JP4927313B2 - 回折顔料薄片および組成物 - Google Patents
回折顔料薄片および組成物 Download PDFInfo
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- JP4927313B2 JP4927313B2 JP2003517160A JP2003517160A JP4927313B2 JP 4927313 B2 JP4927313 B2 JP 4927313B2 JP 2003517160 A JP2003517160 A JP 2003517160A JP 2003517160 A JP2003517160 A JP 2003517160A JP 4927313 B2 JP4927313 B2 JP 4927313B2
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- diffractive
- diffraction
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- pigment
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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
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/328—Diffraction gratings; Holograms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/14—Security printing
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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Description
本発明の1つの観点においては、回折格子理論を利用して、望ましい回折特性を持つ薄片または箔の製造に適する微細構造を選択する設計技術が提供されている。この手法においては、従来の光学ソフトウェアを使用してさまざまな格子形状をモデル化して、鏡面反射と回折次数の強度を抑圧および/または制御して最適な格子設計を得ることができる。モデル化のために、三角対称格子、三角ブレーズド格子、さまざまな上辺サイズの方形波格子、さまざまな溝周波数および深さ輪郭の正弦波格子など、さまざまな格子形状を選択することができる。次に、モデル化の結果を使用して、後述されるように顔料と箔を形成するためにコーティング層を堆積するための格子基板を選択することができる。特定のモデリング結果が、後の例のセクションに記載してある。
Gmλ = sin α + sin β (式1)
この式において、G = 1/dは、溝の密度またはピッチであり、αは、入射光と格子の垂線の間の角度であり、βは、回折されたビームと格子の垂線の間の角度であり、mは、回折次数と称される整数である。m = 0の場合、全波長(λ)についてβ = - αであり、格子は鏡として作用し、波長は互いに分離されていない。これは、鏡面反射または0次と称される。
の間のm次のスペクトルの角度の広がり
の尺度である。これは、
として定義され、この式は、溝の間の間隔が近い(周波数が高い)ほど角分散が強いことを示す。言い換えれば、ある次数mに対し、波長間の角度の分離は、溝の周波数が高いほど増す。
R = Nd(sin α + sin β)/λ (式2)
を得ることができ、この式において、量Ndは、単に格子の幅(W)である。式2によって表されているように、Rは次数にも溝の数にも明示的には依存しない。これらのパラメータは、格子幅と、入射および回折の角度に含まれる。この場合、達成可能な最大解像力は、Rmax = 2W/λである。理論的な解像力が実際に達成される程度は、格子面の光学的品質にも依存する。一般的には、平面格子の場合、平坦からの逸脱がλ/10より大きいと、解像力の損失につながると考えられている。
Gmλ = cos ε (sin α + sin β) (式3)
と修正する必要がある。この式において、εは、入射光の経路と、格子の中心における溝に垂直な平面とがなす角度である。εが0でない幾何学的配置(格子の方位的回転(azimuthal rotation))の場合、回折されたスペクトルは、平面内ではなく円錐上に存在し、従ってこのような場合は円錐回折と称される。
特定の物体の色特性を定量化するためには、国際照明委員会(CIE)によって開発され、現在では業界において色値を正確に記述するための標準として使用されているL*a*b*色座標系を使用することが有用である。この座標系において、L*は明るさを示し、a*とb*は色度座標である。以下の例のいくつかに説明されているさまざまなa*b*図は、選択された回折顔料の色軌跡と色度をプロットしており、このL*a*b*色座標系を使用して作成された。
を通じて比較することができる。このパラメータは、2つの異なる顔料設計の色の差など、L*a*b*色空間内において測定された色の変化を示す。
の数値は、測定されたL*a*b*値を使用して以下の式から計算される。
この式において、記号
は、比較される測定値の差を表す。
回折格子の入射エネルギに対するエネルギの量(効率)は、格子のタイプとその溝幅の関数として変化する。この結果として、特定の波長に対して格子を最適化することができる。任意の波長に対するさまざまな回折次数における光スペクトル分散は、前述されている式1によって与えられる。
1400列/mmのアルミナ化された正弦波回折格子が、従来の光学ソフトウェアを使用してモデル化された。図15と16は、400、550、および700 nmの波長光の垂直と60度入射時の、さまざまな溝深さにおける格子の理論的な効率(反射率割合)を示す。このモデリングの結果から、約160 nm付近の溝深さは、0次の反射率が最小となりかつ1次の反射率が最大となり、従って格子の回折効果を向上させる良好な妥協点であることが示された。
1000列/mmのアルミナ化された正弦波回折格子(例9)と、1000列/mmのアルミナ化された方形波回折格子(例10)が、従来の光学ソフトウェアを使用してモデル化された。例10の格子は、対称的であり、列の上辺の長さと格子の周期の間の比は0.5に等しかった。図17と18は、例9と10の格子について、ほぼ垂直入射時の、さまざまな溝深さにおける550 nmの理論的な効率を示す。
顔料の製造に使用される格子箔は、上記に開示されている理論的な考察に従って得られた。1400列/mmの直線格子は160 nmの深さで得られ、2000列/mmの直線格子は220 nmの溝深さで得られた。1400列/mmの直線格子との比較のため、十字(方形)形態でありかつ1400列/mmの周波数を持つ別の格子も得られた。箔格子の周波数と深さは、原子間力顕微鏡を使用して確認された。高い周波数の格子との比較のため、500列/mmと1000列/mmの追加の格子も得られた。
MgF2 / Al / MgF2
を堆積させることによって、無色のアルミニウム回折顔料が本発明に従って製造された。MgF2層のそれぞれは、550 nmにおける光学的厚さ2 QWOTを持ち、Al層は、約160 nmの物理厚さを持つ。格子箔は、薄膜堆積層を形成するための基板支持体としての役割りを果たす。
図26〜30は、本発明に従って生成されたさまざまな研磨済み回折薄片を操作型電子顕微鏡によって撮影した写真である。具体的には、図26は1400列/mmの直線格子を持つ薄片を示し、図27は1400列/mmの十字格子を持つ薄片を示し、図28は2000列/mmの直線格子を持つ薄片を示しており、これらはすべて例11に関して上述されているように作成された。図29と30は、3000列/mmの直線格子を持つ薄片の写真である。図29と30により、高い格子周波数の場合にも、格子パターンを薄膜堆積層に転送して格子を持つ薄片を作ることができることが確認される。すべての場合において、得られた微細構造は非常に均質であり、このことは格子基板の複製が良好であることを示している。
図31は、格子基板から離層させた回折顔料粒子のコーティング微細構造を示す断面透過電子顕微鏡写真である。具体的には、この顕微鏡写真は、誘電体層206と反射層208を含む多層コーティング構造を形成するために使用された2000列/mmの格子202を示している。離層ゾーン204は、格子202と誘電体層206の間に示されている。誘電体層206は、550 nmにおいてZnSの7 QWOT層であり、反射層208はAlの80 nm層である。ZnS層の物理厚さは約410 nmであり、従って物理コーティング厚さが約490 nmの薄膜堆積層を形成している。この顕微鏡写真は、コーティング層が格子202の輪郭に従っており、従ってコーティングされていない状態の格子の回折光学効果を維持するはずである。
20 箔格子
22 回折構造
24 コーティング層
30 回折薄片
32 反射体層
34、36 誘電体層
40 回折薄片
42 誘電体層
44 反射体層
50 回折顔料薄片
52 支持誘電体層
54a、54b 反射体層
56 回折構造
100 被コーティング物品
102 表面セクション
104 回折コーティング層
106 非回折コーティング層
120 被コーティング物品
122 表面セクション
124 コーティング層
126 回折薄片
128 非回折薄片
202 格子
204 離層ゾーン
206 誘電体層
208 反射層
Claims (20)
- 第一主面と、対向する第二主面と、少なくとも1つの側面とを有する、第一材料を備える、中心反射体層、
前記中心反射体層の前記第一主面を覆う誘電体材料を備える第一誘電体層、及び
前記中心反射体層の前記第二主面を覆う第二誘電体層、
を備える回折顔料薄片であって、
前記中心反射体層、前記第一誘電体層及び第二誘電体層の全てが、少なくとも1,400格子列/mmと少なくとも150 nmの格子深さとを有する回折格子パターンを有する、
回折顔料薄片。 - 前記中心反射体層が、40 nm〜200 nmの物理厚さを有する、請求項1に記載の回折顔料薄片。
- 前記第一および第二誘電体層が、前記第一および第二主面のそれぞれの上に存在するが、前記中心反射体層の前記少なくとも1つの側面上には存在しない、請求項1または2に記載の回折顔料薄片。
- 前記第一および第二誘電体層それぞれが、1ミクロン以下の物理厚さを有する、請求項1〜3の何れかに記載の回折顔料薄片。
- 前記回折格子パターンが、
1400〜3500格子列/mmと、
150 nm〜230 nmの格子深さと、
を有する、請求項1〜4の何れかに記載の回折顔料薄片。 - 前記第一および第二誘電体層が、前記中心反射体層を囲む連続する誘電体層の一部を形成する、請求項1〜5の何れかに記載の回折顔料薄片。
- 前記回折顔料薄片が、500 nm〜1400 nmの物理厚さを有する、請求項1〜6の何れかに記載の回折顔料薄片。
- 前記第一材料が、アルミニウム、銀、銅、金、白金、錫、チタン、パラジウム、ニッケル、コバルト、ロジウム、ニオビウム、クロムと、これらの化合物、混合物、または合金から成るグループから選択される、請求項1〜7の何れかに記載の回折顔料薄片。
- 前記誘電体材料が、フッ化マグネシウム、二酸化ケイ素、酸化アルミニウム、フッ化アルミニウム、フッ化セリウム、フッ化ランタン、フッ化ネオジム、フッ化サマリウム、フッ化バリウム、フッ化カルシウム、フッ化リチウム、及びこれらの混合物から成るグループから選択される、請求項1〜8の何れかに記載の回折顔料薄片。
- 20 nm〜300 nmの溝深さを有する回折格子を備える、請求項1に記載の回折顔料薄片。
- 顔料媒体と、
前記顔料媒体内に分散されている請求項1〜10の何れかに記載の複数の回折顔料薄片と、
を備える回折組成物。 - 前記顔料媒体が、アクリルメラミン、ウレタン、ポリエステル、ビニル樹脂、アクリル酸塩、メタクリル酸メチル、ABS樹脂、エポキシ、スチレン、アルキド樹脂をベースとするインクおよび塗料調合物、並びにこれらの混合物から成るグループから選択される材料を備える、請求項11に記載の回折組成物。
- 前記回折顔料薄片が、凹版印刷、リソグラフィー、シルクスクリーン、グラビア、ドクターブレード、およびウェットコーティングから成るグループから選択される印刷工程において使用するために好適な、前記顔料媒体中におけるあらかじめ選択されたサイズとローディングとを有する、請求項11に記載の回折組成物。
- 前記回折組成物が、インクまたは塗料を備える、請求項11に記載の回折組成物。
- 前記顔料媒体が、化粧品調合品または成形もしくは押出加工することのできるプラスチック材料である、請求項11に記載の回折組成物。
- 前記顔料媒体内に分散された複数の非回折顔料薄片をさらに備える、請求項11に記載の回折組成物。
- 表面を有する物体と、
前記表面の少なくとも一部を覆う回折コーティング層であって、前記コーティング層が、請求項11〜16の何れかに記載の回折組成物を備える、回折コーティング層と、
を備えるコーティングされた物品。 - 前記回折コーティング層の下に下地コーティング層または非回折コーティング層をさらに備える、請求項17に記載のコーティングされた物品。
- 前記回折コーティング層を覆う透明な上面コーティング層または非回折コーティング層をさらに備える、請求項17または18に記載のコーティングされた物品。
- 前記コーティングされた物品が、自動車またはセキュリティ文書である、請求項17、18、または19に記載のコーティングされた物品。
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US09/919,346 | 2001-07-31 | ||
US09/919,346 US6692830B2 (en) | 2001-07-31 | 2001-07-31 | Diffractive pigment flakes and compositions |
PCT/US2002/010241 WO2003011980A1 (en) | 2001-07-31 | 2002-04-02 | Diffractive pigment flakes and compositions |
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JP2004536944A JP2004536944A (ja) | 2004-12-09 |
JP2004536944A5 JP2004536944A5 (ja) | 2006-01-05 |
JP4927313B2 true JP4927313B2 (ja) | 2012-05-09 |
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JP2003517160A Expired - Lifetime JP4927313B2 (ja) | 2001-07-31 | 2002-04-02 | 回折顔料薄片および組成物 |
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US (2) | US6692830B2 (ja) |
EP (1) | EP1414913B1 (ja) |
JP (1) | JP4927313B2 (ja) |
AU (1) | AU2002254497B2 (ja) |
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-
2001
- 2001-07-31 US US09/919,346 patent/US6692830B2/en not_active Expired - Lifetime
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2002
- 2002-04-02 CA CA2449992A patent/CA2449992C/en not_active Expired - Lifetime
- 2002-04-02 JP JP2003517160A patent/JP4927313B2/ja not_active Expired - Lifetime
- 2002-04-02 AU AU2002254497A patent/AU2002254497B2/en not_active Expired
- 2002-04-02 WO PCT/US2002/010241 patent/WO2003011980A1/en active IP Right Grant
- 2002-04-02 EP EP02723729.6A patent/EP1414913B1/en not_active Expired - Lifetime
- 2002-12-10 US US10/315,389 patent/US6749777B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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US20030031870A1 (en) | 2003-02-13 |
AU2002254497B2 (en) | 2007-06-28 |
US6692830B2 (en) | 2004-02-17 |
US20030104206A1 (en) | 2003-06-05 |
WO2003011980A1 (en) | 2003-02-13 |
JP2004536944A (ja) | 2004-12-09 |
EP1414913A1 (en) | 2004-05-06 |
CA2449992C (en) | 2011-02-01 |
CA2449992A1 (en) | 2003-02-13 |
EP1414913B1 (en) | 2017-06-07 |
US6749777B2 (en) | 2004-06-15 |
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