WO2004048480A1 - 近赤外線吸収色素及び近赤外線遮断フィルター - Google Patents
近赤外線吸収色素及び近赤外線遮断フィルター Download PDFInfo
- Publication number
- WO2004048480A1 WO2004048480A1 PCT/JP2003/014642 JP0314642W WO2004048480A1 WO 2004048480 A1 WO2004048480 A1 WO 2004048480A1 JP 0314642 W JP0314642 W JP 0314642W WO 2004048480 A1 WO2004048480 A1 WO 2004048480A1
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- WIPO (PCT)
- Prior art keywords
- group
- absorbing dye
- infrared absorbing
- infrared
- infrared ray
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
- C09B69/06—Dyestuff salts, e.g. salts of acid dyes with basic dyes of cationic dyes with organic acids or with inorganic complex acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B55/00—Azomethine dyes
- C09B55/009—Azomethine dyes, the C-atom of the group -C=N- being part of a ring (Image)
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
Definitions
- the present invention relates to a novel near-infrared absorbing dye comprising a dimodium salt compound having absorption in the near-infrared light region and having excellent heat resistance and heat resistance, and a near-infrared cutoff filter containing the dye.
- PDP plasma display panels
- Near infrared rays are emitted from the PDP, and electronic equipment using a near infrared remote control malfunctions. Therefore, it is necessary to block near infrared rays with a filter using a near infrared absorbing dye.
- Near-infrared cutoff filters are also widely used for applications such as optical lenses, automotive glass, and building material glass.
- the near-infrared cutoff filter used for these applications is required to have a property of absorbing the near-infrared light region effectively while transmitting the visible light region, and further having high heat resistance and moisture resistance.
- the publication discloses various examples of near-infrared absorbing dyes based on dimodium salts. Among them, those having relatively excellent heat resistance and moisture resistance, for example, bis (hexafluoroantimony) having an anion component of bis (hexafluoroantimony) are exemplified. N), N, N ', N'-tetrakis ⁇ p-di (n-butyl) aminophenyl ⁇ -p-phenylenedimonium salt Used.
- the dye is insufficient in heat resistance and moisture resistance, the dye is decomposed during use, the near-infrared absorption ability is reduced, and the aminium salt generated by the decomposition absorbs in the visible light region.
- the visible light transmittance is reduced and the color is turned yellow to deteriorate the color tone.
- the above-mentioned dye contains heavy metal in an anion component, and there is a problem that when used in a large amount, the environment is polluted.
- An object of the present invention is to firstly provide a novel near-infrared absorbing dye which is excellent in heat resistance and moisture resistance and does not decrease near-infrared absorbing ability for a long period of time.
- An object of the present invention is to provide a near-infrared cutoff filter having excellent moisture resistance. Disclosure of the invention
- a near-infrared absorbing dye comprising a dimonium salt having a specific anion component is excellent in heat resistance and moisture resistance, and have completed the present invention.
- the present invention is a near-infrared absorbing dye comprising a dimonium salt containing a sulfonimide represented by the general formula (1) as an anion component.
- R is the same or different and is an alkyl group
- a halogenated alkyl group, 1 ⁇ and 1 ⁇ 2 are the same or different and each represents a fluoroalkyl group, or a group selected from the group consisting of a non-alkyl group, an aryl group, a hydroxyl group, a phenyl group and a phenylalkylene group.
- the present invention is a near-infrared absorbing dye in which, in the general formula (1), R 1 and R 2 are perfluoroalkyl groups having 1 to 8 carbon atoms which may be the same or different.
- the present invention provides a near-infrared absorbing method, wherein, in the general formula (1), the fluoroalkylene group formed by combining R 1 and R 2 is a perfluoroalkylene group having 2 to 12 carbon atoms. It is a pigment.
- the present invention is a near-infrared cutoff filter containing the above-mentioned near-infrared absorbing dye.
- FIG. 1 is a spectrum of transmittance of the near-infrared cutoff filter produced in Example 1.
- the near-infrared absorbing dye of the present invention comprises a dimonium salt containing a sulfonimide represented by the above general formula (1) as an anion component.
- the near-infrared ray means light having a wavelength of 760 to 2000 nm.
- R 1 and R 2 in the anion component in the general formula (1) may be substituted if they are a fluoroalkyl group which may be the same or different, or a fluoroalkylene group formed together.
- the number of fluorine atoms and the number of carbon atoms are not particularly limited. Preferred examples of R 1 and R 2 are the same or different.
- a perfluoroalkyl group having 1 to 8 carbon atoms is an anion component represented by the general formula (3).
- n and n ′ each represent an integer of 1 to 8.
- n and n ′ are more preferably integers of 1 to 4.
- R 1 and R 2 in the anion component in the general formula (1) is a perfluoroalkylene group having 2 to 12 carbon atoms formed by combining them. That is, preferred examples of the anion component include an anion component represented by the general formula (4). -3 ⁇ 4-
- m represents an integer of 2 to 12
- m is preferably 2 to 8, and particularly preferably m is 3, and is represented by the following general formula (5).
- 1,3-disulfonylhexafluoropropylenimide is an example of the anion component.
- the perfluoroalkylene group having 2 to 12 carbon atoms is preferable because the heat resistance is further improved.
- R is a substituent selected from the group consisting of an alkyl group, a halogenated alkyl group, a cyanoalkyl group, an aryl group, a hydroxyl group, a phenyl group and a phenylalkylene group; Or different.
- R is not particularly limited as long as it is the above substituent, but is preferably an alkyl group having 1 to 8 carbon atoms or a straight chain or a side chain, a halogenated alkyl group, a cyanoalkyl group, or the like. Chain alkyl groups are particularly preferred.
- R as R in the general formula (1) include, for example, ethyl, propyl, butyl, amyl, isopropyl, isobutyl,
- R is a phenylalkylene group represented by the general formula (2).
- A represents an alkylene group having a linear or side chain having 1 to 18 carbon atoms
- ring B represents a benzene ring which may have a substituent.
- the alkylene group has 1 to 8 carbon atoms.
- the phenyl group in the phenylalkylene group of the general formula (2) may not have a substituent, but may be an alkyl group, a hydroxyl group, a sulfonic acid group, an alkylsulfonic acid group, a nitro group, an amino group, or an alkoxy group.
- a phenylalkylene group examples include a benzyl group, a phenyl group, a phenylpropylene group, a phenyl_ ⁇ -methylpropylene group, a phenyl-3-methylpropylene group, a phenylbutylene group, a phenylpentylene group, and a phenyl group.
- Octylene group and the like examples include a benzyl group, a phenyl group, a phenylpropylene group, a phenyl_ ⁇ -methylpropylene group, a phenyl-3-methylpropylene group, a phenylbutylene group, a phenylpentylene group, and a phenyl group.
- a phenylalkylene group represented by the above general formula (2) can improve heat resistance, but most preferred are a benzyl group and a phenethyl group.
- the silver sulfonimidate derivative represented by the general formula (6) and the compound represented by the general formula (7) are combined with ⁇ -methyl-2-pyrrolidone, dimethylformamide (hereinafter abbreviated as “DMF”), acetonitrile, etc.
- DMF dimethylformamide
- the reaction was carried out at a temperature of 30 to 150 in an organic solvent of, and after the precipitated silver was filtered off, a solvent such as water, ethyl acetate or hexane was used. And the resulting precipitate is filtered to obtain the near-infrared absorbing dye of the present invention.
- the above-obtained dye is combined with an appropriate polymer resin, and is mixed with a known polymer such as a casting method or a melt extrusion method.
- the near-infrared cutoff filter of the present invention can be produced by forming a film or panel by the method.
- the near-infrared absorbing filter of the present invention is dissolved or dispersed in a solution in which a polymer resin and a solvent are mixed, and then the polyester or polycarbonate or the like is dissolved.
- the solution may be applied to a transparent film, panel, or glass substrate, dried, and formed into a film.
- the polymer resin a known transparent resin is used, and preferably, an acrylic resin, a polyester resin, a polycarbonate, a urethane resin, a cellulose resin, a polyisocyanate, a polyarylate, an epoxy resin, or the like is used. Is used.
- the solvent is not particularly limited, but an organic solvent such as methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, 1,4-dioxane, or a mixture thereof can be used. .
- the near-infrared absorbing dye of the present invention is melted and kneaded in a polymer resin, and then the mixture is extruded. What is necessary is just to shape
- the polymer resin a known transparent resin is used, and preferably, an acrylic resin, a polyester resin, polycarbonate, or the like is used.
- the near-infrared absorbing dye may be used alone, but in order to supplement near-infrared cutoff performance near a wavelength of about 850 nm, phthalocyanine and dithiol-based metal A known dye such as a complex may be added. Further, in order to improve the light resistance, a benzophenone-based or benzotriazole-based ultraviolet absorbing dye may be added and used. Further, if necessary, a known dye having an absorption in the visible light region may be added to change the color tone.
- the near-infrared transmittance of the near-infrared cutoff filter of the present invention can be controlled by changing the mixing ratio of the near-infrared absorbing dye of the present invention to the polymer resin.
- the mixing ratio of the dye to the polymer resin is not particularly limited, but is preferably in the range of 0.01 to 30% by mass (hereinafter abbreviated as “%”) based on the entire polymer resin. is there. If the mixing ratio is less than 0.01%, the near-infrared ray blocking ability may be insufficient, and if it is greater than 30%, the visible light transmittance may decrease. Preferably, it is 0.05 to 30%.
- the near-infrared absorbing dye of the present invention described above is excellent in heat resistance and moisture resistance, does not decrease in near-infrared absorbing ability over a long period of time, and does not contain any heavy metals, so there is no problem for the environment.
- the near-infrared cutoff filter of the present invention containing the near-infrared absorbing dye of the present invention can be used for various applications that require blocking of near-infrared rays. Specifically, it can be used, for example, as a near-infrared cutoff filter for PDP, a near-infrared cutoff filter for automotive glass or building material glass, and particularly preferably used as a near-infrared cutoff filter for PDP.
- the near-infrared absorbing dye of the present invention can also be used as a dye or quencher for optical recording media such as CD-R and DVD-R.
- the filter was stored in an atmosphere at a temperature of 80 and subjected to a heat resistance test.
- the initial molar extinction coefficient at a wavelength of 1000 nm was set to 100%, and the percentage of the molar extinction coefficient after a predetermined time had elapsed was calculated.
- the residual ratio of the dye was taken.
- the transmittance at a wavelength of 480 nm was measured. Table 1 shows the results.
- Example 2 the samples were stored in an atmosphere at a temperature of 60% and a humidity of 95%, and subjected to a moist heat resistance test. As in the heat resistance test, the dye remaining ratio and the transmittance at a wavelength of 480 nm were measured. Table 2 shows the results. Example 2
- Example 2 The procedure of Example 1 was repeated, except that 12.6 parts of silver bis (pentafluoroethanesulfone) imidate was used instead of 10 parts of silver bis (trifluoromethanesulfon) imidate in Example 1. N, N, N ', N'-tetrakis (p-dibutylaminophenyl) -p-phenylenedimonium (trifluoromethanesulfon) imidic acid was obtained.
- This material is the near infrared absorbing dye, 111 & is 10741 m, the molar extinction coefficient of 101000 [L 'mo 1- 1 ⁇ cm-, melting point 185, decomposition point was 30 I.
- Bis (hexafluoro) was prepared in the same manner as in Example 1 except that 8.9 parts of silver hexafluoroantimonate was used instead of 10 parts of silver bis (trifluoromethanesulfon) imidate.
- (Loantimonic acid) N, N, ⁇ ,, N, -tetrakis ⁇ p- (n-butyl) aminophenyl ⁇ 1-p-phenylenedimonium was obtained.
- This material is the near infrared absorbing dye, Amax is 1074 nm, the molar absorption coefficient of 101000 [L ⁇ mo 1- 1 ⁇ cm-, melting point 185, decomposition point was 301.
- a near-infrared cutoff filter was prepared in the same manner as in Example 1, and a heat resistance test was performed. And a wet heat resistance test. The results are shown in Tables 1 and 2.
- the conventional near-infrared absorbing dye used in the comparative example has low heat resistance and low moisture-heat resistance, decomposes over time, and the absorption coefficient in the near infrared region near the wavelength of 100 nm decreases.
- absorption of aluminum chloride and the like generated by decomposition occurs in the visible light region around the wavelength of 480 nm, The transmittance was reduced, and the color turned yellow and the color tone was lost.
- the near-infrared cutoff filter containing the near-infrared absorbing dye of Examples 1 and 2 of the present invention has high heat resistance, high moisture-heat resistance, and a small decrease in absorption in the near-infrared region.
- coloration in the visible light region due to the decomposition of the dye was also unlikely to occur.
- the dye may be a bis (bis (trifluoromethanesulfon) imidic acid ⁇ ⁇ , ⁇ , ⁇ ′, N′-tetrax ( ⁇ -dibenzyla), wherein all of the substituents R in the general formula (1) are benzyl groups.
- Minophenyl It was a ⁇ -phenylenemonium.
- Example 5 In the same manner as in Example 3 except that 58.5 parts of phenethyl iodide was used as the raw material for the substituent in Example 3, bis (bi N, N, N ', N'-tetrax (p-diphenethylaminophenyl) -p-phenylenedimonium was obtained.
- Example 5 bis (bi N, N, N ', N'-tetrax (p-diphenethylaminophenyl) -p-phenylenedimonium was obtained.
- Example 3 was repeated except that 58.5 parts of phenethyl iodide was used as a raw material for a substituent and 33.5 parts of silver 1,3-disulfonylhexafluoropropyleneimide were used as a raw material for an anion.
- One ⁇ -phenylenemonium was obtained.
- Example 3 was repeated except that 46.4 parts of butyl iodide was used as a substituent raw material and 33.5 parts of silver 1,3-disulfonylhexafluoropropyleneimidate was used as a raw material for an anion.
- the near-infrared absorbing dye of the present invention Bis (1,3-disulfonylhexafluoropropyleneimidic acid) N, N, N ', N, -tetrakis (p-dibutylaminophenyl) _p-phenylenedimonium was obtained.
- Example 8
- the near-infrared cutoff filter containing the near-infrared absorbing dye of Examples 3 to 7 of the present invention has high heat resistance, high moisture-heat resistance, and low absorption in the near-infrared region. And the coloration in the visible light region due to the decomposition of the dye was hard to occur.
- the near-infrared absorbing dye of the present invention is excellent in heat resistance and moisture resistance, does not decrease in near-infrared absorbing ability for a long period of time, and does not contain heavy metals, so there is no problem for the environment.
- the near-infrared cutoff filter of the present invention containing the near-infrared absorbing dye of the present invention can be used for various applications, for example, a near-infrared cutoff filter for PDP, a near-infrared cutoff filter for automotive glass or building material glass. These are particularly suitable as a near-infrared cutoff filter for PDP.
- the near-infrared absorbing dye of the present invention can also be used as a dye or quencher for optical recording media such as CD-R and DV-R, which are conventional applications. that's all
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Optical Filters (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Claims
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03772847A EP1564260B1 (en) | 2002-11-22 | 2003-11-18 | Coloring matter absorbing near-infrared ray and filter for cutting off near-infrared ray |
| JP2004554977A JP4168031B2 (ja) | 2002-11-22 | 2003-11-18 | 近赤外線吸収色素及び近赤外線遮断フィルター |
| US10/535,671 US7524619B2 (en) | 2002-11-22 | 2003-11-18 | Coloring matter absorbing near-infrared ray and filter for cutting off near-infrared ray |
| AU2003280844A AU2003280844A1 (en) | 2002-11-22 | 2003-11-18 | Coloring matter absorbing near-infrared ray and filter for cutting off near-infrared ray |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002-339110 | 2002-11-22 | ||
| JP2002339110 | 2002-11-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004048480A1 true WO2004048480A1 (ja) | 2004-06-10 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2003/014642 Ceased WO2004048480A1 (ja) | 2002-11-22 | 2003-11-18 | 近赤外線吸収色素及び近赤外線遮断フィルター |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US7524619B2 (ja) |
| EP (1) | EP1564260B1 (ja) |
| JP (1) | JP4168031B2 (ja) |
| KR (1) | KR101015647B1 (ja) |
| CN (1) | CN100348669C (ja) |
| AU (1) | AU2003280844A1 (ja) |
| TW (1) | TWI331626B (ja) |
| WO (1) | WO2004048480A1 (ja) |
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| WO2005037940A1 (ja) * | 2003-10-20 | 2005-04-28 | Sumitomo Osaka Cement Co., Ltd. | 近赤外線遮蔽用塗料、それから得られる近赤外線遮蔽積層体及びその製造方法 |
| WO2005044782A1 (ja) | 2003-11-10 | 2005-05-19 | Nippon Kayaku Kabushiki Kaisha | ジイモニウム塩化合物およびその用途 |
| WO2006006573A1 (ja) * | 2004-07-12 | 2006-01-19 | Nippon Kayaku Kabushiki Kaisha | フィルタ、及びシアニン化合物 |
| WO2006028006A1 (ja) | 2004-09-06 | 2006-03-16 | Nippon Kayaku Kabushiki Kaisha | ジイモニウム化合物及びその用途 |
| JP2006143674A (ja) * | 2004-11-22 | 2006-06-08 | Yamamoto Chem Inc | ジイモニウム塩化合物、該化合物を含有する近赤外線吸収剤および近赤外線カットフィルター |
| JP2006184820A (ja) * | 2004-12-28 | 2006-07-13 | Toyobo Co Ltd | 近赤外線吸収フィルムおよび近赤外線吸収フィルター |
| JP2006188653A (ja) * | 2004-12-10 | 2006-07-20 | Toyo Ink Mfg Co Ltd | 近赤外線吸収性コーティング剤およびそれを用いてなる近赤外線吸収積層体 |
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| WO2007145289A1 (ja) * | 2006-06-14 | 2007-12-21 | Hitachi Maxell, Ltd. | ジイモニウム塩化合物、およびこれを含む近赤外線吸収組成物、並びに近赤外線吸収フィルタ、ディスプレイ用前面板 |
| WO2008010501A1 (en) * | 2006-07-21 | 2008-01-24 | Nippon Kayaku Kabushiki Kaisha | Near-infrared absorbing film and optical filter for plasma display panel using the same |
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| WO2008038569A1 (fr) * | 2006-09-28 | 2008-04-03 | Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo | Filtre optique |
| JP2009098699A (ja) * | 2003-07-16 | 2009-05-07 | Asahi Glass Co Ltd | 光学フィルム |
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| JP2013502611A (ja) * | 2009-08-18 | 2013-01-24 | インターナショナル・ビジネス・マシーンズ・コーポレーション | 近赤外吸収膜組成物 |
| JP2014006343A (ja) * | 2012-06-22 | 2014-01-16 | Japan Carlit Co Ltd | 近赤外線吸収剤分散液の製造方法及び近赤外線吸収積層体 |
| US9966402B2 (en) | 2014-12-04 | 2018-05-08 | Jsr Corporation | Solid-state imaging device |
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| US7473802B2 (en) * | 2005-09-05 | 2009-01-06 | Fujifilm Corporation | Method of producing near-infrared absorbing dye compound |
| JP2007141876A (ja) * | 2005-11-14 | 2007-06-07 | Sony Corp | 半導体撮像装置及びその製造方法 |
| CN101395501B (zh) * | 2006-03-01 | 2011-01-26 | 日本化药株式会社 | 近红外线吸收薄膜以及使用该薄膜的等离子体显示板用滤光器 |
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| JP5551089B2 (ja) * | 2008-12-25 | 2014-07-16 | 株式会社Adeka | シアニン化合物を用いた近赤外線吸収材料及びシアニン化合物 |
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| WO2014069198A1 (ja) * | 2012-11-01 | 2014-05-08 | 株式会社Adeka | 塗料及び近赤外線吸収フィルター |
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| JP2001133624A (ja) * | 1999-11-05 | 2001-05-18 | Sumitomo Osaka Cement Co Ltd | 近赤外線遮蔽フィルム |
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2003
- 2003-11-18 KR KR1020057008304A patent/KR101015647B1/ko not_active Expired - Lifetime
- 2003-11-18 WO PCT/JP2003/014642 patent/WO2004048480A1/ja not_active Ceased
- 2003-11-18 TW TW092132249A patent/TWI331626B/zh not_active IP Right Cessation
- 2003-11-18 US US10/535,671 patent/US7524619B2/en not_active Expired - Lifetime
- 2003-11-18 EP EP03772847A patent/EP1564260B1/en not_active Expired - Lifetime
- 2003-11-18 JP JP2004554977A patent/JP4168031B2/ja not_active Expired - Lifetime
- 2003-11-18 CN CNB2003801038152A patent/CN100348669C/zh not_active Expired - Lifetime
- 2003-11-18 AU AU2003280844A patent/AU2003280844A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10180922A (ja) | 1996-12-25 | 1998-07-07 | Nippon Kayaku Co Ltd | 赤外線吸収体 |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20060073407A1 (en) | 2006-04-06 |
| CN100348669C (zh) | 2007-11-14 |
| JPWO2004048480A1 (ja) | 2006-03-23 |
| KR101015647B1 (ko) | 2011-02-22 |
| TWI331626B (en) | 2010-10-11 |
| US7524619B2 (en) | 2009-04-28 |
| AU2003280844A1 (en) | 2004-06-18 |
| EP1564260A4 (en) | 2006-01-25 |
| CN1714126A (zh) | 2005-12-28 |
| JP4168031B2 (ja) | 2008-10-22 |
| EP1564260B1 (en) | 2013-03-13 |
| EP1564260A1 (en) | 2005-08-17 |
| KR20050086486A (ko) | 2005-08-30 |
| TW200424295A (en) | 2004-11-16 |
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