WO2014098059A1 - 逆浸透膜の親水化処理方法 - Google Patents

逆浸透膜の親水化処理方法 Download PDF

Info

Publication number
WO2014098059A1
WO2014098059A1 PCT/JP2013/083697 JP2013083697W WO2014098059A1 WO 2014098059 A1 WO2014098059 A1 WO 2014098059A1 JP 2013083697 W JP2013083697 W JP 2013083697W WO 2014098059 A1 WO2014098059 A1 WO 2014098059A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyvinyl alcohol
reverse osmosis
modified polyvinyl
osmosis membrane
membrane
Prior art date
Application number
PCT/JP2013/083697
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
邦洋 早川
孝博 川勝
Original Assignee
栗田工業株式会社
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 栗田工業株式会社 filed Critical 栗田工業株式会社
Priority to AU2013365015A priority Critical patent/AU2013365015B2/en
Priority to CN201380067336.3A priority patent/CN104994937B/zh
Publication of WO2014098059A1 publication Critical patent/WO2014098059A1/ja

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/08—Prevention of membrane fouling or of concentration polarisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/02—Hydrophilization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration

Definitions

  • the present invention relates to a hydrophilic treatment method for a reverse osmosis (RO) membrane using a modified polyvinyl alcohol having a polyalkylene oxide chain, an RO membrane subjected to a hydrophilic treatment by this method, and a hydrophilic treatment agent for the RO membrane. .
  • RO reverse osmosis
  • RO membranes have been widely put into practical use in various water treatment fields for the purpose of desalination and concentration, taking advantage of their characteristics.
  • PVA polyvinyl alcohol
  • the RO membrane When the PVA is brought into contact with the RO membrane, the RO membrane becomes hydrophilic and the permeation performance of the RO membrane is maintained. That is, since PVA has many OH groups and high hydrophilicity, by attaching PVA to the RO membrane, the RO membrane is hydrophilized, and adsorption of proteins and the like to the RO membrane is suppressed, thereby improving the stain resistance. As a result, the transmission performance can be maintained.
  • the present invention solves the above-mentioned conventional problems, can maintain a hydrophilization effect for a long period of time, and can maintain a relatively high flux, and a hydrophilization treatment method and hydrophilization treatment therefor It is an object to provide an agent.
  • the present inventors have been conventionally used by using modified polyvinyl alcohol having a polyalkylene oxide chain, based on the knowledge that polyethylene glycol has high adsorptivity with RO membranes. It has been found that the adsorptivity to the RO membrane is improved as compared with PVA, and therefore, the contamination resistance can be maintained for a long time as compared with PVA.
  • the present invention has been achieved on the basis of such knowledge, and the gist thereof is as follows.
  • a method of hydrophilizing a reverse osmosis membrane comprising bringing a modified polyvinyl alcohol having a polyalkylene oxide chain into contact with the reverse osmosis membrane.
  • a container having a liquid inlet and a liquid outlet is partitioned by the reverse osmosis membrane, and the aqueous solution containing the modified polyvinyl alcohol introduced from the liquid inlet is permeated through the reverse osmosis membrane to allow the liquid outlet.
  • the method for hydrophilizing a reverse osmosis membrane according to any one of [1] to [3], wherein the modified polyvinyl alcohol is brought into contact with the reverse osmosis membrane by draining it from water and passing it through.
  • a hydrophilic treatment agent for a reverse osmosis membrane containing a modified polyvinyl alcohol having a polyalkylene oxide chain containing a modified polyvinyl alcohol having a polyalkylene oxide chain.
  • the present invention by treating the RO membrane with a modified polyvinyl alcohol having a polyalkylene oxide chain, it is possible to impart hydrophilicity and maintain the hydrophilic effect over a long period of time. And if it is a modified polyvinyl alcohol which has a polyalkylene oxide chain, the fall of the flux of RO membrane by a hydrophilic treatment can be suppressed, and the preparation of the aqueous solution is easy compared with conventional PVA. .
  • RO membrane to which the present invention is applied examples include a polyamide-based RO membrane having an aromatic polyamide as a dense layer, but a polyamide-based nanofiltration membrane may also be used. That is, the RO membrane to be treated in the present invention is a broad RO membrane containing a nanofiltration membrane. Also, it can be applied to new films, used films, and deteriorated films without problems.
  • the structure of the RO membrane is not particularly limited, and a flat membrane module, a spiral type module, a hollow fiber module, or the like can be used.
  • the modified polyvinyl alcohol having a polyalkylene oxide chain used for the hydrophilic treatment of the RO membrane is composed of a vinyl alcohol unit and a unit to which a polyalkylene oxide group is bonded, and optionally further includes a vinyl acetate unit.
  • a polyalkylene oxide group having 2 to 4 carbon atoms of an alkylene group such as a polyethylene oxide group, a polypropylene oxide group, or a polybutylene oxide group is preferable.
  • the oxide group is most preferred.
  • the number of repeating alkylene oxide groups in the polyalkylene oxide group is preferably 2 to 300, particularly 4 to 150. If the number of repetitions is too small, the effect of improving the adsorptivity to the RO membrane by the polyalkylene oxide group cannot be sufficiently obtained, and if it is too large, the decrease in the flux of the RO membrane due to the hydrophilization treatment becomes large.
  • the molar fraction of the unit to which the polyalkylene oxide group is bonded in the modified polyvinyl alcohol having a polyalkylene oxide chain is preferably 0.1 to 50 mol%, more preferably 0.3 to 40 mol%, and 0 Particularly preferred is 5 to 30 mol%.
  • the present invention such as improvement of the adsorptivity to the RO membrane and suppression of flux reduction by introducing the polyalkylene oxide chain into the polyvinyl alcohol. If the amount is too large, the molar fraction of the vinyl alcohol unit is relatively small, and the hydrophilization effect tends to be reduced.
  • the molar fraction of the vinyl alcohol unit in the modified polyvinyl alcohol having a polyalkylene oxide chain is preferably 50 to 99.9 mol%, more preferably 60 to 99.7 mol%, and particularly preferably 70 to 99.5 mol%. preferable. If the molar fraction of the vinyl alcohol unit is less than this range, the number of hydroxyl groups in the modified polyvinyl alcohol having a polyalkylene oxide chain is reduced, and sufficient hydrophilization effect and flux stability cannot be obtained. If the amount is too large, the molar fraction of the unit to which the polyalkylene oxide group is bonded is relatively small, and the above-described effect due to the introduction of the polyalkylene oxide chain into polyvinyl alcohol may not be sufficiently obtained.
  • the molar fraction of vinyl acetate units in the modified polyvinyl alcohol having a polyalkylene oxide chain is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, and particularly preferably 0 to 5 mol%.
  • Saponification degree is an index indicating the properties of polyvinyl alcohol.
  • the saponification degree is obtained by dividing the molar fraction of the vinyl alcohol unit by the sum of the molar fractions of the vinyl alcohol unit and the vinyl acetate unit.
  • the degree of saponification of the modified polyvinyl alcohol having a polyalkylene oxide chain is preferably 80% or more, particularly 85% or more, particularly 95% or more.
  • the degree of saponification is less than 80%, the number of hydroxyl groups is small, the hydrophilicity is lowered, and sufficient hydrophilization treatment effect and flux stability tend not to be obtained.
  • the polymerization degree of the modified polyvinyl alcohol having a polyalkylene oxide chain that is, the total number of units is not particularly limited, but is preferably 20 to 20,000. If the degree of polymerization is too low, the adsorptivity to the membrane is deteriorated, and if the degree of polymerization is too large, the RO membrane flux decreases due to the hydrophilic treatment, which is not preferable.
  • Such a modified polyvinyl alcohol having a polyalkylene oxide chain can be obtained by a known synthesis method.
  • Commercial products such as “Ecomati WO-320N” and “Ecomati WO-320R” manufactured by Nippon Synthetic Chemical Industry can also be used.
  • a method for synthesizing a modified polyvinyl alcohol having a polyalkylene oxide chain is a method in which a monomer having a polyalkylene oxide group is polymerized with vinyl acetate, and then a part or all of the vinyl acetate is saponified to obtain a modified polyvinyl alcohol.
  • a monomer having a polyalkylene oxide group is polymerized with vinyl acetate, and then a part or all of the vinyl acetate is saponified to obtain a modified polyvinyl alcohol.
  • other synthetic methods may be used.
  • modified polyvinyl alcohol having a polyalkylene oxide chain only one kind may be used, and two or more kinds having different polyalkylene oxide groups, molar fractions of units, polymerization degree, and the like may be used. You may use it in combination.
  • Such modified polyvinyl alcohol having a polyalkylene oxide chain is usually used for the hydrophilization treatment of the RO membrane as an aqueous solution having a concentration of about 0.1 to 5000 mg / L, preferably about 1 to 1000 mg / L. If this concentration is too low, it takes a long processing time to obtain the desired hydrophilization effect, which is inefficient. Conversely, if this concentration is too high, the viscosity of the aqueous solution increases and the RO membrane is contacted at the time of contact processing. It is not preferable in terms of handling.
  • the modified polyvinyl alcohol having a polyalkylene oxide chain used in the present invention has sufficient solubility in water of about 40 to 60 ° C. unlike simple polyvinyl alcohol, so that an aqueous solution having a predetermined concentration can be prepared by a simple operation. Can do.
  • the water used for preparing the aqueous solution of the modified polyvinyl alcohol having a polyalkylene oxide chain is not particularly limited, and water having a low ion load such as desalted water is used.
  • the RO membrane feed water has a polyalkylene oxide chain. It is also possible to perform treatment by directly adding polyvinyl alcohol.
  • ⁇ Hydrophilic treatment method> There is no particular limitation on the method of bringing the modified polyvinyl alcohol having a polyalkylene oxide chain into contact with the RO membrane, but it is preferable to contact the RO membrane with an aqueous solution of the modified polyvinyl alcohol having a polyalkylene oxide chain under pressure. .
  • a container having a liquid inlet and a liquid outlet is partitioned by a RO membrane to be treated, and an aqueous solution of modified polyvinyl alcohol having a polyalkylene oxide chain is introduced from the liquid inlet and permeated through the RO membrane.
  • the method of discharging is mentioned.
  • the modified polyvinyl alcohol having a polyalkylene oxide chain can be directly added to the RO supply water of the RO membrane module of the normal RO membrane separation apparatus to perform the hydrophilic treatment. That is, in the hydrophilization treatment according to the present invention, a modified polyvinyl alcohol having a polyalkylene oxide chain is added to the RO membrane treatment water during the RO membrane separation treatment to the RO membrane module of the existing RO membrane separation apparatus.
  • the RO membrane separation process can be interrupted.
  • the pressure when an aqueous solution of a modified polyvinyl alcohol having a polyalkylene oxide chain is passed through the RO membrane under pressure but a range of 0.1 to 2.0 MPa is preferable.
  • cleaning of RO membrane is normally used for the water flow to the RO membrane of the modified polyvinyl alcohol aqueous solution which has a polyalkylene oxide chain.
  • the water flow pressure is The range is from 0.1 to 0.5 MPa.
  • the flux when passing water but it is preferably about 0.1 to 1.0 m / day. If this water flow condition is too low, a sufficient hydrophilic effect cannot be obtained, and if it is too high, there is a concern that the flux will decrease greatly.
  • the treatment time is not particularly limited, but is preferably 10 minutes or more and less than 48 hours, more preferably 1 hour or more and less than 24 hours. If the treatment time is short, a sufficient hydrophilic effect cannot be obtained. If the treatment time is long, there is a concern that the RO membrane flux is too low.
  • the temperature (water temperature) during the hydrophilization treatment is preferably 10 to 35 ° C. If the water temperature is too low, the flux decreases and the contact efficiency deteriorates. If the water temperature is too high, problems such as denaturation of the membrane material may occur.
  • the RO membrane treated by the hydrophilization treatment method of the present invention can be suitably used for an ultrapure water production system, a wastewater collection system, and other water treatment systems.
  • Example 1 The RO membrane “ES20” (flat membrane, diameter 32 mm ⁇ ) manufactured by Nitto Denko Corporation was hydrophilized under the following conditions.
  • the modified polyvinyl alcohol having a polyalkylene oxide chain as a hydrophilic treatment agent was used after being dissolved in ultrapure water (60 ° C.). After hydrophilization treatment, we conducted a water flow test using biologically treated water from the wastewater recovery system of Kurita Industrial Co., Ltd., and verified flux stability.
  • Hydrophilization treatment agent “Ecomati WO-320N” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (modified polyvinyl alcohol having a polyethylene oxide chain, saponification degree of 98.5% or more) Concentration: 100 mg / L Water flow time: 5 hours Inlet pressure: 0.75 MPa Flux: 1.0m / day Water temperature: 25 ° C
  • Raw water evaluation raw water Biologically treated water from the wastewater collection system of Kurita Kogyo Co., Ltd. Development Center ("Kuribata EC-503" manufactured by Kurita Kogyo Co., Ltd. added as a countermeasure against slime, 3 mg / L, pH 6.5) Inlet pressure: 0.75 MPa Recovery rate: 60% Water temperature: 25 ° C
  • an aqueous solution of a modified polyvinyl alcohol having a polyalkylene oxide chain is subjected to hydrophilization by passing water through the RO membrane under pressure, and then the above water-flow evaluation raw water is passed through.
  • the change with time (relative value when the flux at the start of water flow is 1) was examined, and the results are shown in FIG.
  • Example 2 The same as in Example 1 except that “Ecomati WO-320R” (modified polyvinyl alcohol having a polyethylene oxide chain, saponification degree: 86.5 to 89.5%) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. was used as the hydrophilic treatment agent. A test was conducted to verify the flux stability. The results are shown in FIG.
  • Example 3 Except that the inlet pressure during the hydrophilization treatment was 0.2 MPa, the same test as in Example 1 was performed to verify the flux stability. The results are shown in FIG.
  • Example 2 Except that polyvinyl alcohol (polymerization degree 2,000, saponification degree 99%) was used as the hydrophilic treatment agent, the same test as in Example 1 was performed to verify the flux stability. The results are shown in FIG.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
PCT/JP2013/083697 2012-12-21 2013-12-17 逆浸透膜の親水化処理方法 WO2014098059A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2013365015A AU2013365015B2 (en) 2012-12-21 2013-12-17 Method for hydrophilizing reverse osmosis membrane
CN201380067336.3A CN104994937B (zh) 2012-12-21 2013-12-17 逆渗透膜的亲水化处理方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-279590 2012-12-21
JP2012279590A JP2014121681A (ja) 2012-12-21 2012-12-21 逆浸透膜の親水化処理方法

Publications (1)

Publication Number Publication Date
WO2014098059A1 true WO2014098059A1 (ja) 2014-06-26

Family

ID=50978386

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/083697 WO2014098059A1 (ja) 2012-12-21 2013-12-17 逆浸透膜の親水化処理方法

Country Status (5)

Country Link
JP (1) JP2014121681A (zh)
CN (1) CN104994937B (zh)
AU (1) AU2013365015B2 (zh)
TW (1) TWI605070B (zh)
WO (1) WO2014098059A1 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018045393A2 (en) * 2016-08-22 2018-03-08 Trevi Systems Inc. Osmotic fluid purification and draw compounds thereof
CN108939923B (zh) * 2018-07-16 2019-07-02 安徽智泓净化科技股份有限公司 一种高通量强抗污的ro反渗透功能膜
WO2020178892A1 (ja) 2019-03-01 2020-09-10 ナンヤン テクノロジカル ユニヴァーシティー ファウリング抑制能付与剤およびそれを用いてなる水処理膜
CN112108009B (zh) * 2020-10-13 2022-04-22 上海希沃环境科技有限公司 一种聚四氟乙烯膜及其亲水处理方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5328083A (en) * 1976-08-10 1978-03-15 Kurita Water Ind Ltd Long term maintaining method for inverse osmotic membrane efficiency
JP2000024471A (ja) * 1998-07-09 2000-01-25 Daicel Chem Ind Ltd 固液分離膜
JP2007289922A (ja) * 2006-03-29 2007-11-08 Kurita Water Ind Ltd ナノろ過膜又は逆浸透膜の阻止率向上剤、阻止率向上方法、ナノろ過膜又は逆浸透膜、水処理方法、及び、水処理装置
JP2009101335A (ja) * 2007-10-01 2009-05-14 Kurita Water Ind Ltd 逆浸透膜、逆浸透膜装置及び逆浸透膜の親水化処理方法
JP2011092931A (ja) * 2009-09-30 2011-05-12 Toray Ind Inc 中空糸膜モジュールおよび中空糸膜モジュールの製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6659171B2 (en) * 2001-03-27 2003-12-09 Nippon Paint Co., Ltd. Hydrophilic modification method and heat exchanger treated thereby
US9486748B2 (en) * 2011-03-14 2016-11-08 W. L. Gore & Associates, Co., Ltd. Filter for water treatment filtering and method for producing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5328083A (en) * 1976-08-10 1978-03-15 Kurita Water Ind Ltd Long term maintaining method for inverse osmotic membrane efficiency
JP2000024471A (ja) * 1998-07-09 2000-01-25 Daicel Chem Ind Ltd 固液分離膜
JP2007289922A (ja) * 2006-03-29 2007-11-08 Kurita Water Ind Ltd ナノろ過膜又は逆浸透膜の阻止率向上剤、阻止率向上方法、ナノろ過膜又は逆浸透膜、水処理方法、及び、水処理装置
JP2009101335A (ja) * 2007-10-01 2009-05-14 Kurita Water Ind Ltd 逆浸透膜、逆浸透膜装置及び逆浸透膜の親水化処理方法
JP2011092931A (ja) * 2009-09-30 2011-05-12 Toray Ind Inc 中空糸膜モジュールおよび中空糸膜モジュールの製造方法

Also Published As

Publication number Publication date
CN104994937A (zh) 2015-10-21
CN104994937B (zh) 2017-03-22
JP2014121681A (ja) 2014-07-03
TWI605070B (zh) 2017-11-11
TW201434873A (zh) 2014-09-16
AU2013365015B2 (en) 2017-11-02
AU2013365015A1 (en) 2015-06-11

Similar Documents

Publication Publication Date Title
Xu et al. Development of an antibacterial copper (II)-chelated polyacrylonitrile ultrafiltration membrane
Nataraj et al. Cellulose acetate-coated α-alumina ceramic composite tubular membranes for wastewater treatment
KR101474587B1 (ko) 역침투막, 역침투막 장치 및 역침투막의 친수화 처리 방법
Liu et al. Polydopamine coating–surface modification of polyester filter and fouling reduction
Wang et al. Fabrication of non-woven composite membrane by chitosan coating for resisting the adsorption of proteins and the adhesion of bacteria
CN112023727B (zh) 一种抗污染抑菌反渗透膜、制备方法及其应用
WO2014115631A1 (ja) ファウリング抑制剤、濾過膜及びその製造法
WO2014098059A1 (ja) 逆浸透膜の親水化処理方法
CN110756061B (zh) 一种耐氧化高通量反渗透膜及其制备方法及应用
JP2012055870A (ja) ポリフッ化ビニリデン多孔質濾過膜の製造方法
JP2009165949A (ja) 抗菌性分離膜、その製造方法、および抗菌性分離膜の製造装置
JPWO2008090854A1 (ja) 逆浸透膜処理方法
JP6303837B2 (ja) 逆浸透膜の耐汚染化処理方法
EP2949378B1 (en) Fouling inhibitor, filtration membrane and method for producing same
JP6667217B2 (ja) ファウリング抑制剤、水処理用多孔質濾過膜、およびその製造方法
JP6998708B2 (ja) ファウリング抑制能付与剤
CN108043233B (zh) 一种耐氧化聚酰胺反渗透膜及其制备方法和应用
JP2016040030A (ja) 水処理システム
JP7256505B2 (ja) ファウリング抑制能付与剤およびそれを用いてなる水処理膜
JP6390326B2 (ja) 水処理用多孔質濾過膜の製造方法
McCloskey Novel surface modifications and materials for fouling resistant water purification membranes
JP2009112927A (ja) 分離膜の改質方法、その方法により改質された分離膜、改質薬品、ならびに分離膜の改質に用いる装置
Waterman Bench-scale analysis of ultrafiltration membranes for investigating fouling by natural organic matter in surface water
JP2015016448A (ja) 複合半透膜の阻止率向上方法
JP2017124341A (ja) 水処理方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13865072

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013365015

Country of ref document: AU

Date of ref document: 20131217

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13865072

Country of ref document: EP

Kind code of ref document: A1