EP0938603B1 - A method and apparatus for the heat treatment of textiles - Google Patents

A method and apparatus for the heat treatment of textiles Download PDF

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Publication number
EP0938603B1
EP0938603B1 EP97909531A EP97909531A EP0938603B1 EP 0938603 B1 EP0938603 B1 EP 0938603B1 EP 97909531 A EP97909531 A EP 97909531A EP 97909531 A EP97909531 A EP 97909531A EP 0938603 B1 EP0938603 B1 EP 0938603B1
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EP
European Patent Office
Prior art keywords
steamer
liquid
pump
vacuum
water
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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 - Lifetime
Application number
EP97909531A
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German (de)
French (fr)
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EP0938603A1 (en
Inventor
Freddy Wanger
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Xorella AG
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Xorella AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B17/00—Storing of textile materials in association with the treatment of the materials by liquids, gases or vapours
    • D06B17/04—Storing of textile materials in association with the treatment of the materials by liquids, gases or vapours in wound form
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B5/00—Forcing liquids, gases or vapours through textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing impregnating
    • D06B5/12—Forcing liquids, gases or vapours through textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing impregnating through materials of definite length

Definitions

  • the present invention relates to a method of heat-treating textiles, in particular spun cops or bobbins, in a heated steamer connected to a water and/or chemical supply and a vacuum pump via valves, and also relates to apparatus for carrying out this method.
  • Texttiles means any structure made of raw textile materials and includes materials in both fibrous and sheet form.
  • Textiles can also be conditioned or finished by treatment in a steam phase, if necessary with the addition of chemicals.
  • Suitable steamers have been known for many years and substantially comprise a cylindrical boiler closable by a pivotable cover. Inside the steamer is a water bath which generates steam by means of a heating device and effects the appropriate heat treatment of the material introduced. To enable the steam to penetrate better the interior of the textiles, a vacuum is generated before the heating device for the water bath is switched on.
  • An object of the invention is to provide a method and apparatus which use less energy, permit better penetration of the material to be treated and, in addition, reduce the cycle times and the overall heat treatment. This problem has been solved by the technical features set out in claims 1 and 9.
  • a vacuum of at least 50 mbar is generated.
  • the method according to the invention produces an energy saving in the order of 12 kWh per cycle or 35 to 40 kWh per treatment. Furthermore, the water vapour pumped off during the formation of the vacuum does not have to be recondensed. The non-recondensed volume saved is approximately 20 litres per treatment cycle.
  • a further advantage consists in the simple and economic supply of chemicals and/or finishing additives which load the vacuum pump only slightly or not at all.
  • the heat treatment or the results achieved may be improved in a simple manner by repeating the second to sixth steps at least once.
  • the heat treatment can be optimised by successively increasing the temperatures of the steam phase from the first to at least one subsequent heat treatment.
  • a steam phase temperature of at least 350 K is established in a first cycle and at least 380 K in a further cycle.
  • Energy may additionally be saved by aeration and the overall treatment time further reduced as a result, ie before the end of the first heat treatment, in an intermediate step, the vacuum is interrupted and then built up again.
  • the water and/or chemicals are supplied from containers dimensioned in accordance with the volume of the liquid bath in the steamer and which, together with the steamer, form a closed system into which only lost liquid is fed back from outside, the lost liquid due to the residual moisture in the steamed material and the evacuation.
  • This permits recirculation of the liquids and/or chemicals and is therefore particularly economical and environmentally friendly.
  • the invention further provides apparatus for carrying out the above method and comprising a heated steamer connected to a water and/or chemical supply and a vacuum pump via valves, wherein at least one container, a pump and at least two valves are provided for the liquid and/or chemical supply, the valves controlling the admission of liquid into and discharge of liquid from the steamer.
  • an electric heating device is provided at least within the space of a liquid bath within the steamer.
  • Such an electric heating device is particularly advantageous because it can be controlled very flexibly and thereby has a favourable effect.
  • Other heating systems for example steam heating systems, may also be used economically depending on the energy available.
  • the vacuum pump is a water-ring pump or a rotary vane pump.
  • a water-ring pump is very cost-effective and suitable for vacuums up to 30 mbar.
  • a rotary vane pump is necessary for vacuums up to 5 mbar.
  • an exhaust line is designated by the reference numeral 1.
  • a vacuum pump 2 with an electric motor M is connected to the exhaust line 1.
  • a vacuum line 3 is connected to the input side of the vacuum pump 2 (a rotary vane pump) and communicates with the interior of a steamer 6 via a valve V1 and a suction line 4.
  • a further valve V2 is also arranged in the suction line 4 and is connected to an air line 5.
  • a liquid bath 8, the aqueous liquid 9 of which can reach a level N1, and an electric heating device 10 are arranged inside the steamer 6 known per se.
  • the steamer 6 is provided with a pivotable cover 7 having a vertical pivoting axis 7a.
  • the material G to be treated is introduced into the steamer 6, where it is steam-treated, by opening the cover 7.
  • Feed lines 11 lead from the electric heating device 10 to a control unit, the regulating function of which is represented by +/-.
  • a liquid line 12 leads from the steamer 6 and is connected to pump lines 13 and supply lines 22.
  • the pump line 13 leads to valves V7, V8, and V9 via a valve V3, a liquid pump 14 with an electric motor M and pressure lines 15.
  • the valves V7 - V9 are for their part connected to the lower parts of liquid containers 19 - 21 via inlet/outlet lines 16 - 18.
  • Each of these liquid containers (tanks) has an aeration line 19' - 21', respectively.
  • Valves V4 - V6 are also arranged on the inlet/outlet lines 16 - 18 and are connected to the supply lines 22.
  • Fig. 1 The operation of the arrangement according to Fig. 1 is relatively simple: the interior of the steamer 6 is evacuated to the desired low pressure via the vacuum lines 3 and 1 by closing the valve V2, opening the valve V1, and switching on the vacuum pump 2. As a result, the material G to be treated also becomes substantially free of entrapped air.
  • valve V4 on the water tank 19 is now opened; the valve V9 remains closed so that water is sucked via the supply line 22 and the liquid line 12 into the steamer, where it fills the liquid bath 8 to the level N1.
  • the valve V4 is then closed and the electric heating device 10 is simultaneously activated by switching on the mains voltage, with the result that a steam phase forms inside the steamer 6 and penetrates the material G as saturated steam.
  • the control unit switches the heating device 10 off, the valves V3 and V9 are opened, the valve V4 remains closed and the liquid pump 14 is switched on; the water is pumped back into the water tank 19 and returns to approximately the level N2. The resultant displaced air can escape via the aeration line 19'.
  • the acids or bases are fed from the chemical tank 20 into the steamer 6 and then pumped back again.
  • a further advantage of this arrangement is the connection to the liquid-wax tank 21 after the last steaming process in order to facilitate processing of the material G, namely spun yarn in the form of cops.
  • Figs. 2 and 3 show the characteristics of a heat treatment for cops carried out in practice, starting from an ambient pressure of 1000 mbar. For graphical reasons, low pressures have been shown in abbreviated form in Fig. 3.
  • the steamer 6 is evacuated to a pressure of 5 mbar, after which water from the water tank 19 is admitted and heated, producing a steam phase having a temperature of approximately 350 K held constant for 2.0 minutes; cf. Fig. 2. During this process, the pressure in the steamer 6 is raised to approximately 420 mbar.
  • the vacuum is then interrupted and a residual quantity of steam is released via the suction line 4 and the valve V2 into the air (aeration); cf. Fig. 1.
  • a vacuum of 5 mbar is subsequently regenerated and a second treatment cycle begins.
  • the temperature of the steam phase is increased to 380 K, the pressure being raised to a positive pressure of 1300 mbar during the heating of the liquid supplied from the chemical tank 20.
  • the first cycle 1.C begins after the first evacuation process 1.v and lasts 3.0 minutes; the second and third cycles 2.C and 3.C each have a durationd of 4.0 minutes.
  • the whole heat treatment is finished after the fourth evacuation process 4.V, during which the residual moisture is removed from the material.
  • the material in question is a spun cotton yarn; the cops have a net weight of 120 g.
  • a steam condenser is additionally connected upstream of the vacuum pump 2.
  • the process may also be carried out under vacuum with a pressure above 50 mbar.
  • the process time is increased and the quality of treatment is reduced, especially when the material is heavy and/or compressed.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Textile Engineering (AREA)
  • Treatment Of Fiber Materials (AREA)

Abstract

Textiles, e.g. cops of spun cotton yarn, are heat treated in steamer 6 by:- evacuating the steamer using pump 2; admitting liquid, e.g. water, into steamer bath 8 from tank 19; heating the bath to form steam for a preselected time; and pumping the liquid back into tank 19 for reuse. The treatment may be repeated with liquid from chemical tank 20, and then with liquid wax from tank 21. The steamer is then evacuated, and the textile cooled and dried. The first vacuum is at least 1000 mbar absolute. The process reduces recondensation and energy losses.

Description

The present invention relates to a method of heat-treating textiles, in particular spun cops or bobbins, in a heated steamer connected to a water and/or chemical supply and a vacuum pump via valves, and also relates to apparatus for carrying out this method.
"Textiles" means any structure made of raw textile materials and includes materials in both fibrous and sheet form.
It is known that heat treatment has a favourable effect on yarns, etc. for further processing.
Textiles can also be conditioned or finished by treatment in a steam phase, if necessary with the addition of chemicals.
Suitable steamers have been known for many years and substantially comprise a cylindrical boiler closable by a pivotable cover. Inside the steamer is a water bath which generates steam by means of a heating device and effects the appropriate heat treatment of the material introduced. To enable the steam to penetrate better the interior of the textiles, a vacuum is generated before the heating device for the water bath is switched on.
These known steamers have the disadvantage that large amounts of energy are needed to form and maintain the vacuum and, furthermore, the steam is removed by the vacuum pump and has to be recondensed. This results in only limited steam penetration of the material to be treated and/or long treatment times.
An object of the invention is to provide a method and apparatus which use less energy, permit better penetration of the material to be treated and, in addition, reduce the cycle times and the overall heat treatment. This problem has been solved by the technical features set out in claims 1 and 9.
Preferably, in the second step a vacuum of at least 50 mbar is generated.
For a liquid bath with a volume of 300 litres, the method according to the invention produces an energy saving in the order of 12 kWh per cycle or 35 to 40 kWh per treatment. Furthermore, the water vapour pumped off during the formation of the vacuum does not have to be recondensed. The non-recondensed volume saved is approximately 20 litres per treatment cycle.
This provides the further advantage that the amount of fresh water needed is also reduced by an order of magnitude on account of the recirculation of the liquid in accordance with the invention.
A further advantage consists in the simple and economic supply of chemicals and/or finishing additives which load the vacuum pump only slightly or not at all.
The heat treatment or the results achieved may be improved in a simple manner by repeating the second to sixth steps at least once.
The heat treatment can be optimised by successively increasing the temperatures of the steam phase from the first to at least one subsequent heat treatment.
Preferably, during the heat treatment, a steam phase temperature of at least 350 K is established in a first cycle and at least 380 K in a further cycle.
By increasing the holding time at a constant temperature during subsequent heat treatments the results may be improved without an increase in energy consumption.
Energy may additionally be saved by aeration and the overall treatment time further reduced as a result, ie before the end of the first heat treatment, in an intermediate step, the vacuum is interrupted and then built up again.
Preferably, the water and/or chemicals are supplied from containers dimensioned in accordance with the volume of the liquid bath in the steamer and which, together with the steamer, form a closed system into which only lost liquid is fed back from outside, the lost liquid due to the residual moisture in the steamed material and the evacuation. This permits recirculation of the liquids and/or chemicals and is therefore particularly economical and environmentally friendly.
The invention further provides apparatus for carrying out the above method and comprising a heated steamer connected to a water and/or chemical supply and a vacuum pump via valves, wherein at least one container, a pump and at least two valves are provided for the liquid and/or chemical supply, the valves controlling the admission of liquid into and discharge of liquid from the steamer.
Preferably an electric heating device is provided at least within the space of a liquid bath within the steamer. Such an electric heating device is particularly advantageous because it can be controlled very flexibly and thereby has a favourable effect. Other heating systems, for example steam heating systems, may also be used economically depending on the energy available.
Preferably, the vacuum pump is a water-ring pump or a rotary vane pump. A water-ring pump is very cost-effective and suitable for vacuums up to 30 mbar. For vacuums up to 5 mbar, a rotary vane pump is necessary.
An embodiment of the invention will now be described, by way of example only, with reference to accompanying drawings, wherein:
Fig.1
is a simplified, schematic representation of steam apparatus for treating cops in accordance with the invention,
Fig.2
is a characteristic temperature graph for the steam phase in the steamer of the installation according to Fig. 1, and
Fig.3
is the pressure graph associated with Fig. 2, in relation to the ambient atmosphere.
In accordance with Fig. 1, an exhaust line is designated by the reference numeral 1. A vacuum pump 2 with an electric motor M is connected to the exhaust line 1. A vacuum line 3 is connected to the input side of the vacuum pump 2 (a rotary vane pump) and communicates with the interior of a steamer 6 via a valve V1 and a suction line 4.
A further valve V2 is also arranged in the suction line 4 and is connected to an air line 5.
A liquid bath 8, the aqueous liquid 9 of which can reach a level N1, and an electric heating device 10 are arranged inside the steamer 6 known per se.
At one end, the steamer 6 is provided with a pivotable cover 7 having a vertical pivoting axis 7a. The material G to be treated is introduced into the steamer 6, where it is steam-treated, by opening the cover 7.
Feed lines 11 lead from the electric heating device 10 to a control unit, the regulating function of which is represented by +/-.
A liquid line 12 leads from the steamer 6 and is connected to pump lines 13 and supply lines 22.
The pump line 13 leads to valves V7, V8, and V9 via a valve V3, a liquid pump 14 with an electric motor M and pressure lines 15. The valves V7 - V9 are for their part connected to the lower parts of liquid containers 19 - 21 via inlet/outlet lines 16 - 18. Each of these liquid containers (tanks) has an aeration line 19' - 21', respectively.
Valves V4 - V6 are also arranged on the inlet/outlet lines 16 - 18 and are connected to the supply lines 22.
The operation of the arrangement according to Fig. 1 is relatively simple: the interior of the steamer 6 is evacuated to the desired low pressure via the vacuum lines 3 and 1 by closing the valve V2, opening the valve V1, and switching on the vacuum pump 2. As a result, the material G to be treated also becomes substantially free of entrapped air.
The valve V4 on the water tank 19 is now opened; the valve V9 remains closed so that water is sucked via the supply line 22 and the liquid line 12 into the steamer, where it fills the liquid bath 8 to the level N1. The valve V4 is then closed and the electric heating device 10 is simultaneously activated by switching on the mains voltage, with the result that a steam phase forms inside the steamer 6 and penetrates the material G as saturated steam.
After a predetermined holding time, the control unit switches the heating device 10 off, the valves V3 and V9 are opened, the valve V4 remains closed and the liquid pump 14 is switched on; the water is pumped back into the water tank 19 and returns to approximately the level N2. The resultant displaced air can escape via the aeration line 19'.
Similarly, the acids or bases are fed from the chemical tank 20 into the steamer 6 and then pumped back again.
A further advantage of this arrangement is the connection to the liquid-wax tank 21 after the last steaming process in order to facilitate processing of the material G, namely spun yarn in the form of cops.
Figs. 2 and 3 show the characteristics of a heat treatment for cops carried out in practice, starting from an ambient pressure of 1000 mbar. For graphical reasons, low pressures have been shown in abbreviated form in Fig. 3.
As shown in Fig. 3, the steamer 6 is evacuated to a pressure of 5 mbar, after which water from the water tank 19 is admitted and heated, producing a steam phase having a temperature of approximately 350 K held constant for 2.0 minutes; cf. Fig. 2. During this process, the pressure in the steamer 6 is raised to approximately 420 mbar.
The vacuum is then interrupted and a residual quantity of steam is released via the suction line 4 and the valve V2 into the air (aeration); cf. Fig. 1.
As shown in Fig. 3, a vacuum of 5 mbar is subsequently regenerated and a second treatment cycle begins. In this case, the temperature of the steam phase is increased to 380 K, the pressure being raised to a positive pressure of 1300 mbar during the heating of the liquid supplied from the chemical tank 20.
The same thing happens in the third cycle, in which an aqueous wax solution from the liquid-wax tank 21 is used to form the liquid bath 8.
Increasing the heating times and the holding times in the subsequent cycles in relation to the first cycle has proved highly advantageous with respect to optimising the heat treatment.
The first cycle 1.C begins after the first evacuation process 1.v and lasts 3.0 minutes; the second and third cycles 2.C and 3.C each have a durationd of 4.0 minutes. The whole heat treatment is finished after the fourth evacuation process 4.V, during which the residual moisture is removed from the material. The material in question is a spun cotton yarn; the cops have a net weight of 120 g.
As can be seen from Figs. 2 and 3, the complete heat treatment, including the application of wax to the yarn, lasts a total of only 18,5 minutes, despite the very large cops.
Depending on the material to be treated and the processing required, for economic reasons it can be advantageous if a steam condenser is additionally connected upstream of the vacuum pump 2.
The process may also be carried out under vacuum with a pressure above 50 mbar. However, the process time is increased and the quality of treatment is reduced, especially when the material is heavy and/or compressed.

Claims (11)

  1. A method of heat-treating textiles (G) in a heated steamer (6) connected via valves (V4-V9) and a pump (14) with a valve (V3) to a water and/or chemical supply (19-21) and connected to a vacuum pump (2) via valves (V1,V2), wherein:
    in a first step the steamer (6) is charged with the material (G) to be treated followed by several consecutive steps of evacuating gas, treating the textiles (G) in a steam phase during a predetermined time, cooling, drying and evacuating and finally removing the textiles (G) from the steamer (6),
    characterized in that:
    in a second step, the vacuum pump (2) is switched on until a vacuum of at least 100 mbar absolute pressure has been reached in the steamer (6),
    in a third step, a feed valve (V7-V9) of the water and/or chemical supply (19-21) is opened and a predetermined volume of liquid is admitted into the steamer to form a liquid bath (9),
    in a fourth step, the liquid bath (9) and the steam phase to be formed are heated by a built in heating device (10) to a predetermined temperature,
    after the material (G) to be treated has been held for a preselected time in the saturated steam phase, the liquid is pumped out of the steamer (6) into a container (19-21),
    in a fifth step, the vacuum pump (2) is reactivated,
    in a sixth step, after a preselected evacuation, cooling and drying time, the vacuum pump (2) is switched off and ambient air is admitted into the steamer (6), and
    in a final step, the material (G) is removed from the steamer (6).
  2. A method according to claim 1, wherein the vacuum generated in the second step is at least 50 mbar.
  3. A method according to claim 1 or 2, wherein the second to sixth steps are repeated at least once.
  4. A method according to claim 2 or 3, wherein the temperatures of steam phase are increased from the first to at least one subsequent heat treatment.
  5. A method according to claim 4, wherein, during the heat treatment, a steam phase temperature of at least 350 K is established in a first cycle and at least 380 K in a further cycle.
  6. A method according to claim 4 or 5, wherein the period of constant temperature during the first heat treatment is shorter than during subsequent heat treatments.
  7. A method according to any one of claims 4 to 6, wherein, before the end of the first heat treatment, in an intermediate step, the vacuum is interrupted and then built up again.
  8. A method according to any one of the preceding claims, wherein the water and/or chemicals are supplied from containers dimensioned in accordance with the volume of the liquid bath in the steamer and which, together with the steamer, form a closed system into which only lost liquid is fed back from outside, the lost liquid being due to the residual moisture in the steamed material and the evacuation.
  9. Apparatus for carrying out the method according to any one of the preceding claims comprising a heated steamer connected to a water and/or chemical supply and a vacuum pump via valves, wherein at least one container, a pump and at least two valves are provided for the liquid and/or chemical supply, the valves controlling the admission of liquid into and discharge of liquid from the steamer.
  10. Apparatus according to claim 9, wherein an electric heating device is provided at least within the space of a liquid bath within the steamer.
  11. Apparatus according to claim 9 or 10, wherein the vacuum pump is a water-ring pump or a rotary vane pump.
EP97909531A 1996-11-14 1997-11-06 A method and apparatus for the heat treatment of textiles Expired - Lifetime EP0938603B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9623730A GB2319263B (en) 1996-11-14 1996-11-14 A method and apparatus for the heat treatment of textiles
GB9623730 1996-11-14
PCT/IB1997/001400 WO1998021390A1 (en) 1996-11-14 1997-11-06 A method and apparatus for the heat treatment of textiles

Publications (2)

Publication Number Publication Date
EP0938603A1 EP0938603A1 (en) 1999-09-01
EP0938603B1 true EP0938603B1 (en) 2005-07-20

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EP97909531A Expired - Lifetime EP0938603B1 (en) 1996-11-14 1997-11-06 A method and apparatus for the heat treatment of textiles

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EP (1) EP0938603B1 (en)
JP (1) JP3856479B2 (en)
KR (1) KR100454847B1 (en)
CN (1) CN1082580C (en)
AT (1) ATE299962T1 (en)
AU (1) AU4719497A (en)
CZ (1) CZ296059B6 (en)
DE (1) DE69733765T2 (en)
ES (1) ES2246509T3 (en)
GB (1) GB2319263B (en)
HK (1) HK1023155A1 (en)
TR (1) TR199900975T2 (en)
WO (1) WO1998021390A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007024205A1 (en) 2007-05-24 2008-12-04 Xorella Ag Method and device for heat treatment of textile goods
DE102008034840A1 (en) * 2008-07-24 2010-02-04 Xorella Ag Method and device for moistening textile goods

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100340242B1 (en) * 2000-01-07 2002-06-12 이두현 Device of sealing with setting a textile
CN103510318A (en) * 2013-09-12 2014-01-15 浙江新澳纺织股份有限公司 Full-wool yarn steaming method
CN104278455B (en) * 2014-09-28 2016-04-20 江苏今达纺织实业有限公司 Vacuum type steams the application process of silk modular system

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB910995A (en) * 1957-12-13 1962-11-21 Michael John Andrew Improvements in or relating to the dyeing and finishing of textiles
CN87203303U (en) * 1987-05-23 1987-12-26 辽宁省农牧机械研究所 Multifunctional vacuum washing machine
CN2157938Y (en) * 1993-06-17 1994-03-02 韩胜国 Vacuum dyeing machine

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007024205A1 (en) 2007-05-24 2008-12-04 Xorella Ag Method and device for heat treatment of textile goods
DE102007024205B4 (en) * 2007-05-24 2015-01-08 Xorella Ag Method and device for heat treatment of textile goods
DE102008034840A1 (en) * 2008-07-24 2010-02-04 Xorella Ag Method and device for moistening textile goods

Also Published As

Publication number Publication date
WO1998021390A1 (en) 1998-05-22
JP2001504168A (en) 2001-03-27
ATE299962T1 (en) 2005-08-15
CZ296059B6 (en) 2006-01-11
CN1082580C (en) 2002-04-10
CN1238017A (en) 1999-12-08
DE69733765T2 (en) 2006-06-01
GB9623730D0 (en) 1997-01-08
DE69733765D1 (en) 2005-08-25
TR199900975T2 (en) 1999-09-21
AU4719497A (en) 1998-06-03
HK1023155A1 (en) 2000-09-01
GB2319263A (en) 1998-05-20
EP0938603A1 (en) 1999-09-01
JP3856479B2 (en) 2006-12-13
GB2319263B (en) 2000-11-15
ES2246509T3 (en) 2006-02-16
KR20000053283A (en) 2000-08-25
CZ168499A3 (en) 1999-08-11
KR100454847B1 (en) 2004-11-03

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