/en not_active Expired - Lifetime
- 2000-09-26 BR BRPI0014560-2A patent/BR0014560B1/en not_active IP Right Cessation
- 2000-09-26 AU AU73050/00A patent/AU7305000A/en not_active Abandoned
- 2000-09-26 CA CA2386553A patent/CA2386553C/en not_active Expired - Fee Related
- 2000-09-26 EP EP00960893A patent/EP1218477B1/en not_active Expired - Lifetime
- 2000-09-26 CZ CZ20021239A patent/CZ20021239A3/en unknown
- 2000-09-26 CN CNB008169055A patent/CN100457881C/en not_active Expired - Fee Related
- 2000-09-26 AT AT00960893T patent/ATE301703T1/en not_active IP Right Cessation
- 2000-09-26 TR TR2002/00925T patent/TR200200925T2/en unknown
- 2000-09-26 HU HU0203581A patent/HUP0203581A2/en unknown
- 2000-10-06 AR ARP000105268A patent/AR025970A1/en unknown
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2002
- 2002-04-05 ZA ZA200202685A patent/ZA200202685B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ZA200202685B (en) | 2003-06-25 |
| CN1409753A (en) | 2003-04-09 |
| HUP0203581A2 (en) | 2003-03-28 |
| DE60021903T2 (en) | 2006-03-30 |
| AR025970A1 (en) | 2002-12-26 |
| ATE301703T1 (en) | 2005-08-15 |
| TR200200925T2 (en) | 2002-06-21 |
| ES2245647T3 (en) | 2006-01-16 |
| PL354930A1 (en) | 2004-03-22 |
| EP1218477B1 (en) | 2005-08-10 |
| GB9923921D0 (en) | 1999-12-08 |
| EP1218477A1 (en) | 2002-07-03 |
| WO2001027232A1 (en) | 2001-04-19 |
| BR0014560B1 (en) | 2010-08-24 |
| AU7305000A (en) | 2001-04-23 |
| DE60021903D1 (en) | 2005-09-15 |
| CN100457881C (en) | 2009-02-04 |
| BR0014560A (en) | 2002-06-11 |
| CZ20021239A3 (en) | 2002-10-16 |
| CA2386553A1 (en) | 2001-04-19 |
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