WO2006022256A1 - 樹脂組成物およびそれを用いた積層体の製造方法 - Google Patents
樹脂組成物およびそれを用いた積層体の製造方法 Download PDFInfo
- Publication number
- WO2006022256A1 WO2006022256A1 PCT/JP2005/015268 JP2005015268W WO2006022256A1 WO 2006022256 A1 WO2006022256 A1 WO 2006022256A1 JP 2005015268 W JP2005015268 W JP 2005015268W WO 2006022256 A1 WO2006022256 A1 WO 2006022256A1
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- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- composition according
- ethylene
- laminate
- polyolefin
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/105—Metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2410/00—Agriculture-related articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/80—Medical packaging
Definitions
- the present invention improves various problems that occur during processing by recovering a laminate containing an ethylene-vinyl acetate copolymer can and adding it again when the laminate is processed. It is related with the rosin composition which can do. Moreover, this invention relates to the method of manufacturing a laminated body using this resin composition.
- Laminated bodies that have strength such as polyolefin, modified polyolefin (adhesive resin) and ethylene acetate butyl copolymer cane (hereinafter also referred to as EVOH) are collected and then processed again for use in the production of laminated bodies. can do.
- EVOH ethylene acetate butyl copolymer cane
- 8-104370 discloses a container in which zeolite is dispersed in a specific layer of a laminate that forms a container in order to prevent the transfer of odors to food inside the container and the container.
- zeolite is dispersed in a specific layer of a laminate that forms a container in order to prevent the transfer of odors to food inside the container and the container.
- no technology has been proposed for adding zeolite to any layer of the laminate. Disclosure of the invention
- the present invention relates to (A) polyolefin, (B) a higher fatty acid metal salt having 12 to 30 carbon atoms, and (C
- Polyolefin force It is preferably polyethylene or polypropylene.
- the melt flow rate of the polyolefin (A) is preferably 0.1 to 50 gZlO.
- the higher fatty acid metal salt preferably has 14 to 22 carbon atoms.
- the higher fatty acid metal salt is preferably a stearate.
- the higher fatty acid metal salt is preferably a calcium salt, a magnesium salt or a zinc salt.
- (A) is preferably a content of force 45 to 95 weight 0/0 of polyolefin.
- the content of the (B) higher fatty acid metal salt is preferably 0.5 to 15% by weight.
- the content of zeolite (C) is preferably 5 wt% or more and less than 50 wt%.
- the melt flow rate of saponified ethylene acetate butyl copolymer at 210 ° C and a load of 2160 g is preferably 0.5 to 200 gZlO.
- the weight ratio of (A) polyolefin to (D) saponified ethylene acetate butyl copolymer is 95.
- ⁇ 30 Preferable to be 5 ⁇ 70!
- the present invention relates to a method for producing a laminate including a step of adding the above-mentioned resin composition to a laminate containing a saponified ethylene acetate butyl copolymer and reprocessing.
- Ethylene acetate Bulle copolymer saponified ethylene content is 20 to 65 mole 0/0 It is preferable that the saponification degree of the butyl acetate component is 90 mol% or more of ethylene acetate butyl copolymer.
- the resin composition of the present invention comprises polyolefin (A) and a higher fatty acid metal salt having 12 to 30 carbon atoms.
- Polyolefin (A) includes high density polyethylene (HDPE), medium density polyethylene (M DPE), low density polyethylene (LDPE), very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), Ethylene acetate butyl copolymer (EVA), polypropylene (PP), etc. can be used.
- HDPE high density polyethylene
- M DPE medium density polyethylene
- LDPE low density polyethylene
- VLDPE very low density polyethylene
- LLDPE linear low density polyethylene
- EVA Ethylene acetate butyl copolymer
- PP polypropylene
- the melt flow rate of polyolefin (A) (according to JIS K 6922-1, hereinafter abbreviated as MFR) is preferably 0.1 to 50 gZlO (190 ° C in the case of PE resin) In the case of PP resin, 230 ° C., load 2160 g), more preferably 0.5 to 30 g / 10 min, and further preferably 1 to 15 g ZlO. If the MFR is too small, the extrusion load at the time of compounding tends to increase and the productivity tends to decrease. Conversely, if it is too large, the compounding failure will occur and the uniformity of the product will soon decrease, and a stable effect will not be obtained. is there.
- the amount of polyolefin (A) in the rosin composition of the present invention is preferably 45 to 95% by weight, more preferably 70 to 90% by weight. If the blending amount is too small, the coconut resin composition tends to be unable to maintain its shape as an additive, and if it is too large, the intended improvement effect of the present invention tends to be insufficient.
- the higher fatty acid metal salt (B) having 12 to 30 carbon atoms is blended as a lubricant.
- Higher fatty acid metal salts having 12 to 30 carbon atoms (B) include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, heptadecylic acid, behenic acid, oleic acid, elaidic acid, erucic acid, linoleic acid Acids, linolenic acid, ricinoleic acid, hydroxystearic acid, montanic acid, isostearic acid, epoxy stearic acid, and the like, and strong metal salts such as alkali metals, alkaline earth metals, and heavy metals can be used.
- the higher fatty acid metal salt (B) has 12 to 30 carbon atoms, preferably 14 to 22 carbon atoms, and more preferably 16 to 20 carbon atoms.
- fatty acid has a small number of carbons
- odor migration prevention performance is insufficient
- the number of carbon atoms is large, the effect of suppressing gelling habits tends to be insufficient.
- the blending amount of the higher fatty acid metal salt (B) having 12 to 30 carbon atoms in the resin composition of the present invention is preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight. If the blending amount is too small, the gelling-inhibiting effect tends to be insufficient, and if the blending amount is too large, the processability tends to be affected, for example, the supply to the extruder becomes unstable.
- Zeolite (C) is generally composed of SiO, Al 2 O, Fe 2 O, MgO, CaO, PO, Na 0, K
- the amount of zeolite (C) is preferably 5% by weight or more and less than 50% by weight, more preferably 7% by weight or more and less than 20% by weight. If the blending amount is too small, the anti-gelling effect and the odor migration preventing performance tend to be insufficient, and if the blending amount is too large, the greaves composition tends not to maintain its shape as an additive.
- the resin composition of the present invention further contains an ethylene-acetic acid copolymer copolymer (D) from the viewpoint of improving the effect of inhibiting gelling.
- the ethylene content of ethylene-vinyl acetate copolymer Keni ⁇ (D) is preferably from 70 to 95 mol%, more preferably 75 to 92 mole 0/0, more preferably 80 to 90 mole 0/0. If the ethylene content is too small, the Gehrich prevention effect and the odor migration preventing performance tend to be insufficient, and if too much, the gelling suppression effect tends to be insufficient.
- the saponification degree of vinyl acetate component of the ethylene-vinyl acetate copolymer saponified (D) is preferably from 85 to: L00 mol%, and more favorable Mashiku is 90 to: L00 mole 0/0, more preferably 95 : it is the L00 mole 0/0. If the degree of chaining of the butyl acetate component is too small, the gelling prevention effect and the odor migration prevention performance tend to be insufficient. Furthermore, the MFR at 190 ° C. and load 2 160 g of the ethylene-butyl acetate copolymer (D) is preferably 0.5 to 200 g / 10 min, more preferably 1 to: L00 g / 10 min.
- the weight ratio of polyolefin (A) to saponified ethylene monoacetate copolymer (D) in the resin composition of the present invention is 95-30: 5-70. More preferably, it is more preferably 90 to 50:10 to 50.
- the resin composition of the present invention is blended as an additive when a laminate (multilayer structure) containing EVOH is recovered and processed again to produce a laminate.
- odorous gases acetoaldehyde, crotonaldehyde, acetone, etc.
- the resin composition of the present invention is added at the time of re-stripping, it is possible to suppress these problems.
- the collected laminate contains an inorganic or organic colorant, EVOH gelling is caused due to aggregation of these colorants during reprocessing. By adding a substance, such gelling can be suppressed.
- the resin composition of the present invention may be blended in any form as an additive.
- polyolefin (A) higher fatty acid metal salt having 12 to 30 carbon atoms
- B higher fatty acid metal salt having 12 to 30 carbon atoms
- C zeolite
- the laminate containing EVOH is not particularly limited as long as it can be recovered and re-carried.
- Various products obtained from various multilayer sheets can be used.
- the rosin composition of the present invention it may be in the form as it is recovered or may be pulverized, or may be remolded into pellets.
- EVOH contained in the laminate in the recovered ethylene content from 20 to 65 mole 0/0 saponification degree 90 mol of acetic Bulle component 0/0 or more, can be used, in general EVOH having an available ethylene content of 26 to 48 mol% and a saponification degree of the vinyl acetate component of 90 mol% or more can be used.
- a thermoplastic resin can also be added together if necessary. The obtained blended product is used again for the production of a laminate together with a thermoplastic resin and an adhesive resin, and forms at least one layer of the laminate.
- the amount of the resin composition of the present invention to be added to the collected laminate is not particularly limited, but is 0.5 to 100 parts by weight with respect to 100 parts by weight of the pulverized laminate or reshaped pellets to be collected. : L0 part by weight is preferred 1 to 5 parts by weight is more preferred. If the addition amount is too small, the gelling prevention effect and odor migration prevention performance tend to be inadequate, and if it is too much, the appearance of the molded product produced by adding the resin composition tends to deteriorate. .
- the laminate produced by blending the resin composition of the present invention can be collected, the resin composition of the present invention can be blended, and the laminate can be produced again. Therefore, by using the resin composition of the present invention, it becomes possible to repeatedly collect and reprocess the laminate containing EVOH without deteriorating the physical properties of the resulting laminate.
- the laminate produced by blending the resin composition of the present invention is useful as a plastic cup, as well as a packaging material for foods, pharmaceuticals, agricultural chemicals, industrial chemicals, and the like.
- LDPE (A) [Nippon Polyethylene Co., Ltd., LF440HB, MFR: 2.8gZlO min (190 ° C, load 2160g), density: 0.925g / cm 3 ], calcium stearate S (B) [Nippon Yushi Co., Ltd.], natural mordenite-based zeolite (C) [manufactured by Nitto Flour Chemical Co., Ltd., SP # 2300] and ethylene acetate butyl saponified copolymer (D) [manufactured by Tosohichi Co., Ltd., Mersen H6051, E styrene content: 89 mol 0/0, saponification degree: 100 mole 0/0, MFR: 5.
- EVOH ethylene content: 32 mol 0/0, saponification degree: 99.6 mole 0/0, MFR: 3. 5 g Zlo min (190 ° C, load 2160 g), terms of boron boric acid 0.03% content]
- thermoplastic resin polypropylene
- AMOC03143 BP AMOCO
- AMOC03143 MFR
- 2.8 gZlO 2 30 ° C, load 2160 g
- adhesive resin maleic anhydride modified LLDPE
- Romuang Supplying Tym OT 1203 manufactured by Dohas Co.
- thermoplastic resin layer 400/25/50/25/500 ( ⁇ m).
- the obtained multilayer sheet was pulverized with a pulverizer (diameter 8 mm ⁇ mesh) to obtain a pulverized product of the laminate (apparent density: 0.42 g / cc).
- the EVOH content in the pulverized product was 6.1% by weight.
- a multilayer sheet (multilayer structure) having a configuration of 0/25/50/25/500 ( ⁇ m) was produced.
- the obtained multilayer sheet was similarly crushed, 5 parts of modified pellets, 100 parts of polypropylene, and 2 parts of white pigment masterbatch were added, and the same operation for producing a multilayer sheet was repeated 20 times.
- Table 1 shows the results of evaluating the long run formability as follows.
- the content of EVOH in the blend is a Oite 9.8 wt% 8. 4 weight 0/0, 20 th in the first, in 1-20 times all times, EVOH The content of is 6.
- Example 1 except that polypropylene [Nippon Polychem Co., Ltd., FY6C, MFR: 2.4 gZ 10 minutes (230 ° C, load 2160 g), density: 0.90 gZcm 3 ] was used instead of LDPE (A). Table 1 shows the results of similar evaluation. [0049]
- polypropylene Nippon Polychem Co., Ltd., FY6C, MFR: 2.4 gZ 10 minutes (230 ° C, load 2160 g), density: 0.90 gZcm 3 ] was used instead of LDPE (A). Table 1 shows the results of similar evaluation. [0049]
- LDPE LDPE
- Table 1 shows the results of evaluation performed in the same manner as in Example 1 except that zinc stearate [EZ-104, manufactured by Eishin Kasei Co., Ltd.] was used instead of calcium stearate (B).
- Comparative Example 1 Table 1 shows the results of evaluation in the same manner as in Example 1 except that no reforming pellets were blended.
- the obtained cup is measured with a turbidimeter and evaluated according to the following criteria.
- ⁇ Haze is less than 10
- ⁇ ⁇ ⁇ ⁇ Haze is 10 or more and less than 15
- TDS thermal extraction device
- the generated gas is condensed at 150 ° C. Collect with a device (CIS: Cooling Concentration Introducing Device) and concentrate for 2 hours. After that, the condenser is rapidly heated to 250 ° C, the condensed components are vaporized, introduced into the analytical column, and analyzed by GC ZMS.
- Table 2 shows the results of producing a multilayer sheet in the same manner as in Comparative Example 1 except that no white pigment master batch was used, and evaluating in the same manner as in Examples 11 to 20.
- Table 2 shows the results of the evaluation conducted in the same manner as in Example 11 except that Hydeguchi Talsite [DHT-4A, manufactured by Kyowa Chemical Co., Ltd.] was used instead of Zeolite (C).
- Hydeguchi Talsite [DHT-4A, manufactured by Kyowa Chemical Co., Ltd.] was used instead of Zeolite (C).
- the results of evaluating the surface smoothness, the number of fish eyes, the pigment dispersibility, and the suppression of phase separation foreign matter using a white pigment master batch were all ⁇ .
- a laminate produced by blending the resin composition of the present invention with a laminate containing EVOH exhibits good strength, generation of residence deterioration products derived from EVOH, gelation of EVOH, and Migration of odorous cracked gas generated by EVOH thermal decomposition to the outside is suppressed. Therefore, by using the obtained laminate, it is possible to produce a safe and inexpensive molded article having an excellent appearance. As described above, the regeneration technology using the resin composition of the present invention greatly contributes to the improvement of productivity of multilayer containers and the like.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006531913A JP4963961B2 (ja) | 2004-08-24 | 2005-08-23 | 樹脂組成物およびそれを用いた積層体の製造方法 |
CN2005800284553A CN101006130B (zh) | 2004-08-24 | 2005-08-23 | 树脂组合物及使用了该树脂组合物的层压体的制造方法 |
EP05775088.7A EP1783166B1 (en) | 2004-08-24 | 2005-08-23 | Resin composition and process for production of laminates by use of the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US10/925,787 | 2004-08-24 | ||
US10/925,787 US7332025B2 (en) | 2004-08-24 | 2004-08-24 | Resin composition and process for preparing multi-layer structure using the same |
Publications (1)
Publication Number | Publication Date |
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WO2006022256A1 true WO2006022256A1 (ja) | 2006-03-02 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2005/015268 WO2006022256A1 (ja) | 2004-08-24 | 2005-08-23 | 樹脂組成物およびそれを用いた積層体の製造方法 |
Country Status (5)
Country | Link |
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US (1) | US7332025B2 (ja) |
EP (1) | EP1783166B1 (ja) |
JP (1) | JP4963961B2 (ja) |
CN (1) | CN101006130B (ja) |
WO (1) | WO2006022256A1 (ja) |
Cited By (23)
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JP2011001436A (ja) * | 2009-06-18 | 2011-01-06 | Tosoh Corp | ポリエステル樹脂組成物 |
JP2012153815A (ja) * | 2011-01-26 | 2012-08-16 | Kuraray Co Ltd | 樹脂組成物及びその製造方法 |
WO2013187455A1 (ja) * | 2012-06-13 | 2013-12-19 | 株式会社クラレ | エチレン-ビニルアルコール樹脂組成物、多層シート、包装材及び容器 |
JP2015006786A (ja) * | 2013-05-29 | 2015-01-15 | 株式会社クラレ | 蒸着フィルム |
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Also Published As
Publication number | Publication date |
---|---|
CN101006130B (zh) | 2010-06-16 |
JP4963961B2 (ja) | 2012-06-27 |
JPWO2006022256A1 (ja) | 2008-05-08 |
US7332025B2 (en) | 2008-02-19 |
EP1783166B1 (en) | 2020-06-17 |
EP1783166A1 (en) | 2007-05-09 |
US20060047040A1 (en) | 2006-03-02 |
EP1783166A4 (en) | 2009-11-11 |
CN101006130A (zh) | 2007-07-25 |
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