AU9361098A

AU9361098A - Laundry treatment products for Spandex containing fabrics

Info

Publication number: AU9361098A
Application number: AU93610/98A
Authority: AU
Inventors: Christopher Francis Clements; Charles Laroche; Angus Peter Macmaster; Keith Douglas Perring
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 1997-10-10
Filing date: 1998-10-09
Publication date: 1999-05-03
Anticipated expiration: 2018-10-09
Also published as: DE69822189T2; PL339767A1; HUP0003663A2; EP1029032A1; AU731714B2; AR015180A1; ES2215320T3; WO1999019452A1; BR9812898A; CA2305529A1; JP2001520322A; PL189691B1; DE69822189D1; IN192710B; EP1029032B1; CN1281504A; CA2305529C; SK285260B6; SK5022000A3; HUP0003663A3

Description

WO 99/19452 PCT/GB98/03053 1 LAUNDRY TREATMENT PRODUCTS FOR SPANDEX CONTAINING FABRICS This invention relates to the treatment of textiles containing spandex fibres. At the present time, many garments are made 5 from fabric which contains a mixture of fibres, a proportion of which are elastic, so that the fabric has the ability to stretch and to recover from stretch. Spandex fibres are commonly used for this purpose. The term "Spandex" has been adopted as a 10 generic term by the United States Federal Trade Commission to denote a manufactured fibre in which the fibre-forming substance is a long chain synthetic polymer composed of at least 85% of a segmented polyurethane. A discussion of such fibres can be found 15 in "History of Spandex Elastomeric Fibres" by A.J. Ultee, which is a chapter starting at page 278 in Man Made Fibres: Their Origin and Development, edited by R.V. Seymour and R.S. Porter, Elsevier 1993. Spandex fibres are also referred to as "elastane" or 20 "elasthane" fibres. Another discussion of such fibres is found under the heading "Segmented Polyurethanes" at page 613 of Handbook of Textile Fibres by J. Gordon Cook, 5th Ed. Merrow Publishing Company 1984. Further 25 description of elastanes and their applications can be WO99/19452 PCT/GB98/03053 2 found in "Synthesefasern: Grundlagen, Technologie, Verarbeitung und Anwendung", B von Falkei (editor), Verlag Chemie (1981). Commercially available elastanes are well known, in particular as sold under the name 5 LYCRA®, a registered trade mark of DuPont de Nemours and Company. Patents relating to such fibres include US-A-5000899, US-A-5288779 and US-A-5362432. The deposition of perfume onto garments and other fabrics during laundering has been established 10 for many years. Perfume is incorporated into laundry products such as detergent compositions for fabric washing and rinse conditioners for softening the fabrics. Although the perfume serves to cover the 15 base odour of such a product and to give the unused product an attractive fragrance, it also deposits on the fabric. Certain perfumes have the ability to provide deodorant action against body odour, either when 20 directly applied to human skin, or when included in a laundry product. Such perfumes are described in EP-B 3172, US-A-4304679, US-A-4278658, US-A-4134838, US-A 4288341 and US-A-4289641, US-A-5482635 and US-A 5554588.

WO99/19452 PCT/GB98/03053 3 Summary of the Invention We have now found that a number of fragrance materials used in perfumery are able to deposit and then be retained better on spandex fibres than on a 5 number of other textile fibres. Therefore in one aspect the present invention provides a fabric treatment product which has a mixture of fragrance materials, for the treatment of garments containing spandex and other 10 fibres, preferably after wearing thereof, to deposit fragrance materials to a greater extent on the spandex fibres than on the other fibres. The invention may, in particular, be applied when the garment fabric was pretreated with perfume 15 prior to first wearing of the garment. Thus, use in accordance with the invention may be use of a fabric treatment product which contains the perfume composition to treat garments containing spandex fibres, the fabric of which garments was treated with 20 a perfume composition (which may be a preferentially deposited such composition) prior to first wearing, so that the said use of a fabric treatment product sustains a presence of fragrance materials on the garments. 25 In a related second aspect, the invention provides a method of treating and maintaining a WO99/19452 PCT/GB98/03053 4 garment containing spandex and other fibres, comprising contacting the fabric of the garment with a perfume composition which is a mixture of fragrance materials, so that fragrance materials are deposited 5 on the fabric and subsequently contacting the garment with a treatment product containing a perfume composition which is also a mixture of fragrance materials, to sustain a presence of deposited fragrance materials on the garment. 10 In significant forms of this invention, the perfume composition used to treat the garment (or the combination of fragrance materials deposited thereon) is a deodorant perfume, so that use in accordance with the invention will provide or sustain a deodorant 15 benefit on the garments. Detailed description The various aspects of this invention, preferred forms and materials useful therein will now be discussed in greater detail. 20 Textiles The garments to which this invention relates are made from fabric which includes spandex and other fibres. As mentioned earlier, this term "spandex" denotes a manufactured fibre in which the fibre WO99/19452 PCT/GB98/03053 5 forming substance is a long chain synthetic polymer compound composed of at least 85% of a segmented polyurethane. Thus the polymer which is spun into spandex 5 fibres is a copolymer incorporating urethane linkages. Generally the polymer contains so-called soft (i.e. lower melting) segments which may be polyalkylene ethers or polyesters and so-called hard (i.e. higher melting) segments which are portions derived from the 10 reaction of an isocyanate and a chain extender which is typically a diamine. The soft segments may be poly(tetramethylene)ethers, possibly containing substituted tetramethylene glycol residues as 15 described in US-A-5000899. Organic diisocyanates which may be used include conventional diisocyanates, such as diphenylmethane-4,4'-diisocyanate, also known as methylene-bis(4-phenylisocyanate) or "MDI", 2,4 tolylene diisocyanate, methylene-bis(4 20 cyclohexylisocyanate), isophorone diisocyanate, tetramethylene-p-xylylene diisocyanate, and the like. MDI is preferred. Chain extenders used in producing the hard segment of the fibres preferably include one or more 25 of ethylenediamine (EDA), 1,3-propylenediamine, 1,4 cyclohexanediamine, hydrogenated m-phenylenediamine WO99/19452 PCT/GB98/03053 6 (HPMD), 2-methylpentamethylene diamine (MPMD) and 1,2 propylene diamine. More preferably, the chain extender is one or more of ethylenediamine, 1,3 propylenediamine, and 1,4-cyclohexanediamine, 5 optionally mixed with HPMD, MPMD and/or 1,2 propylenediamine. Spandex fibres with poly(tetramethylene)ethers as the soft segments are marketed by DuPont de Nemours International S.A. under 10 the registered trade mark LYCRA® of DuPont de Nemours and Company. Spandex fibres are generally mixed with other fibres such as cotton, polyamide, wool, polyester and acrylics and made into yarn which is 15 then made into fabric. The content of spandex fibres is usually in a range from 0.5% by weight of the yarn or fabric up to 50%, more usually from 1% to 30% by weight of the yarn or fabric. A wide range of garments may contain spandex 20 fibres in the fabric, including active sports wear, intimate apparel, hosiery and a variety of ready to wear casual clothing. Fragrance materials We have found that a range of fragrance 25 materials deposit well on, or are retained well on, WO99/19452 PCT/GB98/03053 7 spandex fibres. Such materials include the following two categories: Category A hydroxylic materials which are alcohols, phenols 5 or salicylates, with an octanol/water partition coefficient (P) whose common logarithm (log 10 P) is 2.5 or greater, and a gas chromatographic Kovats index (as determined on polydimethylsiloxane as non-polar stationary phase) of at least 1050. 10 Category B esters, ethers, nitriles, ketones or aldehydes, with an octanol/water partition coefficient (P) whose common logarithm (log 10 P) is 2.5 or greater, and a gas chromatographic Kovats index (as 15 determined on polydimethylsiloxane as non-polar stationary phase) of at least 1300. The octanol-water partition coefficient (or its common logarithm 'logP') is well known in the literature as an indicator of hydrophobicity and water 20 solubility (see Hansch and Leo, Chemical Reviews, 71, 526 to 616, (1971); Hansch, Quinlan and Lawrence, J.Organic Chemistry, 33, 347 to 350 (1968). Where such values are not available in the literature they may be WO99/19452 PCT/GB98/03053 8 measured directly, or estimated approximately using mathematical algorithms. Software providing such estimations are available commercially, for example 'LogP' from Advanced Chemistry Design Inc. 5 A requirement for log 10 P of 2.5 or more calls for materials which are somewhat hydrophobic. Kovats indices are calculated from the retention time in a gas chromatographic measurement referenced to the retention time for alkanes [see Kovats, 10 Helv.Chim.Acta 41, 1915 (1958)]. Indices based on the use of a non-polar stationary phase have been used in the perfumery industry for some years as a descriptor relating to the molecular size and boiling point of ingredients. A review of Kovats indices in the perfume 15 industry is given by T Shibamoto in "Capillary Gas Chromatography in Essential Oil Analysis", P Sandra and C Bicchi (editors), Huethig (1987), pages 259-274. A common non-polar phase which is suitable is 100% dimethyl polysiloxane, as supplied for example under a 20 variety of tradenames such as HP-1 (Hewlett-Packard), CP Sil 5 CB (Chrompack), OV-1 (Ohio Valley) and Rtx-1 (Restek). Materials of low Kovats index tend to be volatile and are not retained well on many fibres. 25 We have found that when perfumery materials have partition coefficient as above and a relatively high WO99/19452 PCT/GB98/03053 9 value of Kovats index, deposition and retention on spandex tends to be greater than on other fibres. Preferably therefore, the perfume composition contains at least 50 wt %, better at least 70 or 80 wt % of 5 materials from the categories above. We have found that there is a particularly high enhancement of deposition and retention on spandex, compared to other fibres, with materials within the above categories and having a Kovats index of not more 10 than 1600. These sub-sets of categories A and B may be termed categories A' and B' Preferably therefore, the perfume composition contains at least 10 wt%, better at least 20 wt % or 25 wt % of such materials. In some preferred perfumes the amount of fragrance materials 15 from categories A' and B' is at least 40 wt % in total. Such fragrance materials are of mid-range volatility (i.e. intermediate between the volatile perfume materials used as "top-notes" and the 20 materials of low volatility which are customarily used as base notes in perfumes). These materials of mid range volatility are often not perceptible on other fabrics such as cotton, polyamide and polyester after washing and drying. 25 Category A includes alcohols of general formula ROH where the hydroxyl group may be primary, secondary WO99/19452 PCT/GB98/03053 10 or tertiary, and the R group is an alkyl or alkenyl group, optionally branched or substituted, cyclic or acyclic, such that ROH has partition coefficient and Kovats properties as defined above. Alcohols of Kovats 5 index 1050 to 1600 are typically monofunctional alkyl or arylalkyl alcohols with molecular weight falling within the range 150 to 230. Category A also includes phenols of general formula ArOH, where the Ar group denotes a benzene 10 ring which may be substituted with one or more alkyl or alkenyl groups, or with an ester grouping -CO 2 A, where A is a hydrocarbon radical, in which case the compound is a salicylate. ArOH has partition coefficient and Kovats index as defined above. 15 Typically, such phenols with Kovats index 1050 to 1600 are monohydroxylic phenols with molecular weight falling within the range 150 to 210. A sub-set of fragrance materials which are particularly preferred are those with a partition 20 coefficient of 1000 or more, i.e. log 10 P of 3 or more, and a Kovats parameter of 1100 up to 1600. Some examples of hydroxylic ingredients which fulfil the above criteria for category A' are listed as a table below. Materials which are in the 25 particularly preferred sub-set are marked with an asterisk. Semitrivial names are those used in standard WO99/19452 PCT/GB98/03053 11 texts known within the perfume industry, particularly: Common Fragrance and Flavor Materials by Bauer, Garbe and Surburg, VCH Publ., 2nd edition (1990), and Perfume and Flavour Materials, Steffen Arctander, 5 published in two volumes by the author (1969). Examples of fragrance materials in category A' 1-(2'-tert-butylcyclohexyloxy)-butan-2-ol* 3-methyl-5-(2',2',3'-trimethylcyclopent-3-enyl) pentan-2-ol* 10 4-methyl-3-decen-5-ol* amyl salicylate* 2-ethyl-4(2',2',3-trimethylcyclopent-3'-enyl)but-2-enol* (Bangalol, TM) borneol* 15 carvacrol* citronellol* 9-decenol* dihydroeugenol* dihydrolinalol* 20 dihydromyrcenol dihydroterpineol * eugenol geraniol* hydroxycitronellal* 25 isoamyl salicylate* isobutyl salicylate* isoeugenol* linalol menthol* 30 nerolidol* nerol* para tert-butyl cyclohexanol* WO99/19452 PCT/GB98/03053 12 phenoxanol* terpineol tetrahydrogeraniol* tetrahydrolinalol 5 tetrahydromyrcenol thymol* 2-methoxy-4-methylphenol (Ultravanil, TM) (4-isopropylcyclohexyl)-methanol* Some examples of fragrance materials which are in 10 category A but which have Kovats index above 1600 (so as to fall outside category A') are: patchouli alcohol farnesol benzyl salicylate 15 cyclohexyl salicylate and hexyl salicylate Category B is esters, ketones, aldehydes, nitriles or ethers which have an octanol-water partition coefficient whose common logarithm (log 10 P) 20 is at least 2.5, and a Kovats index of at least 1300 (non-polar phase). Ingredients of Category B are of general formula RX, where X may be in a primary, secondary or tertiary position, and is one of the following groups: -COA, 25 OA, -CO 2 A, -CN or -CHO. The groups R and A are WO99/19452 PCT/GB98/03053 13 hydrocarbon residues, cyclic or non-cyclic and optionally substituted. In some forms of this invention, category B excludes any material with a free hydroxy group, so that where a hydroxyl group is 5 present, the material should be considered only for Category A membership. Typically, the materials of Category B with Kovats index not exceeding 1600 (which may be called category B') are monofunctional compounds with molecular weights in the range 160 to 10 230. A sub-set of particularly preferred fragrance materials within category B' is those with a Kovats parameter falling within the range 1350 up to 1600, and possessing a molecular structure containing a 15 ring, such as phenyl or cycloalkyl. A number of fragrance materials which fulfil the above criteria for category B' are listed in the table below. Materials which are in the particularly preferred sub-set are marked with an asterisk. 20 Examples of fragrance materials in category B' l-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-l carbaldehyde* 1-(5',5'-dimethylcyclohexenyl)-pent-en-l-one* 2-heptyl cyclopentanone* 25 2-methyl-3-(4'-tert-butylphenyl)propanal 2-methylundecanal 2-undecenal WO99/19452 PCT/GB98/03053 14 2,2-dimethyl-3-(4'-ethylphenyl)-propanal 3-(4'-isopropylphenyl)-2-methylpropanal 4-methyl-4-phenylpent-2-yl acetate* allyl cyclohexyl propionate* 5 allyl cyclohexyloxyacetate* amyl benzoate* methyl ethyl ketone trimers (Azarbre, TM) benzophenone* 3-(4'-tert-butylphenyl)-propanal (Bourgeonal, TM) 10 caryophyllene* cis-jasmone* citral diethyl acetal citronellal diethyl acetal citronellyl acetate 15 phenylethyl butyl ether (Cressanther, TM) damascone, alpha-* damascone, beta-* damascone, delta-* decalactone, gamma-* 20 dihydro isojasmonate* dihydrojasmone* dihydroterpinyl acetate dimethyl anthranilate* diphenyl oxide* 25 diphenylmethane* dodecanal dodecen-2-al dodecane nitrile l-ethoxy-1-phenoxyethane (Efetaal, TM) 30 3-(l'-ethoxyethoxy)-3,7-dimethylocta-1l,6-diene (Elintaal Forte (TM) 4-(4'-methylpent-3'-enyl)-cyclohex-3-enal (Empetaal, TM) ethyl tricyclo[5.2.1.0-2,6-]decane-2-carboxylate* 1-(7-isopropyl-5-methylbicyclo[2.2.2]oct-5-en-2-yl)-1 35 ethanone* (Felvinone, TM) allyl tricyclodecenyl ether* (Fleuroxene, TM) tricyclodecenyl propanoate* (Florocyclene, TM) gamma-undecalactone* WO99/19452 PCT/GB98/03053 15 n-methyl-n-phenyl-2-methylbutanamide* (Gardamide, TM) tricyclodecenyl isobutyrate* (Gardocyclene, TM) geranyl acetate hexyl benzoate* 5 ionone alpha* ionone beta* isobutyl cinnamate* isobutyl quinoline* isoeugenyl acetate* 10 2,2,7,7-tetramethyltricycloundecan-5-one* (Isolongifolanone, TM) tricyclodecenyl acetate* (Jasmacyclene, TM) 2-hexylcyclopentanone (Jasmatone, TM) 4-acetoxy-3-pentyltetrahydropyran* (Jasmopyrane, TM) 15 ethyl 2-hexylacetoacetate (Jessate, TM) 8-isopropyl-6-methylbicyclo[2.2.2]oct-5-ene-2 carbaldehyde (Maceal, TM) methyl 4-isopropyl-l-methylbicyclo[2.2.2]oct-5-ene-2 carboxylate* 20 methyl cinnamate alpha iso methyl ionone* methyl naphthyl ketone* nerolin nonalactone gamma 25 nopyl acetate* para tert-butyl cyclohexyl acetate 4-isopropyl-l-methyl-2-[1'-propenyl]-benzene* (Pelargene,TM) phenoxyethyl isobutyrate* 30 phenylethyl isoamyl ether* phenylethyl isobutyrate* tricyclodecenyl pivalate* (Pivacyclene, TM) phenylethyl pivalate* (Pivarose, TM) phenylacetaldehyde hexylene glycol acetal* 35 2,4-dimethyl-4-phenyltetrahydrofuran (Rhubafuran, TM) rose acetone* terpinyl acetate WO99/19452 PCT/GB98/03053 16 4-isopropyl-l-methyl-2-[l'-propenyl]-benzene (Verdoracine, TM) yara* (4-isopropylcyclohexadienyl)ethyl formate 5 Examples of fragrance materials which lie within category B, but have Kovats index above 1600 and so are outside category B' are listed in the following table: Within category B but outside category B' 10 amyl cinnamate amyl cinnamic aldehyde amyl cinnamic aldehyde dimethyl acetal cinnamyl cinnamate cyclamen aldehyde 15 1,2,3,5,6,7,8,8a-octahydro-l,2,8,8-tetramethyl-2-acetyl naphthalene (iso E super, TM) cyclo-l,13-ethylenedioxytridecan-l,13-dione (ethylene brassylate) 20 cyclopentadecanolide (Exaltolide, TM) 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g] 2-benzopyran (Galaxolide, TM) geranyl phenyl acetate hexyl cinnamic aldehyde 25 6-acetyl-l-isopropyl-2,3,3,5-tetramethylindane (Traseolide, TM) 1,1l,2,4,4,7-hexamethyl-6-acetyl-1,2,3,4 tetrahydronaphthalene (Tonalid, TM) As indicated above, it is particularly preferred 30 to utilise a perfume composition which has deodorant WO99/19452 PCT/GB98/03053 17 properties. Preferably, the perfume is a deodorant perfume giving a Malodour Reduction Value on cotton of at least 0.25, preferably at least 0.5, in the Malodour Reduction Value test described below and 5 which is generally as given in EP-A-147191 and corresponding US-A-4663068. With such perfumes we have observed that there is an enhanced deodorant benefit when the fabrics incorporate spandex fibres, compared to conventional 10 fabrics such as cotton, polyamide and polyester without spandex. This can be measured using the Malodour Reduction Value test, modified by varying the test fabric instead of varying the perfume. The Malodour Reduction Value Test 15 In this test, the Malodour Reduction Value of a deodorant perfume is measured by assessing its effectiveness, when applied to fabric, in reducing body malodour when the fabric so treated is placed in contact with the axillae (armpits) of a panel of human 20 subjects, and held there for a standard period of time. From subsequent olfactory evaluation by trained assessors, a Malodour Reduction Value can be calculated so giving a measure of the effectiveness as a deodorant of the perfume under test. 25 Stage 1 is preparation of the perfume treated WO99/19452 PCT/GB98/03053 18 fabric. A fabric is selected for the test and cut into 20 cm x 20 cm squares. A control fabric is likewise cut into squares. Both fabrics are then washed in a front 5 loading drum-type washing machine with a standard unperfumed washing powder containing the following ingredients: Ingredient Parts by weight Sodium dodecylbenzene sulphonate 9.0 10 Ci 3

-

1 alcohol 7EO 4.0 Sodium tripolyphosphate 33.0 Alkaline sodium silicate 6.0 Sodium carboxymethyl cellulose 1.0 Magnesium silicate 1.0 15 Ethylenediamine tetraacetic acid 0.2 Sodium sulphate 15.0 Water 10.8 The washed pieces of fabric are then rinsed with cold water and finally dried. The fabric squares so 20 obtained represent "untreated" fabric, that is fabric devoid of perfume, other deodorant materials, dressing and other water-soluble substances that subsequently might adversely affect the Malodour Reduction Value Test. 25 The untreated pieces of fabric are divided into two batches, one of which may receive no further WO99/19452 PCT/GB98/03053 19 washing treatment and then represents the control fabric in the test. The other batch of fabric pieces is re-washed in the washing machine with the same standard fabric washing powder to which has been added 5 0.2% by weight of the perfume under test. The perfume treated pieces of fabric are then rinsed with cold water and dried again. The fabric squares so obtained represent "test" fabric, that is fabric onto which the test perfume has been delivered. 10 When this test is used to assess the deodorant effectiveness of a perfume composition, the control and test fabrics are the same, suitably 100% cotton shirt fabric and the "untreated" fabric serves as control without further washing. However, the test can 15 be used to assess other effects, notably to test deposition on different cloths, the test fabric can differ from the control fabric, and both may be washed in the same way with the perfumed washing powder. Stage 2 is the carrying out of the test. A team 20 of three Caucasian female assessors of age within the range of 20 years to 40 years is selected for olfactory evaluation on the basis that each is able to rank correctly the odour levels of the series of standard aqueous solutions of isovaleric acid listed 25 below, and each is able to assign a numerical score, corresponding to the odour intensity of one of these WO99/19452 PCT/GB98/03053 20 solutions, to the body malodour of a shirt insert after has been worn in the axillary region by a male subject for a standard period of time. A panel of 40 human subjects for use in the test 5 is assembled from Caucasian male subjects of age within the range of from 20 to 55 years. By screening, subjects are chosen who develop axillary body malodour that is not unusually strong and who do not develop a stronger body malodour in one axilla compared with the 10 other. Subjects who develop unusually strong body malodour, for example due to a diet including curry or garlic, are not selected for the panel. For two weeks before the start of the test, the panel subjects are assigned an unperfumed, non 15 deodorant soap bar for exclusive use when washing and are denied the use of any other type of deodorant or antiperspirant. At the end of this period, the 40 subjects are randomly divided into two groups of 20. The "test" and "control" fabric pieces are then 20 tacked into 40 clean cotton or polyester cotton shirts in the underarm region in such a manner that in 20 shirts, the control fabric pieces are attached inside the left underarm region, and the test fabric pieces are attached in the right underarm region. For the 25 remaining 20 shirts, the placing of control and test WO99/19452 PCT/GB98/03053 21 pieces of fabric is reversed. The shirts carrying the tacked-in fabric inserts are then worn by the 40 panel members for a period of 5 hours, during which time each panellist performs his 5 normal work function without unnecessary exercise. After this five hour period, the shirts are removed and the inserts detached and placed in polyethylene pouches prior to assessment by the trained panel of assessors. 10 The malodour intensity of each fabric insert is evaluated by all three assessors who, operating without knowledge of which inserts are "test" and which are "control" and, without knowing the scores assigned by their fellow assessors, sniff each fabric 15 piece and assign to it a score corresponding to the strength of the odour on a scale from 0 to 5, with 0 representing no odour and 5 representing very strong odour. Standard aqueous solutions of isovaleric acid 20 which correspond to each of the scores 1, 2, 3, 4 and 5 are provided for reference to assist the assessors in the malodour evaluation. These are shown below: Score Odour level Concentration of aqueous isovaleric acid (ml/l) 0 No odour 0 WO 99/19452 PCT/GB98/03053 22 1 Slight 0.013 2 Definite 0.053 3 Moderate 0.22 4 Strong 0.87 5 5 Very strong 3.57 The scores recorded by each assessor for each fabric piece are averaged. The average score of the "test" fabric pieces is deducted from the average 10 score of the "untreated" control fabric pieces to give a Malodour Reduction Value. As a check that the selection of panel subjects is satisfactory for operation of the test, the average score with untreated fabric pieces should be between 15 2.5 and 3.0. Preferred deodorant perfumes are those which have a Malodour Reduction Value of at least 0.50, or 0.70, or 1.00. The higher the minimum value, the more effective is the perfume as a deodorant as recorded by 20 the assessors in the Malodour Reduction Value Test. It has also been noted that consumers, who are not trained assessors, can detect by self-assessment a noticeable reduction in malodour on soiled fabric such as shirts and underclothes where the Malodour 25 Reduction Value is at least 0.30, so the higher the Malodour Reduction Value above this figure, the more noticeable is the deodorant effect.

WO99/19452 PCT/GB98/03053 23 Selection of a combination of fragrance materials to give a deodorant effect is explained in patents such as US-A-430679 referred to earlier. Further systems of selection are given in US-A-5482635 and US 5 A-5554588 also mentioned above. Such selections can be carried out using materials with preferred values of partition coefficient and Kovats index as discussed above. US-A-5501805 describes perfume compositions made 10 from a combination of fragrance materials, where the composition is a deodorant perfume yet has a relatively low odour. Such "low-odour" deodorant perfumes may be used in the present invention. Fabric treatment products 15 A fabric treatment product, used as a vehicle to deposit perfume on garments after they have been worn may be any of: a detergent composition for fabric washing, a pretreatment composition for application to 20 selected areas of a garment prior to washing, a pretreatment composition used in the soaking of WO99/19452 PCT/GB98/03053 24 entire garments prior to washing, a rinse conditioner for softening washed fabrics during a rinsing step, an additive composition for use jointly with any 5 of the above, a fabric conditioning article intended to be placed with fabrics during drying, or a spray for application directly to dry garments. Such products can take a variety of forms 10 including powders, bars, sticks, tablets, mousses, gels, liquids, sprays, and also fabric conditioning sheets to be placed with fabrics in a tumble dryer. The amount of perfume in such products may lie in a range from 0.1% to 10% by weight of thereof. The 15 incorporation of perfume into products of these types is known, and existing techniques may be used for incorporating perfume for this invention. It may be possible to incorporate perfume directly, but another possibility is to absorb the perfume on a carrier 20 material and then admix the perfume carrier mixture into the fabric treatment product. This approach may notably be used with a solid fabric treatment product WO99/19452 PCT/GB98/03053 25 and on inert particulate carrier. Fabric or laundry treatment products also comprise perfume carrier products intended to be placed near or between garments, such as in linen 5 cupboards and drawers, to deposit the perfume on the garments by diffusion through the air or by direct contact with the garments. Such perfume carrier products may comprise up to 40% by weight of perfume. They preferably comprise a solid carrier material, 10 e.g. in the form of a powder, beads or a sheet or block of a porous material, which is (are) impregnated or loaded with the perfume composition. A detergent composition to be perfumed with a perfume composition according to this invention will 15 normally contain a detersive surfactant in an amount from 2% to 50%, preferably 5% to 40% by weight of the composition, and a detergency builder in an amount from 5% to 80% by weight of the composition. The balance of the composition, if any, may include 20 various ingredients known for inclusion in fabric washing detergents, including bleaching materials. Surfactants may be one or more soap or non-soap anionic, nonionic, cationic, amphoteric or zwitterionic surfactants, or combinations of these. 25 Preferred surfactants which can be used are soaps and synthetic non-soap anionic and nonionic compounds.

WO99/19452 PCT/GB98/03053 26 Mixtures of surfactants, for example mixed anionic or mixed anionic and nonionic compounds, are frequently used in detergent compositions. Detergency builders are materials which function 5 to soften hard water by solubilisation or other removal of calcium and to a lesser extent magnesium salts responsible for water hardness. The commonest water soluble inorganic builder is sodium tripolyphosphate. A further water soluble inorganic 10 builder compound is sodium carbonate which is generally used in conjunction with a seed crystal to accelerate the precipitation of calcium carbonate. Common insoluble inorganic detergency builders are zeolites and layered silicates. Organic detergency 15 builders such as sodium citrate and polyacrylate can also be used. Some detergent compositions, usually liquids, are formulated to contain from 5 wt % to 50 wt % surfactant but little or no detergency builder. 20 Other ingredients which are customarily included in a detergent composition, although not necessarily all together, include alkaline silicate, peroxygen or chlorine bleaches, soil release agents, heavy metal sequestrants, anti-redeposition agents such as sodium 25 carboxymethyl cellulose, enzymes, enzyme stabilisers, fabric softening agents including softening clays, WO99/19452 PCT/GB98/03053 27 fluorescent brighteners, antifoam agents or conversely foam boosters and filler such as sodium sulphate. Pretreatment compositions for soaking of soiled fabrics prior to the main washing step may contain 5 5 wt % to 80 wt % by weight detergency builder with little or no surfactant. Such compositions frequently include enzymes. The amount of perfume in a detergent composition or a presoak composition is likely to lie in a range 10 from 0.1% to 2% by weight of the composition. A fabric conditioning composition may contain from 1% to 40% by weight of a fabric conditioning agent which may be a fabric softening agent, but may contain higher levels in a very concentrated product. 15 Fabric softening agents are frequently nonionic or cationic organic compounds incorporating at least one alkyl, alkenyl or acyl group of 8 or more carbon atoms. These include, but are not limited to: (i) quaternary ammonium and imidazolinium 20 compounds and corresponding tertiary amines and imidazolines incorporating at least one, preferably two, C8 to C30 aklyl or alkenyl groups; also including alkyl groups containing, ether, ester, carbonate or amide 25 linkages, ethoxylated derivatives and WO99/19452 PCT/GB98/03053 28 analogues of such compounds and also including compounds with more than one tertiary or quaternary nitrogen atom, (ii) aliphatic alcohols, esters, amines or 5 carboxylic acids incorporating a C8 to C30 alkyl, alkenyl or acyl group, including esters of sorbitan and of polyhydric alcohols, (iii) silicones, mineral oils and polyols such as 10 polyethylene glycol. A number of fabric conditioning compounds are set out in US-A-4137180, and EP-A-239910. Fabric conditioning compositions for addition to a rinse liquid are frequently in the form 15 of aqueous dispersions of the conditioning agent. They can also be made in the form of powders. The amount of perfume in such conditioning liquids and powders is usually 0.1% to 2% by weight. Preferred levels can vary depending on the 20 concentration of softening agent and requirements of the market. The amount of perfume in very concentrated fabric conditioners may lie in the broader range 0.1% WO99/19452 PCT/GB98/03053 29 to 10% by weight, preferably 2% to 8% by weight. A fabric conditioning sheet is intended to be placed with damp, rinsed, laundry in a tumble dryer. Such a product contains a fabric conditioner, 5 which may be a nonionic compound as mentioned above, soap and/or fatty acide, and which melts at temperatures encountered in a tumble dryer. This is carried on a porous sheet. Silicone oil may be included. The amount of perfume incorporated in such 10 a product is usually from 2% to 10% of the product and frequently from 2% or 4% to 7% or 8% by weight of the product. Another form of product for the treatment of fabrics is a carrier liquid containing perfume and 15 packaged in an applicator which delivers the composition as a spray. Such a spray may be marketed as a "refreshing spray" for garments. In such a product, the content of perfume will generally lie in a range from 0.1% to 10% by weight of the liquid 20 composition. This invention may be utilised to sustain a presence of perfume on garments whose fabric was treated with perfume during the manufacturing process, before the fabric is first worn. Such pretreatment 25 with perfume may be carried out as treatment of yarn which is later made into fabric, or in the "finishing" WO99/19452 PCT/GB98/03053 30 of new fabric in the form of a web or lengths from a web which have not yet been made into garments, or possibly garments which have been made but not yet been worn. That perfume have been a preferentially 5 deposited composition of the invention. Finishing is a step in the processing of fabrics to improve hand or surface appearance of fabric. The fabric will typically be treated with an aqueous treatment liquor containing fabric softener or 10 other material to deposit at a level of up to 3% by weight of the fabric. Perfume may be included in the liquor to deposit at a level of 0.001% to 1% by weight of the fabric. Preferably the treatment with a perfume 15 composition is carried out while treating with other material in a conventional process step, especially a wet stage in which the yarn or fabric is treated with a finishing agent to improve its hand or appearance. The materials which may be applied to fabric 20 in a conventional finishing treatment include resins to confer stiffness, fabric stability or permanent press, fabric softeners, flame retardants, fabric brighteners, anti-snag agents, materials to confer soil or stain resistance and water repellants. 25 Techniques which are conventionally used to apply such materials are padding and exhaustion, both WO99/19452 PCT/GB98/03053 31 well known in the technology of textile manufacture. Example 1 This experiment demonstrates perfume deposition on spandex fibres. A mixture of perfume 5 ingredients was prepared and added to an unperfumed, but otherwise conventional, laundry detergent powder, to provide a perfume concentration of 0.5% by weight. The perfumed powder was used to wash test cloths which had not previously been treated with any 10 perfume. These were either all cotton, or 95% cotton with 5% spandex. After washing, the cloths were rinsed and then line dried overnight. The perfume was extracted from the dry cloths with organic solvent, and the content of the 15 perfume ingredients in the solvent extracts was determined by gas chromatography. If the concentration of an ingredient extracted from the spandex containing cloth was greater than from the all-cotton cloth by a factor of 5 to 20, the result was coded as a medium 20 enhancement(M). If the concentration was greater by 20 or more, it was coded high(H) and if less than 5 or not measurable, it was coded(L). The results obtained were as follows: WO99/19452 PCT/GB98/03053 32 Ingredient K* logP* Enhancement Category * Boisambrene Forte 1714 5.5 M B benzyl acetone 1206 2.0 M citronellol 1209 3.6 H A' 2,6-dimethyl-heptan 5 2-ol 975 2.9 L jasmacyclene 1394 2.9 H B' methyl salicylate 1167 2.3 L 2-phenylethanol 1087 1.4 L terpinyl acetate 1331 4.0 H B' 10 tetrahydrogeraniol 1180 3.6 H A' tetrahydrolinalol 1083 3.5 H A' Tonalid 1840 6.4 M B yara 1416 3.2 H B' * Measured on OV-1 polydimethylsiloxane (Ohio 15 Valley) as stationary phase using capillary gc ** Measured or estimated using 'logP' software from ACD Inc. Example 2 Two perfume compositions contained perfume 20 ingredients in the specified categories, as follows: Perfume Category A Category B within within A within within B A' but not A' B' but not B' A 35.1% 4.5% 46.6% 5.0% B 41.8% 0 43.8% 7.5% 25 C 27.6% 4.0% 29.0% 21.2% WO99/19452 PCT/GB98/03053 33 These were used in the procedure of the Malodour Reduction Value test, as above, using test cloths which were 95% cotton 5% spandex. For the control, unperfumed washing powder was used to wash all-cotton test cloths. 5 The following results were obtained: Perfume A Perfume B Perfume C Average panel 1.04 1.29 1.57 score: Control panel 2.46 2.46 2.46 score: 10 Malodour Reduction 1.42 1.17 0.89 Value Malodour Reduction 57.7% 47.4% 36.1% Value as % of control score 15

Claims

1. A fabric treatment product which includes a perfume composition which is a mixture of fragrance materials which deposits preferentially on spandex fibres. 5

2. A fabric treatment product according to claim 1, which is a laundry treatment product.

3. A fabric treatment product according to claim 2 which is selected from detergent compositions, presoak compositions, rinse conditioners and fabric softening 10 sheets.

4. A fabric treatment product according to claim 3 which is a detergent composition containing a detersive surfactant in an amount from 2% to 50% by weight of the composition, and a detergency builder in an amount from 15 5% to 80% by weight of the composition.

5. A fabric treatment product according to claim 1 formulated as a spray.

6. A fabric treatment product according to claim 1 formulated as a solid carrier material impregnated with 20 the perfume composition. WO99/19452 PCT/GB98/03053 35

7. A fabric treatment product according to any one of the preceding claims wherein the perfume composition contains at least 50% by weight of the perfume composition of fragrance materials selected from: 5 Category A) hydroxylic materials which are alcohols, phenols or salicylates, with an octanol/water partition coefficient (P) whose common logarithm (log 10 P) is 2.5 or greater, and a gas chromatographic Kovats index (as determined on polydimethylsiloxane as non-polar 10 stationary phase) of at least 1050, and Category B) esters, ethers, nitriles, ketones or aldehydes, with an octanol/water partition coefficient (P) whose common logarithm (log 1 ,P) is 2.5 or greater, and a gas chromatographic Kovats index (as determined on 15 polydimethylsiloxane as non-polar stationary phase) of at least 1300.

8. A fabric treatment product according to any one of the preceding claims wherein the perfume composition contains at least 10% by weight of the perfume 20 composition, of fragrance materials selected from: Category A') hydroxylic materials which are alcohols, phenols or salicylates, with an octanol/water partition coefficient (P) whose common logarithm (log 10 P) is 2.5 or 25 greater, and a gas chromatographic Kovats index (as WO99/19452 PCT/GB98/03053 36 determined on polydimethylsiloxane as non-polar stationary phase) lying within the range 1050 to 1600, and Category B') esters, ethers, nitriles, ketones or 5 aldehydes, with an octanol/water partition coefficient (P) whose common logarithm (log 10 P) is 2.5 or greater, and a gas chromatographic Kovats index (as determined on polydimethylsiloxane as non-polar stationary phase) lying within the range 1300 to 1600. 10

9. A method of treating a garment containing spandex and other fibres which comprises contacting the garment with fabric treatment product according to any one of the preceding claims.

10. A method according to claim 9 for sustaining a 15 presence of deposited fragrance materials on the garment, wherein the garment is one which had in a previous treatment been contacted with a perfume composition as defined in any one of claims 1 to 8.