CA2136537A1 - Manufacture of board - Google Patents
Manufacture of boardInfo
- Publication number
- CA2136537A1 CA2136537A1 CA002136537A CA2136537A CA2136537A1 CA 2136537 A1 CA2136537 A1 CA 2136537A1 CA 002136537 A CA002136537 A CA 002136537A CA 2136537 A CA2136537 A CA 2136537A CA 2136537 A1 CA2136537 A1 CA 2136537A1
- Authority
- CA
- Canada
- Prior art keywords
- fiber
- disintegrated
- board
- dried
- glue
- 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.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N1/00—Pretreatment of moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N1/00—Pretreatment of moulding material
- B27N1/003—Pretreatment of moulding material for reducing formaldehyde gas emission
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from fibres
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
- Paper (AREA)
- Laminated Bodies (AREA)
- Multicomponent Fibers (AREA)
- Artificial Filaments (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
- Harvester Elements (AREA)
- Iron Core Of Rotating Electric Machines (AREA)
- Reinforced Plastic Materials (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
A method for the manufacture of fiberboard according to the dry method starting with lignocellulose-containing material which is disintegrated, glued, dried, formed to a web and pressed. Prior to the defibering, the material is treated with an impregnation solution containing fiber surface activating chemicals and preheated.
Description
`i,, ~~ 93/2S358 ~13 6 5 3 7 PC~r/SE93/003g8 Manu~acture of board This invention relates to the manufacture of board of lignocellulose-containing material, such as fiber board.
Board of this kind is manufactured by disintegrating the material to particles containing fiber bundles and fibers. Glue is added to the disintegrated material and the material is dried and a web i5 formed which finally is pressed at increased temperature for curing the glue so that a hGiard is formed. Fiber board is made of material which is disintegrated by defibering, i.e. of more or less free fibers.
The binding agent normally used is urea formaldehyde glue~ whloh is admixed to the disintegrated material. The amount of glue can be 6% or more. The ~lue is relatively expensive, and it is therefore desired to minimize the glue addition. A smaller amount of glue, however, deteriorates the strength of the completed board. In view thereof, the glue addition must be optimized~
i" ~
~` ~ ;At the drying of the glued material, a great or small . .~, ~
~i,! ~ ~ ~' amcunt o~ water soluble formaldehyde is given off from the glue.
After the separation o~ the drying gas from the fiber material, ~h' ~ for example in a cyclonio, the liquid content is condensed ou~ of the gas. In conventional cleaning proc~ses th~ water soluble formaldehyde then causes problems. The formaldehyde following along with the material to the final pressing also can caus~
problems when it is successively given off from the completed board. When glue is added to the material after its drying, the problem with formaldehyde separation arises at the pressing as ~we~ll as from the co~pleted board.
;~Fiber board manufactured according to the dry method ~; ~normally i$ called ~DF ~Medium Density Fiberboard~ and~is a board praduct made of wood fiber. The yield exceeds 95~. The starting material preferably is wood chips, which are defibered with ;relatively low energy input, 100-500 kWh/ton fibers, for freeing the ~i~ers. The defibered fiber material is glued, dried, formed ',J~to a web and pressed in a hot press. Alterna~ively, the material can be dried prior to the gluing. The material normally is preheated prior to the defibering to above 150C whereafter the defibering is carried out under pressure at this high temperature ;l,.
.., W O 93/25358 ~ 1 3 6~ 2 PCT~SE93/00388 in order to facilita~e the freeing of the fibers. At such a high temperature, however, the material can be degrada~ed and ~ miscoloured due to occurring hydrolysis. A short heating time j~ reduces this shortcoming, but miscol~uring yet cannot be avoided, and at the same time the energy consumption increases.
The urea for~aldehyde glue normally used can be mixed with the fiber material on the conveying line (blow line) from the defibering apparatus or in a separate mixing device. The amount of admixed glue can be 6~ or more.
When the fiber material subsequently is dried in a tube drier by means of gas at high temperature, a great or small amount of water soluble formaldehyde is given off from the glue.
~s stated above, the formaldehyde following along with the fiber mate~ial to the final pressing also can cause problems when it is given off successively from the completed board. This applies especially to gluing after the drying of the material, which can be carried out at the manufacture of fiber board.
The aforesaid problems c~n be reduced by the present d~: ~ invention, which simultaneously offers further advantages.
According to the invention, the fiber material is treated with an impregnation liquid containing fiber surface activating chemicals and preheated be~ore it is finally disintegrated.
Examples of~such chemicals are such which affect the lignin, such as Na2503 and NaHS03. These chemicals can be added in an amount of 1-30 kg/ton material expressed as Na2S03. According ;~ to the invention, it is possible to increase the ISO-brightness of the completed product, to reduce the energy consumption at th~
defibering, to reduce the glue amount at maintained strength or to increase the strength at maintained glue amount. Furthermore, al~o ~he formaldehyde separation can ~e reduced substantiaily.
The inYention is described in greater detail in the ollowing with reference to some embodiments thereof.
Fiberboard is manufactured by i~pregnating the raw material in the form of chips of, for example, softwood with lignin affectlng chemicals, such as Na2S03 and NaHS03, in an amount of 1-30, preferably 10-20 kg/ton fiber material expressed 3~ ~ as Na~S03.
' !, ~
.;., I
sr~
~ ~093~25358 ~13 6 5 ~ 7 PCT/SE93/00388 The impregnation, which has to be carried out rapidly, can last some minute. Thereafter the temperature is increased to 150-200C, preferably 160-180C, for 2-3 minutes. However, the preheating can of course be performed prior to or at the same time as the impregnation. The pH value is kept within 2-12. This implies, that an impregnation solution with ~a2S03 and NaHSO3 will contain sulphite in the form of HSO3- and/or S032-. The pH value suitably can be controlled by NaOH. Due to this chemical treatment ~sulphonation~, the subsequent defibering can be carried out to the desired defibering degree with an energy input lower than normal. The energy consumption is in the interval 50-400 kWh/ton fiber material~ The energy saving can amount to about 10% compared with conventional defibering.
Owing to the impregnation, also the brightness of the completed fiber board increases.
As regards the fiber disintegration in the defibered material, it was found that both the fine material content and the shives content were reduced, i.e. the proportion of prima fiber has increased.
It~was also found at the impregnation according to the invention tha~ the strength properties of the complited board have improved substantially. The tensile~strength as well as the elasticity modules and the fiber bond have increased by at least 10%. Alternatively, thi~ effect can be utilized for reducing the amount of~glue addition at main~alned s~rength prop~rties. A 10%
increase in the fiber bond corresponds to a 1% decrease in glue addition. The sulphonation according to the invention also implies, th3it the separation of formaldehyde can be reduced, due ~, ~,!,', ~ ~ ~ to the fact, that the sulphite ions in the impregnation solution s ~ l~ reac~with the formaldehyd~ so that it is bound in thel fiber material instead of bein~ given off from the completed board.
~,, .~
i5'~ ~
.,.,,`, :
r,~
~1 .
EXAMPLE
Raw material in the form of chips was exposed to different impregnation treatment. One batch was treated with ~l 10 kg Na2SO3 per ton chips, and one batch with 10 ~g NaHSO3 per ton chips. A reference batch was not impregnated.
The different batches were preheated to about 170C and `~ thereafter defibered. In the blow line after the defibering, urea ~,j formaldehyde glue of the type E2 was added in an amount of lO~
dry glue cal ulated on dry fiber. The material was thereafter dried to a dry matter content of about 90%. The fibers were dry formed to a mat, which was prepressed with a pressure of about 1.5 MPa and hot pressed for 5-6 minutes at 170C. The board thus manufactured was tested on strength, ISO-brightness and formaldehyde content ~perforator value). The relative energy consumption for the different batches was also measured. The results were as follows:
Property Reference Na2SO3 NaHSO3 batch atch batch_ ; Bending strength MPa 38.4 43.8 40.0 Internal bond strength MPa 1.~ 2.1 2.0 .~
ISO-brightness % 24 26 26 Formaldehyde content ':d::
mg CH20/aOO g 27 ~0 18 Relative energy consumptionl.O 0.95 0.95 ~ .
The results confirm the technical effects stated above.
'~ The invention, of course, is not restricted to the embodiments described above, but can be varied within the scope of the invention idea.
~,,
Board of this kind is manufactured by disintegrating the material to particles containing fiber bundles and fibers. Glue is added to the disintegrated material and the material is dried and a web i5 formed which finally is pressed at increased temperature for curing the glue so that a hGiard is formed. Fiber board is made of material which is disintegrated by defibering, i.e. of more or less free fibers.
The binding agent normally used is urea formaldehyde glue~ whloh is admixed to the disintegrated material. The amount of glue can be 6% or more. The ~lue is relatively expensive, and it is therefore desired to minimize the glue addition. A smaller amount of glue, however, deteriorates the strength of the completed board. In view thereof, the glue addition must be optimized~
i" ~
~` ~ ;At the drying of the glued material, a great or small . .~, ~
~i,! ~ ~ ~' amcunt o~ water soluble formaldehyde is given off from the glue.
After the separation o~ the drying gas from the fiber material, ~h' ~ for example in a cyclonio, the liquid content is condensed ou~ of the gas. In conventional cleaning proc~ses th~ water soluble formaldehyde then causes problems. The formaldehyde following along with the material to the final pressing also can caus~
problems when it is successively given off from the completed board. When glue is added to the material after its drying, the problem with formaldehyde separation arises at the pressing as ~we~ll as from the co~pleted board.
;~Fiber board manufactured according to the dry method ~; ~normally i$ called ~DF ~Medium Density Fiberboard~ and~is a board praduct made of wood fiber. The yield exceeds 95~. The starting material preferably is wood chips, which are defibered with ;relatively low energy input, 100-500 kWh/ton fibers, for freeing the ~i~ers. The defibered fiber material is glued, dried, formed ',J~to a web and pressed in a hot press. Alterna~ively, the material can be dried prior to the gluing. The material normally is preheated prior to the defibering to above 150C whereafter the defibering is carried out under pressure at this high temperature ;l,.
.., W O 93/25358 ~ 1 3 6~ 2 PCT~SE93/00388 in order to facilita~e the freeing of the fibers. At such a high temperature, however, the material can be degrada~ed and ~ miscoloured due to occurring hydrolysis. A short heating time j~ reduces this shortcoming, but miscol~uring yet cannot be avoided, and at the same time the energy consumption increases.
The urea for~aldehyde glue normally used can be mixed with the fiber material on the conveying line (blow line) from the defibering apparatus or in a separate mixing device. The amount of admixed glue can be 6~ or more.
When the fiber material subsequently is dried in a tube drier by means of gas at high temperature, a great or small amount of water soluble formaldehyde is given off from the glue.
~s stated above, the formaldehyde following along with the fiber mate~ial to the final pressing also can cause problems when it is given off successively from the completed board. This applies especially to gluing after the drying of the material, which can be carried out at the manufacture of fiber board.
The aforesaid problems c~n be reduced by the present d~: ~ invention, which simultaneously offers further advantages.
According to the invention, the fiber material is treated with an impregnation liquid containing fiber surface activating chemicals and preheated be~ore it is finally disintegrated.
Examples of~such chemicals are such which affect the lignin, such as Na2503 and NaHS03. These chemicals can be added in an amount of 1-30 kg/ton material expressed as Na2S03. According ;~ to the invention, it is possible to increase the ISO-brightness of the completed product, to reduce the energy consumption at th~
defibering, to reduce the glue amount at maintained strength or to increase the strength at maintained glue amount. Furthermore, al~o ~he formaldehyde separation can ~e reduced substantiaily.
The inYention is described in greater detail in the ollowing with reference to some embodiments thereof.
Fiberboard is manufactured by i~pregnating the raw material in the form of chips of, for example, softwood with lignin affectlng chemicals, such as Na2S03 and NaHS03, in an amount of 1-30, preferably 10-20 kg/ton fiber material expressed 3~ ~ as Na~S03.
' !, ~
.;., I
sr~
~ ~093~25358 ~13 6 5 ~ 7 PCT/SE93/00388 The impregnation, which has to be carried out rapidly, can last some minute. Thereafter the temperature is increased to 150-200C, preferably 160-180C, for 2-3 minutes. However, the preheating can of course be performed prior to or at the same time as the impregnation. The pH value is kept within 2-12. This implies, that an impregnation solution with ~a2S03 and NaHSO3 will contain sulphite in the form of HSO3- and/or S032-. The pH value suitably can be controlled by NaOH. Due to this chemical treatment ~sulphonation~, the subsequent defibering can be carried out to the desired defibering degree with an energy input lower than normal. The energy consumption is in the interval 50-400 kWh/ton fiber material~ The energy saving can amount to about 10% compared with conventional defibering.
Owing to the impregnation, also the brightness of the completed fiber board increases.
As regards the fiber disintegration in the defibered material, it was found that both the fine material content and the shives content were reduced, i.e. the proportion of prima fiber has increased.
It~was also found at the impregnation according to the invention tha~ the strength properties of the complited board have improved substantially. The tensile~strength as well as the elasticity modules and the fiber bond have increased by at least 10%. Alternatively, thi~ effect can be utilized for reducing the amount of~glue addition at main~alned s~rength prop~rties. A 10%
increase in the fiber bond corresponds to a 1% decrease in glue addition. The sulphonation according to the invention also implies, th3it the separation of formaldehyde can be reduced, due ~, ~,!,', ~ ~ ~ to the fact, that the sulphite ions in the impregnation solution s ~ l~ reac~with the formaldehyd~ so that it is bound in thel fiber material instead of bein~ given off from the completed board.
~,, .~
i5'~ ~
.,.,,`, :
r,~
~1 .
EXAMPLE
Raw material in the form of chips was exposed to different impregnation treatment. One batch was treated with ~l 10 kg Na2SO3 per ton chips, and one batch with 10 ~g NaHSO3 per ton chips. A reference batch was not impregnated.
The different batches were preheated to about 170C and `~ thereafter defibered. In the blow line after the defibering, urea ~,j formaldehyde glue of the type E2 was added in an amount of lO~
dry glue cal ulated on dry fiber. The material was thereafter dried to a dry matter content of about 90%. The fibers were dry formed to a mat, which was prepressed with a pressure of about 1.5 MPa and hot pressed for 5-6 minutes at 170C. The board thus manufactured was tested on strength, ISO-brightness and formaldehyde content ~perforator value). The relative energy consumption for the different batches was also measured. The results were as follows:
Property Reference Na2SO3 NaHSO3 batch atch batch_ ; Bending strength MPa 38.4 43.8 40.0 Internal bond strength MPa 1.~ 2.1 2.0 .~
ISO-brightness % 24 26 26 Formaldehyde content ':d::
mg CH20/aOO g 27 ~0 18 Relative energy consumptionl.O 0.95 0.95 ~ .
The results confirm the technical effects stated above.
'~ The invention, of course, is not restricted to the embodiments described above, but can be varied within the scope of the invention idea.
~,,
Claims (5)
1. A method of manufacturing fiberboard according to the dry method starting with lignocellulose-containing material which is disintegrated, glued, dried, formed to a web and pressed, c h a r a c t e r i z e d in that the material, before it is finally disintegrated is treated with an impregnation solution containing fiber surface activating chemicals in an amount of 1-30 kg/ton fiber material, expressed as Na2SO3, and preheated to 150-200°C whereby the pH value is kept within 2-12 and that the disintegration is performed with an energy input of 50-400 kWh/ton fiber material.
2. A method as defined in claim 1, c h a r a c t e r i z e d in that the fiber surface activating chemicals are of a type affecting the lignin.
3. A method as defined in claim 2, c h a r a c t e r i z e d in that the impregnation solution contains Na2SO3 and/or NaHSO3.
4. A method as defined in anyone of claims 1-3, c h a r a c t e r i z e d in that the disintegrated material first is glued and thereafter dried before it is formed to a web.
5. A method as defined in anyone of claims 1-3, c h a r a c t e r i z e d in that the disintegrated material first is dried and thereafter glued before it is formed to a web.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE9201800A SE470330B (en) | 1992-06-11 | 1992-06-11 | Process for making fiberboard according to the dry method |
| SE9201800-1 | 1992-06-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2136537A1 true CA2136537A1 (en) | 1993-12-23 |
Family
ID=20386472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002136537A Abandoned CA2136537A1 (en) | 1992-06-11 | 1993-05-04 | Manufacture of board |
Country Status (29)
| Country | Link |
|---|---|
| EP (1) | EP0647174B1 (en) |
| JP (1) | JPH07507735A (en) |
| KR (1) | KR950701267A (en) |
| CN (1) | CN1029461C (en) |
| AT (1) | ATE143625T1 (en) |
| AU (1) | AU662432B2 (en) |
| BR (1) | BR9306513A (en) |
| CA (1) | CA2136537A1 (en) |
| CZ (1) | CZ281548B6 (en) |
| DE (1) | DE69305165T2 (en) |
| DK (1) | DK0647174T3 (en) |
| ES (1) | ES2095060T3 (en) |
| FI (1) | FI97032C (en) |
| HR (1) | HRP930967A2 (en) |
| HU (1) | HU213466B (en) |
| ID (1) | ID841B (en) |
| IL (1) | IL105811A (en) |
| MY (1) | MY131192A (en) |
| NO (1) | NO944779D0 (en) |
| NZ (1) | NZ253367A (en) |
| PL (1) | PL170405B1 (en) |
| RU (1) | RU2083359C1 (en) |
| SE (1) | SE470330B (en) |
| SI (1) | SI9300293A (en) |
| SK (1) | SK153094A3 (en) |
| TR (1) | TR28107A (en) |
| TW (1) | TW223036B (en) |
| WO (1) | WO1993025358A1 (en) |
| ZA (1) | ZA934108B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TR22594A (en) * | 1987-04-07 | 1987-12-15 | Nur Emaye San Ve Tic Tic A S | STOVE PIPE EXTENSION APPARATUS |
| DE4327774A1 (en) * | 1993-08-18 | 1995-02-23 | Fraunhofer Ges Forschung | Process for the production of medium density fibreboard (MDF) |
| PL184356B1 (en) * | 1996-04-12 | 2002-10-31 | Marlit Ltd | Method of obtaining composite lignocellulose materials |
| GB9625068D0 (en) * | 1996-12-02 | 1997-01-22 | Marlit Ltd | Method for production of lignocellulosic composite materials |
| EP0852174B1 (en) | 1996-12-09 | 2003-07-09 | Plato International Technology B.V. | Process for preparing cellulosic fibrous aggregates |
| EP1011939B1 (en) * | 1997-07-11 | 2001-09-05 | Marlit Ltd. | Manufacture of composite boards |
| EP1799412B1 (en) * | 2004-10-15 | 2011-01-19 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for reducing the release of volatile organic compounds (voc) from wood and wood chip products and wood materials derived therefrom in particular particle boards |
| CN101351313B (en) * | 2005-07-27 | 2011-06-01 | 克罗诺普拉斯技术股份公司 | Method for preparing timber product emitting little chemical compound and timber products produced therefor |
| SE0601816L (en) * | 2006-09-04 | 2008-02-26 | Metso Panelboard Ab | Manufacture of wood fiber board containing on-site generated formaldehyde |
| DE102007054123B4 (en) | 2006-11-15 | 2012-03-15 | Edmone Roffael | Process for the production of fiberboard with reduced formaldehyde emission, high moisture resistance and hydrolysis resistance of the gluing |
| DE102007038041A1 (en) † | 2007-08-10 | 2009-02-12 | Kronotec Ag | Method for preventing the emission of aldehydes and volatile organic compounds from wood-based materials |
| DE102008023007A1 (en) | 2007-11-11 | 2010-06-02 | Roffael, Edmone, Prof. Dr.-Ing. | Method for producing moisture-resistant and hydrolysis-resistant medium density fiberboard from e.g. derived timber product, involves using chemicals for pulping, where chemicals partially or completely replace resin in gluing phase |
| DE102007055415C5 (en) * | 2007-11-19 | 2018-11-29 | SWISS KRONO Tec AG | Method for reducing the emission of saturated and unsaturated aldehydes from wood-based materials |
| DE102008050428A1 (en) | 2008-10-08 | 2010-06-10 | Roffael, Edmone, Prof. Dr.-Ing. | Medium-density fiberboard manufacturing method, involves performing disintegration of fiber plates in presence of accelerator provided for alkaline hardening phenol formaldehyde resin and as potassium carbonate and/or sodium carbonate |
| CN101786286B (en) * | 2010-04-20 | 2012-04-25 | 东北林业大学 | Manufacturing method for modified enzymolysis lignin composite board |
| CN104690804B (en) * | 2015-02-14 | 2017-07-18 | 广西丰林木业集团股份有限公司 | A kind of manufacture method of electro-magnetic screen function fiberboard |
| EP3059056A1 (en) * | 2015-02-23 | 2016-08-24 | Basf Se | Method for producing wood fibres and wood fibre boards |
| CN109986676A (en) * | 2019-04-06 | 2019-07-09 | 安徽凯彦达环保餐具有限公司 | A kind of production technology for the disposable lunch-box that can be degraded in a natural environment |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD205382A1 (en) * | 1981-12-23 | 1983-12-28 | Heinz Pecina | METHOD FOR ACTIVATING WOODEN PARTICLES FOR WOOD PRODUCTION OF MATERIALS |
| DD242193A1 (en) * | 1985-11-06 | 1987-01-21 | Univ Dresden Tech | METHOD FOR PRODUCING WOOD MATERIALS |
| SE466060C (en) * | 1990-02-13 | 1995-09-11 | Moelnlycke Ab | Absorbent chemitermomechanical mass and preparation thereof |
| SU1721149A1 (en) * | 1990-06-25 | 1992-03-23 | Центральный научно-исследовательский институт бумаги | Method of producing thermochemically-treated pulp |
| SU1724763A1 (en) * | 1990-07-10 | 1992-04-07 | Центральный научно-исследовательский институт бумаги | Method of producing bleached wood pulp |
-
1992
- 1992-06-11 SE SE9201800A patent/SE470330B/en not_active IP Right Cessation
-
1993
- 1993-05-04 RU RU9394046252A patent/RU2083359C1/en active
- 1993-05-04 JP JP6501367A patent/JPH07507735A/en active Pending
- 1993-05-04 SK SK1530-94A patent/SK153094A3/en unknown
- 1993-05-04 EP EP93913692A patent/EP0647174B1/en not_active Revoked
- 1993-05-04 KR KR1019940703807A patent/KR950701267A/en not_active Application Discontinuation
- 1993-05-04 BR BR9306513A patent/BR9306513A/en not_active Application Discontinuation
- 1993-05-04 AU AU43633/93A patent/AU662432B2/en not_active Ceased
- 1993-05-04 AT AT93913692T patent/ATE143625T1/en not_active IP Right Cessation
- 1993-05-04 CA CA002136537A patent/CA2136537A1/en not_active Abandoned
- 1993-05-04 DE DE69305165T patent/DE69305165T2/en not_active Revoked
- 1993-05-04 WO PCT/SE1993/000388 patent/WO1993025358A1/en not_active Application Discontinuation
- 1993-05-04 NZ NZ253367A patent/NZ253367A/en unknown
- 1993-05-04 HU HU9403101A patent/HU213466B/en not_active IP Right Cessation
- 1993-05-04 PL PL93306760A patent/PL170405B1/en unknown
- 1993-05-04 DK DK93913692.5T patent/DK0647174T3/en active
- 1993-05-04 CZ CZ943088A patent/CZ281548B6/en unknown
- 1993-05-04 ES ES93913692T patent/ES2095060T3/en not_active Expired - Lifetime
- 1993-05-17 TW TW082103924A patent/TW223036B/zh active
- 1993-05-20 CN CN93106167A patent/CN1029461C/en not_active Expired - Fee Related
- 1993-05-21 MY MYPI93000970A patent/MY131192A/en unknown
- 1993-05-25 IL IL10581193A patent/IL105811A/en not_active IP Right Cessation
- 1993-06-02 SI SI9300293A patent/SI9300293A/en unknown
- 1993-06-08 ID IDP614393A patent/ID841B/en unknown
- 1993-06-10 ZA ZA934108A patent/ZA934108B/en unknown
- 1993-06-11 TR TR00460/93A patent/TR28107A/en unknown
- 1993-06-11 HR HR930967A patent/HRP930967A2/en not_active Application Discontinuation
-
1994
- 1994-12-09 NO NO944779A patent/NO944779D0/en unknown
- 1994-12-09 FI FI945790A patent/FI97032C/en not_active IP Right Cessation
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |