Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0063—Photo- activating compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/168—Organometallic compounds or orgometallic complexes
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3942—Inorganic per-compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/40—Dyes ; Pigments
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/40—Dyes ; Pigments
  • C11D3/42—Brightening agents ; Blueing agents

Definitions

• the present invention concerns improvements relating to malodour and particularly to the in-situ generation of perfume components from sebum by laundry treatment compositions.
• Sebum is a complex mixture of triglycerides (57%) with minor amounts of mono- and di-glycerides, wax esters (26%), squalene (12%), sterol esters (3%) and sterols (1.5%), (all figures being indicative only).
• the transfer of sebum onto the skin surface from the sebaceous glands is a continuous process. Subsequent transfer onto the fabric is mainly through fabric contact with the sebum on the skin by mechanical contact. The amount of body sebum transferred to a shirt in the course of a single day varies between 2 to 8wt% (on cloth) for different individuals and generally is closer to 2%.
• the physio-chemical effects of sebum on textile yellowing and dinginess and the detergency of sebum have been thoroughly studied by Obendorf et al (JAOCS, 71(1), 17-30, 1994 ).
• This auto-oxidation of unsaturated oily soils is associated with, (1) undesirable odours on garments, (2) difficulty in removal of oily soils if larger molecules or polymers form in the auto-oxidation reactions, (3) hydroperoxides and some of their breakdown products cause polymerisation of protein soils in mixed soil systems leading to coloured insoluble complexes, and, as mentioned above, (4) changes in fabric appearance.
• Another less known source of undesirable odorous originates from the action of bacteria on sebum, acting here as a malodour precursor. Poorly deterged sebum or built-up sebum acts as sink for malodours formed on the skin or in the wash and this can impact significantly on the intensity of 'post-wash' malodour build up.
• US2010/0216687 discloses compositions comprising unsaturated fatty chains having reduced or eliminated base off-odour with the incorporation of a photobleach.
• US2010/0216679 discloses fabric conditioner compositions comprising a photobleach, a quaternary ammonium fabric conditioner and a perfume. Freshness and perfume longevity of laundered articles are improved by use of the composition.
• US 2007/0087953 discloses cleaning compositions comprising a photocatalytic material, a sensitiser which may be a photobleach, and a surfactant.
• WO 2005/003277 discloses bleaching compositions comprising a photo-active red dye, a blue dye, bleaching species and further carriers and adjunct materials.
• a process for refreshing cloth which comprises the steps of:
• photo-bleach is any chemical species which forms a reactive bleaching species on exposure to sunlight, and preferably is not permanently consumed in the reaction. Mixtures of photo-bleaches can be used.
• oxidation of sebum by photo-bleach appears to reduce the production of a rancid, oily "off' odour.
• oleic acid oxidises in the presence of photo-bleach to produce nonanal (described as fruity), decanal (waxy orange) and 2tr-decenal (orange peel) and squalene oxidises to produce sweet smells resembling caramel and honey.
• the odour of several of the linear aldehydes is described in further detail below.
• Nonanal and the other C 9 aldehydes are believed to produce a particularly strong impression of freshness which can be compared to that obtained by clean cotton which has been sun-dried. This marked benefit is not obtained when the sebum is removed completely.
• the preferred level of sebum left on the cloth at the end of the wash is between 0.004g sebum per g of fabric to 0.030g/g.
• Levels of photo-bleach used in compositions for use in the method of the invention are typically in the range 0.001-0.2%wt.
• Some of the photo-bleaches impart colour to the fabric.
• blue or violet shading dyes are used in combination with the photo-bleaches.
• Shading dyes and bleaches are quite distinct in their mode of operation to achieve whiteness. Bleaches function by destroying colour, dyes by adding colour which counters the perception of yellowness.
• photo-bleach as envisaged in embodiments of the present invention, and in particular the combination with shading-dye enables the formulator to get a whiteness and freshness improvement which can enhance the overall performance of a laundry washing composition or which can be used, at relatively low cost, to restore the performance of a composition from which relatively expensive components, such as peroxide bleach, surfactant and builder have been removed in part or in total (such that sebum is not fully removed).
• a further advantage of using the photo-bleach and residual sebum to restore freshness instead of using other components to completely remove the sebum is that the photo-bleach based system is notably less bulky that the other components and an effective product can be made with a much lower mass. This brings benefits in terms of shelf-size, transportation and packaging.
• the present invention is of particular benefit when the wash is carried out at a temperature of less that 30 Celsius as under these conditions sebum removal is particularly difficult. Moreover, while the benefit of the invention has been described in relation to obtaining fabrics which are fresh-smelling before they are worn, it is apparent that the photo-bleach will also remain active as regards any new sebum which become deposited on the cloth during further use.
• a laundry treatment composition for fabrics which comprises:
• hydroperoxide intermediates Whilst, the formation of the hydroperoxide intermediates is believed to be relatively rapid in the presence of a photo-bleach (which are generally catalytic in function as explained below), the hydroperoxide intermediates are believed to be relatively stable, and extended periods of time is required to break-down these intermediates to the odiferous decomposition products. This breakdown is advantageously accelerated by the further catalyst.
• Transition metal bleach catalysts are suitable further catalytic agents for use in either the method or the composition of the present invention.
• the transition metal bleach catalyst typically comprises a transition metal ion, preferably selected from transition metal selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(l), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV), more preferably Mn(II), Mn(III), Mn(IV), Fe(II), Fe(lll), Cr(II), Cr(III), Cr(IV), Cr(V), and Cr
• the further catalytic agent may be an enzyme
• PB Singlet oxygen photo-bleaches
• the photo-bleach molecule absorbs light and attains an excited state, PB*.
• This electronically excited state is quenched by triplet oxygen, 3 O 2 , in the surroundings to form singlet 1 O 2 .
• Singlet oxygen is a highly reactive bleach.
• Suitable singlet-oxygen photo-bleaches may be selected from, water soluble phthalocyanine compounds, particularly metallated phthalocyanine compounds where the metal is Zn or Al-Z1 where Z1 is a halide, sulphate, nitrate, carboxylate, alkanolate or hydroxyl ion.
• the phthalocyanin has 1-4 SO 3 X groups covalently bonded to it where X is an alkali metal or ammonium ion.
• X alkali metal or ammonium ion
• Tinolux BMC anionic 15%, a 20/80 Al/Zn sulphonated tetrabenzo tetraazaporphine - available from Ciba
• Tinolux LBS anionic:15%, a 20/80 Al/Zn sulphonated tetrabenzo tetraazaporphine with 10% 6 Caprolactam, also ex. Ciba).
• Xanthene type dyes are also preferred, particularly based on the structure: where the dye may be substituted by halogens and other elements/groups. Particularly preferred examples are Food Red 14 (Acid Red 51), Rose Bengal, Phloxin B and Eosin Y.
• Quantum yields for photosensitized formation of singlet oxygen may be found in J.Phys.Chem.Ref. Data 1993, vol 22, no1 pp113-262 . It is preferred if the quantum yield for singlet oxygen formation measured in an organic solvent or D20 is greater than 0.05, more preferably greater than 0.1.
• the photo-bleach exhibits a peak in its activity when illuminated with light of a wavelength less than 700 nm.
• this enables the benefit of the invention to be obtained when drying articles indoors under fluorescent light. While better results are obtained with direct sunlight, quite adequate benefits can be obtained under fluorescent lighting.
• the singlet oxygen photo-bleaches generally impart some colour to the fabric.
• blue or violet shading dyes are used in combination with the shading dyes as described in WO2005/003274 (Unilever) and WO2005/003277 (Unilever).
• Particularly preferred shading dyes are bis azo direct dyes of the direct violet 9, 35 and 99 type and acid azine dyes such as acid violet 50 and acid blue 98.
• an optional shading dye can be used to counteract the tendency of the photo-bleach to move the hue of fabrics away from white.
• Preferred dyes are violet or blue. Suitable and preferred classes of dyes are discussed below.
• Direct dyes are the class of water soluble dyes which have a affinity for fibres and are taken up directly. Direct violet and direct blue dyes are preferred.
• the dye are bis -azo or tris -azo dyes are used.
• the direct dye is a direct violet of the following structures: or wherein:
• Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99.
• Bis-azo copper containing dyes such as direct violet 66 may be used.
• the benzidene based dyes are less preferred.
• the direct dye is present at 0.00001 wt% to 0.0010 wt% of the formulation.
• the direct dye may be covalently linked to the photo-bleach, for example as described in WO2006/024612 .
• Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.
• non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.
• the acid dye is present at 0.0005 wt% to 0.01 wt% of the formulation.
• the composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores.
• Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
• Preferred dyes include solvent violet 13, disperse violet 27, disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
• the hydrophobic dye is present at 0.0001 wt% to 0.005 wt% of the formulation.
• Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International.
• Preferred examples include triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141.
• Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.
• the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species.
• Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.
• Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue 96.
• Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces.
• Particularly preferred dyes are: direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 99, acid blue 98, acid violet 50, acid blue 59, acid violet 17, acid black 1, acid blue 29, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63, disperse violet 77 and mixtures thereof.
• composition for use in a method of the present invention comprises:
• composition therefore preferably further comprises a fluorescent agent (optical brightener).
• Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
• the total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %.
• Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
• Di-styryl biphenyl compounds e.g. Tinopal (Trade Mark) CBS-X
• Di-amine stilbene di-sulphonic acid compounds e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH
• Pyrazoline compounds e.g. Blankophor SN.
• Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]trazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.
• a shading dye in combination with a fluorescer in order to reduce yellowing due to chemical changes in adsorbed fluorescer.
• the further catalytic agent is a complex. It is not, therefore, molecular titanium oxide.
• the catalytic agent is preferably a complex comprising a metal ion and at least one ligand.
• the ligands may be organic or inorganic, preferably organic.
• the complex preferably comprises at least one organic ligand.
• Preferred organic ligands are nitrogen donating species.
• Preferred nitrogen donating ligands are bispidons, N4py type and TACN-Nx, most preferably bispidons.
• Preferred inorganic ligands are H 2 O, ROH, NR 3 , RCN, OH, OOH, RS', RCOO - RO', OCN - , SCN - , N 3 - , CN - , F - , Cl - , Br - , I - , O 2- , NO 3 - , NO 2 - , SO 4 2- , SO 3 2- , PO 4 3- or aromatic N donors such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles with R being H, optionally substituted alkyl or optionally substituted aryl.
• the preferred transition metal catalyst or precursor thereof is formed from or provided by a tridentate, tetradentate, pentadentate or hexadentate nitrogen donor ligand.
• the transition metal catalyst is preferably provided as a preformed transition metal catalyst.
• the ligand is added to sequester adventitious transition metals or transition metals salts are added.
• the addition of a particular transition metal salt, with respect to the transition metal is preferably employed.
• the tridentate, tetradentate, pentadentate or hexadentate nitrogen donor ligand may be built up within any organic structure which will support coordinating nitrogen atoms.
• Preferred metal ions include iron and manganese.
• the iron ion is selected from Fe(II) and Fe(III) and the manganese ion is selected from Mn(II), Mn(III), and Mn (IV).
• the ligand is present in one or more of the forms: [MnLCl 2 ]; [FeLCl 2 ]; [FeLCl]Cl; [FeL(H 2 O)](PF 6 ) 2 ; [FeL]Cl 2 , [FeLCl]PF 6 and [FeL(H 2 O)](BF 4 ) 2 .
• water soluble counter ions conferring increasing solubility, say over PF 6 , are also preferred.
• the length of any alkyl chain is preferably Cl to C8-alkyl chain and preferably linear. If unspecified the aryl group is a phenyl group.
• the bispidon class are preferably in the form of an iron transition metal catalyst.
• the bispidon ligand is preferably of the form: wherein each R is independently selected from: hydrogen, F, Cl, Br, hydroxyl, Cl-C4-alkylO-, -NH-CO-H, -NH-CO-C1-C4-alkyl, -NH2, -NH-C1-C4-alkyl, and C1-C4-alkyl;
• R1 and R2 are independently selected from:
• R3 R4 and selected from -C(O)-O-CH3, -C(O)-O-CH2CH3, -C(O)-O-CH2C6H5 and CH2OH.
• heteroatom capable of coordinating to a transition metal is pyridin-2-ylmethyl optionally substituted by -CO-C4-alkyl.
• R1 and R2 are CH3, -C2H5, -C3H7, benzyl, -C4H9, - C6H13, -C8H17, -C12H25, and -C18H37 and pyridin-2-yl.
• a preferred class of bispidon is one in which at least one of R1 or R2 is pyridin-2-ylmethyl or benzyl, preferably pyridin-2-ylmethyl.
• a preferred bispidon is dimethyl 2,4-di-(2-pyridyl) -3-methyl-7-(pyridin-2-ylmethyl)-3,7-diaza-bicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (N2py3o-C1) and the iron complex thereof FeN2py3o-C1 which was prepared as described in WO02/48301 .
• methyl group (C1) at the 3 position have longer alkyl chains, namely isobutyl, (n-hexyl) C6, (n-octyl) C8, (n-dodecyl) C12, (n-tetradecyl) C14, (n-octadecyl) C18, which were prepared in an analogous manner.
• Preferred tetradentate bispidons are also illustrated in WO00/60045 and preferred pentadentate bispidons are illustrated in WO02/48301 and WO03/104379 .
• the N4py are preferably in the form of an iron transition metal catalyst.
• N4py type ligands are preferably of the form:
• R1 represents pyridin-2-yl or R2 represents pyridin-2-yl-methyl.
• R2 or R1 represents 2-amino-ethyl, 2-(N-(m)ethyl)amino-ethyl or 2-(N,N-di(m)ethyl)amino-ethyl.
• R5 preferably represents 3-methyl pyridin-2-yl.
• R3 preferably represents hydrogen, benzyl or methyl.
• the preferred ligands are N4Py (i.e. N, N-bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine) which is disclosed in WO95/34628 and MeN4py (i.e. N,N-bis(pyridin-2-yl-methyl-1,1-bis(pyridin-2-yl)-1-aminoethane, as disclosed in EP0909809 .
• the TACN-Nx are preferably in the form of an iron transition metal catalyst.
• the ligands possess the basic 1,4,7-triazacyclononane structure but have one or more pendent nitrogen groups that complex with the transition metal to provide a tetradentate, pentadentate or hexadentate ligand.
• the basic 1,4,7-triazacyclononane structure has two pendent nitrogen groups that complex with the transition metal (TACN-N2).
• the TACN-Nx is preferably of the form: wherein each R20 is selected from: an alkyl, cycloalkyl, heterocycloalkyl, heteroaryl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N+(R21)3 , wherein R21 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether, alkenyl ether, and -CY2-R22, in which Y is independently selected from H, CH3, C2H5, C3H7 and R22 is independently selected from an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazo
• R22 is selected from optionally substituted pyridin-2-yl, imidazol-4-yl, pyrazol-1-yl, quinolin-2-yl groups. Most preferably R22 is either a pyridin-2-yl or a quinolin-2-yl.
• the cyclam and cross bridged ligands are preferably in the form of a manganese transition metal catalyst.
• the cyclam ligand is preferably of the form: wherein: Q is independently selected from: R is independently selected from: hydrogen, C1-C6-alkyl, CH2CH2OH, pyridin-2-ylmethyl, and CH2COOH, or one of R is linked to the N of another Q via an ethylene bridge;
• R1, R2, R3, R4, R5 and R6 are independently selected from: H, C1-C4-alkyl, and C 1-C4-alkylhydroxy.
• Preferred non-cross-bridged ligands are 1,4,8,11-tetraazacyclotetradecane (cyclam), 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (Me4cyclam), 1,4,7,10-tetraazacyclododecane (cyclen), 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane (Me4cyclen), and 1,4,7,10-tetrakis(pyridine-2ylmethyl)-1,4,7,10-tetraazacyclododecane (Py4cyclen). With Py4cyclen the iron complex is preferred.
• a preferred cross-bridged ligand is of the form: wherein "RI” is independently selected from H, and linear or branched, substituted or unsubstituted C1 to C20 alkyl, alkylaryl, alkenyl or alkynyl; and all nitrogen atoms in the macropolycyclic rings are coordinated with the transition metal.
• R1 Me, which is the ligand 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane of which the complex [Mn(Bcyclam)C12] may be synthesised according to WO98/39098 .
• Suitable transition metal bleach catalysts include:
• transition metal bleach catalysts are described in U.S. Pat. No. 5,580,485 , U.S. Pat. No. 4,430,243 ; U.S. Pat. No. 4,728,455 ; U.S. Pat. No. 5,246,621 ; U.S. Pat. No. 5,244,594 ; U.S. Pat. No. 5,284,944 ; U.S. Pat. No. 5,194,416 ; U.S. Pat. No. 5,246,612 ; U.S. Pat. No. 5,256,779 ; U.S. Pat. No. 5,280,117 ; U.S. Pat. No. 5,274,147 ; U.S. Pat. No. 5,153,161 ; U.S.
• Tridentate ligands with manganese Tridentate ligands with manganese:
• terpyridine derivatives could be employed, such as bispyridylpyrimidine or bispyridyltriazine.
• Preferred classes include the ones disclosed in WO2002088289 ; WO2004007657 ; WO2004039933 ; WO2004039934 ; WO2005068075 ; and WO2005068074 ; WO2005105303
• Tetradentate ligands with manganese or iron Tetradentate ligands with manganese or iron:
• the trispicens are preferably in the form of an iron transition metal catalyst.
• the trispicen type ligands are preferably of the form: R17R17N-X-NR17R17 (VI), wherein:
• the heteroatom donor group is preferably pyridinyl optionally substituted by -CO-C4-alkyl.
• heteroatom donor groups are imidazol-2-yl, 1-methyl-imidazol-2-yl, 4-methyl-imidazol-2-yl, imidazol-4-yl, 2-methyl-imidazol-4-yl, 1-methyl-imidazol-4-yl, benzimidazol-2-yl and 1-methyl-benzimidazol-2-yl.
• R17 are CY2-R18.
• the ligand Tpen (i.e. N, N, N', N'-tetra(pyridin-2-yl-methyl)ethylenediamine) is disclosed in WO97/48787 .
• a more preferred transition metal catalyst for the method is as described in EP 0458397 and WO06/125517 ; both of these patents disclose the use of manganese 1,4,7-Trimethyl-1,4,7-triazacyclononane (Me3-TACN) as related compounds as complexes.
• the PF6- ligand of MnMe3-TACN has been commercialised in laundry detergent powders and dish wash tablets.
• a preformed transition metal of Me3-TACN and related compounds is in the form of a salt such that it has a water solubility of at least 50 g/l at 20°C.
• Preferred salts are those of chloride, acetate, sulphate, and nitrate. Most preferred are the acetate and sulphate salts.
• the catalyst is most preferably a mononuclear or dinuclear complex of a Mn II-V transition metal catalyst, the ligand of the transition metal catalyst of formula (I): wherein: p is 3; R is independently selected from: hydrogen, C1-C6-alkyl, C2OH, C1COOH, and pyridin-2-ylmethyl or one of R is linked to the N of another Q via an ethylene bridge; R1, R2, R3, and R4 are independently selected from: H, C1-C4-alkyl, and C1-C4-alkylhydroxy. R is preferably independently selected from: hydrogen, CH3, C2H5, CH2CH2OH and CH2COOH.
• R, R1, R2, R3, and R4 are preferably independently selected from: H and Me.
• 1,4,7-Trimethyl-1,4,7-triazacyclononane (Me3-TACN) and 1,2,-bis-(4,7,-dimethyl-1,4,7,-triazacyclonon-1-yl)-ethane (Me4-DTNE) are most preferred.
• the embodiments of the invention may utilize one or more polymers.
• polymers include carboxymethylcellulose, poly(vinylpyrrolidone), poly (ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
• Modern detergent compositions typically employ polymers as so-called 'dye-transfer inhibitors'. These prevent migration of dyes, especially during long soak times.
• Any suitable dye-transfer inhibition agents may be used in accordance with the present invention.
• such dye-transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese pthalocyanine, peroxidases, and mixtures thereof.
• Nitrogen-containing, dye binding, DTI polymers are preferred. Of these polymers and co-polymers of cyclic amines such as vinyl pyrrolidone, and/or vinyl imidazole are preferred.
• Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
• the amine oxide unit of the polyamine N-oxides has a pK a ⁇ 10, preferably pK a ⁇ 7, more preferably pK a ⁇ 6.
• Any polymer backbone can be used provided the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
• suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
• the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
• the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferably 1,000 to 500,000; most preferably 5,000 to 100,000. This preferred class of materials is referred to herein as "PVNO".
• a preferred polyamine N-oxide is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
• Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred.
• the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000, as determined by light scattering as described in Barth, et al., Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization ".
• the preferred PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched. Suitable PVPVI polymers include Sokalan (TM) HP56, available commercially from BASF, Ludwigshafen, Germany.
• PVP polyvinylpyrrolidone polymers
• PVP's are disclosed for example in EP-A-262,897 and EP-A-256,696 .
• Suitable PVP polymers include Sokalan (TM) HP50, available commercially from BASF.
• Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000.
• the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
• dye transfer inhibiting agents are those from the class of modified polyethyleneimine polymers, as disclosed for example in WO-A-0005334 . These modified polyethyleneimine polymers are water-soluble or dispersible, modified polyamines.
• Modified polyamines are further disclosed in US-A-4,548,744 ; US-A-4,597,898 ; US-A-4,877,896 ; US-A-4,891, 160 ; US-A-4,976,879 ; US-A-5,415,807 ; GB-A-1,537,288 ; GB-A-1,498,520 ; DE-A-28 29022 ; and JP-A-06313271 .
• the composition according to the present invention comprises a dye transfer inhibition agent selected from polyvinylpyrridine N-oxide (PVNO), polyvinyl pyrrolidone (PVP), polyvinyl imidazole, N-vinylpyrrolidone and N-vinylimidazole copolymers (PVPVI), copolymers thereof, and mixtures thereof.
• a dye transfer inhibition agent selected from polyvinylpyrridine N-oxide (PVNO), polyvinyl pyrrolidone (PVP), polyvinyl imidazole, N-vinylpyrrolidone and N-vinylimidazole copolymers (PVPVI), copolymers thereof, and mixtures thereof.
• the amount of dye transfer inhibition agent in the composition according to the present invention will be from 0.01 to 10 %, preferably from 0.02 to 5 %, more preferably from 0.03 to 2 %, by weight of the composition. It will be appreciated that the dye transfer inhibition agents will assist in the preservation of whiteness by preventing the migration of dyes from coloured articles to white ones.
• polymers used in laundry compositions include soil-release, anti-ashing and anti-redeposition polymers as well as polymers which improve powder properties.
• Polymeric dispersing agents can advantageously be utilized in the compositions herein, especially in the presence of layered silicate builders.
• Suitable polymeric dispersing agents include polycarboxylates and polyethylene glycols, although others known in the art can also be used.
• polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release, peptization, and anti-redeposition.
• Polycarboxylate materials which can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, are preferably admixed in their acid form.
• Unsaturated monomeric acids that can be polymerized to form suitable polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
• the presence in the polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight of the polymer.
• Particularly suitable polycarboxylates can be derived from acrylic acid.
• acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
• the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
• Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials.
• Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Pat. No. 3,308,067, issued Mar. 7, 1967 .
• the preferred polycarboxylate is sodium polyacrylate.
• Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
• Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
• the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
• the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1: 1, more preferably from about 10:1 to 2:1.
• Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
• Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published Dec. 15, 1982 , as well as in EP 193,360, published Sep. 3, 1986 , which also describes such polymers comprising hydroxypropylacrylate.
• Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers.
• Such materials are also disclosed in EP 193,360 , including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
• Polyethylene glycol (PEG) can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 3,000 to about 10,000. Polyaspartate and polyglutamate dispersing agents may also be used. Dispersing agents such as polyaspartate preferably have an average molecular weight of about 10,000.
• polymeric soil release agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in compositions according to the invention.
• Polymeric soil release agents are characterised by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
• the soil release polymers will comprise polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols).
• the polymeric soil release agents useful herein especially include those soil release agents having:
• the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
• Suitable oxy C 4 -C 6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO 3 S(CH 2 ) n OCH 2 CH 2 O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink .
• Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C 1 -C 4 alkyl and C 4 hydroxyalkyl cellulose; see U.S. Pat. No. 4,000,093, issued Dec. 28, 1976 to Nicol, et al.
• Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C 1 -C 6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
• poly(vinyl ester) e.g., C 1 -C 6 vinyl esters
• poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
• Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
• One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
• the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Pat. No. 3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadur issued Jul. 8, 1975 .
• Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
• this polymer include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink .
• Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
• These soil release agents are described fully in U.S. Pat. No. 4,968,451, issued Nov. 6, 1990 to J.J. Scheibel and E. P. Gosselink .
• Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Pat. No. 4,711,730, issued Dec. 8, 1987 to Gosselink et al , the anionic end-capped oligomeric esters of U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink , and the block polyester oligomeric compounds of U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink .
• Preferred polymeric soil release agents also include the soil release agents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989 to Maldonado et al , which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
• soil release agents will generally comprise from about 0.01 % to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1 % to about 5%, preferably from about 0.2% to about 3.0%.
• Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units.
• the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
• a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
• Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
• a crystalline-reducing stabilizer preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
• polymeric deposition aid may also be used. These include cationic polymeric deposition aids. Suitable cationic polymeric deposition aids include cationic guar polymers such as Jaguar (ex Rhone Poulenc), cationic cellulose derivatives such as Celquats (ex National Starch), Flocaid (ex National Starch), cationic potato starch such as SoftGel (ex Aralose), cationic polyacrylamides such as PCG (ex Allied Colloids). Cationic polymeric aids are particularly preferred in the absence of any other cationic material in the composition.
• cationic polymeric deposition aids include cationic guar polymers such as Jaguar (ex Rhone Poulenc), cationic cellulose derivatives such as Celquats (ex National Starch), Flocaid (ex National Starch), cationic potato starch such as SoftGel (ex Aralose), cationic polyacrylamides such as PCG (ex Allied Colloids). Cationic polymeric aids are particularly preferred in the absence of any other
• Polymers having amine groups are preferred, especially polyamine polymers as it is believed that these may reversibly react with odoriferous aldehydes and retain them on the fabric for longer.
• compositions for use in the methods of the present invention may be formulated as additives to be used with a separate detergent product.
• a composition for use in the method of the present invention also contains one or more surfactants and/or optionally other ingredients such that the composition is fully functional as a laundry cleaning and/or care composition.
• a composition of the invention may be in dry solid or liquid form.
• the composition may be a concentrate to be diluted, rehydrated and/or dissolved in a solvent, including water, before use.
• the composition may also be a ready-to-use (in-use) composition.
• the present invention is suitable for use in industrial or domestic fabric wash compositions, fabric conditioning compositions and compositions for both washing and conditioning fabrics (so-called through the wash conditioner compositions).
• the present invention can also be applied to industrial or domestic non-detergent based fabric care compositions, for example spray-on compositions.
• Fabric wash compositions according to the present invention may be in any suitable form, for example powdered, tableted powders, liquid or solid detergent bars.
• compositions may also contain other conventional detergent ingredients such as e.g. fabric conditioners including clays, foam boosters, suds suppressors (anti-foams), anti-corrosion agents, anti-microbials or tarnish inhibitors.
• fabric conditioners including clays, foam boosters, suds suppressors (anti-foams), anti-corrosion agents, anti-microbials or tarnish inhibitors.
• Embodiments of the invention preferably utilize a fabric wash detergent material selected from non-soap anionic surfactant, nonionic surfactants, soap, amphoteric surfactants, zwitterionic surfactants and mixtures thereof.
• Detergent compositions suitable for use in domestic or industrial automatic fabric washing machines generally contain anionic non-soap surfactant or nonionic surfactant, or combinations of the two in suitable ratio, as will be known to the person skilled in the art, optionally together with soap.
• the surfactants may be present in the composition at a level of from 0.1 % to 60% by weight.
• Suitable anionic surfactants are well known to the person skilled in the art and include alkyl benzene sulphonate, primary and secondary alkyl sulphates, particularly C 8 -C 15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates, dialkyl sulphosuccinates; ether carboxylates; isethionates; sarcosinates; fatty acid ester sulphonates and mixtures thereof.
• the sodium salts are generally preferred.
• the composition When included therein the composition usually contains from about 1 % to about 50%, preferably 10 wt%-40 wt% based on the fabric treatment composition of an anionic surfactant such as linear alkylbenzenesulfonate, alpha-olefinsulfonate, alkyl sulfate (fatty alcohol sulfate), alcohol ethoxysulfate, secondary alkanesulfonate, alpha-sulfo fatty acid methyl ester, alkyl- or alkenylsuccinic acid or soap.
• Preferred surfactants are alkyl ether sulphates and blends of alkoxylated alkyl nonionic surfactants with either alkyl sulphonates or alkyl ether sulphates.
• Preferred alkyl ether sulphates are C 8 -C 15 alkyl and have 2-10 moles of ethoxylation.
• Preferred alkyl sulphates are alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 .
• the counter ion for anionic surfactants is typically sodium, although other counter-ions such as TEA or ammonium can be used. Suitable anionic surfactant materials are available in the marketplace as the 'Genapol'TM range from Clariant.
• Nonionic surfactants are also well known to the person skilled in the art and include primary and secondary alcohol ethoxylates, especially C 8 -C 20 aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
• Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide). Mixtures of nonionic surfactant may be used.
• the composition When included therein the composition usually contains from about 0.2% to about 40%, preferably 1 to 20 wt%, more preferably 5 to 15 wt% of a non-ionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine ("glucam ides").
• a non-ionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucam ides").
• Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
• hydrotrope generally means a compound with the ability to increase the solubilities, preferably aqueous solubilities, of certain slightly soluble organic compounds, which may include dyes, photo-bleaches, fluorescer and or phobleaches. Hyprotropes are preferably present in embodiments of the invention.
• hydrotropes examples include sodium xylene sulfonate, SCM.
• compositions for use in the inventive method may comprise a solvent such as water or an organic solvent such as isopropyl alcohol or glycol ethers. Solvents are typically present in liquid or gel compositions.
• Compositions for use in the inventive method or which otherwise embody the invention may contain a metal chelating agent such as carbonates, bicarbonates, and sesquicarbonates.
• the metal chelating agent can be a bleach stabiliser (i.e. heavy metal sequestrant).
• Suitable metal chelation agents include ethylenediamine tetraacetate (EDTA), diethylenetriamine pentaacetate (DTPA), ethylenediamine disuccinate (EDDS), and the polyphosphonates such as the Dequests (Trade Mark), ethylenediamine tetramethylene phosphonate (EDTMP) and diethylenetriamine pentamethylene phosphate (DETPMP).
• Suitable builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
• calcium sequestrant builder materials examples include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid.
• precipitating builder materials examples include sodium orthophosphate and sodium carbonate.
• Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070 .
• zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070 .
• composition may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.
• a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.
• Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.
• compositions may suitably contain less than 20%wt, preferably less than 10% by weight, and most preferably less than 10%wt of detergency builder.
• the composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15%w.
• Aluminosilicates are materials having the general formula: 0.8-1.5 M 2 O. Al 2 O 3 . 0.8-6 SiO 2 where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
• the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
• the ratio of surfactants to alumuminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1.
• phosphate builders may be used.
• 'phosphate' embraces diphosphate, triphosphate, and phosphonate species.
• Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
• carbonate including bicarbonate and sesquicarbonate
• citrate may be employed as builders.
• Precipitating and ion-exchange builders are generally absent from liquid compositions.
• One or more enzymes may be present in a composition when practicing a method of the invention, or present in combinations according to the invention.
• an enzyme can be the means by which the hydroperoxide is converted into the odiferous species.
• the same or different enzymes may also be present to assist in cleaning.
• enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof.
• Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces ), e.g. from H. lanuginosa ( T. lanuginosus ) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580 , a Pseudomonas lipase, e.g. from P . alcaligenes or P. pseudoalcaligenes ( EP 218 272 ), P. cepacia ( EP 331 376 ), P. stutzeri ( GB 1,372,034 ), P .
• lipase variants such as those described in WO 92/05249 , WO 94/01541 , EP 407 225 , EP 260 105 , WO 95/35381 , WO 96/00292 , WO 95/30744 , WO 94/25578 , WO 95/14783 , WO 95/22615 , WO 97/04079 and WO 97/07202 .
• LipolaseTM and Lipolase UltraTM, LipexTM are preferred commercially available lipase enzymes.
• phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32.
• phospholipase is an enzyme which has activity towards phospholipids.
• Phospholipids such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol.
• Phospholipases are enzymes which participate in the hydrolysis of phospholipids.
• phospholipases A 1 and A 2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid
• lysophospholipase or phospholipase B
• Phospholipase C and phospholipase D release diacyl glycerol or phosphatidic acid respectively.
• the enzyme and the pro-fragance may show some interaction and should be chosen such that this interaction is not negative. Some negative interactions may be avoided by encapsulation of one or other of enzyme and pro-fragrance and/or other segregation within the product.
• proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically modified or protein engineered mutants are included.
• the protease may be a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease.
• Preferred commercially available protease enzymes include AlcalaseTM, SavinaseTM, PrimaseTM, DuralaseTM, DyrazymTM, EsperaseTM, EverlaseTM, PolarzymeTM, and KannaseTM, (Novozymes A/S), MaxataseTM, MaxacalTM, MaxapemTM, ProperaseTM, PurafectTM, Purafect OxPTM, FN2TM , and FN3TM (Genencor International Inc.).
• the method of the invention may be carried out in the presence of cutinase. classified in EC 3.1.1.74.
• the cutinase used according to the invention may be of any origin.
• Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
• Suitable amylases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in GB 1,296,839 , or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060 .
• amylases are DuramylTM, TermamylTM, Termamyl UltraTM, NatalaseTM, StainzymeTM, FungamylTM and BANTM (Novozymes A/S), RapidaseTM and PurastarTM (from Genencor International Inc.).
• Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307 , US 5,648,263 , US 5,691,178 , US 5,776,757 , WO 89/09259 , WO 96/029397 , and WO 98/012307 .
• cellulases include CelluzymeTM, CarezymeTM, EndolaseTM, RenozymeTM (Novozymes A/S), ClazinaseTM and Puradax HATM (Genencor International Inc.), and KAC-500(B)TM (Kao Corporation).
• Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618 , WO 95/10602 , and WO 98/15257 . Commercially available peroxidases include GuardzymeTM and NovozymTM 51004 (Novozymes A/S).
• Any enzyme present in the composition or when practicing the method may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708 .
• a polyol such as propylene glycol or glycerol
• a sugar or sugar alcohol lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid
• the enzymes mentioned above may be present to assist in cleaning as well as in the role of the catalyst for the decomposition of the hydroperoxide.
• Embodiment of the present invention will preferably also comprise some perfume per se or have additional perfume present during the method steps.
• Useful components of the perfume 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 Nostr and; or Perfume and Flavor Chemicals by
• perfume in this context is not only meant a fully formulated product fragrance, but also selected components of that fragrance, particularly those which are prone to loss, such as the so-called 'top notes'.
• Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955 ]). Examples of well known top-notes include citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. Top notes typically comprise 15-25%wt of a perfume composition and in those embodiments of the invention which contain an increased level of top-notes it is envisaged at that least 20%wt would be present within the encapsulate.
• perfume or pro-fragrance may be encapsulated, typical perfume components which it is advantageous to encapsulate, include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius and pro-fragrances which can produce such components.
• perfume components which have a low Log P (ie. those which will be partitioned into water), preferably with a Log P of less than 3.0.
• materials, of relatively low boiling point and relatively low Log P have been called the "delayed blooming" perfume ingredients and include the following materials:
• compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components from the list given of delayed blooming perfumes given above present in the perfume.
• perfumes with which the present invention can be applied are the so-called 'aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian. By means of the present invention these materials can be transferred to textile articles that will be worn or otherwise come into contact with the human body (such as handkerchiefs and bed-linen).
• essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian.
• the sebum monitors were CS-32-033 (sebum Bey with carbon black) and CS-30-002 (sebum Bey). These monitors were 15x15 cm and weighed about 3.60g impregnated with 0.168g of the sebum model; hence 0.047g/g of fabric or about 4.7% sebum. Table 1 gives the composition of Bey sebum.
• Table 1 The composition of Bey sebum according to Centre for Testmaterials B.V (Netherlands) Component Weight % Beef tallow 32.8 Free fatty acids 18.0 Lanoline 13.8 Hydrocarbon mixture (Squalene) 12.0 Cutina 11.6 Cholesterol 3.7 Fatty acid triglycerides 3.6
• the sebum monitors were made fresh for the purpose of these experiments and vacuum packed in aluminium foils. They were kept in a refrigerator during the length of these experiments to ensure freshness. The monitors were evaluated for odours before every experiment to ensure a lack of oily/fatty rancid malodour originating from the untreated monitors. All monitors used in the experiments were initially odour free.
• the washing was simulated in a LinitestTM machine.
• the Linitest is a laboratory scale washing machine (Ex. Heraeus).
• the equipment is designed and built to comply with the requirements for international standard test specifications. It is used for small scale detergency testing particularly when low liquor to cloth ratio is involved.
• the Linitest model used in the examples had a single rotation speed of 40 rpm.
• the carrier is capable of accommodating twelve steel containers and can be operated at temperatures up to 100°C. Its 20 litre tank and thermostatically controlled heating elements ensure the bath liquor reaches the required temperature.
• the stainless steel construction throughout ensures efficient heat transfer to the specimen containers that are mounted on a rotating horizontal carrier driven by a geared motor. The rotating movement of the carrier 'throws' the liquid from one end of the container to the other in a continuous action. This movement simulates the mechanical washing process.
• the washing process involved the following steps;
• the detergent used was Indian Rin Advanced powder with and without perfume which contains 15 wt% LAS, 30% carbonate, 40% NaCl ⁇ 0.4% perfume and the remainder including minors and calcite (no dyes).
• the two monitors from the same pot are dried one on line inside under fluorescent light (for at least 12 hours) and the second one in a Weather-o-meterTM (WOM) for 30 minutes.
• WOM produces artificial sunlight and was set up at a lamp power of 0.33 W/m 2 at a wavelength of 340nm. The relative humidity remained around 20%.
• the monitors after the drying stage were stored in 60 ml clear class bottles and stored in daylight out of direct sunlight. Storage of the monitors in a glass bottle enhanced their odours and made it easier for the panellists to describe the smells.
• the monitors in the bottles were evaluated by an expert panel and the smell described according to perfumery practices.
• CS-32-033 sinum Bey with carbon black monitors were washed in water (Wirral water) at 40 °C without detergent and treated with AR51 (Acid Red 51), and Tinolux MBC. Table 2 summarises the resulting overall smells as assessed by an expert panel. Table 2. The odour of sebum monitors washed in water with and without photobleach and dried on line (under fluorescent light) or died under artificial sunlight. Treatment Drying method Odours (same day) Auto-oxidation (comparative) Line Light oily/fatty smell, unclean.
• w-o-m Stronger oily; frying oil, rancid, unclean Photo-oxidation (comparative - without surfactant being present) 0.001%AR51 Line Clean, no fat smell. w-o-m Caramel, sweet aldehydic, no oil or fat. 0.002%AR51 Line Clean, no fat, oil smell. w-o-m Relatively strong caramel, waxy. 0.0005%BMC Line No smell of oil or fat, not clean either w-o-m Rich nutty, frying oil. 0.001%BMC Line No smell w-o-m Slight fatty/oily smell, not clean 0.002%BMC Line No fatty /oily or rancid smell, clean. w-o-m Slight sweet caramel smell,
• hydroperoxide intermediates Whilst, the formation of the hydroperoxide intermediates is relatively quick in the presence of a photo-bleach (for example Rose Bengal) the hydroperoxide intermediates are relatively stable, and extended periods of time was required to break-down these intermediates to the odiferous decomposition products. This breakdown can be accelerated with a calatyst.
• a photo-bleach for example Rose Bengal
• SQ squalene
• SQ(OOH) 6 was synthesized from SQ as follows: SQ (1.64 g, 0.1 M) was weighed, dissolved in 40mL of acetone (containing 1 ⁇ 10 -5 M of Rose Bengal as a photosensitizer), and exposed to a Na lamp and oxygen bubbling at 5 °C. The treatment was stopped after 6 hours, and the only species remaining, according to the TLC monitoring, was the SQ(OOH) 6 .
• the medium was evaporated to leave the SQ(OOH) 6 material, which was then re-dissolved in 10 mL of diethyl ether.
• This solution was then loaded onto a Discovery® SPE DSC-Si silica tube (Supelco, Bellefonte, PA). The tube was eluted with an additional 5mL of diethyl ether, and the elutant containing SQ(OOH) 6 was collected. During this procedure, the rose Bengal was retained on the silica phase. Finally, the elutant was evaporated and SQ(OOH) 6 was then stored at -18°C until further use.
• a solution containing SQ(OOH) 6 (0.1 M) in Acetone-d6 was prepared. 500 ⁇ L of this solution was then added in a NMR tube and allowed to age in a thermostatic bath at 60 °C over a 10 hour period. At time periods of 1, 3, 5, 10 hours a spectrum was taken and the hydroperoxide area (4.2-6.0 p.p.m.) was monitored for change along with any appearance of peaks at 7.6-8 p.p.m. typical of aldehyde species.
• the NMR spectrometer consisted of a Bruker Avance 300 MHz Ultrashield and the software used was TopSpin. The 1 H experiments were performed with a pulse at 30° and 32 scans.
• a preferred metal-ion centred catalyst based on an iron centre such as iron(II), in particular, N,N-bis(pyridine-2-yl-methyl)-1,1-bis(pyridine-2-yl)-1-amino-ethane dichloride (IronMeN4py) was employed to increase the rate of hydroperoxide transformation to the end products consisting of fragrance aldehydes along with other odourous materials.
• the first HPLC measurement taken was at t 0 (before addition of Rose Bengal).
• the squalene peak was eluted at 15 minutes, and the hydroperoxides eluted at times between 2-10 minutes.
• the hydroperoxide peaks at 3 and 5.7 minutes after starting the column were monitored for any change in relative peak height.
• Table 4 shows results of photolysis with rose Bengal followed by decomposition of the formed hydroperoxides in the presence of the metal ion catalyst.
• Table 4 Production and Decomposition of Squalene Hydroperoxides in the Presence of Rose-Bengal and Metal ion Catalyst.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)
• Cosmetics (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)

Priority Applications (1)

Applications Claiming Priority (3)

Publications (2)

Family

ID=48142006

Family Applications (1)

Country Status (8)

Families Citing this family (1)

Family Cites Families (5)

• 2013
  • 2013-04-19 IN IN2043MUN2014 patent/IN2014MN02043A/en unknown
  • 2013-04-19 WO PCT/EP2013/058232 patent/WO2013160214A1/en active Application Filing
  • 2013-04-19 CN CN201380031941.5A patent/CN104364361B/zh active Active
  • 2013-04-19 EP EP13717293.8A patent/EP2841543B1/en active Active
  • 2013-04-19 ES ES13717293.8T patent/ES2565503T3/es active Active
  • 2013-04-19 BR BR112014026302A patent/BR112014026302A2/pt not_active Application Discontinuation
  • 2013-04-23 AR ARP130101347A patent/AR090805A1/es unknown
• 2014
  • 2014-10-21 ZA ZA2014/07631A patent/ZA201407631B/en unknown

Also Published As

Similar Documents

Legal Events