WO1994021778A1 - Synthetic detergent bar and manufacture thereof - Google Patents

Synthetic detergent bar and manufacture thereof Download PDF

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Publication number
WO1994021778A1
WO1994021778A1 PCT/EP1994/000792 EP9400792W WO9421778A1 WO 1994021778 A1 WO1994021778 A1 WO 1994021778A1 EP 9400792 W EP9400792 W EP 9400792W WO 9421778 A1 WO9421778 A1 WO 9421778A1
Authority
WO
WIPO (PCT)
Prior art keywords
soap
detergent
water
bars
synthetic
Prior art date
Application number
PCT/EP1994/000792
Other languages
English (en)
French (fr)
Inventor
John George Chambers
Bryan Stuart Joy
Original Assignee
Unilever Plc
Unilever N.V.
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 Unilever Plc, Unilever N.V. filed Critical Unilever Plc
Priority to KR1019950703925A priority Critical patent/KR100200456B1/ko
Priority to BR9406008A priority patent/BR9406008A/pt
Priority to CA002157773A priority patent/CA2157773C/en
Priority to DE69421172T priority patent/DE69421172T2/de
Priority to EP94911169A priority patent/EP0689584B1/en
Priority to PL94310619A priority patent/PL177068B1/pl
Priority to HU9501988A priority patent/HU217658B/hu
Priority to SK1139-95A priority patent/SK113995A3/sk
Priority to AU63771/94A priority patent/AU694728B2/en
Publication of WO1994021778A1 publication Critical patent/WO1994021778A1/en

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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2079Monocarboxylic acids-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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707Polyethers, e.g. polyalkyleneoxides

Definitions

  • This invention relates to synthetic detergent bars and detergent compositions which can be shaped into bars.
  • Washing bars can be classified into soap bars, mixed active bars containing a significant proportion of soap and thirdly synthetic detergent bars containing only a small proportion of soap or none at all.
  • Conventional soap bars comprise a large proportion, typically 60-80% by weight, of fatty acid soap.
  • Fatty acid soaps are selected to provide a balance of soluble and insoluble soaps which provide the required functional properties as regards lather formation and bar structure.
  • Conventional soap bars are manufactured by milling, plodding and stamping a semi-solid mass of soap and other components.
  • Bars which contain a mixture of soap and synthetic detergent where the amount of soap may be less than the amount of synthetic detergent but is nevertheless still a significant contributor to the content of the bar.
  • the content of soap especially the insoluble soap contributes to the structure and physical properties of the bar.
  • the third category is synthetic detergent bars, often known as "Syndet” bars, in which there is no soap or only a small amount and the detergent active is mostly or wholly a synthetic, non-soap, detergent.
  • Such bars contain a substantial proportion of material which is not a detergent and which serves to give structure to the bar.
  • Such "structurants” are normally water- insoluble and include such materials as starch and kaolin.
  • the bars frequently also contain a plasticiser: known plasticisers include stearic acid and cetyl alcohol.
  • known surfactants for Syndet bars include primary alkyl sulphates, alkyl ether sulphates, betaines, sarcosinates, sulphosuccinates and isethionates. These syndet bars containing no soap or only a small proportion of soap are traditionally produced by energetic working of a physical mix of structurant, plasticiser and surfactant, i.e. both the soluble and insoluble components, in a high shear mixer to an end point at which the product is not gritty. The mix is then formed into 'syndet' bars.
  • the known process has several disadvantages in that the physical mixing step is performed batchwise and requires an energetic mixer.
  • syndet bars may be produced by a process which dispenses with the known energetic working step.
  • the invention relies on ingredients which are molten at conveniently accessible temperatures but which are above the temperatures normally encountered during use of "Syndet" bars.
  • the necessary intimate mixing of the ingredients of the bar can be accomplished by simple mixing while the bar composition is liquid rather than by relying on energetic working to achieve intimate mixing of a mixture of solids.
  • the present invention provides a detergent composition which is, or can be shaped into, a synthetic detergent bar, the composition comprising:
  • the content (if any) of material other than said synthetic non-soap detergent (a) which does not melt below 100°C is less than 20% by weight of the composition.
  • the content of the synthetic detergent (a) will lie in the range 10 to 50% by weight.
  • the composition will contain some water, in an amount from 3% or 5% to 20% better at most 15% by weight of the composition.
  • a significant constituent of a composition according to this invention is a water-soluble material which melts at a temperature in the range 40-100°C and serves as a bar structurant.
  • Such a material assists in giving the desired properties notably that the bar has a rigid solid form.
  • the composition of the bar can tolerate the presence of some material which does not melt at temperatures below 100°C.
  • Such material can also serve as a structurant.
  • Such material is not an essential requirement and it may be entirely absent. If such material is present, the molten composition will not be fully liquid at temperatures of up to 100°C unless the non-melting material dissolves in the other materials present.
  • a moderate amount of material which does not melt can be dispersed in the molten composition while it remains sufficiently liquid to be stirred without requiring energetic working.
  • this material which disperses but does not melt may be at least part of the non-soap synthetic detergent (a) and/or material other than this category.
  • Suitable synthetic detergents are: alkyl ether sulphates; alkylethoxylates; alkyl glyceryl ether sulphonates; alpha olefin sulphonates; acyl taurides; methyl acyl taurates; N- acyl glutamates; acyl isethionates; anionic acyl sarcosinates; alkyl phosphates; methyl glucose esters; protein condensates,- ethoxylated alkyl sulphates; alkyl polyglucosides; alkyl amine oxides; betaines; sultaines,- alkyl sulphosuccinates, dialkyl sulphosuccinates, acyl lactylates and mixtures thereof.
  • the above-mentioned detergents are preferably those based upon C 8 to C 24 , more preferably those based upon C 10 to C 18 , alkyl and acyl moieties.
  • the amount of synthetic detergent (a) may lie in the range from 10 to 50% wt . Further preferences are at least 20% and not more than 40%.
  • acyl isethionates are less water-soluble than others. If a detergent of low solubility is used, it is preferably mixed with another synthetic detergent.
  • detergent compositions of this invention may possibly exclude acyl isethionate from the synthetic detergent (a) or may possibly include it jointly with other synthetic detergent.
  • acyl isethionate is not more than 10% by weight of the composition e.g. 5% to 9.5%.
  • further embodiments of the invention include larger quantities of acyl isethionate, e.g. up to 30% by weight of the composition.
  • the water-soluble structurant (b) is required to melt in the temperature range from 40°C to 100°C so that it can be melted to form the bar composition but will be in a solid state at temperatures at which the bar will be used.
  • it has a melting point of at least 50°C, notably in the narrower range from 50°C to 90°C.
  • water-soluble structurant (b) Materials which are envisaged as the water-soluble structurant (b) are moderately high molecular weight polyalkylene oxides of appropriate melting point and in particular polyethylene glycols or mixtures thereof.
  • Polyethylene glycols which are used may have a molecular weight in the range 1500-10,000. However, in some embodiments of this invention it is preferred to include a fairly small quantity of polyethylene glycol with a molecular weight in the range from 50,000 to 500,000, especially molecular weights of around 100,000. Such polyethylene glycols have been found to improve the wear rate of the bars. It is believed that this is because their long polymer chains remain entangled even when the bar composition is wetted during use.
  • the quantity is preferably from 1% to 5%, more preferably from 1% or 1.5% to 4% or 4.5% by weight of the composition.
  • these materials will generally be used jointly with a larger quantity of other water-soluble structurant (b) such as the abovementioned polyethylene glycol of molecular weight 1500 to 10,000.
  • polyethylene oxide-polypropylene oxide block copolymers melt at temperatures in the required range of 40 to 100°C and may be used as part or all of the water- soluble structurant (b) .
  • block copolymers in which polyethylene oxide provides at least 40% by weight of the block copolymer.
  • Such block copolymers may be used, in mixtures with polyethylene glycol or other water-soluble structurant.
  • the total quantity of water-soluble structurant (b) is from 20% to 50% by weight of the composition.
  • the water-insoluble structurants (c) are also required to have a melting point in the range 40-100°C, more preferably at least 50°C, notably 50°C to 90°C.
  • Suitable materials which are particularly envisaged are fatty acids, particularly those having a carbon chain of 12 to 24 carbon atoms. Examples are lauric, myristic, palmitic, stearic, arachidic and behenic acids and mixtures thereof. Sources of these fatty acids are coconut, topped coconut, palm, palm kernel, babassu and tallow fatty acids and partially or fully hardened fatty acids or distilled fatty acids.
  • Other suitable water- insoluble structurants include alkanols of 8 to 20 carbon atoms, particularly cetyl alcohol. These materials generally have a water-solubility of less than 5g/litre at 20°C.
  • the relative proportions of the water-soluble structurants (b) and water-insoluble structurants (c) govern the rate at which the bar wears during use.
  • the presence of the water-insoluble structurant tends to delay dissolution of the bar when exposed to water during use and hence retard the rate of wear.
  • the total quantity of component (c) is from 10% to 40% by weight of the composition.
  • a water-insoluble material which does not melt below 100°C can function as an additional bar structurant. It may be stipulated as a requirement that the content (if any) of water-insoluble material which does not melt below 100°C is less than 20% by weight of the composition.
  • a water-insoluble structurant (c) which does not melt below 100°C may well be selected from plant materials or minerals. Starches, including corn starch, are preferred amongst the plant materials while kaolin and calcite are preferred mineral materials.
  • the ratio of water-soluble structurant (b) to the total of water- insoluble structurants may possibly lie in a range from 2:3 or 1:1 up to 3:1 or 5:1.
  • Some soap that is to say salts of monocarboxylic fatty acids having chain lengths of 8 to 22 carbon atoms may be included in the bar compositions of this invention.
  • the amount is desirably not greater than 10% by weight of the composition.
  • water-insoluble soaps are salts of saturated fatty acids having chain lengths of 16 to 22 carbon atoms, especially 16 and 18.
  • these salts are sodium salts. They melt at temperatures above 100°C and therefore come within a category (e) which is material, other than synthetic detergent, melting above 100°C.
  • water-insoluble soap is present in the composition, the amount of it desirably does not exceed 10% by weight of the composition, for example lying in a range from 3% to 9.5% by weight, more preferably 5% to 9%.
  • soluble structurant a combination of polyethylene glycol with molecular weight 50,000 to 500,000 as at least part of the soluble structurant (b) and water- insoluble soap as at least part of the insoluble material (c) .
  • Use of these materials in combination has been found to improve wear rate of the bars, while also giving them a good feel when handled during use.
  • the preferred amounts, by weight of the composition are: 4 to 9.5% of water-insoluble soap and 1.5 to 4.5% polyethylene glycol with molecular weight in the range from 50,000 to 500,000.
  • Non-soap synthetic detergent which does not completely liquify at temperatures below 100°C, for example acyl isethionates; soap, especially water-insoluble soap, which does not melt below 100°C; other water-insoluble materials which do not melt below 100°C.
  • Materials, other than synthetic detergent, which are water-soluble but do not melt below 100°C are preferably absent, or present only in quantities which are small such as not more than 10% better not more than 5% by weight of the composition.
  • the total quantity of material in the second and third of these categories is not more than 20% by weight of the composition.
  • the total quantity of material which does not melt below 100°C should not exceed 50% by weight of the composition, preferably less, such as not more than 40% or not more than 30%, or even 20% and should not be so much that the molten composition ceases to be stirrable.
  • Bar compositions of this invention will usually contain water, but the amount of water is only a fairly small proportion of the bar. Larger quantities of water reduce the hardness of the bars. Preferred is that the quantity of water is not over 15% by weight of the bars, e.g. lying in a range from 3% or 5% to 14.9% by weight.
  • Bars of this invention may optionally include so-called benefit agents - materials included in relatively small proportions which confer some benefit additional to the basic cleansing action of the bars.
  • benefit agents include emollients such as fatty alcohols and vegetable oils, essential oils, waxes, phospholipids, lanolin, anti-bacterial agents and sanitisers, opacifiers, pearlescers, electrolytes, perfumes, suncreens, fluorescers and colouring agents.
  • Preferred skin conditioning agents comprise silicone oils, mineral oils and/or glycerol .
  • a process for the manufacture of synthetic detergents bars rfhich comprises the steps of :
  • step (ii) cooling the product of step (i) to a temperature at which it solidifies
  • step (iii) forming the product of step (i) into bars.
  • the liquid mixture can be a single or multiple phase system.
  • the single phase can be an isotropic mixture whereas the multiple phase system can comprise either an emulsion or liquid crystal dispersion.
  • the mixture can be prepared by mixing of the components followed by heating of the mixture to the molten state when further mixing will occur, or by heating of the components followed by mixing of the components.
  • Step (i) may be carried out in a stirred, heated vessel.
  • a useful procedure begins with melting the fatty acid in a heated vessel with a stirrer. The stirrer is started, and the polyalkylene oxide is added. At this stage any soap is made in situ by partial neutralisation of the fatty acid.
  • the end result is a macroscopically homogenous molten mixture, with not more than 50% solids present.
  • step (ii) is carried out on a chilled, scraped roller which may be part of a chilled mill.
  • Step (iii) can comprise milling, plodding and stamping, or optional milling followed by compression of the material into a bar shape.
  • the liquid mixture from step (i) is cast into moulds.
  • the casting step can be employed to form a log which is further processed into bars or to form bars directly.
  • the process steps (ii) and (iii) are combined; the moulds which are used can form the final packaging of the bars or the bars can be extracted from the moulds and re-packaged.
  • compositions (A) and (B) were melted together at 80°C to produce a material consisting predominantly of a liquid phase. All amounts are given in percentages by weight .
  • solid, generally cuboid bars were formed from compositions (A) and (B) using a single bar press. Identical compositions were also formed into bars by using a casting process from the hot melt.
  • SLES 3EO denotes sodium lauryl ether sulphate with average 3 ethylene oxide residues.
  • PEG 4000 denotes polyethylene glycol with mean molecular weight 4000.
  • Aerosol OT is dioctylsulphosuccinate
  • a quantity of each melt was processed into bars by a different route.
  • the melt was cooled by passing over a chilled three-roll mill. Small quantities of perfume, opacifier and fluorescer were added, totalling less than 2% by weight of the composition.
  • the resulting composition was re-milled, passed through a vacuum plodder and stamped into the desired bar shape using a manual press .
  • the materials listed in Table 5 below were made into bars by the procedure of Example 2. All amounts are given in percentages by weight.
  • the water-soluble structurant was a mixture of polyethylene glycol and a block copolymer of polyethylene oxideand polypropylene oxide, available as Pluronic F87, ex BASF Germany.
  • the PEG 4000 and stearic acid were the first materials to be heated and melted. When these were molten, a small quantity of sodium hydroxide was added to neutralise a little of the stearic acid to sodium stearate. After this the remaining materials were added and stirred to produce a pumpable, homogeneous liquid.
  • Each melt was cooled by passing over a chilled three- roll mill. 1% of perfume, and 0.3% of titanium dioxide as opacifier were then added, followed by milling and plodding the resulting composition and stamped into the desired bar shape using a manual press.
  • compositions 7C and 7F gave compositions which were too soft to process whereas the remaining compositions could be processed into firm bars .
  • Example 8
  • compositions from the preceding examples were assessed for mildness using a zein test generally as described by Gotte, Proc. Int. Cong. Surface Active Subs., 4th, Brussels, 3., 89-90 (1964) .
  • the test determines the amount of amino acid solubilised from zein under specified conditions.
  • the solubilised material is determined by a nitrogen assay. The results were as follows.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
PCT/EP1994/000792 1993-03-16 1994-03-14 Synthetic detergent bar and manufacture thereof WO1994021778A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
KR1019950703925A KR100200456B1 (ko) 1993-03-16 1994-03-14 합성 세제 바 및 그의 제조 방법
BR9406008A BR9406008A (pt) 1993-03-16 1994-03-14 Composição detergente e processo para a fabricação de um detergente sintético em barra
CA002157773A CA2157773C (en) 1993-03-16 1994-03-14 Synthetic detergent bar and manufacture thereof
DE69421172T DE69421172T2 (de) 1993-03-16 1994-03-14 Synthetises detergensstueck und herstellung davon
EP94911169A EP0689584B1 (en) 1993-03-16 1994-03-14 Synthetic detergent bar and manufacture thereof
PL94310619A PL177068B1 (pl) 1993-03-16 1994-03-14 Kompozycja kostki syntetycznego detergentu
HU9501988A HU217658B (hu) 1993-03-16 1994-03-14 Darabos szintetikus tisztítószer, valamint eljárás előállítására
SK1139-95A SK113995A3 (en) 1993-03-16 1994-03-14 Synthetic detergent bar and manufacture thereof
AU63771/94A AU694728B2 (en) 1993-03-16 1994-03-14 Synthetic detergent bar and manufacture thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9305377.5 1993-03-16
GB939305377A GB9305377D0 (en) 1993-03-16 1993-03-16 Synthetic detergent bar and manufacture thereof

Publications (1)

Publication Number Publication Date
WO1994021778A1 true WO1994021778A1 (en) 1994-09-29

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PCT/EP1994/000792 WO1994021778A1 (en) 1993-03-16 1994-03-14 Synthetic detergent bar and manufacture thereof

Country Status (16)

Country Link
EP (1) EP0689584B1 (pl)
JP (1) JP2740355B2 (pl)
KR (1) KR100200456B1 (pl)
AU (1) AU694728B2 (pl)
BR (1) BR9406008A (pl)
CA (1) CA2157773C (pl)
CZ (1) CZ287044B6 (pl)
DE (1) DE69421172T2 (pl)
ES (1) ES2139738T3 (pl)
GB (1) GB9305377D0 (pl)
HU (1) HU217658B (pl)
IN (1) IN181612B (pl)
PL (1) PL177068B1 (pl)
SK (1) SK113995A3 (pl)
WO (1) WO1994021778A1 (pl)
ZA (1) ZA941813B (pl)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996029388A1 (en) * 1995-03-22 1996-09-26 Unilever Plc Synthetic detergent bars
WO1996034083A1 (en) * 1995-04-28 1996-10-31 Unilever Plc Detergent bars
EP0781838A1 (en) * 1995-12-29 1997-07-02 Colgate-Palmolive Company Detergent composition having improved cleaning power
WO1997030142A1 (en) * 1996-02-15 1997-08-21 Unilever Plc Mild bar compositions comprising blends of polyalkylene glycols
WO1997034992A1 (en) * 1996-03-18 1997-09-25 Unilever Plc Bar composition comprising copolymer mildness actives
WO1997040132A1 (en) * 1996-04-24 1997-10-30 Unilever Plc Bar composition comprising nonionic polymeric surfactants as mildness enhancement agents
WO1997040131A1 (en) * 1996-04-24 1997-10-30 Unilever Plc Synthetic bar composition comprising alkoxylated surfactants
WO1997047722A2 (en) * 1996-06-12 1997-12-18 Unilever Plc Bar composition comprising copolymer mildness actives
GB2316088A (en) * 1996-08-06 1998-02-18 Cussons Int Ltd Lotion Bar
WO1998016619A1 (en) * 1996-10-16 1998-04-23 Unilever Plc Pourable cast melt bar compositions comprising low levels of water and minimum ratios of polyol to water
WO2000012670A1 (en) * 1998-08-26 2000-03-09 Unilever Plc Bars comprising benefit agent and cationic polymer
CN109642189A (zh) * 2016-06-29 2019-04-16 巴克-化学有限责任公司 浴室用颗粒清洁剂

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001524594A (ja) * 1997-11-26 2001-12-04 ザ、プロクター、エンド、ギャンブル、カンパニー 洗剤タブレット
ES2237856T3 (es) * 1997-11-26 2005-08-01 THE PROCTER & GAMBLE COMPANY Pastilla detergente.
ES2142784T3 (es) * 1997-11-26 2003-01-16 Procter & Gamble Metodo para lavar vajilla.

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB783223A (en) * 1954-09-06 1957-09-18 Degussa Process for the production of moulded bodies of detergent sulphonates
US2987484A (en) * 1959-05-29 1961-06-06 Procter & Gamble Closed die molding a detergent bar
CH479695A (de) * 1964-12-11 1969-10-15 Unilever Nv Reinigungsmittelstück
US3687855A (en) * 1969-05-05 1972-08-29 Synergistics Inc Solid iodophor cleansing compositions
GB1294754A (en) * 1969-12-01 1972-11-01 Unilever Ltd Synthetic detergent toilet bars
WO1992013060A2 (en) * 1991-01-28 1992-08-06 The Procter & Gamble Company Binder systems for bar soaps

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB783223A (en) * 1954-09-06 1957-09-18 Degussa Process for the production of moulded bodies of detergent sulphonates
US2987484A (en) * 1959-05-29 1961-06-06 Procter & Gamble Closed die molding a detergent bar
CH479695A (de) * 1964-12-11 1969-10-15 Unilever Nv Reinigungsmittelstück
US3687855A (en) * 1969-05-05 1972-08-29 Synergistics Inc Solid iodophor cleansing compositions
GB1294754A (en) * 1969-12-01 1972-11-01 Unilever Ltd Synthetic detergent toilet bars
WO1992013060A2 (en) * 1991-01-28 1992-08-06 The Procter & Gamble Company Binder systems for bar soaps

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996029388A1 (en) * 1995-03-22 1996-09-26 Unilever Plc Synthetic detergent bars
WO1996034083A1 (en) * 1995-04-28 1996-10-31 Unilever Plc Detergent bars
EP0781838A1 (en) * 1995-12-29 1997-07-02 Colgate-Palmolive Company Detergent composition having improved cleaning power
WO1997030142A1 (en) * 1996-02-15 1997-08-21 Unilever Plc Mild bar compositions comprising blends of polyalkylene glycols
KR100453672B1 (ko) * 1996-02-15 2005-02-24 유니레버 엔.브이. 폴리알킬렌글리콜의블렌드를함유하는마일드바아조성물
CN1109739C (zh) * 1996-02-15 2003-05-28 尤尼利弗公司 含有聚亚烷基二醇混合物的温和块状组合物
EA001464B1 (ru) * 1996-02-15 2001-04-23 Унилевер Н.В. Мягкие композиции в форме куска, содержащие смеси полиалкиленгликолей
AU710771B2 (en) * 1996-03-18 1999-09-30 Unilever Plc Bar composition comprising copolymer mildness actives
WO1997034992A1 (en) * 1996-03-18 1997-09-25 Unilever Plc Bar composition comprising copolymer mildness actives
AU724338B2 (en) * 1996-04-24 2000-09-21 Unilever Plc Synthetic bar composition comprising alkoxylated surfactants
US5795852A (en) * 1996-04-24 1998-08-18 Lever Brothers Company, Division Of Conopco, Inc. Bar composition comprising nonionic polymeric surfacing as mildness enhancement agents
AU728905B2 (en) * 1996-04-24 2001-01-18 Unilever Plc Bar composition comprising nonionic polymeric surfactants as mildness enhancement agents
WO1997040131A1 (en) * 1996-04-24 1997-10-30 Unilever Plc Synthetic bar composition comprising alkoxylated surfactants
WO1997040132A1 (en) * 1996-04-24 1997-10-30 Unilever Plc Bar composition comprising nonionic polymeric surfactants as mildness enhancement agents
WO1997047722A3 (en) * 1996-06-12 1998-01-29 Unilever Plc Bar composition comprising copolymer mildness actives
WO1997047722A2 (en) * 1996-06-12 1997-12-18 Unilever Plc Bar composition comprising copolymer mildness actives
GB2316088A (en) * 1996-08-06 1998-02-18 Cussons Int Ltd Lotion Bar
WO1998016619A1 (en) * 1996-10-16 1998-04-23 Unilever Plc Pourable cast melt bar compositions comprising low levels of water and minimum ratios of polyol to water
AU718166B2 (en) * 1996-10-16 2000-04-06 Unilever Plc Pourable cast melt bar compositions comprising low levels of water and minimum ratios of polyol to water
WO2000012670A1 (en) * 1998-08-26 2000-03-09 Unilever Plc Bars comprising benefit agent and cationic polymer
CZ297811B6 (cs) * 1998-08-26 2007-04-04 Unilever N. V. Mycí prostredek
CN109642189A (zh) * 2016-06-29 2019-04-16 巴克-化学有限责任公司 浴室用颗粒清洁剂

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SK113995A3 (en) 1997-07-09
HU9501988D0 (en) 1995-09-28
PL177068B1 (pl) 1999-09-30
KR100200456B1 (ko) 1999-06-15
HU217658B (hu) 2000-03-28
PL310619A1 (en) 1995-12-27
CZ287044B6 (en) 2000-08-16
DE69421172D1 (de) 1999-11-18
CA2157773C (en) 2000-07-18
AU6377194A (en) 1994-10-11
CA2157773A1 (en) 1994-09-29
HUT73042A (en) 1996-06-28
JP2740355B2 (ja) 1998-04-15
CZ235995A3 (en) 1996-01-17
BR9406008A (pt) 1995-12-26
EP0689584B1 (en) 1999-10-13
AU694728B2 (en) 1998-07-30
IN181612B (pl) 1998-07-25
ES2139738T3 (es) 2000-02-16
JPH08507816A (ja) 1996-08-20
ZA941813B (en) 1995-09-15
GB9305377D0 (en) 1993-05-05
EP0689584A1 (en) 1996-01-03
DE69421172T2 (de) 2000-01-20

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