WO2006064574A1 - Materiau antistatique fibreux et procede de fabrication associe - Google Patents

Materiau antistatique fibreux et procede de fabrication associe Download PDF

Info

Publication number
WO2006064574A1
WO2006064574A1 PCT/JP2004/018992 JP2004018992W WO2006064574A1 WO 2006064574 A1 WO2006064574 A1 WO 2006064574A1 JP 2004018992 W JP2004018992 W JP 2004018992W WO 2006064574 A1 WO2006064574 A1 WO 2006064574A1
Authority
WO
WIPO (PCT)
Prior art keywords
fibrous material
triazine
natural
antistatic
regenerated
Prior art date
Application number
PCT/JP2004/018992
Other languages
English (en)
Inventor
Keiichiro Kanehisa
Shigeo Ozawa
Original Assignee
Kanehisa Co., Ltd.
Office Ozawa Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kanehisa Co., Ltd., Office Ozawa Co., Ltd. filed Critical Kanehisa Co., Ltd.
Priority to US11/721,776 priority Critical patent/US20090241265A1/en
Priority to PCT/JP2004/018992 priority patent/WO2006064574A1/fr
Publication of WO2006064574A1 publication Critical patent/WO2006064574A1/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358—Triazines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material

Definitions

  • the present invention relates to an antistatic fibrous material and a method for manufacturing said material by treating a fibrous material with a compound having at least two reactive halogen atoms.
  • Natural and regenerated fibrous materials are excellent in view of their texture, moisture-absorbing/releasing properties, and their good warmth-retention ability. These properties are known to be based on hydrophilic groups such as -OH and -NH 2 in their chemical structures, which enables them to retain a high moisture content. However, in spite of their high moisture content, such natural and regenerated fibrous materials are still so poor in electrical conductivity that they are likely to store triboelectricity (electrical charge produced by friction between two objects).
  • Natural fibers such as cotton and regenerated fibers such as rayon are usually positively charged by friction, because they are positioned more positively high in the triboelectric series. Furthermore, because fibrous materials are electrically nonconductive, a large amount of electricity that is generated by friction is stored in such materials, and typically little of that is released. In fact, such storage of triboelectricity is sometimes hazardous to human life.
  • One of the most popular methods for controlling the static electricity of fibrous materials is by coating them with resin-type chemicals that contain antistatic agents and/or electrically conductive materials, so as to modify a material's surface properties.
  • This type of chemical function helps first in lowering the friction coefficient of the surface of a fibrous material, and second in releasing the electricity from the material's surface, due to the high conductivity of the chemical coating.
  • a silicon-based or fluorine-based water-repellent agent As a resin-type chemical treatment, a silicon-based or fluorine-based water-repellent agent has been proposed, but it is usually highly charged with voltage due to friction, thereby posing a potential safety problem.
  • a place such as a gas station
  • the frictional electricity on a work uniform that is made of such cloth causes dirt to adhere on the surface of the uniform, so that such cloth is unsuitable for uniforms in various industries, especially information technology and precision processing industries.
  • Prior-art disclosures of antistatic agents include a cation polymer in combination with a guanidine salt and/or an inorganic salt [Japanese Unexamined Published Patent Application No. S61-69884], an aminophosphate-type phosphoric ester in combination with a guanidine salt [Japanese Examined Published Patent Application No. S61-58592], a compound having a specific vapor pressure in combination with a quaternary ammonium salt-type cation detergent and aminophosphate-type phosphoric ester [Japanese Unexamined Published Patent Application No. 2002-054072], and a polyester resin having a tertiary amine or quaternary ammonium salt structure [Japanese Unexamined Published Patent Document No. 2003-073657].
  • one general object of the present invention is to provide novel antistatic natural and/or regenerated fibrous materials that are less electrically charged by friction, that can easily release the charge that is stored on the material's surface, has an improved texture, has a greater durability against washing, and has little toxicity.
  • Another object of the present invention to provide a method of manufacturing natural and/or regenerated fibrous materials such as those mentioned above.
  • the present invention relates to antistatic fibrous materials manufactured by treating a natural and/or regenerated fibrous material with both (1) at least one di-halogeno-s-triazine that has at least one hydrophilic group, and (2) urea, thiourea, or an amino acid, or a combination of two or more of said three compounds.
  • the treatment includes the following steps: (a) saturating a natural or regenerated fibrous material with a solution that contains a di-halogeno-s-triazine that has (1) at least one hydrophilic group, and (2) urea, thiourea, or an amino acid, or a combination of two or more of said three compounds, (b) heating said saturated material at 30 °C-60 °C, and (c) heating said saturated material at 60 °C-90 0 C.
  • the treatment includes the following steps: (a) saturating a natural and/or regenerated fibrous material with a first solution that contains at least one di-halogeno-s-triazine that has at least one hydrophilic group, (b) heating said saturated material at 30 °C-60 0 C, and (c) saturating said fibrous material with a second solution that contains urea, thiourea, or an amino acid, or a combination of two or more of said three compounds, and (d) heating said saturated material at 60 °C-90 0 C.
  • This invention relates to antistatic fibrous materials manufactured by treating natural and/or regenerated fibrous materials with both (1) at least one di-halogeno-s-triazine that has at least one hydrophilic group, and (2) urea, thiourea, or an amino acid.
  • the natural and/or regenerated fibrous materials according to this invention include silk, wool, cotton, linen, viscose rayon, Cuprammonium-Rayon, lyocell, Tencel, mixtures of the preceding materials, and mixtures of said materials with other kinds of fibers, including synthetic fibers.
  • the natural and/or regenerated fibrous materials of diis invention also include any form of fibrous product, including: staple-fiber, filament, thread, textile, and non-woven cloth, as well as cloth used for clothing such as work uniforms, shirts, trousers, underclothes such as shorts, brassieres, and other underwear, pajamas, and gloves and socks; interior-decor materials such as curtains, carpets, cover cloths, and tablecloths, and bed items such as sheets, quilt covers, and pillow cases; and industrial goods such as filters and sheets.
  • the antistatic fibrous materials according to the present invention are manufactured by treating natural and/or regenerated fibrous materials with chemicals that contains (1) at least one di-halogeno-s-triazine that has at least one hydrophilic group (Component A), and (2) urea, thiourea, or an amino acid, or a combination of two or more of said three compounds (Component B).
  • At least one di-halogeno-s-triazine that has at least one hydrophilic group is selected.
  • the di-halogeno-s-triazines having at least one hydrophilic group are, preferably, water-soluble 2,6-dihalogeno-4-Y-l,3,5-triazine expressed by the general formula (1) below, wherein X is a halogen atom selected from Br, Cl, and F, and Y is -OM [wherein M is selected from Na, K, Li, and Mg], or arylamino, aryloxy, arylmercapto, alkylamino, alkoxy, alkylthio, triazinilamino, triaziniloxy, or triazinilthio, and that has at least one group selected from -SO3M, -COOM, -OM, or -SM [wherein M is selected from Na, K, Li, and Mg].
  • a trihalogeno-s-triazine is dissolved in 5-50 times its own weight of a water-soluble solvent, to which an aqueous solution of a compound that has a group that reacts with an active halogen, such as -NH 2 , -OH, or -SH, and at least one hydrophilic group, is dropwise added at 0 °C-30 0 C. While said aqueous solution is being added, the mixture is kept slightly alkaline, at pH 8-9, by simultaneous addition of an aqueous solution of an acid scavenger, such as sodium carbonate, sodium bicarbonate, sodium phosphate, sodium hydroxide, or potassium hydroxide.
  • an acid scavenger such as sodium carbonate, sodium bicarbonate, sodium phosphate, sodium hydroxide, or potassium hydroxide.
  • trihalogeno-s-triazine is hydrolyzed with an alkali, such as sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, or magnesium hydroxide, at a temperature of 0 °C-30 0 C, so as to produce a di-halogeno-hydroxy-s-triazine metallic salt.
  • an alkali such as sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, or magnesium hydroxide
  • at least one compound is selected from urea, thiourea, or an amino acid.
  • One way to manufacture the antistatic fibrous materials of this invention is to treat a natural and/or regenerated fibrous material with both Component A and Component B. This is achieved by the following steps: (1) saturating a natural and/or regenerated fibrous material in a solution that contains Component A and Component B, and (2) heating said saturated material at 30 °C-60 °C, and (3) then heating said saturated material at 60 °C-90 0 C.
  • this can be achieved by the following steps: (1) saturating a natural and/or regenerated fibrous material in a first solution that contains Component A, (2) heating the first solution with the material therein at 30 °C-60 0 C, (3) saturating the material after the preceding step in a second solution that contains Component B, and (4) heating the second solution with the material therein at 60 °C-90 0 C.
  • the ratio of Component A and Component B by weight must be in the range of 1 : (0.1-1.0), preferably in the range of 1 : (0.3-0.7).
  • the methods for saturating a natural and/or regenerated fibrous material with a solution that contains either or both Component A and Component B include a dipping method and a padding method, though the method is not limited to those two methods.
  • the first step is to prepare an aqueous solution that contains Component A and/or Component B.
  • An aqueous solution of Component A is prepared with a bath ratio of 1 : (2-30), so as to contain an active concentration of 0.5%-10.0% o.w.f. (on the weight of fiber), and an aqueous solution of an alkaline agent such as sodium carbonate, sodium bicarbonate, or sodium hydroxide is prepared so as to become 1.0%-30.0% o.w.f. Otherwise, an acid aqueous solution of acetic acid, glacial acetic acid, malic acid, or citric acid is prepared so as to become 0.1%-5.0% o.w.f. When both Component A and Component B are used in the same step, Component A and Component B are mixed in an appropriate ratio in water.
  • the solution should be kept at a temperature of not more than 30 0 C. If the temperature of the solution is more than 30 0 C, the di-halogeno-s-triazine in Component A is hydrolyzed and the activity necessary for attaining the purpose of the invention is lost. If Component A or Component B is used separately from the other component, both of the components are independently solubilized in water in a way similar to that mentioned above.
  • a natural and/or regenerated fibrous material is dipped in a solution of Component A and Component B or a solution of Component A in a bath. While circulating the solution or the fibrous material, the bath is kept, as the first step, at 30 °C-60 °C for 1 min.-l hr, preferably for 2 min.-30 min., and then, as the second step, at 60 °C-90 0 C for 2 min.-2 hrs., preferably for 3 min.-l hr.
  • fibrous materials are dipped in a bath that contains a solution of Component A. While circulating the solution or the fibrous material, the bath is kept, as the first step, at 30 °C-60 0 C for 1 min.-l hr., preferably 2 min.-30 min. Then the treated fibrous material is dipped in a bath that contains a solution of Component B at 60 °C-90 0 C for 2 min.-2 hrs., preferably for 3 min.-l hr. After the first step, the fibrous materials can be taken out of the bath to be lightly squeezed and then dipped in the second solution, which contains Component B.
  • a natural and/or regenerated fibrous material is padded with a solution of Component A and Component B and squeezed until the fibrous material contains 20%-300% of the solution.
  • the separate operations of padding and squeezing can be carried out with a solution of Component A and subsequently with a solution of Component B.
  • the operation of padding and squeezing can be repeated for the purpose of increasing the amount of each Component A and Component B that is applied to the fibrous material. Repeating the padding and the drying several times likely will lead to a good result.
  • the squeezed fibrous material After the squeezed fibrous material has been dried, it can be kept, as the first step, at 30 °C-60 0 C for 1 min.-l hr., preferably for 2 min.-30 min., and then kept, as the second step, at 60 °C-90 0 C for 2 min.-2 hrs., preferably for 3 min.-l hr.
  • the fibrous material is padded with a solution of Component A, squeezed and kept at 30 °C-60 0 C for 1 min.-l hr., preferably for 2 min.-30 min. Then the treated fibrous material is padded again with a solution of Component B, then squeezed and kept at 60 °C-90 0 C for 2 min.-2 hrs., preferably for 3 min.-l hr. After the heat treatment, the fibrous material is soaped and then rinsed with water.
  • Component A reacts with -OH or -NH 2 in the fibrous material so as to make a stable bond between Component A and the fibrous material.
  • the fibrous material contains some hydrophilic Component A that is chemically bonded therein, which helps in controlling static.
  • Component B of this invention promotes the formation of a bond between Component A and the fibrous material.
  • the present invention provides improved antistatic fibrous materials, especially improved antistatic natural or regenerated fibrous materials.
  • the antistatic fibrous materials store only low levels of electricity caused by spontaneous static induction even if the material is electrically charged due to friction.
  • the antistatic performance is stable for a long time even after the material is subject to friction. Also, due to the material's ability to retain a high amount of moisture, a wearer feels warm and comfortable.
  • the cloth was kept at 50 0 C for 20 min. under a condition of 100% humidity, and then at 85 °C under the same humidity condition for another 20 min.
  • the cloth was then soaped in hot water (80 0 C) for 10 min., then rinsed with water, and then dried in dry air of 100 0 C.
  • the half-period of the fiction-charged voltage [time (seconds) required for halving the triboelectric voltage] was measured based on JIS. L 1094 (20 0 C, RH 40%) by a Static Honestmeter H-0110 (trade name) made by Shishido Shokai Co.
  • Wl weight of the sample that was placed for 24 hrs. under the conditions of temperature
  • W2 weight of the sample that was placed for 24 hrs. under the conditions of temperature
  • Comparison Example 2 The same types of cloths were treated in water in a way similar to the cloths in Example 2 but without any chemicals being added to the water.
  • Table 2 shows that the ⁇ MR in Example 2 is larger than that of Comparison Example 2, which means that a larger amount of moisture has been retained.
  • the bath was raised to a temperature of 50 0 C at a rate of 2 °C/min., and kept at 50 0 C for 10 min., then raised to 75 °C and kept at 75 0 C for 20 min. After the water was discharged, the fabric was soaped, then rinsed with water, and then dried.
  • Example 1 As can be seen from Table 1, the triboelectric voltage of Example 1 was significantly less than in than Comparison Example 1, and the electric charge of Example 1 was minus (-).
  • Example 2 As can be seen from Table 2, the triboelectric voltage of Example 2 was halved for a few seconds, and the difference in moisture-retention( ⁇ MR %) of Example 2 were better than that of Comparison Example 2.
  • Example 3 As can be seen from Table 3, the antistatic effects of Example 3 were better than those of Comparison Example 3.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne un matériau antistatique fibreux fabriqué par traitement d'un matériau fibreux naturel et/ou régénéré au moyen : (1) d'au moins une di-halogéno-s-triazine comprenant au moins un groupe hydrophile et (2) d'urée, de thiourée et d'un acide aminé ou d'une combinaison d'au moins deux de ces composés. Le traitement comprend les étapes suivantes consistant: (a) à saturer un matériau fibreux naturel et/ou régénéré au moyen d'une solution renfermant : (1) une di-halogéno-s-triazine possédant au moins un groupe hydrophile et (2) de l'urée, de la thiourée et un acide aminé ou une combinaison d'au moins deux de ces composés ; (b) à chauffer le matériau saturé à une température comprise entre 30 °C et 60 °C; et (c) à chauffer le matériau saturé à une température comprise entre 60 °C et 90 °C.
PCT/JP2004/018992 2004-12-14 2004-12-14 Materiau antistatique fibreux et procede de fabrication associe WO2006064574A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US11/721,776 US20090241265A1 (en) 2004-12-14 2004-12-14 Antistatic fibrous material and method for manufacturing same
PCT/JP2004/018992 WO2006064574A1 (fr) 2004-12-14 2004-12-14 Materiau antistatique fibreux et procede de fabrication associe

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2004/018992 WO2006064574A1 (fr) 2004-12-14 2004-12-14 Materiau antistatique fibreux et procede de fabrication associe

Publications (1)

Publication Number Publication Date
WO2006064574A1 true WO2006064574A1 (fr) 2006-06-22

Family

ID=34960983

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/018992 WO2006064574A1 (fr) 2004-12-14 2004-12-14 Materiau antistatique fibreux et procede de fabrication associe

Country Status (2)

Country Link
US (1) US20090241265A1 (fr)
WO (1) WO2006064574A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107059243A (zh) * 2017-05-02 2017-08-18 深圳市新纶科技股份有限公司 一种抗静电粘胶纤维无纺布及其制备方法
CN109235045A (zh) * 2018-09-06 2019-01-18 合肥必更赢科技有限公司 一种天丝纤维用柔顺剂及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1107789A (en) * 1966-02-08 1968-03-27 Bayer Ag Microbicidal finishing of cellulose-containing textile materials
WO2001023661A1 (fr) * 1999-09-30 2001-04-05 The Procter & Gamble Company Amelioration durable pour tissu
JP2004346471A (ja) * 2003-05-20 2004-12-09 Yoshiki Hagiwara 真珠粉末を用いた天然繊維材料の改質加工法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1107789A (en) * 1966-02-08 1968-03-27 Bayer Ag Microbicidal finishing of cellulose-containing textile materials
WO2001023661A1 (fr) * 1999-09-30 2001-04-05 The Procter & Gamble Company Amelioration durable pour tissu
JP2004346471A (ja) * 2003-05-20 2004-12-09 Yoshiki Hagiwara 真珠粉末を用いた天然繊維材料の改質加工法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 200505, Derwent World Patents Index; Class A11, AN 2005-042637, XP002344471 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107059243A (zh) * 2017-05-02 2017-08-18 深圳市新纶科技股份有限公司 一种抗静电粘胶纤维无纺布及其制备方法
CN107059243B (zh) * 2017-05-02 2019-10-29 深圳市新纶科技股份有限公司 一种抗静电粘胶纤维无纺布及其制备方法
CN109235045A (zh) * 2018-09-06 2019-01-18 合肥必更赢科技有限公司 一种天丝纤维用柔顺剂及其制备方法

Also Published As

Publication number Publication date
US20090241265A1 (en) 2009-10-01

Similar Documents

Publication Publication Date Title
US7736696B2 (en) Methods, systems, and compositions for fire retarding substrates
US20080005852A1 (en) Durable multifunctional finishing of fabrics
US3857727A (en) Textile finishing
EP1368524A2 (fr) Procede de production de gaines proteiques autour de fibres textiles, et textiles obtenus par ce procede
EP1156152A1 (fr) Tissu absorbant et libérant l'humidité et procédé pour sa production
US6491727B1 (en) Methods for reducing the flammability of cellulosic substrates
WO2006042055A2 (fr) Tissu ionise performant
CN1107916A (zh) 抗菌防臭纺织材料的加工方法及其制品
CA2350497A1 (fr) Procedes de reduction de l'inflammabilite de substrats cellulosiques
JPH06313271A (ja) セルロース繊維の防汚加工方法
EP1425461A2 (fr) Procede de production de gaines cellulosiques attachees autour de fibres de textiles et textiles produits de cette maniere
WO2006064574A1 (fr) Materiau antistatique fibreux et procede de fabrication associe
US6511929B1 (en) Method of improving washfastness of metallized fabric
US6673125B2 (en) Chemically modified nonwoven articles and method for producing the same
WO2013109416A1 (fr) Mélange de fibres, filé de fibres, matière textile, et procédé d'utilisation de la matière textile
US3640823A (en) Flame-retardant composition
US3855349A (en) Method and composition for imparting fire-proofness to synthetic shaped articles
CA2601262A1 (fr) Traitement anti-statique resistant au lavage pour les textiles et textiles ainsi traites
JPH11189978A (ja) ポリエステル繊維構造物およびその製造方法
US2549059A (en) Method of treating fibrous cellulosic materials to impart flame resistance thereto, composition therefor, and products thereof
US6602437B1 (en) Chemically modified nonwoven articles and method for producing the same
US3258358A (en) Process for producing an antistatic finish on hydrophobic materials
CN101080529A (zh) 一种抗静电纤维材料及其制备方法
JP2941089B2 (ja) 繊維製品の汚れ防止加工方法
JPH04108185A (ja) 繊維構造物の耐洗濯性抗菌加工方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 11721776

Country of ref document: US

Ref document number: 200480044621.4

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 04807349

Country of ref document: EP

Kind code of ref document: A1