ZA200102469B - Method of producing a wetlaid thermobonded web-shaped fibrous material and material produced by the method. - Google Patents
Method of producing a wetlaid thermobonded web-shaped fibrous material and material produced by the method. Download PDFInfo
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- ZA200102469B ZA200102469B ZA200102469A ZA200102469A ZA200102469B ZA 200102469 B ZA200102469 B ZA 200102469B ZA 200102469 A ZA200102469 A ZA 200102469A ZA 200102469 A ZA200102469 A ZA 200102469A ZA 200102469 B ZA200102469 B ZA 200102469B
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- fibrous web
- paper
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Description
Ce. )
Method of producing a wetlaid thermobonded web-shaped fibrous material and material produced by the method
The present invention refers to a method of producing a wetlaid fibrous web-shaped ~~ material, such as paper or nonwoven, having a three dimensional pattern of alternating raised and recessed portions, which have been provided in connection with impulse drying, at which the wet fibrous web is passed through at least one press nip comprising a rotatable roll which is heated and that the fibrous web during the passage through the press nip is given a three dimensional pattern of alternating raised and recessed portions either by means of a patterned wire and/or by a pattcrn on the heated roll and where said pattern is pressed into the fibrous web against a counter means. The invention further refers to a web-shaped material produced by the method.
Moist paper webs are usually dried against one or more heated rolls. A method which is commonly used for tissue paper is so called Yankec drying. At Yankee drying the moist : 20 paper web is pressed against a steam-heated Yankee cylinder, which can have a very large diameter. Further heat for drying is supplied by blowing of heated air. If the paper to be produced is soft paper the paper web is usually creped against the Yankee cylinder. The drying against the Yankee cylinder is preceded by a vacuum dewatering and a wet pressing, in which the water is mechanically pressed out of the paper web.
Another drying method is so called through-air-drying (TAD). In this method the paper is dried by means of hot air which is blown through the moist paper web, often without a preceding wet pressing. The paper web which enters the through-air-dryer is then only vacuum dewatered and has a dry content of about 25-30% and is dried in the through- air-dryer to a dry content of about 65-95%. The paper web is transferred to a special drying fabric and is passed over a so called TAD cylinder having an open structure. Hot
. . aL :
WO (0/20682 PCT/SES9/01722- air is blown through the paper web during its passage over the TAD cylinder. Paper produced in this way, mainly soft paper, becomes very soft and bulky. The method however is very energy-consuming since all water that is removed has to be evaporated.
In connection with the TAD drying the pattern structure of the drying fabric is transferred to the paper web. This structure is essentially maintained also in wet condition of the paper, since it has been imparted to the wet paper web. A description of the TAD technique can be found in e g US-A-3,301,746. ’
Impulse drying of a paper web is disclosed in e g SE-B-423 118 and shortly involves that the moist paper web is passed through the press nip between a press roll and a heated roll, which is heated to such a high temperature that a quick and strong steam generation occurs in the interface between the moist paper web and the heated roll. The heating of the roll is e g accomplished by gas burners or other heating devices, e g by means of electromagnetic induction. By the fact that the heat transfer to the paper mainly occurs in a press nip an extraordinarily high heat transfer speed is obtained. All water that is removed from the paper web during the impulse drying is not evaporated, but the steam on its way through the paper web carries along water from the pores between the fibers in the paper web. The drying efficiency becomes by this very high.
In EP-A- 0 490 655 there is disclosed the production of a paper web, especially soft . paper, where the paper simultaneously with impulse drying is given an embossed surface. This embossment is made by pressing a pattcrn into the paper from one or both ; sides against a hard holder-on. This gives a compression of the paper and by this a higher density in certain portions just opposite the impressions and a lower density in the intermediate portions.
In DE-A-26 15 889 there is disclosed a thermobonded embossed soft paper. Thermo- plastic fibers are added to the paper web and after drying thereof the paper web is heated to a temperature exceeding the softening temperature of the thermoplastic fibers.
Simultaneously with this heating the paper is pattern embossed. Through-air-drying is mentioned as a drying method.
Ce
The object and most important features of the invention
The object of the present invention is to provide a method of producing a wetlaid impulse dried web-shaped fibrous material having a three-dimensional pattern, e g a wiping material or a soft paper intended as toilet paper, kitchen rolls, paper ) handkerchiefs, table napkins and the like, and where the paper has a high bulk, high elasticity and a high softness. The structure of the material, e g the paper, should essentially be maintained also in wet condition. This has according to the invention ~~ been provided by adding to the fibrous web a material that softens or melts in the temperature interval 100-400°C and that at lcast the parts of the fibrous web that is located closest to the raised portions of the heated roll are heated to such a high temperature that said material softens or melts and by that provides an increased amount of bonding points in the fibrous web.
By the fact that drying, thermobonding and pattern embossing takes place in one and the same step - the impulse drying step - there is achieved a more stable fiber structure with a low degree of inner stresses, which otherwise easily occur if the fibrous web is dried and by that the fiber structure locked before thermobonding.
The invention also refers to a wetlaid impulse dried web-shaped fibrous material, e g paper or nonwoven, provided with a three dimensional pattern with alternating raised and recessed portions, which have been provided in connection with the impulse . drying, wherein the fibrous web contains at least 5% by weight, calculated on the dry weight of the fibrous web, of a material that softens or melts in the temperature interval 100-400°C.
Further features and advantages of the invention are disclosed in the following description and in the dependant claims.
: ENE
The invention will in the following be closer described with reference to some embodiments shown in the accompanying drawings.
Fig. 1-4 are schematic side views of an impulse drying device according to some different embodiments.
Fig. 5 is a schematic side view of a device for producing a foam-formed fibrous web which is hydroentangled before impulse drying. :
Fig. 1 shows schematically a device for performing impulse drying of a paper web.
The wet paper web 10 which is dewatered over suction boxes (not shown) is supported by a wire or felt 11 and is brought into a press nip 12 between two rotatable rolls 13 and 14, at which the roll 13 which is in contact with the paper web is by a heating device 15 heated to a temperature which is sufficiently high for providing drying of the paper web. The surface temperature of the heated roll can vary depending on such factors as the moisture content of the paper web, thickness of the paper web, the contact time between the paper web and the roll and the desired moisture content of the completed paper web. The surface temperature should of course not be so high the paper web is damaged. An appropriate temperature should be in the interval 100-400°C, preferably 150-350°C and most preferably 200-350°C.
The paper web is pressed against the heated roll 13 by means of the roll 14. The press . device may of course be designed in many other ways. Two and more press devices may also be arranged afier each other. The holder-on 14 may also be a press shoe. It is also possible that the paper web 11 is passed into the press nip unsupported, i e not supported by any wire or felt.
A very rapid, violent and almost explosive steam generation takes place in the interface between the heated roll 13 and the moist paper web, at which the generated steam on its way through the paper web carries away water. For a further description of the impulse
© WO 00/20682 PCT/SE99/01722 drying technique reference is made to the above mentioned SE-B-423 118 sand e g to
EP-A- 0 337 973 sand US-A-5,556,511.
The paper is after drying wound on a wind-up roll 16. If desired the paper can be creped before winding. It is however noted that the need for creping the paper in order to impart softness and bulk which is aimed at for soft paper, is reduced when using the impulse drying method according to the invention, since the paper by the three- ’ dimensional structure and the chosen pattern is imparted bulk and softness.
The paper web can before it is brought into the impulse dryer either can be only dewatered over suction boxes or besides slightly pressed.
Simultaneously with the impulse drying the paper is given a three-dimensional structure. This can be made as shown in Fig. 1 by the fact that the heated roll 13 is provided with an embossing pattern consisting of alternating raised and recessed areas.
This structure is substantially maintained also in a later wetted condition of the paper, since it has been imparted the wet paper web in connection with drying thereof.
Since the term embossing is normally used for a shaping performed on dried paper we have in the following used the term press moulding for the three-dimensional shaping of the paper that occurs simultaneously with the impulse drying. By this press moulding the bulk and absorption capacity of the paper is increased, which are important qualities : for soft paper.
The paper web can be pressed against a non-rigid surface, i € a compressible press felt 11. The roll 14 can also have an elastically yielding surface, e g an envelope surface of rubber. The paper is herewith given a three-dimensional structure the total thickness of which is greater than the thickness of the unpressed paper. By this the paper is imparted a high bulk, high absorption capacity and high softness. Besides the paper will be elastic. At the same time a locally varying density is obtained in the paper.
The paper can also be pressed against a hard surface, e g a wire 11 and/or a roll 14 having a hard surface, at which the pattern of the heated roll 13 is pressed into the paper web under a heavy compression of the paper opposite the impressions, while the portions therebetween are kept uncompressed.
The embodiment shown in Fig. 2 differs from what is shown in Fig. 1 by the fact that under the wire 11 there is arranged a felt 17, which extends around the roll 14. The ; function of the felt 17 is to improve the dewatering effect and extend the press nip.
According to the embodiment shown in Fig. 3 the paper web 10 is during the drying supported by a wire 11 having a pattern, which is press moulded into the paper web when this passes through the press nip 12 between the rolls 13 and 14. The roll 13 can either be smooth, as is shown in Fig. 3, or have an embossing pattern. In the case the roll 13 is smooth the press moulded paper will have one smooth surface and one surface with impressions. In the case the roll 13 has an embossing pattern this will also be pressed into the paper, which thus on one side will have a pattern corresponding to the structure of the wire 11 and on the opposite side having a pattern corresponding to the embossing pattern of the roll. The patterns may but need not coincide and/or be the same or different. :
According to the embodiment shown in Fig. 4 the three-dimensional pattern in the paper web is produced by a pattern band or belt 11, which extends around and is heated by the cylinder 13. The pattern of the band 11 is press moulded into the paper web as this passes through the press nip 12 between the rolls 13 and 14. The paper web is supported by a felt 17 through the press nip.
According to the invention a material is added to the paper web, said material softens or melts in the temperature interval 100-400°C. Said material can be synthetic or natural polymers in the presence of softeners. The material can be in the form of powder, flakes, fibers, continuous filaments or an aqueous suspension, e g a latex dispersion.
Examples of thermoplastic polymers are polyolefines such as polyethylene and polypropylene, polyesters, polyamides, polylactides, conjugate fibers etc.
The material can be added in the paper making process together with the pulp fibers before forming and dewatering the paper web. It can also be added in the form of a suspension which is brought to flow out on the forming wire through a separate headbox arranged either before or after the headbox for the pulp suspension. Altema- ~ tively the material may in the form of a suspension be added through a certain section in a multilayer headbox and where the pulp suspension is added through the other sections of the multilayer headbox.
It is also possible to add the material to the formed paper web in the form of a liquid suspension through spraying or through contact with a rotating transfer roll.
The material can either be added to the entire paper web or only to the portions thereof which are intended to be located closest to the heated roll 13 especially close to the raised portions thereof.
By mixing the material with the pulp fibers before the headbox there is acheived a substantially homogeneous admixture of the material in the entire paper web. If however the material is added through a separate headbox or through a special section . in a multilayer hcadbox or alternatively is sprayed onto or printed on the already formed paper web the material will mainly be located in a certain layer of the paper web, preferably in the layer which will be located closest to the heated roll 13 during the impulse drying.
In case the material is printed on the formed paper web by a transfer roll it is possible that the material is printed in a pattern essentially corresponding to the pattern of the heated roll 13 in the form of raised and recessed portions, so that the paper web will contain the softening or melting material only in the portions thereof which will be in contact with the raised portions of the roll 13.
By adding to the paper web said material, which is brought to soften or melt, there is achieved an increased amount of bonding sites in the paper web. By this the basis weight variation and three-dimensional structure, that has been imparted to the paper web in connection with the combined impulse drying and press moulding, is effectively permanented. This structure is maintained also in thc wet condition of the paper.
A further advantage of the invention is that drying, thermobonding and pattern : embossing takes place in one and the same step - the impulse drying step - at which there is achieved a morc stable paper structure with a low degree of inner stresses, which otherwise will easily occur if the paper is dried and the fibrous structure by this is locked before the thermobonding.
In the embodiment show in Fig. 5 the thermoplastic material consists of continuous filaments 20, such as spunbond or meltblown fibers, which are formed by a meltblown- or spunbond equipment 21 and laid down on a wire 22 where they form a rclatively loose, open gauze-like fibrous structure in which the fibers are relatively free from each other. This is achieved either by the fact that the distance between the meltblown- /spunbond nozzle and the wire is relatively large, so that the fibers will have time to cool down before landing o the wire 22, at which their adhesiveness is reduced.
Alternativly the cooling of the metlblown/spunbond fibers before they are laid down on the wire, is provided in a different way, e g by spraying with liquid.
On top of the meltblown/spunbond layer a foam formed fibrous web 23 from a headbox 24 is laid. Foam forming means that a fiber web is formed from a dispersion of pulp fibers in a foamed liquid containing water and a surfactant. The foam forming technique is for example disclosed in GB 1,329,409, US 44,443,297 and in WO 96/02701. A foam formed fiber web has a very uniform fiber formation. For a more detailed description of the foam forming technique reference is made to the above mentioned documents. By the intensc foaming effect there will already during this step be an admixture of the meltblown/spunbond fibers in the foamed fiber dispersion. Air bubbles from the intense turbulent foam leaving the headbox 24 will penetrated into and push apart the mobile meltblown fibers, so that the somewhat more coarse fibers are integrated with the meltblown fibers. After this step there will therefore mainly be an integrated fiber web and no longer layers of different fiber webs. Besides pulp fibers the foam formed fiber web may also contain fibers, both synthetic and natural, of other types.
The foam is sucked through the wire 22 and the fiber web of meltblown/spunbond ’ fibers laid on the wire, by means of suction boxes (not shown) arranged under the wire.
The integrated fiber web of meltblown/spunbond fibers and other fibers are then hydroentangled while it is still supported by the wire 22 and herewith form a composite material. Optionally the fiber web can before hydroentangling be transferred to a special entangling wire. The entangling station 25 comprises several rows of nozzles from which very fine water jets under very high pressure are directed against the fiber webs and provide an entangling of the fibers.
For further description of the hydroentangling- or as it is also called the spunlace technique, reference is made to e g CA patent 841,938.
The meltblown/spunbond fibers will thus before the hydroentangling be mixed into and integrated with the fibers in the foam formed fiber web due to the foaming effect.
During the subsequent hydroentangling an entangling of the different fiber types take place and there is provided a composite material, in which all fiber types are essentially homogeneously mixed and integrated with each other. The thin mobile meltblown fibers are easily twisted around and entangled with the other fibers which gives a material of high strength. The energy input required at the hydroentangling is relatively low, i e the material is easy to entangle. The energy input at the hydroentangling is preferably in the interval 50-300 kWh/ton.
After hydroentangling the paper web is impulse dried and press moulded ina corresponding way as disclosed above. The hydroentangling step can however be eliminated, at which impulse drying takes place directly after draining of the foam oy formed fiber web. The hydroentangling contributes in an essentially improved wet strength of the material, by the fact that the fibers are entangled with each other. This enhanced wet strength is desired especially for applications where the material is to be used as a wiping material. However the high wet strength that is given the material through the thermobonding is sufficient for many applications.
Alternative performances of the above described method is the use of a preformed ’ tissue layer or the like on which the meltblown/spunbond fibers 20 are laid, after which the foam formed fiber web 23 is laid on top of the meltblown/spunbond fibers. A layer of meltblown/spunbond fibers can also be laid between two foam formed paper webs.
Paper can be produced by a number of different pulp types. If one disregards recovery pulp, which today is used to a great extent mainly for toilet paper and kitchen rolls, the most commonly used pulp type for soft paper is chemical pulp. The lignin content in such pulp is practically zero and the fibers, which mainly consist of pure cellulose, are relatively thin and flexible. Chemical pulp is a low yield pulp since it gives a yield of only about 50% calculated on the wooden raw material used. It is therefore a relatively expensive pulp.
It is therefore common to use cheaper so called high yield pulps, e g mechanical, : thermomechanical pulp, chemomechanical pulp (CMP) or chemothermomechanical pulp (CTMP) in soft paper as well as in other types of paper, e g newsprint paper, cardboard etc. In high yield pulps the fibers are coarser and contain a high amount of lignin, resins and hemicellulose. The lignin and the resins gives the fibers more hydrophobic properties and a reduced ability to form hydrogen bonds. The admixture of a certain amount of chemothermomechanical pulp in soft paper has due to the reduced fiber-fiber bonding a positive effect on properties like bulk and absorption capacity.
A special variant of chemothermomechanical pulp (CTMP) is so called high temperature chemothermomechanical pulp (HT-CTMP), the production of which differs from the production of CTMP of conventional type mainly by using a higher
“ 'v a temperature for impregnation, preheating and refining, preferably no lower than 140°C.
For a more detailed description of the production method for HT-CTMP reference is made to WO 95/3471 1. Characterizing for HT-CTMP is that it is a long fibrous-, easily dewatered- and bulky high yield pulp with a low shives content and low fines content.
It has according to the invention been found that high yield pulp is especially suitable for impulse drying since it is pressure insensitive, easily dewatered and has an open ~~ structure which admits the generated steam to pass through. This minimizes the risk for the paper to be overheated and destroyed during the impulse drying, which is performed at considerably higher temperatures than in other drying methods. The pressure insensitivity and the open structure depends on that the fibers in high yield pulp are relatively coarse and stiff as compared to the fibers in chemical pulp.
Impulse drying takes place at a considerably higher temperature than e g Yankee drying or through-air-drying, at which according to a theory, to which however the invention is not bound, the softening temperature of the lignin present in the high yield pulp is reached during the simultaneous impulse drying and press moulding. When the paper becomes cooler the lignin stiffens again and contributes in permanenting the three- dimensional structure that has been given the paper. This is therefore essentially maintained also in the wet condition of the paper, which strongly improves the bulk and absorption qualities of the paper.
According to one embodiment of the invention the paper contains a certain amount of a high yield pulp, said amount should be at least 10 weight% calculated on the dry fiber weight, preferably at least 30 weight% and more preferably at least 50 weight%.
Admixture of a certain amount of another pulp with high strngth properties, such as chemical pulp, preferably long-fibrous kraft pulp, or recycled pulp provide a high strength of the paper. The invention is however not bound to the use of a certain type of pulp in the paper, but may be applied with an optional pulp or pulp mixture.
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In all cases it is also possible to let the moist paper web pass through at least two consecutive press nips 12 each comprising a rotatable roll 13 which is heated and provided with a pattern of alternating raised and recessed portions intended to be pressed into the paper web against a holder-on. The second press nip is in this case preferably reversed as compared to the first press nip, at which one side of the paper web attains the highest temperature in the first press nip while the other side attains the highest temperature in the second press nip. :
According to one embodiment of the invention the paper web has a varying material composition as seen in its thickness direction, in such a way that it at least in the layer(s) that will be located closest to heated roll 13 in connection with the impulse drying contains a certain amount of a said material which softens or melts in the temperature interval 100-400°C. By this the paper will get a surface layer which contributes in reinforcing the structural stability of the paper also in wet condition. The pulp composition in the rest of the paper layers can on the other hand be chosen for optimizing other properties such as softness, strength, bulk and draping qualities.
Common additives such as wet strength agents, softening agents, fillers etc may of course also be used in the paper. The paper web can after impulse drying undergo different types of per se known treatments such as addition of different chemicals, : further embossing, lamination etc. It is also possible when transferring the paper web between two different wires, ¢ g from a dewatering wire to a drying wire, to have a } speed difference between the wires so that the paper web is slowed down in connection with the transfer. The paper web will then be compacted to a certain extent, which further increases the softness qualities.
The web-shaped material has in the above description been called paper for the sake of simplicity. In case other fibers than pulp fibers are admixed in the material the term nonwoven would be a more accurate term and is of course included in the invention.
Claims (23)
1. Method of producing a wetlaid fibrous web-shaped material, such as paper or nonwoven, having a three dimensional pattern of alternating raised and recessed portions, which have been provided in connection with impulse drying, at which the wet fibrous web (10) is passed through at least one press nip (12) comprising a rotatable roll (13) which is heated and that the fibrous web during the passage through the press - nip is given a three dimensional pattern of alternating raised and recessed portions either by means of a patterned wire (11) and/or by a pattern on the heated roll (13) and where said pattern is pressed into the fibrous web against a counter means, characterized in adding to the fibrous web (10) a matcrial that softens or melts in the temperature interval 100-400°C and that at least the parts of the fibrous web that is located closest to the raised portions of the heated roll (13) are heated to such a high temperature that said material softens or melts and by that provides an increased amount of bonding points in the fibrous web.
2. Method as claimed in claim 1, characterized in that said material comprises synthetic or natural polymers with thermoplastic properties, chemically modified lignin and/or synthetic or natural polymers together with softeners.
3. Method as claimed in claim 1 or 2, characterized in that said material is in the form of powder, flakes, fibers or an acqueous suspension, e g a latex suspension.
4. Method as claimed in any of the preceding claims, characterized in that said material is in the form of continuous filaments.
5. Method as claimed in claim 4, characterized in that the continuous filaments (20) are meltblown- and/or spunbond fibers.
6. Method as claimed in any of the preceding claims, characterized in that the fibrous web is foam-formed. -
7. Method as claimed in any of claims 4-6, characterized in foam-forming a fibrous web and mixing the foamed fiber dispersion (23) with the continuous filaments (20), and impulse drying the drained fibrous web.
8. Method as claimed in claim 7, characterized in hydroentangling the foamed fiber dispersion and the continuous filaments.
9. Method as claimed in any of claims 1-3, characterized in that said material is added to the fiber dispersion before forming and dewatering the : fibrous web.
10. Method as claimed in any of claims 1-3, characterized in that said material is added to the fibrous web in the form of a suspension which is spread on the forming wire through a separate headbox.
11. Method as claimed in any of claims 1-3, characterized in
© WO 00120682 ie PCT/SE99/01722 . oe that said material in the form of a suspension is added through at least one separate section in a multilayer headbox and where the other fiber dispersion is added through other sections of the multilayer headbox.
12. Method as claimed in any of claims 1-3, characterized in that said material is added to the formed fibrous web in the form of a liquid suspension’ by spraying or by contact wih a rotatable transfer roll.
13. Method as claimed in any of the preceding claims, characterized in that said material is added to the fibrous web only in the parts thereof which are intended to be closest to the heated roll (13) especially close to the raised portions thereof.
14. Method as claimed in any of the preceding claims, characterized in that the counter means (11,14) is provided with a non-rigid surface so that the paper web is given a three dimensional structure having a total thickness greater than the thickness of the unpressed paper web.
. 15. Method as claimed in claim 14, characterized in that the fibrous web is supported by a compressible press felt (11) through the press nip (12), said press felt makes said non-rigid counter means.
16. Method as claimed in claim 14, characterized in that the press felt (11) is pressed against a resilient surface (14) in the press nip (12).
17. Method as claimed in anyof the preceding claims, characterized in that the pulp fibers included in the fibrous web contain at least 10% by weight, preferably at least 30 % by weight and more preferably 50% by weight, calculated on the dry fiber weight, of a high yield pulp, such as mechanical pulp, thermomechanical pulp (TMP) or chemithermomechanical pulp (CTMP).
18. Method as claimed in anyof the preceding claims, characterized in that a wet strength agent is added to the fiber dispersion or the fibrous web before impulse drying.
19. Impulse dried wetlaid fibrous web-shaped material, such as paper or nonwoven, having a three dimensional pattern of alternating raised and recessed portions, which has been provided in connection with impulse drying, characterized in that the fibrous web contains at least 5% by weight, calculated on the dry weight of the fibrous web, of a material thta softens or melts in the temperature interval 100-400°C.
20. Web-shaped fibrous material as claimed in claim 19, characterized in that the thermoplastic material comprises synthetic or natural polymers with thermo- plastic properties, chemically modified lignin and/or synthetic or natural polymers together with softeners. :
21. A method as claimed in claim 1, substantially as herein described and illustrated.
22. Material as claimed in claim 19, substantially as herein described and illustrated.
23. A new method of producing material, or new material, substantially as herein described. AMENDED SHEET
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE9803360A SE9803360D0 (en) | 1998-10-01 | 1998-10-01 | Method of making a thermobonded paper and a paper made according to the method |
Publications (1)
Publication Number | Publication Date |
---|---|
ZA200102469B true ZA200102469B (en) | 2002-09-26 |
Family
ID=20412812
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
ZA200102469A ZA200102469B (en) | 1998-10-01 | 2001-03-26 | Method of producing a wetlaid thermobonded web-shaped fibrous material and material produced by the method. |
Country Status (2)
Country | Link |
---|---|
SE (1) | SE9803360D0 (en) |
ZA (1) | ZA200102469B (en) |
-
1998
- 1998-10-01 SE SE9803360A patent/SE9803360D0/en unknown
-
2001
- 2001-03-26 ZA ZA200102469A patent/ZA200102469B/en unknown
Also Published As
Publication number | Publication date |
---|---|
SE9803360D0 (en) | 1998-10-01 |
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