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Title:
USE OF A LIQUID LAUNDRY COMPOSITION
Document Type and Number:
WIPO Patent Application WO/2023/232516
Kind Code:
A1
Abstract:
Use of a liquid laundry composition comprising: microcapsules; free perfume; and 0 to 2 wt.% surfactant selected from anionic surfactant cationic surfactant, or combinations thereof; wherein the microcapsules have a microcapsule wall and the microcapsule wall comprises protein polymers, polysaccharide polymers, or combinations thereof; to provide fabric care to a laundered fabric.

Inventors:
BOARDMAN CHRISTOPHER (NL)
HENDERSON ANDREW (NL)
JONES CRAIG WARREN (NL)
Application Number:
PCT/EP2023/063571
Publication Date:
December 07, 2023
Filing Date:
May 22, 2023
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
UNILEVER IP HOLDINGS B V (NL)
UNILEVER GLOBAL IP LTD (GB)
CONOPCO INC DBA UNILEVER (US)
International Classes:
C11D3/00; C11D3/22; C11D3/38; C11D3/50; C11D17/00
Domestic Patent References:
WO2004054362A12004-07-01
WO2017192648A12017-11-09
WO2016172699A12016-10-27
Foreign References:
US20170360676A12017-12-21
US20210106966A12021-04-15
US20220071865A12022-03-10
US20220152572A12022-05-19
US20140017287A12014-01-16
Other References:
DUKHINGOETZ: "Ultrasound for characterizing colloids", 2002, ELSEVIER
"Surfactant Series", vol. 100, 2001, MARCEL DEKKER, article "Reaction and Synthesis in Surfactant Systems"
ANDREWS P.: "Estimation of the Molecular Weight of Proteins by Sephadex Gel Filtration", BIOCHEM J, vol. 91, 1964, pages 222 - 233
G. SCHUSTERA. DOMSCH, SOAPS AND OILS, vol. 108, 1982, pages 177
H.W. STEISSLINGER: "Cosm.Toil", PARF.KOSM., vol. 99, 1984, pages 63
F. AURICH ET AL., TENS.SURF. DET., vol. 29, 1992, pages 389
Attorney, Agent or Firm:
OATES, Elizabeth, Ellen (NL)
Download PDF:
Claims:
CLAIMS

1. Use of a liquid laundry composition comprising: a. Microcapsules; b. Free perfume; c. 0 to 2 wt.% surfactant selected from anionic surfactant, cationic surfactant or combinations thereof; wherein the microcapsules have a microcapsule wall and the microcapsule wall comprises protein polymers, polysaccharide polymers, or combinations thereof; to provide fabric care to a laundered fabric.

2. Use of a liquid laundry composition according to claim 1 , wherein the microcapsules encapsulate fabric benefit agents.

3. Use of a liquid laundry composition according to any preceding claim wherein the microcapsules encapsulate fabric benefit agents comprising perfume.

4. Use of a liquid laundry composition according to any preceding claim, wherein the laundry composition comprises comprises 0.01 to 20 wt.% microcapsules by weight of the laundry composition.

5. Use of a liquid laundry composition according to any proceeding claim, wherein the microcapsules comprise 20 wt.% to 98 wt.% protein and/or polysaccharide, by weight of the microcapsule.

6. Use of a liquid laundry composition according to any proceeding claim, wherein the microcapsule wall comprises protein selected from: pea, potato proteins, brown rice, white rice, wheat, egg, barley, pumpkin seed, oat, almond, whey, casein, silk, gelatin, algae, rye, spelt, gluten, rapeseed, sunflower, corn, soybean, bean, chickpea, lentil, lupin, peanut, alfalfa, hemp, chitosan, proteins resulting from fermentation, proteins from food waste and combinations thereof. 7. Use of a liquid laundry composition according to any preceding claim, wherein the microcapsule wall comprises polysaccharides selected from: fibers, starch, sugar alcohols, sugars and mixtures thereof.

8. Use of a liquid laundry composition according to any proceeding claim, wherein the microcapsules are crosslinked.

9. Use of a liquid laundry composition according to claim 8, wherein the microcapsules comprise a crosslinking agent selected from: isocyanate crosslinking, salt bridge cross linking, internal crosslinking and combinations thereof.

10. Use of a liquid laundry composition according to claim 8, wherein the microcapsules comprise 0.1 wt.% to 10 wt.% crosslinking agent by weight of the microcapsule.

11. Use of a liquid laundry composition according to any preceding claim, wherein the composition comprises 0.01 to 20 wt. % free perfume by weight of the liquid laundry composition.

12. Use of a liquid laundry composition according to any proceeding claim, wherein the composition further comprises 0.5 to 15 wt.% non-ionic surfactant.

13. Use of a liquid laundry composition according to any proceeding claim, wherein the composition further comprises a film forming polymer.

14. Use of a liquid laundry composition according to any proceeding claim, wherein the composition further comprises a rheology modifier.

15. Use of a laundry composition according to any proceeding claim, wherein the composition is added to the rinse stage of the laundry process.

Description:
USE OF A LIQUID LAUNDRY COMPOSITION

Field of the Invention

The present invention relates to liquid laundry compositions.

Backqround of the Invention

Laundry products are used for various reasons, traditionally detergents are used for cleaning and fabric conditioners are used for softening and perfuming fabrics. However, there is an increased demand for laundry compositions which provide fabric care benefits to fabrics.

Various ingredients have been added to laundry products to provide fabric care. However, the addition of ingredients to a laundry composition has the drawback of increased complexity in formulations, increased cost and ingredients which may not meet the environmental credentials desired by the consumers.

Microcapsules are used in various laundry applications to deliver active materials to fabrics. Microcapsules are known to provide various benefits, such as delayed release of the active material or protection of the active material from other ingredients in the laundry composition. Conventional microcapsules typically have a microcapsule wall formed of a synthetic polymer such as a melamine formaldehyde polymer or polyacrylate polymer.

There remains a need for laundry compositions which provide fabric care to fabrics.

Summary of the Invention

It has been found that the use of a microcapsules comprising protein or polysaccharides in low cationic and/or anionic surfactant liquid laundry compositions leads to improved fabric care, in particular improved hand of fabrics.

Accordingly in a first aspect of the present invention is provided use of a liquid laundry composition comprising: a. Microcapsules; b. Free perfume; and c. 0 to 2 wt.% surfactant selected from: anionic surfactant, cationic surfactant; and combinations thereof; wherein the microcapsules have a microcapsule wall and the microcapsule wall comprises protein polymers, polysaccharide polymers, or combinations thereof; to provide fabric care to a laundered fabric.

Detailed Description of the Invention

These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. For the avoidance of doubt, any feature of one aspect of the present invention may be utilised in any other aspect of the invention. The word “comprising” is intended to mean “including” but not necessarily “consisting of” or “composed of.” In other words, the listed steps or options need not be exhaustive. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to those examples per se.

Similarly, all percentages are weight/weight percentages unless otherwise indicated. Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word “about”. Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "from x to y", it is understood that all ranges combining the different endpoints are also contemplated.

By microcapsule composition it is herein understood to mean the composition comprising microcapsules which is added to a liquid laundry composition. The microcapsule composition may comprise only microcapsules or may be in the form of a slurry comprising microcapsules.

By microcapsule it is herein understood to mean the microcapsule (wall and core) i.e. , without a solvent or slurry.

The liquid laundry products for use in the present invention comprise microcapsules. The microcapsules may be provided simply as microcapsules but preferably are provided in a microcapsule composition comprising microcapsules in a slurry. The microcapsules comprise a microcapsule core comprising an active ingredient and microcapsule wall encapsulating the core. The microcapsule wall comprises a wall polymer and preferably a crosslinking agent. Typically, the microcapsules comprise 10 wt.% to 98 wt.% core materials, 1 wt.% to 20 wt.% wall polymer and optionally 0.2 wt.% to 6 wt.% crosslinking agent.

The microcapsules may be prepared by any suitable process including those exemplary processes described here.

Microcapsule wall materials

The microcapsule wall may also be referred to as the microcapsule shell. The microcapsule wall comprises protein polymers, polysaccharide polymers, combinations thereof. The protein and/or polysaccharide may be treated by various processes to provide derivatives, including but not limited to hydrolysis, condensation, functionalising such as ethoxylating, crosslinking, etc.

Without wishing to be bound by theory, it is believed that the use of proteins or polysaccharides improves the ‘hand’ of a fabric when treated with compositions comprising the microcapsules described herein. The microcapsule wall materials are preferably in an aqueous solution. The microcapsule wall preferably comprises 20 wt.% to 100 wt.% protein, polysaccharide, or combinations thereof, more preferably 30 wt.% to 98 wt.%, more preferably 35 wt.% to 95 wt.%, and most preferably 65 wt.% to 90 wt.% by weight of the microcapsule wall.

As is conventional in the art, a “polypeptide” or “protein” is a linear organic polymer composed of amino acid residues bonded together in a chain, forming part of (or the whole of) a protein molecule. “Polypeptide” or “protein” as used herein means a natural polypeptide, polypeptide derivative, and/or modified polypeptide. The polypeptide may exhibit an average molecular weight of from 1 ,000 Da to 40,000,000 Da, preferably greater than 10,000 Da, more preferably, 100,000 Da, most preferably greater than 1,000,000 Da and preferably less than 3,000,000 Da.

Suitable proteins for use in this invention include whey proteins, plant proteins and gelatine. Preferably the plant proteins are used. Suitable preferred proteins include proteins selected from: pea, potato proteins, brown rice, white rice, wheat, egg, barley, pumpkin seed, oat, almond, whey, casein, silk, gelatin, algae, rye, spelt, gluten, rapeseed, sunflower, corn, soybean, bean, chickpea, lentil, lupin, peanut, alfalfa, hemp, proteins resulting from fermentation, proteins from food waste and combinations thereof. Particularly preferred proteins include proteins selected from chickpea, pea proteins, potato proteins, brown rice proteins, white rice proteins, wheat proteins, barley proteins, pumpkin seed proteins, oat proteins, almond proteins, and combinations thereof. This includes derivatives of the aforementioned proteins.

As used herein, whey protein refers to the protein contained in whey, a dairy liquid obtained as a supernatant of curds when milk or a dairy liquid containing milk components, is processed into cheese curd to obtain a cheese-making curd as a semisolid. Whey protein is generally understood in principle to include the globular proteins b-lactoglobulin and a-lactalbumin at various ratios such as 1: 1 to 5: 1 (e.g., 2: 1). It may also include lower amounts of serum albumin, immunoglobulin and other globulins. The term whey protein is also intended to include partially or completely modified or denatured whey proteins. Purified b-lactoglobulin and/or a- lactalbumin polypeptides may also be used in preparation of microcapsules of this invention.

Gelatin refers to a mixture of proteins produced by partial hydrolysis of collagen extracted from the skin, bones, and connective tissues of animals. Gelatin can be derived from any type of collagen, such as collagen type I, II, III, or IV. Such proteins are characterized by including Gly- Xaa-Yaa triplets wherein Gly is the amino acid glycine and Xaa and Yaa can be the same or different and can be any known amino acid. At least 40% of the amino acids are preferably present in the form of consecutive Gly-Xaa-Yaa triplets.

A preferred class of proteins are plant proteins. Plant proteins are proteins that accumulate in various plant tissues. Preferred plant proteins can be classified into two classes: seed or grain proteins and vegetable proteins. Seed/grain proteins are a set of proteins that accumulate to high levels in seeds/grains during the late stages of seed/grain development, whereas vegetable proteins are proteins that accumulate in vegetative tissues such as leaves, stems and, depending on plant species, tubers.

Preferred examples of seed/grain/legumes storage proteins are proteins from: soya, lupine, pea, chickpea, alfalfa, horse bean, lentil, and haricot bean; from oilseed plants such as colza, cottonseed and sunflower; from cereals like wheat, maize, barley, malt, oats, rye and rice (e.g., brown rice protein), or a combination thereof.

Preferred examples of vegetable protein are proteins form: potato or sweet potato tubers.

The term plant protein is intended to include a plant protein isolate, plant protein concentrate, or a combination thereof. Plant protein isolates and concentrates are generally understood to be composed of several proteins. For example, pea protein isolates and concentrates may include legumin, vicilin and convicilin proteins. Similarly, brown rice protein isolates may include albumin, globulin and glutelin proteins. The term “plant protein” is also intended to include a partially or completely modified or denatured plant storage protein. Individual polypeptides (e.g., legumin, vicilin, convicilin, albumin, globulin or glutelin) may also be used in preparation of microcapsules of this invention.

A native protein maybe preferred. However, the process may include a step of denaturing the protein by pH adjustment, heat, or adding a chaotropic agent to the oil-in-water emulsion or to the protein before adding to the oil-in-water emulsion.

Denaturation is a process in which proteins (polypeptides) lose the quaternary structure, tertiary structure, and secondary structure present in their native state, by application of a denaturation condition. During denaturation, proteins change their conformational structure by unfolding, thereby making amine and hydroxyl groups available for crosslinking (such as crosslinking with polyisocyanate) to form a microcapsule wall. Exemplary conditions for protein denaturation include, but are not limited to, radiation, exposure to heat or cold, changes in pH with an acid or base, exposure to denaturing agents such as detergents, inorganic salt, organic solvent (e.g., alcohol, ethyl acetate, and chloroform), urea, or other chaotropic agents, or mechanical stress including shear. Exemplary chaotropic agents are guanidine salts (e.g., guanidine hydrochloride and guanidine carbonate), urea, polysorbate, sodium benzoate, vanillin, o-cresol, phenol, propanol, formamide, ethanol, fructose, ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium phosphate, potassium sulfate, potassium chloride, potassium iodide, potassium nitrate, potassium phosphate, sodium sulfate, sodium chloride, sodium bromide, sodium nitrate, sodium phosphate, guanidine thiocyanate, xylose, glycerol, benzyl alcohol, ethyl acetate, triton X-100, ethyl acetate, cetyltrimethylammonium halide, acetone, sodium dodecyl sulfate (SDS), hydrochloric acid, sulfuric acid, polyethylene glycol, glutaraldehyde, and combinations thereof. Any amount of the chaotropic agent can be used.

It may be preferred that the protein is denatured with a chaotropic agent so that 20 wt. % to 100 wt.% preferably 40 wt. % to 100 wt. %, more preferably 60 wt.% to 100 wt.%, most preferably 90 wt.% to 100 wt.% of the protein used in the preparation of the microcapsules is denatured.

The protein used in the microcapsule can also be derivatized or modified (e.g., derivatized or chemically modified). For example, the protein can be modified by covalently attaching sugars, lipids, cofactors, peptides, or other chemical groups including phosphate, acetate, methyl, and other natural or unnatural molecule. Polysaccharides are a class of carbohydrates comprising multiple monosaccharide units. “Polysaccharide” as used herein means a natural polysaccharide, polysaccharide derivative, and/or modified polysacharide. Suitable polysaccharides maybe selected from the group consisting of fibres, starch, sugar alcohols, sugars and mixtures thereof.

Examples of suitable fibres include: particular cellulose, cellulose derivatives such as hydroxyethyl cellulose, in particular quaternized hydroxyethyl cellulose, carboxymethylcellulose (CMC) and microcrystalline cellulose (MCC), hemicelluloses, lichenin, chitin, chitosan, lignin, xanthan, plant fibers, in particular cereal fibers, potato fibers, apple fibers, citrus fibers, bamboo fibers, extracted sugar beet fibers; oat fibers and soluble dietary fibers, in particular inulin, especially native inulin, highly soluble inulin, granulated inulin, high performance inulin, pectins, alginates, agar, carrageenan, gum arabic (Senegal type, Seyal type), konjac gum, gellan gum, curdlan (paramylon), guar gum, locust bean gum, xanthan gum, raffinose, xylose, polydextrose and lactulose and combinations thereof. This includes derivatives of the aforementioned polysaccharides.

Examples of suitable starches include starch from: wheat, potatoes, corn, rice, tapioca and oats, modified starch, and starch derivatives, e.g., dextrins or maltodextrins, in particular dextrins and maltodextrins from wheat, potatoes, corn, rice, pea, chickpea and oats, oligosaccharides, in particular oligofructose. Preferred starches are selected from: corn starch, potato starch, rye starch, wheat starch, barley starch, oat starch, rice starch, pea starch, chickpea starch, tapioca starch, and mixtures thereof.

Examples of suitable sugar alcohols include: sorbitol, mannitol, isomalt, maltitol, maltilol syrup, lactitol, xylitol, erythritol.

An example of suitable sugar includes: glucose.

Particularly preferred polysaccharides include: gum Arabic, dextrins and maltodextrins are particularly preferred.

The polysaccharide used in the microcapsule can also be derivatized or modified (e.g., derivatized or chemically modified). For example, the protein can be modified by covalently attaching sugars, lipids, cofactors, peptides, or other chemical groups including phosphate, acetate, methyl, and other natural or unnatural molecule. Examples of suitable polysaccharide derivatives include: starch glycolate, carboxymethyl starch, hydroxyalkyl cellulose and crosslinked modified cellulose. The microcapsules as described herein may optionally comprise additional polymers in the microcapsule walls. Such additional polymers may include: a sol-gel polymer (e.g., silica), polyacrylate, polyacrylamide, poly(acrylate-co-acrylamide), polyurea, polyurethane, starch, gelatin and gum Arabic, poly(melamine-formaldehyde), poly(urea-formaldehyde), and combinations thereof. However preferably the microcapsule wall polymers consist essentially of proteins, polysaccharides, or combinations thereof.

The microcapsule preferably comprises from 0.1 wt.% to 30 wt.% microcapsule wall, preferably 0.5 wt.% to 25 wt.%, more preferably 1 wt.% to 20 wt.% and 2 wt.% to 15 wt.% microcapsule wall by weight of the microcapsule.

The microcapsule wall polymers described herein are preferably crosslinked. Suitable methods of crosslinking include: isocyanate crosslinking, salt bridge cross linking and internal crosslinking within the microcapsule wall polymer structures (including the formation of a coacervate). Where a cross linking agent is used, such as polyisocyanate crosslinking agents or ionic crosslinking agents the cross linking agent is preferably present at a level of 0.1 wt.% to 10 wt.% by weight of the microcapsule, preferably 0.5 wt.% to 9 wt.% by weight of the microcapsule, even more preferably 1 to 8 wt.% by weight of the microcapsule.

One preferred method of cross linking is using polyisocyanates. Without wishing to be bound by theory, the selection of an isocyanate cross linking agent improves the softening of a fabric treated with a composition comprising the microcapsules.

Polyisocyanates each have at least two isocyanate (-NCO) groups reactive towards proteins or polysaccharides. The polyisocyanate can be aromatic, aliphatic, linear, branched, or cyclic, preferably the polyisocyanate comprises polyisocyanates selected from aliphatic, cycloaliphatic, hydroaromatic, aromatic or heterocyclic polyisocyanate, their substitution products and mixtures thereof, most preferably selected from aromatic, aliphatic polyisocyanate and combinations thereof. It is particularly preferred, that more than one polyisocyanate is present. The isocyanate may be, water soluble or water dispersible, alternatively, it can be soluble in an organic solvent or fragrance oil. Preferably, the polyisocyanate is water insoluble. Preferably, the polyisocyanate comprises, 2 to 4 isocyanate groups. More preferably, the polyisocyanate comprises 3 to 4 isocyanate functional groups.

Examples of suitable polyisocyanate include a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate, a biuret of hexamethylene diisocyanate, a polyisocyanurate of toluene diisocyanate, a trimethylol propane-adduct of toluene diisocyanate, a trimethylol propane - adduct of xylylene diisocyanate, and combinations thereof.

Preferably the polyisocyanate used in this invention is an aromatic poly isocyanate. Preferably, the aromatic polyisocyanate includes a phenyl, tolyl, xylyl, naphthyl or diphenyl moiety as the aromatic component. Particularly preferably, the aromatic polyisocyanate is a polyisocyanurate of toluene diisocyanate, a trimethylol propane -adduct of toluene diisocyanate or a trimethylol propane -adduct of xylylene diisocyanate.

One class of suitable aromatic polyisocyanates are those having the generic structure shown below, and its structural isomers wherein n can vary from zero to a desired number (e.g., 0-50, 0-20, 0-10, and 0-6) depending on the type of crosslinker used. Preferably, the number of n is limited to less than 6. The starting polyisocyanate may also be a mixture of polyisocyanates where the value of n can vary from 0 to 6. In the case where the starting polyisocyanate is a mixture of various polyisocyanates, the average value of n preferably falls in between 0.5 and 1.5.

Commercially-available polyisocyanates include products under the trade names of LUPRANATE® M20 (chemical name: polymeric methylene diphenyl diisocyanate, i.e.,“PMDI”; commercially available from BASF containing isocyanate group “NCO” 31.5 wt%), where the average n is 0.7; PAPI™ 27 (PMDI commercially available from Dow Chemical having an average molecular weight of 340 and containing NCO 31.4 wt%) where the average n is 0.7; MON DUR® MR (PMDI containing NCO at 31 wt% or greater, commerciallyavailable from Covestro, Pittsburg, Pennsylvania) where the average n is 0.8; MONDUR® MR Light (PMDI containing NCO 31.8 wt%, commercially available from Covestro) where the average n is 0.8; MONDUR® 489 (PMDI commercially available from Covestro containing NCO 30-31.4 wt%) where the average n is 1; poly[(phenylisocyanate)-co-formaldehyde] (Aldrich Chemical, Milwaukee, Wl), other isocyanate monomers such as DESMODUR® N3200 (poly(hexamethylene diisocyanate) commercially available from Covestro), and Takenate™ D-l 10N (trimethylol propane -adduct of xylylene diisocyanate, Mitsui Chemicals America, Inc., Rye Brook, NY, containing NCO 11.5 wt%), DESMODUR® L75 (a polyisocyanate base on toluene diisocyanate commercially available from Covestro), and DESMODUR® IL (another polyisocyanate based on toluene diisocyanate commercially available from Covestro).

An alternate suitable class of polyisocinates are diisocyanates with the general structure O=C=N-R-N=C=O, wherein R represents aliphatic, alicyclic or aromatic radicals, are used. Preferably, the radicals have five or more carbon atoms.

Other examples of the aromatic polyisocyanate include 1,5-naphthylene diisocyanate, 4,4'- diphenylmethane diisocyanate (MDI), hydrogenated MDI, xylylene diisocyanate (XDI), tetramethylxylol diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4- phenylene diisocyanate, the isomers of tolylene diisocyanate (TDI), 4,4'-diisocyanatophenyl- perfluoroethane, phthalic acid bisisocyanatoethyl ester, also polyisocyanates with reactive halogen atoms, such as 1 -chloromethylphenyl 2,4-diisocyanate, 1 -bromomethyl -phenyl 2,6- diisocyanate, and 3,3-bischloromethyl ether 4,4'-diphenyldiisocyanate, and combinations thereof.

The weight average molecular weight of useful polyisocyanates is preferably from 200 Da to 2500 Da, more preferably 250 Da to 1000 Da and most preferably from 275 Da to 500 Da.

The polyisocyanate is preferably present in the wall in an amount of 0.1 wt.% to 40 wt.%, more preferably 0.2 wt.% to 25 wt.%, even more preferably 0.25 wt.% to 15 wt.%, and most preferably 0.5 wt.% to 5 wt.%, by weight of the microcapsule wall. Preferably the ratio of polysaccharide and/or protein to polyisocyanate is 1 : 1 to 10: 1.

During the process of preparing the microcapsule composition of this invention, polyisocyanate can be added to the aqueous phase, the oil phase, or the oil-in-water emulsion.

More suitable polyisocyanate examples can be found in WO 2004/054362 and WO 2017/192648.

An alternative crosslink agent suitable for use in the present invention are ionic crosslinking agents. Ionic crosslinking agents are multivalent ions which are capable of forming salt bridges with the functional groups of the protein or polysaccharide polymers. Without wishing to be bound by theory, it is believed that the use of an ionic crosslinking agent leads to improved drape and resilience of a fabric treated with a composition comprising a microcapsule as described herein. Suitable ionic crosslinking agents maybe selected from: calcium, copper, aluminum, magnesium, strontium, barium, zinc, tin, organic cations, poly(amino acids), poly(ethyleneimine), poly(vinylamine), poly(allyl amine) and polysaccharides, dicarboxylic acids, sulfate ions, carbonate ions, poly(acrylic acids), poly(methacrylic acids), copolymers of acrylic acid or methacrylic acid, sulfonated poly(styrene) and poly(styrene) with carboxylic acid groups and mixtures thereof. Particularly preferred are calcium salts, magnesium, sodium, potassium, strontium, barium, zinc.

Internal cross linking is cross linking between the microcapsule wall polymers, without the use of a crosslinking agent. The internal crosslinking maybe crosslinking with the same polymer (i.e. a polymer with both positive and negative charges) or between two different polymers forming the microcapsule wall. When two different polymers of opposite charges are utilised, this is referred to as a coacervate formed by coacervation.

Preferably a coacervate is formed between a first protein or polysaccharide of one charge and a second protein or polysaccharide of an opposite charge. The ratio between polymer with a positive charge and polymer with a negative charge is preferably between 10/0.1 to 0.1/10, more preferably between 10/1 and 1/10 and most preferably between 6/1 and 1/6.

An example of a protein with a positive charge maybe gelatin and the protein or polysaccharide with a negative charge maybe selected from the group consisting of gum arabic, xanthan, alginate salts, pectinate salts, carrageenan, polyacrylic and methacrylic acid, xanthan gum and plant gums and mixtures thereof.

Microcapsules which are internally cross linked, i.e. have electrostatic interaction between positive and negative monomers within the microcapsule wall polymers, can be further crosslinked or ‘hardened’ using salt bridges or isocyanate as described above.

The microcapsule may optionally comprise further crosslinking agents. The further crosslinking agent maybe selected from the group consisting of transglutaminase, peroxidase, secondary plant substances selected from the group consisting of polyphenols, in particular tannin, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, and mixtures of two or more of the aforementioned crosslinking agents. Microcapsule core materials

The core may also be referred to as the internal phase. The core of the microcapsule comprises active material and optionally further comprises solvents, crosslinking agents as described above or combinations thereof. The core is preferably non-aqueous.

The internal non-aqueous phase may preferably comprise from 20 to 80 wt.%, preferably from 25 to 75 wt.% and even more preferably from 33 to 50 wt.% active material to be encapsulated and preferably from 0.1 to 5 wt.%, preferably from 0.15 to 3.5 wt.% and even more preferably from 0.5 to 2.5 wt.% crosslinking agent and the remaining composition solvent.

Exemplary active materials include: fragrance; malodour agents for example: uncomplexed cyclodextrin, odor blockers, reactive aldehydes, flavonoids, zeolites, activated carbon, and mixtures thereof; dye transfer inhibitors; shading dyes; silicone oils, resins, and modifications thereof such as linear and cyclic polydimethylsiloxanes, amino-modified, allcyl, aryl, and alkylaryl silicone oils, which preferably have a viscosity of greater than 50,000 cst; insect repellents; organic sunscreen actives, for example, octylmethoxy cinnamate; antimicrobial agents, for example, 2-hydroxy-4, 2,4- trichlorodiphenylether; ester solvents, for example isopropyl myristate; lipids and lipid like substance, for example, cholesterol; hydrocarbons such as paraffins, petrolatum, and mineral oil; fish and vegetable oils; hydrophobic plant extracts; waxes; pigments including inorganic compounds with hydrophobically- modified surface and/ or dispersed in an oil or a hydrophobic liquid; sugar-esters, such as sucrose polyester (SPE); and combinations thereof.

The benefit agents may be dissolved in a solvent. Examples of suitable solvents include vegetable oils, glycerides, esters of fatty acids and branched alcohols, hydrocarbon, etc. specific examples include: diethyl phthalate, isopropyl myristate, Abalyn® (rosin resins, available from Eastman), benzyl benzoate, ethyl citrate, limonene or other terpenes, triacetin or isoparaffins, preferably Abalyn®, benzyl benzoate, limonene or other terpenes, isoparaffins, or combinations thereof. Preferably, if present, the solvent is 0 to 30 wt.% of the active material, more preferably 0 to 20 wt.% and most preferably 0 to 10 wt.% of the active material.

Most preferably the active material comprises fragrance. Perfume components are well known in the art. Useful perfume components may include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA). These substances are well known to the person skilled in the art of perfuming, flavouring, and/or aromatizing consumer products.

Particularly preferred perfume components are blooming perfume components and substantive perfume components. Blooming perfume components are defined by a boiling point less than 250°C and a LogP greater than 2.5. Preferably encapsulated perfume compositions comprise at least 20 wt.% blooming perfume ingredients, more preferably at least 30 wt.% and most preferably at least 40 wt.% blooming perfume ingredients. Substantive perfume components are defined by a boiling point greater than 250°C and a LogP greater than 2.5. Preferably encapsulated perfume compositions comprises at least 10 wt.% substantive perfume ingredients, more preferably at least 20 wt.% and most preferably at least 30 wt.% substantive perfume ingredients. Boiling point is measured at standard pressure (760 mm Hg). Preferably a perfume composition will comprise a mixture of blooming and substantive perfume components. The perfume composition may comprise other perfume components.

It is commonplace for a plurality of perfume components to be present in a microcapsule. In the compositions for use in the present invention it is envisaged that there will be three or more, preferably four or more, more preferably five or more, most preferably six or more different perfume components in a microcapsule. An upper limit of 300 perfume components may be applied.

Preferably the amount of encapsulated active material is from 5 wt.% to 95 wt.%, preferably 10 wt.% to 90 wt.% more preferably 15 wt.% to 85 wt.%, and most 20 wt.% to 80 wt.% by weight of the microcapsule.

Additional microcapsule ingredients

The microcapsule composition may comprise further ingredients. A preferred further ingredient are polyphenols. Particularly preferred are phenols having a 3,4,5-trihydroxyphenyl group or 3,4-dihydroxypheny group such as tannic acid. In additional to polyphenols, other polyols can also be used to prepare the microcapsule compositions of this invention. Examples include pentaerythritol, dipentaerythritol, glycerol, polyglycerol, ethylene glycol, polyethylene glycol, trimethylolpropane, neopentyl glycol, sorbitol, erythritol, threitol, arabitol, xylitol, ribitol, mannitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, maltotriitol, maltotetraitol, polyglycitol, polyphenol, and combinations thereof. Polyphenols, polyols, and multi-functional aldehydes are preferably present at a level of 0 wt.% to 40 wt.%, preferably 1 wt.% to 35 wt.% more preferably 5 wt.% to 35 wt.% and most preferably 10 wt.% to 30 wt.%.

Microcapsule composition

The microcapsules described herein preferably have a diameter of 0.1 microns to 1000 microns, more preferably 0.5 microns to 500 microns, even more preferably 1 micron to 200 microns, and most preferably 1 micron to 100 microns.

The microcapsules can be positively or negatively charged with a zeta potential of preferably - 200 mV to +200 mV, more preferably 25 mV to 200 mV, and most preferably 40 mV to 100 mV. Preferably, the microcapsules are positively charged. Zeta potential is a measurement of electrokinetic potential in the microcapsule. From a theoretical viewpoint, zeta potential is the potential difference between the water phase (i.e. , the dispersion medium) and the stationary layer of water attached to the surface of the microcapsule. The zeta potential can be calculated using theoretical models and an experimentally-determined electrophoretic mobility or dynamic electrophoretic mobility. The zeta potential is conventionally measured by methods such as microelectrophoresis, or electrophoretic light scattering, or electroacoustic phenomena. For more detailed discussion on measurement of zeta potential, see Dukhin and Goetz, "Ultrasound for characterizing colloids", Elsevier, 2002.

The microcapsule composition of this invention can be a slurry containing a solvent, preferably water. The microcapsules are preferably present in the slurry as 0.1 wt.% to 80 wt.%, more preferably 1 wt.% to 65 wt.% and most preferably 5 wt.% to 45 wt.% by weight of the microcapsule composition. The slurry may comprise a thickening or suspending agent such as xanthan gum, carboxymethyl cellulose (CMC), microcrystalline cellulose (MCC) or guar gum.

Alternatively, the microcapsule composition of this invention can also be dried, e.g., spray dried, heat dried, and belt dried, to a solid form.

The microcapsule composition maybe purified by washing the capsule slurry with water until a neutral pH (pH of 6 to 8) is achieved. For the purposes of the present invention, the capsule suspension can be washed using any conventional method including the use of a separatory funnel, filter paper, centrifugation and the like. The capsule suspension can be washed one, two, three, four, five, six, or more times until a neutral pH, e.g., pH 6-8 and 6.5-7.5, is achieved. The pH of the purified capsules can be determined using any conventional method including, but not limited to pH paper, pH indicators, or a pH meter. In certain embodiments of this invention, the purification of the capsules includes the additional step of adding a salt to the capsule suspension prior to the step of washing the capsule suspension with water. Exemplary salts of use in this step of the invention include, but are not limited to, sodium chloride, potassium chloride or bi-sulphite salts. See US 2014/0017287.

Preparation of the microcapsules

When preparing the microcapsule, the polymers may be provided in a solvent. Suitable solvents for preparing the microcapsule wall include water or mixtures of water with at least one water- miscible organic solvent. Suitable organic solvents include glycerol, 1 ,2-propanediol, 1 ,3- propanediol, ethanediol, diethylene glycol, triethylene glycol, and other analogues. Preferably the solvent is water.

A stabiliser may also be present. A stabiliser maybe be selected from acrylic co-polymers, preferably with sulphonate groups, copolymers of acrylamides and acrylic acid, copolymers of alkyl acrylates and N-vinylpyrrolidone, such as LUVISKOL® K15, K30 or K90 (BASF); sodium polycarboxylates, sodium polystyrene sulfonates, vinyl and methyl vinyl ether-maleic acid anhydride copolymers as well as ethylene, isobutylene or styrene-maleic acid anhydride copolymers, microcrystalline cellulose, which is commercially available, for example, under the name VIVAPUR®, diutan gum, xanthan gum or carboxymethyl celluloses.

The crosslinking of the microcapsule preferably involves a catalyst. The catalyst may be present in the microcapsule core active material or added separately to the oil-in-water emulsion or dispersion. A preferred catalyst for the formation of microcapsules according to the present invention is diazabicyclo[2.2.2]octane (DABCO), also known as triethylenediamine (TEDA). Also suitable are catalysts based on bismuth or tin, transglutaminase, peroxidase, secondary plant compounds selected from the group, which consists of polyphenols, in particular tannin, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, and mixtures thereof.

Alternatively, or additionally the formation of the microcapsules may be catalyst by heating the oil-in-water emulsion or dispersion. For example, heating to a temperature range of a temperature in the range of 60 °C to 90 °C.

Various suitable methods of production may be implemented to produce the microcapsules suitable for use in the present invention. One suitable method if interfacial polymerization. An examples of interfacial polymerization involves the steps of:

(i) Providing the microcapsule core materials including at least one first crosslinking agent, wherein the crosslinking agent is substantially dissolved together with the core materials, this is the oil phase. A non-aqueous solvent many optionally be present;

(ii) Providing the microcapsule wall materials comprising at least one protein, at least one polysaccharide, or combinations thereof. This is the aqueous phase. An aqueous solvent many optionally be present;

(iii) Emulsifying or dispersing the microcapsule core materials with the microcapsule wall materials. Preferably in a ratio of from 70 : 30 to 60 : 40, preferably in a range from 30 : 70 to 60 : 40. Optionally an emulsifier may be used. Emulsification may be achieved by use of high-speed mixing. After completion of this stage, an oil-in-water emulsion or dispersion is present in which the internal phase with the active materials to be encapsulated is finely emulsified or dispersed in the external wall material phase in the form of droplets;

(iv) First crosslinking optionally by the addition of at least one catalyst to obtain a microcapsule slurry, optionally with the addition of further protein polymers, polysaccharide polymers, or combinations thereof;

(v) Curing the microcapsule slurry, preferably at a temperature of at least 60 °, preferably for at least 30 minutes, followed by cooling;

(vi) Optionally drying, using methods such as spray drying, filtration, or freeze drying.

An alternative method involves 3D printing the microcapsules. Both the microcapsule shell and microcapsule core can be printed using a printing system. See WO2016172699A1. The printing steps generally include depositing the active materials and the microcapsule shell material in a layer-by-layer fashion, preferably through separate printer heads.

Liquid laundry compositions

The compositions for use in the present invention comprise 0.01 to 20 wt.% microcapsules, by weight of the composition. More preferably 0.05 to 15 wt.% microcapsules, most preferably 0.1 to 12 wt.% microcapsules. The compositions for use in the present invention comprise free oil perfume in addition to any perfume enclosed in the microcapsules. Free perfume may preferably be present in an amount from 0.01 to 20 wt. %, more preferably 0.1 to 15 wt.%, more preferably from 0.1 to 10 wt.%, even more preferably from 0.1 to 6.0 wt.%, most preferably from 0.5 to 6.0 wt. %, based on the total weight of the composition.

Useful perfume components may include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA). These substances are well known to the person skilled in the art of perfuming, flavouring, and/or aromatizing consumer products.

Particularly preferred perfume components are blooming perfume components and substantive perfume components. Blooming perfume components are defined by a boiling point less than 250°C and a LogP greater than 2.5. Substantive perfume components are defined by a boiling point greater than 250°C and a LogP greater than 2.5. Preferably a perfume composition will comprise a mixture of blooming and substantive perfume components. The perfume composition may comprise other perfume components.

It is commonplace for a plurality of perfume components to be present in a free oil perfume composition. In the compositions for use in the present invention it is envisaged that there will be three or more, preferably four or more, more preferably five or more, most preferably six or more different perfume components. An upper limit of 300 perfume ingredients may be applied.

The compositions for use in the present invention preferably comprise low levels or most preferably no anionic or cationic surfactant.

The liquid laundry composition for use in the present invention comprise 0 to 2 wt.% a surfactant selected from anionic surfactant, cationic surfactant or combinations thereof, more preferably, 0 to 1 wt.%, even more preferably 0 to 0.85 wt. % and most preferably 0 to 0.5 wt. % surfactant selected from anionic surfactant, cationic surfactant or combinations thereof. The composition can be completely free of anionic and cationic surfactant. Cationic and anionic surfactants are defined according to the common general knowledge, for example: Surfactant Series Volume 100; Reaction and Synthesis in Surfactant Systems, edited by John Texter, published 2001 by Marcel Dekker.

Without wishing to be bound by theory it is believed that the fabric care benefit provided by the compositions described herein is enhanced by the low levels of anionic and cationic surfactants in the compositions.

The fabric softening composition may preferably comprise non-ionic surfactant, in addition to any non-ionic surfactant in the microcapsules or microcapsule slurry. Preferably the composition comprises 0.5 to 15 wt.% non-ionic surfactant, more preferably 0.5 to 10 wt.% non- ionic surfactant, most preferably 0.5 to 8 wt.% non-ionic surfactant. The correct amount of non- ionic surfactant is important to achieve the desired delivery of the perfume. The compositions may require sufficient non-ionic surfactant to carry the benefit agent, however too much non- ionic surfactant will interfere with the action of the laundry liquid or powder with which it is used and will prevent release of the perfume due to insufficient dilution.

The non-ionic surfactants will preferably have an HLB value of 12 to 20, more preferably 14 to 18.

Examples of non-ionic surfactant materials include: ethoxylated materials, polyols such as polyhydric alcohols and polyol esters, alkyl polyglucosides, EO-PO block copolymers (Poloxamers). Preferably, the non-ionic surfactant is selected from ethoxylated materials. Preferred ethoxylated materials include: fatty acid ethoxylates, fatty amine ethoxylates, fatty alcohol ethoxylates, nonylphenol ethoxylates, alkyl phenol ethoxylate, amide ethoxylates, Sorbitan(ol) ester ethoxylates, glyceride ethoxylates (castor oil or hydrogenated castor oil ethoxylates) and mixtures thereof.

More preferably, the non-ionic surfactant is selected from ethoxylated surfactants having a general formula: R 1 O(R 2 O) X H

R 1 = hydrophobic moiety.

R 2 = C2H4 or mixture of C2H4 and C3H6 units x = 4 to 120

R 1 preferably comprises 8 to 25 carbon atoms and mixtures thereof, more preferably 10 to 20 carbon atoms and mixtures thereof most preferably 12 to 18 carbon atoms and mixtures thereof. Preferably, R is selected from the group consisting of primary, secondary and branched chain saturated and/or unsaturated hydrocarbon groups comprising an alcohol, carboxy or phenolic group. Preferably R is a natural or synthetic alcohol.

R 2 preferably comprises at least 50% C2H4, more preferably 75% C2H4, most preferably R 2 is C2H4. x is preferably 8 to 90 and most preferably 10 to 60.

Examples of commercially available, suitable non-ionic surfactants include: Genapol C200 ex. Clariant and Eumulgin CO40 ex. BASF.

The compositions for use in the present invention may optionally comprise film forming polymers. The term film forming polymer is well known in the art and refers to polymers which deposit on the surface of a fabric and provide a so-called film on the surface of the fabric.

The film-forming polymers may be selected from synthetic organic polymers, natural polymers, modified natural polymers and combinations thereof.

Examples of suitable film forming polymers include: polyvinyl alcohol; polyvinyl pyrroiidone; polyethylene glycols; polyvinylpyrrolidones; polyacrylates including methacrylates; polyacrylamides; polymeric polycarboxylates such as water-soluble acrylate (co)polymers; ethoxylated hexamethylene diamine quaternary compounds; polyesters including copolyesters; polyurethanes; vinylpyrrolidone I vinyl ester copolymers; Polyquaternium polymers such as polyquaternium -1 , 2, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 24, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 39, 45, 46, 47, 48, 49, 50, 55, 56; siloxanes; polysaccharides such as starch, glucose, chitosan, gum arabic, xanthan, carrageenan; proteins such as collagen; modified starches; modified proteins such as hydrolysed proteins from animals, such as collagen, keratin and milk or from plants, such as wheat, corn, rice, potatoes, soybeans or almonds, from marine life forms, such as collagen, fish or algae or biotechnology- derived protein and derivatives of hydrolysed proteins; polymers synthesised from plant materials such as rice bran soybean extract, cellulose derivatives such as carboxymethylcellulose, hydroxymethyl cellulose, methylcellulose, hydroxypropyl methylcellulose, hydroxycellulose, ethylcellulose, carboxymethyl cellulose, hydroxypropyl cellulose, nitrocellulose, cellulose acetate propionate and cellulose acetate butyrate; and combinations thereof.

The film forming polymer preferably has a weight-average molecular weight Mw in the range from 300 g I mol to 5,000,000 g I mol, preferably from 300 g I mol to 3,000,000 g I mol and more preferably from 500 g I mol to 2,000,000 g I mol. The average molecular weight Mw can be determined, for example, by gel permeation chromatography (GPC) (Andrews P., "Estimation of the Molecular Weight of Proteins by Sephadex Gel Filtration"; Biochem J., 1964, 91, pages 222 to 233). The use of protein hydrolysates with average molecular weights in this range leads to a particularly effective perfume benefits.

Preferred film forming polymers are selected from polymers comprising: polyvinyl alcohol; polyvinyl pyrroiidone; cellulose derivatives such as methylcellulose, hydroxypropyl methylcellulose, hydroxycellulose, ethylcellulose, carboxymethyl cellulose, hydroxypropyl cellulose; polyethylene glycol; polyethylene oxide; polysaccharides such as chitosan, gum arabic, xanthan, carrageenan; polyesters including co-polyesters; hydrolysed proteins and derivatives thereof or any combinations thereof. More preferably the film forming polymer is selected from polymers comprising: hydrolysed proteins or polyesters, including co-polyesters, polysaccharides.

Protein hydrolysates for use in the present invention are proteins which are obtainable by hydrolysis of proteins. Hydrolysis can be achieved by chemical reactions, in particular by alkaline hydrolysis, acid hydrolysis, enzymatic hydrolysis or combinations thereof. For alkaline or acid hydrolysis, methods such as prolonged boiling in a strong acid or strong base may be employed. For enzymatic hydrolysis, all hydrolytic enzymes are suitable, for example alkaline proteases. The production of protein hydrolysates is described, for example, by G. Schuster and A. Domsch in soaps and oils Fette Wachse 108, (1982) 177 and Cosm.Toil, respectively. 99, (1984) 63, by H.W. Steisslinger in Parf.Kosm. 72, (1991) 556 and F. Aurich et al. in Tens. Surf. Det. 29, (1992) 389 appeared. The hydrolysed proteins of the present invention may come from a variety of sources. The proteins may be naturally sourced, e.g., from plants or animal sources, or they may be synthetic proteins. Preferably the protein is a naturally sourced protein or a synthetic equivalent of a naturally sourced protein. A preferred class of proteins are plant proteins, i.e. , proteins obtained from a plant or synthetic equivalents thereof. Preferably the protein is obtained from a plant. Preferred plant sources include nuts, seeds, beans, and grains.

Particularly preferred plant sources are grains. Examples of grains include cereal grains (e.g., millet, maize, barley, oats, rice and wheat), pseudoceral grains (e.g., buckwheat and quinoa), pulses (e.g., chickpeas, lentils and soybeans) and oilseeds (e.g. mustard, rapeseed, sunflower seed, hemp seed, poppy seed, flax seed). Most preferred are cereal grains, in particular wheat proteins or synthetic equivalents to wheat proteins.

It is preferred that the protein hydrolysate is cationically modified. Preferably, a cationically modified wheat protein hydrolysate. Preferably the hydrolyses protein is a quaternised protein. Preferably the hydrolysed protein contains at least one radical of the formula:

R1-N + (CH 3 ) 2 -CH 2 -CH(OH)-CH 2 -XR

R1 is an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 1 to 30 carbon atoms, or a hydroxyalkyl group having 1 to 30 carbon atoms. R1 is preferably selected from, a methyl group, a C 10-18 alkyl, or a C 10-13 alkenyl group, X is O, N or S

R represents the protein residue. The term "protein residue" is to be understood as meaning the backbone of the corresponding protein hydrolyzate formed by the linking of amino acids, to which the cationic group is bound.

The cationization of the protein hydrolysates with the above-described residues can be achieved by reacting the protein hydrolyzates, in particular the reactive groups of the amino acids of the protein hydrolysates, with halides which otherwise correspond to compounds of the above formula (wherein the X-R moiety is replaced by a halogen).

The hydrolysed protein may a be hydrolysed protein-silicone copolymer. The silicone component may be covalently bonded to amino groups of the protein groups. Silicone components may form cross-links between different protein chains. The protein component of a protein-silicone copolymer may represent from 5 to 98% by weight of the copolymer, more preferably from 50 to 90%.

Preferably, the silicone component is organofunctional silane/silicone compounds. The protein- silicone copolymer may be prepared by covalently attaching organofunctional silane/silicone compounds to the protein amino groups to form larger polymer molecules including protein cross-linking. In addition, further polymerisation may occur through condensation of silanol groups, and such further polymerisation increases the amount of cross-linking. The organofunctional silicone compounds used for reaction with the protein component to form the copolymer must contain a functional group capable of reacting with the chain terminal and/or side chain amino groups of the protein. Suitable reactive groups include, for example, acyl halide, sulphonyl halide, anhydride, aldehyde and epoxide groups. The silicone component may be any compound which contains a siloxane group (Si-O-Si) or any silane capable of forming a siloxane in situ by condensation of silanol (Si-OH) groups or any alkoxysilane or halosilane which hydrolyses to form a corresponding silanol and then condenses to form a siloxane group.

Wheat protein hydrolysates are commercially available, for example, from Croda under the trade name ColtideRadiance.

Polyester polymers for use in the invention may include a variety of charged (e.g., anionic) as well as non-charged monomer units and structures may be linear, branched or star shaped. The polyester structure may also include capping groups to control molecular weight or to alter polymer properties such as surface activity.

Polyesters for use in the invention may suitably be selected from copolyesters of dicarboxylic acids (for example adipic acid, phthalic acid or terephthalic acid), diols (for example ethylene glycol or propylene glycol) and polydiols (for example polyethylene glycol or polypropylene glycol). The copolyester may also include monomeric units substituted with anionic groups, such as for example sulfonated isophthaloyl units. Examples of such materials include oligomeric esters produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”) and poly(ethyleneglycol) (“PEG”); partly- and fully-anionic-end-capped oligomeric esters such as oligomers from ethylene glycol (“EG”), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; nonionic-capped block polyester oligomeric compounds such as those produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate. Suitable polyesters can be obtained from Clariant under the trade name Texcare®.

Preferred polyesters for use in the invention include copolyesters formed by condensation of terephthalic acid ester and diol, preferably 1 ,2 propanediol, and further comprising an end cap formed from repeat units of alkylene oxide capped with an alkyl group. Examples of such materials have a structure corresponding to general formula (III): in which R 1 and R 2 independently of one another are X-(OC2H4)n-(OC3H6)m ; in which X is C1.4 alkyl and preferably methyl; n is a number from 12 to 120, preferably from 40 to 50; m is a number from 1 to 10, preferably from 1 to 7; and a is a number from 4 to 9.

Because they are averages, m, n and a are not necessarily whole numbers for the polymer in bulk.

Mixtures of any of the above-described materials may also be used.

The compositions described herein preferably comprise 0.005 to 10 wt.% film forming polymer, by weight of the composition, more preferably 0.01 to 5 wt.%, even more preferably 0.02 to 4 wt.% and most preferably 0.05 to 3 wt.%.

The compositions described herein preferably comprise a rheology modifier. Rheology modifiers are particularly preferred in compositions comprising microcapsules. Rheology modifiers may be inorganic or organic, polymeric or non polymeric. Non-limiting examples of suitable rheology modifiers include: pectine, alginate, arabinogalactan, carageenan, gellan gum, polysaccharides such as xanthum gum, guar gum, acrylates/acrylic polymers, water-swellable clays, fumed silicas, acrylate/aminoacrylate copolymers, salts and mixtures thereof.

Preferred rheology modifier for compositions comprising microcapsules herein include those selected from the group consisting of acrylate/acrylic polymers, gellan gum, fumed silicas, acrylate/aminoacrylate copolymers, water-swellable clays, polysaccharides such as xanthum gum and mixtures thereof. Most preferably the rheology modifier is selected from polysaccharides such as xanthum gum, acrylate/acrylic polymers, acrylate/aminoacrylate copolymers, and water-swellable clays. Most preferred rheology modifier are polysaccharides such as xanthum gum.

When present, a rheology modifier is preferably present in an amount of 0.001 to 10 wt.% percent, preferably from 0.005 to 5 wt.%, more preferably 0.01 to 3 wt.% of the composition.

The composition for use in the present invention preferably comprises preservatives. Preservatives are preferably present in an amount of 0.001 to 1 wt.% of the composition. More Preferably 0.005 to 0.5 wt. %, most preferably 0.01 to 0.1 wt.% of the composition.

Preservatives can include anti-microbial agents such as isothiazolinone-based chemicals (in particular isothiazol-3-one biocides) or glutaraldehyde-based products. Also suitable are preservatives such as organic acids, sorbates and benzoates. Examples of suitable preservatives include Benzisothiazoline, Cloro-methyl-isothiazol-3-one, Methyl-isothiazol-3-one and mixtures thereof. Suitable preservatives are commercially available as Kathon CG ex. Dow and Proxel ex Lonza.

The compositions for use in the present invention may contain further optional laundry ingredients. Such ingredients include pH buffering agents, perfume carriers, hydrotropes, polyelectrolytes, anti-shrinking agents, anti-oxidants, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, antifoams, colorants, pearlisers and/or opacifiers, natural oils/extracts, processing aids, e.g. electrolytes, hygiene agents, e.g. anti-bacterials and antifungals, thickeners, low levels of cationic surfactants such as quaternary ammonium compounds and skin benefit agents.

Preferably the liquid laundry composition is an aqueous composition. The viscosity of the composition is preferably 30 to 15000 mPa.s, more preferably 50 to 1000 mPa.s, most preferably 80 to 800 mPa.s. The viscosity measurement can be carried out at 25°C, using a 4cm diameter 2°cone and plate geometry on a DHR-2 rheometer ex. TA instruments. In detail, the measurement can be conducted using a TA-lnstruments DHR-2 rheometer with a 4cm diameter 2 degree angle cone and plate measuring system. The lower Peltier plate is used to control the temperature of the measurement to 25°C. The measurement protocol is a ‘flow curve’ where the applied shear stress is varied logarithmically from 0.01 Pa to 400 Pa with 10 measurement points per decade of stress. At each stress the shear strain rate is measured over the last 5 seconds of the 10 second period over which the stress is applied with the viscosity at that stress being calculated as the quotient of the shear stress and shear rate.

The composition as described herein may be manufactured simply by adding mixing the ingredients with stirring. If a rheology modifier is present, preferably it is pre-dispersed in water to form a homogenous mixture.

In use

The liquid laundry compositions for use in the present invention may be used to replace traditional fabric conditioner compositions or may be used in addition to a traditional fabric conditioner composition, i.e. , the compositions may be used by the consumer to supplement the benefits delivered by their traditional fabric conditioner.

The composition may be added to the laundry process in either the wash or the rinse phase of the laundry process. Preferably the composition is added during the rinse phase of the laundry process.

The compositions comprise 0 to 2 wt. % surfactant selected from cationic surfactant, anionic surfactant, or combinations thereof. Therefore, the composition alone does not deliver any detersive action, nor does it deliver fabric softening cationic surfactants. The compositions are intended for use either alone, or in combination with traditional laundry liquids (detergent or fabric conditioner) or powder. The compositions described herein maybe used as a replacement for a fabric conditioner.

Preferably 2-150 ml, more preferably a volume of 2-100 ml, even more preferably a volume of ml 2-75ml, most preferably 2-50ml of the composition is added to the laundry process. The liquid laundry compositions described herein provide improved fabric care, in particular improved hand of fabrics. Accordingly, there is provided a use of the liquid laundry composition to provide fabric care, wherein the composition is added to the rinse stage of the laundry process. Also provided is a use of the liquid laundry composition to provide fabric care to a laundered fabric. Alternatively this may be expressed as the use of the microcapsules as described herein in a liquid laundry composition as described herein to provides fabric care to a laundered fabric. Fabric care may be defined by various parameters, in particular fabric hand, softness and resilience. These are measures which decrease as a fabric is damaged. In other words fabric care may be considered the prevention of damage or the maintenance of fabric. Fabric hand is defined as the estimated quality of a fabric, evaluated when a consumer touches a fabric. Important components of fabric hand include smoothness, compressibility and elasticity of the textile sample. The compositions described herein may also provide improved softening and/or resilience to fabrics treated with the composition. Resilience is the ability of a fiber to spring back to its natural position after folding, creasing or deformation. An improvement in fabric hand, resilience or softening may be measured using a sensorial evaluation. Alternatively, machine measurements can be used. Suitable machines for measuring the relative hand value, resilience or softness are a PhabrOmeter® supplied by Nu Cybertek, Inc. An improvement in fabric hand can be measured using AATCC TM202-2012 (2020), Relative Hand Value of Textiles: Instrumental Method.

The following microcapsules as suitable for use in compositions of the present invention were used to assess the effects of the compositions described herein:

• Microcapsules 1 - Pea protein and sodium alginate mix and with salt crosslinking

• Microcapsules 2 - Pea protein and crosslinked with polyisocyanate (Poly[(phenyl isocyanate-co-formaldehyde])

Microcapsule 1 was prepared as follows: a 10% w/v solution of pea protein was prepared in demineralised water and the pH was adjusted to pH9 using a few drops of sodium carbonate solution. This was heated to 85 °C and mixed at 300RPM mixed on a tornado mixer for 2hrs. After 2hrs the pH was dropped to pH7 with a few drops of 2M HCI solution and 1.5g of sodium alginate was added.

This was further mixed at 300RPM for 90min until homogeneous and then was left overnight to cool down. Once cool the next day 22.5g of fragrance oil was added and mixed at 300RPM for 1 hr. The prepolymer mix was then added into a 80ml solution containing tween 80, calcium chloride and DI water at varying concentrations. The solution was homogenised to produce a suspension.

Table 1: Microcapsule 1 composition

Microcapsule 2 was prepared as follows: an oil phase was first prepared by mixing 23.2g of a model fragrance and 4.8g of caprylic/capric triglyceride, 0.38g of benzyl benzoate and an aromatic polyisocyanate 0.38g. In a separate beaker, an aqueous solution was obtained by mixing 1.182g of a pea protein isolate in 170g of water. The oil phase was then emulsified into the aqueous phase to form an oil-in-water emulsion using an ultra turrax mixer at a shear rate of 5000 Revolutions Per Minute (RPM). The oil-in-water emulsion was then cured at 55°C for 2 hours.

Table 2: Microcapsule 2 composition

Table 3: Example compositions:

The composition may be prepared by dispersing the xanthan gum in cold water. Adding the xanthan dispersion to hot water and mixing. Separately melting the non-ionic surfactant and fragrance oil together. Adding the non-ionic and fragrance melt to the xanthan and water. Finally adding the perfume microcapsules and cooling to room temperature.




 
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