TW201925363A - 非對稱色素 - Google Patents

非對稱色素 Download PDF

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Publication number
TW201925363A
TW201925363A TW107141403A TW107141403A TW201925363A TW 201925363 A TW201925363 A TW 201925363A TW 107141403 A TW107141403 A TW 107141403A TW 107141403 A TW107141403 A TW 107141403A TW 201925363 A TW201925363 A TW 201925363A
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Taiwan
Prior art keywords
fabry
pigment
perot structure
quarter
layer
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TW107141403A
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English (en)
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TWI700338B (zh
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克隆尼斯 珍 迪爾斯特
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美商菲爾薇解析公司
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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
    • 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
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0051—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index
    • C09C1/0057—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index comprising at least one light-absorbing layer
    • 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
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • 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
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    • B41M3/148—Transitory images, i.e. images only visible from certain viewing angles
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    • B42D25/30—Identification or security features, e.g. for preventing forgery
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    • 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
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    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
    • C09C1/003—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index comprising at least one light-absorbing layer
    • C09C1/0033—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index comprising at least one light-absorbing layer consisting of a metal or an alloy
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    • 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
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
    • C09C1/003—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index comprising at least one light-absorbing layer
    • C09C1/0039—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index comprising at least one light-absorbing layer consisting of at least one coloured inorganic material
    • 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
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0051—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index
    • C09C1/0057—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index comprising at least one light-absorbing layer
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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    • C09C1/0051—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index
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    • 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
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    • C09D5/035—Coloring agents, e.g. pigments
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Abstract

本發明揭示一種非對稱色素，包括：第一法布里-珀羅結構；及第二法布里-珀羅結構；其中第一法布里-珀羅結構及第二法布里-珀羅結構具有在+/- 45度內之類似色調角。亦揭示其他非對稱色素以及製造所揭示色素之方法。

Description

非對稱色素
本發明大體上係關於非對稱色素，可（i）包括可見的角度下色彩（color at angle），（ii）色移，及（iii）具有小色素尺寸。亦揭示製造該等非對稱色素之方法。
自隱藏觀點來看，藉由干涉反射峰處之2個或4個四分之一波長厚度的光學厚度基於色彩對磁性色素進行色移可為有吸引力的，此係因為薄片較薄。然而，這些薄片具有若干缺陷。詳言之，當看見角度下色彩所需之傾斜角較高時，此色彩可能並不清晰可見。高傾斜角導致大多數光照條件下之低光反射。另外，薄片難以破裂成小色素尺寸，此係因為不透明磁芯相對較強且每薄片重量較低。
先前，為了達成在高傾斜角下可見且易於更改（例如）成薄片之濃重色彩，製造具有光學厚層之對稱色素。然而，具有光學較厚層之色素之製造更為昂貴。為了使成本最小化，製造具有光學較薄層之色素。然而，具有光學較薄層之色素無法產生濃重色彩效果，且難以更改（例如）成薄片，此係因為其具有高的相對金屬內容物及低的重量-表面比率。儘管具有光學較薄層之色素之製造更便宜，但其展現低色彩及/或色移效果，且為在色移著色劑中可見的較大大小之薄片。
雙腔設計色素可達成2個四分之一波或4個四分之一波單腔設計無法達成之色彩。然而，生產並不簡單，且雙腔設計色素相對較厚、重且昂貴。
在一態樣中，揭示一種非對稱色素，包含：第一法布里-珀羅（Fabry-Perot）結構；及第二法布里-珀羅結構；其中第一法布里-珀羅結構及第二法布里-珀羅結構具有在+/- 45度內之類似色調角，且其中第一法布里-珀羅結構及第二法布里-珀羅結構之平均厚度的比率為1:1.5至1:2.5。
在另一態樣中，揭示一種非對稱色素，包含：法布里-珀羅結構；及雙腔；其中法布里-珀羅結構及雙腔具有在+/- 45度內之類似色調角。
在另一態樣中，揭示一種形成非對稱色素之方法，包含：將第一法布里-珀羅結構沉積於基板上；及將第二法布里-珀羅結構沉積於第一法布里-珀羅結構上；其中第一法布里-珀羅結構及第二法布里-珀羅結構具有在+/- 45度內之類似色調角。
在另一態樣中，揭示一種用於製造色素之方法，包含：將法布里-珀羅結構沉積於基板上；及將雙腔沉積於法布里-珀羅結構上；其中法布里-珀羅結構及雙腔具有在+/- 45度內之類似色調角。
在另一態樣中，揭示一種用於製造色素之方法，包含：將雙腔沉積於基板上；及將法布里-珀羅結構沉積於雙腔上；其中法布里-珀羅結構及雙腔具有在+/- 45度內之類似色調角。
在以下描述中將部分闡述各種實施例之額外特徵及優點，且將部分自該描述顯而易見，或可藉由對各種實施例的實踐習得。藉助於本文中之描述中特別指出之元件及組合，將實現及達成各種實施例之目標及其他優點。
應理解，前述一般描述及以下詳細描述兩者皆僅為例示性及解釋性的，且意欲提供對本發明教示之各種實施例的解釋。
在其廣泛及變化實施例中，本文中揭示色素10（諸如非對稱色素）及製造色素10之方法。色素10可與液體介質摻合以形成色移著色劑。在一態樣中，非對稱設計可導致較低的角度下色度，從而導致色彩暗偏移（dark shift）。用於磁性對準之色素，此可為有吸引力的態樣，此係因為其可導致具有區域由豐富色彩包圍，或毗鄰相比於對稱色素之情況展示低得多的色彩之區域。彩色區域可似乎隨視角改變而移動。
根據各種實施例，圖1、圖3及圖4A至圖4C說明各種色素10，諸如呈薄片、箔片或薄板形式之光學裝置。儘管，這些圖說明呈特定次序之特定層，但一般熟習此項技術者將瞭解，色素10可包括呈任何次序之任何數目個層。另外，任何特定層之組成可與任何其他層之組成相同或不同。亦設想本文中所揭示之色素10可包括額外層，諸如中間層或介入層。亦設想色素10之層可諸如藉由氧化來表面修飾。應瞭解，所揭示之色素10可在尺寸上非對稱，亦即，色素之一側可較薄，例如可相比於色素10之相對側在實體上及/或光學上不太厚，相對側可較厚，諸如在實體上及/或光學上較厚。
本文中所揭示之色素10可提供成本與色彩效果之間的平衡。亦即，色素10為非對稱的，其在一側上具有光學較薄層，亦即，以達成較低成本，且在相對側上具有光學較厚層，亦即，以達成較強的角度下色彩效果。非對稱設計可能導致高於光學較薄對稱薄片之每薄片重量，且可改良色素破裂成色素薄片。另外，包括色素10之色移著色劑可具有每薄片重量之均質分佈，以便避免在製備、儲存或應用階段中塗料或油墨媒劑中的重量誘發之分離。舉例而言，色素10在色移著色劑中之使用可能導致色素10之任一側面向上的機率為50/50，此係因為存在於色移著色劑中之所有色素10可具有相同重量。舉例而言，色素10中之一些可定位成例如第一法布里-珀羅結構20側向上，且色素10中之一些可定位成第二法布里-珀羅結構20'側向上。在另一態樣中，色素10中之一些可定位成法布里-珀羅結構20（諸如2個或4個四分之一波堆疊)側向上，且色素10中之一些可定位成雙腔26側向上。
色素10可為非對稱的，其包括光學較薄側及光學較厚側。如圖1中所示，在一態樣中，色素10可包括：第一法布里-珀羅結構20；及第二法布里-珀羅結構20'；其中第一法布里-珀羅結構及第二法布里-珀羅結構具有在+/- 45度內之類似色調角，且其中第一法布里-珀羅結構及第二法布里-珀羅結構之平均厚度的比率為1:1.5至1:2.5。第一法布里-珀羅結構及第二法布里-珀羅結構之平均厚度的比率為2:2.5至2:3.5，例如，比率為1:2.5至1:3.5。在另一態樣中，非對稱色素可包括：第一法布里-珀羅結構；及第二法布里-珀羅結構；其中第一法布里-珀羅結構及第二法布里-珀羅結構具有在+/- 45度內之類似色調角。法布里-珀羅結構（第一20、第二20'、第三20'''等）可各自獨立地包括反射體層14、介電層12及吸收體層18，如圖2A至圖2C中所示。應當理解的是，在形成色素10之過程中可使用任何兩個法布里-珀羅結構20，只要每一法布里-珀羅結構20具有不同光學厚度即可。
在一態樣中，第一法布里-珀羅結構20及第二法布里-珀羅結構20'中之每一者的光學厚度可為不同的。舉例而言，第一法布里-珀羅結構20可包括在約200 nm至約400 nm範圍內之2個四分之一波光學厚度或在約400 nm至約600 nm範圍內之4個四分之一波光學厚度。作為另一實例，第二法布里-珀羅結構20可包括在約400 nm至約600 nm範圍內之4個四分之一波光學厚度或在約600 nm至約800 nm範圍內之6個四分之一波光學厚度。
諸如圖1中所示之非對稱色素10可包括：第一法布里-珀羅結構20，其包括在約200 nm至約400 nm範圍內之2個四分之一波光學厚度；及第二法布里-珀羅結構20'，其包括在約400 nm至約600 nm範圍內之4個四分之一波光學厚度。
在另一態樣中，非對稱色素10可包括第一法布里-珀羅結構20'，其包括在約400 nm至約600 nm範圍內之4個四分之一波光學厚度；及第二法布里-珀羅結構20''，其包括在約600 nm至約800 nm範圍內之6個四分之一波光學厚度。
非對稱色素10可與液體介質組合以形成色移著色劑。色移著色劑可為例如油墨或塗料。液體介質之非限制性實例可包括溶劑，例如乙酸酯，諸如乙酸乙酯、乙酸丙酯及乙酸丁酯；丙酮；水；酮，諸如二甲基酮（dimethyl ketone；DMK）、甲基乙基酮（methylethyl ketone；MEK）、仲丁基甲基酮（sec butyl methyl ketone；SBMK）、第三丁基甲基酮（ter-butyl methyl ketone；TBMK）、環戊酮及苯甲醚；乙二醇及乙二醇衍生物，諸如丙二醇甲醚及丙二醇甲醚乙酸酯；醇，諸如異丙醇及二丙酮醇；酯，諸如丙二酸鹽；雜環溶劑，諸如正甲基吡咯啶酮；烴，諸如甲苯及二甲苯；聚結溶劑，諸如二醇醚；及其混合物。在一態樣中，以相對於色移著色劑之總重量的重量計，液體介質可以在約0%至約99.9%，例如約0.005%至約99%且作為另一實例約0.05%至約90%的範圍內之量存在。
所揭示例示性色素10中之每一者可更改，諸如以機械方式更改，例如藉由破裂，以形成薄片、箔片或薄板。色素10可形成為尺寸在約2微米至約40微米範圍內之薄片、箔片或薄板。色素10可具有20微米之D50（色素之50%大於20微米且50%小於20微米），以及4微米之D0.01（色素之99.9%大於4微米）及80微米之D99.99（色素之0.01%小於80微米）。具有在5至15微米D50範圍內之小色素尺寸的色素10可能導致粒狀印刷（grainy print）較少，但此薄片大小可能難以在不使用非對稱組態之情況下達成濃重的干涉色，如金色、橙色及紅色，此係因為基於空氣之研磨系統中之光學較薄、較輕重量的薄片之碰撞衝擊較小。在一態樣中，色素10可具有大約11微米之D50，且可擁有濃重的干涉色。
色素10可各自具有類似（在加或減45度內）色調角，例如圖6中所示。色素10之每一側的藉由加性摻合產生第三色彩之兩個更明顯不同的色彩不在範圍內。製造每一側上之介電層厚度略微不同的色移干涉色素以允許對色度及色調進行摻合控制係常見的。此不在本發明之範圍內。此微小厚度差可能導致色調角不同，但不會顯著影響角度下色彩或破裂特性。
在一些實施例中，色素10可展現光學干涉。替代地，在一些實施例中，色素10無法展現光學干涉。在一態樣中，色素10可採用干涉來生成色彩。在另一態樣中，色素10無法採用干涉來生成色彩。
在另一態樣中，非對稱色素10可包括包夾在第一法布里-珀羅結構20與第二法布里-珀羅結構20'之間的含磁性層16，如圖3中所示。在一態樣中，含磁性層16可包夾在第二法布里-珀羅結構20'與第三法布里-珀羅結構20''（未圖示）之間。非對稱色素10可包括包夾在法布里-珀羅結構20與雙腔之間的含磁性層16，如圖4C中所示。如本文中更完全地論述，反射體層14及/或吸收體層18可各自獨立地包括含磁性材料，其亦可充當法布里-珀羅結構20、20'或20''中之任一者的含磁性層16。
含磁性層16可包括磁性可滲透、磁性可定向材料、磁性材料，及其組合。諸如鐵磁性及次鐵磁性材料之磁性材料包括但不限於鎳、鈷、鐵、釓、鋱、鏑、鉺及其摻合物、合金或氧化物。摻合物或合金之其他實例包括但不限於Fe/Si、Fe/Ni、Fe/Co、Fe/Ni/Mo、Fe/Cr、Ni/Cr，及其組合。在一態樣中，含磁性層16可包括含有氧化鐵顆粒之聚合物。類型SmCo5 、NdCo5 、Sm2 Co17 、Nd2 Fe14 B、Sr6 Fe2 O3 、TbFe2 、Al—Ni—Co及其組合之硬磁鐵亦可用作類型Fe3 O4 、NiFe2 O4 、MnFe2 O4 、CoFe2 O4 之尖晶石肥粒鐵(spinel ferrite)或類型YIG或GdIG之石榴石，及其組合。在一態樣中，磁性材料可為肥粒鐵不鏽鋼。可針對磁性材料之反射或吸收屬性以及其磁屬性來選擇磁性材料。含磁性層16可由具有磁性及非磁性顆粒或非磁性介質內之磁性顆粒的材料形成，例如，沉積於基板上之鈷摻雜之氧化鋅膜。含磁性層16可為不同層，或可充當反射體層14或吸收體層18。
儘管可使用此寬廣範圍之磁性材料，但在一態樣中可使用「軟（soft）」磁鐵。如本文中所使用，術語「軟磁鐵（soft magnets）」係指展現鐵磁屬性但具有在曝露於磁力之後實質上為零之頑磁的任何材料。軟磁鐵可展示對所施加磁場之快速回應，但具有極低（矯頑場（Hc）=0.05至300奧斯特（Oe））或零磁性特徵，或在移除磁場之後保持極低磁力線。類似地，如本文中所使用，術語「硬磁鐵（hard magnets）」（亦稱為永久磁鐵）係指展現鐵磁屬性且在曝露於磁化力之後具有持久頑磁之任何材料。鐵磁性材料為滲透率實質上大於1且展現磁滯屬性之任何材料。在一態樣中，可在含磁性層16中使用任何磁性材料，只要該材料實現色素10在磁場中之定向即可。
含磁性層16可具有在約10 nm至約100 nm，例如約35 nm至約45 nm，且作為另一實例約40 nm至約45 nm之範圍內的厚度。含磁性層16可經沉積至使得其實質上不透明之厚度。在一態樣中，含磁性層16可經沉積至使得其實質上並非不透明之厚度。
可使用習知沉積製程來形成含磁性層16，這些製程諸如物理氣相沉積技術；以及包括磁控濺鍍之濺鍍；熱蒸發；電子束蒸發；及陰極電弧蒸發。在一態樣中，亦可使用液態塗佈製程來形成含磁性層16。
在另一態樣中，非對稱色素10可包括：法布里-珀羅結構20及雙腔26，如圖4A至圖4C中所示，其中法布里-珀羅結構及雙腔具有在+/- 45度內之類似色調角。法布里-珀羅結構20可如關於圖1及圖2A至圖2C所描述。
雙腔26可包括反射體層14，及交替的介電層12與吸收體層18之堆疊，如圖5A至圖5C中所示。舉例而言，交替的介電層12與吸收體層18之堆疊可包括第一介電層12、第一吸收體層18、第二介電層12'及第二吸收體層18'。交替的介電層12與吸收體層18之堆疊可包括任何數目之每一層。
第一介電層12可包括選自2個四分之一波光學厚度、4個四分之一波光學厚度及6個四分之一波光學厚度之四分之一波光學厚度。第二介電層12'可包括選自2個四分之一波光學厚度、4個四分之一波光學厚度及6個四分之一波光學厚度之四分之一波光學厚度。
如圖5A中所示，雙腔26可包括具有在約200 nm至約400 nm範圍內之2個四分之一波光學厚度道第一介電層12；及具有在約200 nm至約400 nm範圍內之2個四分之一波光學厚度的第二介電層12'。在另一態樣中，如圖5B中所展示，雙腔26可包括具有在約200 nm至約400 nm範圍內之2個四分之一波光學厚度的第一介電層12；及具有在約400 nm至約600 nm範圍內之4個四分之一波光學厚度的第二介電層12'。在另一態樣中，如圖5C中所展示，雙腔26可包括具有在約400 nm至約600 nm範圍內之4個四分之一波光學厚度的第一介電層12；及具有在約600 nm至約800 nm範圍內之6個四分之一波光學厚度的第二介電層12'。
法布里-珀羅結構20及/或雙腔26之反射體層14可為寬頻反射體，例如光譜及朗伯（Lambertian）反射體（例如，白色TiO2 ）。反射體層14可各自獨立地包括金屬、非金屬及/或金屬摻合物或合金。除非另外陳述，否則本文中所使用之術語「金屬（metallic）」或「金屬層（metallic layer）」意欲包括所有金屬、金屬摻合物及合金、純金屬或含有材料、化合物、組成物及/或層之金屬合金。
在一個實例中，反射體層14之材料可包括在所要光譜範圍內具有反射特性之任何材料。例如，在所要光譜範圍內具有在50%至100%範圍內之反射率的任何材料。反射材料之實例可為鋁，其具有良好反射特性，便宜，且易於形成為薄層或沉積為薄層。亦可使用其他材料來代替鋁。舉例而言，銅、銀、金、鉑、鈀、鎳、鈷、鈮、鉻、錫及組合、此等或其他金屬之摻合物或合金可用作反射材料。在一態樣中，反射體層14之材料可為白色或淡色金屬。在其他實例中，反射體層14可包括但不限於過渡及鑭系金屬及其組合；以及金屬碳化物、金屬氧化物、金屬氮化物、金屬硫化物、其組合，或金屬與這些材料中之一或多種的混合物。
反射體層14之厚度可在約5 nm至約5000 nm範圍內，儘管此範圍不應被視為限定性的。舉例而言，可選擇較低厚度，使得反射體層14提供最大透射率0.8。另外或替代地，對於包括鋁之反射體層14，約550 nm之波長下的最小光學密度（optical density；OD）可為約0.1至約4。
為了獲得足夠光學密度及/或達成所要效果，取決於反射體層14之組成可能需要較高或較低的最小厚度。在一些實例中，上限可為約5000 nm，約4000 nm，約3000 nm，約1500 nm，約200 nm，及/或約100 nm。在一個態樣中，反射體層14之厚度可在約10 nm至約5000 nm，例如約15 nm至約4000 nm，約20 nm至約3000 nm，約25 nm至約2000 nm，約30 nm至約1000 nm，約40 nm至約750 nm，或約50 nm至約500 nm，諸如約60 nm至約250 nm或約70 nm至約200 nm之範圍內。
在一個態樣中，法布里-珀羅結構20及/或雙腔26之介電層12可安置於反射體層14上。介電層12可具有大於或小於約1.5之折射率。舉例而言，介電層12可具有大致1.5之折射率。介電層12之折射率可經選擇以提供所需色變（color travel）之程度，其中色變可定義為以檢視角度在L*a*b*色彩空間中所量測的色調角之改變。
光學厚度為被定義為產品ηd之熟知光學參數，其中η為層之折射率且d為層之實體厚度。典型地，層之光學厚度以等於4ηd/λ之四分之一波光學厚度（quarter wave optical thickness；QWOT）表達，其中λ為QWOT條件發生之波長。取決於所要之色移，介電層12之光學厚度可在約200 nm之設計波長下約2 QWOT至約700 nm之設計波長下約9 QWOT的範圍內，且例如在200 nm至800 nm之設計波長下2至6 QWOT。介電層12之適合材料包括具有「高（high）」折射率（在本文中定義為大於約1.65）之材料以及具有「低（low）」折射率（在本文中定義為約1.65或更小）之材料。出於本說明書之目的，檢核2個、4個或6個四分之一波檢核係基於圖6進行，圖6標繪法線角下之色調角與介電層厚度。作為一實例，在140 nm（2個四分之一波）、280 nm（4個四分之一波）及430 nm（6個四分之一波）之光學厚度下達成金色（大約90度色調角）。以特定四分之一波計數達成之色彩中之一些歸因於低色度或低亮度而對於人眼不太具吸引力，但可以至少2個四分之一波計數製造可見光譜中之大多數色彩。在大於2個四分之一波下，多個反射峰適於可見光譜且此影響特定色調角度下之色度。2個四分之一波綠色具有極低色度，且此色彩通常被製成4個或6個四分之一波堆疊。6個四分之一波綠色在藍色中具有反射峰，且因此在製成帶藍色的綠色時將具有較高色度。洋紅或紅色極好地用作2個或4個四分之一波堆疊，但6個四分之一波堆疊並不如此，此係因為其具有不吸引人的低亮度。
適合於介電層12之高折射率材料之實例包括硫化鋅（ZnS）、氧化鋅（ZnO）、氧化鋯（ZrO2 ）、二氧化鈦（TiO2 ）、碳（C）、氧化銦（In2 O3 ）、氧化銦錫（ITO）、五氧化鉭（Ta2 O5 ）、氧化鈰（CeO2 ）、氧化釔（Y2 O3 ）、氧化銪（Eu2 O3 ）、氧化鐵（諸如（III）氧化（II）二鐵（Fe3 O4 ）及氧化三鐵（Fe2 O3 ））、氮化鉿（HfN）、碳化鉿（HfC）、氧化鉿（HfO2 ）、氧化鑭（La2 O3 ）、氧化鎂（MgO）、氧化釹（Nd2 O3 ）、氧化鐠、（Pr6 O11 ）、氧化釤（Sm2 O3 ）、二氧化二銻（Sb2 O3 ）、碳化矽（SiC）、氮化矽（Si3 N4 ）、一氧化矽（SiO）、三氧化硒（Se2 O3 ）、氧化錫（SnO2 ）、三氧化鎢（WO3 ）、其組合，及其類似物。
適合於介電層12之低折射率材料包括二氧化矽（SiO2 ）、氧化鋁（Al2 O3 ）、金屬氟化物，諸如氟化鎂（MgF2 ）、氟化鋁（AlF3 ）、氟化鈰（CeF3 ）、氟化鑭（LaF3 ）、鈉鋁氟化物（例如，Na3 AlF6 或Na5 Al3 F14 ）、氟化釹（NdF3 ）、氟化釤（SmF3 ）、氟化鋇（BaF2 ）、氟化鈣（CaF2 ）、氟化鋰（LiF）、其組合，或具有約1.65或更小之折射率的任何其他低折射率材料。舉例而言，有機單體及聚合物可用作低折射率材料，包括二烯或烯烴，諸如丙烯酸酯（例如，甲基丙烯酸脂）、全氟烯烴、聚四氟乙烯（特氟隆）、氟化乙烯丙烯（fluorinated ethylene propylene；FEP）、其組合，及其類似物。
介電層12可經沉積或印刷或以其他方式塗佈為具有預定數目個層之介電質堆疊。在此實例中，堆疊可包括低折射率材料之一或多個層及高折射率材料之一或多個層。具有低折射率材料之層（低折射率層）及具有高折射率材料之層（高折射率層）可交替。舉例而言，高折射率層可經沉積或印刷於反射體層14上。低折射率層可接著沉積於其對應的高折射率層上。此製程可根據需要重複許多次以產生介電層12。交替層可一任何序列堆疊，例如，該等層可以(H/L)n 、(H/L)n H或L(H/L)n 之序列堆疊，其中H表示較高折射率層，且L表示較低折射率層。交替的低折射率層及高折射率層之數目（n）可在約2至超過約75之範圍內，諸如約10個交替層至約50個交替層，或例如約5個交替層至約25個交替層。在一個態樣中，介電質堆疊可包含在組成上交替之液態塗佈印刷層，其增大另一層之有效折射率。可使用任何數目種不同材料來印刷任何數目個層。以此方式，藉由控制層厚度及每一介電層12之折射率，調節光學設計係可能的。
在每一態樣中，介電層12可為透明層，或可為有色層。介電層12之效能可基於對存在於介電層12中之材料之選擇來判定。一般相信介電層12可基於介電層12之組成達成光之傳輸、反射及吸收的高效能。在一態樣中，介電層12可包括允許經組態以增加介電層12之光學效能之控制的較寬範圍之材料的組成物。在一態樣中，介電層12可改良以下屬性中之至少一者：金屬層之薄片處置、腐蝕、對準及環境效能
介電層可具有在約130 nm至約450 nm範圍內之標稱光學厚度。介電層12之厚度可用以判定總體色彩。當與標稱光學厚度之偏差變化過多時，不同區域或薄片具有不同或甚至互補的色彩，且當摻合時，觀測到色度損失。
吸收體層18可安置於介電層12上。吸收體層18可獨立地包括金屬、非金屬或金屬摻合物或合金。在一個實例中，吸收體層18之材料可包括任何吸收體材料，包括選擇性吸收材料及非選擇性吸收材料兩者。舉例而言，吸收體層18可由非選擇性吸收金屬材料形成，其經沉積至層為至少部分地吸收或半不透明之厚度。非選擇性吸收材料之實例可為灰色金屬，諸如鉻或鎳。選擇性吸收材料之實例可為銅或金。在一態樣中，吸收材料可為鉻。適合吸收體材料之非限制性實例包括金屬吸收體，諸如鉻、鋁、銀、鎳、鈀、鉑、鈦、釩、鈷、鐵、錫、鎢、鉬、銠、鈮、銅，以及其他吸收體，諸如碳、石墨、矽、鍺、金屬陶瓷、三價鐵氧化物或其他金屬氧化物、混合於介電基質中之金屬，及能夠充當可見光譜中之均勻或選擇性吸收體的其他物質。上述吸收體材料之各種組合、混合物、化合物或合金可用以形成吸收體層18。
上述吸收體材料之適合合金之實例可包括英高鎳（Ni-Cr-Fe）、不鏽鋼、赫史特合金（Ni-Mo-Fe；Ni-Mo-Fe-Cr；Ni-Si-Cu）及鈦基合金，諸如與碳混合之鈦（Ti/C）、與鎢混合之鈦（Ti/W）、與鈮混合之鈦（Ti/Nb）及與矽混合之鈦（Ti/Si），及其組合。適合於吸收體層18之化合物之其他實例包括但不限於鈦基化合物，諸如矽化鈦（TiSi2）、硼化鈦（TiB2），及其組合。替代地，吸收體層18可由沉積於Ti之基質中的鈦基合金構成，或可由沉積於Ti鈦基合金或摻合物之基質中的Ti構成。舉例而言，吸收體層18可包括鉻。
吸收體層18亦可由磁性材料形成，諸如鈷鎳合金或摻合物，或鐵鉻合金或摻合物。此可藉由減少所需材料之數目來簡化磁性色移裝置或結構之製造。
取決於吸收體層材料之光學常數及所要峰移位，吸收體層18可形成為具有在約1 nm至約50 nm，諸如約5 nm至約10 nm範圍內之實體厚度。若多於一個吸收體層18存在於色素10中，諸如圖5C中所示，則吸收體層18可由相同材料或不同材料構成，且每一層可具有相同或不同的實體厚度。
亦揭示一種用於製造色素10之方法，如本文中所描述。方法可包含將第一法布里-珀羅結構20沉積於基板上；及將第二法布里-珀羅結構20'沉積於第一法布里-珀羅結構20上。在另一態樣中，方法可包括將第二法布里-珀羅結構20'沉積於基板上；及將第一法布里-珀羅結構20沉積於第二法布里-珀羅結構20'上。
在另一態樣中，用於製造色素10之方法可包含將雙腔26沉積於基板上；及將法布里-珀羅結構20沉積於雙腔26上。在另一態樣中，用於製造色素10之方法可包含將法布里-珀羅結構20沉積於基板上；及將雙腔26沉積於法布里-珀羅結構20上。
基板可由可撓性材料製成。基板可為可收納經沉積層之任何適合材料。適合基板材料之非限制性實例包括聚合物板，諸如聚對苯二甲酸伸乙酯（polyethylene terephthalate；PET）、玻璃、矽晶圓等。基板可包括剝離層。
色素10之任何或所有層可藉由習知沉積製程沉積至基板上，製程可諸如為物理氣相沉積、化學氣相沉積、薄膜沉積、原子層沉積等，包括經修改之技術，諸如電漿增強及流化床。可使用液態塗佈製程，使用例如槽模設備來沉積該等層中之一或多者。液態塗佈製程包括但不限於：單層及多層塗佈中之槽珠、滑珠、槽幕、滑幕，張緊之網槽、凹版、滾塗，及將液體施加至基板上以形成隨後乾燥及/或烘烤之液體層或膜的其他液態塗佈及印刷製程。相比於諸如氣相沉積之其他沉積技術，液態塗佈製程可允許組成物以更快的速率轉移。
基板可接著自經沉積層剝離以產生色素10，例如圖1、圖3及圖4A至圖4C中所示。在一態樣中，基板可經冷卻以使相關聯剝離層脆化。在另一態樣中，可例如藉由用光子或電子束能量加熱及/或烘烤以增大交聯度來使剝離層脆化，此將實現汽提。可接著以機械方式，諸如藉由表面之急劇彎曲或塗刷來對經沉積層進行汽提。可使用已知技術將經剝離及汽提之層大小設定成色素10，諸如呈薄片、箔片或薄板形式之光學裝置。
在另一態樣中，經沉積層可自基板轉移至另一表面。經沉積層可經衝壓或切割以產生具有定義明確之大小及形狀的大薄片。
亦揭示一種形成非對稱色素之方法，其包含：將第一法布里-珀羅結構沉積於基板上；及將第二法布里-珀羅結構沉積於第一法布里-珀羅結構上；其中第一法布里-珀羅結構及第二法布里-珀羅結構具有在+/- 45度內之類似色調角。
亦揭示一種用於製造色素之方法，其包含：將法布里-珀羅結構沉積於基板上；及將雙腔沉積於法布里-珀羅結構上；其中法布里-珀羅結構及雙腔具有在+/- 45度內之類似色調角。
亦揭示一種用於製造色素之方法，其包含：將雙腔沉積於基板上；及將法布里-珀羅結構沉積於雙腔上；其中法布里-珀羅結構及雙腔具有在+/- 45度內之類似色調角。
自前述描述，熟習此項技術者可瞭解，本發明教示可以多種形式實施。因此，雖然已結合特定實施例及其實例描述了此等教示，但本發明教示之實際範圍不應限於此。因此，可在不背離本文中之教示之範圍的情況下進行各種改變及修改。
將廣泛地解釋此範圍揭示內容。既定本發明揭示用以達成本文中所揭示之裝置、活動及機械動作的等效物、構件、系統和方法。對於所揭示之每一裝置、色素、方法、構件、機械元件或機制，既定本發明亦在其揭示內容及教示中涵蓋用於實踐本文中所揭示之許多態樣、機制及裝置的等效物、構件、系統和方法。另外，本發明係關於塗層及其許多態樣、特徵及元件。此類裝置在其使用及操作中可為動態的，既定本發明涵蓋製造之裝置及/或色素之使用的等效物、構件、系統及方法及其許多態樣，其與本文中所揭示之操作及功能之描述及精神一致。同樣應廣泛地解釋本申請之申請專利範圍。
本文中之發明在其許多實施例中之描述在本質上僅僅為例示性的，且因此，不背離本發明之要旨的變化意欲在本發明之範圍內。此類變化不應視為背離本發明之精神及範圍。
在本發明之若干態樣及實施例中，可自詳細描述及附圖更完全地理解本發明，其中：
圖1為根據本發明之一態樣之非對稱色素的橫截面圖；
圖2A為根據本發明之一態樣之法布里-珀羅結構的橫截面；
圖2B為根據本發明之另一態樣之法布里-珀羅結構的橫截面；
圖2C為根據本發明之另一態樣之法布里-珀羅結構的橫截面；
圖3為根據本發明之另一態樣之非對稱色素的橫截面圖；
圖4A為根據本發明之另一態樣之非對稱色素的橫截面圖；
圖4B為根據本發明之另一態樣之非對稱色素的橫截面圖；
圖4C為根據本發明之另一態樣之非對稱色素的橫截面圖；
圖5A為根據本發明之一態樣之雙腔的橫截面；
圖5B為根據本發明之另一態樣之雙腔的橫截面；
圖5C為根據本發明之另一態樣之雙腔的橫截面；且
圖6為說明色調角之L.*a*b*圖表。
在本說明書及圖示中，相似的參考編號標識相似元件。

Claims (20)

  1. 一種非對稱色素，包含： 第一法布里-珀羅(Fabry-Perot)結構；及 第二法布里-珀羅結構； 其中該第一法布里-珀羅結構及該第二法布里-珀羅結構具有在+/- 45度內之類似色調角； 且其中該第一法布里-珀羅結構及該第二法布里-珀羅結構之平均厚度的比率為1:1.5至1:2.5。
  2. 如請求項1所述之色素，其中該第一法布里-珀羅結構及該第二法布里-珀羅結構各自獨立地包括反射體層、介電層及吸收體層。
  3. 如請求項1所述之色素，其中該第一法布里-珀羅結構及該第二法布里-珀羅結構中之每一者之光學厚度為不同的。
  4. 如請求項1所述之色素，其中該第一法布里-珀羅結構包括在約200 nm至約400 nm範圍內之2個四分之一波光學厚度。
  5. 如請求項1所述之色素，其中該第一法布里-珀羅結構及該第二法布里-珀羅結構可各自獨立地包括在約400 nm至約600 nm範圍內之4個四分之一波光學厚度。
  6. 如請求項1所述之色素，其中該第二法布里-珀羅結構包括在約600 nm至約800 nm範圍內之6個四分之一波光學厚度。
  7. 如請求項1所述之色素，其中該第一法布里-珀羅結構包括在約200 nm至約400 nm範圍內之2個四分之一波光學厚度；且 其中該第二法布里-珀羅結構包括在約400 nm至約600 nm範圍內之4個四分之一波光學厚度。
  8. 如請求項1所述之色素，其中該第一法布里-珀羅結構包括在約400 nm至約600 nm範圍內之4個四分之一波光學厚度；且 其中該第二法布里-珀羅結構包括在約600 nm至約800 nm範圍內之6個四分之一波光學厚度。
  9. 如請求項1所述之色素，進一步包含安置於該第一法布里-珀羅結構與該第二法布里-珀羅結構之間的含磁性層。
  10. 一種色移著色劑，包含： 如請求項1所述之色素；及 液體介質。
  11. 一種非對稱色素，包含： 法布里-珀羅結構；及 雙腔； 其中該法布里-珀羅結構及該雙腔具有在+/- 45度內之類似色調角。
  12. 如請求項11所述之色素，進一步包含安置於該法布里-珀羅結構與該雙腔之間的含磁性層。
  13. 如請求項11所述之色素，其中該法布里-珀羅結構包括在約200 nm至約400 nm範圍內之2個四分之一波光學厚度。
  14. 如請求項11所述之色素，其中該法布里-珀羅結構包括在約400 nm至約600 nm範圍內之4個四分之一波光學厚度。
  15. 如請求項11所述之色素，其中該雙腔包含反射體層及交替的介電層與吸收體層之堆疊。
  16. 如請求項15所述之色素，其中交替的介電層與吸收體層之該堆疊可包括第一介電層、第一吸收體層、第二介電層及第二吸收體層。
  17. 如請求項15所述之色素，其中該第一介電層及該第二介電層各自獨立地可包括選自2個四分之一波光學厚度、4個四分之一波光學厚度及6個四分之波光學厚度之四分之一波光學厚度。
  18. 如請求項15所述之色素，其中該雙腔包含具有在約200 nm至約400 nm範圍內之2個四分之一波光學厚度的該第一介電層；及 具有在約400至約600 nm範圍內之4個四分之一波光學厚度的該第二介電層。
  19. 如請求項18所述之色素，其中該雙腔包含具有在約400 nm至約600 nm範圍內之4個四分之一波光學厚度的該第一介電層；及 具有在約600 nm至約800 nm範圍內之6個四分之一波光學厚度的該第二介電層。
  20. 一種色移著色劑，包含： 如請求項14所述之非對稱色素；及液體介質。
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WO2019103937A1 (en) 2019-05-31
EP3714006A4 (en) 2021-08-04
TWI715418B (zh) 2021-01-01
US20210147688A1 (en) 2021-05-20
US20190153233A1 (en) 2019-05-23
US10899930B2 (en) 2021-01-26
CN111556885A (zh) 2020-08-18
EP3714006A1 (en) 2020-09-30
TW202020064A (zh) 2020-06-01
CN114163842B (zh) 2024-07-16
CN114163842A (zh) 2022-03-11

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