Background and Prior Art A broad range of textile material treatments are known which involve the use of polymeric materials, both for treatment of textile materials in the form of whole cloth and in the form of finished garments. Some of these polymers are substantive. Many of these treatments are used in the garment supply chain to modify the finish'of garments.

Polyamide-epichlorohydrin (PAE) resins are one particular class of materials which are known for the treatment of both keratinaceous and cellulosic materials. JP 07324284 A2 describes the use of PAE resins for the treatment of wool, whereas WO 9207124 Al describes the use of PAE resins on regenerated cellulose to reduce fibrillation.

The epichlorohydrin resins are sometimes referred to below as amine-epichlorohydrin resins and polyamine- epichlorohydrin (PAE) resins (the two terms being used synonymously) although these terms encompass both the amine

and amide resins of the invention and their derivatives.

The resins may also have a mixture of amine and amide groups.

The amine-or amide-epichlorohydrin resins may have one or more functional groups capable of forming azetidinium groups and/or one or more azetidinium functional groups.

Alternatively, or additionally, the resins may have one or more functional groups that contain epoxide groups or derivatives thereof e. g. Kymene 450 (ex Hercules).

Suitable polyamine-epichlorohydrin (PAE) resins include those described in"Wet Strength Resins and Their Application", pp 16-36, ed. LL Chan, Tappi Press, Atlanta, 1994. Suitable resins can be identified by selecting those resins, which impart increased wet strength to paper, after treatment, in a relatively simple test.

WO 9742287 Al, WO 9829530 A2 and US 6140292 Al (P&G) describe the use of PAE resins in a laundry detergent to impart appearance benefits to garments. WO 0008127 Al describe the use of PAE resins in a laundry powder as wrinkle-reducing agents. WO 0015747 Al, WO 0015748 Al describe the use of PAE resins in laundry rinse products to impart various benefits (appearance, wrinkle-reduction) to

garments. WO 0015755 Al and US 6277810 B1 describes the use of PAE resins delivered in the tumble dryer to impart appearance benefits to garments.

As noted above, PAE resins are also well-known in the paper industry as alkaline curing wet-strength resins. As a result of cross-linking that occurs during the curing reaction, covalent bonds are formed between polymers and fibres and between polymer molecules themselves. It is believed that similar reactions occur on textile materials and that these impart benefits to the textile. Textiles differ from paper in many important respects, not the least of which is that textiles are knitted or woven rather than being formed by the aggregation of fibres. In addition, the properties which are sought in textile treatment, particularly in laundry treatment, are distinct from those which are sought in paper manufacture.

Silicone polymers are also known as active components of fabric treatment compositions. These may be used in combination with other polymers. WO 0131112 A2, WO 0131113 Al, EP 0978556 Al, EP1096056 Al, EP 1096060 Al, EP 1096056 Al and EP 1096060 Al (P&G) describe the use of a mixture of PAE resin and a silicone polymer for wrinkle reduction.

Within the domestic laundry process treatment conditions are somewhat different from those found in the paper manufacturing industry and the garment supply chain. It is known that the polyamide-epichlorohydrin resins can impart laundry benefits such as wear resistance (abrasion, pilling, fuzzing), wrinkle reduction, softness, enhanced perfume,

shape and size retention, body and ease of ironing. The incorporation of a separate silicone has shown to improve the wrinkle reduction above of the polymer alone. Such is the importance of further improvements in, for example, ease of ironing and wrinkle reduction that there remains considerable scope for improvement.

Definition Of The Invention We have now determined that benefits can be attained by using a PAE/silicone condensation polymer rather than a mixture of PAE and silicone.

Accordingly, the present invention provides a method of treating textile materials which comprises the step of contacting the textile material with a condensation polymer of a polyamide epichlorohydrin resin and a silicone.

The method can be used on any natural fibres in the form of textiles, but is preferably applied to finished garments in a domestic laundry process.

It is believed that by such a method the deposition of the silicone is enhanced, since the polymer to which it is attached is cationic. This is also believed to reduces the quantity of silicone that is lost (to the drain) during use.

Furthermore, it is believed that incorporating the silicone moiety into the polymer backbone provides improved chain

flexibility and increases the thermo-elastic properties of the polymer.

It is also believed that incorporating the silicone as a side-chain on the polymer produces a layer of silicone on the surface of the fabric which improves the wrinkle behaviour and handle of the fabric.

By careful selection of the silicone, these and other properties of the polyamide-silicone polymer can be adjusted to suit the benefits required.

According to a further aspect of the present invention there is provided a composition for the treatment of finished garments as part of a laundry process, wherein said composition comprises, a textile compatible carrier and a condensation polymer of a polyamide epichlorohydrin resin and a silicone.

Preferably, the textile compatible carrier comprises a surfactant.

It is envisaged that this composition will give even better wrinkle reduction than a mixture of the polymer and silicone. Softness should also be improved.

Detailed Description of the Invention In order that the invention may be better understood it will be further described below with reference to various

preferred features and in particular with reference to the nature of the polymer and the carrier.

Polymers Patent US 6,235, 155 (Schroeder) describes the synthesis of various polymers in which a silicone component is incorporated into a polymer backbone. It is believed that these polymers would be suitable for use in embodiments of the present invention. Several preferred forms of polymer and their methods of synthesis are described in further detail below.

Where the silicone is incorporated into the polymer backbone, any suitable silicone with two end-groups which are reactive to amine or carboxylic acids can be used. Such groups include amines, carboxylates, acid chlorides, esters and isocyanates. The silicone backbone can possess pendant groups such as ethylene oxide and amino-containing side- chains.

Where the silicone is incorporated as a side-chain, the basic polymer is modified by the addition of suitable anchor point e. g. 1- [N, N-Bis (2-hydroxyethyl) amino]-2-propanol. The silicone selected possesses a suitable group which can react with the hydroxyl group.

A typical scheme for incorporation of the silicone moiety into the polymer backbone using dicarboxylic acid functional silicone is shown below: A typical R group is shown below, where a is 0-1000 and b is 1-1000

In a alternative preparation the silicone moiety is incorporated into the polymer backbone using a diamino- functional silicone. A typical schema for this is shown below: In this case, a typical Z group is of the formula given below with a = 0-100 and b = 1-1000 As yet another alternative the silicone moiety may be attached to the polymer via the azetidinium group. A typical schema for this is shown below:

In yet another alternative silicone is attached using hydroxy-functional reactive group. Again a typical schema for this is shown below:

A typical X group is of the general formula given below, wherein: a, b = 1-1000 n >= 2 x, y >= 1 Typically, the amount of epichlorohydrin used is such that 10-90% of the secondary amines present on the backbone are reacted to form azetidinium groups. Preferably, 30-70% are functionalised. Ideally, 50% are functionalised.

Carriers In the context of the present invention the term"textile compatible carrier"is a component which can assist in the interaction of the polymer with the textile. The carrier can also provide benefits in addition to those provided by the first component e. g. softening, cleaning etc. The carrier may be a detergent-active compound or a textile softener or conditioning compound or other suitable detergent or textile treatment agent.

In a washing process, as part of a conventional textile washing product, such as a detergent composition, the textile-compatible carrier will typically be a detergent- active compound. Whereas, if the textile treatment product is a rinse conditioner, the textile-compatible carrier will be a textile 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 polymer is preferably used to treat the textile in the rinse cycle of a laundering process. The rinse cycle preferably follows the treatment of the textile 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 Cg-Ci5 ; primary and secondary alkylsulphates, particularly Cg-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 Cl-so aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the Clo-Cl5 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 Rl is a Cg-C22 alkyl group, preferably a

Cg-C1o 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.

Builders : 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 15 to 50% by weight.

The detergent composition may contain as builder a 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 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.

Textile Softening and/or Conditioner Compounds: If the composition of the present invention is in the form of a textile conditioner composition, the textile-compatible carrier will be a textile softening and/or conditioning compound (hereinafter referred to as"textile 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 textile 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 textile 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. More preferably, softening compounds comprise a polar head group and two alkyl or alkenyl chains having an average chain length greater than or equal to C14. Preferably the textile 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 textile 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 textile softening compounds are preferably compounds that provide excellent softening, and are characterised by a chain melting Lp to La transition temperature greater than 25°C, preferably greater than 35°C, most preferably greater than 45°C. This Lp to La transition can be measured by DSC as defined in"Handbook of Lipid Bilayers", D Marsh, CRC Press, Boca Raton, Florida, 1990 (pages 137 and 337).

Substantially water-insoluble textile softening compounds are defined as textile softening compounds having a solubility of less than 1 x 10 wt % in demineralised water at 20°C. Preferably the textile softening compounds have a solubility of less than 1 x 10-4 wt%, more preferably less than 1 x 10-8 to 1 x 10-6 wt%.

Especially preferred are cationic textile softening compounds that are water-insoluble quaternary ammonium materials having two C12-22 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 III: (CH2) p-T-R2 wherein each R1 group is independently selected from Cul-4 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 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 (IV): CH200CR2 wherein R1, 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 textile softeners, as described in GB 2 039 556B (Unilever).

The compositions may comprise a cationic textile softening compound and an oil, for example as disclosed in EP-A-0829531.

The compositions may alternatively or additionally contain nonionic textile softening agents such as lanolin and derivatives thereof.

Lecithins are also suitable softening compounds.

Nonionic softeners include Lp 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 Cg to C22 alcohols alkoxylated with 10 to 20 moles of alkylene oxide, C1o to C20 alcohols, or mixtures thereof.

Advantageously the nonionic stabilising agent is a linear Cg 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 Cg to C24 alkyl or alkenyl monocarboxylic acids or polymers thereof. Preferably saturated fatty acids are used, in particular, hardened tallow C16 to C18 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.

Textile 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 include a soaking product, a rinse treatment (e. g. conditioner or finisher) or a main-wash 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.

Liquid 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 (TiO2) coated mica.

Liquid compositions may be in the form of emulsions or emulsion precursors thereof.

The composition of the invention may further comprise a separate silicone component. It is preferred if the silicone component is a dimethylpolysiloxane with amino alkyl groups.

It may be used in the context of the present invention as an emulsion in water.

It is preferred if the silicone component is present in a ratio of first component: silicone of from 1: 1 to 30: 1, preferably 1 : 1 to 20: 1, more preferably 2: 1 to 20: 1 and most preferably 5: 1 to 15: 1.

Silicone suitable for use in textile conditioning compositions include predominately linear polydialkylsiloxanes, e. g. polydimethylsiloxanes or aminosilicones containing amine-functionalised side chains.

Composition may comprise soil release polymers such as block copolymers of polyethylene oxide and terephthalate.

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.

In addition, compositions may comprise one or more of 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. The lists of optional components are not intended to be exhaustive.