EP0707631B1 - Improvements relating to soap bars - Google Patents

Improvements relating to soap bars Download PDF

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Publication number
EP0707631B1
EP0707631B1 EP94920970A EP94920970A EP0707631B1 EP 0707631 B1 EP0707631 B1 EP 0707631B1 EP 94920970 A EP94920970 A EP 94920970A EP 94920970 A EP94920970 A EP 94920970A EP 0707631 B1 EP0707631 B1 EP 0707631B1
Authority
EP
European Patent Office
Prior art keywords
fatty acid
soap
soap bar
bar according
oil
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
EP94920970A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0707631A1 (en
Inventor
John George Chambers
Geoffrey Irlam
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 EP0707631A1 publication Critical patent/EP0707631A1/en
Application granted granted Critical
Publication of EP0707631B1 publication Critical patent/EP0707631B1/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
    • 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
    • C11D9/225—Polymers
    • 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
    • C11D9/267—Organic compounds, e.g. vitamins containing oxygen containing free fatty acids
    • 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
    • C11D1/66—Non-ionic compounds

Definitions

  • the present invention relates to improved soap bars and a process for the manufacture of said bars.
  • 'bars' is intended to mean generally solid bodies whether in the form of a bar, tablet, stick, block or other three-dimensional shape.
  • 'soap bars' relates to bars comprising fatty acid soaps or blends of fatty acid soaps with one or more synthetic detergents.
  • soap bars have been manufactured from fats by conversion of triglyceride components of fats into fatty acid salts and the formation of these 'soaps' into bars.
  • a general review is to be found in Woollatt, 'The Manufacture of Soaps, Other Detergents and Glycerine', John Wiley & Sons, 1985.
  • the longer chain fatty acid soaps particularly the less expensive C 16 and C 18 soaps (as obtained from tallow and palm oils) provide structure in the finished soap bars and prevent or retard disintegration of the soap bar on exposure to water.
  • the more expensive, shorter chain, lauric fat-derived, (i.e. lauric acid salts) and other soluble soaps typically as obtained from coconut and palm kernel oil contribute to the lathering properties of the overall composition.
  • soap bars contain from 90-50% fatty acid soaps obtained from tallow (i.e. non-lauric fats) and 10-50% of fatty acid soaps obtained from coconut (i.e. lauric fats).
  • tallow i.e. non-lauric fats
  • coconut i.e. lauric fats
  • most commercial soap formulations comprise 80% tallow and 20% coconut oil. In countries where tallow is unacceptable other non-lauric oils and fats, such as palm oil, replace tallow.
  • toilet soap bars can contain free fatty acid.
  • free fatty acid is known as 'superfatting' and superfatting at a 5-10% free fatty acid level is known to give a copious, creamy lather.
  • Other superfatting agents include citric and other acids which function by promoting the formation of free fatty acids in the fat blend.
  • a known disadvantage of superfatted products in bar form is a reduction in the physical stability of the bar, often revealed by an increased 'mushing' on prolonged exposure to water.
  • compositions containing fatty acid soap are harshness, a property which is determined by a number of tests as will be elaborated upon hereafter.
  • Known solutions to the problem of harshness include reduction of the level of soap present and replacement of the balance of the composition by so-called co-active surfactants.
  • Megson et al, US 3576749 suggests that superfatting of toilet soap bars, as described above, improves mildness but the improvement is not considered as significant as that obtained by the use of co-actives.
  • a recognised problem engendered by the presence of co-actives is a loss of product structure in the resulting soap bars.
  • GB 2001098 discloses that superfatted soap bars can advantageously be prepared from compositions comprising predominantly sodium soap of the higher fatty acids and minor proportions of superfatting higher fatty acids, water and up to 4%, preferably less, high molecular weight polyethylene glycol polymer.
  • the advantage of such a composition is said to be that the bars give a rich and creamy lather but are firm and resistant to cracking.
  • soap bars comprising at least 5% of a relatively low molecular weight polyalkylene glycol and fatty acid in a ratio of 1:3 to 3:1 exhibit surprisingly improved properties compared with bars having a equivalent coconut based soap content.
  • a soap bar comprising:
  • Fatty acid soaps at a level of 44-86.5%wt on product are an essential component of the present invention.
  • the average chain length of the fatty acid soaps falls into the range C 12 -C 22 .
  • Sources of such fatty acids include animal fats/fatty acids, e.g. tallow and lard and the fatty acid derived therefrom, and also vegetable derived oils, particularly fats/fatty acids rich in palmitic and stearic acid such as palm oils and fractions thereof.
  • fatty acids are derived from oil-sources yielding fatty acids with a high degree of unsaturation, such as soya bean oil, sunflower oil, rice bran oil, linseed oil, rapeseed oils, ground nut oil, marine oils and the like
  • the oil stocks are preferably hardened or fractionated to yield partially or fully hardened fatty acid mixtures and or stearines.
  • the bulk of the fats and fatty acids are derived from tallow except where nut-oil or other vegetable substitutes are employed for cultural reasons.
  • compositions of the present invention comprise 10-50% of lauric soaps, i.e. those having an average chain length of less than C 16 .
  • the most preferable fat blends comprise around 80% tallow and or palm oil and around 20% coconut oil.
  • the iodine value of the non-lauric soaps ranges from 10 to 55, and is more preferably 45 to 55.
  • Preferred soap levels on product fall in the range 50-80%wt on product, more preferably 55-70%.
  • Polyalkylene glycol, a polymer, at a level of 5-30%wt on product is an essential component of the compositions according to the present invention.
  • the polyalkylene glycol is polyethylene glycol (PEG).
  • the preferred level of polymer is about 7.5-25%, most preferably 9-20% on product.
  • the PEG has a molecular weight below 100000 Dalton.
  • the polyethylene glycol has a molecular weight in the range of 100-10000 Dalton, and is preferably 400-5000 Dalton.
  • the preferred PEG's are miscible with water. PEG's with molecular weights above 10000 are markedly less water soluble and form increasingly viscous liquids above their melting points. This leads to processing difficulties. While it is envisaged that products can be prepared by dry mixing of high molecular weight PEG and a dry soap base, this would not give the molecular-level mixing believed necessary to achieve the required properties.
  • An advantage of the low molecular weight PEG's is that they can be added as melted liquids or as low viscosity aqueous solutions. Addition of the PEG can occur at any stage in the soap making process, including addition to the dried soap or to the wet soap prior to drying.
  • Fatty acid at a level 2.5-20%wt on product, is an essential component of the compositions according to the present invention.
  • This level of free fatty acids can be obtained by the addition of free fatty acids per se or by the addition of a non-fatty acid superfatting agent which protonates a portion of the fatty acid soaps present to form the free fatty acid.
  • Suitable fatty acid superfatting agents include tallow, coconut, palm and palm-kernel fatty acids. Other fatty acids can be employed although the low melting point fatty acids, particularly the laurics, are preferred for ease of processing. Preferred levels of fatty acid are 5-15%, most preferably around 10% on product.
  • the free fatty acids can be added as such or generated in situ by the addition of non-fatty acid superfatting agents, such as inorganic or organic acids, preferably citric acid.
  • non-fatty acid superfatting agents such as inorganic or organic acids, preferably citric acid.
  • formulations according to the present invention can comprise one or more plasticisers, preferably selected from the group comprising fatty alcohols, paraffin waxes, glycerol, monoglycerides and mixtures thereof.
  • composition further comprises at least one synthetic anionic active at a level of not more than 20%wt, preferably at a level of not more than 10%wt, on product.
  • the synthetic anionic is selected from the group comprising:- alkyl sulphates, alkyl ether sulphates, alpha-olefin sulphonates, fatty isethionates, alkyl glyceryl ether sulphonates, mono-alkyl glyceryl sulphates, alkyl sarcosinates, alkyl taurides, alkyl sulphosuccinates, alkyl phosphates, and mixtures thereof.
  • Preferred amongst the anionic actives are sodium lauryl ether sulphate (SLES), alpha-olefin sulphonates and sodium fatty isethionates.
  • Sodium lauryl ether sulphate (SLES) and sodium fatty isethionates are particularly preferred.
  • compositions will further comprise a synergistic mildness active.
  • the synergistic mildness active is selected from the group consisting of nonionic surfactants, amphoteric surfactants and mixtures thereof.
  • the synergistic mildness active should be present at a level of at least 5%wt of the total active level.
  • Particularly useful compositions comprise 5-25%wt, preferably 8-20%wt, more preferably 9-18%wt of synergistic mildness active on total actives.
  • Suitable nonionic surfactants include:- polyethoxylated alcohols, polyethoxylated alkyl phenols, alkyl polyglycosides, sorbitan esters, polysorbates, alkanolamides, poloxamers, and mixtures thereof.
  • Preferred amongst the nonionic surfactants are polyethoxylated alcohols, particularly alkyl ethoxylates.
  • the preferred alkyl ethoxylates have an average alkyl chain length of 10-25 carbons and an average ethoxylate content of 3-250 units.
  • Suitable amphoteric surfactants include:- amine oxides, aminimides, betaines, amido betaines and sulphobetaines, and mixtures thereof. Coco-amido-propyl betaines and tegobetaines are particularly preferred due to their low potential nitrosamine-precursor content.
  • the total water content of the soap bar ranges from 6 to 20%wt of the soap bar.
  • the water content falls into the range 8-17%wt, and is most preferably 9-15%wt.
  • the most preferred level of water in the final bar is a normal water content for soap bars (around 12% of the bar) hence conventional driers can be used to achieve this level.
  • the electrolyte content of the bars can vary. In practice the electrolyte level will lie between 0 and 1.5% on product. Some or all of this electrolyte can be residue from the saponification processes typically employed in soap making, as is known in the art. It is also known that the level of electrolyte can have some slight influence on the eventual hardness of the product. This variation modifies the hardness of the soap bars and can be used to control the final hardness within production limits. It is preferred that the electrolyte content lies between 0.2-1.5wt% on product.
  • the preferred electrolyte is sodium chloride at a level of 0.2-0.8%.
  • Other electrolytes can be employed either alone or in admixture.
  • the alternative preferred electrolytes are sodium sulphate and sodium carbonate.
  • compositions according to the present invention may comprise one or more of the following optional ingredients: preservatives, perfumes, colours, opacifiers and optical brighteners, moisturisers, emollients, germicides and other medicinal ingredients.
  • Typical preservatives include substances which negate or reduce the adverse catalytic effects of heavy metals, particularly iron and copper. These preferably comprise organic sequestrants, such as EDTA or NTA. However it is known that high levels of EDTA can form coloured complexes with iron and it is therefore commonplace to use EHDP (ethane-1-hydroxy-1,1-diphosphonic acid) in admixture with EDTA. Preferred levels of preservative are generally in the range 0.01-0.1%wt on product.
  • Typical opacifiers include titanium dioxide, preferably at levels of around 0.2-0.4%wt on product.
  • Typical emollient/moisturising ingredients are selected from the group comprising stearyl alcohol, glyceryl monolaurate, glyceryl monoricinoleate, glyceryl monostearate, propane-1.2-diol, butane-1.3 diol, docosan-1.2-diol, mink oil, cetyl alcohol, isopropyl isostearate, stearic acid, isobutyl palmitate, isocetyl stearate, oleyl alcohol, isopropyl laurate, hexyl laurate, decyl oleate, octadecan-2-ol, isocetyl alcohol, eicosanyl alcohol, behenyl alcohol, cetyl palmitate, silicone oils such as dimethylpolysiloxane, di-n-butyl sebacate, isopropyl myristate, isopropyl palmitate, isopropyl stea
  • a preferred electrolyte which may be added to compositions according to the present invention is a simple sodium isethionate, preferably unsubstituted. This may be present as 0.1 to 50% of the composition, preferably 0.5% to 25%, more preferably 2% to about 15% by weight.
  • compositions as given in Table 1 were prepared as follows:
  • products may be prepared by adding a mixture of PEG (PA or PB) and superfatting agents (CA or ST) to dried soap chips in a suitable mixer eg. a mill or Z-blade mixer.
  • a suitable mixer eg. a mill or Z-blade mixer.
  • Lather volume was measured by a handwash method which closely approximates normal consumer habit. The test involves the use of 20 untrained volunteers. Each volunteer wears a pair of surgical gloves and lathers the bar in a still body of water at a temperature of 30°C. The volume of the lather produced is measured by submersion of the panellists hands under an inverted, calibrated collecting funnel.
  • LVE lather volume
  • CR creaminess
  • Mush was determined by immersing portions of a weighed bar in distilled water at 20°C for two hours and the increase in weight noted.
  • the 'mush value' is the increase in weight per 50 cm 2 of surface mushed.
  • Wear was determined as the percentage loss of weight of the bar as a result of a controlled wash-down procedure.
  • Panellists wash down pre-weighed bars using a prescribed action, each bar being washed by every panellist each day for four days. After this time the bars are allowed to dry out for 24 hours and are then weighed again. The difference in weight is expressed as a percentage wear-rate.
  • Example 1 is a comparative example using a conventional 80/20 soap.
  • Examples 2 and 4 show the addition of PEG to conventional 80/20 soap. Wear rates are increased, and there is no significant change in the lather volume or creaminess.
  • Examples 3, 5 and 6 show the benefits of adding both PEG and fatty acid as a superfatting agent. In each case, the lather volume and creaminess have been significantly increased, while maintaining acceptable mush and wear rates.
  • compositions in Tables 2 to 4 were prepared as follows:
  • Example 15 which contained no fatty acid suffered from severe processing problems, especially at the plodding and stamping stages with the resulting bars showing severe cracking and surface damage even when lubricant was used on the die surfaces of the stamper.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
EP94920970A 1993-07-05 1994-07-05 Improvements relating to soap bars Expired - Lifetime EP0707631B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB939313859A GB9313859D0 (en) 1993-07-05 1993-07-05 Improvements relating to soap bars
GB9313859 1993-07-05
PCT/EP1994/002191 WO1995002035A1 (en) 1993-07-05 1994-07-05 Improvements relating to soap bars

Publications (2)

Publication Number Publication Date
EP0707631A1 EP0707631A1 (en) 1996-04-24
EP0707631B1 true EP0707631B1 (en) 1997-03-05

Family

ID=10738311

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94920970A Expired - Lifetime EP0707631B1 (en) 1993-07-05 1994-07-05 Improvements relating to soap bars

Country Status (16)

Country Link
EP (1) EP0707631B1 (enrdf_load_stackoverflow)
JP (1) JP2703826B2 (enrdf_load_stackoverflow)
AU (1) AU699797B2 (enrdf_load_stackoverflow)
BR (1) BR9406919A (enrdf_load_stackoverflow)
CA (1) CA2163977C (enrdf_load_stackoverflow)
CZ (1) CZ286673B6 (enrdf_load_stackoverflow)
DE (1) DE69401956T2 (enrdf_load_stackoverflow)
ES (1) ES2098970T3 (enrdf_load_stackoverflow)
GB (1) GB9313859D0 (enrdf_load_stackoverflow)
HU (1) HU216060B (enrdf_load_stackoverflow)
IN (1) IN181732B (enrdf_load_stackoverflow)
MY (1) MY116211A (enrdf_load_stackoverflow)
PL (1) PL174919B1 (enrdf_load_stackoverflow)
SK (1) SK996A3 (enrdf_load_stackoverflow)
WO (1) WO1995002035A1 (enrdf_load_stackoverflow)
ZA (1) ZA944811B (enrdf_load_stackoverflow)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HUP0000247A3 (en) * 1996-10-16 2001-05-28 Unilever Nv Formed skin cleaning composition
US5888952A (en) * 1997-06-13 1999-03-30 Colgate-Palmolive Co. Solid cleansing composition comprising tetrasodium pyrophosphate
GB9718235D0 (en) 1997-08-28 1997-11-05 Unilever Plc Soap bars
US6143704A (en) * 1998-10-13 2000-11-07 Lever Brothers Company, Division Of Conopco, Inc. Soap bars with little or no synthetic surfactant comprising organic salts
US6218348B1 (en) 2000-04-26 2001-04-17 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Process of making soap bar with enhanced skin benefits comprising adding salts of specific protic acid
US6342470B1 (en) * 2000-04-26 2002-01-29 Unilever Home & Personal Care Usa Bar comprising soap, fatty acid, polyalkylene glycol and protic acid salts in critical ratios and providing enhanced skin care benefits
WO2001080820A2 (en) * 2000-04-26 2001-11-01 Unilever Plc Method of cleansing skin and improving skin care in bar comprising soap, fatty acid and polyalkylene glycol
US6630432B2 (en) 2001-04-18 2003-10-07 Unilever Home & Personal Care Usa, Division Of Conopco Processable soap based bars comprising soaps of α hydroxy acid and minimum amount of free fatty acid and/or monoglyceride
US6458751B1 (en) 2001-07-23 2002-10-01 Unilever Home & Personal Care Usa Skin cleansing bar comprising a fatty alcohol with low mush
US6809070B2 (en) 2001-09-28 2004-10-26 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Toilet bar having a latent acidifier
US6706675B1 (en) 2002-08-30 2004-03-16 The Dial Corporation Translucent soap bar composition and method of making the same
US7838479B2 (en) * 2003-06-09 2010-11-23 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Packaged product containing an extrudable multiphase composition of a free fatty acid phase and a soap phase
JP5572271B1 (ja) 2014-03-26 2014-08-13 株式会社ピーアンドピーエフ 固形石鹸
JP2016113489A (ja) * 2014-12-11 2016-06-23 花王株式会社 固形石鹸

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3598746A (en) * 1969-05-09 1971-08-10 Armour Dial Inc Cosmetic soap bar
ZA773077B (en) * 1976-06-04 1979-01-31 Colgate Palmolive Co Process for making a toilet soap bar
SE439646B (sv) * 1977-07-15 1985-06-24 Colgate Palmolive Co Komposition for framstellning av toaletttval i styckeform och forfarande for framstellning av kompositionen
DE3320101A1 (de) * 1983-06-03 1984-12-06 Henkel KGaA, 4000 Düsseldorf Stiftseife
CA2080154C (en) * 1991-10-14 1999-04-06 John G. Chambers Toilet soap bars

Also Published As

Publication number Publication date
EP0707631A1 (en) 1996-04-24
CZ3096A3 (en) 1996-05-15
ZA944811B (en) 1996-01-04
JPH09500666A (ja) 1997-01-21
SK996A3 (en) 1996-05-08
ES2098970T3 (es) 1997-05-01
DE69401956T2 (de) 1997-06-12
JP2703826B2 (ja) 1998-01-26
HU216060B (hu) 1999-04-28
PL174919B1 (pl) 1998-10-30
AU7187494A (en) 1995-02-06
BR9406919A (pt) 1996-07-30
GB9313859D0 (en) 1993-08-18
CZ286673B6 (en) 2000-06-14
CA2163977A1 (en) 1995-01-19
PL312430A1 (en) 1996-04-29
CA2163977C (en) 1999-11-30
HUT74084A (en) 1996-10-28
DE69401956D1 (de) 1997-04-10
AU699797B2 (en) 1998-12-17
WO1995002035A1 (en) 1995-01-19
HU9503760D0 (en) 1996-02-28
MY116211A (en) 2003-12-31
IN181732B (enrdf_load_stackoverflow) 1998-09-12

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