TW200946366A - Machine readable security elements and products containing them - Google Patents
Machine readable security elements and products containing them Download PDFInfo
- Publication number
- TW200946366A TW200946366A TW097118258A TW97118258A TW200946366A TW 200946366 A TW200946366 A TW 200946366A TW 097118258 A TW097118258 A TW 097118258A TW 97118258 A TW97118258 A TW 97118258A TW 200946366 A TW200946366 A TW 200946366A
- Authority
- TW
- Taiwan
- Prior art keywords
- dopant
- emission
- pigment
- band
- security element
- Prior art date
Links
- 239000000049 pigment Substances 0.000 claims abstract description 67
- 239000002019 doping agent Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims description 25
- 238000010521 absorption reaction Methods 0.000 claims description 23
- 238000007639 printing Methods 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- -1 rare earth ions Chemical class 0.000 claims description 15
- 230000003595 spectral effect Effects 0.000 claims description 14
- 230000005855 radiation Effects 0.000 claims description 11
- 230000005540 biological transmission Effects 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 238000001514 detection method Methods 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 9
- 238000001228 spectrum Methods 0.000 claims description 7
- 230000005670 electromagnetic radiation Effects 0.000 claims description 6
- 238000007646 gravure printing Methods 0.000 claims description 6
- 238000001459 lithography Methods 0.000 claims description 5
- 238000007650 screen-printing Methods 0.000 claims description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 4
- 239000002223 garnet Substances 0.000 claims description 3
- 238000007641 inkjet printing Methods 0.000 claims description 3
- 238000000206 photolithography Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- 150000004645 aluminates Chemical class 0.000 claims 1
- 230000001680 brushing effect Effects 0.000 claims 1
- 244000309464 bull Species 0.000 claims 1
- 239000013522 chelant Substances 0.000 claims 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims 1
- 238000012423 maintenance Methods 0.000 claims 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims 1
- 150000004763 sulfides Chemical class 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 description 27
- 239000002245 particle Substances 0.000 description 20
- 238000000295 emission spectrum Methods 0.000 description 16
- 230000005284 excitation Effects 0.000 description 14
- 150000002910 rare earth metals Chemical class 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000011358 absorbing material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 208000027534 Emotional disease Diseases 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 241000288906 Primates Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000001856 aerosol method Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 201000001883 cholelithiasis Diseases 0.000 description 1
- 230000006690 co-activation Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- KNKDMYNCMPEAPN-UHFFFAOYSA-K sodium strontium trifluoride Chemical compound [F-].[F-].[F-].[Na+].[Sr+2] KNKDMYNCMPEAPN-UHFFFAOYSA-K 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
- B42D25/29—Securities; Bank notes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
- B42D25/378—Special inks
-
- B42D2033/20—
-
- B42D2035/34—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
- B42D25/378—Special inks
- B42D25/382—Special inks absorbing or reflecting infrared light
Landscapes
- Business, Economics & Management (AREA)
- Accounting & Taxation (AREA)
- Finance (AREA)
- Credit Cards Or The Like (AREA)
- Luminescent Compositions (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Printing Methods (AREA)
- Inspection Of Paper Currency And Valuable Securities (AREA)
Abstract
Description
200946366 九、發明說明： 【發明所屬之技術領域】 本發明係關於機器可判讀之保全元件及 要機器可判讀之保全元件的產品包括(例如)有：需 如，紙及塑膠基材材料，例如，鈔β 據（例 办示、護照、簽證、及 如此類）、標籤、票據及身份證。 荷 【先前技術】 ❹ ❹ 為防止僞造及仿造，在卫業中已經努力 之保全元件構造應保護之產品以便未經授權的人不可U 為人知的改變或複製該等產品。 在該項技術中已經習知摻雜有稀土離子之主體晶格的用 途。该等化合物可在吸收一個頻率的輕射’並發射不同頻 率的輪射，其中輻射係指υν、可見光、近紅外及紅外輪 射。當用既定波長輻射轄照時，該等化合物在第二波長下 發光且該Μ可由檢須j器檢測。該等發光化合物係稱為 π發光體"’其可為離子或化合物。 摻雜有發光體化合物之主體晶格具有吸收及發射曲線， 其通常為離子的特性曲線，但因受納入晶體主體晶格中之 影響而改變。可利用電流實驗室設備量測吸收及發射二 者。 較佳掩飾由發光體所產生之光譜以使潑在僞造者難以對 保王特徵進行反向工程。可藉由使用一種以上的稀土金屬 及/戈主體晶格來掩飾該發射。 WO 2006/024530 Α1揭示使用至少兩種具有重疊光譜發 131511.doc 200946366 射頻帶之發光材料作為發光保全特徵系統。較佳地，該等 發光材料具有相同主體晶格但不同發光體，或者具有不同 主體晶格但相同發光體，其中該發光體可為稀土金屬。 WO 2005/03 5271 A2揭示用於保全檔之機器可判讀之編 . 碼系統，其包含第一及第二發光物質，該兩種物質係在可 見光譜範圍以外的共同發射範圍中發光。該第一及第二發 光物質之發射光譜在已知發射範圍的至少一部分區域中重 ❹ 疊從而使得該第一發光物質之發射光譜之特性可由該第二 發光物質之發射光譜加以補充，其中該等發光物質可為摻 雜有稀土金屬之主體晶格。 發光體之發射光譜可藉由使用吸收材料來掩飾。吸收材 料之吸收光譜與發光體之發射光譜或激發光譜重疊或將其 覆蓋並以特性方式改變其。該等改變可藉由（例如）”限制" 光譜範圍或使激發及/或發射光譜"變形”來實施。在最簡單 實例中’該限制係藉由分離光譜之邊緣區實現，而該變形 〇 可藉由寬頻帶光譜之窄光譜區的經設計阻尼或藉由消除既 定光譜譜線來實現。 美國專利第445 1530號揭示改變已知發射光譜並使用特 -性改變之部分用於保全檔之鑑別。該保全元件係由摻雜有 ‘ 發光體（例如，稀土元素）之無機主體晶格及一或多種吸收 材料（例如’染料）構成，該等吸收材料藉由限制光譜範圍 或藉由使激發及/或發射光譜變形來改變該發光體之發射 光譜。 美國專利第6506476 B1號揭示使用摻雜有至少一種稀土 '31511.doc 200946366 金屬（包㈣）之無機线晶格作為印刷有價單據之鑑別特 徵。該μ別特徵可印刷於該印刷有價單據上或添加於紙榘 中該纪摻雜主體晶格主要在光譜的可見光區吸收並激發 且在紅外光譜的至少―部分中透明。該主體晶格以高效率 將所吸收能量轉移給録。較佳地，該等發光物質之量子產 率在5〇與啊之間之範圍内。藉由吸收，主體晶格抑制链 在可見光且可能近紅外區中出現之發射譜線。 美國專利第6344261 B1號揭示具有至少一種鑑別特徵之 印刷有價單據’該鑑別特徵呈以換雜有至少—種稀土金屬 之主體晶格為主之發光物質的形式。該主體晶格主要在光 譜的整個可見光區中吸收’纟包含鉻作為吸收物質。該主 體晶格之此極寬頻帶吸收使得來自所摻雜稀土金屬之譜線 位於此被抑制區中，’發生自該主體晶格至所摻雜稀 土金屬之能量轉移’藉此誘導該發光物質發射。對稀土金 屬進行更有效激勵亦產生更高發射強度。 ❹ 美國專利第_133㈣揭示使用推雜有兩種稀土金屬 (即’録及鈥）之無機主體晶格作為印刷有價單據的鑑別特 徵。該鐘別特徵可包埋於紙渡中或添加於印刷油墨中。該 主體晶格包含寬頻帶吸I组份且以高效率將所吸收能量轉 移給該稀土摻雜金屬。較佳地，料發光物質之量子產率 在5〇與_之間之範圍内。該稀土金屬之發射光譜以特性 方式受吸收組份的影響。 美國專利第4463970號揭示使用僞裝材料（其可為發光 體）來防止借助化學實驗室分析間接檢測到可激發標記材 131511.doc 200946366 料之圖案。該等可激發標記材料係用於記錄編碼中之資 讯。舉例而言，編碼中所用欲隱藏信號可涉及僞裝材料 (包括發光體）之發射光譜。該等僞裝材料可為寬頻帶發射 材料，例如有機發光體。因此，只能注意到該可激發標記 材料之特性信號作為小尖峰添加到發射光譜中。或者，可 . 添加一或多種在不同於欲量測信號之波長處發射之窄頻帶 發光體且因此使發射光譜變得複雜。 0 該項技術中已習知兩種發光物質可用作印刷有價單據之 保全特徵。一種發光物質作為吸收體且另一種發光物質作 為發射體。自吸收體至發射體可存在足夠的能量轉移。 WO 2006/099642 A1揭示在保全元件中使用兩種無機發 光物質用於保全檔。第一發光物質係藉由入射輕射激發。 能量在第一與第二發光物質之間轉移，因此一種發光物質 之激發頻率範圍對應於另一種發光物質之激發頻率範圍。 曰本專利第2002212552號揭示包含一無機材料之紅外發 # 螢光物質，該無機材料係與在紅外範圍中具有吸收之鉉及 與铥I級相匹配以有效傳輸所吸收光能且作為可選活性元 素在紅外範圍内具有發光之鈥共活化。 ㉟洲專利第1241242 A2號揭示反斯托克斯磷光體㈣“ ‘ Stokes phosphor) ’其係用於保全檔中之發光體，其中發射 波頻帶具有比吸收波頻帶短的波長。該反斯托克斯鱗光體 係摻雜有兩種稀土離子之主體晶格。該等摻雜物中之一者 (例如镱）形成吸收體且另—種摻雜物（例如铥）形成發射 體。個別發射譜線群組間之強度等級係可變的且取決㈣ 131511.doc 200946366 光體中吸收體及/或發射體濃度。 【發明内容】 機==_二# 1#包含至少兩種合物之 m §之呆全"°件’其中第—顏料包含具有在第-發 =皮長頻帶處發射電磁韓射之第一發光 二發 無機主體晶格，且第二_七人 雕于的第一 二無機主體晶格，兑中該第：：機有至夕兩種摻雜物之第 ❹ ❹ 與該第-發光摻雜物離子相：：第二:::之第—接雜物 其能夠⑴藉助來自該第-無機“糸稀土離子， 个曰4弟一無機主體晶格之第— 輻射能量轉移而激發且（⑴ /雜物之非 磁.3射^ # (11)在第-發射波長頻帶處發射電 長頻田帶之可忽略該第二發射波長頻帶與該第-發射波 ’ 疊且该第二摻雜物可基本上淬滅該第二無機羊 體曰曰格之第—摻雜物在—或多個發射峰處的發射。 明:據第二態樣’提供一種物件，其包含攜载本發200946366 IX. Description of the Invention: [Technical Field] The present invention relates to a machine-readable security component and a machine-readable security component including, for example, a paper and plastic substrate material, for example , banknotes beta (such as instructions, passports, visas, and so on), labels, tickets and identity cards. [Previous Technology] ❹ ❹ In order to prevent counterfeiting and counterfeiting, the security components in the industry have been designed to protect the products so that unauthorized persons cannot change or copy them. The use of a host lattice doped with rare earth ions is well known in the art. Such compounds can absorb light at a frequency and emit at different frequencies, where radiation refers to υν, visible, near-infrared, and infrared radiation. When illuminated by a given wavelength of radiation, the compounds illuminate at a second wavelength and the enthalpy can be detected by a sniffer. These luminescent compounds are referred to as π illuminants "' which may be ions or compounds. The host lattice doped with the illuminant compound has an absorption and emission curve, which is usually a characteristic curve of the ion, but is changed by the influence of inclusion in the crystal lattice of the crystal body. Current laboratory equipment can be used to measure both absorption and emission. It is preferred to mask the spectrum produced by the illuminator so that it is difficult for the counterfeiter to reverse engineer the Baowang feature. The emission can be masked by using more than one rare earth metal and/or a host lattice. WO 2006/024530 Α1 discloses the use of at least two luminescent materials having an overlapping spectral illuminating 131511.doc 200946366 RF band as a luminescent preservation feature system. Preferably, the luminescent materials have the same host lattice but different illuminants, or have different host lattices but the same illuminants, wherein the illuminants can be rare earth metals. WO 2005/03 5271 A2 discloses a machine-readable code system for preserving files comprising first and second luminescent substances which illuminate in a common emission range outside the visible spectral range. The emission spectra of the first and second luminescent materials are overlapped in at least a portion of the known emission range such that the characteristics of the emission spectrum of the first luminescent material are supplemented by the emission spectrum of the second luminescent material, wherein The luminescent material may be a host lattice doped with a rare earth metal. The emission spectrum of the illuminant can be masked by the use of an absorbing material. The absorption spectrum of the absorbing material overlaps with or covers the emission or excitation spectrum of the illuminant and changes it in a characteristic manner. Such changes can be implemented by, for example, "limiting" the spectral range or causing excitation and/or emission spectra "deformation". In the simplest case, the limitation is achieved by separating the edge regions of the spectrum, which can be achieved by design damping of the narrow spectral region of the broadband spectrum or by eliminating a given spectral line. U.S. Patent No. 4,445,315 discloses the use of a portion that changes the known emission spectrum and uses a characteristic change for the preservation of the file. The security element is comprised of an inorganic host lattice doped with an 'emitter (eg, a rare earth element) and one or more absorber materials (eg, 'dyes') by limiting the spectral range or by exciting / or emission spectrum deformation to change the emission spectrum of the illuminant. U.S. Patent No. 6,506,476 B1 discloses the use of an inorganic wire lattice doped with at least one rare earth '31511.doc 200946366 metal (Package (4)) as a discriminating feature for printed value documents. The features can be printed on the printed document or added to the stack. The doped body lattice is primarily absorbed and excited in the visible region of the spectrum and is transparent in at least a portion of the infrared spectrum. The host lattice transfers the absorbed energy to the recording with high efficiency. Preferably, the quantum yield of the luminescent materials is in the range between 5 Å and Å. By absorption, the host lattice inhibits the emission line of the chain in the visible and possibly near-infrared region. U.S. Patent No. 6,344,261 B1 discloses a printed document of value having at least one identifying feature in the form of a luminescent material dominated by a host lattice of at least one rare earth metal. The host lattice absorbs mainly in the entire visible region of the spectrum, and contains chromium as an absorbing material. The extremely broadband absorption of the host crystal lattice causes the line from the doped rare earth metal to be located in the suppressed region, 'the energy transfer from the host lattice to the doped rare earth metal' thereby inducing the luminescent material emission. More efficient excitation of rare earth metals also produces higher emission intensities. ❹ U.S. Patent No. _133(4) discloses the use of an inorganic host lattice with two kinds of rare earth metals (i.e., 录 and 鈥) as the identification feature of the printed value document. The characteristics of the clock can be embedded in the paper or added to the printing ink. The host lattice contains a broadband I component and transfers the absorbed energy to the rare earth doped metal with high efficiency. Preferably, the quantum yield of the luminescent material is in the range between 5 Å and _. The emission spectrum of the rare earth metal is affected by the absorption component in a characteristic manner. U.S. Patent No. 4,463,970 discloses the use of camouflage materials (which may be illuminants) to prevent indirect detection of the pattern of excitable marker material 131511.doc 200946366 by chemical laboratory analysis. The excitable marking materials are used to record the information in the encoding. For example, the signal to be hidden used in the encoding may relate to the emission spectrum of the camouflage material, including the illuminant. The camouflage material can be a broadband emission material such as an organic illuminant. Therefore, only the characteristic signal of the excitable marking material can be noted as a small spike added to the emission spectrum. Alternatively, one or more narrow-band illuminators that emit at a different wavelength than the signal to be measured are added and thus the emission spectrum is complicated. 0 It is known in the art that two luminescent materials can be used as a security feature for printing value documents. One luminescent substance acts as an absorber and the other luminescent substance acts as an emitter. There may be sufficient energy transfer from the absorber to the emitter. WO 2006/099642 A1 discloses the use of two inorganic luminescent materials in a security element for security. The first luminescent material is excited by incident light. The energy is transferred between the first and second luminescent substances, so that the excitation frequency range of one luminescent substance corresponds to the excitation frequency range of the other luminescent substance.曰 Patent No. 2002212552 discloses an infrared ray-emitting material comprising an inorganic material which is compatible with 铉 in the infrared range and 铥I grade to effectively transmit absorbed light energy and is optional The active element has co-activation of luminescence in the infrared range. 35 Patent No. 1241222 A2 discloses an anti-Stokes phosphor (4) "'Stokes phosphor'' which is used in the illuminator in the preservation mode, in which the transmitted wave band has a shorter wavelength than the absorption band. The X-ray system is doped with a host lattice of two rare earth ions. One of the dopants (for example, ruthenium) forms an absorber and another dopant (such as ruthenium) forms an emitter. The intensity level between the line groups is variable and depends on (4) 131511.doc 200946366 The concentration of the absorber and / or emitter in the light body. [Invention] Machine ==_二# 1# contains at least two compounds m §的呆全"°件' The first--pigment contains the first luminescent two-inorganic host lattice with electromagnetic radiation emitted at the first-length=skin length band, and the second _ seven people carved in the first One or two inorganic host lattices, in the first:: the machine has the first two kinds of dopants ❹ ❹ and the first - luminescent dopant ion phase:: second::: the first - the inclusions Capable of (1) by means of the first-inorganic "cerium rare earth ion, the first of the inorganic body lattices" Excitation of energy transfer and ((1) / non-magnetic non-magnetic. 3 shot ^ # (11) transmitting the long-frequency band in the first-transmitting wavelength band, the second transmit wavelength band and the first-transmitted wave are negligible Stacking and the second dopant substantially quenches the emission of the first dopant of the second inorganic sheep body at - or a plurality of emission peaks. Object, which contains the hair
2材可為紙或塑膠產品，其包含紙漿或聚合物材料及至 ==之混合物，其中當將顏料在造紙期間添加於紙 2在擠出期間添加於聚合物中以在紙或 成呆全元件時，該混合物係如本發明第一態 Z 物:據本發明第三態樣，提供-批根據本發明第二::之 混含媒劑'及至少兩種顏料 :〉由墨’其中當將該油墨施加於基材以形成保全元 0，，該混合物係如本發明第一態樣中所定義。’、 131511.doc 200946366 根據本發明第五態樣，提供—種印刷方法，其中基材用 本發明第四態樣之油墨來印刷。 根據本發明第六態樣，提供一種檢測本發明第一賤樣之 保全元件是否存在之方法，其中該元件利用入射_以一 或多個波長（包括第一摻雜物/第一顏料吸收波長及第一摻 雜物/第二顏料吸收波長)輻照並藉由使用檢測器在第一發 射頻帶及第二發射頻帶中檢測發射。 ❹ Ο 【實施方式】 根據本發明第-態樣’提供一種包含至少兩種顏料混合 物之機器可判讀之保全元件，其中第—顏料包含具以第 一發射波長頻帶處發射電磁輻射之第—發光摻雜物離子的 第-無機主體晶格，且第二顏料包含具有至少兩種摻雜物 之第二無機主體晶格’纟中該第二無機主體晶格之第一摻 雜物與該第一發光摻雜物離子相同且第二摻雜物係稀土離 子，其能多句⑴藉助來自該第二無機主體晶格之第一推雜物 的非轄射能量轉移而激發及⑼在第二發射波長頻帶處發 射電磁輻射’其中可忽略該第二發射波長頻帶與該第一發 射波長頻帶之重疊且該第二摻雜物基本上可淬滅該第二無 機主體晶格之第一摻雜物在一或多個發射峰處的發射。 "基本上淬滅”係指使發射峰淬滅以便該發射峰之最大強 度實質降低’較佳該發射峰降至小於第一顏料中該峰最大 強度的2〇%、更佳小於第一顏料中該峰最大強度的10%且 最佳小於第-顏料中該峰最大強度的5%，以便其不會容 易地自光譜之背景雜訊識別出來。 131511.doc 200946366 在一個實施例中’該第一摻雜物名筮 _ ^ 〇滩物在第一吸收波長處吸收 υν、可見光或紅外光譜區中之雷 τ之電磁輻射，且較佳在該第 一發射波長頻帶中發射υν、可見光或紅外㈣區中之電 磁輻射’該第—發射波長頻帶係在比第—摻雜物吸收波長 局的波長處。 第-發光離子可為過渡金屬，例如，鉻H、欽、The 2 material may be a paper or plastic product comprising a pulp or polymer material and a mixture to ==, wherein the pigment is added to the paper during the papermaking period during the papermaking to be added to the polymer during extrusion to form a full component in the paper. When the mixture is as in the first aspect of the invention Z: according to the third aspect of the invention, the invention provides a second batch according to the invention: a mixed vehicle 'and at least two pigments:> The ink is applied to a substrate to form a security of 0, which is as defined in the first aspect of the invention. According to a fifth aspect of the present invention, there is provided a printing method in which a substrate is printed with the ink of the fourth aspect of the invention. According to a sixth aspect of the present invention, there is provided a method of detecting the presence or absence of a security element of a first aspect of the invention, wherein the element utilizes incident _ at one or more wavelengths (including a first dopant/first pigment absorption wavelength) And the first dopant/second pigment absorption wavelength) is irradiated and the emission is detected in the first emission band and the second emission band by using a detector.实施 Ο [Embodiment] According to a first aspect of the present invention, there is provided a machine readable security element comprising at least two pigment mixtures, wherein the first pigment comprises a first luminescence emitting electromagnetic radiation at a first emission wavelength band a first inorganic host lattice of dopant ions, and the second pigment comprises a first dopant of the second inorganic host lattice having at least two dopants, and a first dopant of the second inorganic host lattice a luminescent dopant ion is the same and the second dopant is a rare earth ion, which can be excited by a multi-sentence (1) by non-regular energy transfer from the first primate of the second inorganic host lattice and (9) in the second Emiting electromagnetic radiation at an emission wavelength band 'wherein the overlap of the second emission wavelength band and the first emission wavelength band can be ignored and the second dopant substantially quenches the first doping of the second inorganic host lattice The emission of one or more emission peaks. "substantially quenching" means quenching the emission peak so that the maximum intensity of the emission peak is substantially reduced. Preferably, the emission peak is reduced to less than 2% of the maximum intensity of the peak in the first pigment, more preferably less than the first pigment. The maximum intensity of the peak is 10% and is preferably less than 5% of the maximum intensity of the peak in the pigment - so that it is not readily recognizable from spectral background noise. 131511.doc 200946366 In one embodiment 'this a dopant name ^ ^ 〇 υ υ 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 (4) Electromagnetic radiation in the zone 'The first-emission wavelength band is at the wavelength of the absorption wavelength of the first dopant. The first-luminous ion may be a transition metal, for example, chromium H, chin,
❹ 鎳、鐵或鈷。較佳地，一發光離子係稀土離子、更佳 鑭。實例在下文給出。 第一及第二發射二者皆可在汛範圍内。 用於顏料之主體晶格可為銘酸鹽、溴化物、氣化物、氣 化物、鎵酸鹽、石榴石（包括所有混合石權石）、鍺酸鹽、 钥酸鹽、鈮酸鹽、氧化物、減化物、氧硫化物、氟化釔 鈉、石夕酸鹽、硫酸鹽、硫化物、鈦酸鹽、鎢酸鹽、及釩酸 鹽。主體晶格可為任何用於稀土陽離子之f知主體無機晶 格’例如任何彼等揭示於WO2006/024530 A1中者。 用於該第一及第二顏料之主體晶格可相同或不同。在一 個實施例中，虽主體晶格不同時，第一摻雜物吸收較佳在 相同光譜區中，且對於第一及第二顏料二者皆可在數奈米 内以便對於兩種顏料能夠使用相同入射輻射源。 激發第一顏料中之第一摻雜物的入射輻射及激發第二顏 料中之第一摻雜物的入射輻射可來自不同源。在使用窄頻 帶激發源之情況下，當兩種主體晶格實質上不同時，將使 知·第一及第二顏料中之第一摻雜物的吸收頻帶極為不同， 因此窄頻帶激發無法充分激發兩種主體晶格中之初級離 131511 .doc 12 200946366 子，故需要來自不同 在許多波長下實施。其 > *射。第—摻雜物之激發可 目的，波純a '"於產生更緊凑、更高強度激發源之 目的波長組合可能係有益的 * 全元件時。此一情 ，*兩個光源射向保 匱况之實例應係有多個 式之吸收峰的情況。 扠供期望问此態形 第一與第二發射頻帶通常 佔兩括姑』丨L 主^ 50奈米。期望結果係 使兩種顏料大體上單激發 f各早獨顏料之所得光譜輸镍 Nickel, iron or cobalt. Preferably, a luminescent ion is a rare earth ion, more preferably ruthenium. Examples are given below. Both the first and second shots can be within the range of 汛. The host lattice used for the pigment may be a salt, a bromide, a vapor, a vapor, a gallium, a garnet (including all mixed stone), a citrate, a citrate, a citrate, an oxidation Substance, reducer, oxysulfide, sodium strontium fluoride, sulphate, sulfate, sulfide, titanate, tungstate, and vanadate. The host lattice can be any of the known host inorganic crystals for rare earth cations' such as any of those disclosed in WO2006/024530 A1. The host lattices for the first and second pigments may be the same or different. In one embodiment, the first dopant absorption is preferably in the same spectral region, although the host lattice is different, and may be within a few nanometers for both the first and second pigments to enable use for both pigments. The same source of incident radiation. The incident radiation that excites the first dopant in the first pigment and the incident radiation that excites the first dopant in the second pigment can come from different sources. In the case of using a narrow-band excitation source, when the two host lattices are substantially different, the absorption band of the first dopant in the first and second pigments is made very different, so the narrow-band excitation is insufficient. Exciting the primary in the two host lattices away from 131511.doc 12 200946366, so it needs to be implemented from many different wavelengths. Its > * shot. The excitation of the first-dopant can be aimed at, and the wave-purity a '" combination of wavelengths for the purpose of producing a more compact, higher-intensity excitation source may be beneficial. In this case, the case where the two light sources are directed to the protection condition should have multiple absorption peaks. The fork is expected to ask this state. The first and second emission bands usually account for two nucleus 丨L main ^ 50 nm. The desired result is that the two pigments are substantially single-excited.
物％: 離，即使其共同含有至少-種發射掺雜 物。该發射可為窄或寬頻帶、或任-組合且最大強度處之 波長較佳相距至少50奈米。 第m料t第—摻㈣源H發射頻帶中產生發射之 相同躍遷的發射峰基本上經第二摻雜物淬滅。 入射輻射之最有效來源係光更充分地由光譜吸收特徵吸 收者。若需要高效率’則應避免可能為不與吸收特徵重疊 之激發源之-部分的光發射。可選擇使用相對寬波頻帶 源，例如LED，此乃因其在市場上易購得、運作上堅固耐 用且易於維護而具經濟優勢。由於窄頻帶雷射光源可能更 有效且LED之適宜波長可能不適用於一些適宜顏料組合之 吸收光谱’而且對於運行及維護亦較昂貴，故窄頻帶雷射 光源可能更有利。熟悉該項技術者應選擇適宜源以滿足系 統要求。應能夠充分激發，且系統功能應符合所有其他性 能標準。該等標準包括壽命、環境因素、眼睛安全及經濟 利益。 入射光可具有窄波頻帶且波長可比該第一及第二發射頻 131511.doc •13· 200946366 帶短至少50奈米。 入射光可具有極寬波頻帶，例如，白熾燈或閃光燈。可 過濾該入#光以防止保全元件被與該第一或第二發射相同 波長的光輻照、且隨後由檢測器檢測。入射源之頻帶可比 習用白熾燈窄’但比雷射寬，例如，LED。 。在較佳 入射輻射較佳在光谱之uv、可見光及IR區中 實施例中，第"及第二顏料之主體晶格二者在可見光範圍 ❹%: away, even if they together contain at least one type of emissive dopant. The emission can be narrow or broadband, or any-combination and the wavelength at the maximum intensity is preferably at least 50 nanometers apart. The emission peak of the same transition in which the emission of the mth-t-th (d) source H emission band is generated is substantially quenched by the second dopant. The most efficient source of incident radiation is that the light is more fully absorbed by the spectral absorption features. If high efficiency is required, then the light emission that may be part of the excitation source that does not overlap the absorption feature should be avoided. A relatively wide-band source, such as an LED, can be used, which is economical because it is readily available on the market, is robust and easy to maintain. Narrow-band laser sources may be more advantageous because narrow-band laser sources may be more efficient and the appropriate wavelengths of the LEDs may not be suitable for the absorption spectrum of some suitable pigment combinations' and are also expensive to operate and maintain. Those familiar with the technology should choose the appropriate source to meet the system requirements. It should be fully motivated and the system functions should meet all other performance criteria. These criteria include longevity, environmental factors, eye safety and economic benefits. The incident light may have a narrow wave band and the wavelength may be at least 50 nm shorter than the first and second transmission frequencies 131511.doc •13·200946366. The incident light can have an extremely wide wave band, such as an incandescent lamp or a flash. The incoming light can be filtered to prevent the security element from being irradiated with light of the same wavelength as the first or second emission and subsequently detected by the detector. The frequency band of the incident source can be narrower than conventional incandescent lamps' but wider than the laser, for example, LEDs. . In preferred embodiments, the incident radiation is preferably in the uv, visible, and IR regions of the spectrum. In both embodiments, the "and the host lattice of the second pigment are in the visible range.
中基本上係透明’即在較佳實施例中，該等主體晶格實質 上係無色，但此並非必要條件。該等顏料實質上無色之優 點在於即使將大量施加於基材（例如在印刷元件中”與無 負載狀況相比亦不會實質上改變油墨之顏色。若顏料並非 實質上無色，則在一些實施例中可以足夠低含量使用以避 免基材改變顏色，或在其他實施例中以使顏色肉眼可見光 之含量使用。 S玄第一及第二摻雜物可為M2+(例如Eu、Co、V及Dy)、 M3+(例如 Cr、Ho、Pr及 Nd)、M4+(例如 Cr)或 m5+(例如 離 子），較佳為Μ3 ，其中M係稀土元素，較佳係鑭或（例如） 對於該第一摻雜物而言為過渡金屬，且數字+代表離子之 價態。價態影響元素之發射性質。該主體晶格係經選擇以 適應元素之價態。 第一及第二顏料中之第一摻雜物亦可在一或多個額外發 射波長頻帶處在高於第一摻雜物吸收波長之波長處發射電 磁輕射。一或多個該等發射可能不會被第二顏料中之第二 捧雜物實質上淬滅。此可用於檢測兩種顏料中第一摻雜物 13151I.doc • 14- 200946366 之該等其他發射。 在另一實施例中，另_ 發射波長係比第一摻雜物吸收波 長及第一發射波長高的 择认墙 门的波長，且在該第二顏料中，足夠濃 ^的第二穆雜物可基本上淬滅來自第二顏料中該第一推雜 物之另-發射。經淬減之發射可對應於第一顏料中第一換 雜物發生之另一發射。 、針對欲檢測發射之波長選擇檢測器，若需要使用滤波器Medium is substantially transparent', i.e., in the preferred embodiment, the host lattices are substantially colorless, but this is not a requirement. The advantage of such pigments being substantially colorless is that even a large amount of application to a substrate (eg, in a printing element) does not substantially alter the color of the ink compared to an unloaded condition. If the pigment is not substantially colorless, then in some implementations In an example, it may be used at a sufficiently low level to avoid color change of the substrate, or in other embodiments to allow the color to be visible to the naked eye. The S-first and second dopants may be M2+ (eg, Eu, Co, V, and Dy), M3+ (eg, Cr, Ho, Pr, and Nd), M4+ (eg, Cr), or m5+ (eg, ion), preferably Μ3, wherein M is a rare earth element, preferably a lanthanum or, for example, for the first The dopant is a transition metal, and the number + represents the valence state of the ion. The valence state affects the emission properties of the element. The host lattice is selected to accommodate the valence state of the element. The first of the first and second pigments The dopant may also emit electromagnetic light at a wavelength above the absorption wavelength of the first dopant at one or more additional emission wavelength bands. One or more of the emissions may not be the second of the second pigments The two holdings are virtually quenched. Detecting the other emissions of the first dopant 13151I.doc • 14- 200946366 of the two pigments. In another embodiment, the other _ emission wavelength is higher than the first dopant absorption wavelength and the first emission wavelength Selecting the wavelength of the wall gate, and in the second pigment, the second dopant sufficient to substantially quench the additional-emission from the first dopant in the second pigment. The emission may correspond to another emission occurring in the first pigment in the first pigment. Selecting a detector for the wavelength of the emission to be detected, if a filter is needed
、將z第#第一（及其他）發射分離。檢測器具有基於各 種要长及條件之6又计參數。可由熟悉該項技術者基於(例 如ί光譜靈敏度、雜訊特性、阻抗、成本、迷度、實用性 及諸如此類針對特定系統要求來選擇。檢測器包括(例如) 光電倍增管、Si、Pbs、Cds、pbSe、inAs inSb Ge、, separating the first (and other) emissions of z#. The detector has parameters based on various lengths and conditions. It can be selected by those skilled in the art based on (eg, spectral sensitivity, noise characteristics, impedance, cost, fascination, utility, and the like for specific system requirements. Detectors include, for example, photomultiplier tubes, Si, Pbs, Cds , pbSe, inAs inSb Ge,
HgCdTe、GaP、InGaAs檢測器及其他。 石夕檢測器可檢測高達i丨〇 〇奈米之光子且基於砍之檢測器 展示極低雜訊。當磷光體之發射能級極低而需要較高電子 放大時此特徵有利。矽檢測器亦具有易於獲得且便宜之優 點。HgCdTe, GaP, InGaAs detectors and others. The Shixi detector detects photons up to i丨〇 〇 nanometer and displays very low noise based on the chop detector. This feature is advantageous when the emission level of the phosphor is extremely low and higher electron amplification is required. Helium detectors also have the advantage of being easy to obtain and inexpensive.
InGaAs檢測器可用於檢測較高波長。其具有較低信雜 比，通常較昂貴，且具有較少的市售供應商。此一檢測器 在本發明中用於檢測大於9〇〇奈米之發射同時一些檢測 器型號展示超過2600奈求之檢測能力。然而，在較高波長 處展示靈敏度之檢測器型號具有遠高的雜訊及降低的分路 電阻。 可同時量測第一及第二發射頻帶，且各個磷光體較佳具 13151I.doc 200946366 有相似哀減時間常數’但此並非必要條件。InGaAs detectors can be used to detect higher wavelengths. It has a lower signal to noise ratio, is generally more expensive, and has fewer commercial suppliers. This detector is used in the present invention to detect emissions greater than 9 nanometers while some detector models exhibit detection capabilities in excess of 2,600. However, detector models that exhibit sensitivity at higher wavelengths have far higher noise and reduced shunt resistance. The first and second emission bands can be measured simultaneously, and each phosphor preferably has a similar lag time constant '13151I.doc 200946366' but this is not a requirement.
熟悉該項技術者應能夠根據用於檢測第一及第二發射之 檢測器選擇保全元件中第一及第二顏料之適宜量。舉例而 言，矽檢測器展示極小NEP(雜訊等效功率），因此可將信 號放大至比(例如)具有遠高的雜訊特性之檢測器為 高的程度。熟悉該項技術者應根據發射波長、發射強度、 發射囊聚光學器件（若需要）、〉慮波器參數、檢測器類型、 曰應靈敏面積、&丨兄條件及相關電子放大需求決定保全 特徵之置以在保全特徵及檢測系統之所有預期運行條件内 獲得滿意信雜比。期望保全元件中具有最少量的顏料、及 摻雜物以使僞造者難以對保全元件進行反向工程。熟悉該 項技術者可在主體晶格選擇、產生發光顏料之能力、顏料 尺寸要求、發射波長方面評估摻雜物，且根據期望用途評 估檢測系統。（參見PHOSPH〇R handb〇〇k，由灿州Those skilled in the art should be able to select the appropriate amount of the first and second pigments in the security component based on the detector used to detect the first and second emissions. For example, the chirp detector exhibits a very small NEP (noise equivalent power), so the signal can be amplified to a higher degree than, for example, a detector with far higher noise characteristics. Those familiar with the technology should determine the preservation based on the emission wavelength, emission intensity, emission optics (if needed), filter parameters, detector type, sensitive area, & The feature is set to achieve a satisfactory signal-to-noise ratio within all expected operating conditions of the security feature and the detection system. It is desirable to have a minimum amount of pigment, and dopants in the security component to make it difficult for counterfeiters to reverse engineer the security component. Those skilled in the art can evaluate dopants in terms of host lattice selection, ability to produce luminescent pigments, pigment size requirements, emission wavelengths, and evaluate the detection system based on the intended use. (See PHOSPH〇R handb〇〇k, by Cancun
Shl_ya、WiUiam M. Yen編輯，CRC Press 1999, ISBN 0-8493-7560-6)。 ’ 、期望第二顏料中具有足夠量的第二摻雜物以基本上 使第二顏^中第—摻雜物之—或多個發射峰淬滅。推雜物 之相對含置可由熟悉該項技術者根據關於發光效率及非輻 射能量轉移效率之有用資訊、及/或根據經驗來選擇。^ 根據本發明之第二態樣，提供—種包含其上攜载保全元 件之基材的物件。 該物件可為有價單據（例如，紙或塑膠基材材料，例 如^不、護照、簽證、及諸如此類）、標籤、票據及身 13I511.doc ❹ Ο 200946366 份證 較佳當基材為紙或塑膠時保全元件可納入該基材本體 中，或較佳當保全元件於油墨中時可施加於基材。熟悉該 項技術者應此夠針對各應用來選擇適宜粒徑。顏料混合物 可在紙或塑膠製備期間納入。 美國專利第4874188號揭示在製備紙時將顆粒（例如，細 粒：糰粒或纖維)納入紙漿。該等細粒、糰粒具有大約 微米之橫截面且纖維長度或糰粒直徑約為數毫米。本發明 中所用粒徑隨應用而變，但可為約Q，丨至5〇微米。 第一及第二顏料各自具有粒徑分佈，其特徵可由市售實 ，室設備（例如，Microtrac之雷射繞射粒徑量測系統）確 疋赛於半的體積係由小於特定直徑之顆粒組成，故分 佈通常由D50值表徵。亦可參考謂、收或⑽之值。存 在其中D50與D90、D95或⑽值可能相差極大之情況。粒 徑分佈係根據其預期應用及最終檢測方法來選擇。確定必 要條件以便當使用該等顆粒時，發光方面之性能在特定容 限内。若粒徑太大’則所檢測發射標準偏差可能不期望的 1。若粒徑太小，則兩種顏料之發射強度可能降低，此使 传很難檢測。 該物件可具有提供於層中或基材上之保全元件，1較佳 :乍為不連續層以(例如)在基材上形成預定圖案。可將混合 物納入編織成基材之纖維+ ° 一 〒以形成圖帛或隨意納人。可將 包3顏料之聚合物薄骐條納入 間。 巧仟中，例如夾於外層之 131511 .d〇c 200946366 声具有藉由印刷以不連續層提供之保全元件且該 層可包含其他油墨組份。 卞 根據本發明第三態樣，提 物杜 .^ 抵根據本發明第二態樣之 ，/、中在各物品中保全元彳φ_ π 70件相㈤，例如，-批所有皆 八有相同保全元件之不同面額 的务市。此外，可提供一批 〃中各保全元件在基材上之 疋圖案互不相同之物件，例 如，各面額的鈔票具有不同印刷圖案。Shl_ya, edited by WiUiam M. Yen, CRC Press 1999, ISBN 0-8493-7560-6). It is desirable to have a sufficient amount of the second dopant in the second pigment to substantially quench the first dopant or the plurality of emission peaks in the second pigment. The relative inclusion of the tweezers can be selected by those skilled in the art based on useful information regarding luminous efficiency and non-radiative energy transfer efficiency, and/or empirically. According to a second aspect of the present invention, there is provided an article comprising a substrate on which a security element is carried. The item may be a value document (eg, paper or plastic substrate material such as ^, passport, visa, and the like), label, note, and body 13I511.doc ❹ Ο 200946366. The certificate is preferably when the substrate is paper or plastic. The time-keeping component can be incorporated into the substrate body or, preferably, the substrate can be applied to the substrate while the component is in the ink. Those skilled in the art should be able to select the appropriate particle size for each application. Pigment mixtures can be incorporated during paper or plastic preparation. U.S. Patent No. 4,874,188 discloses the incorporation of granules (e.g., granules: agglomerates or fibers) into the pulp during the preparation of the paper. The fine particles, agglomerates have a cross section of about micrometers and the fiber length or agglomerate diameter is about several millimeters. The particle size used in the present invention varies depending on the application, but may be about Q, 丨 to 5 Å. The first and second pigments each have a particle size distribution characterized by commercially available, chamber equipment (eg, Microtrac's laser diffraction particle size measurement system) that the volume of the semi-volume is less than a particle of a particular diameter. Composition, so the distribution is usually characterized by the D50 value. You can also refer to the value of y, y, or (10). There are cases where D50 and D90, D95 or (10) values may differ greatly. The particle size distribution is selected based on its intended application and final testing method. The necessary conditions are determined so that when the particles are used, the performance in terms of luminescence is within a certain tolerance. If the particle size is too large, the detected emission standard deviation may be undesired. If the particle size is too small, the emission intensity of the two pigments may be lowered, which makes the transmission difficult to detect. The article may have a security element provided in or on the substrate, preferably 1 : a discontinuous layer to, for example, form a predetermined pattern on the substrate. The mixture can be incorporated into the fibers woven into the substrate + ° to form a pattern or randomly. The polymer thin strip of the 3 pigment can be included. In the case of, for example, the outer layer of 131511.d〇c 200946366 sound has a security element provided by printing in a discontinuous layer and the layer may contain other ink components.卞 According to the third aspect of the present invention, the extract is in accordance with the second aspect of the present invention, and in the article, the element 彳 φ π π 70 pieces (five) are preserved in each article, for example, the - batches all have the same eight Preserve the different denominations of the components. In addition, it is possible to provide a plurality of articles in which the security elements of the security elements on the substrate are different from each other, for example, the banknotes of each denomination have different printed patterns.
根據本發明第四態樣，油墨包含媒劑及混合物，其中當 將该油墨施加於基材以形成保全元件時，該混合物係如本 發明第—態樣中所定義。 該油墨可用於光刻、平板印刷、凹板印刷、柔性版印 刷、凹印輪轉印刷、喷墨、凸印或絲網印刷方法中。各方 2皆具有由所用印刷方法類型所規定之要求。較大顆粒可 此阻塞某些印刷轉移表面，㈣於其他表面而言可係可接 受的。絲網印刷方法可適應相當大的顆粒。 各印刷方法之適宜粒徑可如適宜媒劑及添加劑、以及調 配方法一樣可由熟悉該項技術者選擇。英國專利第 2258660號揭示適用於印刷技術範圍之顆粒具有不超過如 微米、較佳不超過20微米、且最佳低於1〇微米（例如丨微米 至5微米或甚至丨微米至2微米）之最大直徑。本發明中可使 用該等粒徑。 根據本發明第五態樣，本發明第四態樣之油墨可用於在 基材上印刷，較佳藉由光刻、平板印刷、凹板印刷、柔性 版印刷、凹印輪轉印刷、噴墨、凸印及絲網印刷方法。 131511.doc 200946366 2據本發明第六態樣，提供一種檢測本發明第一態樣之 保王元件之存在性之方法。通常，在該方法中，該元件利 用射輻射以一或多個波長（包括第一摻雜物/第一顏料吸 收波長及第一摻雜物/第二顏料吸收波長）輻照並藉由使用 檢測器在第一發射頻帶及第二發射頻帶中檢測發射。 在-個實施例中’使用不同檢測器來檢測第一及第二發 八中轄射視’丨月況在到達各個檢測器之前穿過濾波器， ❹According to a fourth aspect of the invention, the ink comprises a vehicle and a mixture, wherein when the ink is applied to a substrate to form a security element, the mixture is as defined in the first aspect of the invention. The ink can be used in photolithography, lithography, gravure printing, flexographic printing, gravure rotary printing, ink jet, embossing or screen printing processes. Each party 2 has the requirements specified by the type of printing method used. Larger particles can block some of the printed transfer surfaces and (iv) can be acceptable for other surfaces. The screen printing method can accommodate quite large particles. Suitable particle sizes for each printing process can be selected by those skilled in the art, as are suitable vehicles and additives, and methods of formulation. British Patent No. 2,258,660 discloses that particles suitable for use in the printing arts range have no more than, for example, micrometers, preferably no more than 20 micrometers, and most preferably less than 1 micrometer (e.g., micron to 5 micron or even micron to 2 micron). The maximum diameter. These particle sizes can be used in the present invention. According to a fifth aspect of the present invention, the ink of the fourth aspect of the present invention can be used for printing on a substrate, preferably by photolithography, lithography, gravure printing, flexographic printing, gravure printing, ink jetting, Embossing and screen printing methods. According to a sixth aspect of the invention, there is provided a method of detecting the presence of a security element of the first aspect of the invention. Typically, in the method, the element is irradiated with radiation at one or more wavelengths (including the first dopant/first pigment absorption wavelength and the first dopant/second pigment absorption wavelength) and used by The detector detects the transmission in the first transmit band and the second transmit band. In an embodiment, different detectors are used to detect the first and second shots. The month of the month passes through the filter before reaching each detector, ❹
該濾波器經選擇以便允許第一及第二發射中之一者透射並 防止第-及第二發射中之另—者透射。該等檢測器可為相 同類型或者不同類型。 也'、、虞特疋工作之要求選擇檢測器。此應基於性能、環 桃實用性及經濟。本發明要求欲檢測之各發射具有其自 檢測ή m系統可包括適宜檢卿及濾波器。 =明第六態樣之另—實施例包括藉由機械輸送帶使保 正確製造亨伴… 口出現在物件製造期間以確保The filter is selected to allow transmission of one of the first and second emissions and to prevent transmission of the other of the first and second emissions. The detectors can be of the same type or of different types. Also, ',, 虞 special work requirements to select the detector. This should be based on performance, practicality and economy. The present invention requires that each of the emissions to be detected have its own self-detecting system. = Another example of the sixth aspect - the embodiment consists of ensuring the correct manufacture of the henry by means of a mechanical conveyor belt... The mouth appears during the manufacture of the object to ensure
Ik 4保王疋件。當保全元件需要驗證時此亦可 段:該輸送帶可以或可不必使保全元件固定在 :允4輸送帶係機^的組件，該機11包含檢測器 造以用該保全元件之機器可判讀性。檢測器亦可經製 以以用於靜態量測，例如， 表 器之設計考量可隨特… 制中。各種類型檢測 T▼里了隨特定需求而變。 X、技術:習知有若干方法可用於製備用於印刷中且納 =有價單據之基材中之適宜尺寸顏料顆項 技術者應能夠針對本發財利兩種_中之每 131511.doc -19- 200946366 料之可能途徑； 請專利範圍之範 顆粒。 適宜方法。下文所列示之方法係可製備顏 然而’該等並非意欲以任何方式限制申 圍。應瞭解，可使用其他適宜方法來製備 〇 ο 、德國專利第刪6462 A1號揭示—種製備發光材料之方 法。該方法包含利用稀土金屬陽離子使離子交換劑帶電荷 並熱處理該帶電荷之離子交換劑^稀土陽離子之實例^ 竹與&陽離子、或_&陽離子或YbM陽離子或外陽 離子之混合物。較佳地，在熱處理之前或之後，較佳藉由 碾磨將該帶電荷離子交換劑碾至顏料尺寸。較佳地，^離 子交換劑為石夕酸鹽，最佳為彿石。熱處理係在ιι〇::至 1200°C、較佳1150°C下實施2-5小時。 格 歐洲專利第A2號揭示一種製備粉末狀產物之氣 溶膠方法及隨时置，其涉及使用超音波氣㈣發生器， 其包括複數個位於形成氣溶膠液滴之液體進料容器下面並 以超音波方式供能之超音波轉換器。藉由複數個自氣體輸 送系統輸送氣體之氣體輸送埠將載氣輸送至該容器之不同 部分。使該氣料熱分解以形成難，然後將其冷卻並收 集之。粉末狀產物可包括摻雜有稀土金屬離子之無機主體 曰曰 W〇2006/078826 A2揭示一種在火焰喷射系統中形成奈 米顆粒之方法，其中所揭示之奈米顆粒包括摻雜有稀土金 屬離子之無機主體晶格。該方法包含以下步驟：⑷將包含 液體媒劑及前體之前體介f提供給組件；及（b)在有效形成 奈米顆粒群之條件下火焰噴射該前體介質，其中如此形成 i31511.doc -20- 200946366 之奈米顆粒包含小於約5體積％粒獲大於1微米之顆粒。 美國專利第6344261 B1號揭示碾磨並研磨摻雜有稀土離 子之無機主體晶格以產生平均粒徑小於1微米之顆粒。Ik 4 Warranty. This may also be used when the security component requires verification: the conveyor belt may or may not have the security component fixed to: a component of the conveyor belt system, the machine 11 including the detector for reading the machine with the security component Sex. The detector can also be made for static measurement, for example, the design considerations of the meter can be used. Various types of detection T▼ vary with specific needs. X. Technology: There are several methods that can be used to prepare suitable sizes of pigments in substrates for printing and nano-valuable documents. The technicians should be able to target the two types of money. Each of the 131511.doc -19 - 200946366 Possible route; Please refer to the patent scope. Suitable method. The methods set forth below can be used to prepare a face. However, such is not intended to limit the scope in any way. It will be appreciated that other suitable methods can be used to prepare the method of preparing a luminescent material as disclosed in German Patent No. 6,462 A1. The method comprises charging an ion exchanger with a rare earth metal cation and heat treating the charged ion exchanger, an example of a rare earth cation, a mixture of bamboo and & cation, or _&cation or YbM cation or external cation. Preferably, the charged ion exchanger is preferably milled to the pigment size by milling prior to or after the heat treatment. Preferably, the ion exchanger is a sulphate, preferably a buddha. The heat treatment is carried out at ιι〇:: to 1200 ° C, preferably at 1150 ° C for 2-5 hours. European Patent No. A2 discloses an aerosol method for preparing a powdery product and a ready-to-use method, which relates to the use of an ultrasonic gas (four) generator comprising a plurality of liquid feed containers located below the aerosol-forming droplets and super Ultrasonic transducer powered by sound wave. The carrier gas is delivered to a different portion of the vessel by a plurality of gas delivery gases that deliver gas from the gas delivery system. The gas material is thermally decomposed to form a hard, and then it is cooled and collected. The powdered product may comprise an inorganic host doped with a rare earth metal ion. 〇W/2006/078826 A2 discloses a method of forming nanoparticle in a flame spray system, wherein the disclosed nanoparticle comprises a rare earth metal ion doped Inorganic host lattice. The method comprises the steps of: (4) providing a liquid medium and a precursor precursor to the module; and (b) flame spraying the precursor medium under conditions effective to form the nanoparticle group, wherein i31511.doc is formed The nanoparticle of -20-200946366 comprises less than about 5% by volume of the particles having a particle size greater than 1 micron. U.S. Patent No. 6,344,261 B1 discloses the grinding and grinding of inorganic host crystal lattice doped with rare earth ions to produce particles having an average particle size of less than 1 micron.
該等圖係使用高分辨光譜計產生。圖1之曲線係藉由監 '則發射峰並在期望激發範圍内（例如，500-1000奈米）掃描 來獲得。在圖1中，激發結果係因掃描在所示波長範圍處 之私定發射峰而產生。圖2係藉由設定激發波長並由檢測 器在所監測之指定發射光譜範圍内掃描來產生。 現在將藉由以下實例闞釋本發明，該等實例並不意欲以 任何方式限制申請專利範圍之範圍。該等實例中之顔料係 以粉末形式在不含光亮劑之紙背襯上在由可調激發及可變 發射檢測組成的多光柵光譜計佈置中進行評價。 實例la 該第—顏料係摻雜有丨.〇%(原子。/〇)Tm2Y2〇2S。使用普 通磷光體製備方法製得含㈣雜物之第一顏料顆粒。該 第一顏料可使用（例如）7GG奈米、805奈米或91G奈米對應於 圖中所不吸收峰之光激發。適宜led係自油ner_ laSer.C〇m獲得。發射光譜展示於圖2中。以約1800奈米為 〜、m發射係、藉由經擴展InGaAs檢測器以及高分辨光 :。十進仃檢測。此發射可對應於本發明中之該第—發射頻 ^顏料係摻雜有1鳥（原子％) （原子。/。）H〇 之2 2S。使用普通嶙光體製備方法製得含Tm及Ho兩種摻 131511.doc 200946366 雜物之第二顏料顆粒。該第二顏料係使用與實例la中相同 之光源激發。吸收光譜實質上與圖1相同。在實例la中以 約1_奈米為中心存在之Tm發射（圖2，迹線A)在第二顏料 中實質上被淬滅，如自圖2中蹤迹B所看出。Ho在一個頻 帶内發射，其中主峰在1975奈米及2050奈米處。在此光譜 範圍内之Ho發射可使用經擴展InGaAs檢測器以及高分辨 光譜計進行檢測。此發射可對應於本發明中之該第二發射 頻帶。 ❹ 實例1 c 分別製備第一及第二顏料。該第一顏料係如實例la中所 述製得且該第二顏料係如實例lb中所述製得。然後將兩種 顏料以1:1比率混合在一起並攪拌以產生均相混合物。使 用此混合物作為機器可判讀之保全元件。該第一及第二發 射頻帶可如實例丨&及lb中所述量測。 實例1 d 〇 可將實例1 e中所述之混合物與媒劑混合以產生印刷油 墨。當此油墨用於印刷基材時，使該油墨乾燥，該油墨可 利用實例la之光源照射。實例1&及lb中所述之檢測系統將 鏗別本發明之第一及第二發射頻帶。 【圖式簡單說明】 以下係圖示簡單說明： 圖1展示摻雜有1.0%(原子％)1'111之Y202S的吸收光譜，其 實質上與摻雜有1.0%(原子％)Trn及2.〇%(原子％讲〇之Y202S 的吸收光譜相同； ^ 3151 ] .doc •22- 200946366 圖2展示摻雜有1.0%(原子％)Tm之Y202S的發射光譜；以 及摻雜有1.0%(原子％)Tm及2.0%(原子％)11〇之Y202S的發射 光譜。These figures were generated using a high resolution spectrometer. The curve of Figure 1 is obtained by monitoring the emission peak and scanning within the desired excitation range (e.g., 500-1000 nm). In Figure 1, the excitation results are produced by scanning a private emission peak at the indicated wavelength range. Figure 2 is generated by setting the excitation wavelength and scanning by the detector over the specified emission spectral range being monitored. The invention is now illustrated by the following examples, which are not intended to limit the scope of the claims. The pigments in these examples were evaluated in powder form on a paper backing without a brightener in a multi-grating spectrometer arrangement consisting of tunable excitation and variable emission detection. Example la The first pigment is doped with 丨.〇% (atoms./〇) Tm2Y2〇2S. The first pigment particles containing the (tetra) impurity are obtained by a conventional phosphor preparation method. The first pigment can be excited using, for example, 7GG nanometers, 805 nm or 91G nanometers corresponding to the light of the absorption peaks in the figure. Suitable for the led system is obtained from the oil ner_ laSer.C〇m. The emission spectrum is shown in Figure 2. Approximately 1800 nm is the ~, m emission system, with an extended InGaAs detector and high resolution light: Shijin detection. This emission may correspond to the first-emission frequency pigment in the present invention being doped with 1 bird (atomic %) (atoms) of H 2 2 2S. The second pigment particles containing Tm and Ho doped with 131511.doc 200946366 were prepared using a conventional phosphor preparation method. The second pigment was excited using the same source as in Example la. The absorption spectrum is substantially the same as in FIG. The Tm emission (Fig. 2, trace A) present in the example la centered around about 1 nm is substantially quenched in the second pigment, as seen from trace B in Figure 2. Ho is launched in a frequency band with the main peak at 1975 nm and 2050 nm. Ho emission in this spectral range can be detected using an extended InGaAs detector and a high resolution spectrometer. This transmission may correspond to the second transmission band in the present invention.实例 Example 1 c The first and second pigments were prepared separately. The first pigment was prepared as described in Example la and the second pigment was prepared as described in Example lb. The two pigments are then mixed together in a 1:1 ratio and stirred to produce a homogeneous mixture. Use this mixture as a security component that can be interpreted by the machine. The first and second RF bands can be measured as described in the Examples & Example 1 d 混合物 The mixture described in Example 1 e can be mixed with a vehicle to produce a printing ink. When the ink is used to print a substrate, the ink is allowed to dry, and the ink can be irradiated with the light source of Example la. The detection systems described in Examples 1 & lb and lb will identify the first and second transmission bands of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS The following is a brief description of the drawings: Figure 1 shows the absorption spectrum of Y202S doped with 1.0% (atomic%) 1'111, which is substantially doped with 1.0% (atomic%) Trn and 2 .〇% (Atomic% Y202S has the same absorption spectrum; ^ 3151 ] .doc •22- 200946366 Figure 2 shows the emission spectrum of Y202S doped with 1.0% (atomic%) Tm; and doping with 1.0% ( Atomic %) Tm and 2.0% (atomic %) 11 〇 Y202S emission spectrum.
131511.doc -23-131511.doc -23-
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2008/062911 WO2009136921A1 (en) | 2008-05-07 | 2008-05-07 | Machine readable security elements and products containing them |
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| TW200946366A true TW200946366A (en) | 2009-11-16 |
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| TW097118258A TW200946366A (en) | 2008-05-07 | 2008-05-16 | Machine readable security elements and products containing them |
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| JP (1) | JP5416764B2 (en) |
| CN (1) | CN102026819B (en) |
| BR (1) | BRPI0822680A2 (en) |
| ES (1) | ES2389278T3 (en) |
| TW (1) | TW200946366A (en) |
| WO (1) | WO2009136921A1 (en) |
| ZA (1) | ZA201007428B (en) |
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| DE102009058669A1 (en) | 2009-12-16 | 2011-06-22 | Giesecke & Devrient GmbH, 81677 | Authenticity feature in the form of luminescent substances |
| US8277612B2 (en) * | 2009-12-17 | 2012-10-02 | Honeywell International Inc. | Controlling the detectability of an article and method for authenticating the article |
| US8328102B2 (en) * | 2009-12-21 | 2012-12-11 | Honeywell International Inc. | Method and authentication apparatus for authenticating value documents |
| DE102010028818A1 (en) * | 2010-05-10 | 2011-11-10 | Swiss Authentication Research And Development Ag | Combination of luminescent substances |
| US8742369B2 (en) * | 2010-11-01 | 2014-06-03 | Honeywell International Inc. | Value documents and other articles having taggants that exhibit delayed maximum intensity emissions, and methods and apparatus for their authentication |
| US20130048874A1 (en) | 2011-08-31 | 2013-02-28 | Honeywell International Inc. | Articles with confounded emission characteristics and methods and apparatus for their authentication |
| US8975598B2 (en) * | 2012-01-17 | 2015-03-10 | Honeywell International Inc. | Articles incorporating thermographic phosphors, and methods and apparatus for authenticating such articles |
| CN106147398A (en) * | 2015-04-15 | 2016-11-23 | 佛山市高明区(中国科学院)新材料专业中心 | A kind of Anti-false ceramic ink |
| KR102141124B1 (en) * | 2018-01-30 | 2020-08-04 | (주)바이오니아 | Double-stranded Oligonucleotide Complex comprising Double― stranded miRNA and Uses thereof |
| DE102018007289A1 (en) | 2018-09-14 | 2020-03-19 | Giesecke+Devrient Currency Technology Gmbh | Document of value system |
| GB2580324B (en) * | 2018-12-28 | 2022-09-14 | Guy Stevens Henry | Paint including a taggant |
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| DE19804032A1 (en) * | 1998-02-02 | 1999-08-05 | Giesecke & Devrient Gmbh | Value document |
| EP1117060A1 (en) * | 2000-01-10 | 2001-07-18 | Sicpa Holding S.A. | Authentication of a security article |
| JP2002212552A (en) * | 2001-01-22 | 2002-07-31 | Hitachi Maxell Ltd | Infrared light emitting fluorophor and printed matter |
| CN101076835B (en) * | 2004-09-02 | 2012-12-12 | 德国捷德有限公司 | Value document with luminescent properties |
| EP1812884A4 (en) * | 2004-10-22 | 2009-09-02 | Parallel Synthesis Technologie | Rare earth downconverting phosphor compositions for optically encoding objects and methods and apparatus relating to same |
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2008
- 2008-05-07 BR BRPI0822680-6A patent/BRPI0822680A2/en not_active Application Discontinuation
- 2008-05-07 JP JP2011508462A patent/JP5416764B2/en not_active Expired - Fee Related
- 2008-05-07 CN CN2008801290589A patent/CN102026819B/en not_active Expired - Fee Related
- 2008-05-07 EP EP08755124A patent/EP2271504B1/en not_active Revoked
- 2008-05-07 WO PCT/US2008/062911 patent/WO2009136921A1/en active Application Filing
- 2008-05-07 ES ES08755124T patent/ES2389278T3/en active Active
- 2008-05-16 TW TW097118258A patent/TW200946366A/en unknown
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| JP2011526548A (en) | 2011-10-13 |
| CN102026819A (en) | 2011-04-20 |
| ZA201007428B (en) | 2012-01-25 |
| BRPI0822680A2 (en) | 2015-06-30 |
| WO2009136921A1 (en) | 2009-11-12 |
| EP2271504B1 (en) | 2012-06-27 |
| EP2271504A1 (en) | 2011-01-12 |
| JP5416764B2 (en) | 2014-02-12 |
| ES2389278T3 (en) | 2012-10-24 |
| CN102026819B (en) | 2013-09-04 |
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