EP0507559B1 - Detergent composition - Google Patents

Detergent composition Download PDF

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Publication number
EP0507559B1
EP0507559B1 EP19920302847 EP92302847A EP0507559B1 EP 0507559 B1 EP0507559 B1 EP 0507559B1 EP 19920302847 EP19920302847 EP 19920302847 EP 92302847 A EP92302847 A EP 92302847A EP 0507559 B1 EP0507559 B1 EP 0507559B1
Authority
EP
European Patent Office
Prior art keywords
composition
soap
detergent
bars
weight
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
EP19920302847
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0507559A2 (en
EP0507559A3 (en
Inventor
Stuart Keith Unilever Research Pratley
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
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 NV filed Critical Unilever PLC
Publication of EP0507559A2 publication Critical patent/EP0507559A2/en
Publication of EP0507559A3 publication Critical patent/EP0507559A3/en
Application granted granted Critical
Publication of EP0507559B1 publication Critical patent/EP0507559B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions 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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0095—Solid transparent soaps or detergents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2044—Dihydric alcohols linear
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/26—Organic compounds, e.g. vitamins containing oxygen
    • 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/30—Organic compounds, e.g. vitamins containing nitrogen
    • 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/48—Superfatting agents
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/126—Acylisethionates
    • 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
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/201—Monohydric alcohols linear

Definitions

  • This invention relates to soap bars, especially for personal washing, and to their production.
  • One known procedure for the production of soap bars is to form an isotropic melt containing the soap and various organic solvents and cast the resulting melt directly into bars. This process has the advantage that in only a single step is goes from a shapeless melt of constituents to cast bars having the desired shape.
  • the cast bars do of course contain solvent as well as soap and may be transparent or translucent.
  • a soap composition which, aside from any non-detergent particulates, comprises: 25-60% of anionic, nonionic, zwitterionic or amphoteric detergent active including soap of saturated C16 to C22 fatty acids in an amount which is 8-32%; 10-50% of one or more alcohols, including one or more solvent alcohols selected from ethanol, propanol, ethylene glycol, 1,2-propane diol, 1,3-propane diol, ethanolamines and propanolamines, the amount of solvent alcohol being 5-30%; not more than 30% water; and 1-20% of an oily skin-benefit agent, the above percentages being based on the weight of the composition excluding any dispersed non-detergent particulates.
  • the present invention also provides a process for the manufacture of soap bars comprising forming an isotropic melt of composition as set forth above and casting the molten composition into solid bars.
  • soap of the saturated C16 to C22 fatty acids One essential constituent is soap of the saturated C16 to C22 fatty acids.
  • fatty acid signifies monocarboxylic acids. Generally, more than half of this probably substantially all of it will be soap of the saturated C16 and C18 fatty acids, which are palmitic and stearic acid respectively. Soaps of these C16 to C22 saturated fatty acids are frequently referred to as insoluble soaps because of their poor solubility in water. These provide structural strength in the eventual soap bars. Mixtures of these chain lengths are preferred.
  • the remainder of the anionic detergent active may consist of soap of other fatty acids which are more soluble and so provide a lather when brought into contact with water. In this event it is preferred that there is from 4% up to 30%, or the balance of the detergent active, if this is less than 30%, of soap of C10 to C14 fatty acids and/or unsaturated C16 to C22 fatty acids. Soap of these acids is generally referred to as soluble soap.
  • Significant chain lengths, which may contribute at least a majority of the soluble soap and at least 4% of the composition, are C12, C14 and unsaturated C16 and C18.
  • the saturated C16 to C22 soaps contribute structural strength and hardness whereas the other detergents, i.e. shorter chain soaps, unsaturated soaps and/or non-soap detergent, contribute to lather generation, it is preferred that both are present and that the saturated C16 to C22 soap and the other detergent are in a weight ratio from 3:1 to 1:3, better 2:1 to 1:2 and yet more preferably 1.5:1 to 1:1.5.
  • the detergent active may also include some non-soap detergent which provides a lather in contact with water.
  • This may be anionic, nonionic, zwitterionic or amphoteric.
  • this may be one of the non-soap detergents known for use in combination with soap in personal washing bars.
  • fatty acyl isethionates include fatty acyl isethionates, acyl taurides, alkyl sarcosinates, mono and dialkyl sulphosuccinates, alkane sulphonates, alkyl ether sulphates, alkyl benzene sulphonates, alkyl sulphates and alpha-olefin sulphonates, having in each case an alkyl or acyl chain comprising 8 to 18 carbon atoms.
  • nonionic, zwitterionic or amphoteric detergent is used in conjunction with anionic non-soap detergent.
  • nonionic detergents are alkyl ethoxylates, alkyl polyglutamates, alkyl ethanolamides and amine oxides.
  • zwitterionics are betaines and amidobetaines. Such materials could act as at least a partial replacement for soluble soap. Accordingly the quantity of detergent active selected from the group consisting of C12 to C14 fatty acids, C16 to C22 unsaturated fatty acids and non-soap detergent active will generally lie within a range from 4 to 30% (but not exceeding the balance of the detergent active).
  • Anionic non-soap detergent may be present jointly with soluble soap.
  • the amount of non-soap detergent, if present at all, may lie in a range from 1 to 30% based on the weight of the composition excluding any dispersed non-soap particulates.
  • Some non-soap detergent actives will solidify to opaque particles on cooling from the molten state. This may be acceptable, but preferably such a detergent has a Krafft point which is not substantially above 40°C.
  • both the insoluble soap of saturated C16 to C18 fatty acids and any other soap present may possibly be all or substantially all sodium soap, so that at least 90wt% of even 95 or 97wt% of the soap counter ions are sodium.
  • some other counter ions such as potassium and trialkanolammonium may be present. If other counter ions are present they will generally constitute a minor proportion, up to 30 or 40wt% of the soap counter ions present.
  • the soap may be derived from fats and oils conventionally used in soap making.
  • the fats and oils and the amounts used must be chosen to provide the required quantities of C16 to C18 and other soap.
  • a mixture of chain lengths meeting the requirements of this invention can be provided by a conventional soap such as conventional 80 : 20 tallow : coconut soap or by a blend of conventional soaps such as 80 : 20 soap augmented with additional soap made from coconut oil as the only triglyceride source.
  • Any other alcohol present is preferably a polyhydric alcohol.
  • the alcohol must at least include solvent alcohol chosen from a small group of short chain monohydric alcohols, short chain diols and alkanolamines with short carbon chains. These materials are good solvents for insoluble soap.
  • Preferred within this group are ethanol, isopropanol, 1,2-propane diol, triethanolamine and triisopropanolamine.
  • glycerol a sugar such as sucrose or glucose and yet a further possibility is a sugar derivative such as sorbitol.
  • polyethylene glycol of fairly low molecular weight, such as about 400.
  • polyhydric alcohol(s) is believed to help mitigate shrinkage of the bar as it is cast from a melt.
  • the skin benefit agent is a compound or mixture of compounds which is an oil at room temperature. Generally it will contain at least one C8 to C22 saturated aliphatic hydrocarbon chain. More particularly the oily skin benefit agent may be hydrocarbon oil such as petrolatum, mineral oil or nujol; alternatively it may be an ester of a C8 to C22 fatty acid and/or a C8 to C22 fatty alcohol. Such an ester could be a triglyceride.
  • the skin benefit oil may in particular be a known emollient and specific possibilities include: natural oils such as jojoba oil, coconut oil, mink oil, sesame oil, arachis oil, sunflower seed oil, evening primrose oil and castor oil; hydrocarbons such as nujol, mineral oil and petrolatum; lanolin and lanolin alcohols; C12 - C24 alcohols such as stearyl alcohol, cetyl alcohol, octadecan-2-ol; esters of C8 - C22 acids and C21 - C24 alcohols (including di-acids, diols, tri-acids and triols, not necessarily with all acid-hydroxy groups esterified) such as glyceryl monoricinoleate, glyceryl monostearate, mink oil, isopropyl isostearate, isobutyl palmitate, isocetyl stearate, isopropyl laurate, hexyl laurate, decyl ole
  • the amounts of the constituents of a soap bar in accordance with this invention are related to each other.
  • the amount and nature of the solvents needs to be such as to enable dissolution of the soaps while at the same time being sufficiently restricted that the setting temperature is reasonably high such as at least 50°C.
  • the amounts of the constituent materials may fall within one of the following three sets of ranges which represent preferred possibilities with different levels of saturated C16 - C18 soap.
  • the weight percentage range for total detergent imposes an additional limitation on the amounts of saturated C16 - C18 soap and other detergent. For instance in the middle set of ranges, if there was 12% of saturated C16 - C18 soap, at least 18% of other detergent would be needed to achieve the minimum of 30% total detergent.
  • Soap bars in accordance with this invention may contain various other materials, especially if the amount of them is restricted so as not to exceed 10% or even 5%.
  • a soap composition can contain small amounts of conventional additives, e.g. electrolytes, perfume, preservatives, dyes and pearlescent agents.
  • Bars according to this invention may include some free fatty acid. However, this provides little advantage and may not be adequately soluble. It is therefore preferred that the amount of free fatty acid in a bar is less than 10%.
  • a soap composition in accordance with this invention may well be transparent or at least translucent. However, if this property is not required then the soap composition may contain a particulate filler which is insoluble both in water and in the said alcohols. It is possible to add modest proportions of such a filler without it having any serious effect on the behaviour of the remainder of the composition to form a melt with the filler dispersed therein and subsequently to set to solid bars still with the filler dispersed therein. Consequently, percentages of the composition given above are based on the weight of the composition excluding any dispersed non-soap solid particulates. Possible fillers include kaolin, silica and starch. The amount of any particulate filler which is included will generally not exceed 20% by weight of the total composition. Particle sizes desirably lie in the range 1.0 to 20 microns. As mentioned above, some non-soap detergents will alo render a bar opaque.
  • a second aspect of the present invention is a method for making soap bars comprising forming a melt of the composition and casting the melt into solid bars, e.g. by casting the melt into moulds and allowing the melt to set.
  • the composition is preferably heated to a temperature of between 70 and 90°C more preferably between 80 and 85°C, and maintained at such a raised temperature, below the boiling point of the solution, until all solids present have dissolved which is typically between 30 and 60 minutes e.g. 45 minutes.
  • the cooling can take place at a rate determined by the ambient temperature. If desired, however, forced cooling can be employed.
  • the ingredients are added in the form in which they will be present in the final product.
  • a particular composition includes a trialkanolamine soap then the starting materials to be added are preferably the equivalent fatty acids and their stoichiometric equivalent of trialkanolamine, which will preferably be present as a proportion of the total trialkanolamine required by the composition having regard to the solvent system.
  • Sodium soaps can either be added as ready made or can be made in situ from fatty acids and sodium hydroxide.
  • any perfume and free fatty acids liable to thermal degradation may be added following any heating step and immediately prior to casting the melt into moulds.
  • the composition can be removed from the moulds and subjected to any necessary finishing including, if necessary, cutting and/or pressing into a desired final shape, followed by packaging.
  • the melt is cast into individual moulds which additionally serve as a means of packaging the resulting soap bar. Removal of the bar from the mould will then occur when the consumer opens the pack immediately prior to use.
  • the mould can be filled fully with the melt and air-tightly sealed.
  • the resulting bar can thus have an attractive shape and surface appearance determined by the shape and inner surface of the mould. Providing an air-tight seal additionally inhibits any tendency for any volatile components of the bar to escape during storage.
  • Examples of items which can act both as a mould and also a package are rigid or semi-rigid plastic boxes such as those described in for example US 3149188 and FR 910256.
  • the melt is cast into packs according to the invention disclosed in our published European patent application EP-A-321179.
  • EP-A-321179 the use of a flexible film as the material from which the pack is made.
  • the molten soap composition is cast directly into the pack which is then air-tightly sealed.
  • the flexible film is preferably shaped or is thermoplastic so that the heat of the melt causes the film pack to adjust to a wrinkle-free fit around the composition, which can if desired be lightly moulded during the time it is setting.
  • the film is preferably transparent so that the resulting product displays the soap bar.
  • Bars were prepared with the following two formulations in which percentages are by weight of the final composition.
  • the bars were prepared by the method stated above, in which the ingredients are heated at a temperature of 70 to 90°C until all are molten, adding perfume after the other ingredients have melted and then casting the melt in moulds.
  • Hardened tallow soap contains almost entirely insoluble soap with a small percentage of soluble short chain soap.
  • Industrial Methylated spirit is 90% ethanol, 10% methanol.
  • Example 1A comparative
  • Example 1B comparative
  • Example 1C 64%
  • the fatty acids were neutralised by the triethanolamine so as to form triethanolammonium soap.
  • the amount of saturated C16 - C18 soap in the bars was approximately 20% by weight.
  • the amount of free triethanolamine in the formulation would thus be reduced by about 3 to 5% from the quantity originally incorporated.
  • the skin was scored by an assessor who judged both dryness and erythema (the latter as in Example 1) and assessed by the panellist against a standard scale for overall skin condition. The cumulative results were
  • Example 2B were also assessed by panellists in a sensory evaluation comparing them with conventional 80/20 tallow/coconut toilet soap and with the melt cast bars of Example 5A below which did not contain oil but did contain cocoisethionate, which is regarded as a mild detergent.
  • Bars were prepared with the following two formulations, using the same general method as before.
  • the amount of saturated C16 - C18 soap in these bars was approximately 20%.
  • the amount of free triethanolamine in the formulation would thus be reduced by about 3 to 5% from the quantity originally incorporated.
  • the bars were used to wash the skin of volunteers, and the effect on moisture content was determined by a test instrument as in Example 1.
  • the bars were also tested by a procedure in which samples are left partially submerged in water under standardised conditions, the soft material is then scraped off the sample surface, and the percentage weight loss determined.

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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)
  • Cosmetics (AREA)
EP19920302847 1991-04-03 1992-03-31 Detergent composition Expired - Lifetime EP0507559B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9106959 1991-04-03
GB919106959A GB9106959D0 (en) 1991-04-03 1991-04-03 Detergent composition

Publications (3)

Publication Number Publication Date
EP0507559A2 EP0507559A2 (en) 1992-10-07
EP0507559A3 EP0507559A3 (en) 1993-01-07
EP0507559B1 true EP0507559B1 (en) 1995-07-19

Family

ID=10692564

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19920302847 Expired - Lifetime EP0507559B1 (en) 1991-04-03 1992-03-31 Detergent composition

Country Status (5)

Country Link
EP (1) EP0507559B1 (ja)
JP (1) JP2574592B2 (ja)
DE (1) DE69203507T2 (ja)
ES (1) ES2075616T3 (ja)
GB (1) GB9106959D0 (ja)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005097964A1 (en) * 2004-04-07 2005-10-20 Derichem (M) Sdn Bhd Improved saturated soap
US8080503B2 (en) 2005-06-18 2011-12-20 The Procter & Gamble Company Cleansing bar compositions comprising a high level of water
US8129327B2 (en) 2006-12-01 2012-03-06 The Procter & Gamble Company Packaging for high moisture bar soap

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FR2694569B1 (fr) * 1992-08-10 1994-10-07 Icc France Article d'hygiène solide et transparent, notamment sous forme de pain dermatologique, et son procédé de préparation.
US5387362A (en) * 1992-10-13 1995-02-07 The Procter & Gamble Company Personal cleansing bar with tailored base soaps with mixed counterions for improved mildness and processability without lather negatives
EP0775194A1 (en) * 1994-08-03 1997-05-28 The Procter & Gamble Company Transparent personal cleansing bar
MA23637A1 (fr) * 1994-08-03 1996-04-01 Procter & Gamble Procede exempt de monoalcool pour la production d'un pain nettoyant corporel transparent, moule par coulage
US5703025A (en) * 1994-08-03 1997-12-30 The Procter & Gamble Company Monohydric alcohol-free process for making a transparent pour molded personal cleansing bar
WO1997022684A1 (en) * 1995-12-20 1997-06-26 The Procter & Gamble Company Pour molded personal cleansing bar
AU724338B2 (en) * 1996-04-24 2000-09-21 Unilever Plc Synthetic bar composition comprising alkoxylated surfactants
WO1998016611A1 (en) * 1996-10-11 1998-04-23 The Procter & Gamble Company Laundry bar compositions comprising dihydric alcohol
GB9709500D0 (en) * 1997-05-09 1997-07-02 Unilever Plc Casting of soft solid shaped articles
US6310015B1 (en) 1999-08-10 2001-10-30 The Dial Corporation Transparent/translucent moisturizing/cosmetic/personal cleansing bar
WO2001011001A1 (en) * 1999-08-10 2001-02-15 The Dial Corporation Transparent/translucent moisturizing/cosmetic/personal cleansing bar
US6689728B2 (en) 2001-04-06 2004-02-10 The Dial Company Composite transparent bar soap containing visible soap insert(s)
US6440913B1 (en) * 2001-04-26 2002-08-27 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Soap bar comprising about 6% and greater triglycerides which structure well and have desirable user properties
WO2013144603A1 (en) * 2012-03-30 2013-10-03 Reckitt & Colman (Overseas) Limited Bar soaps

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JPS5165105A (en) * 1974-12-04 1976-06-05 Jee Fuerara Piitaa Setsukensoseibutsu oyobi sonoseiho
ZA771556B (en) * 1976-04-22 1978-10-25 Colgate Palmolive Co Transparent detergent pellets
JPS5853999A (ja) * 1981-09-25 1983-03-30 株式会社コンゴ 化粧石鹸
ES2034203T3 (es) * 1988-03-31 1993-04-01 Unilever Nv Barra de jabon transparente.
GB8807754D0 (en) * 1988-03-31 1988-05-05 Unilever Plc Transparent soap bars
GB8816201D0 (en) * 1988-07-07 1988-08-10 Unilever Plc Detergent bar
GB8928902D0 (en) * 1989-12-21 1990-02-28 Unilever Plc Detergent bar

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005097964A1 (en) * 2004-04-07 2005-10-20 Derichem (M) Sdn Bhd Improved saturated soap
US8080503B2 (en) 2005-06-18 2011-12-20 The Procter & Gamble Company Cleansing bar compositions comprising a high level of water
US8129327B2 (en) 2006-12-01 2012-03-06 The Procter & Gamble Company Packaging for high moisture bar soap

Also Published As

Publication number Publication date
ES2075616T3 (es) 1995-10-01
JP2574592B2 (ja) 1997-01-22
EP0507559A2 (en) 1992-10-07
DE69203507D1 (de) 1995-08-24
DE69203507T2 (de) 1995-12-21
EP0507559A3 (en) 1993-01-07
GB9106959D0 (en) 1991-05-22
JPH0598299A (ja) 1993-04-20

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