WO2000070004A1 - Compositions adoucissantes pour tissus - Google Patents

Compositions adoucissantes pour tissus Download PDF

Info

Publication number
WO2000070004A1
WO2000070004A1 PCT/GB2000/001699 GB0001699W WO0070004A1 WO 2000070004 A1 WO2000070004 A1 WO 2000070004A1 GB 0001699 W GB0001699 W GB 0001699W WO 0070004 A1 WO0070004 A1 WO 0070004A1
Authority
WO
WIPO (PCT)
Prior art keywords
cpe
rse
antioxidant
composition according
composition
Prior art date
Application number
PCT/GB2000/001699
Other languages
English (en)
Inventor
David Stephen Grainger
Frans Jos Jansen
Original Assignee
Unilever Plc
Unilever Nv
Hindustan Lever Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10853610&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2000070004(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to JP2000618411A priority Critical patent/JP2002544406A/ja
Priority to MXPA01011697A priority patent/MXPA01011697A/es
Priority to HU0201469A priority patent/HU228798B1/hu
Priority to BRPI0010574-0A priority patent/BR0010574B1/pt
Priority to AU47679/00A priority patent/AU768506B2/en
Application filed by Unilever Plc, Unilever Nv, Hindustan Lever Ltd. filed Critical Unilever Plc
Priority to ROA200101223A priority patent/RO121134B1/ro
Priority to PL351739A priority patent/PL191651B1/pl
Priority to DE60026988T priority patent/DE60026988T2/de
Priority to CA2367033A priority patent/CA2367033C/fr
Priority to EP00929672A priority patent/EP1179037B1/fr
Publication of WO2000070004A1 publication Critical patent/WO2000070004A1/fr

Links

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
    • C11D3/0084—Antioxidants; Free-radical scavengers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • 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
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds

Definitions

  • the present invention relates to fabric softening compositions, in particular to those that soften without affecting the absorbency of the fabric and which suffer from a reduced tendency to develop malodour during manufacture, storage or use.
  • Rinse added fabric softener compositions are well known.
  • a disadvantage associated with conventional rinse conditioners is that although they increase the softness of a fabric they often simultaneously decrease its absorbency. This means that its ability to take up water decreases. This is particularly disadvantageous with towels where the consumer requires the towel to be soft, and yet, have a high absorbency.
  • W098/16538 discloses fabric conditioning compositions comprising liquid or soft solid derivatives of a cyclic polyol or a reduced saccharide which give good softening and retain a ⁇ sorbency of the fabric.
  • EP 0 380 406 discloses detergent compositions comprising a saccharide or reduced saccharide ester containing at least one fatty acid chain.
  • WO 95/00614 discloses softening compositions comprising polyhyd ⁇ c alcohol esters and catiomsed cellulose.
  • WO 96/15213 discloses textile softening agents containing alkyl , alkenyl and/or acyl group containing sugar derivatives, which are solid after esterification, m combination with noniomc and cationic emulsifiers.
  • a liquid or soft solid fabric softening agent e.g. a CPE or RSE as herein-defined which addresses the above absorbency problem, is obtained by using unsaturated, usually predominantly unsaturated , fatty acid chains on the ester or ether functions.
  • unsaturated, usually predominantly unsaturated , fatty acid chains on the ester or ether functions.
  • Such compositions may suffer from tne development of product malodour upon manufacture, storage or use. This is obviously highly undesirable .
  • W0 97/13828 discloses fabric conditioning compositions comprising a heavy metal sequestran .
  • W0 96/21714 and WO 96/21715 disclose fabric conditioning compositions comprising chelatmg agents.
  • W0 96/03481 'P&G discloses fabric conditioning compositions corrronsinq 1 to 20 wt% antioxidant.
  • the present invention is directed towards alleviating the above-mentioned problems.
  • compositions of the present invention soften fabrics without detriment to the absorbency of the fabric, they are easily manufactured and do not suffer from unacceptable levels of malodour development upon manufacture, storage or use.
  • a fabric softening composition comprising:
  • CPE cyclic polyol
  • RSE reduced saccharide
  • a method of reducing malodour upon manufacture, storage or use m a composition comprising a CPE or RSE as herein described by the addition of a least one antioxidant.
  • the initials CPE or RSE stand for a derivative of a cyclic polyol or of a reduced saccharide respectively which results from 35 to
  • the CPE or RSE having two or more ester or ether groups independently of one another attached to a Q to C 22 alkyl or alkenyl chain, and m which at least one of the chains attached to the ester or ether groups has at least one unsaturated bond.
  • the CPE or RSE The CPE or RSE
  • the CPE or RSE used according to the invention does not have any substantial crystalline character at 20 C. Instead it is preferably m a liquid or soft solid state as herein defined at 20°C.
  • the liquid or soft solid (as neremafter defined) CPEs or RSEs of the present invention result from 35 to 100% of the hydroxyl groups of the starting cyclic polyol or reduced saccharide being esterified or etherified with groups such that the CPEs or RSEs are m the required liquid or soft solid state. These groups typically contain unsaturation, branching or mixed chain lengths.
  • the CPEs or RSEs have 3 or more ester or ether groups or mixtures thereof, for example 3 to 8 , especially 3 to 5. It is preferred if two or more of the ester or ether groups of the CPE or RSE are independently of one another attached to a C 3 to C 22 alkyl or alkenyl chain.
  • C 22 alkyl or alkenyl groups may be branched or linear carbon chains.
  • 35 to 85% of the hydroxyl groups most preferably 40-80%, even more preferably 45-75%, such as 45-70% are esterified or etherified.
  • the CPE or RSE contains at least 35% t ⁇ or higher esters, eg at least 40%.
  • the CPE or RSE has at least one of tne chains independently attached to the ester or ether groups having at least one unsaturated bond. This provides a cost effective way of making the CPE or RSE a liquid or a soft solid. It is preferred if predominantly unsaturated fatty chains, derived from, for example, rape oil, cotton seed oil, soybean oil, oleic, tallow, palmitoleic, Imoleic, erucic or other sources of unsaturated vegetable fatty acids, are attached to the ester/ether groups .
  • ester or ether chains of the CPE or RSE.
  • the ester or ether chains of the CPE or RSE are preferably predominantly unsaturated.
  • Preferred CPEs or RSEs include sucrose tetratallowate , sucrose tetrarapeate , sucrose tetraoleate, sucrose tetraesters of soybean oil or cotton seed oil, cellobiose tetraoleate, sucrose t ⁇ oleate, sucrose t ⁇ apeate, sucrose pentaoleate, sucrose pentarapeate , sucrose hexaoleate, sucrose hexarapeate, sucrose t ⁇ esters, pentaesters and hexaesters of soybean oil or cotton seed oil, glucose tiroleate, glucose tetraoleate, xylose t ⁇ oleate, or sucrose tetra-,tr ⁇ -, penta- or hexa- esters with any mixture of predominantly unsaturated fatty acid chains .
  • CPEs or RSEs are those with monosaturated fatty acid chains, i.e. where any polyunsaturation has been removed by partial hydrogenation.
  • CPEs or RSEs based on polyunsaturated fatty acid chains eg sucrose tetralmoleate, may be used provided most of the polyunsaturation has been removed by partial hydrogenation .
  • liquid CPEs or RSEs are any of the above but where the polyunsaturation has been removed through partial hydrogenation.
  • 40% or more of the fatty acid cnams contain an unsaturated bond, more preferably 50% or more, most preferably 60% or more. In most cases 65% to 100%, e.g. 65% to 95% contain an unsaturated bond.
  • CPEs are preferred for use with the present invention.
  • Inositol is a preferred example of a cyclic polyol. Inositol derivatives are especially preferred.
  • cyclic polyol encompasses all forms of saccha ⁇ oes . Indeed saccha ⁇ des are especially preferred for use with this invention. Examples of preferred saccharides for the CPEs or RSEs to be derived from are monosaccharides and disaccharides .
  • Examples of monosaccharides include xylose, arabmose, galactose, fructose, sorbose and glucose. Glucose is especially preferred.
  • Examples of disaccna ⁇ des include maltose, lactose, cellobiose and sucrose. Sucrose is especially preferred.
  • An example of a reduced saccharide is sorbitan .
  • the liquid or soft solid CPEs can be prepared by methods well known to those skilled in the art. These include acylation of the cyclic polyol or reduced saccharide with an acid chloride; trans-este ⁇ fication of the cyclic polyol or reduced saccharide fatty acid esters using a variety of catalysts; acylation of the cyclic polyol or reduced saccharide with an acid anhydride and acylation of the cyclic polyol or reduced saccharide with a fatty acid. See for instance US 4 386 213 and AU 14416/88 (both P&G) .
  • the CPE or RSE has 3 or more, preferably 4 or more ester or ether groups. If the CPE is a disaccharide it is preferred if the disaccharide has 3 or more ester or ether groups. Particularly preferred CPEs are esters with a degree of este ⁇ fication of 3 to 5, for example, sucrose tri, tetra and penta esters.
  • tne cyclic polyol is a reducing sugar it is advantageous if each ring of the CPE has one ether or ester group, preferably at the Ci position. Suitable examples of such compounds include methyl glucose derivatives.
  • CPEs examples include esters of alkyl (poly) glucosides , m particular alkyl glucoside esters having a degree of polymerisation from 1 to 2.
  • the length of the unsaturated (and saturated if present) chains m the CPE or RSE is C 8 -C 22 , preferably C 12 -C 22 . It is possible to include one or more chains of Ci-C ⁇ , however these are less preferred.
  • the liquid or soft solid CPEs or RSEs of the present invention are characterised as materials having a sol ⁇ d:l ⁇ qu ⁇ d ratio of between 50:50 and 0:100 at 20 C as determined by T 2 relaxation time N R, preferably between 43:57 and 0:100, most preferably between 40:60 and 0:100, such as, 20:80 and 0:100.
  • the T 2 N R relaxation time is commonly used for characterising solid: liquid ratios m soft solid products such as fats and margarines.
  • any component of the signal with a T 2 of less than 100 ⁇ s is considered to be a solid component and any component with T 2 ⁇ 100 ⁇ s is considered to be a liquid component.
  • the prefixes e.g. tetra and penta
  • tne average degrees of esterification only indicate tne average degrees of esterification.
  • the compounds exist as a mixture of materials ranging from the monoester to the fully esterified ester. It is the average degree of esterification which is used herein to define the CPEs and RSEs .
  • the HLB of the CPE or RSE is typically between 1 and 3.
  • the CPE or RSE s preferably present in the composition m an amount of 0.5-50% by weight, based upon tne total weight of the composition, more preferably 1-30% by weight, such as 2-25%, eg 2-20%.
  • the CPEs and RSEs for use m the compositions include those recited m the following examples, including, sucrose tetraoleate, sucrose pentaerucate , sucrose tetraerucate and sucrose pentaoleate.
  • a deposition aid is defined as any material that aids deposition of the selected CPE or RSE onto a fabric during the laundering process.
  • the deposition aid may be selected from cationic compounds, such as cationic surfactants, noniomc surfactants, anionic surfactants, polymeric deposition aids or mixtures thereof. Quaternary ammonium compounds have been found to be particularly advantageous. A class of preferred deposition aids is fabric softening compounds.
  • the deposition aid is cationic m nature. If a cationic surfactant or cationic softening aid is not present m the formulation it is preferred if a cationic polymeric deposition aid is present. Most preferably the deposition aid is both cationic m nature and is a fabric softening compound.
  • deposition aids may be used, for example, a mixture of a cationic surfactant and a noniomc surfactant, or a fabric softening compound and a polymeric deposition aid.
  • Suitable cationic deposition aids include water soluble single chain quaternary ammonium compounds. Examples include cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, or any of those listed m European Patent No. 258 923 (Akzo Nobel) .
  • the deposition aid is a substantially water insoluble fabric softening compound.
  • substantially water insoluble quaternary ammonium materials comprising a single alkyl or alkenyl chain having an average length equal to or greater than C 20 are preferred.
  • Even more preferable are compounds comprising a polar head group and two alkyl or alkenyl chains each having an average chain length equal to or greater than C 14 .
  • Preferred fabric softening deposition aids have two long alkyl or alkenyl chains with an average chain length equal to or greater than C 14 . More preferably each chain has an average chain length greater than Ci ⁇ • Most preferably at least 50% of each long chain alkyl or alkenyl group has a chain length of Cis .
  • the long chain alkyl or alkenyl groups of the fabric softening deposition aid are predominantly linear .
  • the fabric softening deposition aids used m the compositions of the invention are molecules which provide excellent softening.
  • Substantially water insoluble fabric compounds m the context of this invention are defined as fabric compounds having a solubility less than 1 x 10 wt% m demmeralised water at 20 C.
  • the fabric softening deposition aids have a solubility less than 1 x 10 wt%
  • the fabric softening deposition aids have a solubility at 20 C m demmeralised water from 1 x 10 to 1 x 10 " wt%.
  • Preferred fabric softening deposition aids are quaternary ammonium compounds, preferably those with at least one ester link.
  • the fabric softening deposition aid is a water insoluble quaternary ammonium material which comprises a compound having two C 12 - 18 alkyl or alkenyl groups connected to the molecule via at least one ester link. It is more preferred if the quaternary ammonium material has two ester links present.
  • An especially preferred ester-linked quaternary ammonium material for use m the invention can be represented by the formula (I) :
  • each R group is independently selected from C 1 - 4
  • each R group is independently selected from Cg_28 alkyl or alkenyl groups
  • T is -O-C- or • 0-
  • X is any suitable anion and n is 0 or an integer from 1-5.
  • Preferred materials of this class include
  • a second preferred type of quaternary ammonium material can be represented by the formula (II) :
  • the quaternary ammonium material is biologically degradable.
  • Preferred materials of this class such as 1,2 bis [hardened tallowovloxv] -3 - trimethylammonium DroDane chloride and their method of preparation are, for example, described in
  • US 4 137 180 (Lever Brothers) .
  • these materials comprise small amounts of the corresponding monoester as described m US 4 137 180 for example 1-hardened tallowoyloxy -2 -hydroxy 3 - t ⁇ methylammonium propane chloride .
  • the fabric softening deposition aid of the composition may also be compounds having the formula ⁇ III) :
  • X is an anion
  • A is an (m+n) valent radical remaining after the removal of (m+n) hydroxy groups from an aliphatic polyol having p hydroxy groups and an atomic ratio of carbon to oxygen in the range of 1.0 to 3.0 and up to 2 groups per hydroxy group selected from ethylene oxide and propylene oxide
  • m is 0 or an integer from 1 to p-n
  • n is an integer from 1 to p-m
  • p is an integer of at least 2
  • B is an alkylene or alkylidene group containing 1 to 4 carbon atoms
  • R , R , R and R are, independently from each other, straight or brancned cr.am C 1 -C 43 alkyl or alkenyl groups, optionally with substitution by one or more functional groups and/or interruption by at most 10 ethylene oxide and/or propylene oxide groups, or by at most two functional groups selected from
  • R 11 12 or R and R may form a ring system containing 5 or 6 atoms m the ring, with the proviso that the average compound either has at least one R group having 22-48 carbon atoms, or at least two R groups having 16-20 carbon atoms, or at least three R groups having 10-14 carbon atoms.
  • Preferred compounds of this type are described m EP 638 639 (Akzo) .
  • the deposition aid may also comprise a mixture of different fabric softening compounds, for example a mixture of compounds of Formula (I) and Formula (II) .
  • the deposition aid may also be a noniomc surfactant, such as a noniomc ethoxylated surfactant having an HLB of from about 10 to about 20. It is advantageous f the surfactant alkyl group contains at least 12 carbon acorns.
  • Suitable polymeric deposition aids for use with the invention include cationic and noniomc polymeric deposition aids .
  • Suitable cationic polymeric deposition aids include cationic guar polymers such as; the Jaguar series of polymers (ex Rhodia) , cationic cellulose derivatives such as Celquats, (ex National Starch) , Ucare polymers (ex Amerchol) , cationic starches e.g. potato starch such as SoftGels and Solvitose such as BDA (ex Avebe , C* bond polymers series from Cerestar, cationic pclyacrylamides such as PCG (ex Allied Colloids), Flocaid series of polymers (ex National Starch) and cationic chitosan and derivatives.
  • Cationic polymeric aids are particularly preferred m the absence of any other cationic material m the composition.
  • Suitable noniomc deposition aids include Pluromcs (ex BASF), dialkyl PEGs , cellulose derivatives as described m GB 213 730 (Unilever; , hydroxy ethyl cellulose, starch, and hydrophobically modified noniomc polyols such as Acusol 880/882 (ex Rohm & Haas) .
  • Mixtures of any of the aforementioned deposition aids may be used .
  • the weight ratio of CPE or RSE to deposition aid is preferably within the range of from 15:1 to 1:10, more preferably within the range from 10:1 to 1:5, most preferably 8:1 to 1:3.
  • the weight ratio of CPE or RSE to deposition aid is at least 1:1 (especially if the deposition aid is a fabric softening compound) .
  • the weight ratio of a softening deposition aid to CPE or RSE is at least 2:3, oreferaolv at least 1:1.
  • the weight ratio of softening deposition aid to CPE or RSE s from 3:2 to 1:10, more preferably from 2:3 to 1:10.
  • the fabric softening compositions comprise one or more antioxidants m a weight ratio to the CPE or RSE of 20:1 or more .
  • the deposition aid is preferably present in the compositions m an amount of 0.05-15% by weight, based upon the total weight of the composition, more preferably 0.1-10%, such as 0.5-7.5%.
  • any suitable antioxidant may be used according to the invention.
  • the antioxidant comprises at least one initiation inhibitor antioxidant or at least one propagation inhibitor. Mixtures of these two types of antioxidants have been found to be particularly beneficial, especially m reducing medium to long term malodour. Any antioxidant referred to in the following examples may be used.
  • compositions preferably comprise 0.0001% to 1% by weight (m total) , based on the total weight of the composition, of antioxidants, more preferably 0.00015% to 0.75%, even more preferably 0.002 to 0.5%, e.g. 0.002 to 0.45%.
  • initiation inhibitors antioxidants can give good short and long term malodour suppression but a mixture of propagation inhibitor and initiation inhibitor antioxidants can give a surprisingly good short and long term malodour suppression.
  • Suitable initiation inhibitor antioxidants include peroxide decomposers (e.g. sulphides, aryl and alkyl phosphites, metal salts of some thiodipropionates , xanthates and dithiophosphates) .
  • peroxide decomposers e.g. sulphides, aryl and alkyl phosphites, metal salts of some thiodipropionates , xanthates and dithiophosphates.
  • Suitable peroxide decomposers include (RO 2 CCH 2 CH 2 ) 2 s where
  • R Ci 2 H 25 , C 14 H 29 o C 18 H 37 i.e. TNPP (tris- nonylphenylphosphite) available as Irgafos 186; Sandostab P- EPQ; and Irgafos P-EPQ respectively.
  • peroxide decomposers are preferably present at a level of between 0.001% to 0.5% by weight, most preferably 0.005% to 0.1%.
  • Suitable initiation inhibitor antioxidant are metal ion sequestrants or deactivators .
  • Suitable such types include N, N ' -d ⁇ sal ⁇ cyl ⁇ dene-1 , 2 -propanediamme ; oxalyl bis- (benzylidenehydrazide) ; ethylenediammetetraacetic acid (EDTA) ; ethylenediamme- N, N ' -disuccimc acid (EDDS); N-hydroxyethylene-diamme triacetic acid; mtrilotriacetic acid (NTA) ; ethylene diamme tetrapropiomc acid; ethylenediamme-N, N ' -diglutamic acid; 2 -hydorxypropylenediamme-N, N ' -disuccimc acid; triethylenetriamme hexacetic acid; diethylenet ⁇ amme pentacetic acid (DETPA) ; trans 1,2-d ⁇ ammo
  • Propagation inhibitor antioxidants consist primarily of hindered phenols/polyphenols . These can include those which are commonly used m the foods or plastics industries, such as butylated hydroxyanisole (BHA) ; butylated hydroxytoluene (BHT) ; tert -butyl hydroqu one (TBHQ) ; tocopherols ; tocot ⁇ enols ; ascorbic acid; ascobyl palmitate; octyl gallate; propyl gallate; lauryl gallate; N, N-bis (ethyl 3 5' -di -tert -butyl -4 -hydroxybenzoate; 2- (N, N-dimethyl - ammo) ethyl 3 5' -di-tert -butyl -4 ' hydroxybenzoate-N- cocoamme; 2 - (N-methyl -N-cocammo) ethyl 3 ' , 5 '
  • Inhibitor antioxidants are preferably present at a level of 0.0001% to 0.5% by weight, based on the total weight of the composition, more preferably 0.0002% to 0.05%, most preferably 0.0002% to 0.02%.
  • the weight ratio of the initiation inhibitor X) to the propagation inhibitor (ii) is preferably within the range 10:1 to 1:10, more preferably 10:1 to 1:5, even more preferably 8:1 to 1:1, e.g. 6:1 to 1:1.
  • the weight ratio of CPE or RSE to total antioxidant is 20:1 or greater, preferably 50:1 or greater, more preferably 75:1 or greater.
  • the weight ratio may be as high as 1500:1 or greater. It is preferred that the weight ratio has an upper limit of 3000:1, e.g. 2500:1.
  • compositions of the invention preferably nave a pH from 1.5 to 7, more preferably from 1.5 to 5.
  • compositions can also contain fatty acids, for example C ⁇ - C 24 alkyl or alkenyl monocarboxylic acids, or, polymeric carboxylic acids.
  • fatty acids for example C ⁇ - C 24 alkyl or alkenyl monocarboxylic acids, or, polymeric carboxylic acids.
  • saturated fatty acids are used, particular, hardened tallow C ⁇ 6 -C ⁇ 8 fatty acids.
  • the composition can also contain one or more optional ingredients, selected from electrolytes, non-aqueous solvents, pH buffering agents, perfumes, perfume carriers, fluorescers, colorants, hydrotropes, antifoam g agents, antiredeposition agents, polymeric and other thickeners, enzymes, optical brightening agents, opacifiers, anti- shrinking agents, anti-wrmkle agents, anti-spottmg agents, germicides, fungicides, anti -corrosion agents, drape imparting agents, antistatic agents, sunscreens, colour care agents and ironing aids.
  • optional ingredients selected from electrolytes, non-aqueous solvents, pH buffering agents, perfumes, perfume carriers, fluorescers, colorants, hydrotropes, antifoam g agents, antiredeposition agents, polymeric and other thickeners, enzymes, optical brightening agents, opacifiers, anti- shrinking agents, anti-wrmkle agents, anti-spottmg agents, germicides, fung
  • any viscosity control agent used with rinse conditioners is suitable for use with the present invention, for example biological polymers such as Xanthum gum (Kelco ex Kelsan and Rhodopol ex Rhone- Poulenc) , Guar gum (Jaguar ex Rhone-Poulenc) , starches and cellulose ethers.
  • biological polymers such as Xanthum gum (Kelco ex Kelsan and Rhodopol ex Rhone- Poulenc) , Guar gum (Jaguar ex Rhone-Poulenc) , starches and cellulose ethers.
  • Synthetic polymers are useful viscosity control agents such as polyacrylic acid, poly vinyl pyrrolidone, polyethylene, carbomers, cross linked polyacrylamides such as Acosol 880/882 polyethylene and polyethylene glycols.
  • compositions are substantially free of bleaches.
  • compositions are entirely free of bleaches .
  • Suitable as viscosity modifiers are decoupling polymers and deflocculatmg polymers.
  • compositions may be m any form conventionally used for fabric softening compositions e.g., powder, paste, gel or liquid. Liquids, especially emulsions are preferred.
  • compositions may be prepared by any suitable method.
  • the antioxidant is oil soluble, e.g. the propagation inhibitor, the antioxidant is suitably pre-added with the CPE or RSE.
  • the antioxidant is water soluble, e.g. the initiation inhibitor, especially metal sequestrants , the inhibitor is typically post-dosed to a pre-formed emulsion containing the CPE or RSE. Examples
  • %'s are by weight based on the total weight of the composition and represent the amount of active compound. Examples 1 and 14 are controls which do not contain antioxidant. In Ryoto 0-170, 85% or greater of the fatty acid chains contain an unsaturated bond.
  • Examples 2 to 13 were prepared by dissolving the propagation inhibitor antioxidant (Irganox 1330 or Irganox 1010) m the CPE (Ryoto 0-170) and adding this to a separate mixture of a cationic and water (in an amount to make the composition up to 100 weight %) .
  • the resultant composition was mixed using a low shear Heidolph mixer to produce an emulsion.
  • the initiation inhibitor antioxidant (Dequest 2066) was post-dosed to this emulsion.
  • Examples 14 to 24 were prepared by mixing the cationic surfactant (CTAC) with water and then addin ⁇ to this mixture the CPE (Ryoto O-170) at room temperature under conditions of high shear to produce an emulsion.
  • CAC cationic surfactant
  • the propagation inhibitor antioxidant (Irganox 1010) was dissolved m the CPE prior to emulsification.
  • the initiation inhibitor antioxidant (Dequest 2066, DTPA or Na IDS) was post-dosed into the final emulsion.
  • sucrose pentaoleate from Mitsubishi-Kagaku Food Corporation
  • cetyl trimethyl ammonium chloride from Aldrich (as a 25% solution)
  • diethylene triammepenta methylene phosphonate
  • A is Irganox 1330; 1 , 3 , 5-t ⁇ methyl-2 , 4 , 6- t ⁇ s- (3 ' , 5 ' di- tert -butyl -4 ' -hydroxybenzyl ) benzene .
  • B is Irganox 1010; Tetrakis [methylene (3 , 5-d ⁇ -tert-butyl • 4 -hydroxyhydrocmnamate )] methane (Both from Ciba Geigy) .
  • the samples were stored m screw-top glass bottles at 37°C to 45 °C. At the intervals given m Tables 3 and 4 the bottles were removed from storage and the samples assessed for the development of malodour (which was determined by assessing the level of a rancid 'fatty' smell present) . Before each assessment the samples allowed to equilibrate at room temperature. The malodour was assessed at room temperature by sniffing the odours from the equilibrated sample and assigning a value between 0 and 5 to indicated the level of malodour. Zero was given if the sample had no perceivable rancid smell and five was given for a very strong rancid smell . At least ten people assessed each sample and the average value was calculated from their response.
  • Example 1 - 13 and 14 - 24 are shown m Tables 3 and 4 respect ively .
  • Table 3 shows the malodour values determined for examples 1-13 over a 27 week testing period with storage between 37 C-45°C.
  • Table 4 shows the malodour values determined for examples 14-24 over a 4 week testing period with storage at
  • compositions which have improved malodour suppression m the presence of propagation and the initiation inhibitor are given m the following examples.
  • Examples 25 to 28 in Table 5 below were prepared by mixing the listed components together m water.
  • Irganox 1010, Dequest 2066 and CTAC are described above.
  • the Ryoto products are available from Mitsubishi -Kagaku Food
  • HEQ is 1,2 bis [hardened tallowoyloxy] -3 - trimethylammonium propane chloride available from Hoechst .
  • Arquad 2-HT is ditallow dimethyl ammonium chloride Example 35
  • Example 35 was prepared as a 5% total active emulsion/dispersion m water comprising 4.5% sucrose tetraerucate (oily liquid, Ryoto ER 290), 0.5% CTAC, 0.01% Dequest 2066, 0.0045% Irganox 1010 and 0.2% of a polymer deposition aid as given below: -
  • Example 35a FlocAid 34 (ex National Starch)
  • Example 35b Softgel BDA (ex Avebe)
  • Example 36 was prepared as a 1:4 emulsion/dispersion (5% total active) of DEEDMAC : sucrose pentaoleate (Ryoto 0-170) by mixing at high temperatures. To this is added , 0.01% Dequest 2066 and 0.004% Irganox 1010.
  • a fully formulated fabric softening composition as according to the present invention was prepared as below:
  • Coco alcohol 15EO (ex Cla ⁇ ant) dodec l benzene sulphomc acid sodium salt (ex Aldrich Chemical Company) C Softqel BDA (ex Aveoe)
  • Table 8 shows the T 2 NMR solid: liquid ratio of CPEs and RSEs used according to the present invention. The ratios were measured at 20 C. The degree of esterification /ethe ⁇ fication is stated.
  • compositions m table 9 were prepared as follows: The propagation inhibitor was dissolved in the sucrose tetraoleate a weight ratio of 99.9:0.1. This mixture was then comelted with the TEA and Coco-15EO and then added to water at 60 C with stirring using a low shear Heidolph mixer. The resulting mixture was stirred for 10 minutes before being cooled to room temperature. Where an initiation inhibitor was used, it was post-dosed to the final mixture as a 5% solution m water with mixing.
  • Table 10 shows the malodour values determined for examples 39-52 over a 9 week testing period with storage at

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Detergent Compositions (AREA)
  • Fats And Perfumes (AREA)

Abstract

L'invention concerne une composition adoucissante pour tissus offrant une résistance accrue aux mauvaises odeurs et comprenant i) un dérivé liquide ou solide mou d'un polyol cyclique (CPE) ou d'un saccharide réduit (RSE) obtenu à partir de 35 % à 100 % des groupes hydroxy du polyol ou du saccharide en cours d'estérification ou d'étherification, le CPE ou le RSE comportant au moins 2 groupes ester ou éther fixés indépendamment à une chaîne C8-C22 alkyle ou alcényle, l'une des chaînes fixées aux groupes ester ou éther comprenant une liaison non saturée, ii) un agent favorisant le dépôt, et iii) un ou plusieurs antioxydants, le rapport de poids entre i) et iii) étant de 20:1 ou plus. L'invention concerne également un procédé de réduction des mauvaises odeurs, dans une composition contenant un CPE ou un RSE tels que définis ci-dessus, par addition d'au moins un antioxydant.
PCT/GB2000/001699 1999-05-17 2000-05-03 Compositions adoucissantes pour tissus WO2000070004A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
EP00929672A EP1179037B1 (fr) 1999-05-17 2000-05-03 Compositions adoucissantes pour tissus
MXPA01011697A MXPA01011697A (es) 1999-05-17 2000-05-03 Composiciones de suavizantes de telas.
HU0201469A HU228798B1 (en) 1999-05-17 2000-05-03 Fabric softening composition and a method for reducing its unpleasant odour
BRPI0010574-0A BR0010574B1 (pt) 1999-05-17 2000-05-03 composição amaciante para tecidos, e, processo para redução de mau cheiro em uma composição.
AU47679/00A AU768506B2 (en) 1999-05-17 2000-05-03 Fabric softening compositions
JP2000618411A JP2002544406A (ja) 1999-05-17 2000-05-03 繊維製品柔軟化組成物
ROA200101223A RO121134B1 (ro) 1999-05-17 2000-05-03 Compoziţie de emoliere a ţesăturilor
PL351739A PL191651B1 (pl) 1999-05-17 2000-05-03 Kompozycja do zmiękczania tkanin i sposób zmniejszania przykrego zapachu kompozycji do zmiękczania tkanin
DE60026988T DE60026988T2 (de) 1999-05-17 2000-05-03 Textilweichmacherzusammensetzungen
CA2367033A CA2367033C (fr) 1999-05-17 2000-05-03 Compositions adoucissantes qui comprennent des antioxydants attenuant les mauvaises odeurs

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9911434.0A GB9911434D0 (en) 1999-05-17 1999-05-17 Fabric softening compositions
GB9911434.0 1999-05-17

Publications (1)

Publication Number Publication Date
WO2000070004A1 true WO2000070004A1 (fr) 2000-11-23

Family

ID=10853610

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2000/001699 WO2000070004A1 (fr) 1999-05-17 2000-05-03 Compositions adoucissantes pour tissus

Country Status (21)

Country Link
EP (1) EP1179037B1 (fr)
JP (1) JP2002544406A (fr)
CN (1) CN1225530C (fr)
AR (1) AR023998A1 (fr)
AT (1) ATE321835T1 (fr)
AU (1) AU768506B2 (fr)
BR (1) BR0010574B1 (fr)
CA (1) CA2367033C (fr)
CZ (1) CZ298908B6 (fr)
DE (1) DE60026988T2 (fr)
ES (1) ES2258006T3 (fr)
GB (1) GB9911434D0 (fr)
HU (1) HU228798B1 (fr)
MX (1) MXPA01011697A (fr)
MY (1) MY154358A (fr)
PL (1) PL191651B1 (fr)
RO (1) RO121134B1 (fr)
RU (1) RU2227804C2 (fr)
TR (1) TR200103291T2 (fr)
WO (1) WO2000070004A1 (fr)
ZA (1) ZA200107246B (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001046363A1 (fr) * 1999-12-22 2001-06-28 Unilever Plc Procede de preparation de compositions d'adoucissement de textiles
WO2001046361A1 (fr) * 1999-12-22 2001-06-28 Unilever Plc Compositions d'assouplissement de tissu
US6503490B2 (en) 2000-10-09 2003-01-07 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Deodorant products
WO2005121184A1 (fr) * 2004-06-09 2005-12-22 Unilever Plc Composition d'entretien des textiles
WO2006076952A1 (fr) * 2005-01-18 2006-07-27 Unilever Plc Compositions de conditionnement de tissus
WO2007078782A1 (fr) * 2005-12-15 2007-07-12 The Procter & Gamble Company Compositions pour l'entretien des textiles ayant un effet adoucissant, antistatique et parfume
US7749952B2 (en) 2006-12-05 2010-07-06 The Procter & Gamble Company Fabric care compositions for softening, static control and fragrance benefits
US7776813B2 (en) 2004-09-15 2010-08-17 The Procter & Gamble Company Fabric care compositions comprising polyol based fabric care materials and deposition agents
WO2022235655A1 (fr) 2021-05-04 2022-11-10 Nutrition & Biosciences USA 4, Inc. Compositions comprenant un alpha-glucane insoluble
WO2023287684A1 (fr) 2021-07-13 2023-01-19 Nutrition & Biosciences USA 4, Inc. Dérivés d'ester de glucane cationique
WO2023081346A1 (fr) 2021-11-05 2023-05-11 Nutrition & Biosciences USA 4, Inc. Dérivés de glucane pour la lutte antimicrobienne
WO2023114942A1 (fr) 2021-12-16 2023-06-22 Nutrition & Biosciences USA 4, Inc. Compositions comprenant des éthers d'alpha-glucane cationiques dans des solvants organiques polaires aqueux
WO2024015769A1 (fr) 2022-07-11 2024-01-18 Nutrition & Biosciences USA 4, Inc. Dérivés amphiphiles d'ester de glucane
WO2024081773A1 (fr) 2022-10-14 2024-04-18 Nutrition & Biosciences USA 4, Inc. Compositions comprenant de l'eau, un éther d'alpha-1,6-glucane cationique et un solvant organique

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6846786B1 (en) * 2003-10-09 2005-01-25 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Process for making low surfactant, high sugar bars
GB0511313D0 (en) * 2005-06-03 2005-07-13 Unilever Plc Incorporation of antioxidant in detergent composition
EP3733824B1 (fr) * 2019-05-03 2023-09-20 The Procter & Gamble Company Procédés de traitement de tissus contenant de l'élasthane avec des compositions de traitement de tissus contenant un antioxydant pour ralentir la formation d'espèces malodorantes générées par auto-oxydation des salissures
JP6982917B1 (ja) * 2021-04-27 2021-12-17 株式会社 きものブレイン 柔軟剤

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0325184A1 (fr) * 1988-01-21 1989-07-26 Colgate-Palmolive Company Ethers de sucre acetylé utilisés comme activateurs de blanchiment, agent d'amélioration du lavage et agent adoucissant pour tissu
EP0530958A2 (fr) * 1991-09-06 1993-03-10 Colgate-Palmolive Company Produits adoucissants pour le linge à base d'une combination d'un composé de pentaérythritol et bentonite
WO1996003492A1 (fr) * 1994-07-26 1996-02-08 The Procter & Gamble Company Produit de traitement du linge en sechoir contenant des antioxydants et des ecrans solaires protegeant le linge de la decoloration sous l'effet du soleil
WO1996015213A1 (fr) * 1994-11-14 1996-05-23 Henkel Kommanditgesellschaft Auf Aktien Agents assouplissants pour textiles
JPH08158258A (ja) * 1994-12-09 1996-06-18 Kao Corp 抗菌性柔軟剤組成物
WO1998016538A1 (fr) * 1996-10-16 1998-04-23 Unilever Plc Composition adoucissant les tissus

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0325184A1 (fr) * 1988-01-21 1989-07-26 Colgate-Palmolive Company Ethers de sucre acetylé utilisés comme activateurs de blanchiment, agent d'amélioration du lavage et agent adoucissant pour tissu
EP0530958A2 (fr) * 1991-09-06 1993-03-10 Colgate-Palmolive Company Produits adoucissants pour le linge à base d'une combination d'un composé de pentaérythritol et bentonite
WO1996003492A1 (fr) * 1994-07-26 1996-02-08 The Procter & Gamble Company Produit de traitement du linge en sechoir contenant des antioxydants et des ecrans solaires protegeant le linge de la decoloration sous l'effet du soleil
WO1996015213A1 (fr) * 1994-11-14 1996-05-23 Henkel Kommanditgesellschaft Auf Aktien Agents assouplissants pour textiles
JPH08158258A (ja) * 1994-12-09 1996-06-18 Kao Corp 抗菌性柔軟剤組成物
WO1998016538A1 (fr) * 1996-10-16 1998-04-23 Unilever Plc Composition adoucissant les tissus

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 10 31 October 1996 (1996-10-31) *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001046361A1 (fr) * 1999-12-22 2001-06-28 Unilever Plc Compositions d'assouplissement de tissu
WO2001046363A1 (fr) * 1999-12-22 2001-06-28 Unilever Plc Procede de preparation de compositions d'adoucissement de textiles
US6503490B2 (en) 2000-10-09 2003-01-07 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Deodorant products
US7357987B2 (en) 2004-06-09 2008-04-15 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Fabric care composition comprising a polysaccharide-grafted polymer particle
WO2005121184A1 (fr) * 2004-06-09 2005-12-22 Unilever Plc Composition d'entretien des textiles
US7776813B2 (en) 2004-09-15 2010-08-17 The Procter & Gamble Company Fabric care compositions comprising polyol based fabric care materials and deposition agents
WO2006076952A1 (fr) * 2005-01-18 2006-07-27 Unilever Plc Compositions de conditionnement de tissus
WO2007078782A1 (fr) * 2005-12-15 2007-07-12 The Procter & Gamble Company Compositions pour l'entretien des textiles ayant un effet adoucissant, antistatique et parfume
US7749952B2 (en) 2006-12-05 2010-07-06 The Procter & Gamble Company Fabric care compositions for softening, static control and fragrance benefits
WO2022235655A1 (fr) 2021-05-04 2022-11-10 Nutrition & Biosciences USA 4, Inc. Compositions comprenant un alpha-glucane insoluble
WO2023287684A1 (fr) 2021-07-13 2023-01-19 Nutrition & Biosciences USA 4, Inc. Dérivés d'ester de glucane cationique
WO2023081346A1 (fr) 2021-11-05 2023-05-11 Nutrition & Biosciences USA 4, Inc. Dérivés de glucane pour la lutte antimicrobienne
WO2023081341A1 (fr) 2021-11-05 2023-05-11 Nutrition & Biosciences USA 4, Inc. Compositions comprenant un dérivé d'alpha-1,6-glucane cationique et un alpha-1,3-glucane
WO2023114942A1 (fr) 2021-12-16 2023-06-22 Nutrition & Biosciences USA 4, Inc. Compositions comprenant des éthers d'alpha-glucane cationiques dans des solvants organiques polaires aqueux
WO2024015769A1 (fr) 2022-07-11 2024-01-18 Nutrition & Biosciences USA 4, Inc. Dérivés amphiphiles d'ester de glucane
WO2024081773A1 (fr) 2022-10-14 2024-04-18 Nutrition & Biosciences USA 4, Inc. Compositions comprenant de l'eau, un éther d'alpha-1,6-glucane cationique et un solvant organique

Also Published As

Publication number Publication date
DE60026988T2 (de) 2006-09-21
ZA200107246B (en) 2002-09-02
MXPA01011697A (es) 2002-05-14
AR023998A1 (es) 2002-09-04
EP1179037A1 (fr) 2002-02-13
JP2002544406A (ja) 2002-12-24
CA2367033C (fr) 2010-04-06
PL191651B1 (pl) 2006-06-30
CZ298908B6 (cs) 2008-03-12
AU4767900A (en) 2000-12-05
CN1225530C (zh) 2005-11-02
BR0010574A (pt) 2002-02-19
TR200103291T2 (tr) 2002-04-22
CZ20014054A3 (cs) 2002-08-14
ES2258006T3 (es) 2006-08-16
BR0010574B1 (pt) 2009-08-11
HUP0201469A2 (en) 2002-08-28
AU768506B2 (en) 2003-12-11
RU2227804C2 (ru) 2004-04-27
ATE321835T1 (de) 2006-04-15
CA2367033A1 (fr) 2000-11-23
CN1350572A (zh) 2002-05-22
DE60026988D1 (de) 2006-05-18
HU228798B1 (en) 2013-05-28
RO121134B1 (ro) 2006-12-29
PL351739A1 (en) 2003-06-02
GB9911434D0 (en) 1999-07-14
MY154358A (en) 2015-05-29
EP1179037B1 (fr) 2006-03-29
HUP0201469A3 (en) 2004-03-01

Similar Documents

Publication Publication Date Title
EP1240292B1 (fr) Compositions d'assouplissement de tissu
AU768506B2 (en) Fabric softening compositions
EP0507478B1 (fr) Composition adoucissante pour le linge
CA2395565C (fr) Stabilisation de compositions adoucissantes a l'aide d'un derive de sucre a composante lipidique
EP1283859B1 (fr) Procede de fabrication d'une composition adoucissante
US20010034315A1 (en) Fabric softening compositions and compounds
US6436896B2 (en) Method for preparing fabric softening compositions
US20010006938A1 (en) Use of fabric conditioning compositions for ironing benefits
CA2233229C (fr) Composition assouplissante pour textiles

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 00807530.1

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2367033

Country of ref document: CA

Ref document number: 2367033

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2001/07246

Country of ref document: ZA

Ref document number: 200107246

Country of ref document: ZA

WWE Wipo information: entry into national phase

Ref document number: 2000929672

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 47679/00

Country of ref document: AU

ENP Entry into the national phase

Ref document number: 2000 618411

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PV2001-4054

Country of ref document: CZ

Ref document number: IN/PCT/2001/01399/MU

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: PA/a/2001/011697

Country of ref document: MX

Ref document number: 2001/03291

Country of ref document: TR

Ref document number: A 2001 01223

Country of ref document: RO

WWP Wipo information: published in national office

Ref document number: 2000929672

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: PV2001-4054

Country of ref document: CZ

WWG Wipo information: grant in national office

Ref document number: 47679/00

Country of ref document: AU

WWG Wipo information: grant in national office

Ref document number: 2000929672

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: PV2001-4054

Country of ref document: CZ