CN1268599A - Pulp of paper for decoration use - Google Patents
Pulp of paper for decoration use Download PDFInfo
- Publication number
- CN1268599A CN1268599A CN00108301A CN00108301A CN1268599A CN 1268599 A CN1268599 A CN 1268599A CN 00108301 A CN00108301 A CN 00108301A CN 00108301 A CN00108301 A CN 00108301A CN 1268599 A CN1268599 A CN 1268599A
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- CN
- China
- Prior art keywords
- paper
- pulp
- decoration use
- cation
- mixture
- Prior art date
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/20—Chemically or biochemically modified fibres
- D21H11/22—Chemically or biochemically modified fibres cationised
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Paper (AREA)
- Laminated Bodies (AREA)
Abstract
A decorative paper base for manufacturing decorative papers or decorative films, formed out of a paper pulp containing pulp fibers and fillers, has a non-modified and cationically modified pulp as the pulp mixture, which yields an improved strength of the decorative paper base.
Description
The present invention relates to a kind of pulp of paper for decoration use, decorating film or the decoration laminated plastic of making by it.
In the furniture manufacture process and when carrying out inner finishing process, preferably use that to decorate with coating material be that so-called pulp of paper for decoration use or decorating film are used for surface coated.Decorating film comprises that artificial resin floods or artificial resin dipping and paper web surface treated, printing or that do not print.Decorating film is adhered on the pressing plate.
Have the classification that difference between the decorating film of the decorating film of thorough impregnation refill and prepreg depends on impregnation technology, in the decorating film of prepreg, paper is only at ground, paper machine top dipping.Laminated plastic (high-pressure laminating material) is to make by several impregnated papers that are laminated together are suppressed.The structure of these laminated plastics generally is by a transparent overlay coating (can produce the highest skin resistance), and an artificial resin impregnation facing paper and scribbles the brown paper of phenolic resins and forms.Hardboard, shaving board and glued board are the materials that can be used as base material.
In pressing the laminated material (low-pressure lamination material) of short period explained hereafter, the facing paper that is impregnated with artificial resin directly under low pressure is embossed in the base material of for example backing plate.
The facing paper that uses in above-mentioned coating material can be white or painted and can have and not have additional impression.
As the original material that is used to make above-mentioned coating material, this pulp of paper for decoration use has special requirement, for example to have high opacity for better covering substrates, sheet material formation uniformly and grammature are to guarantee uniform resin paper injection, high light resistance, high purity and color uniformity are to guarantee the well reproduced of pattern to be printed, high resistance to water is to guarantee carrying out smoothly of dipping process, suitable absorbability is to realize required resin saturation degree, the dry strength when carrying out the dry strength during the processing of roll-in again on the paper machine and printing on printing machine.
Pulp of paper for decoration use generally is by the high white sulfate pulp that is mainly hard wood pulp, reaches as high as 45% pigment and filler and wet strength agent, and retention agents and fixative are formed.What pulp of paper for decoration use was different with conventional paper is that it contains very a high proportion of filler, and does not use known sizing agent to resemble alkyl ketene dimer paper is carried out conventional inside or top sizing.
Opaque is to decorate one of most important characteristic of paper substrate.It is characterized in that covering power with respect to base material.Opaque fully in order to guarantee, the filler of adding high-load in fibrous material.For filler well is retained in the sheet material, various retention agents are added in the paper pulp.Can be on the other hand, along with the increase of pigment and proportion of filler, the intensity of paper and saturating machine will be detracted.
Passing printing machine or carrying out on paper machine in the process of the processing of roll-in again, the intensity of pulp of paper for decoration use particularly dry strength is very important for continuous production.
When using the water-soluble resin system to come dipping decorative paper, wet tensile (strength) is very important.Wet tensile (strength) is defined as the mechanical load ability under wet condition.And this generally is to realize by adding wet strength agent in the process of papermaking.
Because the requirement that will make pulp of paper for decoration use satisfy each side simultaneously is difficult to, so still need to improve known pulp of paper for decoration use.Particularly aspect the opaque and strength character of paper substrate.
Therefore, the purpose of this invention is to provide a kind of high mechanical properties that has, the pulp of paper for decoration use of high opaque and sufficient absorbability (dipping capacity).
This purpose realizes by using pulp of paper for decoration use, and the paper pulp that this paper substrate is made up of paper pulp fiber and filler and traditional auxiliary agent constitute, and wherein paper pulp fiber is made up of with cation-modified pulp mixture non-modification.
Even do not add dry strength agent in paper suspension, but its dry strength of surprised discovery is improved.Add cation-modified paper pulp and can not reduce other important performance of pulp of paper for decoration use, for example flood capacity or opacity.
Cation-modified equal paper pulp comprises that those come from DASPAPIER, Issue12 (1980), the paper pulp that pp.575-579 is known.Their the uses in pulp of paper for decoration use and the increase of the intensity that realized all can not be collected from prior art.
Pulp mixture preferably contains with respect to the weight of the pulp mixture cation-modified paper pulp fiber of 5wt.% ratio at least.The ratio that has now confirmed the cation-modified paper pulp in the pulp mixture is that 10～50wt.% is especially favourable during 10～20wt.% particularly.
In a specific embodiment of the present invention, being contained in the shown effective cationic charge that goes out of cation-modified paper pulp in the paper pulp is 20～300mmol/kg paper pulp, and it is to measure according to the internalist methodology 4 of DarmstadtTechnical University.Preferably has the paper pulp fiber that charge density is 30～200mmol/kg, particularly 30～100mmol/kg.Term " effectively cationic charge " is understood that charge density, and this charge density will distinguish with the charge density in the paper pulp of non-cationicization.Charge density in the paper pulp depends on the amount of employed cation reagent.The amount of cationics is every 1kg paper pulp 0.005～200g.
Paper pulp fiber cation-modified by fiber and epoxychloropropane and reactive tertiary amine are realized, or by for example chloro hydroxypropyl trimethyl ammonium chloride or glycidyl trimethylammonium chloride reaction realize with aliquat.
In addition, paper pulp fiber can through charged monomer for example [2-(methacryl oxygen base) ethyl] trimethyl ammonium chloride (TMAEMA) stop up with free radical and realize cationization such as the neutral comonomer of acrylamide.
In a preferred embodiment of the invention, used paper pulp fiber is glycidol functional group in quaternary ammonium compound and the addition reaction between the hydroxyl in the paper pulp and carry out cation-modified.
The paper pulp of non-modification and cation-modified paper pulp preferably have the staple fibre paper pulp that average fiber length is 0.5～0.7mm, but also can use the mixture of long fibered pulp or two kinds of paper pulp types.Staple fibre paper pulp comprises willow, beech or by tree bardwood pulp, preferred eucalyptus.The preferred freedom value of paper pulp is 30～45 ° of SR.
Appropriate filler comprises titanium dioxide, particularly rutile-type, zinc sulphide, calcium carbonate, kaolin, talcum or its mixture.Especially preferably use Al
2O
3Carry out the surface-treated rutile titanium dioxide.The ratio of filler reaches as high as 55wt.% in pulp of paper for decoration use, especially between 20～45wt.%.
Wet strength agent comprises melamine/formaldehyde resin, polyamine derivatives or polyamide derivative, and its consumption is 0.3～2wt.% with respect to the weight of paper pulp.
The material that pulp of paper for decoration use can contain other for example organically and the pigment of organic coloring, dyestuff, Optical Bleaching Agent and dispersion, they can add when the paper suspension of manufacturing pulp of paper for decoration use.
Pulp of paper for decoration use of the present invention can be produced on paper machine in known manner, and its grammature scope is at 50～200g/m
2Between.For this purpose, it is 30～45 ° of SR that the pulp mixture of being made up of the paper pulp of cation-modified paper pulp and non-modification is refined into the freedom value, and concentration is 2～4wt.%.Filler and warm strength agents are added in the mixing channel and with pulp mixture and mix up hill and dale.It is about 1% that the thick material that obtains in this way is diluted into concentration, if necessary, can with other auxiliary agent retention agents for example, defoamer, aluminum sulfate and possible wet strength agent are used in combination.This rare material was collected wet end through the flow box of paper machine.Fibrous web is formed, and in dehydration, obtains pulp of paper for decoration use after the drying.
In order to make facing paper, flood or saturated pulp of paper for decoration use with the artificial resin dispersion that is generally used for this purpose.The artificial resin dispersion that is generally used for this purpose comprises based on those of polypropylene-base ester or polypropylene-base methyl ester, polyvinyl acetate, polyvinyl chloride or based on phenol/formaldehyde, the artificial resin solution of urea/formaldehyde or melamine/formaldehyde precondensate or its compatible blend.
Dipping also can carry out in the process of the size press of paper machine.Flooding pulp of paper for decoration use in this way is in order not allow paper on thorough impregnation on its entire path of passing through.This facing paper is also referred to as prepreg members.In the case, the ratio that is incorporated into resin in the pulp of paper for decoration use through dipping is 25～30wt.% with respect to the weight of paper.
After drying, saturated paper also can paint and print, and can be applied to a base material subsequently for example on the plank.Product japanning and printing (if necessary) is commonly referred to as decorating film.
The present invention will do to describe in further detail with the following examples.Except illustrating separately, data all are the percentage by weights with respect to paper pulp weight.
Embodiment 1
One pulp mixture, it by 16.7wt.% through glycidyl trimethylammonium chloride (Quab
151) eucalyptus pulps of modification, its charge density are 34.8mmol/kg and have the standard eucalyptus pulps composition that flat fibre length is the 83.3wt.% of 0.7mm that this pulp mixture is refined into the freedom value under 3% concentration be 33 ° of SR.Then, with 100wt.%TiO
2(rutile, d=3.9g/m
3) and 2wt.% polyamide/polyamine-epichlorohydrin resin be added in the pulp suspension, be 97g/m by its G.S.M of paper substrate of its manufacturing
2
Embodiment 2
One pulp mixture, it is by the eucalyptus pulps through the glycidyl trimethylammonium chloride modification of 50wt.%, its charge density is that the standard eucalyptus pulps of 34.8mmol/kg and 50wt.% is formed, and this pulp mixture is refined into the freedom value under 3% concentration be 33 ° of SR.Other material of enumerating in embodiment 1 is added in the pulp suspension, is 95g/m by its G.S.M of paper substrate of its manufacturing
2
Embodiment 3
One pulp mixture, it by 16.7wt.% through glycidyl trimethylammonium chloride (Quab
151) eucalyptus pulps of modification, its charge density are that the standard eucalyptus pulps of 65.5mmol/kg and 83.3wt.% is formed, and this pulp mixture is refined into the freedom value under 3% concentration be 38 ° of SR.Then, other material of enumerating in embodiment 1 is added in the pulp suspension, is 95g/m by its G.S.M of paper substrate of its manufacturing
2
Embodiment 4
One pulp mixture, it by 16wt.% through 3-chloro-2-hydroxypropyl dimethyl dodecyl chlorination ammonium (Quab
342) eucalyptus pulps of modification, its charge density is that the standard eucalyptus pulps of 56.5mmol/kg and 84wt.% is formed, this pulp mixture under 3% concentration, be refined into the freedom value be 39 ° of SR. then, other material of enumerating in embodiment 1 is added in the pulp suspension, is 95g/m by its G.S.M of paper substrate of its manufacturing
2
Embodiment 5
One pulp mixture; it is that the 16.7wt.% of 153.7mmol/kg forms through 2-(methacryl oxygen base) ethyl-trimethyl salmiac and acrylic amide modified eucalyptus pulps and the standard eucalyptus pulps of 83.3wt.% by having charge density; this pulp mixture is made with extra care according to the method for embodiment 1 and is processed into paper substrate with same material (pigment and wet strength agent), and its G.S.M is 96g/m
2
Comparative example
By embodiment 1 various materials are added in the pulp suspension, it is that the standard eucalyptus pulps of 36 ° of SR is formed that this suspension has 3% concentration and paper pulp fiber freedom value by 100wt.%, is 94g/m by the paper substrate G.S.M of its manufacturing
2
The test of the pulp of paper for decoration use that obtains according to embodiment and comparative example
Test program below using is assessed the pulp of paper for decoration use of making
The cationic charge of measurement in paper pulp
Measure according to Darmstadt Technical University internalist methodology 4.The measuring method that is used for measuring the paper pulp cation group is a kind of colorimetric program.Colorimetric method use the dyestuff ion of dyestuff methyl orange come in and in the fiber and the electric charge on the fiber.Dyestuff ion in this process in the solution is depleted gradually.The available UV spectroscope of the minimizing of this concentration is surveyed.The amount of the methyl orange of being adsorbed by cation group count the amount of the methyl orange of colorimetric estimation in blank sample (blind sample) and the amount of the methyl orange in residual sample, measured between difference.The content of cation group is represented with mmol/kg.
Resin absorption [%]
The purpose of this test is the ability that the assessment facing paper absorbs melamine resin.For this purpose, (15 * 100mm) are immersed among the melamine resin MW550, on the flat surface blotting paper being placed between two bars, load for 15 seconds with contact weight, and then weigh with two test bars.The absorption of resin is calculated with the weighed amount percentage composition.
Opaque
Opaque is the photopermeability that is used for measuring paper.Use the Elrepho2000 colorimeter to measure to 8 * 8cm paper test bar.
Dry tensile strength
This test is used for measuring the tensile strength and the extensibility of paper substrate.The paper slip that it uses 15 * 200mm is by Lorentzen﹠amp; Finish according to DIN53112 on the tensile test instrument that Wettre makes and represent this value with N.Numerical value is high more, and dry strength is just good more.
Wet tensile (strength)
The test of being carried out is to be used for assessing the wet tensile (strength) of paper substrate.For this purpose, test bar that 15mm is wide is immersed in the distilled water 5 minutes.Then, the wet tensile (strength) of the wet bar of test on tensile testing machine.The value of measuring is represented with N.Numerical value is low more, and wet strength is just poor more.
Content of ashes
1g was handled 30 minutes under 23 ℃/50% relative humidity with the paper of bar form at least, be introduced into then to burn in the incinerator and incinerate.Ash content is transported in the porcelain crucible and weighs.The ash content of representing with % comes from the amount that weighs up with g * 100.This content of ashes can be converted into g/m
2
Table 1 has been summed up the result of test.
Table 1
| Test | Embodiment | Comparative example | ||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ||
| Dry tensile strength, N | ??30.0 | ???32.0 | ??29.6 | ???25.1 | ???29.6 | ???24.4 |
| Wet tensile (strength) [N] | ???6.1 | ????6.0 | ???4.8 | ????4.8 | ????6.1 | ????6.1 |
| Content of ashes [g/m 2] | ??33.2 | ???34.0 | ??32.4 | ???32.0 | ???32.4 | ???32.0 |
| Opaque [%] | ??91.4 | ???91.0 | ??91.7 | ???91.4 | ???91.0 | ???91.1 |
| Resin absorption [%] | ??85.5 | ???85.5 | ??84.6 | ???84.8 | ???85.0 | ???85.4 |
The result shows that the dry strength of decorating paper substrate is improved by using cation-modified paper pulp, does not wherein need to use in addition dry strength agent.Dipping capacity and opacity that the present invention decorates paper substrate are very excellent.Even can be observed the raising of used filler retention.
All observing in several tests by the ratio of increase wet strength agent or by adding anionic species to make wet strength be reduced to desirable degree.
Claims (8)
1. pulp of paper for decoration use, it is formed by the paper pulp that contains paper pulp fiber and filler, it is characterized in that described paper pulp contains a pulp mixture, and this mixture is made up of with cation-modified paper pulp non-modification.
2. according to the pulp of paper for decoration use of claim 1, it is characterized in that effective cationic charge that cation-modified paper pulp demonstrates is 20～300mmol/kg.
3. according to the pulp of paper for decoration use of claim 1 or 2, it is characterized in that paper pulp fiber comes modification with the quaternary ammonium compound with glycidol functional group.
4. according to the pulp of paper for decoration use of one of claim 1～3, it is characterized in that the amount of the cation-modified paper pulp in pulp mixture is at least 5wt.%.
5. according to the pulp of paper for decoration use of one of claim 1～4, it is characterized in that cation-modified paper pulp is staple fibre paper pulp.
6. according to the pulp of paper for decoration use of one of claim 1～5, it is characterized in that paper pulp contains wet strength agent, its content is 0.3～2wt.% with respect to paper pulp amount.
7. according to the pulp of paper for decoration use of one of claim 1～5, it is characterized in that filler is a titanium dioxide, calcium carbonate, kaolin, talcum or its mixture.
8. facing paper or decorating film contain the pulp of paper for decoration use of one of with good grounds claim 1～7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19912149A DE19912149C2 (en) | 1999-03-18 | 1999-03-18 | Decorative paper with improved dry strength as well as decor paper or decorative foil produced with it |
| DE19912149.4 | 1999-03-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1268599A true CN1268599A (en) | 2000-10-04 |
| CN1330826C CN1330826C (en) | 2007-08-08 |
Family
ID=7901468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001083015A Expired - Lifetime CN1330826C (en) | 1999-03-18 | 2000-03-17 | Pulp of paper for decoration use |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP1036881B1 (en) |
| JP (1) | JP3242388B2 (en) |
| CN (1) | CN1330826C (en) |
| AT (1) | ATE280858T1 (en) |
| BR (1) | BR0001377B1 (en) |
| CA (1) | CA2301300C (en) |
| DE (2) | DE19912149C2 (en) |
| ES (1) | ES2231060T3 (en) |
| PL (1) | PL198822B1 (en) |
| PT (1) | PT1036881E (en) |
| SI (1) | SI1036881T1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108824089A (en) * | 2018-08-16 | 2018-11-16 | 佛山舒宜添科技有限公司 | A kind of decorating base paper and its preparation process with good crack resistance energy |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10057294C5 (en) * | 2000-11-17 | 2005-06-30 | Technocell Dekor Gmbh & Co. Kg | Decorative paper with high opacity, as well as decorative paper or decorative foil |
| ES2234748T3 (en) | 2000-11-17 | 2005-07-01 | TECHNOCELL DEKOR GMBH & CO. KG | PAPER DECORATIVE SUPPORT OF A HIGH OPACITY. |
| DE10115570B4 (en) * | 2001-03-28 | 2005-09-08 | Technocell Dekor Gmbh & Co. Kg | Decorative paper with improved opacity |
| DE20318290U1 (en) * | 2003-11-26 | 2004-04-01 | M. Kaindl | Antistatic paper and panel |
| CA2709822C (en) * | 2007-12-17 | 2014-10-07 | Technocell Dekor Gmbh & Co. Kg | Compressible decorative paper impregnate which can be printed by the ink jet method |
| DE102010016864B4 (en) | 2010-05-10 | 2018-09-27 | Papierfabrik Julius Schulte Söhne GmbH & Co. KG | Fibrous core paper, process for its preparation and its use |
| DE102013100353A1 (en) | 2012-01-12 | 2013-08-22 | Bene_Fit Systems Gmbh & Co. Kg | Reactive composite, useful as filler in paper, comprises carrier and titanium dioxide that are connected to form stable aggregates, and organic reaction product as binder adapted to form chemical and/or physical bond by a reaction |
| WO2014166972A1 (en) | 2013-04-12 | 2014-10-16 | Bauschlinnemann Gmbh | Decorative self-adhesive film |
| DE202013003421U1 (en) | 2013-04-12 | 2013-04-30 | Bauschlinnemann Gmbh | Decorative self-adhesive film |
| DE102013006278A1 (en) | 2013-04-12 | 2014-10-16 | Bauschlinnemann Gmbh | Decorative self-adhesive film |
| CN103510429B (en) * | 2013-10-31 | 2015-05-20 | 浙江科技学院 | Compound flame-retardant paper-based material and preparation method thereof |
| PT2944621T (en) | 2014-05-15 | 2017-07-05 | Omya Int Ag | Fiber board product comprising a calcium carbonate-containing material |
| DE102014009273A1 (en) | 2014-06-26 | 2016-01-14 | Hülsta-Werke Hüls Gmbh & Co. Kg | Decor system for a floor, wall or ceiling covering or for a furniture component |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5496521A (en) * | 1978-01-17 | 1979-07-31 | Toppan Printing Co Ltd | Dress paper for gypsum board and method of making dressed gypsum board |
| US4505775A (en) * | 1983-06-24 | 1985-03-19 | Weyerhaeuser Company | Method for preparation of cationic cellulose |
| JPH06184999A (en) * | 1990-12-28 | 1994-07-05 | Pioneer Cone Corp | Dyeing of decorative paper |
| JP3711477B2 (en) * | 1995-07-19 | 2005-11-02 | 三島製紙株式会社 | Multifunctional decorative paper |
| DE19728796A1 (en) * | 1997-07-05 | 1999-01-07 | Robert Cordier Ag | Raw decorative paper |
-
1999
- 1999-03-18 DE DE19912149A patent/DE19912149C2/en not_active Expired - Lifetime
-
2000
- 2000-03-11 SI SI200030528T patent/SI1036881T1/en unknown
- 2000-03-11 ES ES00105181T patent/ES2231060T3/en not_active Expired - Lifetime
- 2000-03-11 DE DE50008377T patent/DE50008377D1/en not_active Expired - Fee Related
- 2000-03-11 EP EP20000105181 patent/EP1036881B1/en not_active Expired - Lifetime
- 2000-03-11 AT AT00105181T patent/ATE280858T1/en not_active IP Right Cessation
- 2000-03-11 PT PT00105181T patent/PT1036881E/en unknown
- 2000-03-17 CA CA002301300A patent/CA2301300C/en not_active Expired - Lifetime
- 2000-03-17 JP JP2000075192A patent/JP3242388B2/en not_active Expired - Fee Related
- 2000-03-17 CN CNB001083015A patent/CN1330826C/en not_active Expired - Lifetime
- 2000-03-17 PL PL339072A patent/PL198822B1/en unknown
- 2000-03-20 BR BRPI0001377-3A patent/BR0001377B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108824089A (en) * | 2018-08-16 | 2018-11-16 | 佛山舒宜添科技有限公司 | A kind of decorating base paper and its preparation process with good crack resistance energy |
Also Published As
| Publication number | Publication date |
|---|---|
| SI1036881T1 (en) | 2005-02-28 |
| EP1036881B1 (en) | 2004-10-27 |
| PT1036881E (en) | 2005-02-28 |
| ATE280858T1 (en) | 2004-11-15 |
| CA2301300A1 (en) | 2000-09-18 |
| DE19912149C2 (en) | 2003-05-15 |
| PL339072A1 (en) | 2000-09-25 |
| DE19912149A1 (en) | 2000-09-28 |
| PL198822B1 (en) | 2008-07-31 |
| JP2000282387A (en) | 2000-10-10 |
| EP1036881A1 (en) | 2000-09-20 |
| DE50008377D1 (en) | 2004-12-02 |
| CA2301300C (en) | 2006-05-16 |
| BR0001377B1 (en) | 2010-04-06 |
| ES2231060T3 (en) | 2005-05-16 |
| JP3242388B2 (en) | 2001-12-25 |
| CN1330826C (en) | 2007-08-08 |
| BR0001377A (en) | 2000-10-17 |
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