EP1141228B1 - Improved detergent bar composition - Google Patents

Improved detergent bar composition Download PDF

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Publication number
EP1141228B1
EP1141228B1 EP99973608A EP99973608A EP1141228B1 EP 1141228 B1 EP1141228 B1 EP 1141228B1 EP 99973608 A EP99973608 A EP 99973608A EP 99973608 A EP99973608 A EP 99973608A EP 1141228 B1 EP1141228 B1 EP 1141228B1
Authority
EP
European Patent Office
Prior art keywords
soap
bar composition
lather
weight
fatty acid
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.)
Expired - Lifetime
Application number
EP99973608A
Other languages
German (de)
French (fr)
Other versions
EP1141228A1 (en
Inventor
Atul Hindustan Lever Ltd BHATIA
Ravi Hindustan Lever Ltd HARIKIRAN
Vineet Hindustan Lever Ltd MITAL
Devarakonda Hindustan Lever Ltd 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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP1141228A1 publication Critical patent/EP1141228A1/en
Application granted granted Critical
Publication of EP1141228B1 publication Critical patent/EP1141228B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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 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.
  • EP-A-0311343 describes a toilet bar composition
  • a toilet bar composition comprising: (a) from about 45% to about 90% by weight of soluble alkali metal soap of C 8 -C 24 fatty acids; (b) from 0.5% to about 45% of an ethoxylated nonionic surfactant having an HLB in the range of from about 12 to about 19.5; and (c) from about 0.01% to about 5% of a water-soluble polymer.
  • US 4,290,904 describes a transparent low alkalinity bar soap comprising a tetrakis (hydroxyalkyl) ethylene diamine, a sodium soap prepared by saponification of fatty oil, a polyhydric alcohol to ensure transparency and a fatty acid superfatting agent.
  • 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:
  • soap varies from 40 to 85% by weight and it essentially comprises of C 8 -C 14 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 2 O) 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 2 to C 8 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 C 6 -C 18 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.
  • a superfatting agent such as a triglyceride of fatty acids of C 6 -C 18 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.
  • Lather/Rate of wear Example 1
  • Example 3 Example 4 Soft water 2940 3556 4000 3684 Hard water 3046 3545 3891 3623
  • 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.
  • 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.

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  • 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

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.
JP 05-262639A discloses a detergent composition for reducing eye-stimulating tendency comprising: (a) a higher fatty acid soap(s) in an amount of from 5-50 wt.%; and (b) 0.1 to 15 wt.% of a compound of formula X1O(CH2CH2O)nX2 (A) where X1 and X2 are each H or -COR and where R is 7-17C, opt. branched (un)satd. hydrocarbon and n = 3 - 2000.
EP-A-0311343 describes a toilet bar composition comprising: (a) from about 45% to about 90% by weight of soluble alkali metal soap of C8-C24 fatty acids; (b) from 0.5% to about 45% of an ethoxylated nonionic surfactant having an HLB in the range of from about 12 to about 19.5; and (c) from about 0.01% to about 5% of a water-soluble polymer.
US 4,290,904 describes a transparent low alkalinity bar soap comprising a tetrakis (hydroxyalkyl) ethylene diamine, a sodium soap prepared by saponification of fatty oil, a polyhydric alcohol to ensure transparency and a fatty acid superfatting agent.
US 5,300,694 discloses novel substituted alkoxylated phenol compounds for use in cosmetic stick formulations.
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.
According to the present 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 0.1 to 3% pertume
  • iv. other conventional ingredients.
  • In the above detergent composition of the invention soap varies from 40 to 85% by weight and it essentially comprises of C8-C14 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(CH2CH2O)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 C2 to C8 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 C6-C18 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:
    Composition (% wt.) Example 1 Example 2 Example 3 Example 4
    Soap 55.0 55.0 55.0 55.0
    Isostearic acid - 2.0 - -
    Isostearic acid EO 3 - - 2.0 -
    Isostearic acid EO 5 - - - 2.0
    Fillers 29.0 29.0 29.0 29.0
    Perfume 1.5 1.5 1.5 1.5
    Minor ingredients 2.0 2.0 2.0 2.0
    to 100% with water
    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.
    Lather/Rate of wear Example 1 Example 2 Example 3 Example 4
    Soft water 2940 3556 4000 3684
    Hard water 3046 3545 3891 3623
    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).
    Composition (% wt.) Example 5 Example 6
    Soap 82.0 80.0
    Isostearic acid 3EO 0.0 2.0
    Perfume 1.5 1.5
    Minor ingredients 2.0 2.0
    Water To 100 To 100
    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.
    Attribute Example 5 Example 6
    Tablet wear (g) 20 16
    % wear 27% 16%
    Lather volume (ml) 396 405
    Mush volume 1.83 1.25
    Feel:
    Lather creaminess
    3.42 3.71
    In-use feel:
    Draggy-slippery 3.3 3.5
    Post wash feel:
    Slimy-squeaky 3.35 3.29
    Dry-Moist 3.25 3.36
    Perfume:
    Initial Impact 7.0 7.0
    Impact after 24 weeks 4.5 5.0
    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 (5)

    1. A soap bar composition comprising 40-85% by weight soap, 0.1 - 10% by weight of a branched chain nonionic fatty acid ethoxylate surfactant and 0.1 to 3% by weight of perfume, characterised in that the branched chain fatty acid ethoxylate surfactant has an EO number not greater than 7.
    2. A bar composition according to claim 1 wherein the soap comprises C8-C14 fatty acids in an amount of up to 50%, more preferably up to 25% by weight.
    3. A bar composition according to claim 1 or 2 wherein the EO number is in the range 3-5.
    4. A bar composition according to any one of the preceding claims additionally comprising a C2-C12 dicarboxylic acid.
    5. 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.
    EP99973608A 1999-01-11 1999-11-03 Improved detergent bar composition Expired - Lifetime EP1141228B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    GB9900539 1999-01-11
    GB9900539 1999-01-11
    PCT/EP1999/008327 WO2000042160A1 (en) 1999-01-11 1999-11-03 Improved detergent bar composition

    Publications (2)

    Publication Number Publication Date
    EP1141228A1 EP1141228A1 (en) 2001-10-10
    EP1141228B1 true EP1141228B1 (en) 2004-03-03

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    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP99973608A Expired - Lifetime EP1141228B1 (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)

    Families Citing this family (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE19937296A1 (en) * 1999-08-06 2001-02-15 Cognis Deutschland Gmbh Bar soaps

    Family Cites Families (8)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    BE809782A (en) * 1973-01-15 1974-07-15 DETERGENT BREADS
    US4290904A (en) * 1980-12-01 1981-09-22 Neutrogena Corporation Transparent soap
    GB8723776D0 (en) * 1987-10-09 1987-11-11 Procter & Gamble Ltd Toilet compositions
    JPH036299A (en) * 1989-06-02 1991-01-11 Nippon Oil & Fats Co Ltd Solid soap
    US5258136A (en) * 1992-03-04 1993-11-02 Application Chemicals, Inc. Alkoxylated compounds and their use in cosmetic stick formulations
    JPH05262639A (en) * 1992-03-19 1993-10-12 Johnson & Johnson Kk Detergent composition
    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

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    Publication number Publication date
    ZA200104733B (en) 2002-06-11
    ID29445A (en) 2001-08-30
    CN1332794A (en) 2002-01-23
    BR9916859B1 (en) 2010-07-13
    WO2000042160A1 (en) 2000-07-20
    JP4537586B2 (en) 2010-09-01
    DE69915353D1 (en) 2004-04-08
    AU1158700A (en) 2000-08-01
    CA2359135A1 (en) 2000-07-20
    AU762285B2 (en) 2003-06-19
    DE69915353T2 (en) 2004-07-22
    JP2002534598A (en) 2002-10-15
    CN1179031C (en) 2004-12-08
    BR9916859A (en) 2001-10-30
    CA2359135C (en) 2008-01-15
    ATE260969T1 (en) 2004-03-15
    EP1141228A1 (en) 2001-10-10

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