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WO2000042160A1 - Improved detergent bar composition - Google Patents

Improved detergent bar composition Download PDF

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Publication number
WO2000042160A1
WO2000042160A1 PCT/EP1999/008327 EP9908327W WO0042160A1 WO 2000042160 A1 WO2000042160 A1 WO 2000042160A1 EP 9908327 W EP9908327 W EP 9908327W WO 0042160 A1 WO0042160 A1 WO 0042160A1
Authority
WO
WIPO (PCT)
Prior art keywords
soap
bar composition
lather
fatty acid
branched chain
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP1999/008327
Other languages
French (fr)
Inventor
Atul Bhatia
Ravi Harikiran
Vineet Mital
Devarakonda Saikrishna
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hindustan Unilever Ltd
Unilever NV
Original Assignee
Hindustan Lever Ltd
Unilever NV
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
Application filed by Hindustan Lever Ltd, Unilever NV filed Critical Hindustan Lever Ltd
Priority to AT99973608T priority Critical patent/ATE260969T1/en
Priority to CA002359135A priority patent/CA2359135C/en
Priority to JP2000593717A priority patent/JP4537586B2/en
Priority to BRPI9916859-6A priority patent/BR9916859B1/en
Priority to AU11587/00A priority patent/AU762285B2/en
Priority to DE69915353T priority patent/DE69915353T2/en
Priority to EP99973608A priority patent/EP1141228B1/en
Publication of WO2000042160A1 publication Critical patent/WO2000042160A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/006Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00Compositions of detergents, not provided for by one single preceding group
    • C11D10/04Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/04Carboxylic acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/04Carboxylic acids or salts thereof
    • C11D1/06Ether- or thioether carboxylic acids

Definitions

  • the invention relates to a detergent composition with superior sensory and in-use properties.
  • Soaps have long been manufactured from fats by conversion of triglyceride components of fats into fatty acid salts, followed by the formation of these 'soaps' into various product forms such as bars, liquids, gels etc.
  • fatty acid soaps have various shortcomings such as depression of lather in hard water, formation of lime soap curd, cracking and embrittlement of the bars, poor sensory properties, harshness on the skin and other problems.
  • GB 931,731 discloses the use of non-ionic surfactants such as ethoxylated and propoxylated alkanol amides in soap bars to prevent lime soap formation during use in hard water.
  • Fatty alcohol ethoxylates in soap bars (such as e.g.
  • WO9317088 or EP363215 have been known to reduce lime soap formation, and hence prevents soap residue on skin. This results in improved mildness and product properties such as lathering, reduced mush etc.
  • Straight or branched fatty acid ethoxylates are known to impart superior detergency against heavy chains, make-up and are known to generate good foam and have conditioning effect on hair and skin. These disclose liquid formulations containing straight or branched fatty acid ethoxylates with a degree of ethoxylation greater than 7 and incorporation levels of 10-60% by weight.
  • perfumes are incorporated into soap formulations to mask the soap base odour and provide a sensory attribute.
  • the perfume impact of soaps reduces on storage, and as a result only a part of the initial perfume added at the time of manufacture is perceived by the end user.
  • Another object of the present invention is to provide detergent composition with superior sensory and in-use properties which would be simple to manufacture, and will be cost-effective .
  • a detergent composition comprising of: i. 40 to 85% soap ii . 0.1-10% branched chain non-ionic surfactant and iii . other conventional ingredients.
  • a detergent composition comprising of: i. 40 to 85% soap ii. 0.1-10% branched chain fatty acid ethoxylate and iii. other conventional ingredients.
  • a detergent composition comprising of: i. 40 to 85% soap ii 0.1-10% branched chain fatty acid ethoxylate with
  • soap varies from 40 to 85% by weight and it essentially comprises of Cg-C]_ 4 fatty acids soaps in an amount of up to 50% by weight, and preferably up to 25% by weight.
  • the balance soap is selected from palmitic, stearic, oleic and linoleic fatty acids such that the Iodine Value of the final soap composition varies from 0-60, preferably in the range of 30- 50.
  • Non-ionic surfactants used in the composition of the invention is preferably selected from branched chain fatty acid ethoxylates with a general formula RCOO (CH 2 CH 0) n H, where n varies from 1 to 7.
  • the preferred fatty acid is isostearic acid, and the preferred level of ethoxylation in the range 3-5.
  • the non-ionic surfactant is incorporated in the final soap composition at 0.1-10% by weight and preferably from 1-5% by weight.
  • Optional ingredients such as polycarboxylic acid, alkylsulphate ethoxylates, super fatting agent such as fatty acids, and moisturising agents such as glycerine to improve the performance may be incorporated.
  • Other conventional ingredients for e.g. fillers, perfumes, opacifiers, preservatives, antimicrobial agents, as required are added to the formulation.
  • Any polycarboxylic acids in the composition are generally aliphatic and branched or straight chained.
  • the polycarboxylic acid is preferably a C 2 -C 12 dicarboxylic acid and more preferably a C to Cg dicarboxylic acid.
  • the superfatting may be provided in the composition of the invention either by the addition of a superfatting agent such as a triglyceride of fatty acids of Cg-Ci 8 carbon atoms or by the addition of fatty acids of C 6 -C 18 type.
  • a superfatting agent such as a triglyceride of fatty acids of Cg-Ci 8 carbon atoms or by the addition of fatty acids of C 6 -C 18 type.
  • Superfatting can also be achieved by addition of polycarboxylic acids or mineral acids to soap.
  • Fillers may be incorporated at 0-40% and selected from hydrated magnesium silicate, hydrated aluminium silicate or any other suitable material .
  • Perfumes can be used in formulating the product at a level of from 0.1 to 3% of the composition.
  • Lather of the soap bar was determined both in soft water (4 deg. French hardness) and hard water (24 deg. French hardness) by a panel of five members.
  • the soap bar was rotated in the palm 20 times approx. with a little water and the lather generated was poured into a measuring jar to determine the quantity in millilitres. An average of 15 such measurements were reported as the final value of lather.
  • Rate of wear was determined by a panel of five members who used the personal wash bar with 10 rubs a day for four days. At the end of four days, each tablet was washed free of the mush and was weighed to determine the final weight and the difference between the initial and final weights is reported as % wear.
  • Lather/rate of wear (ROW) index which is determined using the above mentioned information on lather volume and rate of wear is an indicator of the user value perception, wherein a lower number would mean that the lather generated per unit rate of wear is low, and the consumer has to use more quantity of soap per bath.
  • the data presented in Table 2 shows that this lather/ROW index has improved after incorporation of isostearic acid with 3 or 5 EO and is superior to the Control and that with unbranched isostearic acid.
  • In-use properties such as lather volume, rate of wear and sensory properties such as after wash feel, in-use feel and lather characteristics and perfume impact on storage were analyzed using control bars, and those according to the invention, which contained 2% by weight of branched isostearic acid with 3EO (Table 3) .
  • Rate of wear was determined by a panel of five members who used the personal wash bar with 10 rubs a day for four days. At the end of four days, each tablet was washed free of the mush, and was weighed to determine the final weight and the difference between the initial and final weights is reported as % wear.
  • Lather of the soap bar was determined both in soft water (4 deg. French hardness) and hard water (24 deg. French hardness) by a panel of five members.
  • the soap bar was rotated in the palm 20 times approx. with a little water, and the lather generated was poured into a measuring jar to determine the quantity in millilitres. An average of 15 such measurements were reported as the final value of lather.
  • the feel assessment was carried out by an internal panel to evaluate the lather, in-use feel and post wash feel qualitatively, and expressed quantitatively on a scale of 1 - 5.
  • the soap bar was wetted and applied on the forearm by the panelist, and observed for performance with respect to the above mentioned parameters.
  • Perfume impact was assessed by a panel of expert perfumers on a scale of 1-10. This was done initially and after a period of storage up to 24 weeks.
  • Table 4 shows that the formulation according to the invention shows that the % wear and mush volume is reduced whereas the lather volume is increased and the lather generated is creamier and that the in-use and after wash feel is superior.
  • the impact of the perfume gradually reduces due to storage but in the formulation prepared according to the invention even after storage the perfume impact is maintained significantly superior.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Abstract

A soap bar composition comprising 40-85% soap and 0.1-10% of a branched chain nonionic fatty acid ethoxylate surfactant. Preferably the fatty acid ethoxylate surfactant has an EO number no greater than 7.

Description

IMPROVED DETERGENT BAR COMPOSITION
The invention relates to a detergent composition with superior sensory and in-use properties.
Soaps have long been manufactured from fats by conversion of triglyceride components of fats into fatty acid salts, followed by the formation of these 'soaps' into various product forms such as bars, liquids, gels etc. However, fatty acid soaps have various shortcomings such as depression of lather in hard water, formation of lime soap curd, cracking and embrittlement of the bars, poor sensory properties, harshness on the skin and other problems.
There have been several approaches to solve these problems. GB 931,731 discloses the use of non-ionic surfactants such as ethoxylated and propoxylated alkanol amides in soap bars to prevent lime soap formation during use in hard water.
Fatty alcohol ethoxylates in soap bars (such as e.g.
WO9317088 or EP363215) have been known to reduce lime soap formation, and hence prevents soap residue on skin. This results in improved mildness and product properties such as lathering, reduced mush etc.
Straight or branched fatty acid ethoxylates (such as in e.g. JP59179599, JP05117138 or JP07179322) are known to impart superior detergency against heavy chains, make-up and are known to generate good foam and have conditioning effect on hair and skin. These disclose liquid formulations containing straight or branched fatty acid ethoxylates with a degree of ethoxylation greater than 7 and incorporation levels of 10-60% by weight.
Conventionally perfumes are incorporated into soap formulations to mask the soap base odour and provide a sensory attribute. The perfume impact of soaps reduces on storage, and as a result only a part of the initial perfume added at the time of manufacture is perceived by the end user.
We have now found that surprisingly using certain branched chain nonionic surfactants at very low levels in a soap formulation gives improved perfume impact even after prolonged storage of the formulation under various environmental conditions. It also gives enhanced benefit with respect to performance, and sensory properties even under hard water conditions.
It is the basic objective of the present invention to provide a detergent composition with enhanced perfume impact on storage along with improved sensory and in-use properties .
Another object of the present invention is to provide detergent composition with superior sensory and in-use properties which would be simple to manufacture, and will be cost-effective .
Thus according to the present invention there is provided a detergent composition comprising of: i. 40 to 85% soap ii . 0.1-10% branched chain non-ionic surfactant and iii . other conventional ingredients. According to a preferred aspect of the invention there is provided a detergent composition comprising of: i. 40 to 85% soap ii. 0.1-10% branched chain fatty acid ethoxylate and iii. other conventional ingredients.
According to a more preferred aspect of the invention there is provided a detergent composition comprising of: i. 40 to 85% soap ii 0.1-10% branched chain fatty acid ethoxylate with
EO not greater than 7 and iii. other conventional ingredients.
In the above detergent composition of the invention soap varies from 40 to 85% by weight and it essentially comprises of Cg-C]_4 fatty acids soaps in an amount of up to 50% by weight, and preferably up to 25% by weight. The balance soap is selected from palmitic, stearic, oleic and linoleic fatty acids such that the Iodine Value of the final soap composition varies from 0-60, preferably in the range of 30- 50.
Non-ionic surfactants used in the composition of the invention is preferably selected from branched chain fatty acid ethoxylates with a general formula RCOO (CH2CH 0) nH, where n varies from 1 to 7. The preferred fatty acid is isostearic acid, and the preferred level of ethoxylation in the range 3-5. The non-ionic surfactant is incorporated in the final soap composition at 0.1-10% by weight and preferably from 1-5% by weight. Optional ingredients such as polycarboxylic acid, alkylsulphate ethoxylates, super fatting agent such as fatty acids, and moisturising agents such as glycerine to improve the performance may be incorporated. Other conventional ingredients for e.g. fillers, perfumes, opacifiers, preservatives, antimicrobial agents, as required are added to the formulation.
Any polycarboxylic acids in the composition are generally aliphatic and branched or straight chained. The polycarboxylic acid is preferably a C2-C12 dicarboxylic acid and more preferably a C to Cg dicarboxylic acid.
The superfatting may be provided in the composition of the invention either by the addition of a superfatting agent such as a triglyceride of fatty acids of Cg-Ci8 carbon atoms or by the addition of fatty acids of C6-C18 type.
Superfatting can also be achieved by addition of polycarboxylic acids or mineral acids to soap.
Fillers may be incorporated at 0-40% and selected from hydrated magnesium silicate, hydrated aluminium silicate or any other suitable material .
Perfumes can be used in formulating the product at a level of from 0.1 to 3% of the composition.
The invention will now be described with reference to the following non-limiting examples. EXAMPLES :
Different soap compositions under Examples 1 and 2 (Controls) and Examples 3 and 4 (in accordance with the invention) detailed in Table 1 were prepared as toilet soap bars as described hereunder:
Table 1
Figure imgf000007_0001
Method of manufacture followed:
480 kg of neat soap was taken in the holding tank and spray dried into noodles of moisture content of about 14%, which was then taken in a conventional sigma mixer. The other specific ingredients mentioned for the different Examples were added during mixing to obtain the specific formulation. Other minor ingredients and water was added and mixed, milled and plodded into bars and stamped subsequently.
Lather/Rate of wear index:
Lather of the soap bar was determined both in soft water (4 deg. French hardness) and hard water (24 deg. French hardness) by a panel of five members. The soap bar was rotated in the palm 20 times approx. with a little water and the lather generated was poured into a measuring jar to determine the quantity in millilitres. An average of 15 such measurements were reported as the final value of lather. Rate of wear was determined by a panel of five members who used the personal wash bar with 10 rubs a day for four days. At the end of four days, each tablet was washed free of the mush and was weighed to determine the final weight and the difference between the initial and final weights is reported as % wear.
Lather/rate of wear (ROW) index which is determined using the above mentioned information on lather volume and rate of wear is an indicator of the user value perception, wherein a lower number would mean that the lather generated per unit rate of wear is low, and the consumer has to use more quantity of soap per bath. The data presented in Table 2 shows that this lather/ROW index has improved after incorporation of isostearic acid with 3 or 5 EO and is superior to the Control and that with unbranched isostearic acid.
Table 2
Figure imgf000008_0001
Improvement in in-use properties:
In-use properties such as lather volume, rate of wear and sensory properties such as after wash feel, in-use feel and lather characteristics and perfume impact on storage were analyzed using control bars, and those according to the invention, which contained 2% by weight of branched isostearic acid with 3EO (Table 3) .
Table 3
Figure imgf000009_0001
Rate of wear:
Rate of wear was determined by a panel of five members who used the personal wash bar with 10 rubs a day for four days. At the end of four days, each tablet was washed free of the mush, and was weighed to determine the final weight and the difference between the initial and final weights is reported as % wear.
Lather:
Lather of the soap bar was determined both in soft water (4 deg. French hardness) and hard water (24 deg. French hardness) by a panel of five members. The soap bar was rotated in the palm 20 times approx. with a little water, and the lather generated was poured into a measuring jar to determine the quantity in millilitres. An average of 15 such measurements were reported as the final value of lather. Feel
The feel assessment was carried out by an internal panel to evaluate the lather, in-use feel and post wash feel qualitatively, and expressed quantitatively on a scale of 1 - 5. The soap bar was wetted and applied on the forearm by the panelist, and observed for performance with respect to the above mentioned parameters.
Perfume impact :
Perfume impact was assessed by a panel of expert perfumers on a scale of 1-10. This was done initially and after a period of storage up to 24 weeks.
Table 4
Figure imgf000010_0001
The data presented in Table 4 shows that the formulation according to the invention shows that the % wear and mush volume is reduced whereas the lather volume is increased and the lather generated is creamier and that the in-use and after wash feel is superior. The impact of the perfume gradually reduces due to storage but in the formulation prepared according to the invention even after storage the perfume impact is maintained significantly superior.

Claims

1. A soap bar composition comprising 40-85% soap and 0.1- 10% of a branched chain nonionic fatty acid ethoxylate surfactant .
2. A bar composition according to claim 1 wherein the branched chain fatty acid ethoxylate surfactant has an EO number not greater than 7.
A bar composition according to claim 1 or claim 2 wherein the soap comprises Cg-C14 fatty acids in an amount of up to 50%, more preferably up to 25% by weight .
A bar composition according to claim 2 or 3 wherein the EO number is in the range 3-5.
5. A bar composition according to any one of the preceding claims additionally comprising a C2-Cι2 dicarboxylic acid.
6. A bar composition according to any one of the preceding claims, wherein the branched chain nonionic surfactant is present at a level of 1-5% by weight.
PCT/EP1999/008327 1999-01-11 1999-11-03 Improved detergent bar composition Ceased WO2000042160A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AT99973608T ATE260969T1 (en) 1999-01-11 1999-11-03 IMPROVED SOAP BAR COMPOSITION
CA002359135A CA2359135C (en) 1999-01-11 1999-11-03 Improved detergent bar composition
JP2000593717A JP4537586B2 (en) 1999-01-11 1999-11-03 Improved solid cleaning composition
BRPI9916859-6A BR9916859B1 (en) 1999-01-11 1999-11-03 Bar soap composition.
AU11587/00A AU762285B2 (en) 1999-01-11 1999-11-03 Improved detergent bar composition
DE69915353T DE69915353T2 (en) 1999-01-11 1999-11-03 IMPROVED SOAP COMPOSITION
EP99973608A EP1141228B1 (en) 1999-01-11 1999-11-03 Improved detergent bar composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9900539 1999-01-11
GB9900539.9 1999-01-11

Publications (1)

Publication Number Publication Date
WO2000042160A1 true WO2000042160A1 (en) 2000-07-20

Family

ID=10845839

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/008327 Ceased WO2000042160A1 (en) 1999-01-11 1999-11-03 Improved detergent bar composition

Country Status (11)

Country Link
EP (1) EP1141228B1 (en)
JP (1) JP4537586B2 (en)
CN (1) CN1179031C (en)
AT (1) ATE260969T1 (en)
AU (1) AU762285B2 (en)
BR (1) BR9916859B1 (en)
CA (1) CA2359135C (en)
DE (1) DE69915353T2 (en)
ID (1) ID29445A (en)
WO (1) WO2000042160A1 (en)
ZA (1) ZA200104733B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001010999A1 (en) * 1999-08-06 2001-02-15 Cognis Deutschland Gmbh Soap bars

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4290904A (en) * 1980-12-01 1981-09-22 Neutrogena Corporation Transparent soap
EP0311343A2 (en) * 1987-10-09 1989-04-12 The Procter & Gamble Company Toilet composition
JPH05262639A (en) * 1992-03-19 1993-10-12 Johnson & Johnson Kk Detergent composition
US5300694A (en) * 1992-03-04 1994-04-05 Smith Ronald J Alkoxylated compounds and their use in cosmetic stick formulations

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1460442A (en) * 1973-01-15 1977-01-06 Unilever Ltd Detergent bars
JPH036299A (en) * 1989-06-02 1991-01-11 Nippon Oil & Fats Co Ltd Solid soap
JPH06287599A (en) * 1993-03-30 1994-10-11 Shiseido Co Ltd Production of soap composition
JP3486444B2 (en) * 1994-01-31 2004-01-13 株式会社資生堂 Skin cleanser

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4290904A (en) * 1980-12-01 1981-09-22 Neutrogena Corporation Transparent soap
EP0311343A2 (en) * 1987-10-09 1989-04-12 The Procter & Gamble Company Toilet composition
US5300694A (en) * 1992-03-04 1994-04-05 Smith Ronald J Alkoxylated compounds and their use in cosmetic stick formulations
JPH05262639A (en) * 1992-03-19 1993-10-12 Johnson & Johnson Kk Detergent composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 199345, Derwent World Patents Index; AN 357130, XP002127395 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001010999A1 (en) * 1999-08-06 2001-02-15 Cognis Deutschland Gmbh Soap bars

Also Published As

Publication number Publication date
ATE260969T1 (en) 2004-03-15
CA2359135C (en) 2008-01-15
DE69915353T2 (en) 2004-07-22
BR9916859A (en) 2001-10-30
ID29445A (en) 2001-08-30
JP2002534598A (en) 2002-10-15
EP1141228A1 (en) 2001-10-10
AU762285B2 (en) 2003-06-19
BR9916859B1 (en) 2010-07-13
EP1141228B1 (en) 2004-03-03
CN1179031C (en) 2004-12-08
CA2359135A1 (en) 2000-07-20
ZA200104733B (en) 2002-06-11
AU1158700A (en) 2000-08-01
DE69915353D1 (en) 2004-04-08
CN1332794A (en) 2002-01-23
JP4537586B2 (en) 2010-09-01

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