EP0260205A2 - Reinigungsmittelzusammensetzung für sanitäre Anlagen - Google Patents
Reinigungsmittelzusammensetzung für sanitäre Anlagen Download PDFInfo
- Publication number
- EP0260205A2 EP0260205A2 EP87420234A EP87420234A EP0260205A2 EP 0260205 A2 EP0260205 A2 EP 0260205A2 EP 87420234 A EP87420234 A EP 87420234A EP 87420234 A EP87420234 A EP 87420234A EP 0260205 A2 EP0260205 A2 EP 0260205A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition according
- betaine
- salt
- weight
- acid
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 238000004140 cleaning Methods 0.000 title claims abstract description 8
- 238000009434 installation Methods 0.000 title description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229960003237 betaine Drugs 0.000 claims abstract description 26
- 239000002304 perfume Substances 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003899 bactericide agent Substances 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 239000003086 colorant Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000001913 cellulose Chemical class 0.000 description 2
- 229920002678 cellulose Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- -1 alkaline earth metal sulfates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
Definitions
- the invention relates to cleaning compositions and more particularly to compositions which are used in sanitary installations, for example toilet bowls.
- compositions which contain at least one acid, such as hydrochloric, phosphoric, sulfuric, acetic or fumaric acid.
- compositions containing hydrochloric acid are corrosive and dangerous and it is preferred to use weak acids.
- anionic and / or nonionic surfactants or other thickeners such as polyethoxylated amines or cellulose derivatives, such as carboxymethylcellulose, are commonly added.
- these thickeners require additives for their implementation, for example alcohols to dissolve the carboxymethylcellulose in water.
- the pH range must be chosen so that the introduction and the stability of the perfumes in the composition are not difficult. Indeed, pH below 1.5 leads to a breakdown of the constituents of most perfumes.
- the viscosity of such compositions must also be chosen so as to obtain a satisfactory descaling power and a persistence of the perfumes desired by the users.
- an insufficient viscosity does not allow the cleaning composition to adhere sufficiently to the walls, which reduces the contact time of the composition with the tartar.
- too high a viscosity prevents a diffusion of the perfume in the air surrounding the toilet or a diffusion in the stagnant water at the bottom of the toilet.
- An object of the invention is therefore to be able to provide a thickened acidic aqueous composition, not containing strong acid, but having a satisfactory descaling power.
- a second object of the invention is to provide such a descaling composition having a viscosity which can be adjusted to allow good adhesion to inclined walls and at the same time a diffusion of the perfume in the ambient atmosphere.
- a third object of the invention is to provide a thickened, scented acidic aqueous composition which is at the same time colored, clear and limpid, stable at room temperature and at + 40 ° C., for several months.
- Another object of the invention is to provide a descaling composition for cleaning sanitary facilities, comprising a single thickening surfactant, so as to reduce the manufacturing cost.
- thickening systems which consist of an amido-betaine of formula: in which R is an alkyl or alkenyl radical containing from 9 to 17 carbon atoms, n is an integer from 2 to 4, y is 0 or is an integer from 1 to 3, and a salt chosen from alkali or alkaline earth metal sulfates.
- compositions can be in the form of gels if a thickener is added to them, such as a surfactant, for example an ethoxylated nonylphenol, or such as a polymer, for example a cellulose derivative.
- a thickener such as a surfactant, for example an ethoxylated nonylphenol, or such as a polymer, for example a cellulose derivative.
- a betaine not comprising an amido group can, in the presence of weak acids, be thickened by halides or sulfates of alkali metals or alkaline earth.
- betaines selected by the applicant to thicken aqueous compositions containing at least one weak acid, in the presence of an alkali or alkaline earth metal halide are chosen from betaines having the following general formula: or the following general formula: in which R is a C9-C17 alkyl or alkenyl radical, x and y are independent of each other and are integers between 0 and 5.
- the betaines of formula III and IV not only thicken the aqueous weak acid compositions, and this in the presence of an alkali or alkaline earth metal halide, but also make it possible to disperse the perfumes which may be introduced at the end of mixing without separation into two phases.
- the fact of adding a perfume at the end of the formulation constitutes a great advantage for the manufacturer. Indeed, it can manufacture a mixture comprising no perfume and, with the same mixture, it can introduce at the final stage a perfume which it can vary according to the tastes and habits of the consumers.
- the betaines selected by the applicant also make it possible to obtain clear and clear compositions which are stable over time, at ambient temperature and up to + 40 ° C.
- the invention therefore relates to a thickened acidic aqueous composition for cleaning sanitary facilities, characterized in that it contains at least one betaine chosen from betaines having the formula (III) or (IV), at least one weak acid, at least one salt, optionally a perfume, optionally a bactericide, optionally a dye, and water.
- the salt / betaine weight ratio is preferably less than about 1.5: 1.
- the composition contains from 0.5 to 10% by weight of at least one betaine of formula (III) or (IV) and of 0, 1 to 15% by weight of at least one salt.
- It preferably contains from 2 to 8% by weight of at least one betaine of formula (III) or (IV), from 0.5% to 6% by weight of at least one weak acid, from 0.2 to 10% by weight of a salt.
- the weak acid is preferably chosen from formic, acetic, citric, lactic, succinic, gluconic, glutaric, adipic, malic acids or their mixtures.
- the salt can be chosen from chlorides, bromides, iodides and sulfates of alkali or alkaline earth metals.
- the composition is remarkable because it makes it possible to mix all the constituents and to add the perfume in the final stage.
- REWOTERIC AM-TEG betaine (manufactured by REWO, containing 35 to 40% betaine (III), 4.5% to 6.0% NaCl, qs 100% water).
- REWOTERIC AM-TEG betaine (manufactured by REWO, containing 35 to 40% betaine (III), 4.5% to 6.0% NaCl, qs 100% water).
- - 4 g HCl (37%) - 0.20 ml of dye (1% solution in water) - 0.25 ml of perfume - 0.53 g of bactericidal agent (50%) - qs 100 g of water.
- a composition is obtained having a viscosity of 150 m Pa.S, measured with an Epprecht viscometer, with a mobile 2, at a speed of 200 revolutions / minute.
- This composition is not viscous (less than 50 mPa.s).
- this example shows that betaine AMTEG mixed with weak acids does not make it possible to obtain a viscous composition.
- a composition is obtained having a viscosity of 160 mPa.s measured with mobile Epprecht 2, speed 200 revolutions / minute.
- This composition is clear and limpid, stable on storage.
- Example 1 is repeated, replacing the formic acid with acetic acid and adding 3 g of NaCl.
- a composition is obtained having a viscosity of 180 mPa.s, clear and limpid, stable.
- a 145 mPa.s viscosity composition is obtained containing 2% formic acid and 1% phosphoric acid.
- the amount of salt added must not be too large; in any case, it has been observed that the salt / betaine ratio must be less than 2: 1 and preferably equal to 1: 1.
- the amount of betaine must be greater than 3% by weight, preferably 3.6% by weight, and the amount of NaCl must be substantially equal, in% by weight.
- Example 3 The same mixture is carried out as in Example 3, but a mixture is introduced as acid: - 1/3 of glutaric acid - 1/3 adipic acid - 1/3 of succinic acid, sold by BASF under the trade name SOKALAN DCS.
- a viscosity of 200 mPa.s. is obtained.
- the following mixture is carried out: - 0.5% citric acid - 0.5% phosphoric acid - 2% formic acid - 3.6% betaine from the AM-TEG product (in 100%) - 0.002% dye - 0.265% bactericide - 3% NaCl - qs 100% water.
- a composition having a viscosity of 520 mPa.s.
- a viscosity of between 100 and 400 mPa.s is obtained.
- Example 3 The same mixing is carried out as in Example 3, but the order of introduction is modified, namely that the perfume is introduced at the end of formulation. A stable formula is obtained, the cloud point of which is greater than + 80 ° C.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Catching Or Destruction (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT87420234T ATE83796T1 (de) | 1986-09-08 | 1987-09-07 | Reinigungsmittelzusammensetzung fuer sanitaere anlagen. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8612571 | 1986-09-08 | ||
FR8612571A FR2603601B1 (fr) | 1986-09-08 | 1986-09-08 | Composition de nettoyage d'installations sanitaires |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0260205A2 true EP0260205A2 (de) | 1988-03-16 |
EP0260205A3 EP0260205A3 (en) | 1989-02-22 |
EP0260205B1 EP0260205B1 (de) | 1992-12-23 |
Family
ID=9338774
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87420234A Expired - Lifetime EP0260205B1 (de) | 1986-09-08 | 1987-09-07 | Reinigungsmittelzusammensetzung für sanitäre Anlagen |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0260205B1 (de) |
AT (1) | ATE83796T1 (de) |
DE (1) | DE3783185T2 (de) |
DK (1) | DK170947B1 (de) |
ES (1) | ES2044967T3 (de) |
FR (1) | FR2603601B1 (de) |
GR (1) | GR3007440T3 (de) |
NO (1) | NO174674C (de) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4900467A (en) * | 1988-05-20 | 1990-02-13 | The Clorox Company | Viscoelastic cleaning compositions with long relaxation times |
EP0649834A1 (de) * | 1993-10-20 | 1995-04-26 | Kao Corporation | Carboxybetaine und Sulfobetaine und diese enthaltende Reinigungszusammensetzung und kosmetische Zusammensetzung |
WO1999015610A1 (de) * | 1997-09-25 | 1999-04-01 | Cognis Deutschland Gmbh | Verwendung von ungesättigten betaintensiden als verdickungsmittel |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NZ529554A (en) | 2003-11-14 | 2006-08-31 | Fonterra Cooperative Group Ltd | Dairy product and process |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2087635A5 (de) * | 1970-05-22 | 1971-12-31 | Kao Corp | |
EP0077674A2 (de) * | 1981-10-19 | 1983-04-27 | Unilever Plc | Viskose Zusammensetzungen, die Amidobetaine und Salze enthalten |
DE3544236A1 (de) * | 1984-12-18 | 1986-06-19 | Colgate-Palmolive Co., New York, N.Y. | Konzentrierte, waessrige, einphasige, homogene builder enthaltende, fluessige waschmittelzusammensetzung |
EP0228501A2 (de) * | 1985-12-05 | 1987-07-15 | Joh. A. Benckiser GmbH | Flüssige Sänitärreinigungs- und Entkalkungsmittel und Verfahren zu deren Herstellung |
-
1986
- 1986-09-08 FR FR8612571A patent/FR2603601B1/fr not_active Expired
-
1987
- 1987-09-07 ES ES87420234T patent/ES2044967T3/es not_active Expired - Lifetime
- 1987-09-07 AT AT87420234T patent/ATE83796T1/de not_active IP Right Cessation
- 1987-09-07 DE DE8787420234T patent/DE3783185T2/de not_active Expired - Lifetime
- 1987-09-07 NO NO873732A patent/NO174674C/no unknown
- 1987-09-07 EP EP87420234A patent/EP0260205B1/de not_active Expired - Lifetime
- 1987-09-08 DK DK469287A patent/DK170947B1/da active IP Right Grant
-
1993
- 1993-03-23 GR GR930400627T patent/GR3007440T3/el unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2087635A5 (de) * | 1970-05-22 | 1971-12-31 | Kao Corp | |
EP0077674A2 (de) * | 1981-10-19 | 1983-04-27 | Unilever Plc | Viskose Zusammensetzungen, die Amidobetaine und Salze enthalten |
DE3544236A1 (de) * | 1984-12-18 | 1986-06-19 | Colgate-Palmolive Co., New York, N.Y. | Konzentrierte, waessrige, einphasige, homogene builder enthaltende, fluessige waschmittelzusammensetzung |
EP0228501A2 (de) * | 1985-12-05 | 1987-07-15 | Joh. A. Benckiser GmbH | Flüssige Sänitärreinigungs- und Entkalkungsmittel und Verfahren zu deren Herstellung |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4900467A (en) * | 1988-05-20 | 1990-02-13 | The Clorox Company | Viscoelastic cleaning compositions with long relaxation times |
EP0649834A1 (de) * | 1993-10-20 | 1995-04-26 | Kao Corporation | Carboxybetaine und Sulfobetaine und diese enthaltende Reinigungszusammensetzung und kosmetische Zusammensetzung |
WO1999015610A1 (de) * | 1997-09-25 | 1999-04-01 | Cognis Deutschland Gmbh | Verwendung von ungesättigten betaintensiden als verdickungsmittel |
Also Published As
Publication number | Publication date |
---|---|
NO873732L (no) | 1988-03-09 |
ATE83796T1 (de) | 1993-01-15 |
EP0260205A3 (en) | 1989-02-22 |
DE3783185D1 (de) | 1993-02-04 |
EP0260205B1 (de) | 1992-12-23 |
GR3007440T3 (de) | 1993-07-30 |
NO174674C (no) | 1994-06-15 |
DE3783185T2 (de) | 1993-07-01 |
FR2603601A1 (fr) | 1988-03-11 |
ES2044967T3 (es) | 1994-01-16 |
NO174674B (no) | 1994-03-07 |
FR2603601B1 (fr) | 1988-11-10 |
DK170947B1 (da) | 1996-03-25 |
DK469287A (da) | 1988-03-09 |
DK469287D0 (da) | 1987-09-08 |
NO873732D0 (no) | 1987-09-07 |
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