EP0112044B1 - Detergenszusammensetzungen - Google Patents

Detergenszusammensetzungen Download PDF

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Publication number
EP0112044B1
EP0112044B1 EP83306946A EP83306946A EP0112044B1 EP 0112044 B1 EP0112044 B1 EP 0112044B1 EP 83306946 A EP83306946 A EP 83306946A EP 83306946 A EP83306946 A EP 83306946A EP 0112044 B1 EP0112044 B1 EP 0112044B1
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Prior art keywords
composition according
detergent composition
detergent
alkyl
weight
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English (en)
French (fr)
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EP0112044A1 (de
Inventor
Appaya Raghunath Naik
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Unilever NV
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Unilever NV
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Priority to AT83306946T priority Critical patent/ATE22574T1/de
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • the present invention relates to high-foaming liquid detergent compositions suitable for use in fabric washing, shampoos, and above all, in manual dishwashing operations in both hard and soft water.
  • GB-A-1 429 637 discloses hand dishwashing compositions containing as detergent-active material a water-soluble salt of a di(C,-C9) alkyl ester of sulphosuccinic acid, in combination with an alkyl sulphate or an alkyl ether sulphate.
  • Various C"-C,5 alkyl ether sulphates having different chain length distributions and degrees of ethoxylation are used, as follows:
  • the present invention is based on the observation that in liquid detergent compositions based on dialkyl sulphosuccinates and alkyl ether sulphates both formulation and performance benefits may be obtained by using a particular selected group of alkyl ether sulphates. These benefits are especially apparent at relatively low ratios of sulphosuccinate to ether sulphate.
  • the present invention accordingly provides a foaming liquid detergent composition in the form of a stable aqueous solution containing at least 2% by weight of an active detergent mixture comprising:
  • the concentration of the active detergent mixture in the composition may be as high as desired, provided that an aqueous solution can be obtained, it is preferably in the 2 to 60% by weight range and more preferably in the 5 to 40% by weight range.
  • composition of the present invention may if desired contain other detergent-active materials within its active detergent mixture, provided that the composition is substantially free of alkyl polyethoxy sulphates (ether sulphates) other than those defined under (b) above. It is, however, preferred that at least 2% by weight of the whole composition, preferably at least 5% and more preferably 10%, is constituted by dialkyl sulphosuccinate(s). Preferred additional ingredients are discussed in more detail below.
  • the dialkyl sulphosuccinate component (a) may if desired be constituted by a mixture of materials of different chain lengths, of which the individual dialkyl sulphosuccinates themselves may be either symmetrical (both alkyl groups the same) or unsymmetrical (with two different alkyl groups).
  • the detergent-active dialkyl sulphosuccinates are compounds of the formula I: wherein each of R, and R 2 , which may be the same or different, represents a straight-chain or branched-chain alkyl group having from 3 to 12 carbon atoms, preferably from 4 to 10 carbon atoms and more preferably from 6 to 8 carbon atoms, and X, represents a solubilising cation, that is to say, any cation yielding a salt of the formula I sufficiently soluble to be detergent-active.
  • the solubilising cation X will generally be monovalent, for example, alkali metal, especially sodium; ammonium; or substituted ammonium, for example, ethanolamine. Certain divalent cations, notably magnesium, are however also suitable.
  • the alkyl groups R, and R 2 are preferably straight-chain or (in mixtures) predominantly straight-chain.
  • dialkyl sulphosuccinates that may advantageously be used in the composition of the invention are the C 6 /C 8 unsymmetrical materials described and claimed in GB-A-2 105 325 (Unilever); the dioctyl sulphosuccinate/dihexyl sulphosuccinate mixtures described and claimed in GB-A-2 104 913 (Unilever); and the mixtures of symmetrical and unsymmetrical dialkyl sulphosuccinates described and claimed in GB-A-2 108 520 (Unilever).
  • the composition of the invention may additionally include one or more of the sulphonate-type detergents conventionally used as the main detergent-active agent in liquid compositions, for example, alkylbenzene sulphonates (especially C 9 ⁇ C 15 linear alkylbenzene sulphonates), secondary alkane sulphonates, alpha-olefin sulphonates, alkyl glyceryl ether sulphonates, and fatty acid ester sulphonates.
  • dialkyl sulphosuccinates are themselves sulphonate-type detergents. If such additional sulphonate-type materials are present, the total sulphonate preferably predominates in the active detergent mixture of the composition of the invention. If no such additional sulphonate-type materials are present, the sulphosuccinate alone preferably predominates.
  • the alkyl polyethoxy sulphates or alkyl ether sulphates constituting component (b) of the composition of the invention are compounds of the general formula II: wherein R 3 is an alkyl group having from 10 to 18 carbon atoms, X 2 is a solubilising cation, and n, the average degree of ethoxylation, is from 1 to 12, preferably from 1 to 8.
  • R 3 is an alkyl group having from 10 to 18 carbon atoms
  • X 2 is a solubilising cation
  • n the average degree of ethoxylation, is from 1 to 12, preferably from 1 to 8.
  • n the average degree of ethoxylation
  • the unethoxylated material is, of course, alkyl sulphate.
  • additional alkyl sulphate may be admixed with the alkyl ether sulphate, to give a mixture in which the ethoxylation distribution is more weighted towards lower values.
  • the particular ether sulphates used according to the present invention are derived from primary aliphatic alcohols and are distinguished by a content of 20% by weight or less of material having a chain length of C, 4 and above.
  • the content of such long-chain material is preferably less than 10% by weight, and it is especially advantageous to use an ether sulphate substantially free of such material.
  • the content of C" and shorter chain length material is as low as possible.
  • the ether sulphate used according to the present invention preferably consists predominantly of C, 2 and C, 3 material.
  • Table 1 shows typical chain length distributions for some commercially available alkyl ether sulphates. Degrees of ethoxylation are omitted from the Table since most manufacturers provide a range of differently ethoxylated materials.
  • Preferred materials for use in the present invention are the Dobanol (Trade Mark) 23 series from Shell, which are virtually free of C 14 and higher chain length material.
  • the ether sulphates used according to the present invention containing 20% or less of C 14 and above chain length material are preferably based on straight-chain or predominantly straight-chain alcohols.
  • hydrotropes examples include lower aliphatic alcohols, especially ethanol; urea; lower alkylbenzene sulphonates such as sodium toluene and xylene sulphonates; and combinations of these.
  • the lower alcohols function mainly as viscosity reducers, and urea and lower alkylbenzene sulphonates mainly as solubilisers.
  • Hydrotropes are expensive and take up room in a formulation without contributing to its performance, and it is therefore desirable to use as small quantities of them as possible.
  • compositions based on dialkyl sulphosuccinates and conventional ether sulphates such as Dobanol 25 can be improved by lowering the ratio of sulphosuccinate to ether sulphate, but this also causes a drop in foaming performance. With the specific ether sulphates used according to the invention, however, the ratio can be lowered much further without a drop in performance, so that compositions having both acceptable physical characteristics and excellent foaming performance can be obtained.
  • sulphosuccinate/Dobanol 25 and sulphosuccinate/Dobanol 23 mixtures have very similar foaming performances at a ratio of 4: 1, but at 2:1 the performance of the former mixture has deterioriated considerably while that of the latter mixture is virtually unchanged.
  • the ether sulphate used in the composition of the invention has a degree of ethoxylation n of 1 to 12, preferably 1 to 8. Materials having n values of 2, 3 and 6.5 have all been found to give excellent results in compositions according to the invention. The range of 1 to 8 apparently gives optimum detergent properties in conjunction with the predominant chain lengths of C 12 and C, 3 .
  • ether sulphates other than those specified under (b) above are absent.
  • the ether sulphates may be supplemented or partially replaced by other sulphate-type detergents, notably primary and secondary alkyl sulphates, and/or by ethoxylated nonionic detergents having from 8 to 15 carbon atoms and average degrees of ethoxylation of from 5 to 14.
  • Preferred nonionic detergents are short-chain high-foaming ethoxylated alcohols of the general formula III: wherein R 4 is an alkyl group, preferably straight-chain, having from 8 to 12 carbon atoms, and the average degree of ethoxylation m is from 5 to 12.
  • the weight ratio of alkyl ether sulphate to nonionic detergent is preferably at least 1:1 and more preferably within the range of from 1.5:1 to 3:1, especially about 2:1.
  • An especially preferred nonionic detergent is Dobanol (Trade Mark) 91-8 ex Shell, in which R 4 is Cg-Cl, (predominantly straight-chain) and m is 8.
  • the stable liquid detergent compositions of the invention may be used for all normal detergent purposes where foaming is advantageous, for example, fabric washing products, general purpose domestic and industrial cleaning compositions, carpet shampoos, car wash products, personal washing products, shampoos, foam bath products, and, above all, manual dishwashing.
  • compositions may contain the usual minor ingredients such as perfume, colour, preservatives and germicides.
  • the dialkyl sulphosuccinate used was a statistical mixture (mole ratio 1:2:1) of di-n-octyl sulphosuccinate, n-hexyl n-octyl sulphosuccinate and di-n-hexyl sulphosuccinate (sodium salts), prepared from a 1:1 mixture of n-hexanol and n-octanol by the method described in Example 1 of GB-A-2 108 520 (Unilever).
  • the total active detergent concentration in each formulation tested was 25%.
  • Comparison of Compositions A and B shows that a reduction in the (a):(b) ratio from 4:1 to 2:1 gives a considerable performance reduction.
  • Compositions 1, 2 and 3 according to the invention are compared it may be seen that at 2:1 the performance is not significantly worse than at 4:1, and even at 1:1 it has not fallen as low as that of Composition B.
  • the hard water performance of the dialkyl sulphosuccinate/Dobanol 23-3A system at an (a):(b) ratio of 2:1 was compared with those of similar systems containing three other alkyl ether sulphates, the tests being carried out at product dosages of both 1.0 and 1.5 g/litre.
  • the ether sulphates used were Dobanol 23-3A and Dobanol 25-3A as in Example 1; Empimin 3003 ex Albright & Wilson, as used in GB-A-1 429 637 (Unilever) discussed previously, and Dobanol 23-6.5A ex Shell, which has an average degree of ethoxylation of 6.5 but is otherwise similar to Dobanol 23-3A.
  • the chain length distributions of all these materials are given in Table 1 previously.
  • Each test formulation contained 16% by weight of the dialkyl sulphosuccinate mix used in earlier Examples and 8% by weight of the ether sulphate.
  • compositions containing the sulphosuccinate mix of previous Examples and various ether sulphates were prepared and their physical characteristics were measured.
  • Comparative Compositions A1 and A2 correspond in active detergent constituents and levels to Comparative Composition A in Examples 1 to 3, and Composition 5 here corresponds to Composition 5 of Example 5.
  • Dobanol 23-2S is the sodium salt corresponding to Dobanol 23-2A used in Example 4.
  • Comparative Example A1 shows a 4:1 dialkyl sulphosuccinate/ether sulphate composition outside the invention; the relatively high level (20%) of hydrotrope will be noted. Comparative Example A2 shows that when an attempt was made to reduce that level to 12%, a completely unstable product was obtained. Stability was regained only by reducing the sulphosuccinate to ether sulphate ratio to 2:1, as in Compositions 5, 7 and 8 according to the invention. These Compositions also exhibited the advantageous attribute of higher viscosity.
  • Composition 9 according to the invention having a higher active detergent level, required some ethanol as well as urea to achieve a low cloud point, and the viscosity was lower, but not unacceptably so.
  • compositions of the invention were investigated in both hard and soft water, at a dosage of 1.0 g/litre.
  • the nonionic detergent used was Dobanol 91-8 ex Shell, which as mentioned previously is C 9 ⁇ C 11 predominantly straight-chain primary alcohol with an average degree of ethoxylation of 8.
  • the ratio of sulphosuccinate to the other detergents was 2:1 in each case, the total active detergent concentration being 27%.
  • a composition according to the invention containing an additional ingredient-primary alkyl sulphate- was prepared.
  • This latter material was Dobanol 23-A ex Shell, which is the unethoxylated analogue of Dobanol 23-3A.
  • the composition contained 12% by weight of the dialkyl sulphosuccinate mix used in previous Examples, 8% by weight of Dobanol 23-A, and 8% by weight of Dobanol 23-3A. It required only 4% by weight of urea to achieve a cloud point of ⁇ 4°C, and its viscosity-430 mPa . s-was high.

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  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Claims (16)

1. Schäumende, flüssige Detergenszusammensetzung in Form einer stabilen, wäßrigen Lösung, enthaltend mindestens 2 Gew.-% einer aktiven Detergensmischung, umfassend
a) ein wasserlösliches Salz eines Dialkylesters der Sulfobernsteinsäure der Formel I
Figure imgb0011
worin jeder der Reste R, und R2, die gleich oder unterschiedlich sein können, eine geradkettige oder verzweigtkettige Alkylgruppe mit 3 bis 12 Kohlenstoffatomen darstellt, und X, ein solubilisierendes Kation darstellt und
b) ein Alkylpolyethoxysulfat, wobei das Gewichtsverhältnis von (a) zu (b) innerhalb des Bereiches von 5:1 bis 0,5:1 ist, dadurch gekennzeichnet, daß das Alkylpolyethoxysulfat (b) ein C10―C18-primäres Alkylpolyethoxysulfat ist, das 20 Gew.-% oder weniger an Material von Ci4- und höherer Kettenlänge enthält und einen durchschnittlichen Ethoxylierungsgrad von 1 bis 12 hat.
2. Detergenszusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Alkylpolyethoxysulfat (b) weniger als 10% Material von C14- und höherer Kettenlänge enthält.
3. Detergenszusammensetzung nach Anspruch 2, dadurch gekennzeichnet, daß das Alkylpolyethoxysulfat (b) im wesentlich frei von Material von C14- und höherer Kettenlänge ist.
4. Detergenszusammensetzung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Alkylpolyethoxysulfat (b) einen durchschnittlichen Ethoxylierungsrad von 1 bis 8 hat.
5. Detergenszusammensetzung nach Anspruch 4, dadurch gekennzeichnet, daß das Alkylpolyethoxysulfat (b) einen durchschnittlichen Ethoxylierungsgrad von 6 bis 7 hat.
6. Detergenszusammensetzung nach Anspruch 4, dadurch gekennzeichnet, daß das Alkylpolyethoxysulfat (b) einen durchschnittlichen Ethoxylierungsgrad von 2 bis 3 hat.
7. Detergenszusammensetzung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Alkylpolyethoxysulfat (b) von geradkettigen oder überweigend geradkettigen aliphatischen Alkoholen abstammt.
8. Detergenszusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß sie 2 bis 60 Gew.-% der aktiven Detergensmischung enthält.
9. Detergenszusammensetzung nach Anspruch 8, dadurch gekennzeichnet, daß sie 5 bis 40 Gew.-% der aktiven Detergensmischung enthält.
10. Detergenszusammensetzung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das Gewichtsverhältnis von (a) zu (b) innerhalb des Bereiches von 4:1 bis 1:1 liegt.
11. Detergenszusammensetzung nach Anspruch 10, dadurch gekennzeichnet, daß das Gewichtsverhältnis von (a) zu (b) innerhalb des Bereiches von 3:1 zu 1:1 liegt.
12. Detergenszusammensetzung nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß das Dialkylsulfosuccinat (a) mindestens 5 Gew.-% der gesamten Zusammensetzung ausmacht.
13. Detergenszusammensetzung nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß die Alkylgruppen R, und R2 des Dialkylsulfosuccinats (a) jeweils 4 bis 10 Kohlenstoffatome haben.
14. Detergenszusammensetzung nach Anspruch 13, dadurch gekennzeichnet, daß die Alkylgruppen R1 und R2 des Dialkylsulfosuccinats (a) jeweils 6 bis 8 Kohlenstoffatome haben.
15. Detergenszusammensetzung nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß die aktive Detergensmischung außerdem ein ethoxyliertes nichtionisches Detergens mit einer Alkylkettenlänge von C8 bis C15 und einem durchschnittlichen Ethoxylierungsgrad von 5 bis 14 umfaßt.
16. Detergenszusammensetzung nach Anspruch 15, dadurch gekennzeichnet, daß das Gewichtsverhältnis des Alkylpolyethoxysulfats (b) zu dem nichtionischen Detergens mindestens 1:1 ist.
EP83306946A 1982-11-16 1983-11-14 Detergenszusammensetzungen Expired EP0112044B1 (de)

Priority Applications (1)

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AT83306946T ATE22574T1 (de) 1982-11-16 1983-11-14 Detergenszusammensetzungen.

Applications Claiming Priority (2)

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GB8232686 1982-11-16
GB8232686 1982-11-16

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EP0112044A1 EP0112044A1 (de) 1984-06-27
EP0112044B1 true EP0112044B1 (de) 1986-10-01

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EP (1) EP0112044B1 (de)
JP (1) JPS59102994A (de)
AT (1) ATE22574T1 (de)
AU (1) AU549661B2 (de)
BR (1) BR8306254A (de)
CA (1) CA1220695A (de)
DE (1) DE3366631D1 (de)
DK (1) DK523283A (de)
GB (1) GB2130238B (de)
GR (1) GR81285B (de)
IN (1) IN158157B (de)
NO (1) NO834150L (de)
NZ (1) NZ206209A (de)
PH (1) PH17916A (de)
PT (1) PT77671A (de)
ZA (1) ZA838427B (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU573338B2 (en) * 1984-05-11 1988-06-02 Unilever Plc Homogenous foaming liquid composition
GB8412046D0 (en) * 1984-05-11 1984-06-20 Unilever Plc Detergent compositions
GB8412045D0 (en) * 1984-05-11 1984-06-20 Unilever Plc Detergent compositions
GB8420945D0 (en) * 1984-08-17 1984-09-19 Unilever Plc Detergents compositions
GB8515721D0 (en) * 1985-06-21 1985-07-24 Unilever Plc Detergent compositions
CA1276852C (en) * 1985-06-21 1990-11-27 Francis John Leng Liquid detergent composition
GB8528521D0 (en) * 1985-11-20 1985-12-24 Procter & Gamble Liquid detergent compositions
DE3838533A1 (de) * 1988-11-14 1990-05-17 Henkel Kgaa Fluessiges reinigungsmittel fuer harte oberflaechen
DE3902619A1 (de) * 1989-01-30 1990-08-02 Henkel Kgaa Fluessige reinigungsmittel
DE4137893A1 (de) * 1991-11-18 1993-05-19 Henkel Kgaa Waessrige detergensgemische
JP4888989B2 (ja) * 2001-09-27 2012-02-29 エステー株式会社 硬質表面洗浄剤組成物

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1429637A (en) 1972-04-06 1976-03-24 Unilever Ltd Dishwashing compositions
AU543814B2 (en) 1981-07-24 1985-05-02 Unilever Plc Sulphosucinate and protein detergent compositions
NZ201308A (en) 1981-07-24 1985-08-16 Unilever Plc Dialkyl sulphosuccinates and detergent compositions
NZ201306A (en) * 1981-07-24 1985-08-16 Unilever Plc Detergent compositions containing dialkyl sulphosuccinates

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DK523283A (da) 1984-05-17
BR8306254A (pt) 1984-06-19
DE3366631D1 (en) 1986-11-06
GR81285B (de) 1984-12-11
GB2130238A (en) 1984-05-31
GB8330369D0 (en) 1983-12-21
PH17916A (en) 1985-01-25
ATE22574T1 (de) 1986-10-15
NO834150L (no) 1984-05-18
ZA838427B (en) 1985-07-31
JPS59102994A (ja) 1984-06-14
GB2130238B (en) 1986-08-20
PT77671A (en) 1983-12-01
IN158157B (de) 1986-09-20
EP0112044A1 (de) 1984-06-27
NZ206209A (en) 1986-01-24
AU2136483A (en) 1984-05-24
DK523283D0 (da) 1983-11-15
CA1220695A (en) 1987-04-21
AU549661B2 (en) 1986-02-06

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