EP0253676B2 - Amine-acid thickening compositions - Google Patents

Amine-acid thickening compositions Download PDF

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Publication number
EP0253676B2
EP0253676B2 EP87306355A EP87306355A EP0253676B2 EP 0253676 B2 EP0253676 B2 EP 0253676B2 EP 87306355 A EP87306355 A EP 87306355A EP 87306355 A EP87306355 A EP 87306355A EP 0253676 B2 EP0253676 B2 EP 0253676B2
Authority
EP
European Patent Office
Prior art keywords
acid
composition
salt
thickening agent
viscosity
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
EP87306355A
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German (de)
English (en)
French (fr)
Other versions
EP0253676A2 (en
EP0253676A3 (en
EP0253676B1 (en
Inventor
Raymond Neville Silvester
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.)
R&C Products Pty Ltd
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R&C Products Pty Ltd
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Filing date
Publication date
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Application filed by R&C Products Pty Ltd filed Critical R&C Products Pty Ltd
Priority to AT87306355T priority Critical patent/ATE64753T1/de
Publication of EP0253676A2 publication Critical patent/EP0253676A2/en
Publication of EP0253676A3 publication Critical patent/EP0253676A3/en
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/40—Monoamines or polyamines; 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
    • C11D1/38—Cationic compounds
    • C11D1/58—Heterocyclic 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
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/08—Acids

Definitions

  • the present invention relates to aqueous compositions of acids or acidic salts and more particularly to novel compositions of these acids or acidic salts which include a thickening agent.
  • acidic salts refer to those compounds which in an aqueous solution liberate protons.
  • compositions for cleaning include toilet bowl cleaners, metal cleaners and brighteners, rust stain removers, denture cleansers, metal descalers, general hard surface cleaners and disinfectants.
  • compositions have sufficient viscosity so as to allow the composition to be effectively applied to surfaces, for example, by brushing, or to allow the composition to remain in contact with the surface for a sufficient time to act.
  • the latterfunc- tion has particular relevance to the cleaning of angular surfaces such as those found in toilet bowls where prolonged contact between the composition and the bowl is required for effective cleaning.
  • compositions known in the art that have the requisite viscosity characteristics. Most of such compositions achieve their viscosity through the use of one or more of the following thickening agents:-
  • the cellulose derivatives and gums tend to hydrolyse on storage which results in a reduction in viscosity of the composition. They are also generally difficult to dissolve, in some cases intensive mixing being required in order to bring them into solution.
  • Acrylic acid polymers are generally only useful in solutions which have a pH near neutral and above. They also tend to hydrolyse on storage and to achieve viscosity, need to be neutralized with a fairly strong alkali.
  • Nonionic surfactants have the disadvantage that usually high levels of about 5-10% are required to achieve satisfactory viscosity, thus making them expensive to use.
  • poly(ethyleneoxide) water soluble resins also require generally high levels to achieve desirable composition viscosity and additionally, in some acid solutions show significant instability.
  • Sodium silicates are able to produce aqueous acid or acidic salt gel compositions.
  • the viscosity generally develops over a long period of time, for example, as much as twelve hours. In commercial manufacturing processes, this is often inconvenient. It is also to be noted that on storage, such gels tend to break down into small pieces which in many instances is undesirable.
  • thickening agents and compositions disclosed in the art which relate to an aqueous acid and/or acidic salt compositions include:-GB-A-1,443,244 (Reckitt & Colman Products Limited) which discloses a thickening agent of the formula: for thickening aqueous compositions of mineral acids and acid salts of strong inorganic acids.
  • GB-A-2,071,688 (Jeyes Limited) which discloses as a thickening agent a mixture of:
  • compositions require a substantially acid soluble cationic or nonionic surfactant to achieve thickening.
  • US-A-3520820 discloses amine-containing corrosion inhibitors which contain aliphatic amines and acetic acid and which are mixed with non-ionic emulsifiers to form liquid, cold water dispersible emulsions.
  • the compositions contain only from 0.1 to 0.6 mole of acid per mole of the fatty amine and thus are not acidic compositions.
  • US-A-3925229 discloses the production of a phosphoric acid containing paste intended for use in the cleaning of metals. No compositions are disclosed which are not in paste form.
  • FR-A-2459830 discloses cleaning compositions which may be for the cleaning and removal of tartar from sanitary ware, such as toi let bowls.
  • the invention is directed to aqueous solutions of sulfamic acid, the viscosity of which is adjusted and stabilized by the addition of four types of viscosity adjusting or thickening agents.
  • US-A-4021377 discloses liquid detergent compositions which comprise the reaction product of citric acid and a water-soluble or water-dispersible amine.
  • the reaction product is said to be a mixture of amine salts of citric acid and citric acid amides.
  • EP-A-0228501 discloses a thickened aqueous liquid toilet bowl clearer which may comprise citric acid or a citrate and an amine as thickener. The document also suggests that another dicarboxylic acid may be substituted for the citric acid.
  • the present inventor has recognized the difficulties of the prior art thickening agents for such aqueous acid or acidic salt compositions. Accordingly, the present invention seeks to provide alternative composition to those of the prior art.
  • the present invention provides a thickened aqueous liquid toilet bowl cleansing composition having a pH of not more than 6.5 and having a viscosity of not less than 30 mPas at 25°C when measured with a Brookfield RVT viscometer at 50 rpm using a No. 1 spindle, which composition comprises at least one acid or acidic salt, optionally a strong ionic salt, and, as the sole organic agent to thicken the composition and impart said viscosity to the composition in an amount of from 0.1 to 10% w/w, at least one compound of the formula: in which R contains 8 to 24 carbon atoms and is a substituted or unsubstituted alkyl, aryl.
  • R 1 is hydrogen, a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group
  • R 2 is hydrogen, a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, provided that if either R, R 1 or R 2 is an alkyl or alkenyl group derived from a fatty acid obtained from a natural oi or fat or an equivalent synthetic fatty acid, or is an alkaryl group containing from 8 to 12 carbon atoms in the alkyl moiety, then the other substituents are not respectively of the formulae: [A] x - H and [A]y - H, where A is either ethoxy or propoxy and x, y are independently 1, 2 or 3, the thickening agent and the acid or acidic salt being together substantially water soluble; with the exception where the acid is citric acid or
  • the present invention consists in a method of forming a thickened aqueous solution, comprising dissolving in water (a) at least one compound selected from the group consisting of acids and acidic salts, (b) a thickening agent which is at least one of the compounds selected from the group consisting of compounds of the formula: in which R, R 1 and R 2 are as above defined. and optionally (c) a strong ionic salt, said thickening agent and the salts being together substantially water soluble, in amounts sufficient to produce a viscosity of not less than 30 mPa s at 25°C when measured with a Brookfield RVT viscometer at 50 rpm using a No. 1 spindle; with the exception where the acid is citric acid or a dicarboxylic acid or the acidic salt a citrate or the salt of a dicarboxylic acid.
  • substantially water soluble means that a thickening agent and an acid or acidic salt selected in accordance with the invention, will together either be soluble in water at 25°C or at most will form a hazy solution that does not separate into two phases during normal storage.
  • compositions of the present invention may be readily distinguished over those disclosed in the aforementioned patent application GB-A-2071688 (Jeyes Limited) in that the compositions claimed therein are directed towards substantially acid insoluble amines or amine oxides, which require a substantially acid soluble cationic or nonionic surfactant to achieve thickening.
  • the present invention is limited to amines which together with the selected acid or acidic salt are substantially water soluble, without a cationic or nonionic surfactant being required to achieve solution and thickening. It is also to be noted that in GB-A-2071688 it is stated that neither of the amine, cationic surfactant or nonionic surfactant alone with an aqueous solution of an inorganic acid or acid salt will cause thickening.
  • Bolsing in the simplest embodiment of his invention disperses the selected amine in water, heats the dispersion to between 40°C and 100°C and then adds to it at least a neutralising amount of phosphoric acid, preheated to between 40°C and 120°C. Stirring is continued until the temperature falls to between 5°C and 25°C and the resultant composition is a paste consisting of the reaction products between phosphoric acid and selected amine.
  • Bolsing also discloses that other acids such as sulphuric, hydrochloric, tartaric, oxalic, hydrofluoric and nitric may be used as an additive to a base paste of his invention. He further discloses that other amines may also be used as additives.
  • the present invention may be distinguished over Bolsing when it is considered that the amines of the Bolsing invention must be derivatives of substituted or unsubstituted hydrocarbons having 8-24 carbon atoms, the selected amine must be reacted by heating with phosphoric acid to achieve viscosity and there is no hint or suggestion that acids other than phosphoric acid are operative. Additionally, with respect to acidic salts, it is noted that Bolsing refers to ammonium chloride as an auxiliary.
  • the present invention teaches that thickening can be achieved with a range of acids and acidic salts, no heating is required to obtain thickening and the present inventor believes that amines additional to those of Bolsing are operative.
  • the group R contains from 8 to 24 carbon atoms.
  • the group R contains from 8 to 24 carbon atoms in an unsubstituted alkyl or alkenyl group.
  • the group R 1 and R 2 are independently a hydrogen atom or a lower unsubstituted alkyl group, where lower refers to groups containing 1 to 4 carbon atoms or a substituted alkyl group. More preferably the groups R 1 and R 2 are independently a hydrogen atom or a lower unsubstituted alkyl group. Most preferably, the groups R 1 and R 2 are independently a hydrogen atom or a methyl group.
  • Preferred thickening agents of the present invention that are primary amines include Farmin O (Farmin is a registered trade mark of Kao Soap Co.) or Genamin OL-100D (Genamin is a registered trade mark of Hoechst), both of which are mainly oleylamine and Farmin T or Genamin TA100D, both of which are tallow fatty amine distilled.
  • These thickening agents are able to thicken organic acids including formic, acetic, DL lactic, glycollic, pentetic, ascorbic, chloroacetic, and propionic acids. In some cases a small addition of a strong ionic salt such as sodium chloride is required to achieve adequate composition viscosity in the preferred concentration range of thickening agent.
  • thickening agent will increase viscosity in many cases.
  • extra thickening agent may increase the pH and thereby decrease the efficiency of a composition.
  • Preferred thickening agents of the present invention that are tertiary amines include Genamin S0302D (dimethyl soya bean oil fatty amine distilled) and Genamin TA302D (dimethyl tallow fatty amine distilled). These amines are able to thicken organic acids including formic acid, acetic acid, DL lactic acid, ethylenediaminetetraacetic acids, glycollic, and propionic acid and inorganic acids including sulfamic acid, phosphoric acid, boric, hydrofluoric and sulphuric acid. Generally, for reasons outlined above, these amines require the addition of a strong ionic salt, such as sodium chloride in order to achieve adequate composition viscosity in the preferred concentration range of thickening agent.
  • a strong ionic salt such as sodium chloride
  • Preferred thickening agents of the present invention that are tertiary amines able to ticken acidic salts include Genamin TA302D and Genamin S0302D.
  • Genamin S0302D is able to thicken aqueous solutions of aluminium sulphate. sodium hydrogen sulphate, sodium dihydrogen orthophosphate, disodium ethylenediaminetetraacetate and aluminium potassium sulphate with a small addition of a strong ionic salt such as sodium chloride required in some cases; the sodium chloride being required to achieve adequate composition viscosity as previously described.
  • Preferred thickening agents of the present invention that are primary amines able to thicken acidic salts include Farmin O, Genamin OL-100D, Farmin T and Genamin TA-1 OOD. These amines are able to thicken aqueous solutions of aluminium acetate.
  • the abovementioned preferred amines are in fact mixtures of a number of amines with one amine being predominant.
  • the present inventor believes that the predominant amine may function to solubilize the minor amines in compositions of the present invention.
  • Farmin O is predominantly oleylamine having an approximate alkyl content of 6% C 14 , 13% C 16 and 81% C 18
  • Genamin S0302D has an approximate average chain length distribution of 2% C 14 , 15% C 16 and 83% C 18
  • Genamin TA302D has an approximate average chain length distribution of 5% C 14 , 30% C 16 and 65% C 18 .
  • amines of the invention may be generally derived from natural or synthetic sources of tallow, soya bean oil, oleic acid, palmitic acid, myristic acid, linoleic acid, linolenic acid, ricinoleic acid or hexadecanoic acid.
  • the acids to which the present invention is directed include inorganic acids such as sulphuric, hydrofluoric, boric, sulphamic and phosphoric acids and the organic acids formic, acetic, DL lactic, propionic, and ethylenediaminetetraacetic acid, glycollic, ascorbic, pentetic and chloroacetic acids.
  • inorganic acids such as sulphuric, hydrofluoric, boric, sulphamic and phosphoric acids
  • organic acids formic acetic, DL lactic, propionic, and ethylenediaminetetraacetic acid, glycollic, ascorbic, pentetic and chloroacetic acids.
  • the acidic salts to which the present invention is directed include the acid salts of inorganic or organic acids such as sodium hydrogen sulphate, sodium dihydrogen orthophosphate, disodium ethylenediaminetetraacetate, aluminium acetate, aluminium sulphate and aluminium potassium sulphate.
  • inorganic or organic acids such as sodium hydrogen sulphate, sodium dihydrogen orthophosphate, disodium ethylenediaminetetraacetate, aluminium acetate, aluminium sulphate and aluminium potassium sulphate.
  • the concentration of acid or acidic salt may be varied over a wide range depending on the end use of the composition. In some cases, particularly where a strong acid such as hydrofluoric acid is used and a near neutral product is required, the concentration of acid or acidic salt may be as low as 0.01 % w/w.
  • the concentration of acid or acidic salt may be in excess of 90%.
  • the concentration of acid or acidic salt will lie in the range of from 0.1 to 30% w/w.
  • the thickening agent will be present in a concentration in the composition of from 0.1 to 10% w/w.
  • concentration in the composition will lie in the range of from 0.4 to 5.0% w/w.
  • the concentration of the thickening agent may be varied appropriately. However, in some cases, it has been found that it is not possible to achieve sufficient composition viscosity for some applications. In such cases, the addition of a salt which has high ionic strength has been found to enhance the viscosity of these compositions. In most cases however, the concentration of thickening agent and high ionic strength salt will be optimized in order to produce a cost effective composition of the desired viscosity.
  • the ionic salts will be selected from alkali metal halides or sulphates and ammonium halides or sulphates. Suitable such salts include sodium chloride, sodium sulphate, potassium sulphate, potassium chloride, ammonium chloride and the like.
  • compositions of the invention may be added to compositions of the invention depending on their end use.
  • germicides surfactants including anionic, nonionic, cationic and amphoteric, sequestering agents, corrosion inhibitors, perfumes and colouring agents may be added.
  • a principal advantage of the present invention is that an aqueous acid or acidic salt solution may be readily and easily thickened.
  • steps of obtaining such thickened compositions will be - (a) add an appropriate amount of acid or acidic salt to water and stir to dissolve, (b) add a thickening agent of the present invention to the solution and stir until dissolved and (c) add other ingredients if required, stirring to dissolve.
  • the thickening agent of the present invention is defined to be soluble in the selected acidic salt or acid solution, and as it wi generally be easily wet, the step (b) above will be relatively rapid unlike many of the prior art thickening agents, which whilst they may be soluble are frequently difficult to wet.
  • thickening agents of the present invention are relatively inexpensive and in use produce smooth, homogeneous immediate thickening. Furthermore, thickened compositions are stable with respect to viscosity. For example, the present inventor has found that a citric acid composition thickened with Farmin O had no substantial change in viscosity when stored at room temperature for 12 months.
  • compositions of the invention have some surfactant and corrosion inhibition properties.
  • the formerfinding means that water immiscible substances such as fragrances may be directly solubilized in a composition of the invention without requiring the addition of emulsifiers or auxiliary solvents, and in compositions in which the surface active properties are required, potentially less or no additional surfactant would be required.
  • the present inventor has also found that if only sufficient of an acid or an acidic salt is present to just dissolve a thickening agent of the present invention, then a composition of near neutral pH may be obtained.
  • Farmin O may be used to thicken lactic acid at a pH of 6.5.
  • the advantage of this finding is that it may be used in aqueous liquid cleaners in general.
  • an acid or acidic salt which is usually considered to be water insoluble at room temperature may be brought into solution through the use of a thickening agent of the present invention, with thickening occurring.
  • the viscosity may be increased through the use of a strong ionic salt such as sodium chloride.
  • a strong ionic salt such as sodium chloride.
  • compositions of this type include ethylenediaminetetraacetic acid with Genamin S0302D as the thickening agent, and pentetic acid with Farmin 0 as thickening agent.
  • examples 1 to 35 of the present invention, together with comparative examples 1A and 1 B, in which the viscosity, in mPa s, of each was determined using a Brookfield RVT viscometer using a spindle and speed as appropriate at 25°C. Note that the thickening agent is asterixed in each case.
  • Examples 17 and 27 were prepared by dispersing the acid or acid salt in water, adding the thickening agent and mixing until solution occurred, followed by sodium chloride (if required) until a satisfactory viscosity was achieved.
  • Example 1 when compared with the viscosity of water (1A) and 5% w/w citric acid (1 B), is substantially greater. A comparison with an aqueous solution of the thickening agent in this case was not possible as the thickening agent is water insoluble.
  • the examples 1 to 35 disclosed herein may be used for example as toilet bowl cleaners. metal cleaners and brighteners and the like as well as applications such as gel batteries.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
  • Lubricants (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Medicinal Preparation (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Confectionery (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
EP87306355A 1986-07-17 1987-07-17 Amine-acid thickening compositions Expired - Lifetime EP0253676B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87306355T ATE64753T1 (de) 1986-07-17 1987-07-17 Aminsaeure-verdickungsmittel.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU6989/86 1986-07-17
AUPH698986 1986-07-17

Publications (4)

Publication Number Publication Date
EP0253676A2 EP0253676A2 (en) 1988-01-20
EP0253676A3 EP0253676A3 (en) 1988-09-21
EP0253676B1 EP0253676B1 (en) 1991-06-26
EP0253676B2 true EP0253676B2 (en) 1994-08-03

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ID=3771719

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87306355A Expired - Lifetime EP0253676B2 (en) 1986-07-17 1987-07-17 Amine-acid thickening compositions

Country Status (21)

Country Link
EP (1) EP0253676B2 (da)
JP (1) JPS6324000A (da)
KR (1) KR950006289B1 (da)
AT (1) ATE64753T1 (da)
AU (1) AU602707B2 (da)
BR (1) BR8703747A (da)
DE (1) DE3771008D1 (da)
DK (1) DK170538B1 (da)
EG (1) EG18545A (da)
ES (1) ES2022360T5 (da)
GR (1) GR3002573T3 (da)
IE (1) IE60070B1 (da)
IN (1) IN172271B (da)
MX (1) MX170920B (da)
MY (1) MY102871A (da)
NO (1) NO175967C (da)
NZ (1) NZ221105A (da)
PT (1) PT85352B (da)
ZA (1) ZA875279B (da)
ZM (1) ZM5787A1 (da)
ZW (1) ZW13287A1 (da)

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EP0788536A1 (en) * 1994-10-28 1997-08-13 The Procter & Gamble Company Hard surface cleaning compositions comprising protonated amines and amine oxide surfactants
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EP0808892A1 (en) * 1996-05-21 1997-11-26 The Procter & Gamble Company Acidic cleaning compositions
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US6617293B2 (en) 2001-08-06 2003-09-09 3M Innovative Properties Company Thickening on dilution liquid soap
US9668471B2 (en) 2003-05-28 2017-06-06 AgQuam LLC Manufacture and use of agricultural spray adjuvants for hard water conditions
FR2897611B1 (fr) * 2006-02-20 2008-05-30 Gilles Allard Produit de traitement d'un reservoir et d'une cuvette de chasse d'eau
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Publication number Publication date
ES2022360T5 (es) 1995-08-16
ZA875279B (en) 1988-04-27
NO175967C (no) 1995-01-11
IE60070B1 (en) 1994-06-01
AU602707B2 (en) 1990-10-25
NO873000D0 (no) 1987-07-17
ATE64753T1 (de) 1991-07-15
PT85352A (en) 1987-08-01
JPS6324000A (ja) 1988-02-01
NO175967B (no) 1994-10-03
ES2022360B3 (es) 1991-12-01
DK372187D0 (da) 1987-07-16
GR3002573T3 (en) 1993-01-25
MX170920B (es) 1993-09-22
BR8703747A (pt) 1988-03-29
MY102871A (en) 1993-03-31
IN172271B (da) 1993-05-29
AU7578787A (en) 1988-01-21
EP0253676A2 (en) 1988-01-20
NZ221105A (en) 1990-01-29
PT85352B (pt) 1990-04-30
EP0253676A3 (en) 1988-09-21
DK372187A (da) 1988-01-18
KR880001797A (ko) 1988-04-26
DK170538B1 (da) 1995-10-16
DE3771008D1 (de) 1991-08-01
ZW13287A1 (en) 1987-10-28
IE871943L (en) 1988-01-17
ZM5787A1 (en) 1989-09-29
EG18545A (en) 1993-07-30
NO873000L (no) 1988-01-18
KR950006289B1 (ko) 1995-06-13
EP0253676B1 (en) 1991-06-26

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