JP6723936B2 - 金属表面用インジケータ塗料 - Google Patents
金属表面用インジケータ塗料 Download PDFInfo
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- JP6723936B2 JP6723936B2 JP2017013061A JP2017013061A JP6723936B2 JP 6723936 B2 JP6723936 B2 JP 6723936B2 JP 2017013061 A JP2017013061 A JP 2017013061A JP 2017013061 A JP2017013061 A JP 2017013061A JP 6723936 B2 JP6723936 B2 JP 6723936B2
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/41—Organic pigments; Organic dyes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
- C23F11/185—Refractory metal-containing compounds
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- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
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- Y10T428/00—Stock material or miscellaneous articles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
に好適な金属陽イオンとしては、セリウム、イットリウム、プラセオジム、ジルコニウム、リチウムおよび亜鉛が挙げられる。
物が特に除外される。本明細書において用いられる「蛍光インジケータ」およびこれに類する語は、紫外光または可視光に曝されると蛍光を発するか、または蛍光を発しない場合は呈色するであろう化合物、分子、顔料および/または染料を指す。「蛍光を発する」とは、光または他の電磁放射を吸収した後に光を放出することと理解されるであろう。「標識(tag)」と称されることも多いこの種のインジケータの例としては、アクリジン、アントラキノン、クマリン、ジフェニルメタン、ジフェニルナフチルメタン、キノリン、スチルベン、トリフェニルメタン、アントラシン(anthracine)ならびに/またはこれらのいずれかの部分および/もしくはこれらのいずれかの誘導体を含む分子(ローダミン類、フェナントリジン類、オキサジン類、フルオロン類、シアニン類および/またはアクリジン類等)が挙げられる。
尿素系化合物、錯形成剤、原子価安定剤(valence stabilizer)、米国特許出願公開第2013/0034742号明細書の第[0035]段落および第[0036]段落に記載されているものなどの反応促進剤およびフィラー(これらの段落を本明細書の一部を構成するものとしてここに援用する)に加えて、他の慣用の助剤が挙げられる。他の任意的な成分としては、アラントイン、ポリビニルピロリドン、キレート剤(EDTA、TEA、クエン酸、ヘキサメチレンテトラミン、チオ尿素等)および/またはアルコール類(エタノールおよび/またはイソプロパノール等)またはアゾール類(2,5−ジメルカプト−1,3,4−チアジアゾール、1H−ベンゾトリアゾール、1H−1,2,3−トリアゾール、2−アミノ−5−メルカプト−1,3,4−チアジアゾールおよび2−アミノ−1,3,4−チアジアゾール等)が挙げられる。本開示を参照することにより当業者に理解されるように、表面塗料処方の技術分野において知られている他の好適な添加剤も本発明による組成物にさらに使用することができる。
ボネート、ポリカーボネートアクリロブタジエンスチレン(「PC/ABS」)、ポリアミド、木材、単板、複合木材、パーティクルボード、中密度ファイバーボード、セメント、石材、ガラス、紙、厚紙、繊維製品、皮革(天然および合成)および他の非金属基材が挙げられる。本発明に使用するのに好適な金属基材としては、自動車車体の組立て、自動車部品、航空宇宙用部品および他の物品(締結具、すなわち、ナット、ボルト、ネジ、ピン、釘、クリップ、ボタン等の小型の金属部品等)によく使用されているものが挙げられる。好適な金属および合金基材の具体例としては、これらに限定されるものではないが、冷間圧延鋼、熱間圧延鋼、金属亜鉛、亜鉛化合物または亜鉛合金で被覆した鋼(電気亜鉛メッキ鋼、溶融亜鉛メッキ鋼、合金化溶融亜鉛メッキ鋼および亜鉛合金メッキ鋼等)も挙げられる。同様に、アルミニウム合金、アルミニウムメッキ鋼およびアルミニウム合金メッキ鋼も基材として使用することができる。他の好適な非鉄金属として、銅およびマグネシウム等に加えてこれらの金属の合金が挙げられる。さらに、特定の実施形態においては、基材は、地金基材(通常であれば残りの面が処理および/または被覆されている、基材の切り口等)であってもよい。本発明の方法に従い処理される金属基材は、例えば、金属のシートまたは加工部品の形態であってもよい。
本発明の特定の実施形態においては、本組成物を基材と接触させた後に、皮膜形成樹脂を含む塗料組成物と接触させる。基材にこの種の塗料組成物を接触させるために、例えば、刷毛塗り、浸し塗り、流し塗り、吹き付け等の任意の好適な技法を用いることができる。特定の実施形態においては、この種の接触は、電着可能な組成物を電着により金属基材上に堆積させる電気塗装ステップを含む。電着の過程においては、電極の役割を果たす被処理金属基材と導電性を有する対電極とが、イオン性を有する電着可能な組成物と接触す
るように配置される。電着可能な組成物と接触させたまま電極と対電極との間に電流を流すと、金属基材上に電着可能な組成物の接着性を有する膜が実質的に連続な形で堆積するであろう。電着塗装の方法も当該技術分野においてよく知られている。
99W009等の高機能トップコート(advanced performance topcoat)である。他の好適なトップコートの例は、ピー・アール・シー・デソト・インターナショナル・インコーポレーテッド(PRC−DeSoto International,Inc.)よりデソタン(DESOTHANE)の商品名で市販されているものであり、これらに限定されるものではないが、ピー・アール・シー・デソト・インターナショナル・インコーポレーテッド(PRC−DeSoto International,Inc.)より市販されているデソタン(DESOTHANE)HS CA 8000ポリウレタントップコートのいずれかのポリウレタントップコートが挙げられる。他のトップコートおよび高性能トップコートも、本開示を参照することにより当業者に理解されるように、本発明による塗膜系に使用することができる。
NまたはMIL−PRF−23377 Class Nに適合する他のクロメートフリーのプライマー等も本発明と一緒に用いることができる。プライマー塗膜はカリフォルニア州アーバイン(Irvine,CA)のピー・アール・シー・デソト・インターナショナル・インコーポレーテッド(PRC−DeSoto International,Inc.)より、品番デフト(Deft)02GN083またはデフト(Deft)02GN084として入手可能である。プライマー塗膜は、本発明により形成した層の上に、処理および/または塗膜を介在させるかまたは介在させずに堆積させることができ、このプライマーの上にトップコートまたは他の1または複数の塗膜層を堆積させることができる。
明による塗膜系と一緒に使用することができる。
本明細書において用いられる、数値、範囲、量または百分率を表すものなどのあらゆる数字は、特に明記しない限り、例えその語が明確に記載されていなくても「約」という単語で修飾されているものと解釈することができる。本明細書において引用されるあらゆる数値範囲は、その中に組み込まれているあらゆる下位範囲を包含することを意図している。複数形は単数形を包含し、その逆も同様である。例えば、本発明について「1種の」腐食抑制金属陽イオン、「1種の」共役化合物、「1種の」インジケータ化合物等に関し説明してきたが、これらと他の成分との混合物を使用することもできる。また、本明細書において用いられる「ポリマー」という語は、プレポリマー、オリゴマーならびにホモポリマーおよびコポリマーの両方を意味する。「ポリ」という接頭辞は2以上を指す。範囲を示した場合、これらの範囲の任意の端点および/またはこれらの範囲に含まれる任意の数を本発明の範囲内で組み合わせることができる。「含む」、「等」、「例えば」等の語は、「これらに限定されるものではないが、含む/等/例えば」を意味する。
本発明の範囲に包含される製造可能な組成物の例を以下に開示する。これらの例が包括的なものではなく、他の組成物も本発明の範囲内に包含されることが理解されるであろう。
本組成物の特定の実施形態は、インジケータ化合物および1種以上の希土類元素イオンを含むことができる。この実施形態によれば、本組成物は、水性担体、インジケータ化合物ならびに第1および第2希土類元素の塩を含むことができ、塩はそれぞれ陰イオンおよび陽イオンを含み、第1塩および第2塩の陰イオンは異なっており、第1塩および第2塩の陽イオンは同一であるかまたは異なっており、各陽イオンは、個々に、希土類元素である。プラセオジム、セリウム、ネオジム、サマリウムおよびテルビウムの塩等の希土類元素の塩が化成皮膜処理組成物中に混合された場合(この塩は、ハロゲン化物イオンや硝酸イオン等の複数種の陰イオンの混合物である)、これらは結果として得られる希土類元素塗膜の堆積パラメータ(結果として得られる塗膜の形態および性能を含む)に大きく影響
することが見出されたが、本発明者はこのことに束縛されるつもりはない。この実施形態による組成物は、インジケータ化合物、少なくとも1種の希土類元素(セリウムまたはセリウムおよびイットリウムの両方)の塩ならびに硝酸イオンおよびハロゲン化物イオンの組合せならびに場合によりH2O2等の酸化剤を含む。この組成物のpHは中性になるであろう。
本発明の他の実施形態によれば、本組成物は、水性担体、インジケータ化合物およびジルコニウムイオンを含む金属イオン(硝酸ジルコニルおよびヘキサフルオロジルコン酸塩またはこれらの組合せ等)を含むことができる。他の塩、特に硝酸金属(イットリウム等)塩を本実施形態に従い組成物に加えることができる。この組成物用の添加剤としては、ハロゲン化物供給源、界面活性剤およびポリビニルピロリドンが挙げられる。本実施形態に従う組成物を下の表に示す。
本発明の他の実施形態によれば、本組成物は、水性担体、インジケータ化合物および第IA族金属イオン(リチウム、ナトリウムおよびカリウムまたはこれらの組合せ等)を含む金属イオンを含む。第IA族金属をベースとする塗料組成物は、水酸化物イオン、ハロゲン化物イオン、リン酸イオンおよび炭酸イオンまたはこれらの組合せ等の対イオンをさらに含むことができる。一実施形態においては、本組成物は、水性担体、インジケータ化合物およびリチウムイオン(炭酸リチウム等)を含むことができる。本実施形態による組成物は、さらにハロゲン化物供給源(フッ化物供給源、例えば、フッ化亜鉛)を含むことができる。例示的な組成物を下の表に示す。
Claims (6)
- a)腐食抑制金属陽イオンと、
b)0.01g/1000g〜3g/1000gの量で存在する、金属とともに錯体を形成可能な共役化合物と、
c)水性媒体と、
を含み、前記共役化合物がインジケータ化合物を含み、
前記インジケータ化合物が、
i)金属基材中の金属イオンとともに金属イオン錯体を形成すると、
ii)アルカリ性のpHに曝されると、または、
iii)酸性のpHに曝されると、
色が変化する、化成皮膜組成物。 - 腐食抑制金属陽イオンが、希土類元素およびリチウムの少なくとも一方の陽イオンを含む、請求項1に記載の組成物。
- 前記組成物が、アゾール化合物、酸化剤、およびポリビニルピロリドンの少なくとも1つをさらに含む、請求項1に記載の組成物。
- 前記組成物が、クロム酸塩および重金属リン酸塩の少なくとも一方を実質的に含まない、請求項1に記載の組成物。
- 金属基材を処理するための方法であって、
a)前記基材の少なくとも一部に請求項1に記載の組成物を適用するステップ
を含む、方法。 - a)請求項1に記載の組成物に由来する堆積層と、
b)その少なくとも一部の上に堆積した塗膜層と
を含む基材。
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JP2010022899A (ja) * | 2008-07-16 | 2010-02-04 | Miura Co Ltd | 水中の水処理剤の濃度管理方法、ボイラ水中の水処理剤の濃度管理方法、及びこれら管理方法に用いられる水処理剤 |
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EP2554961A4 (en) * | 2010-03-31 | 2013-10-30 | Nichu Giken Kogyo Kk | TEMPERATURE ADMINISTRATION ADVERTISING AND EQUIPPED STRUCTURE |
US9347134B2 (en) * | 2010-06-04 | 2016-05-24 | Prc-Desoto International, Inc. | Corrosion resistant metallate compositions |
US8859288B2 (en) * | 2011-07-11 | 2014-10-14 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | pH-sensitive microparticles with matrix-dispersed active agent |
US10017861B2 (en) | 2011-08-03 | 2018-07-10 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing a rare earth metal, associated methods for treating metal substrates, and related coated metal substrates |
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2013
- 2013-06-10 RU RU2014152643A patent/RU2619376C2/ru active
- 2013-06-10 US US14/405,580 patent/US20150140338A1/en not_active Abandoned
- 2013-06-10 WO PCT/US2013/044983 patent/WO2013185131A1/en active Application Filing
- 2013-06-10 EP EP13732312.7A patent/EP2859132B1/en active Active
- 2013-06-10 ES ES13732312T patent/ES2882529T3/es active Active
- 2013-06-10 CN CN201380030202.4A patent/CN104487610B/zh active Active
- 2013-06-10 CA CA2875335A patent/CA2875335C/en active Active
- 2013-06-10 JP JP2015516272A patent/JP6314133B2/ja active Active
- 2013-06-10 EP EP21178445.9A patent/EP3896194A1/en not_active Withdrawn
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2015
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Also Published As
Publication number | Publication date |
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WO2013185131A1 (en) | 2013-12-12 |
ES2882529T3 (es) | 2021-12-02 |
JP2020100836A (ja) | 2020-07-02 |
US20220025521A1 (en) | 2022-01-27 |
JP2015528853A (ja) | 2015-10-01 |
RU2014152643A (ru) | 2016-07-27 |
JP2017122227A (ja) | 2017-07-13 |
EP2859132A1 (en) | 2015-04-15 |
CA2875335A1 (en) | 2013-12-12 |
EP2859132B1 (en) | 2021-08-04 |
CN104487610A (zh) | 2015-04-01 |
RU2619376C2 (ru) | 2017-05-15 |
US20150140338A1 (en) | 2015-05-21 |
EP3896194A1 (en) | 2021-10-20 |
CN104487610B (zh) | 2022-10-21 |
CA2875335C (en) | 2019-04-30 |
JP6314133B2 (ja) | 2018-04-18 |
HK1204019A1 (en) | 2015-11-06 |
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