WO1999019431A1 - Alkoxylated amines and their use in cleaning compositions - Google Patents

Alkoxylated amines and their use in cleaning compositions Download PDF

Info

Publication number
WO1999019431A1
WO1999019431A1 PCT/EP1998/006633 EP9806633W WO9919431A1 WO 1999019431 A1 WO1999019431 A1 WO 1999019431A1 EP 9806633 W EP9806633 W EP 9806633W WO 9919431 A1 WO9919431 A1 WO 9919431A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition according
amine
saturated
range
mole ratio
Prior art date
Application number
PCT/EP1998/006633
Other languages
French (fr)
Inventor
Marcella Margherita Leda Bartoletti
Giuseppe Vincenzo Bolzoni
Emanuela Ferro
Marco Galli
Ronald Meredith Morris
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 PL98339808A priority Critical patent/PL188434B1/en
Priority to AU12298/99A priority patent/AU735924B2/en
Priority to BR9813044-7A priority patent/BR9813044A/en
Priority to JP2000515989A priority patent/JP4323093B2/en
Priority to HU0004913A priority patent/HU224521B1/en
Priority to CA2305193A priority patent/CA2305193C/en
Priority to DE69821636T priority patent/DE69821636T2/en
Priority to EP98955491A priority patent/EP1023423B1/en
Priority to SK530-2000A priority patent/SK5302000A3/en
Priority to KR1020007003926A priority patent/KR20010015748A/en
Publication of WO1999019431A1 publication Critical patent/WO1999019431A1/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
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/42Amino alcohols or amino ethers
    • C11D1/44Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • 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
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/042Acids
    • 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
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3942Inorganic per-compounds
    • 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
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3947Liquid compositions
    • C11D2111/14

Definitions

  • the present invention relates to acidic cleaning compositions, and in particular to acidic antimicrobial cleaning composition suitable for use on hard surfaces.
  • compositions generally comprise sufficient acid to give a low pH and may comprise a thickening agent to as to cause the composition to be retained on sloping surfaces, such as the inside of toilet bowls.
  • thickeners include both ethoxylated and unethoxylated tertiary amines, either alone or in combination with a hydrotrope.
  • acids for use in such compositions include sulphamic and phosphoric acids.
  • GB 1443244 relates to acid cleaners and descalers which comprise as a thickening agent an ethoxylated tertiary amine of which ETHOMEEN S12 (N,N-dihydroxyethyl-oleylamine) is given as an example.
  • the composition also comprises acids which are selected from mineral acids and acid salts of strong inorganic acids such as sulphamic acid. Bacteriocides are an additional, optional component.
  • FR 2459830 discloses compositions which comprise non- ethoxylated and ethoxylated amines together with sulphamic acid.
  • the composition may also comprise disinfectants.
  • AU-A-57022/86 relates to cleaning systems which comprise a mixture of sulphamic and phosphoric acids and an acid stable surfactant.
  • Bacteriocides are optional and formalin is disclosed as a bacteriocide which improves the antibacterial effect of the acids.
  • EP-B-0276501 discloses thickened aqueous cleaning compositions which comprise 0.1-50%wt of a weak acid having a pK >2 (of which sulphamic acid is given as an example) , 0.1-20%wt of an amine which can include 2% of oleyl-bis(2- hydroxyethy1 ) amine and 0.01%-5%wt hydrotrope (sodium xylene-sulphonate is given as an example) . Disinfecting agents are optional .
  • EP-A-0314232 relates to compositions which undergo a viscosity increase on dilution and discloses that thickened liquid detergent compositions can be prepared with an amine oxide, amine (such as ETHOMEEN S12) , betaine or quaternary ammonium compound and hydrotrope (sodium xylene- sulphonate) . It is stated in the specification that amine oxides and quaternary ammonium compounds are known to have biocidal properties and that further microbiocides including organic peracids are optional. These compositions can be of acidic, neutral or alkaline pH.
  • One problem with the known compositions is that the viscosity of the compositions drifts with time, and, in particular falls when the product is stored.
  • compositions which comprise a specific mixture of both saturated and unsaturated alkoxylated aliphatic amines in the presence of an anionic surfactant show an improved stability of viscosity on storage.
  • anionic surfactant hydrotrope to these formulations has the additional benefit that the surface energy of surfaces treated with the composition is reduced and the subsequent deposition of limescale is retarded.
  • a cleaning composition which comprises a) 0.01-15%wt an alkoxylated aliphatic amine with 8-18 carbon atoms and 1-8 moles ethoxylation wherein the mole ratio of saturated to unsaturated aliphatic residues falls in the range 40:60 to 80:20, and
  • a process for retarding the deposition of limescale on a surface which comprises the step of treating said surface with a cleaning composition having a pH of less than 1 which comprises:
  • the alkoxylated aliphatic amine is an ethoxylated tertiary amine of the general formula:
  • R is an alkyl or alkenyl group comprising 8-18 carbon atoms
  • A is an ethoxy or propoxy group
  • x and y may be the same or different and are integers from 1-3.
  • the preferred materials are ethoxylated amines wherein A is -OCH 2 CH 2 - .
  • R is mixed saturated and unsaturated C14-C18 alkyl and is most preferably derived from fatty acids residues of which the majority correspond to oleic and/or stearic acids.
  • the mole ratio of saturated to unsaturated fatty acids falls into the range 50:50 to 66:33.
  • a particularly suitable alkoxylated aliphatic amine is a material known as ETHOMEEN BTB/12TM, available from AKZO.
  • BTB/12 is believed to be a mixture of material derived from fully hardened tallow and the oleyl derivative in a 65/35 ratio.
  • Such a mixed material can be prepared by synethesis using an appropriate ratio of mixed starting materials or obtained by mixing an alkoxylated aliphatic amine such as
  • ETHOMEEN S12 (ex AKZO) is N,N- (dihydroxyethyl ) -oleylamine .
  • the preferred levels of the alkoxylated aliphatic amine are l-10%wt on product with levels of 2-6%wt on product being particularly preferred.
  • the alkoxylated aliphatic amine is present together with an anionic surfactant.
  • the levels of these materials are such that they interact so as to thicken the composition
  • Suitable anionic surfactants include the sulphonate hydrotropes.
  • Preferred surfactants are alkylarylsulphonates such as salts, particularly alkali metal salts, of toluene, cumene or xylene sulphonate .
  • the preferred anionic surfactant is sodium cumenesulphonate .
  • TM is ELTESOL SC 40 (ex. Albright and Wilson) .
  • Typical levels of anionic surfactant range from 0.05-2%wt on product.
  • formulations comprising the alkylaryl sulphonates are formulated at a pH below 1.
  • the ethoxylated amine behaves as a cationic surfactant and interacts with the alkylaryl sulphonate to form a water- insoluble gel which deposits as a monolayer on surfaces. It is believed that this monolayer lowers the surface energy of the surface and retards or prevents the deposition of further limescale.
  • the preferred mole ratio of the ethoxylated amine and the anionic surfactant is 3-3.5, more preferably 3.25-3.5.
  • the preferred viscosity of the cleaning compositions according to the present invention is between 50 mPas and 1000 mPas when measured at 11.7 sec shear and at 25°C using Haake RV2 rotoviscometer (RTM) and an MVl bob
  • cleaning compositions which embody the present invention comprise 0.01-15%wt of a limescale removing acid, preferably an organic acid and more preferably sulphamic acid.
  • a limescale removing acid preferably an organic acid and more preferably sulphamic acid.
  • typical levels of the acid range from l-10%wt on product with levels of 2-6% on product being particularly preferred.
  • the pH of the compositions according to the invention should have a pH of ⁇ 2.0, more preferably a pH ⁇ 1.0.
  • Preferred embodiments of the invention are cleaning and ' /or hygiene compositions which comprises a peroxygen compound.
  • typical sources of peroxygen species include one or more of hydrogen peroxide, peracetic acid and/or other organic or inorganic peroxygen sources.
  • Hydrogen peroxide is a preferred source of peroxygen species.
  • Typical levels of hydrogen peroxide range from l-10%wt on product with levels of 3-8% being particularly preferred.
  • compositions according to the invention additionally comprise nonionic surfactant.
  • Suitable nonionic surfactants include alkoxylated alcohols, preferably ethoxylated alcohols.
  • Suitable nonionic detergent active compounds can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements .
  • the preferred alkoxylated alcohols are selected from the group comprising ethoxylated alcohols of the general formula :
  • R ⁇ is straight or branched, C 8 to C 18 alkyl or hydroxyalkyl and m is, on average, 1-14.
  • Ethoxylated alcohols suitable for use in the present invention include LIAL 111.10EO [TM] available in the marketplace from DAC. Typical levels of nonionic surfactant in products according to the present invention range from 0-5%.
  • compositions according to the present invention comprise: a) l-10%wt, preferably 3-5%wt sulphamic acid, b) l-10%wt, preferably 2-5%wt ethoxylated amine, c) 0-5%wt, preferably 0.05-l%wt, nonionic surfactant, d) 0.05-2%wt, preferably 0.4-l.l%wt, anionic surfactant hydrotrope, e) l-10%wt, preferably 4-6%wt, hydrogen peroxide
  • compositions of the invention provide a thickening effect it is possible to add other thickeners.
  • Gums, particularly xanthan gums are suitable thickeners.
  • TM gums are the Kelzan series (available from Kelco Corp) . Typical levels of xanthan gum range from 0.05-lwt%.
  • the resulting viscosity of the composition is preferably in the range 10-200 mPas at 20 sec shear and 25°C, using an MVl bob. More preferably the viscosity is 10-100 mPas under the conditions mentioned above.
  • Metal ion sequestrants such as ethylene diamine tetraacetates, amino-poly phosphonates (such as those in
  • TM the DEQUEST range ex. Monsanto
  • phosphates and a wide variety of other poly-functional organic acids and salts can also optionally be employed.
  • Preferred metal ion complexing agents are selected from dipicolinic acid, ethylene diamine tetra acetic acid (EDTA) and its salts, hydroxy-ethylidene diphosphonic acid (Dequest 2010) , ethylenediamine-tetra (methylene phosphonic acid) (Dequest 2040), diethylene-triamine-penta (methylene phosphonic acid) (Dequest 2060) .
  • minor components also include those typically found in cleaning compositions and are selected from opacifiers, colours perfumes and fluorescers.
  • Preferred levels of perfume range from 0.05-2%wt. Acid stable perfumes are available from a variety of sources.
  • composition according to the present invention comprises:
  • Typical products having the above formulation made with 3.0%wt of the amine and around 0.56%wt of the SCS are preferably clear, have a specific gravity of 1.040 g/ml, an initial viscosity at 106 sec " (at 25°C) of 120mPas, an initial viscosity at 11.7 sec “1 (at 25°C) of 300-600 mPas and pH 0.9 (at 25°C) .
  • Figure 1 shows the viscosity of materials according to the present invention and comparative examples in mPas at 11.7 sec as measured using on a Haake RV2 rotoviscometer and an MVl bob after storage at room temperature.
  • Figure 2 shows the viscosity of materials according to the present invention and comparative examples in mPas at 106 s-1, as measured using on a Haake RV2 rotoviscometer (RTM) and an MVl bob after storage at room temperature.
  • RTM Haake RV2 rotoviscometer
  • Figure 3 shows the viscosity of materials according to the present invention and comparative examples in mPas at 106 s-1, as measured using on a Haake RV2 rotoviscometer and an MVl bob after storage at 37°C.
  • Figure 4 shows the viscosity of materials according to the present invention and comparative examples in mPas at 11.7 sec measured on a Haake RV2 rotoviscometer and an MVl bob after storage at 37°C.
  • composition was prepared as follows
  • compositions having a viscosity between 50 mPas and 1000 mPas were flowable compositions which were suitable for use as toilet cleaners. Compositions with a lower viscosity were too thin to stay on sloping surfaces, while those with a higher viscosity could not be dispensed with ease. Compositions with a viscosity of from 200-700 mPas were particularly suited to this purpose.
  • compositions of the type described above were prepared with differing degrees of saturation in the ethoxylated amine.
  • the materials used were:
  • Figure 1 shows the viscosity of materials according to the present invention and comparative examples in mPas at 11.7 sec , as measured using on a Haake RV2 rotoviscometer and an MVl bob after storage at room temperature. It can be seen that the viscosity of the , HT12' sample rose with time until the product became a non-flowing gel. The viscosity of the ⁇ S12' sample fell, such that the product eventually became too thin to be retained on sloping surfaces. The viscosities of the products containing a mixture of hardened and unhardened tallow remained in the acceptable range on storage.
  • Figure 2 shows the viscosity of materials according to the present invention and comparative examples in mPas at 106 sec , as measured using on a Haake RV2 rotoviscometer and an MVl bob after storage at room temperature. It can be seen that the viscosity of the V HT12' sample first fell and then rose. The viscosity of the S12' sample fell, such that the product eventually became too thin to be retained on sloping surfaces. The viscosities of the products containing a mixture of hardened and unhardened materials remained in the acceptable range on storage .
  • Figure 3 shows the viscosity of materials according to the present invention and comparative examples in mPas at 106 sec , as measured using on a Haake RV2 rotoviscometer and an MVl bob after storage at 37°C. It can be seen that the viscosity of the ⁇ HT12' sample again first fell and then rose. The viscosity of the ' S12' sample fell, such that the product eventually became too thin to be retained on sloping surfaces. The viscosities of the products containing a mixture of hardened and unhardened materials remained in the acceptable range on storage.
  • Figure 4 shows the viscosity of materials according to the present invention and comparative examples in mPas at 11.7 sec , as measured using on a Haake RV2 rotoviscometer and an MVl bob after storage at 37°C. It can be seen that the viscosity of the ⁇ HT12' sample again rose. The viscosity of the ' S12' sample fell, such that the product eventually became too thin to be retained on sloping surfaces. The viscosities of the products containing a mixture of hardened and unhardened materials remained in the acceptable range on storage.
  • Hard water of -60 degrees French was prepared by flushing carbon dioxide through tap-water containing both calcite and dolomite overnight. Pairs of tiles were cleaned with a detergent composition and ethanol and rinsed with tap water. One of the tile was treated with a composition - I S
  • Example 2 that of Example 1 , with a contact time of 20 minutes: the tile was then rinsed with water. The hard water was then dripped onto the tiles for 24 hours, allowing one drop to fall onto each tile every five minutes.
  • the limescale was titrated after dissolution with dilute HCl. The results of titration are expressed in mg of calcium carbonate per tile in Table 3 below. Examples were performed in replicates A, B and C.

Abstract

The invention provides an alkoxylated aliphatic amine with 8-18 carbon atoms and 1-8 moles ethoxylation wherein the mole ratio of saturated to unsaturated aliphatic residues falls in the range 40:60 to 80:20. The invention also provides a cleaning composition which comprises: (a) 0.01-15 wt.% an alkoxylated aliphatic amine with 8-18 carbon ataoms and 1-8 moles ethoxylation wherein the mole ratio of saturated to unsaturated aliphatic residues falls in the range 40:60 to 80:20, and (b) 0.01-15 wt.% of an anionic surfactant. Cleaning compositions which comprise the amine show improved viscosity stability on storage. In the presence of the anionic surfactant at low pH the deposition of limescale on surfaces which have been treated with the composition is retarded.

Description

ALKOXYLATED AMINES AND THEIR USE IN CLEANING COMPOSITIONS
Technical Field
The present invention relates to acidic cleaning compositions, and in particular to acidic antimicrobial cleaning composition suitable for use on hard surfaces.
Background to the Invention
Many formulations have been proposed in the literature for so-called 'descaler' compositions. These generally comprise sufficient acid to give a low pH and may comprise a thickening agent to as to cause the composition to be retained on sloping surfaces, such as the inside of toilet bowls. As described in more detail below, known thickeners include both ethoxylated and unethoxylated tertiary amines, either alone or in combination with a hydrotrope. Known acids for use in such compositions include sulphamic and phosphoric acids.
GB 1443244 relates to acid cleaners and descalers which comprise as a thickening agent an ethoxylated tertiary amine of which ETHOMEEN S12 (N,N-dihydroxyethyl-oleylamine) is given as an example. The composition also comprises acids which are selected from mineral acids and acid salts of strong inorganic acids such as sulphamic acid. Bacteriocides are an additional, optional component. FR 2459830 discloses compositions which comprise non- ethoxylated and ethoxylated amines together with sulphamic acid. The composition may also comprise disinfectants.
AU-A-57022/86 relates to cleaning systems which comprise a mixture of sulphamic and phosphoric acids and an acid stable surfactant. Bacteriocides are optional and formalin is disclosed as a bacteriocide which improves the antibacterial effect of the acids.
EP-B-0276501 discloses thickened aqueous cleaning compositions which comprise 0.1-50%wt of a weak acid having a pK >2 (of which sulphamic acid is given as an example) , 0.1-20%wt of an amine which can include 2% of oleyl-bis(2- hydroxyethy1 ) amine and 0.01%-5%wt hydrotrope (sodium xylene-sulphonate is given as an example) . Disinfecting agents are optional .
EP-A-0314232 relates to compositions which undergo a viscosity increase on dilution and discloses that thickened liquid detergent compositions can be prepared with an amine oxide, amine (such as ETHOMEEN S12) , betaine or quaternary ammonium compound and hydrotrope (sodium xylene- sulphonate) . It is stated in the specification that amine oxides and quaternary ammonium compounds are known to have biocidal properties and that further microbiocides including organic peracids are optional. These compositions can be of acidic, neutral or alkaline pH. One problem with the known compositions is that the viscosity of the compositions drifts with time, and, in particular falls when the product is stored.
Brief Description of the Invention
We have determined that compositions which comprise a specific mixture of both saturated and unsaturated alkoxylated aliphatic amines in the presence of an anionic surfactant show an improved stability of viscosity on storage. Surprisingly, we have found that the addition of a anionic sulphonate surfactant hydrotrope to these formulations has the additional benefit that the surface energy of surfaces treated with the composition is reduced and the subsequent deposition of limescale is retarded.
Detailed Description of the Invention
According to a first aspect of the present invention there is provided an alkoxylated aliphatic amine with 8-18 carbon atoms and 1-8 moles ethoxylation wherein the mole ratio of saturated to unsaturated aliphatic residues falls in the range 40:60 to 80:20.
According to a second aspect of the present invention there is provided a cleaning composition which comprises a) 0.01-15%wt an alkoxylated aliphatic amine with 8-18 carbon atoms and 1-8 moles ethoxylation wherein the mole ratio of saturated to unsaturated aliphatic residues falls in the range 40:60 to 80:20, and
b) 0.01-15%wt of an anionic surfactant.
According to a third aspect of the present invention there is provided a process for retarding the deposition of limescale on a surface which comprises the step of treating said surface with a cleaning composition having a pH of less than 1 which comprises:
a) 0.01-15%wt an alkoxylated aliphatic amine with 8-18 carbon atoms and 1-8 moles ethoxylation wherein the mole ratio of saturated to unsaturated aliphatic residues falls in the range 40:60 to 80:20, and,
0.01-15%wt of an anionic surfactant,
Amines
Typically, the alkoxylated aliphatic amine is an ethoxylated tertiary amine of the general formula:
H(A). -N(R)-(A)yH wherein R is an alkyl or alkenyl group comprising 8-18 carbon atoms, A is an ethoxy or propoxy group and x and y may be the same or different and are integers from 1-3.
The preferred materials are ethoxylated amines wherein A is -OCH2CH2- .
Preferably x and y are both 1. In preferred embodiments of the invention R is mixed saturated and unsaturated C14-C18 alkyl and is most preferably derived from fatty acids residues of which the majority correspond to oleic and/or stearic acids.
Preferably the mole ratio of saturated to unsaturated fatty acids falls into the range 50:50 to 66:33.
A particularly suitable alkoxylated aliphatic amine is a material known as ETHOMEEN BTB/12™, available from AKZO. BTB/12 is believed to be a mixture of material derived from fully hardened tallow and the oleyl derivative in a 65/35 ratio. Such a mixed material can be prepared by synethesis using an appropriate ratio of mixed starting materials or obtained by mixing an alkoxylated aliphatic amine such as
TM
ETHOMEEN HT12 (ex AKZO) with an unsaturated material such
TM as ETHOMEEN S12. ETHOMEEN S12 (ex AKZO) is N,N- (dihydroxyethyl ) -oleylamine .
In embodiments of the invention as cleaning products, the preferred levels of the alkoxylated aliphatic amine are l-10%wt on product with levels of 2-6%wt on product being particularly preferred.
Anionic Surfactants
In particularly preferred embodiments of the invention the alkoxylated aliphatic amine is present together with an anionic surfactant. Preferably, the levels of these materials are such that they interact so as to thicken the composition
Suitable anionic surfactants include the sulphonate hydrotropes. Preferred surfactants are alkylarylsulphonates such as salts, particularly alkali metal salts, of toluene, cumene or xylene sulphonate . The preferred anionic surfactant is sodium cumenesulphonate . A suitable material
TM is ELTESOL SC 40 (ex. Albright and Wilson) . Typical levels of anionic surfactant range from 0.05-2%wt on product.
Preferably, formulations comprising the alkylaryl sulphonates are formulated at a pH below 1. Without wishing to limit the invention by reference to any theory of operation, it is believed that at a pH below 1, the ethoxylated amine behaves as a cationic surfactant and interacts with the alkylaryl sulphonate to form a water- insoluble gel which deposits as a monolayer on surfaces. It is believed that this monolayer lowers the surface energy of the surface and retards or prevents the deposition of further limescale.
The preferred mole ratio of the ethoxylated amine and the anionic surfactant is 3-3.5, more preferably 3.25-3.5.
The preferred viscosity of the cleaning compositions according to the present invention is between 50 mPas and 1000 mPas when measured at 11.7 sec shear and at 25°C using Haake RV2 rotoviscometer (RTM) and an MVl bob
Acids
Typically, cleaning compositions which embody the present invention comprise 0.01-15%wt of a limescale removing acid, preferably an organic acid and more preferably sulphamic acid. In such embodiments, typical levels of the acid (for instance the amino sulphonic acid) range from l-10%wt on product with levels of 2-6% on product being particularly preferred.
It is preferred that the pH of the compositions according to the invention should have a pH of <2.0, more preferably a pH <1.0. Peroxygen Sources
Preferred embodiments of the invention are cleaning and'/or hygiene compositions which comprises a peroxygen compound.
Where present, typical sources of peroxygen species include one or more of hydrogen peroxide, peracetic acid and/or other organic or inorganic peroxygen sources. Hydrogen peroxide is a preferred source of peroxygen species.
Typical levels of hydrogen peroxide range from l-10%wt on product with levels of 3-8% being particularly preferred.
Nonionic Surfactants
Preferred compositions according to the invention additionally comprise nonionic surfactant.
Suitable nonionic surfactants include alkoxylated alcohols, preferably ethoxylated alcohols. Suitable nonionic detergent active compounds can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements .
The preferred alkoxylated alcohols are selected from the group comprising ethoxylated alcohols of the general formula :
R. 1-(OCH, λCH 2, ) rrt-OH
wherein Rχ is straight or branched, C8 to C18 alkyl or hydroxyalkyl and m is, on average, 1-14. Ethoxylated alcohols suitable for use in the present invention include LIAL 111.10EO [TM] available in the marketplace from DAC. Typical levels of nonionic surfactant in products according to the present invention range from 0-5%.
Particularly preferred compositions according to the present invention comprise: a) l-10%wt, preferably 3-5%wt sulphamic acid, b) l-10%wt, preferably 2-5%wt ethoxylated amine, c) 0-5%wt, preferably 0.05-l%wt, nonionic surfactant, d) 0.05-2%wt, preferably 0.4-l.l%wt, anionic surfactant hydrotrope, e) l-10%wt, preferably 4-6%wt, hydrogen peroxide
Minors
While the combination of the surfactants in the compositions of the invention provide a thickening effect it is possible to add other thickeners. Gums, particularly xanthan gums are suitable thickeners. Preferred xanthan
TM gums are the Kelzan 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) is preferably in the range 10-200 mPas at 20 sec shear and 25°C, using an MVl bob. More preferably the viscosity is 10-100 mPas under the conditions mentioned above.
Metal ion sequestrants such as ethylene diamine tetraacetates, amino-poly phosphonates (such as those in
TM , the DEQUEST range ex. Monsanto) and phosphates and a wide variety of other poly-functional organic acids and salts, can also optionally be employed. Preferred metal ion complexing agents are selected from dipicolinic acid, ethylene diamine tetra acetic acid (EDTA) and its salts, hydroxy-ethylidene diphosphonic acid (Dequest 2010) , ethylenediamine-tetra (methylene phosphonic acid) (Dequest 2040), diethylene-triamine-penta (methylene phosphonic acid) (Dequest 2060) .
Optional, minor components also include those typically found in cleaning compositions and are selected from opacifiers, colours perfumes and fluorescers.
Preferred levels of perfume range from 0.05-2%wt. Acid stable perfumes are available from a variety of sources.
A particularly preferred composition according to the present invention comprises:
Figure imgf000013_0001
*variable to adjust viscosity
Typical products having the above formulation made with 3.0%wt of the amine and around 0.56%wt of the SCS are preferably clear, have a specific gravity of 1.040 g/ml, an initial viscosity at 106 sec" (at 25°C) of 120mPas, an initial viscosity at 11.7 sec"1 (at 25°C) of 300-600 mPas and pH 0.9 (at 25°C) .
In order that the present invention may be further understood it will be illustrated hereafter with reference to the following non-limiting examples and with reference to the accompanying figures wherein:
Figure 1 shows the viscosity of materials according to the present invention and comparative examples in mPas at 11.7 sec as measured using on a Haake RV2 rotoviscometer and an MVl bob after storage at room temperature.
Figure 2 shows the viscosity of materials according to the present invention and comparative examples in mPas at 106 s-1, as measured using on a Haake RV2 rotoviscometer (RTM) and an MVl bob after storage at room temperature.
Figure 3 shows the viscosity of materials according to the present invention and comparative examples in mPas at 106 s-1, as measured using on a Haake RV2 rotoviscometer and an MVl bob after storage at 37°C.
Figure 4 shows the viscosity of materials according to the present invention and comparative examples in mPas at 11.7 sec measured on a Haake RV2 rotoviscometer and an MVl bob after storage at 37°C.
EXAMPLES :
Example 1: Viscosity Stability
A composition was prepared as follows
Figure imgf000015_0001
In order to demonstrate the interaction of the ethoxylated amine and the anionic surfactant, the other components were each under and over dosed at +/- 10%. Results are shown in Table 1 below, for an initial viscosity of 500 m.Pas at 11.7 sec shear. TABLE 1
Figure imgf000016_0001
From the above it can be seen that the greatest modification of viscosity occurs when the relative levels of the anionic surfactant and the ethoxylated amine are varied, and that variation in the levels of the other components has little effect.
As shown by the figures in Table 2 below, the molar ratio of the ethoxylated amine / anionic surfactant can be modified to give thickening at a range of viscosities. Again, a finished product similar to that described above was used. Table 2 (all with 3.0 Ethomeen BTB12)
Figure imgf000017_0001
Compositions having a viscosity between 50 mPas and 1000 mPas (a molar ratio of from 3-3.5) were flowable compositions which were suitable for use as toilet cleaners. Compositions with a lower viscosity were too thin to stay on sloping surfaces, while those with a higher viscosity could not be dispensed with ease. Compositions with a viscosity of from 200-700 mPas were particularly suited to this purpose.
A range of compositions of the type described above were prepared with differing degrees of saturation in the ethoxylated amine. The materials used were:
,S12' an N,N-dihydroxyethyl-oleylamine (ETHOMEEN S12) , * HT12' a fully hardened N,N-dihydroxyethyl-tallowylamine (ETHOMEEN HT12) , v50/50' an equal weight mixture of *S12' and ,HT12Z and λ 66/33' a mixture of ΗT12' and S12' in a 66:33 weight ratio (similar to BTB12)
The effect of storage on viscosity is shown in figures 1-4.
Figure 1 shows the viscosity of materials according to the present invention and comparative examples in mPas at 11.7 sec , as measured using on a Haake RV2 rotoviscometer and an MVl bob after storage at room temperature. It can be seen that the viscosity of the ,HT12' sample rose with time until the product became a non-flowing gel. The viscosity of the λ S12' sample fell, such that the product eventually became too thin to be retained on sloping surfaces. The viscosities of the products containing a mixture of hardened and unhardened tallow remained in the acceptable range on storage.
Figure 2 shows the viscosity of materials according to the present invention and comparative examples in mPas at 106 sec , as measured using on a Haake RV2 rotoviscometer and an MVl bob after storage at room temperature. It can be seen that the viscosity of the VHT12' sample first fell and then rose. The viscosity of the S12' sample fell, such that the product eventually became too thin to be retained on sloping surfaces. The viscosities of the products containing a mixture of hardened and unhardened materials remained in the acceptable range on storage . Figure 3 shows the viscosity of materials according to the present invention and comparative examples in mPas at 106 sec , as measured using on a Haake RV2 rotoviscometer and an MVl bob after storage at 37°C. It can be seen that the viscosity of the λ HT12' sample again first fell and then rose. The viscosity of the ' S12' sample fell, such that the product eventually became too thin to be retained on sloping surfaces. The viscosities of the products containing a mixture of hardened and unhardened materials remained in the acceptable range on storage.
Figure 4 shows the viscosity of materials according to the present invention and comparative examples in mPas at 11.7 sec , as measured using on a Haake RV2 rotoviscometer and an MVl bob after storage at 37°C. It can be seen that the viscosity of the λ HT12' sample again rose. The viscosity of the ' S12' sample fell, such that the product eventually became too thin to be retained on sloping surfaces. The viscosities of the products containing a mixture of hardened and unhardened materials remained in the acceptable range on storage.
Example 2 ; Limescale Prevention
Hard water of -60 degrees French was prepared by flushing carbon dioxide through tap-water containing both calcite and dolomite overnight. Pairs of tiles were cleaned with a detergent composition and ethanol and rinsed with tap water. One of the tile was treated with a composition - I S
according to the present invention (that of Example 1) , with a contact time of 20 minutes: the tile was then rinsed with water. The hard water was then dripped onto the tiles for 24 hours, allowing one drop to fall onto each tile every five minutes. Results for treated and untreated tiles were compared visually using a panel of ten people, scoring on a scale of 0=limescale absent and 5= more encrusted tile: results being presented in Table 3 below. In addition the limescale was titrated after dissolution with dilute HCl. The results of titration are expressed in mg of calcium carbonate per tile in Table 3 below. Examples were performed in replicates A, B and C.
Table 3
Figure imgf000021_0001
It can be seen from these results that the treatment of the tile had a measurable effect on the degree of limescale deposited on the tile in the test both as measured chemically and as seen on the surface.

Claims

1. An alkoxylated aliphatic amine with 8-18 carbon atoms and 1-8 moles ethoxylation wherein the mole ratio of saturated to unsaturated aliphatic residues falls in the range 40:60 to 80:20.
2. A cleaning composition which comprises a) 0.01-15%wt an alkoxylated aliphatic amine with 8- 18 carbon atoms and 1-8 moles ethoxylation wherein the mole ratio of saturated to unsaturated aliphatic residues falls in the range 40:60 to 80:20. b) 0.01-15%wt of an anionic surfactant.
3. A composition according to claim 1 or 2 wherein the alkoxylated aliphatic amine is an ethoxylated tertiary amine of the general formula:
H(A) -N(R)-(A) H
wherein R is an alkyl or alkenyl group comprising 8-18 carbon atoms, A is an ethoxy or propoxy group and x and y may be the same or different and are integers from 1-3.
4. A composition according to claim 3 wherein A is
-OCH2CH2-
5. A composition according to claim 3 wherein x and y are both 1.
6. A composition according to claim 3 wherein R is mixed saturated and unsaturated C14-C18 alkyl.
7. A composition according to claim 1 wherein the mole ratio of saturated to unsaturated fatty acids in the alkoxylated aliphatic amine falls into the range 50:50 to 66:33.
8. A composition according to claim 2 wherein the pH of the composition is less than 1.0.
9. A composition according to claim 2 wherein the mole ratio of the ethoxylated amine and the anionic surfactant is 3-3.5, more preferably 3.25-3.5.
10. A composition according to claim 2 having a viscosity between 50 mPas and 1000 mPas when measured at 11.7 sec shear and at 25┬░C using Haake RV2 rotoviscometer and an MVl bob.
11. A composition according to claim 2 comprising 0.01- 15%wt of a limescale removing acid.
12. A composition according to claim 2 which further comprises a peroxygen compound.
13. A composition according to claim 2 which comprises: a) l-10%wt, preferably 3-5%wt sulphamic acid, b) l-10%wt, preferably 2-5%wt ethoxylated amine, c) 0-5%wt, preferably 0.05-l%wt, nonionic surfactant, d) 0.05-2%wt, preferably 0.4-l.l%wt, anionic surfactant hydrotrope, and, e) l-10%wt, preferably 4-6%wt, hydrogen peroxide
14. A process for retarding the deposition of limescale on a surface which comprises the step of treating said surface with a cleaning composition according to any of claims 8-13 said composition having a pH of less than 1 and comprising: a) 0.01-15%wt an alkoxylated aliphatic amine with 8- 18 carbon atoms and 1-8 moles ethoxylation wherein the mole ratio of saturated to unsaturated aliphatic residues falls in the range 40:60 to 80:20, and, b) 0.01-15%wt of an anionic surfactant.
PCT/EP1998/006633 1997-10-13 1998-10-09 Alkoxylated amines and their use in cleaning compositions WO1999019431A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
PL98339808A PL188434B1 (en) 1997-10-13 1998-10-09 Alkoxylated amined and their application in cleaning compositions
AU12298/99A AU735924B2 (en) 1997-10-13 1998-10-09 Alkoxylated amines and their use in cleaning compositions
BR9813044-7A BR9813044A (en) 1997-10-13 1998-10-09 Alkylated aliphatic amine, cleaning composition, and process to delay the deposition of lime scale on a surface
JP2000515989A JP4323093B2 (en) 1997-10-13 1998-10-09 Alkoxylated amines and their use in cleaning compositions
HU0004913A HU224521B1 (en) 1997-10-13 1998-10-09 Alkoxylated aliphatic amines and cleaning compositions containing this amines and process for preventing of calk sedimentation
CA2305193A CA2305193C (en) 1997-10-13 1998-10-09 Alkoxylated amines and their use in cleaning compositions
DE69821636T DE69821636T2 (en) 1997-10-13 1998-10-09 ALCOXYLATED AMINES AND THEIR USE IN DETERGENTS
EP98955491A EP1023423B1 (en) 1997-10-13 1998-10-09 Alkoxylated amines and their use in cleaning compositions
SK530-2000A SK5302000A3 (en) 1997-10-13 1998-10-09 CLEANING COMPOSITION AND METHOD OF RETARDING THE DEPOSITION OFì (54) LIMESCALE ON SURFACE
KR1020007003926A KR20010015748A (en) 1997-10-13 1998-10-09 Alkoxylated Amines and Their Use in Cleaning Compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9721691.5A GB9721691D0 (en) 1997-10-13 1997-10-13 Improvements relating to acidic cleaning compositions
GB9721691.5 1997-10-13

Publications (1)

Publication Number Publication Date
WO1999019431A1 true WO1999019431A1 (en) 1999-04-22

Family

ID=10820480

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/006633 WO1999019431A1 (en) 1997-10-13 1998-10-09 Alkoxylated amines and their use in cleaning compositions

Country Status (19)

Country Link
EP (1) EP1023423B1 (en)
JP (1) JP4323093B2 (en)
KR (1) KR20010015748A (en)
AR (1) AR017315A1 (en)
AU (1) AU735924B2 (en)
BR (1) BR9813044A (en)
CA (1) CA2305193C (en)
DE (1) DE69821636T2 (en)
ES (1) ES2214747T3 (en)
GB (1) GB9721691D0 (en)
HU (1) HU224521B1 (en)
ID (1) ID24420A (en)
IN (1) IN185797B (en)
MY (1) MY123176A (en)
PL (1) PL188434B1 (en)
SK (1) SK5302000A3 (en)
TR (1) TR200000972T2 (en)
WO (1) WO1999019431A1 (en)
ZA (1) ZA989144B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000042140A1 (en) * 1999-01-11 2000-07-20 Huntsman Petrochemical Corporation Surfactant compositions containing alkoxylated amines
WO2003076559A1 (en) * 2002-03-13 2003-09-18 Cognis Iberia, S.L. Concentrated peroxide solutions
WO2009112794A1 (en) * 2008-03-14 2009-09-17 Reckitt Benckiser Inc. Thickened hard surface cleaning compositions comprising fatty amine alkoxylate

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004055492A1 (en) * 2004-11-17 2006-07-13 Chemische Fabrik Dr. Weigert Gmbh & Co. Kg Clean rinse, useful in machine cleaning of plastic parts, tableware, medical and surgical instruments, comprises an alkyl-bis(2-hydroxyalkyl)amine and an acid e.g. citric acid
US9006286B2 (en) 2011-05-10 2015-04-14 Ecolab Usa Inc. Couplers for medium-chain fatty acids and disinfecting compositions
DE102022207153A1 (en) * 2022-07-13 2024-01-18 Henkel Ag & Co. Kgaa Detergent-active compounds based on a combination of anions and cationic surfactant

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2459830A1 (en) * 1979-06-26 1981-01-16 Voreppe Ind Chimiques Cleaning and descaling compsn. based on aq. sulphamic acid soln. - contg. fatty alkylamine and various ethoxylated cpds.
EP0231886A2 (en) * 1986-02-06 1987-08-12 Henkel Kommanditgesellschaft auf Aktien Use of ethoxylated fatty amines as solubilizers
EP0276501A2 (en) * 1987-01-24 1988-08-03 Akzo Nobel N.V. Thickening compositions and thickened aqueous acid solutions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2459830A1 (en) * 1979-06-26 1981-01-16 Voreppe Ind Chimiques Cleaning and descaling compsn. based on aq. sulphamic acid soln. - contg. fatty alkylamine and various ethoxylated cpds.
EP0231886A2 (en) * 1986-02-06 1987-08-12 Henkel Kommanditgesellschaft auf Aktien Use of ethoxylated fatty amines as solubilizers
EP0276501A2 (en) * 1987-01-24 1988-08-03 Akzo Nobel N.V. Thickening compositions and thickened aqueous acid solutions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000042140A1 (en) * 1999-01-11 2000-07-20 Huntsman Petrochemical Corporation Surfactant compositions containing alkoxylated amines
US6617303B1 (en) 1999-01-11 2003-09-09 Huntsman Petrochemical Corporation Surfactant compositions containing alkoxylated amines
WO2003076559A1 (en) * 2002-03-13 2003-09-18 Cognis Iberia, S.L. Concentrated peroxide solutions
WO2009112794A1 (en) * 2008-03-14 2009-09-17 Reckitt Benckiser Inc. Thickened hard surface cleaning compositions comprising fatty amine alkoxylate

Also Published As

Publication number Publication date
DE69821636D1 (en) 2004-03-18
EP1023423A1 (en) 2000-08-02
CA2305193C (en) 2010-03-23
GB9721691D0 (en) 1997-12-10
ES2214747T3 (en) 2004-09-16
AU1229899A (en) 1999-05-03
BR9813044A (en) 2000-08-15
AR017315A1 (en) 2001-09-05
PL339808A1 (en) 2001-01-02
HU224521B1 (en) 2005-10-28
HUP0004913A2 (en) 2001-05-28
KR20010015748A (en) 2001-02-26
EP1023423B1 (en) 2004-02-11
SK5302000A3 (en) 2000-09-12
MY123176A (en) 2006-05-31
ZA989144B (en) 2000-04-07
AU735924B2 (en) 2001-07-19
JP4323093B2 (en) 2009-09-02
CA2305193A1 (en) 1999-04-22
IN185797B (en) 2001-05-05
HUP0004913A3 (en) 2005-06-28
JP2001520259A (en) 2001-10-30
TR200000972T2 (en) 2000-11-21
DE69821636T2 (en) 2004-07-29
PL188434B1 (en) 2005-01-31
ID24420A (en) 2000-07-20

Similar Documents

Publication Publication Date Title
EP0598694B1 (en) Stable compositions with persulfate salts
EP0273472B1 (en) Aqueous detergent compositions containing diethyleneglycol monohexyl ether solvent
AU728470B2 (en) Reduced residue hard surface cleaner comprising hydrotrope
EP0151517A2 (en) Liquid detergent composition
AU750959B2 (en) Acid cleaning compositions containing alkoxylated amines and their use
EP0758017B1 (en) Acidic cleaning compositions
EP1023423B1 (en) Alkoxylated amines and their use in cleaning compositions
US4938893A (en) Detersive systems and low foaming aqueous surfactant solutions containing a mono (C1-4 alkyl)-di(C6-20 alkyl)-amine oxide compound
EP0601792A1 (en) Lavatory cleansing compositions
MXPA00003494A (en) Alkoxylated amines and their usein cleaning compositions
AU724373B2 (en) Improvements relating to bleaching compositions
MXPA00003225A (en) Acid cleaning compositions containing alkoxylated amines and their use
EP0808892A1 (en) Acidic cleaning compositions
AU678313B2 (en) Limescale removing composition
EP0808891A1 (en) Acidic cleaning compositions
EP0742279A1 (en) Acidic aqueous liquid compositions
MXPA01007619A (en) Germicidal blooming type compositions containing biphenyl solvents

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 1998955491

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 12298/99

Country of ref document: AU

ENP Entry into the national phase

Ref document number: 2305193

Country of ref document: CA

Ref document number: 2305193

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PA/a/2000/003494

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 5302000

Country of ref document: SK

WWE Wipo information: entry into national phase

Ref document number: 1020007003926

Country of ref document: KR

Ref document number: 2000/00972

Country of ref document: TR

Ref document number: 98810101.7

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: PV2000-1336

Country of ref document: CZ

WWE Wipo information: entry into national phase

Ref document number: 09529347

Country of ref document: US

WWR Wipo information: refused in national office

Ref document number: PV2000-1336

Country of ref document: CZ

WWP Wipo information: published in national office

Ref document number: 1998955491

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1020007003926

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 12298/99

Country of ref document: AU

WWW Wipo information: withdrawn in national office

Ref document number: 1020007003926

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 1998955491

Country of ref document: EP