EP0730628A1 - Limescale removing composition - Google Patents

Limescale removing composition

Info

Publication number
EP0730628A1
EP0730628A1 EP95900745A EP95900745A EP0730628A1 EP 0730628 A1 EP0730628 A1 EP 0730628A1 EP 95900745 A EP95900745 A EP 95900745A EP 95900745 A EP95900745 A EP 95900745A EP 0730628 A1 EP0730628 A1 EP 0730628A1
Authority
EP
European Patent Office
Prior art keywords
acid
alpha
maleic acid
composition according
hydroxy carboxylic
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.)
Granted
Application number
EP95900745A
Other languages
German (de)
French (fr)
Other versions
EP0730628B1 (en
Inventor
Elaine Ann Bowden
Alan John Fry
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
Priority claimed from GB939324126A external-priority patent/GB9324126D0/en
Priority claimed from GB9412377A external-priority patent/GB9412377D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0730628A1 publication Critical patent/EP0730628A1/en
Application granted granted Critical
Publication of EP0730628B1 publication Critical patent/EP0730628B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D1/83—Mixtures of non-ionic with 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to compositions for the removal of limescale.
  • Limescale mainly comprises calcium and magnesium carbonates, and can contain lesser amounts of soap scum, protein, particulates and other soils. Limescale is formed on evaporation of water containing said soils. While the deposit formed by evaporation is initially paste-like, it hardens with time to form a recalcitrant deposit.
  • Conventional cleaning compositions are generally buffered at alkaline pH so as to attack fatty soils. Limescale is resistant to the action of alkali and specialist cleaning compositions, of acid pH, are used to remove it.
  • a plurality of limescale removing compositions are disclosed in EP 0253676. These compositions are thickened by means of an amine or an a ine oxide and comprise an acid which may be organic or inorganic.
  • EP 0496188 (P&G) relates to compositions with 1-15% nonionic and 4-25% of maleic acid, having a pH of 1-4.
  • Preferred compositions are formulated at pH 1-4 and comprise maleic and nonionic at specified levels but which are substantially free of both ionic detergents and phosphoric acid.
  • Maleic acid is produced from petrochemical sources and potentially oxidises to produce rancid odours.
  • Maleic acid is a relatively toxic material and is moderately expensive.
  • Other organic acids, such as citric and lactic acids are available from renewable resources, are less toxic and less prone to oxidation.
  • compositions comprising citric acid together with nonionic surfactants are unstable.
  • limescale-removing compositions of pH 1-4 comprising maleic acid, a nonionic surfactant, an anionic surfactant, a perfume and an alpha- hydroxy carboxylic acid are stable.
  • alpha-hydroxy carboxylic acid is less toxic and less prone to decomposition than an equivalent amount of maleic acid, i.e. an amount which provides comparable limescale- removing performance.
  • the alpha-hydroxy carboxylic acid interacts with the nonionic surfactant to destabilise the product in the absence of the anionic surfactant.
  • compositions comprise a fragrance.
  • a fragrance is important both to meet consumer expectations and to mask any off odours resulting from decomposition of the organic acids.
  • the presence of the anionic detergent is essential in order that the perfume can be solubilised in the composition.
  • Typical levels of maleic acid in the product range from 2- 6%wt. It is preferable that the level of maleic acid is below 4%wt so as reduce toxicity and prevent the development of excessive off odours. The most preferred level of maleic acid falls into the range more than 3.0%wt and less than 4.0%wt.
  • Preferred alpha-hydroxy carboxylic acids are lactic acid, glycolic acid and citric acid.
  • Polycarboxylic acids, particularly citric acid is the most preferred for reasons of cost, ease of availability and weight-effectiveness.
  • citric acid The preferred of citric acid are 2.5-10wt%, most preferably 2.5-7.5wt%. It is particularly preferably that the alpha-hydroxy carboxylic acid should be present in weight excess relative to the maleic acid. Ratio of alpha-hydroxy carboxylic acid to maleic acid is preferably in the range 1-2:1.
  • nonionic surfactants should not include any significant amounts of amine oxide.
  • the preferred nonionic surfactants are alkoxylated alcohols.
  • the preferred alkoxylated alcohols are selected from the group comprising ethoxylated alcohols of the general formula:
  • R x is straight or branched, C 8 to C 18 alkyl or hydroxyalkyl and m is, on average, 1-14.
  • the alkyl chain length is C 8 -C n . It is believed that this reduces the strength of the interaction with the alpha-hydroxy carboxylic acd.
  • the preferred average degree of ethoxylation m is 6-9 for good fatty soil detergency and high solubility in the composition.
  • the nonionic surfactant should have a HLB in the range 12-16.
  • nonionic surfactant ranges from 0.5- 7%wt, more preferably 0.75-3%wt.
  • anionic surfactant comprises one or more of the group comprising: primary and secondary alcohol sulphates, alcohol alkoxy sulphates, primary and secondary alkane sulphonates and alkyl aryl sulphonates.
  • the preferred anionic surfactants are the secondary alkane sulphonates. Most preferably the secondary alkane sulphonate is a C 12 -C 18 average chain length secondary alkane sulphonate.
  • Preferred levels of anionic surfactant range from l-10%wt, more preferably l-6%wt. It is particularly preferred that the weight ratio between the anionic surfactant to nonionic is 3:1-1:1. It is also preferable that the alpha-hydroxy carboxylic acid is present in weight excess over the total surfactant content.
  • a thickener when present are xanthan gums.
  • Preferred xanthan gums are the Kelzan (RTM) series (available from Kelco Corp) . Typical levels of xanthan gum range from 0.05-lwt%.
  • the resulting viscosity of the composition, as measured on a Haake RV2 rotoviscometer (RTM) is preferably in the range 10-200 Pas at 20 reciprocal seconds shear and 25 Celcius, using an MV1 bob. More preferably the thickened compositions have a viscosity of 10-100 mPas under the conditions mentioned above.
  • compositions of the present invention include opacifiers, colours, preservatives and fluorescers.
  • Preferred formulations comprise:
  • compositions having a pH of 1-3 and a viscosity of 3- 7 mPas as measured on a Haake RV2 rotoviscometer (RTM) at 20 reciprocal seconds shear and 25 Celcius, using an MV1 bob.
  • RTM Haake RV2 rotoviscometer
  • compositions were prepared by:
  • compositions were prepared as given in Table 1 below, all components being given as 100%wt.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Detergent Compositions (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Processing Of Solid Wastes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides limescale-removing compositions of pH 1-4, comprising maleic acid, a nonionic surfactant, an anionic surfactant, a perfume and an alpha-hydroxy carboxylic acid (preferably citric acid). It is believed that the combination of alpha-hydroxy carboxylic acid with maleic acid is less toxic and less prone to decomposition than an equivalent amount of maleic acid, i.e. an amount which provides comparable limescale-removing performance. However, it is also believed that the alpha-hydroxy carboxylic acid interacts with the nonionic surfactant to destabilise the product in the absence of the anionic surfactant. Thus, there is believed to a synergistic interaction between the components which provides a stable and effective composition containing the alpha-hydroxy fatty acid as a partial replacer for the maleic acid.

Description

LIMESCALE REMOVING COMPOSITION
Technical Field
The present invention relates to compositions for the removal of limescale.
Background to the Invention
Limescale mainly comprises calcium and magnesium carbonates, and can contain lesser amounts of soap scum, protein, particulates and other soils. Limescale is formed on evaporation of water containing said soils. While the deposit formed by evaporation is initially paste-like, it hardens with time to form a recalcitrant deposit.
Conventional cleaning compositions are generally buffered at alkaline pH so as to attack fatty soils. Limescale is resistant to the action of alkali and specialist cleaning compositions, of acid pH, are used to remove it.
A plurality of limescale removing compositions are disclosed in EP 0253676. These compositions are thickened by means of an amine or an a ine oxide and comprise an acid which may be organic or inorganic.
It is known that the use of strong acids, such as hydrochloric acid will result in prompt removal of limescale but will also result in damage to surrounding surfaces, such as bath enamels, metals and certain polymers, where these are susceptible to attack by strong acids. Limescale removing compositions of maleic acid in combination with nonionic surfactants, either in further combination with ionic detergents or with phosphoric acid are known. In the absence of nonionic surfactants cleaning efficiency is greatly reduced. Maleic acid is known to be a particularly effective limescale remover and is less prone to attack surfaces than the inorganic acids.
EP 0496188 (P&G) relates to compositions with 1-15% nonionic and 4-25% of maleic acid, having a pH of 1-4. Preferred compositions are formulated at pH 1-4 and comprise maleic and nonionic at specified levels but which are substantially free of both ionic detergents and phosphoric acid.
Maleic acid is produced from petrochemical sources and potentially oxidises to produce rancid odours. Maleic acid is a relatively toxic material and is moderately expensive. Other organic acids, such as citric and lactic acids are available from renewable resources, are less toxic and less prone to oxidation. However, compositions comprising citric acid together with nonionic surfactants are unstable.
Brief Description of the Invention
We have now determined that limescale-removing compositions of pH 1-4, comprising maleic acid, a nonionic surfactant, an anionic surfactant, a perfume and an alpha- hydroxy carboxylic acid are stable.
Without wishing to be limited by any theory of operation, it is believed that the combination of alpha-hydroxy carboxylic acid with maleic acid is less toxic and less prone to decomposition than an equivalent amount of maleic acid, i.e. an amount which provides comparable limescale- removing performance. However it is also believed that the alpha-hydroxy carboxylic acid interacts with the nonionic surfactant to destabilise the product in the absence of the anionic surfactant. Thus, there is believed to be a synergistic interaction between the components which provides a stable and effective composition containing the alpha-hydroxy carboxylic acid as a partial replacer for the maleic acid.
Detailed Description of the Invention
It is essential that the above-mentioned compositions comprise a fragrance. The presence of a fragrance is important both to meet consumer expectations and to mask any off odours resulting from decomposition of the organic acids. In is believed that the presence of the anionic detergent is essential in order that the perfume can be solubilised in the composition.
Typical levels of maleic acid in the product range from 2- 6%wt. It is preferable that the level of maleic acid is below 4%wt so as reduce toxicity and prevent the development of excessive off odours. The most preferred level of maleic acid falls into the range more than 3.0%wt and less than 4.0%wt.
Preferred alpha-hydroxy carboxylic acids are lactic acid, glycolic acid and citric acid. Polycarboxylic acids, particularly citric acid is the most preferred for reasons of cost, ease of availability and weight-effectiveness.
The preferred of citric acid are 2.5-10wt%, most preferably 2.5-7.5wt%. It is particularly preferably that the alpha-hydroxy carboxylic acid should be present in weight excess relative to the maleic acid. Ratio of alpha-hydroxy carboxylic acid to maleic acid is preferably in the range 1-2:1.
It is preferred that the nonionic surfactants should not include any significant amounts of amine oxide.
The preferred nonionic surfactants are alkoxylated alcohols.
The preferred alkoxylated alcohols are selected from the group comprising ethoxylated alcohols of the general formula:
R1-(OCH2CH2)m-OH
wherein Rx is straight or branched, C8 to C18 alkyl or hydroxyalkyl and m is, on average, 1-14.
Preferably, the alkyl chain length is C8-Cn. It is believed that this reduces the strength of the interaction with the alpha-hydroxy carboxylic acd. The preferred average degree of ethoxylation m is 6-9 for good fatty soil detergency and high solubility in the composition. Generally, the nonionic surfactant should have a HLB in the range 12-16.
The starting materials for the synthesis of these ethoxylated alcohols, are available from both natural and synthetic sources.
Preferred levels of nonionic surfactant range from 0.5- 7%wt, more preferably 0.75-3%wt. Preferably the anionic surfactant comprises one or more of the group comprising: primary and secondary alcohol sulphates, alcohol alkoxy sulphates, primary and secondary alkane sulphonates and alkyl aryl sulphonates.
The preferred anionic surfactants are the secondary alkane sulphonates. Most preferably the secondary alkane sulphonate is a C12-C18 average chain length secondary alkane sulphonate.
Preferred levels of anionic surfactant range from l-10%wt, more preferably l-6%wt. It is particularly preferred that the weight ratio between the anionic surfactant to nonionic is 3:1-1:1. It is also preferable that the alpha-hydroxy carboxylic acid is present in weight excess over the total surfactant content.
The presence of a thickener is optional. Preferred thickeners, when present are xanthan gums. Preferred xanthan gums are the Kelzan (RTM) series (available from Kelco Corp) . Typical levels of xanthan gum range from 0.05-lwt%. The resulting viscosity of the composition, as measured on a Haake RV2 rotoviscometer (RTM) is preferably in the range 10-200 Pas at 20 reciprocal seconds shear and 25 Celcius, using an MV1 bob. More preferably the thickened compositions have a viscosity of 10-100 mPas under the conditions mentioned above.
We have determined that thin compositions have advantages over thickened compositions in certain circumstances. In particular it is believed that products having a lower viscosity exhibit a more rapid removal of limescale. Suitable viscosities fall in the range 2-10 mPas, measured as described above, with preferred viscosities being in the range 3-7 mPas. Preferred levels of perfume range from 0.1-l%wt. Acid stable perfumes are available from a variety of sources including the Quest company.
Various minor components may be present in the compositions of the present invention, these include opacifiers, colours, preservatives and fluorescers.
Preferred formulations comprise:
a) 2-4%wt maleic acid,
b) 0.75-3%wt ethoxylated alcohol of HLB 12-16
c) l-6%wt secondary alkane sulphonate,
d) 2.5-7.5%wt citric acid, and,
e) 0.1-0.5%wt perfume,
said compositions having a pH of 1-3 and a viscosity of 3- 7 mPas as measured on a Haake RV2 rotoviscometer (RTM) at 20 reciprocal seconds shear and 25 Celcius, using an MV1 bob.
The present invention will be further described with reference to the following non-limiting examples.
Examples
Materials used in the examples are identified as follows maleic acid maleic acid, ex. Croda. DOBANOL 91-8 (RTM) ethoxylated alcohol, ex. Shell, SAS 30-X secondary alkane sulphonate, ex.
Hoechst citric acid citric acid, ex. Biacor, perfume GC-1462, ex. Quest, dye Basacid Blue 755 (RTM) ex. BASF.
Compositions were prepared by:
a) preparing a main mix of maleic acid in water, followed by addition of citric acid solution, and,
b) adding the SAS, DOBANOL, dye and finally perfume.
Compositions were prepared as given in Table 1 below, all components being given as 100%wt.
TABLE 1
maleic acid 3.5%wt
DOBANOL 91-8 (RTM) 1.0%wt
SAS 30-X 2.0%wt citric acid 5.0%wt perfume 0.3%wt dye 0.001%wt water to 100%wt
The results given in Table 2 show the rates at which MMF5 calcite is dissolved by the composition given above (thin product) and a further example which contains a Kelzan (TM) gum thickening agent (thick product) . The thick product had as viscosity of 40 mPas whereas the thin product had a viscosity of 5 mPas.
TABLE 2
Treatment Time (sec) Thin Product Thick Product (Calcite dissolved g)
20 0.30 0.10
40 0.45 0.30
60 0.60 0.50
80 0.70 0.60
120 0.75 0.65
150 0.80 0.75
180 0.85 0.80
It can be seen that products having a lower viscosity show improved performance as regards their immediate effect as compared with the product having a higher viscosity.
Moreover, in comparisons between the thick and thin maleic/citric products described above and a commercially available product believed to be based simply on maleic acid, using a trained panel, it was found that users perceived that the thin product showed improvements over the two other products as regards limescale removal, ease of rinsing and odour.

Claims

1. Stable, viscous, limescale-removing compositions of pH 1-4, comprising maleic acid, a nonionic surfactant, a perfume, an anionic surfactant and an alpha-hydroxy carboxylic acid.
2. Composition according to claim 1, comprising 2-4%wt maleic acid.
3. Composition according to claim 1, comprising 2.5- 10wt% alpha-hydroxy carboxylic acid.
4. Composition according to claim 1, wherein the alpha- hydroxy carboxylic acid is citric acid.
5. Composition according to claim 1 comprising 0.75-3%wt nonionic surfactant.
6. Composition according to claim 1 wherein the nonionic surfactant is an alkoxylated alcohol.
7. Composition according to claim 1 comprising 1-10% anionic surfactant.
8. Composition according to claim 1 having a viscosity of the as measured on a Haake RV2 rotoviscometer (RTM) in the range 3-7 mPas at 20 reciprocal seconds shear and 25 Celcius, using an MVl bob.
9. Composition according to claim 1 comprising:
a) 2-4%wt maleic acid,
b) 0.75-3%wt ethoxylated alcohol of HLB 12-16 c) l-6%wt secondary alkane sulphonate,
d) 2.5-7.5%wt citric acid, and,
e) 0.1-0.5%wt perfume.
EP95900745A 1993-11-24 1994-11-12 Limescale removing composition Expired - Lifetime EP0730628B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB9324126 1993-11-24
GB939324126A GB9324126D0 (en) 1993-11-24 1993-11-24 Limescale removing composition
GB9412377 1994-06-21
GB9412377A GB9412377D0 (en) 1994-06-21 1994-06-21 Limescale removing composition
PCT/EP1994/003790 WO1995014756A1 (en) 1993-11-24 1994-11-12 Limescale removing composition

Publications (2)

Publication Number Publication Date
EP0730628A1 true EP0730628A1 (en) 1996-09-11
EP0730628B1 EP0730628B1 (en) 1998-03-25

Family

ID=26303909

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95900745A Expired - Lifetime EP0730628B1 (en) 1993-11-24 1994-11-12 Limescale removing composition

Country Status (7)

Country Link
EP (1) EP0730628B1 (en)
AU (1) AU678313B2 (en)
BR (1) BR9408132A (en)
CA (1) CA2175677A1 (en)
DE (1) DE69409254T2 (en)
ES (1) ES2113723T3 (en)
WO (1) WO1995014756A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE226623T1 (en) * 1995-08-09 2002-11-15 Procter & Gamble ACIDIC CLEANING COMPOSITIONS
GB9610965D0 (en) * 1996-05-24 1996-07-31 Unilever Plc Improvements relating to limescale removing compositions

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049467A (en) * 1976-04-23 1977-09-20 Lever Brothers Company Method and compositions for removal of hard surface manganese ion-derived discolorations
JPS6369895A (en) * 1986-09-12 1988-03-29 花王株式会社 Liquid cleanser composition
JP2559448B2 (en) * 1988-02-26 1996-12-04 花王株式会社 Liquid detergent composition
EP0496188B1 (en) * 1991-01-22 1997-10-22 The Procter & Gamble Company Limescale removing composition
WO1994005758A1 (en) * 1992-09-01 1994-03-17 The Procter & Gamble Company Liquid or gel detergent compositions containing calcium and stabilizing agent thereof
EP0601990B1 (en) * 1992-12-04 1998-10-14 The Procter & Gamble Company Self-thickened acidic cleaning composition

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 8818, Derwent Publications Ltd., London, GB; AN 88-124390 & *
JP,A,63 069 895 (KAO) 29 March 1988 *
See also references of WO9514756A1 *

Also Published As

Publication number Publication date
DE69409254T2 (en) 1998-07-16
ES2113723T3 (en) 1998-05-01
CA2175677A1 (en) 1995-06-01
AU678313B2 (en) 1997-05-22
EP0730628B1 (en) 1998-03-25
WO1995014756A1 (en) 1995-06-01
BR9408132A (en) 1997-08-05
DE69409254D1 (en) 1998-04-30
AU8143694A (en) 1995-06-13

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