JP4634856B2 - 白色プリプレグ、白色積層板、及び金属箔張り白色積層板 - Google Patents
白色プリプレグ、白色積層板、及び金属箔張り白色積層板 Download PDFInfo
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- JP4634856B2 JP4634856B2 JP2005140406A JP2005140406A JP4634856B2 JP 4634856 B2 JP4634856 B2 JP 4634856B2 JP 2005140406 A JP2005140406 A JP 2005140406A JP 2005140406 A JP2005140406 A JP 2005140406A JP 4634856 B2 JP4634856 B2 JP 4634856B2
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- Prior art keywords
- white
- epoxy resin
- laminate
- prepreg
- glycidyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
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- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
- B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
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- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C08G59/226—Mixtures of di-epoxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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- H05K1/0274—Optical details, e.g. printed circuits comprising integral optical means
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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Description
(1)本発明の白色プリプレグは、脂環式エポキシ樹脂(A1)を含むエポキシ樹脂(A)、グリシジル(メタ)アクリレート系ポリマー(B)、白色顔料(C)、及び硬化剤(D)を必須成分とする樹脂組成物(E)を、シート状ガラス繊維基材に含浸、乾燥させてなることを特徴とする。
(2)本発明の白色プリプレグは、好ましくは前記脂環式エポキシ樹脂(A1)を含むエポキシ樹脂(A)が、ビスフェノール類のジグリシジルエーテル型、フェノール類のノボラック型、グリシジルアミン型、及びグリシジルエステル型の中から選ばれる汎用エポキシ樹脂(A2)を、エポキシ樹脂(A)中に5〜60重量%含有することを特徴とする。
(3)本発明の白色プリプレグは、好ましくは前記樹脂組成物(E)が、(A);20〜85重量%、(B);5〜40重量%、(C);10〜75重量%、(D);(E)に含まれるエポキシ基1当量当り0.5〜2の当量比となる配合量、の組成比からなることを特徴とする。
(4)本発明の白色プリプレグは、好ましくは前記脂環式エポキシ樹脂(A1)が下記式(1)で表される構造を有することを特徴とする。
………式(1)
式(1)中、Rは、水素または炭素数1〜5の直鎖若しくは側鎖を有するアルキル基を表す。また、nは1から30の整数を表す。
(5)本発明の白色プリプレグは、好ましくは前記グリシジル(メタ)アクリレート系ポリマー(B)が、グリシジル(メタ)アクリレートホモポリマーであることを特徴とする。
(6)本発明の白色プリプレグは、好ましくは前記グリシジル(メタ)アクリレート系ポリマー(B)が、グリシジル(メタ)アクリレートとラジカル重合性モノマーとの共重合体であることを特徴とする。
(7)本発明の白色プリプレグは、好ましくは前記白色顔料(C)が酸化亜鉛、炭酸カルシウム、二酸化チタン、アルミナ、及び合成スメクタイトから選ばれる1種類、又は2種類以上であることを特徴とする。
(8)本発明の白色プリプレグは、好ましくは前記白色顔料(C)が二酸化チタンであることを特徴とする。
(9)本発明の白色プリプレグは、好ましくは前記硬化剤(D)が、潜在性硬化剤であることを特徴とする。
(10)本発明の白色積層板は、好ましくは(1)〜(9)に記載の白色プリプレグ1枚、又は複数枚積層したものを加熱加圧成形してなることを特徴とする。
(11)本発明の金属箔張り白色積層板は、好ましくは(1)〜(9)に記載の白色プリプレグ1枚、又は複数枚積層したものに、更に金属箔を積層配置したものを加熱加圧成形してなることを特徴とする。
(12)(10)項記載の白色積層板は、好ましくはチップ型発光ダイオードを実装するためのプリント配線基板として使用する。
(13)(11)項記載の金属箔張り白色積層板は、好ましくはチップ型発光ダイオードを実装するためのプリント配線基板として使用する。
脂環式エポキシ樹脂:EHPE−3150(ダイセル化学工業(株)製)50重量部 、ビスフェノールA型エポキシ樹脂:AER−6051EK75(旭化成工業(株)製)40重量部、並びにグリシジルメタクリレートコポリマー:マープルーフG−0150M(日本油脂(株)製)10重量部をメチルエチルケトン(以下MEKと表記)50重量部に溶解させた。…(ワニスA)
硬化剤としてDICY3重量部、硬化促進剤としてC11Z−CN(四国化成工業(株)製、1−シアノエチル−2−ウンデシルイミダゾール)0.1重量部をジメチルホルムアミド(以下DMFと表記)25重量部に溶解させた。…(ワニスB)
ワニスAとワニスBを混合し、白色顔料としてルチル型二酸化チタンR−21(堺化学工業(株)製)73重量部、蛍光増白剤としてHR−101(中央合成化学(株)製、ピラゾリン誘導体、放射波長:450nm)0.3重量部を添加し、室温で1時間攪拌して白色エポキシワニスを得た。
この白色エポキシワニスを0.1mm厚ガラスクロスWEA−116E(日東紡(株)製)に含浸させ、150℃で5分間予備乾燥し、樹脂組成物含有量50%のプリプレグを得た。このプリプレグ1枚、4枚、及び10枚積層したものに対し、その上下に18μm厚さの銅箔を重ね、圧力40kgf/cm2、温度170℃で加熱加圧成形して、0.1mm厚、0.4mm厚、及び1mm厚の金属箔張り白色積層板をそれぞれ得た。
白色エポキシワニスの組成を次のように変え、他は実施例1と同様にして白色積層板を得た。
ビスフェノールA型エポキシ樹脂:AER−6051EK75(旭化成工業(株)製)50重量部、クレゾールノボラック型エポキシ樹脂:YDCN−704(東都化成(株)製)50重量部をMEK40重量部に溶解させた。…(ワニスC)
硬化剤としてDDS19重量部、硬化促進剤として2P4MZ(四国化成工業(株)製、2−フェニル−4−メチルイミダゾール)0.4重量部をDMF30重量部に溶解させた。…(ワニスD)
ワニスCとワニスDを混合し、白色顔料としてアナターゼ型二酸化チタンTA−500(富士チタン工業(株)製)73重量部、蛍光増白剤としてHR−101(中央合成化学(株)製)0.3重量部を添加して白色エポキシワニスを得た。
得られた白色エポキシワニスを用い、実施例1と同様にしてプリプレグを作成し、それを積層し、上下に銅箔を重ねて加熱加圧成形して0.1mm厚、0.4mm厚、及び1mm厚の金属箔張り白色積層板をそれぞれ得た。
1)耐熱変色性
実施例1、比較例1で得られた0.1mmの金属箔張り白色積層板の銅箔をエッチング処理によって除去した後、該基板表面の可視光反射率をJIS−Z8722に準拠して測定し、さらに180℃で4時間加熱処理した後の可視光反射率を同様に測定した。
結果は図1に示した。図1から明らかなように、実施例1の基板は、比較例1の基板と比べて短波長領域での劣化が少なく、耐熱性が向上しているのが分かる。
2)耐紫外線性
実施例1、比較例1で得られた0.1mm厚の金属箔張り白色積層板の銅箔をエッチング処理によって除去した後、該基板表面の可視光反射率をJIS−Z8722に準拠して測定し、さらに400Wの高圧水銀灯光(紫外部発光スペクトル:253.7nm,365nm)を基板に対して照射距離45cm(照射強度=約6W/m2)で500時間照射処理した後の可視光反射率を同様に測定した。
結果は図2に示した。図2から明らかなように、実施例1の基板は、比較例1の基板と比べて短波長領域での劣化が少なく、耐紫外線性が向上しているのが分かる。
3)ガラス転移温度
ガラス転移温度はJIS−C6481に準拠して求めた。すなわち実施例1、比較例1で得られた0.4mm厚の金属箔張り白色積層板の銅箔をエッチング処理によって除去した後、7mm×70mmの大きさに切り出し、自由減衰型動的粘弾性測定装置(レスカ社製、型番:AD−1100AD)を用いて昇温速度2℃/分で測定し、測定データの損失正接のピーク温度からガラス転移温度を求めた。
実施例1、比較例1の白色積層板(金属箔除去後)のガラス転移温度は、それぞれ200℃、190℃であった。この結果から実施例1、比較例1の白色積層板は、いずれも実用上十分な耐熱性を有していたが、その中でも実施例1の白色積層板の方が耐熱性が優れていることが分かる。
4)板厚精度
実施例1、比較例1で得られた1mm厚の金属箔張り白色積層板(1000mm×1000mm)の板厚を、1/1000mmのマイクロメータを用いて縦250mm間隔および横70mm間隔で計60箇所測定し、板厚範囲、及び最大値と最小値の差を求めた。
実施例1、比較例1の金属箔張り白色積層板の板厚データを表1に示した。実施例1及び比較例1の板厚の最大値と最小値の差は、夫々0.055mm、0.115mmであった。
この結果から明らかなように実施例1の金属箔張り白色積層板は比較例1に比べて板厚の精度が向上し、要求精度を十分満たしていることが分かる。
Claims (13)
- 脂環式エポキシ樹脂(A1)を含むエポキシ樹脂(A)、グリシジル(メタ)アクリレート系ポリマー(B)、白色顔料(C)、及び硬化剤(D)を必須成分とする樹脂組成物(E)を、シート状ガラス繊維基材に含浸、乾燥させてなることを特徴とする白色プリプレグ。
- 前記脂環式エポキシ樹脂(A1)を含むエポキシ樹脂(A)が、ビスフェノール類のジグリシジルエーテル型、フェノール類のノボラック型、グリシジルアミン型、及びグリシジルエステル型の中から選ばれる汎用エポキシ樹脂(A2)を、エポキシ樹脂(A)中に5〜60重量%含有することを特徴とする請求項1に記載の白色プリプレグ。
- 前記樹脂組成物(E)が、(A);20〜85重量%、(B);5〜40重量%、(C);10〜75重量%、(D);(E)に含まれるエポキシ基1当量当り0.5〜2の当量比となる配合量、の組成比からなることを特徴とする請求項1又は請求項2に記載の白色プリプレグ。
- 前記グリシジル(メタ)アクリレート系ポリマー(B)が、グリシジル(メタ)アクリレートホモポリマーであることを特徴とする請求項1乃至請求項4のいずれかに記載の白色プリプレグ。
- 前記グリシジル(メタ)アクリレート系ポリマー(B)が、グリシジル(メタ)アクリレートとラジカル重合性モノマーとの共重合体であることを特徴とする請求項1乃至請求項4のいずれかに記載の白色プリプレグ。
- 前記白色顔料(C)が酸化亜鉛、炭酸カルシウム、二酸化チタン、アルミナ、及び合成スメクタイトから選ばれる1種類、又は2種類以上であることを特徴とする請求項1乃至請求項6のいずれかに記載の白色プリプレグ。
- 前記白色顔料(C)が二酸化チタンであることを特徴とする請求項1乃至請求項6のいずれかに記載の白色プリプレグ。
- 前記硬化剤(D)が、潜在性硬化剤であることを特徴とする請求項1乃至請求項8のいずれかに記載の白色プリプレグ。
- 請求項1乃至請求項9のいずれかに記載の白色プリプレグ1枚、又は複数枚積層したものを加熱加圧成形してなることを特徴とする白色積層板。
- 請求項1乃至請求項9のいずれかに記載の白色プリプレグ1枚、又は複数枚積層したものに、更に金属箔を積層配置したものを加熱加圧成形してなることを特徴とする金属箔張り白色積層板。
- 請求項10記載の白色積層板を使用してなるチップ型発光ダイオードを実装するためのプリント配線基板。
- 請求項11記載の金属箔張り白色積層板を使用してなるチップ型発光ダイオードを実装するためのプリント配線基板。
Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
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JP2005140406A JP4634856B2 (ja) | 2005-05-12 | 2005-05-12 | 白色プリプレグ、白色積層板、及び金属箔張り白色積層板 |
TW095112838A TWI403545B (zh) | 2005-05-12 | 2006-04-11 | 白色預浸片、白色積層板及金屬箔貼面積層板 |
US11/920,399 US20090194320A1 (en) | 2005-05-12 | 2006-05-10 | White Prepreg, White Laminated Plate, and Metal Foil Clad White Laminated Plate |
DE602006011456T DE602006011456D1 (de) | 2005-05-12 | 2006-05-10 | Weisses prepreg, weisse laminatplatte und mit weisser laminatplatte ummantelte metallfolie |
EP06746232A EP1887031B1 (en) | 2005-05-12 | 2006-05-10 | White prepreg, white laminated plate, and metal foil clad white laminated plate |
CN200680024753XA CN101218285B (zh) | 2005-05-12 | 2006-05-10 | 白色预浸料、白色层压板和覆金属箔的白色层压板 |
AT06746232T ATE453679T1 (de) | 2005-05-12 | 2006-05-10 | Weisses prepreg, weisse laminatplatte und mit weisser laminatplatte ummantelte metallfolie |
MYPI20062142A MY144427A (en) | 2005-05-12 | 2006-05-10 | White prepreg, white laminates, and metal foil-cladded white laminates |
KR1020077028311A KR100940232B1 (ko) | 2005-05-12 | 2006-05-10 | 백색 프리프레그, 백색 적층판, 및 금속박 백색적층판 |
CA2608179A CA2608179C (en) | 2005-05-12 | 2006-05-10 | White prepreg, white laminates, and metal foil-cladded white laminates |
PCT/JP2006/309422 WO2006121090A1 (ja) | 2005-05-12 | 2006-05-10 | 白色プリプレグ、白色積層板、及び金属箔張り白色積層板 |
HK09100274.8A HK1120283A1 (en) | 2005-05-12 | 2009-01-09 | White prepreg, white laminated plate, and metal foil clad white laminated plate |
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JP2005140406A JP4634856B2 (ja) | 2005-05-12 | 2005-05-12 | 白色プリプレグ、白色積層板、及び金属箔張り白色積層板 |
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JP4634856B2 true JP4634856B2 (ja) | 2011-02-16 |
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US (1) | US20090194320A1 (ja) |
EP (1) | EP1887031B1 (ja) |
JP (1) | JP4634856B2 (ja) |
KR (1) | KR100940232B1 (ja) |
CN (1) | CN101218285B (ja) |
CA (1) | CA2608179C (ja) |
DE (1) | DE602006011456D1 (ja) |
HK (1) | HK1120283A1 (ja) |
MY (1) | MY144427A (ja) |
TW (1) | TWI403545B (ja) |
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JP2008223167A (ja) * | 2007-03-12 | 2008-09-25 | Hideki Ueshiba | 発光標識体 |
JP5421546B2 (ja) * | 2007-07-05 | 2014-02-19 | 日立化成株式会社 | 熱硬化性光反射用樹脂組成物、並びにその樹脂組成物を用いた光半導体素子搭載用基板及び光半導体装置 |
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EP1887031A4 (en) | 2009-05-13 |
US20090194320A1 (en) | 2009-08-06 |
KR100940232B1 (ko) | 2010-02-04 |
TWI403545B (zh) | 2013-08-01 |
HK1120283A1 (en) | 2009-03-27 |
WO2006121090A1 (ja) | 2006-11-16 |
DE602006011456D1 (de) | 2010-02-11 |
KR20080014830A (ko) | 2008-02-14 |
TW200704688A (en) | 2007-02-01 |
CN101218285B (zh) | 2011-03-30 |
CA2608179C (en) | 2010-06-29 |
JP2006316173A (ja) | 2006-11-24 |
MY144427A (en) | 2011-09-15 |
CA2608179A1 (en) | 2006-11-16 |
EP1887031A1 (en) | 2008-02-13 |
EP1887031B1 (en) | 2009-12-30 |
CN101218285A (zh) | 2008-07-09 |
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