CA1172826A - Thermostable lead carbonate, process for its manufacture and articles of thermoplastic and elastic polymers pigmented therewith - Google Patents
Thermostable lead carbonate, process for its manufacture and articles of thermoplastic and elastic polymers pigmented therewithInfo
- Publication number
- CA1172826A CA1172826A CA000363206A CA363206A CA1172826A CA 1172826 A CA1172826 A CA 1172826A CA 000363206 A CA000363206 A CA 000363206A CA 363206 A CA363206 A CA 363206A CA 1172826 A CA1172826 A CA 1172826A
- Authority
- CA
- Canada
- Prior art keywords
- lead
- composition
- sheet
- lead carbonate
- oxide
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/14—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/14—Compounds of lead
- C09C1/16—White lead
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyesters Or Polycarbonates (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Abstract of the Disclosure When dissolving highly pure lead(II)oxide in aqueous acetic acid, introducing carbon dioxide under slight pressure at a temperature of 10 to 40°C until a pH of 7 is reached, removing the precipitate and drying it under mild conditions a "white lead" (basic lead carbonated is obtained which is free of lead oxides, has a remission of at least 60 % at 300 to 800 nm and is thermostable up to 300°C. Therefore, this product is useful as a pigment even for polyolefins, especial-ly polyethylene, and apt for preparing flat structures showing the remission properties of snow.
Description
J~;
Thl~ invention relates to materials f'or calnouflage having the same emission characteristics as freshly fallen snow or old snow. Flat sSructures pigmented ~ith - the usual white pigments, such as titanium dioxide, zinc sulfide, chalk, barium sulfate and mixtures thereof ensure a camouflage against visual disc~very but they fail when dlsplay units and film material of modified sensitivity are used as in the latter case the emission characteristics diff'erent from that of snow are detected. White lead pigments such a lead phosphate and lead carbonate do have more advantageous properties in this respect, but these properties change by ageing and especially at elevated temperature. Pigments of !this type are, therefore, unsuitable for processing thermoplastic materials, for example into sheets.
It is the object of t~e present invention to pro-': vide a white lead (basic lead carbonate) which does not have the aforesaid disadvantages and which is, there-fore, excellently suitable for pigmenting materials for camouflage. The basic lead carbonate of the inven-~ tion is practically free from lead oxide, has a re-- mission of at least 60 ~, and preferably at least 70 ';;~ in the ultraviolet range at 300 to ~00 nm and it i~
thermostable at a temperature up to 300C.
Z5 '~he terril "pract:ically free" :is intended to rnean that the content of lead ox:ide :is below the limit of de~ection (de~ree of~ whiteness, hollow cone method).
'~ It is another object of the invention to provide a process for the manufacture of the aforesaid new type of basic lead carbonate, which comprises dissolving highly pure lead(II)oxide in acetic acid, precipitating basic lead carbonate with carbon dioxide at temperatu-res of 10 to 40~, isolating the basic lead carbonate j and drying it under mlld conditions.
l~t li.S a further object of the present invention to provide articles of thermoplastic and elastic polymer.s which have been pigrllented with the thermostable basic lead carbonate of the invention, especia11~ sheets and other f`lat structures to be used for camouflage.
In the following preferreci embodiments of the inventioll are described in detail.
Thermostable basic leaci carbonate having an especially high degree of whiteness and a high remission in the indicated range, in pa~ticular at about 330 nm, is obtained by dissolving highl~ pure lead(II)oxide in aqueous acetic acid at room temperaSure and precipitat-ing the basic lead carbonate from this solution during a period of 1 to 3 hours and under a slight carbon di-oxide excess pressure. Alternatively, lead~II)oxide is suspended in ~ater, glacial acetic acid is added and the suspension obtained is treated with carbon dioxide under a slight excess pressure. After adjustment of a pH of 7 the introduction of carbon dioxide is terminated.
It might be advantageous to treat the suspension ` obtained with sulfurous acid. The reaction product is then isolated and dried under rnild conditions.
The lead oxide used as starting material should not contain metallic lead ~preferably less than 50 ppm), ; red lead and l:itharge of the red modification.
The lead carbonate is preferably precipitated within a period of 2 hours at room temperature under a carbon dioxide excess pressure of about 0.5 bar.
! 25 "Drying under mild oond:itions" shal.l rnean that the (Iry:ing temperature and time have to be chosen in a manner such that decomposit:ion of the reaction product i.s avolded. Preferred clrying temperatures are in the range of from 80 to 150C, in particular 100 to 120C.
For incorporating the basic lead carbonate pigment into thermoplastic and elastic polymers it should be cvnverted first into a preparation suitable for the respective purpose of application. Care has to be taken that dur:ing dispersion of the plgment no disturbing impurities, in particular no metal.lic contaminants such as abraded iron are introduced. It is quite obvious that on~y auxiliaries should be used that have the rec,uired s~ability and compatibility with basic lead carbonate.
~ 4 preparation suitable for incorporation into polyethylene she~ting is obtained by blending the pulverulent pigment with a mixture of low density polye~,hylene and low rnolecular wei~ht polyethylene, plasticizing the blend in an extruder and producing granules therefrom.
It is likewise possible to incorporate the pigment into spread coating pastes, i.e. solvent-free, homogene-ous and thermoplastic materials having a relativelyhigh plasticizer content (so-called plastisols). The thermoplast used for this purpose is preferably a , polymer on the basis of vinyl chloride or polyurethane 'or a precursor of a polyurethane. The spread coating pastes are applied in known manner onto carrier mate-rials such as fibrous materials and sheets and then ~, finished.
.
Preferred camouflage materials are sheets, in particular laMinate sheets, rnade from thermoplastic and - 20 elastic polymers into which the thermostable basic lead carbonate is incorporated. Sheet thickness and degree of pigmentation are chosen in such a manner that a complete covering is achieved. In practice, the sheets have a thickness of at least 100 l~rn, pref'erably 150 to 250 ~m. Consequently, the pigment content varies withir relatively wi,de llmit~c~ f'rom about 5 to about 80 % by weight. In the case of` em:ission ofl electromagnetic radiatiol1 in the range of 300 nm such a camouflage material according to the invention reflects 70 % of the emitted radiation. In the case of electromagnetic radiation ~i.th longer waves up to about 900 nm, the degree of remission increases to approximately 90 ~, whereas with still longer waves the degree of remission decreases again to about 60 to 70 % as it is the case with snow.
The aforesaid physical properties of the camou-flage material do not change even after prolonged time in the open. It is the same with other f'lat structures ' .
~7~26 onto which the p:Lgment of the invention has been applled by spread:ing or spraying :i.n suitable manner.
.In order to improve the mechanical stability of `.the camouflage the pigmented flat structure can be :5 stabilized by a carrier, for example a textile fabric, a wire net or another sheet, preferably a grated sheet.
The following examples illustrate the invention.
A) Preparation of the thermostable basic lead carbonate ;. , Example 1 . 2 kg of lead oxide are dissolved at room tempera-ture in 40 ~ acetic acid whereupon basic lead carbonate is precipitated from the solution under a C02 excess pressure of 0.5 bar. When a pH of 7 is reached, the suspension is decanted, mother liquor and product slurrly are separated from each other and the basic ; lead carbonate is dried at 105C.
Thl~ invention relates to materials f'or calnouflage having the same emission characteristics as freshly fallen snow or old snow. Flat sSructures pigmented ~ith - the usual white pigments, such as titanium dioxide, zinc sulfide, chalk, barium sulfate and mixtures thereof ensure a camouflage against visual disc~very but they fail when dlsplay units and film material of modified sensitivity are used as in the latter case the emission characteristics diff'erent from that of snow are detected. White lead pigments such a lead phosphate and lead carbonate do have more advantageous properties in this respect, but these properties change by ageing and especially at elevated temperature. Pigments of !this type are, therefore, unsuitable for processing thermoplastic materials, for example into sheets.
It is the object of t~e present invention to pro-': vide a white lead (basic lead carbonate) which does not have the aforesaid disadvantages and which is, there-fore, excellently suitable for pigmenting materials for camouflage. The basic lead carbonate of the inven-~ tion is practically free from lead oxide, has a re-- mission of at least 60 ~, and preferably at least 70 ';;~ in the ultraviolet range at 300 to ~00 nm and it i~
thermostable at a temperature up to 300C.
Z5 '~he terril "pract:ically free" :is intended to rnean that the content of lead ox:ide :is below the limit of de~ection (de~ree of~ whiteness, hollow cone method).
'~ It is another object of the invention to provide a process for the manufacture of the aforesaid new type of basic lead carbonate, which comprises dissolving highly pure lead(II)oxide in acetic acid, precipitating basic lead carbonate with carbon dioxide at temperatu-res of 10 to 40~, isolating the basic lead carbonate j and drying it under mlld conditions.
l~t li.S a further object of the present invention to provide articles of thermoplastic and elastic polymer.s which have been pigrllented with the thermostable basic lead carbonate of the invention, especia11~ sheets and other f`lat structures to be used for camouflage.
In the following preferreci embodiments of the inventioll are described in detail.
Thermostable basic leaci carbonate having an especially high degree of whiteness and a high remission in the indicated range, in pa~ticular at about 330 nm, is obtained by dissolving highl~ pure lead(II)oxide in aqueous acetic acid at room temperaSure and precipitat-ing the basic lead carbonate from this solution during a period of 1 to 3 hours and under a slight carbon di-oxide excess pressure. Alternatively, lead~II)oxide is suspended in ~ater, glacial acetic acid is added and the suspension obtained is treated with carbon dioxide under a slight excess pressure. After adjustment of a pH of 7 the introduction of carbon dioxide is terminated.
It might be advantageous to treat the suspension ` obtained with sulfurous acid. The reaction product is then isolated and dried under rnild conditions.
The lead oxide used as starting material should not contain metallic lead ~preferably less than 50 ppm), ; red lead and l:itharge of the red modification.
The lead carbonate is preferably precipitated within a period of 2 hours at room temperature under a carbon dioxide excess pressure of about 0.5 bar.
! 25 "Drying under mild oond:itions" shal.l rnean that the (Iry:ing temperature and time have to be chosen in a manner such that decomposit:ion of the reaction product i.s avolded. Preferred clrying temperatures are in the range of from 80 to 150C, in particular 100 to 120C.
For incorporating the basic lead carbonate pigment into thermoplastic and elastic polymers it should be cvnverted first into a preparation suitable for the respective purpose of application. Care has to be taken that dur:ing dispersion of the plgment no disturbing impurities, in particular no metal.lic contaminants such as abraded iron are introduced. It is quite obvious that on~y auxiliaries should be used that have the rec,uired s~ability and compatibility with basic lead carbonate.
~ 4 preparation suitable for incorporation into polyethylene she~ting is obtained by blending the pulverulent pigment with a mixture of low density polye~,hylene and low rnolecular wei~ht polyethylene, plasticizing the blend in an extruder and producing granules therefrom.
It is likewise possible to incorporate the pigment into spread coating pastes, i.e. solvent-free, homogene-ous and thermoplastic materials having a relativelyhigh plasticizer content (so-called plastisols). The thermoplast used for this purpose is preferably a , polymer on the basis of vinyl chloride or polyurethane 'or a precursor of a polyurethane. The spread coating pastes are applied in known manner onto carrier mate-rials such as fibrous materials and sheets and then ~, finished.
.
Preferred camouflage materials are sheets, in particular laMinate sheets, rnade from thermoplastic and - 20 elastic polymers into which the thermostable basic lead carbonate is incorporated. Sheet thickness and degree of pigmentation are chosen in such a manner that a complete covering is achieved. In practice, the sheets have a thickness of at least 100 l~rn, pref'erably 150 to 250 ~m. Consequently, the pigment content varies withir relatively wi,de llmit~c~ f'rom about 5 to about 80 % by weight. In the case of` em:ission ofl electromagnetic radiatiol1 in the range of 300 nm such a camouflage material according to the invention reflects 70 % of the emitted radiation. In the case of electromagnetic radiation ~i.th longer waves up to about 900 nm, the degree of remission increases to approximately 90 ~, whereas with still longer waves the degree of remission decreases again to about 60 to 70 % as it is the case with snow.
The aforesaid physical properties of the camou-flage material do not change even after prolonged time in the open. It is the same with other f'lat structures ' .
~7~26 onto which the p:Lgment of the invention has been applled by spread:ing or spraying :i.n suitable manner.
.In order to improve the mechanical stability of `.the camouflage the pigmented flat structure can be :5 stabilized by a carrier, for example a textile fabric, a wire net or another sheet, preferably a grated sheet.
The following examples illustrate the invention.
A) Preparation of the thermostable basic lead carbonate ;. , Example 1 . 2 kg of lead oxide are dissolved at room tempera-ture in 40 ~ acetic acid whereupon basic lead carbonate is precipitated from the solution under a C02 excess pressure of 0.5 bar. When a pH of 7 is reached, the suspension is decanted, mother liquor and product slurrly are separated from each other and the basic ; lead carbonate is dried at 105C.
2.3 kg of basic lead carbonate are obtained having a remission value in UV light (wave length 330 nm) of 84 %.
Example 2 ` 2 kg of lead oxide are suspensed in 9 l o~ water ~fter addition of 6 ml g 100 % aoeti.c aci.d, the suspen-sion is treated with carbon diox:ide under an exoess pressure of` 0.5 t1ar. When the pH is 7, the introduct.ion of carbon dioxide ls term:inated and the suspension obtained is treated with 20 ml of sulfurous acid. The reaction mixture is decanted and the reaction product is dried at 105C. 2.3 kg of basic lead carbonate are obtained having a remission value in UV light (wave length 330 nm) of 74 %.
! . ~) Prepapration of a pigr~ nt preparation Example 3 700 g of basic lead carbonate according to Exam-ple 1 are blended for 5 rninutes at 1,400 rpm with 200 g of low density polyethylene (density range 1, melt index range 3 according to DIN 77ll0) and 100 g of low ';
::
molecular weight ~olyetllylelle (polyethylene wax, densit~ 0.931~ m~lt viscosity 800 mPas at 140~C, drop :~ point 120C) in a rapi.d mixer. The blend is then plasticized in a double screw extruder with screws ro tating in opposite di.rections and mixing elements (screw diameter 34 rnm, screw length 408 mm, temperature i.n feeding zone 130C, in plastification zone 135 to 140C
and in the die 140C). The extruded strand ls cooled with water and air and cut into small cylinder granules having a diameter of 2.5 mm and a length of 3 mrn.
C) _reparation of a pigmented sheet _ample 4 25 parts by weight of the pigment preparation of Example 3 are blended with 75 parts by weight of low .; 15 density polyethylene and a 200 lum thick sheet is produced therefrom in known manner in a single screw extruder with chromium plated screw, chromium plated cylinder and chromium plated flat die.
..
.
~-' .
Example 2 ` 2 kg of lead oxide are suspensed in 9 l o~ water ~fter addition of 6 ml g 100 % aoeti.c aci.d, the suspen-sion is treated with carbon diox:ide under an exoess pressure of` 0.5 t1ar. When the pH is 7, the introduct.ion of carbon dioxide ls term:inated and the suspension obtained is treated with 20 ml of sulfurous acid. The reaction mixture is decanted and the reaction product is dried at 105C. 2.3 kg of basic lead carbonate are obtained having a remission value in UV light (wave length 330 nm) of 74 %.
! . ~) Prepapration of a pigr~ nt preparation Example 3 700 g of basic lead carbonate according to Exam-ple 1 are blended for 5 rninutes at 1,400 rpm with 200 g of low density polyethylene (density range 1, melt index range 3 according to DIN 77ll0) and 100 g of low ';
::
molecular weight ~olyetllylelle (polyethylene wax, densit~ 0.931~ m~lt viscosity 800 mPas at 140~C, drop :~ point 120C) in a rapi.d mixer. The blend is then plasticized in a double screw extruder with screws ro tating in opposite di.rections and mixing elements (screw diameter 34 rnm, screw length 408 mm, temperature i.n feeding zone 130C, in plastification zone 135 to 140C
and in the die 140C). The extruded strand ls cooled with water and air and cut into small cylinder granules having a diameter of 2.5 mm and a length of 3 mrn.
C) _reparation of a pigmented sheet _ample 4 25 parts by weight of the pigment preparation of Example 3 are blended with 75 parts by weight of low .; 15 density polyethylene and a 200 lum thick sheet is produced therefrom in known manner in a single screw extruder with chromium plated screw, chromium plated cylinder and chromium plated flat die.
..
.
~-' .
Claims (30)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Basic lead carbonate substantially free of lead oxide (that is below the limit of detection when measuring degree of whiteness by the hollow cone method), showing a remission of at least 60% at 300 to 800 nm and being thermo-stable up to 300°C.
2. Basic lead carbonate as claimed in claim 1, showing a remission of at least 70% at 300 to 800 nm.
3. Basic lead carbonate as claimed in claim 1, showing a remission at 330 nm of more than 70%.
4. A process for preparing the lead carbonate as claimed in claim 1, which comprises dissolving lead(II)oxide, which contains at most 50 ppm of metallic lead, red lead, and litharge in the red modification, in aqueous acetic acid, precipitating basic lead carbonate by introducing carbon dioxide at 10 to 40°C
under slight pressure, removing the precipitate and drying it at a temperature in the range of from 80°C to 150°C to avoid decomposition.
under slight pressure, removing the precipitate and drying it at a temperature in the range of from 80°C to 150°C to avoid decomposition.
5. A process as claimed in claim 4, wherein the lead(II)oxide contains at most 50 ppm of metallic lead.
6. A process as claimed in claim 4, wherein the lead(II)oxide is dissolved in about 40% by weight acetic acid at about room temperature.
7. A process as claimed in claim 4, wherein the lead(II)oxide is suspended in water and dissolved by adding concentrated acetic acid to this suspension.
8. A process as claimed in claim 4, wherein the carbon dioxide is introduced under an overpressure of about 0.5 bar.
9. A process as claimed in claim 4, wherein carbon dioxide is introduced until the pH of the reaction mixture reaches 7.
10. A process as claimed in claim 4, wherein the precipitate is aftertreated with sulfurous acid.
11. A process as claimed in claim 4, wherein the precipitate is dried at a temperature of 80 to 150°C.
12. A process as claimed in claim 4, wherein the precipitate is dried at 100 to 120°C.
13. A process as claimed in claim 4, which comprises dissolving the lead(II)oxide at about room tempera-ture in aqueous acetic acid, introducing at about room temperature carbon dioxide under an overpressure of up to 0.5 bar until a pH of 7 is reached, removing the precipitate and drying it at 100 to 120°C.
14. A composition of matter comprising a lead carbonate pigment as defined in claim 1 and an inert carrier material.
15. A composition as claimed in claim 14, wherein the carrier material is a thermoplastic or elastic polymer.
16. A composition as claimed in claim 14, which is a master-batch consisting essentially of the lead carbonate and a thermoplastic or elastic polymer.
17. A composition as claimed in claim 16, wherein the polymer is polyethylene.
18. A composition as claimed in claim 17, wherein the polymer is a mixture of low-density polyethylene and polyethylene wax.
19. A composition as claimed in claim 15 which is a spread coating paste containing a vinyl chloride polymer or a polyurethane.
20. A composition as claimed in claim 14, wherein the carrier material is formed as a flat structure.
21. A composition as claimed in claim 20 which forms one outer layer of a composite material.
22. A composition as claimed in claim 20 which is a plastic sheet.
23. A composition as claimed in claim 20 which is a polyolefin sheet.
24. A composition as claimed in claim 20 which is a polyethylene sheet.
25. A sheet as claimed in claim 24 which has a thick-ness of at least 100 µm.
26. A sheet as claimed in claim 24 which has a thick-ness of 150 to 250 µm.
27. A sheet as claimed in claim 24 which contains 5 to 80 % by weight of the lead carbonate.
28. A sheet as claimed in claim 24 which contains 5 to 20 % by weight of the lead carbonate.
29. A sheet as claimed in claim 24 which is a composite film.
30. A sheet as claimed in claim 24 showing a remission at 300 nm of about 70 %, up to 900 nm of up to about 90 % and above 900 nm of 60 to 70 %.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19792943454 DE2943454A1 (en) | 1979-10-27 | 1979-10-27 | THERMOSTABLE LEAD WHITE, METHOD FOR THE PRODUCTION THEREOF AND ITS PIGMENTED ITEMS FROM THERMOPLASTIC AND ELASTIC POLYMERS |
| DEP2943454.6 | 1979-10-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1172826A true CA1172826A (en) | 1984-08-21 |
Family
ID=6084515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000363206A Expired CA1172826A (en) | 1979-10-27 | 1980-10-24 | Thermostable lead carbonate, process for its manufacture and articles of thermoplastic and elastic polymers pigmented therewith |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0027992B1 (en) |
| JP (1) | JPS5663822A (en) |
| AT (1) | ATE4121T1 (en) |
| CA (1) | CA1172826A (en) |
| DE (2) | DE2943454A1 (en) |
| DK (1) | DK151384B (en) |
| NO (1) | NO156824C (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE263471C (en) * | ||||
| GB191208547A (en) * | 1912-04-11 | 1913-04-11 | Samuel Pope | Improvements in the Manufacture of White Lead. |
| FR520201A (en) * | 1914-10-13 | 1921-06-22 | William Phillips Thompson | White lead manufacturing process |
| GB273287A (en) * | 1926-06-22 | 1928-09-17 | Frank Taylor Bailey | Improvements in or relating to the production of white lead |
| GB500961A (en) * | 1937-08-17 | 1939-02-17 | Robinson Bros Ltd | Improvements in the manufacture of white lead |
| DE855434C (en) * | 1950-12-21 | 1952-11-13 | Fritz Dipl-Ing Lehmann | Process for the production of white lead |
| US3706585A (en) * | 1970-10-22 | 1972-12-19 | Cities Service Co | Method for producing pearlescent basic lead carbonate |
-
1979
- 1979-10-27 DE DE19792943454 patent/DE2943454A1/en not_active Withdrawn
-
1980
- 1980-10-21 DE DE8080106400T patent/DE3064149D1/en not_active Expired
- 1980-10-21 AT AT80106400T patent/ATE4121T1/en not_active IP Right Cessation
- 1980-10-21 EP EP80106400A patent/EP0027992B1/en not_active Expired
- 1980-10-24 NO NO803188A patent/NO156824C/en unknown
- 1980-10-24 JP JP14827580A patent/JPS5663822A/en active Pending
- 1980-10-24 CA CA000363206A patent/CA1172826A/en not_active Expired
- 1980-10-24 DK DK452280AA patent/DK151384B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5663822A (en) | 1981-05-30 |
| DK151384B (en) | 1987-11-30 |
| DE2943454A1 (en) | 1981-04-30 |
| DK452280A (en) | 1981-04-28 |
| NO156824C (en) | 1987-12-02 |
| ATE4121T1 (en) | 1983-07-15 |
| NO156824B (en) | 1987-08-24 |
| NO803188L (en) | 1981-04-28 |
| EP0027992B1 (en) | 1983-07-13 |
| DE3064149D1 (en) | 1983-08-18 |
| EP0027992A1 (en) | 1981-05-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |