AU607813B2 - Sanitizer - Google Patents
Sanitizer Download PDFInfo
- Publication number
- AU607813B2 AU607813B2 AU23454/88A AU2345488A AU607813B2 AU 607813 B2 AU607813 B2 AU 607813B2 AU 23454/88 A AU23454/88 A AU 23454/88A AU 2345488 A AU2345488 A AU 2345488A AU 607813 B2 AU607813 B2 AU 607813B2
- Authority
- AU
- Australia
- Prior art keywords
- composition according
- composition
- weight ratio
- weight
- alkali metal
- 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.)
- Ceased
Links
- 239000000203 mixture Substances 0.000 claims description 23
- 239000007844 bleaching agent Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- -1 silicate ions Chemical class 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 5
- 238000011012 sanitization Methods 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 239000003518 caustics Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 230000000881 depressing effect Effects 0.000 claims 1
- 229910052913 potassium silicate Inorganic materials 0.000 claims 1
- 235000019353 potassium silicate Nutrition 0.000 claims 1
- 235000011121 sodium hydroxide Nutrition 0.000 claims 1
- 238000005260 corrosion Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 235000019832 sodium triphosphate Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 4
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 208000004434 Calcinosis Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZVXSESPJMKNIQA-YXMSTPNBSA-N Lys-Thr-Pro-Pro Chemical compound NCCCC[C@H](N)C(=O)N[C@@H]([C@H](O)C)C(=O)N1CCC[C@H]1C(=O)N1[C@H](C(O)=O)CCC1 ZVXSESPJMKNIQA-YXMSTPNBSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005406 washing Methods 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
- C11D3/3956—Liquid compositions
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)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
1.1 12.0
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O68L99tCI-' x~~sb0U111 61), zAXMAnis80dONW fio~~ 1HO CW 'd 8 O68L9g1C[ zAXMAnsjbdouwp!!q5Jepxqo ZAxMAnisNdONWINrIH0 10ODV 'Id 01.
111 1.1, 111112-.0 11111 1.8 1.25 _.4 1.2511.4
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AUSTRALIA
PATENTS ACT 1952 COMPLETE SPECIFICATION Form
(ORIGINAL)
FOR OFFICE USE urn-c') tent contains the amendments made tinder Section 49 and is cprrect for printing Short Title: Int. Cl: Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: *~Priority: :'"Related Art: TO B "Name of Applicant: .'"Addre~ss of Applicant: I f ,,Actual inventor: 4jfAddress for Service: E COMPLETED BY APPLICANT UNILEVER PLC UNILEVER HOUSE
BLACKFRIARS
LONDON EC4
ENGLAND
GRIFFITH HACK CO., 601 St. Kilda Road, Melbourne, Victoria 3004, Australia.
Complete Specification for the invention entitled:
SANITIZER
The following statement is a full description of this invention including the best method of performing it known to me:- M00345 05/ 10/8
I
li v I-.1 -i Imnmax: 1 II;- 1. I C 3194 (R)
SANITIZER
The present invention is concerned with a sanitizing product which contains a hypohalite bleach.
In industrial machines for bulk warewashing or fabrics washing, it is often desired to add a bleach-based sanitizing product during one or more wash cycles, to ensure an acceptable level of hygiene.
to Unfortunately, for optimum sanitizing performance and acceptable cost, it is necessary to use a hypohalite bleach which, with prolonged use, can lead to spot corrosion of some stainless steel parts. This especially occurs when the machine is not operating, and particularly at spots which are near the spray nozzles 5 for tle sanitizer solution.
t .9 ,a 1 O 9 1 o9 0 9 eo t. Although it has been known in the past to use an agent like sodium metasilicate to inhibit corrosion, there are problems in using this effectively in sanitizers of the aforementioned kind. First, any putative corrosion inhibitor must be soluble in an aqueous liquid (such sanitizers must be dosed as liquids). Second, an insufficient level of such inhibitor actually increases corrosion as compared to that observed with equivalent products totally devoid of any inhibitor. Third, at effective levels of inhibitor, there is a real danger of premature decomposition of the bleach.
We have now found that these problems can be overcome by providing a liquid sanitizer composition comprising at least 2% by weight of a caustic agent, from 0 to 1% of a surfactant and at least 3% by weight of a hypohalite bleach and an amount of an alkali metal neutral silicate such that the weight ratio of silicate ions to free halogen is at least 1:5 and the weight ratio of the :r
S;;
i do C 3194 (R) 2 hypohalite bleach to other water-soluble electrolyte in the composition is at most 1:1.
Hypohalites, such as sodium hypochlorite, exert their sanitizing action by release of free oxygen to leave sodium chloride. Commercially available hypochlorites do indeed contain trace impurities of the corresponding Schloride. Thus, in the context of the present invention, the term "free halogen" means the total halogen in the composition, whether as a halide ion or in the form of S the corresponding hypohalite.
t t t t Commercially available hypochlorite compositions are characterized by their content of "available chlorine".
i'riS Methods for determining the "available chlorine" of S compositions containing chlorine bleach are well known in the art. In accordance with usual practice, the available chlorine is defined in this application as the S amount of chlorine which can be liberated from a S ',20 composition by acidification and addition of at least one molar equivalent of chloride ions.
For the best corrosion inhibition performance, it is preferred that the weight ratio of silicate ions to free j halogen is from 1:5 to 1:1.5.
To guard against premature decomposition of the bleach, it is most preferred that the weight ratio of hypohalite bleach to other water-soluble electrolyte in the j 30 composition is from 1:2 to 1:1.
The most preferred hypohalite bleaches are the alkali metal hypochlorites, especially the sodium salt.
Preferably also, to inhibit calcium deposits on metal surfaces, especially aluminium, the composition further comprises from 1 to 5% of an alkali metal condensed ""f~lW r t; r; I C 3194 (R) phosphate builder, such as sodium or potassium tripolyphosphate.
For optimum bleach stability and performance, it is also preferred that the pH of the composition is at least 12.0.
The caustic agent in the composition is an alkali metal hydroxide or metasilicate, such as sodium hydroxide, potassium hydroxide, sodium metasilicate or potassium S metasilicate. The relative amount of sodium and potassium ions in the total composition should be chosen such that there is no precipitation of any tripoly phosphate present, in the form of a precipitate of the sodium salt.
The surfactant, which may be present in an amount of 0.1% by weight, is essentially a foam depressor.
St i The term alkali metal neutral silicate means one in which the ratio of silicate to alkali metal oxide species is greater than 3:1. A typical example is sodium neutral silicate having an SiO 2 :Na20 ratio of 3.4:1.
The present invention will now be explained better by way of the following Examples.
s"h i r i; C 3194 (R) Examples 1-8* The following compositions were formulated using 6% by weight of a concentrated stock solution of potassium hydroxide containing 50% by weight of potassium hydroxide, and 31.3% by weight of a concentrated stock solution of sodium hypochlorite containing 19.2% by weight of sodium hypochlorite-(calculated as available chlorine).
Examples 1-4 were formulated using a low sodium chloride impurity bleach, whereas Examples 5-8 were formulated using a regular grade, resulting in NaCl contents in the total composition of 3 and 5% by weight, respectively.
The sodium silicate was added as a concentrated stock solution containing 34% by weight of active SiO 2 :Na20 in a ratio of 3.4:1.
t t I The solution was applied neat to stainless steel discs and left for sufficient time for visible corrosion to be apparent. The corrosion apparent was rated on an arbitrary scale of 1-10 where 1 refers to no corrosion and 10 refers to severe attack.
Examples 9-12 The following compositions were prepared using the same stock solutions as in Examples 1-8, but additionally containing potassium tripolyphosphate. The latter was added as a concentrated stock solution containing 50% by weight of potassium tripolyphosphate. Clear solutions were obtained without any signs of precipitates being formed. The corrosion ratings were similar to those of Examples 1-4 or 5-8, depending on the amount of NaCl impurity of the sodium hypochlorite solution used.
i
I
I I1' C 3194 (R) Ex 1 2 3 4 6 7 8 Wt.% silicate* Wt.% SiO 2 0 0 4 1.05 8 2.10 12 3.15 0 0 4 1.05 8 2.10 12 3.15 Wt.% NaCi Impurity 3.0 of It 5.0 if It Wt. ratio Si2:free halogen 1:4.59 1:2.30 1:1.53 1:5.74 1:2.87 1:1.91 Wt. ratio bleach other electrolyte 1:0.95 1:1.17 1:1.38 1:1.60 1:1.27 1:1.49 1:1.70 1:1.92 corrosion rating 6 1 2 2 6 4 3 2 34% active SiO 2 :Na 2 o 3.4:1 -i
U
I?'
4
I
I
i~i
LI
II
ii ii
H
2 0 KOH (50%) KTPP (50%) Na-silicate (34%) NaOC1 (19.2%) pH Ex 9 59.7 6 3 0 31.3 13 .65 (by weight) 10 11 55.7 51.7 6 6 3 3 4 8 31.3 31.3 13.60 13.55 C 3194 (R) 12 47.7 6 3 12 31.3 13 I 4
I,
Claims (7)
1. A liquid sanitizer composition comprising at least 2% by weight of a caustic agent selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium metasilicate and potassium-metasilicate, from 0 to 1% of a foam depressing surfactant and at least 3% by weight of a hypohalite bleach and an amount of an alkali metal neutral silicate such that the weight ratio of silicate ions to free halogen is at least 1:5 and the weight ratio of the hypohalite bleach to other water-soluble electrolyte in the composition is at most 1:1.
2. A composition according to Claim 1, wherein the weight ratio of silicate ions to free halogen is from to 1:1.5.
3. A composition according to Claim 1 or Claim 2, wherein the weight ratio of hypohalite bleach to other water-soluble electrolyte in the composition is from 1:2 to 1:1.
4. A composition according to any preceding claim, wherein the hypohalite bleach is an alkali metal hypochlorite.
A composition according to any preceding claim, further comprising from 1 to 5% of an alkali metal S condensed phosphate builder. c
6. A composition according to any preceding claim, b r" wherein the pH is at least 12.0. It I 2. A opsto codn oCam1 hri h wegh raitfslct ost fe aoe sfo If,, 8
7. A process of mechanical warewashing comprising dosing an effective sanitizing amount of a composition according to any preceding claim into the wash liquor in a warewashing machine. DATED THIS 11TH DAY OF DECEMBER 1990 UNILEVER PLC By its Patent Attorneys: GRIFFITH HACK CO. Fellows Institute of Patent Attorneys of Australia. i *000 o *o 0 0 000 0 C. Ci 0 0 01 0 00r *r S 0 @0 01 I 11 l.i i i iii~ 1
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB878723675A GB8723675D0 (en) | 1987-10-08 | 1987-10-08 | Sanitizer |
| GB8723675 | 1987-10-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2345488A AU2345488A (en) | 1989-04-13 |
| AU607813B2 true AU607813B2 (en) | 1991-03-14 |
Family
ID=10625009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU23454/88A Ceased AU607813B2 (en) | 1987-10-08 | 1988-10-05 | Sanitizer |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0311175B1 (en) |
| JP (1) | JPH01128907A (en) |
| AU (1) | AU607813B2 (en) |
| BR (1) | BR8805157A (en) |
| DE (1) | DE3886873T2 (en) |
| ES (1) | ES2061634T3 (en) |
| GB (1) | GB8723675D0 (en) |
| NO (1) | NO173023C (en) |
| ZA (1) | ZA887548B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3802127C1 (en) * | 1988-01-26 | 1988-12-01 | Kaiser, H.-G. | |
| JPH0214298A (en) * | 1988-06-30 | 1990-01-18 | Matsushita Electric Ind Co Ltd | Detergent for vessel of cleaner and method for cleaning thereof |
| GB9213578D0 (en) * | 1992-06-26 | 1992-08-12 | Unilever Plc | Improvements to bleaching compositions |
| DK0653483T3 (en) * | 1993-11-11 | 1999-10-25 | Procter & Gamble | Use of silicates in hypochlorite bleaching compositions |
| US5843190A (en) * | 1993-11-11 | 1998-12-01 | The Procter & Gamble Company | Hypochlorite bleaching compositions |
| US6297209B1 (en) | 1996-05-10 | 2001-10-02 | The Clorox Company | Sequesterants as hypochlorite bleach enhancers |
| GB0222501D0 (en) * | 2002-09-27 | 2002-11-06 | Unilever Plc | Composition and method for bleaching a substrate |
| DE102005062008B3 (en) | 2005-12-22 | 2007-08-30 | Henkel Kgaa | Odor reduction of hypochlorite-containing agents |
| DE102005063065A1 (en) * | 2005-12-29 | 2007-07-12 | Henkel Kgaa | Corrosion inhibition of liquid hypochlorite detergent |
| DE102005063177A1 (en) | 2005-12-30 | 2007-07-05 | Henkel Kgaa | Use of diethylene-penta-methylene phosphonic acid for the stabilization of optical brightener in aqueous liquid detergent containing alkali hypochlorite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU458559B2 (en) * | 1970-12-09 | 1975-02-27 | Kao Soap Co., Ltd | Cleaning and bleaching liquid composition |
| AU7742787A (en) * | 1986-09-05 | 1988-03-10 | Colgate-Palmolive Company, The | Thixotropic clay aqueous suspensions |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB490092A (en) * | 1936-10-10 | 1938-08-09 | Ig Farbenindustrie Ag | Process for the production of cleansing agents |
| GB1320919A (en) * | 1969-11-07 | 1973-06-20 | Albright & Wilson | Detergent composition |
| US3697431A (en) * | 1971-01-22 | 1972-10-10 | Clorox Co | Liquid drain opening composition and method |
| US4339235A (en) * | 1979-12-06 | 1982-07-13 | Economics Laboratory, Inc. | Methods and compositions for bleaching of mycological stain |
| JPS5690898A (en) * | 1979-12-25 | 1981-07-23 | Nippon Rasukatsuto Kk | Cleaning agent for household bath tub |
| JPS58196297A (en) * | 1982-05-12 | 1983-11-15 | ア−ス製薬株式会社 | Bath boiler detergent |
-
1987
- 1987-10-08 GB GB878723675A patent/GB8723675D0/en active Pending
-
1988
- 1988-09-27 ES ES88202094T patent/ES2061634T3/en not_active Expired - Lifetime
- 1988-09-27 EP EP88202094A patent/EP0311175B1/en not_active Expired - Lifetime
- 1988-09-27 DE DE3886873T patent/DE3886873T2/en not_active Expired - Fee Related
- 1988-10-05 AU AU23454/88A patent/AU607813B2/en not_active Ceased
- 1988-10-06 BR BR8805157A patent/BR8805157A/en not_active IP Right Cessation
- 1988-10-06 NO NO884451A patent/NO173023C/en unknown
- 1988-10-07 JP JP63253623A patent/JPH01128907A/en active Pending
- 1988-10-07 ZA ZA887548A patent/ZA887548B/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU458559B2 (en) * | 1970-12-09 | 1975-02-27 | Kao Soap Co., Ltd | Cleaning and bleaching liquid composition |
| AU7742787A (en) * | 1986-09-05 | 1988-03-10 | Colgate-Palmolive Company, The | Thixotropic clay aqueous suspensions |
Also Published As
| Publication number | Publication date |
|---|---|
| NO173023B (en) | 1993-07-05 |
| NO884451L (en) | 1989-04-10 |
| EP0311175A3 (en) | 1990-04-11 |
| AU2345488A (en) | 1989-04-13 |
| NO173023C (en) | 1993-10-13 |
| ZA887548B (en) | 1990-06-27 |
| JPH01128907A (en) | 1989-05-22 |
| ES2061634T3 (en) | 1994-12-16 |
| GB8723675D0 (en) | 1987-11-11 |
| NO884451D0 (en) | 1988-10-06 |
| EP0311175A2 (en) | 1989-04-12 |
| EP0311175B1 (en) | 1994-01-05 |
| DE3886873T2 (en) | 1994-05-19 |
| DE3886873D1 (en) | 1994-02-17 |
| BR8805157A (en) | 1989-05-16 |
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