TW201339253A - 效果顏料 - Google Patents
效果顏料 Download PDFInfo
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- TW201339253A TW201339253A TW101148112A TW101148112A TW201339253A TW 201339253 A TW201339253 A TW 201339253A TW 101148112 A TW101148112 A TW 101148112A TW 101148112 A TW101148112 A TW 101148112A TW 201339253 A TW201339253 A TW 201339253A
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Classifications
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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
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
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- C09C1/3018—Grinding
-
- 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
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
-
- 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
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- A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
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- A23G3/343—Products for covering, coating, finishing, decorating
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- A—HUMAN NECESSITIES
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- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
- A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
- A23G3/50—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by shape, structure or physical form, e.g. products with supported structure
- A23G3/54—Composite products, e.g. layered, coated, filled
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/40—Colouring or decolouring of foods
- A23L5/42—Addition of dyes or pigments, e.g. in combination with optical brighteners
- A23L5/47—Addition of dyes or pigments, e.g. in combination with optical brighteners using synthetic organic dyes or pigments not covered by groups A23L5/43 - A23L5/46
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Abstract
本發明係關於效果顏料,該效果顏料以圓形形狀因子為1.2-2的薄片形式基材為底並塗覆以至少一層高折射指數層,及關於其用途,尤其是在塗漆、塗料、印墨、塑料和在化妝品調合物中上之用途。
Description
本發明係關於效果顏料,該效果顏料以圓形形狀因子為1.2-2的薄片形式基材為底並塗覆以至少一層高折射指數層,及關於其用途,尤其是在塗漆、塗料、印墨、塑料和在化妝品調合物中上之用途。
效果顏料,如,例如,珠光顏料或金屬效果顏料,用於工業的許多領域,特別是用於汽車塗漆、工業塗料、裝飾性塗料、塑料、塗漆、印墨和化妝調合物領域。此類型的顏料以具有單一或多重塗層之薄片形式的橢圓形基材為底。
在效果顏料的情況中,通常未限制基材本身的尺寸且可符合特別的應用。通常,薄片形式和橢圓形基材的厚度介於0.1和5微米之間,特別是介於0.2和4.5微米之間。兩個不同維次的尺寸通常介於1和250微米之間,較佳地介於2和200微米之間且特別介於5和60微米之間。市面上供應的效果顏料的特點通常在於寬廣的粒子尺寸和厚度分佈。
效果顏料的光學性質,如,例如,顏色和顏色變化(colour flop)(即,亦為與角度相關的色相角度、飽和度和亮度)取決於基材薄片上的干擾層的折射指數及其幾何厚度。但是,效果顏料通常具有遮蔽力不足和色彩飽和
度不足的缺點。
本發明的目的係尋求具有高色彩飽和度並同時具有高遮蔽力且不會損失其光學性質(特別是光澤度和色純度)且具有有利的施用性質特徵之效果顏料。
令人驚訝地,現已發現,相較於自先前技術之以具有橢圓形及較大邊緣糙度的基材為底的效果顏料,以具有圓形形狀之薄片形式基材為底之效果顏料的具有提高的色彩飽和度和提高的遮蔽力。
本發明因此係關於一種以薄片形式基材為底的效果顏料,其中,圓形形狀因子(circular form factor)(圓周2/標準化成圓形的面積)為12-2的基材經至少一層折射指數n1.8的高折射指數層塗覆。
此申請案中的圓形形狀因子定義為在光學顯微鏡穿透的光放大30倍成像的各粒子之圓周平方對面積的比。為加以簡化,其結果除以4 π,如此理想圓形的圓形形狀因子為1。被評估的粒子在成像平面上實質扁平,且被評估的粒子的數目與圓形形狀因子平均於統計上充分相關(N=2000)。
本發明另關於根據本發明之顏料之用途,其係用於塗漆、汽車塗漆、工業塗料、塗料、印墨、塑料、按鈕膠
(button pastes)、陶瓷材料、玻璃、用於種籽著色、作為塑料、玻璃、厚紙板和紙的雷射標記之吸收劑、作為塑料的雷射熔接之吸收劑、作為食物和醫藥產品的著色之添加劑、作為食物和醫藥產品的塗料之著色之添加劑、用於化妝品調合物、用於製造顏料組成物和無水製劑、及用於有價防偽文件。
用於根據本發明之效果顏料之適當的基材係透明的薄片形式基材。較佳的基材係頁矽酸鹽,例如,天然或人造雲母、滑石、高嶺土、石墨、薄片形式的鐵氧化物、玻璃薄片、SiO2薄片、Al2O3薄片、TiO2薄片或人造的陶瓷薄片、人造的無載體薄片、LCP(液晶聚合物)或其他可相容的材料。極特別佳的基材薄片係天然或人造雲母薄片、玻璃薄片、Al2O3薄片和SiO2薄片。
用於根據本發明之效果顏料,所用基材薄片的圓形形狀因子為1.2-2,較佳地為1.2-1.8,且極特別佳地為1.2-1.7。
較佳的基材薄片之粒子尺寸為5-60微米,特別是5-40微米。較佳的基材薄片之厚度較佳地為0.2-0.6微米。
本專利申請案中,藉Malvern UK Mastersizer 2000之助測定粒子尺寸。
基材薄片可以,例如,藉以下方式製造:
使用已知的機械粉碎法,基材塊經粉碎和層離,例如,藉研磨,並根據關於薄片的對等直徑和厚度之要求,藉沉降、傾析、空氣分離和/或過篩而分級。
嫻於此技術者已知的所有研磨機和攪拌機皆可用於此研磨法,特別是所有的高速攪拌機、分散機或轉子-定子研磨機。
基材薄片,例如雲母或玻璃薄片,係藉研磨相當大塊或粗薄片的方式製得。所形成的基材薄片,通常直徑為50-200微米,於之後被引至粉碎機(例如轉子-定子研磨機)中,並添加水和/或有機溶劑(較佳為水)。以此方式形成的懸浮液在粉碎機中機械處理數小時,該期間內,薄片表面同時被拋平。選擇粒子在此步驟期間內的機械載量,使得永久切變導致粒子的進一步和緩層離、及邊緣和表面的平滑。並藉由後續之多個(至少2個,較佳地3個)沉降步驟形式的分級步驟達到窄的粒子尺寸分佈。以此方式製造之薄且圓的薄片之粒子尺寸分佈為5-60微米,厚度分佈為0.2-0.6微米,且經拋平的表面僅具有少數的尖銳邊緣。圓形形狀因子為1.2-2。
研磨和分級期間內,移除相當小且相當厚的粒子以及相當大且相當薄的粒子,即,大粒子僅經粉碎,而相當小的粒子經層離和/或藉分級而移除。
額外的機械處理和相關的拋光作用使得基材粒子表面平滑,此外,橢圓形薄片被轉變成圓形薄片。圓形形狀因子降低且與基材邊緣相關的橢圓本質變得更平滑且基材呈圓形。
用以作為效果顏料之基材且非粗塊或粗薄片形式的人造基材,例如,Al2O3、SiO2、Fe2O3、TiO2、玻璃,係直
接供料至粉碎機(例如轉子-定子研磨機)以進行粉碎和拋光表面。其圓形形狀因子亦為1.2-2。
顯微照片(圖1和2:影像細節測量43×35微米)顯示相較於的橢圓形基材薄片(圖2),圓形基材薄片(圖1)具有明顯較低的邊緣糙度,如以下的圖像所示:
在薄片表面上之較低的邊緣糙度和減少的步驟通常在基材薄片塗層上得到極均勻的塗層。相較於先前技術的效果顏料,此一方面有關於干擾顏色的局部均勻度以及降低散射光之影響,因而產生整體較高的色彩飽和度。
圓形基材薄片可作為填料,特別是作為化粧品填料,或作為製造效果顏料的基底基材。此情況中,圓形基材薄片具有一或多個塗層,較佳地為金屬氧化物層。
此圓形基材薄片較佳地經至少一個高折射指數層(n1.8)塗覆。
在基材薄片對於酸和/或鹼敏感的情況中,諸如,例如,玻璃薄片,通常建議其在確實塗覆之前,先覆以薄保護層,以便,例如,防止基板於塗覆期間內漏出和/或溶脹。但是,保護層亦可用以達到更平滑的基板表面。此保護層通常極薄,較佳地<20奈米,並因此而對於最終效果顏料的光學性質僅具有極小的影響,或完全無影響。此保
護層較佳地為SiO2層。
此專利申請案中,高折射指數是指折射指數n1.8,較佳地n2.0。此專利申請案中,低折射指數層是指折射指數層n<1.8)。
適當的層材料為嫻於此技術者已知的所有高折射指數材料,其可以類似膜的方式施用且對於基材粒子具有持久性,例如,金屬氧化物、金屬氧化物混合物、水合金屬氧化物、金屬硫化物、鈦酸鐵、水合氧化鐵、次氧化鈦、金屬、和所述化合物之混合物或混合相。特別適用者為金屬氧化物或金屬氧化物混合物,例如,TiO2、BiOCl、Ce2O3、Cr2O3、CoO、Co3O4、Fe2O3、Fe3O4、FeOOH、NiO、SnO2、VO2、V2O3、ZrO2、ZnO、CoAl2O4、BiVO4、鈦酸鐵、水合氧化鐵、次氧化鈦(部分還原的TiO2),其氧化數由<4至2,如Ti3O5、Ti2O3至TiO)、和金屬硫化物(例如,Ce2S3、MoS2)、及所述化合物彼此或與其他金屬氧化物和金屬(例如,鋁、鉻、鎳、銀、金、鈦、銅、或彼等的合金)之混合物或混合相。
若在基材薄片的基材表面上直接覆以一、二或更多層高折射指數層,則此塗層較佳地為TiO2、Fe2O3、或TiO2/Fe2O3之混合物層、或TiO2塗層接著Fe2O3層。
具有至少三層的多層顏料較佳地具有高-和低-折射指數層的交替塗層。特別佳者係在基材薄片上的三層系統為高折射指數-低折射指數-高折射指數,諸如,例如,TiO2-SiO2-TiO2塗層。
高折射指數層的厚度通常為20-500奈米,較佳地為30-400奈米,且特別是40-350奈米。
適用於塗層之無色的低折射指數材料較佳地為金屬氧化物或對應的水合氧化物,諸如,例如,SiO2、Al2O3、AlO(OH)、B2O3、MgF2、MgSiO3或所述化合物之混合物。低折射指數層較佳地由SiO2、Al2O3或MgF2所組成,特別是SiO2。
低折射指數層的厚度較佳地為10-200奈米,特別是10-80奈米,且極佳地為20-80奈米。
除了該高-和低-折射指數層以外,效果顏料可以另覆以吸收劑層作為最終層。此效果顏料於之後較佳地覆以柏林藍(Berline Blue)、胭脂紅(Carmine Red)、硫靛(thioindigo)或氧化鉻。
此吸收劑層較佳地具有層厚度為3-300奈米。
用以製造銀白效果顏料,述於例如EP 1865032 A2,建議以高折射指數層(除了二氧化鈦以外,另包含至少一種低溶解度鹼土金屬化合物)塗覆基材薄片。此層的折射指數1.9,較佳地2.0且特別是2.1。此高折射指數塗層可由TiO2和低溶解度鹼土金屬化合物和/或氧化鋅之混合物或兩個分離的層所組成。此情況中,低溶解度鹼土金屬化合物或氧化鋅的薄層施加於TiO2層。
高折射指數塗層中的二氧化鈦可為金紅石或銳鈦改質物(modification)形式,較佳地為金紅石形式。製造金紅石的方法述於先前技術中,例如述於U.S.5,433,779、
U.S.4,038,099、U.S.6,626,989、DE 25 22 572 C2、EP 0 271 767 B1。於TiO2沉澱之前,作為用以得到金紅石相的TiO2之添加劑的二氧化錫薄層(<10奈米)較佳地施加於基材薄片(較佳為天然或合成的雲母薄片)。
根據本發明,較佳的效果顏料的基材薄片表面上直接具有以下塗層:
基材薄片+TiO2(銳鈦)
基材薄片+SnO2+TiO2(金紅石)
基材薄片+TiO2+鈦酸鹼土金屬鹽
基材薄片+SnO2+TiO2+鈦酸鹼土金屬鹽
基材薄片+TiO2+Fe2O3
基材薄片+SnO2+TiO2+Fe2O3
基材薄片+TiO2+Fe3O4
基材薄片+SnO2+TiO2+Fe3O4
基材薄片+TiO2+Cr2O3
基材薄片+SnO2+TiO2+Cr2O3
基材薄片+TiO2+胭脂紅
基材薄片+SnO2+TiO2+胭脂紅
基材薄片+TiO2+柏林藍
基材薄片+SnO2+TiO2+柏林藍
基材薄片+TiO2/Fe2O3
基材薄片+SnO2+TiO2/Fe2O3
基材薄片+TiO2+SiO2+TiO2
基材薄片+SnO2+TiO2+SiO2+SnO2+TiO2
基材薄片+Fe2O3
基材薄片+Fe3O4
基材薄片+TiO2+SiO2+TiO2/Fe2O3
基材薄片+SnO2+TiO2+SiO2+TiO2/Fe2O3
基材薄片+TiO2+SiO2+TiO2+TiO2/Fe2O3
基材薄片+SnO2+TiO2+SiO2+TiO2+TiO2/Fe2O3
基材薄片+SnO2+TiO2+SiO2+SnO2+TiO2+TiO2/Fe2O3
基材薄片+TiO2/Fe2O3+SiO2+TiO2+TiO2/Fe2O3
基材薄片+TiO2/Fe2O3+SiO2+SnO2+TiO2+TiO2/Fe2O3
基材薄片+TiO2/Fe2O3+SiO2+TiO2
基材薄片+TiO2/Fe2O3+SiO2+SnO2+TiO2
基材薄片+TiO2/Fe2O3+SiO2+TiO2/Fe2O3
基材薄片+TiO2+SiO2+Fe3O4
基材薄片+TiO2+SiO2+Cr2O3
基材薄片+Cr2O3
基材薄片+Ag
基材薄片+Au
基材薄片+Fe2O3+SiO2+TiO2/Fe2O3
基材薄片+SiO2+TiO2(銳鈦)
基材薄片+SiO2+SnO2+TiO2(金紅石)
基材薄片+SiO2+TiO2+鈦酸鹼土金屬鹽
基材薄片+SiO2+SnO2+TiO2+鈦酸鹼土金屬鹽
基材薄片+SiO2+TiO2+Fe2O3
基材薄片+SiO2+SnO2+TiO2+Fe2O3
基材薄片+SiO2+TiO2+Fe3O4
基材薄片+SiO2+SnO2+TiO2+Fe3O4
基材薄片+SiO2+TiO2+Cr2O3
基材薄片+SiO2+SnO2+TiO2+Cr2O3
基材薄片+SiO2+TiO2+胭脂紅
基材薄片+SiO2+SnO2+TiO2+胭脂紅
基材薄片+SiO2+TiO2+柏林藍
基材薄片+SiO2+SnO2+TiO2+柏林藍
基材薄片+SiO2+TiO2/Fe2O3
基材薄片+SiO2+SnO2+TiO2/Fe2O3
基材薄片+SiO2+TiO2+SiO2+TiO2
基材薄片+SiO2+SnO2+TiO2+SiO2+SnO2+TiO2
基材薄片+SiO2+Fe2O3
基材薄片+SiO2+Fe3O4
基材薄片+SiO2+TiO2+SiO2+TiO2/Fe2O3
基材薄片+SiO2+SnO2+TiO2+SiO2+TiO2/Fe2O3
基材薄片+SiO2+TiO2+SiO2+TiO2+TiO2/Fe2O3
基材薄片+SiO2+SnO2+TiO2+SiO2+TiO2+TiO2/Fe2O3
基材薄片+SiO2+SnO2+TiO2+SiO2+SnO2+TiO2+TiO2/Fe2O3
基材薄片+SiO2+TiO2/Fe2O3+SiO2+TiO2+TiO2/Fe2O3
基材薄片+SiO2+TiO2/Fe2O3+SiO2+SnO2+TiO2+TiO2/Fe2O3
基材薄片+SiO2+TiO2/Fe2O3+SiO2+TiO2
基材薄片+SiO2+TiO2/Fe2O3+SiO2+SnO2+TiO2
基材薄片+SiO2+TiO2/Fe2O3+SiO2+TiO2/Fe2O3
基材薄片+SiO2+TiO2+SiO2+TiO2/Fe2O3
基材薄片+SiO2+TiO2+SiO2+Fe3O4
基材薄片+SiO2+TiO2+SiO2+Cr2O3
基材薄片+SiO2+Cr2O3
基材薄片+SiO2+Ag
基材薄片+SiO2+Au
基材薄片+SiO2+Fe2O3+SiO2+TiO2/Fe2O3
基材薄片+TiO2(銳鈦)+SiO2
基材薄片+SnO2+TiO2(金紅石)+SiO2。
圓形形狀因子為1.2-2的圓形基材薄片之塗覆較佳地藉濕式化學法進行。關於此,較佳地使用為製造珠光顏料而開發的濕式化學塗覆法。此類型的方法述於,例如,DE 14 67 468、DE 19 59 988、DE 20 09 566、DE 22 14 545、DE 22 15 191、DE 22 44 298、DE 23 13 331、DE 25 22 572、DE 31 37 808、DE 31 37 809、DE 31 51 343、DE 31 51 354、DE 31 51 355、DE 32 11 602、DE 32 35 017或嫻於此技術者已知的其他專利文件和其他論文。
根據本發明之效果顏料通常藉由將圓形基材薄片懸浮於水中並於適合沉澱的pH(選擇方式為在此pH下金屬氧化物或水合金屬氧化物直接沉積在薄片上且無明顯的二次沉澱發生)添加一或多種可水解的金屬鹽的方式製造。此
pH通常藉同時計量添加鹼或酸而維持恆定。過濾和清洗之後,經塗覆的基材先於50-150℃,較佳地為80-120℃之溫度乾燥20-60分鐘,及之後於600至1200℃,較佳地為700-1000℃,特別是700-900℃,鍛燒0.3-1小時,較佳地為0.5-0.8小時。
此塗覆,例如以TiO2層塗覆,亦可以進一步地在流化床反應器中藉氣相塗覆法進行,其可能對應地使用,例如,EP 0 045 851 A1和EP 0 106 235 A1中提出之製造珠光顏料的方法。
基材薄片以二氧化鈦塗覆較佳地藉濕化學法藉氯化物或硫酸鹽法進行。
欲另提高對光、水和氣候的安定性,通常建議使最終的效果顏料接受後塗覆或後處理,此取決於應用領域。適當的後塗覆或後處理為,例如,德國專利案22 15 191、DE-A 31 51 354、DE-A 32 35 017或DE-A 33 34 598中描述的方法。此後塗覆進一步提高化學安定性或簡化顏料的處理,特別是摻入各種介質。為改良潤濕性、分散性和/或與使用者媒介的相容性,可以將包含Al2O3或ZrO2或彼等之混合物或混合相之官能性塗料施於顏料表面。此外,可以使用例如,矽烷,進行有機或合併的有機/無機後塗覆,此述於例如EP 0090259、EP 0 634 459、WO 99/57204、WO 96/32446、WO 99/57204、U.S.5,759,255、U.S.5,571,851、WO 01/92425、WO 2006/021386 A1或J.J.Ponjeé,Philips Technical
Review,Vol.44,No.3,81ff及P.H.Harding,J.C.Berg,J.Adhesion Sci.Technol.Vol.11,No.4,pp.471-493。
外部任意的保護層較佳地由一或兩層Si、Al或Ce元素的金屬氧化物層所組成。此處特別佳者係首先施用氧化鈰層,之後施用SiO2層的層序列,此述於例如WO 2006/021386 A1。
外部保護層的表面可以進一步經有機化學方式修飾。例如,一或多層矽烷可施用於此外部保護層。此矽烷可為具有具1至24 C原子(較佳地6至18 C原子)之具有支鏈或非支鏈烷基的烷基矽烷。
但是,此矽烷亦可為有機官能性烷基,而有助於化學結合至塑料、表面塗料之黏合劑或墨等。
較佳地作為表面修飾劑之含有適當官能基的有機官能性矽烷為市售品並例如由德國Degussa,Rheinfelden製造,並以商標名稱“Dynasylan®”售於市面上。其他產品可購自OSi Specialties(Silquest® silanes)或購自Wacker,例如GENIOSIL®產品系列的標準和α-矽烷。
彼等的例子為3-甲基丙烯醯氧基丙基三甲氧基矽烷(Dynasylan MEMO,Silquest A-174NT)、乙烯基三(甲)乙氧基矽烷(Dynasylan VTMO或VTEO,Silquest A-151或A-171)、3-巰基丙基三甲(或乙)氧基矽烷(Dynasylan MTMO或3021;Silquest A-189)、3-縮水甘油氧基丙基三甲氧基矽烷(Dynasylan GLYMO,Silquest A-187)、參-(3-三甲氧基矽烷基丙基)異氰尿酸酯
(Silquest Y-11597)、γ-巰基丙基三甲氧基矽烷(Silquest A-189)、雙-(3-三乙氧基矽烷基丙基)多硫化物(Silquest A-1289)、雙-(3-三乙氧基矽烷基)二硫化物(Silquest A-1589)、β-(3,4-環氧基環己基)乙基三甲氧基矽烷(Silquest A-186)、雙(三乙氧基矽烷基)乙烷(Silquest Y-9805)、γ-異氰酸基丙基三甲氧基矽烷(Silquest A-Link 35,GENIOSIL GF40)、(甲基丙烯醯氧基甲基)三甲(或乙)氧基矽烷(GENIOSIL XL 33,XL 36)、(甲基丙烯醯氧基甲基)甲(或乙)基二甲氧基矽烷(GENIOSIL XL 32,XL 34)、(異氰酸基甲基)三甲氧基矽烷(GENIOSIL XL 43)、(異氰酸基甲基)甲基二甲氧基矽烷(GENIOSIL XL 42)、(異氰酸基甲基)三甲氧基矽烷(GENIOSIL XL 43)、3-(三乙氧基矽烷基)丙基丁二酸酐(GENIOSIL GF 20)、(甲基丙烯醯氧基甲基)甲基二乙氧基矽烷、2-丙烯醯氧基乙基甲基二甲氧基矽烷、2-甲基丙烯醯氧基乙基三甲氧基矽烷、3-丙烯醯氧基丙基甲基二甲氧基矽烷、2-丙烯醯氧基乙基三甲氧基矽烷、2-甲基丙烯醯氧基乙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三丙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙醯氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、乙烯基三氯矽烷、乙烯基三甲氧基矽烷(GENIOSIL XL 10)、乙烯基參(2-甲氧基乙氧基)矽烷(GENIOSIL GF 58)、乙烯基三乙醯氧基矽烷。
但是,根據本發明之效果顏料上也可以使用其他有機官能性矽烷。
此外,可以使用水性預水解物,其為市售品,例如,得自Degussa。這些尤其包括水性無醇的胺基矽烷水解物(Dynasylan Hydrosil 1151)、水性無醇的胺基/烷基-官能性矽氧烷共-低聚物(Dynasylan Hydrosil 2627)、水性無醇的二胺基/烷基-官能性矽氧烷共-低聚物(Dynasylan Hydrosil 2776)、水性無醇的胺基/乙烯基-官能性矽氧烷共-低聚物(Dynasylan Hydrosil 2907)、水性無醇的胺基/烷基官能性矽氧烷共-低聚物(Dynasylan Hydrosil 2909)、水性無醇的環氧基官能性矽氧烷低聚物(Dynasylan Hydrosil 2926)或水性無醇的胺基/甲基丙烯酸酯官能性矽氧烷共-低聚物(Dynasylan Hydrosil 2929)、低聚的二胺基矽烷系統(Dynasylan 1146)、乙烯基/烷基-官能性矽氧烷共-低聚物(Dynasylan 6598)、含乙烯基-和甲氧基-的乙烯基矽烷縮合物(低聚矽氧烷)(Dynasylan 6490)或低聚合的短鏈烷基-官能性矽烷(Dynasylan 9896)。
較佳具體實施例中,此有機官能性矽烷混合物除了至少一種不含官能性鍵結基團的矽烷以外,另包含至少一種胺基官能性矽烷。此胺基官能性係能夠與通常存在於黏合劑中的基團進行一或多個化學交互作用之官能基。此可包括共價鍵,諸如,例如,與黏合劑的異氰酸酯或羧酸酯官能性,或氫鍵,例如與OH或COOR官能性,或亦為離子
交互作用。因此,胺基官能性非常適用於效果顏料與不同類型的黏合劑之化學結合之目的。
較佳地,以下化合物用於此目的:
胺基丙基三甲氧基矽烷(Dynasylan AMMO;Silquest A-1110)、胺基丙基三乙氧基矽烷(Dynasylan AMEO)或N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷(Dynasylan DAMO,Silquest A-1120)或N-(2-胺基乙基)-3-胺基丙基三乙氧基矽烷、三胺基官能性三甲氧基矽烷(Silquest A-1130)、雙(γ-三甲氧基矽烷基丙基)胺(Silquest A-1170)、N-乙基-γ-胺基異丁基三甲氧基矽烷(Silquest A-Link 15)、N-苯基-γ-胺基丙基三甲氧基矽烷(Silquest Y-9669)、4-胺基-3,3-二甲基丁基三甲氧基矽烷(Silquest Y-11637)、N-環己基胺基甲基甲基二乙氧基矽烷(GENIOSIL XL 924)、(N-環己基胺基甲基)三乙氧基矽烷(GENIOSIL XL 926)、(N-苯基胺基甲基)三甲氧基矽烷(GENIOSIL XL 973)和彼等之混合物。
其他較佳的具體實施例中,不含官能性鍵結基的矽烷係烷基矽烷。此烷基矽烷較佳地具有式R(4-z)Si(X)z
其中z是1至3的整數,R是經取代或未經取代、無支鏈或支鏈之具10至22 C原子的烷基,X代表鹵素和/或烷氧基。較佳地,烷基矽烷的烷基鏈具有至少12 C原子。R亦可以環狀鍵結至Si,此情況中,z通常是2。
此類型的矽烷對於顏料表面具有較強的疏水化效果。此使得經此方式塗覆的效果顏料有向上浮現在表面塗層中的趨勢。在薄片形式的效果顏料的情況中,將此類型的行為稱為“浮起(leafing)”行為。
由至少一種含有至少一個有助於鍵結至黏合劑的官能基之矽烷和不含胺基的烷基矽烷(其不溶或難溶於水)所構成之矽烷組成物有助於效果顏料的最適施用性質。此類型的有機化學表面修飾使得效果顏料在表面塗層或塗漆層中之排列極為良好,即,基本上平面平行於經塗覆或經塗漆的基材,且同時以化學方式與表面塗層或塗漆的黏合劑系統反應並因此而共價鍵結於表面塗層或塗漆層中。此類型的表面塗層或塗漆層對環境影響(例如氣候等)具有提高的機械和化學耐受力。
除了高色彩飽和度和極亮和高光澤度以外,根據本發明之效果顏料的特點在於極高的遮蔽力和低邊緣糙度。此顏料由於其良好的膚感,因此而非常適用於化粧品調合物。
由於根據本發明之效果顏料除了高遮蔽力以外,亦具有亮度和強烈光澤及高色彩飽和度,所以使用彼可以在各種應用介質中達到特別有效的效果。
無庸置疑地,用於各種應用,根據本發明之效果顏料亦可以合宜地以與有機染料、有機顏料或無機顏料(諸如,例如,透光和不透光的白色、彩色和黑色顏料)及薄片形氧化鐵、全像攝影(holographic)顏料、LCP(液晶
聚合物)或與珠光顏料等之混合物使用。未限制混合比和濃度。
根據本發明之效果顏料可以與市售顏料和填料以任何重量比混合。較佳的比率為1:1至9:1。若根據本發明之效果顏料與填料混合,則混合比亦可為99:1至1:99。
根據本發明之效果顏料與多種著色系統相容,較佳為來自塗漆、塗料和印墨領域。用以製造用於例如凹版印刷(gravure printing)、膠版印刷(flexographic printing)、套版印刷(offset printing)、套版覆印清漆(offset over-print varnishing)的印墨,多種黏合劑適用,特別是水溶性等級者,其由例如,BASF、Marabu、Pröll、Sericol、Hartmann、Gebr.Schmidt、Sicpa、Aarberg、Siegberg、GSB-Wahl、Follmann、Ruco或Coates Screen INKS GmbH公司售於市面。此印墨可以是以水為底或以溶劑為底者。此外,根據本發明之效果顏料亦適用於紙和塑料的雷射標記,或施用於農業區域,例如溫室薄片,和,例如,用於防水布之著色。
根據本發明之效果顏料可以用於表面塗料、印墨、塑料、農用薄片、種籽塗料、食品著色物、按鈕膠、醫藥產品塗料或化粧品調合物(如唇膏、指甲油、粉餅、洗髮精、皂、蜜粉和凝膠)之著色。待著色的施用系統中的顏料濃度通常介於0.1和70重量%之間,較佳地介於0.1和50重量%之間,且特別是介於0.5和10重量%之間,以系
統的固體總含量計。此通常取決於特定應用。
根據本發明之效果顏料在塑料中的含量較佳為0.01至50重量%,特別是0.1至7重量%時,可達到特別佳的顏色效果。
在表面塗料領域(特別是汽車塗漆)中,效果顏料的用量為0.1-20重量%,較佳地為1至10重量%,此包括3塗層系統。
表面塗料中,根據本發明之效果顏料的優點在於藉單層修整劑(單一塗層系統或二層塗層系統中之底塗)達到目標光澤。相較於包含,例如,以雲母為底的多層顏料或以具有寬厚度分佈的基材為底的慣用珠光顏料代替根據本發明之效果顏料之修整劑,包含根據本發明之效果顏料的修整劑具有較通透的深度效果和更顯著的色彩和光澤效果。
根據本發明之效果顏料亦可以合宜地用於裝飾和保養用化粧品。使用濃度範圍自洗髮精中的0.01重量%至蜜粉情況的100重量%。根據本發明之顏料與填料(較佳地為球狀填料,例如,SiO2)之混合物的情況中,在調合物中之濃度可為0.01-70重量%。化粧品產品,例如,指甲油、粉餅、洗髮精、蜜粉和凝膠,的特點在於特別感興趣的色彩效果和高光澤度。
此外,根據本發明之效果顏料可用於沐浴添加劑、牙膏和食品修整劑,例如氣泡糖果、酒膠,例如膠質軟糖、胡桃糖、甘草根、糕點、硬糖棒、牛奶凍、氣泡飲料、汽
水等,的整體上色和/或塗層,或作為塗料,例如,用於醫藥產品領域的糖衣或錠。
根據本發明之效果顏料可以進一步與市售填料混合。可用的填料係,例如,天然和人造合成雲母、尼龍粉末、純或經填充的三聚氰胺樹脂、滑石、玻璃、高嶺土、鋁、鎂、鈣、鋅的氧化物或氫氧化物、BiOCl、硫酸鋇、硫酸鈣、碳酸鈣、碳酸鎂、碳、及這些物質的物理或化學組合。未限制填料的粒子形狀。必要時,其可為,例如,薄片狀、球狀或針狀。
根據本發明之效果顏料當然也可以與具有任何類型的化粧品原料和輔助劑混合成為調合物。這些尤其包括油、脂、蠟、成膜劑、防腐劑和通常依施用性質而定的輔助劑,例如,稠化劑和流變添加劑,例如,膨潤土、水輝石(hectorite)、二氧化矽、矽酸鈣、明膠、高分子量碳水化合物和/或表面活性輔助劑等。
包含根據本發明之效果顏料之調合物可以為親脂、親水或疏水類型。在具有不連續水相和非水相之非均相調合物的情況中,根據本發明之效果顏料在各情況中可僅存於兩相中之一相或交替地分佈於兩相中。
此調合物的pH可介於1和14之間,較佳地介於2和11之間,且特別佳地介於5和8之間。
未限制根據本發明之效果顏料在調合物中之濃度。取決於應用,可以介於0.001(可沖洗的產物,例如浴沐膠)和100%(例如用於特別應用的光澤效果物件)之
間。
根據本發明之效果顏料亦可以進一步與化粧品活性成份合併。適當的活性成份係,例如,驅蟲劑、UV A/BC保護性濾光劑(例如OMC、B3和MBC)、抗老化活性成份、維生素和其衍生物(例如維生素A、C、E等)、自身曬黑劑(尤其例如DHA、赤藻酮糖)、和其他的化粧品活性成份,例如甜沒藥萜醇(bisabolol)、LPO、甲基四氫嘧啶羧酸(ectoin)、油柑子(emblica)、尿囊素(allantoin)、生物類黃酮(bioflavonoid)和彼等之衍生物。
黏合劑系統(例如,用於凹版印刷、套版印刷或網版印刷的表面塗料和印墨,或者作為印墨之先質)之著色中,已經證實以高度著色糊、顆粒、粒料等形式使用之根據本發明之效果顏料特別合適。此效果顏料摻入印墨中的量通常是2-35重量%,較佳地為5-25重量%,且特別是8-20重量%。套版印墨的顏料含量可高至40重量%或更高。除了黏合劑和添加劑之外,印墨的先質,例如顆粒、粒子、磚等形式,包含高至98重量%根據本發明之顏料。包含根據本發明之顏料的印墨之色相比慣用的效果顏料來得純。根據本發明之效果顏料的粒子厚度相對較小並因此而得到特別良好的印刷性。
根據本發明之效果顏料另外亦適用以製造可流動的顏料組成物和無水製劑,特別是用於印墨,其包含一或多種根據本發明之顏料、黏合劑和任意的一或多種添加劑。
本發明另係關於根據本發明之效果顏料的用途,其係用於塗漆、塗料、粉末塗料、汽車塗漆和工業塗料、印墨、塑料、按鈕膠、陶瓷材料、玻璃、用於種籽塗覆、作為塑料、玻璃、厚紙板和紙的雷射標記之吸收劑、作為塑料的雷射熔接之吸收劑、用於食物和醫藥產品的著色、用於食物和醫藥產品的塗料之著色、用於化妝品調合物、及用於有價防偽文件(例如,支票、信用卡、識別文件等)。此外,根據本發明之顏料亦適用於製造顏料組成物和製造無水製劑,例如,顆粒、片、粒子、磚等。此無水製劑特別適用於印墨和用於化粧品調合物。
本發明因此亦係關於包含根據本發明之效果顏料的調合物。
特別地,本發明係關於調合物,其除了根據本發明之效果顏料以外,另外包含至少一種選自下列的組份:吸收劑、收斂劑、抗菌物質、抗氧化劑、制汗劑、消泡劑、抗頭皮屑活性成分、抗靜電劑、黏合劑、生物添加劑、漂白劑、螯合劑、除臭劑、柔軟劑、乳化劑、乳液安定劑、染料、保濕劑、成膜劑、填料、氣味物質、調味物質、驅蟲劑、防腐劑、抗蝕劑、化妝油、溶劑、氧化劑、植物成分、緩衝物質、還原劑、界面活性劑、推進氣、遮光劑、UV濾光劑和UV吸收劑、變性劑、黏度調節劑、香料和維生素。
下列實例用以解釋本發明,但未限制本發明。
藉Koller方法,1公斤白雲母(其為粗薄片形式)研磨至粒子尺寸低於200微米。以此方式形成的細雲母薄片引至轉子-定子研磨機中,並添加1升去離子水。所得懸浮液在研磨機中研磨5小時,此期間內,同時將薄片表面拋平。選擇粒子於研磨步驟期間內的機械載量,使得永久切變導致粒子的進一步和緩層離、及邊緣和表面的平滑。藉多個(至少3個步驟)沉降步驟的形式之後續分級步驟達到窄粒子尺寸分佈。以此方式製造的雲母薄片的粒子尺寸分佈為10-40微米,厚度分佈為0.2至0.6微米(各情況中,所有粒子的90%)且拋平的表面僅具有幾個尖銳邊緣。圓形形狀因子為1.6。
1公斤人造雲母薄片以類似於實例1a的方式處理。得到圓形形狀因子為1.6的人造雲母薄片。
100克實例1a的天然雲母薄片在2升去離子水中於攪拌時溫熱至75℃。藉由逐滴添加SnCl4溶液(22克/升)而得到pH 1.8的塗覆液。之後計量添加剩餘的100
毫升SnCl4溶液(22克/升)。此添加期間內,使用32%氫氧化鈉溶液,使pH維持恆定於1.8。添加完全時,此混合物再攪拌10分鐘。
於恆定pH,之後計量稱入490毫升TiOCl2溶液(400克TiCl4/升)直到達到顏色終點(黃色),此期間內,藉由同時逐滴添加32%氫氧化鈉溶液,使pH恆定於1.8。
添加完全之後,混合物再攪拌10分鐘,懸浮液經抽氣過濾並以去離子水清洗直到無鹽。於120℃乾燥(24小時)之後,顏料於800℃鍛燒45分鐘。
得到具有黃色干擾色之高光澤、顏色強烈的顏料。
75克實例1b的人造雲母薄片與1500毫升去離子水中於攪拌時溫熱至75℃。之後使用氫氯酸(15% HCl)將此懸浮液的pH調整至1.8。之後計量稱入75毫升SnCl4溶液(22克/升)。此添加期間內,使用32%氫氧化鈉溶液,使pH維持恆定於1.8。添加完全時,此混合物再攪拌10分鐘。
之後計量稱入TiOCl2溶液(400克TiCl4/升)直到達到顏色終點(黃色),此期間內,藉由同時逐滴添加32%氫氧化鈉溶液,使pH恆定於1.8。
藉由塗覆法期間內的顏色測定,偵測製造顏料的期間內的色彩性質並根據色相(色相角度反正切(b*/a*))控制沉澱法。
中止塗覆,之後持續攪拌15分鐘。
之後使用稀氫氧化鈉溶液,將pH調整至pH=9.0。之後添加100毫升含量為2%的水玻璃溶液,此期間內,藉氫氯酸(10% HCl)使pH維持恆定。之後,此混合物再攪拌30分鐘。
藉由逐滴添加氫氯酸(w=20%)而使pH降至1.8。計量稱入75毫升SnCl4溶液(22克/升)。此添加期間內,使用32%氫氧化鈉溶液,使pH恆定維持於1.8。添加完全之後,混合物再攪拌10分鐘。於恆定pH,定量稱入300毫升TiOCl2溶液(400克TiCl4/升)直到達到顏色終點(綠色),此期間內,藉由同時逐滴添加32%氫氧化鈉溶液,使pH恆定於1.8。
15分鐘的後攪拌之後,藉過濾自所得反應溶液的上層清液分離顏料並清洗直到無鹽。於120℃乾燥24小時之後,此顏料於800℃鍛燒45分鐘。
得到具有綠色干擾色之高光澤、顏色強烈的顏料。
對照Merck KGaA提供的Iriodin® 205(在雲母薄片上的黃色干擾顏料)及得自實例2.1的顏料之黑/白塗覆卡(NC lacquer),定出Lab值(使用Eta測定儀器,於測定角度75°/95°測定):
根據本發明之顏料之明顯提高的a和b值意謂達到明顯改良的色度,而高L值代表提高的光澤。
用於A相,將干擾顏料攪入水中。於攪拌時,緩慢地散佈於Keltrol T中並攪拌直到其溶解。於緩慢攪拌時,連續添加B相和C相,直到全數均勻分佈。pH調整至6.0
至6.4。
此干擾顏料與清漆基底一起稱得,以手使用刮杓充分混合並於之後於1000 rpm攪拌10分鐘。
90重量% 無色Hydroglasur BG/S(以水為底的塗料,得自Ernst Diegel GmbH)
10重量% 得自實例2.2的顏料
於80℃藉噴上而塗覆
於80℃預先乾燥5分鐘
於180℃烘烤20分鐘
1公斤聚苯乙烯顆粒以5克偶合劑在顛動混合機中均勻潤濕。之後添加42克得自實例2.2的綠色干擾顏料,
此混合物混合2分鐘。在射出模製機中,於慣用條件下,這些顆粒轉變成尺寸為4 x 3 x 0.5公分的步進板。此步進板的特點在於其顯著的閃耀效果。
原料:白色氣泡糖(fizzy boiled sweets white)
噴霧溶液:
94%含醇的蟲膠溶液,得自Kaul
6%得自實例2.1的效果顏料
此氣泡糖經干擾顏料/蟲膠溶液噴灑直到達到所欲的顏色施用。之後可以使用冷空氣加以乾燥。
得自實例2.2的顏料可以輕易地摻入汽車塗漆中。此處,於攪拌時,得自實例2.2的顏料加至塗漆基底中。持續此攪拌操作直到顏料均勻地分佈於塗漆中。經著色的塗漆噴在經黑和白色塗覆的鋁測試片上。
經塗漆的片之製造:
塗漆:Herberts底塗419982
著色:5%
乾層厚度:15微米
噴槍:Sprimag S 233;噴嘴直徑:1.5毫米
噴霧壓力:4巴
噴嘴/基材距離:27公分
得自實例2.1的顏料事先以預潤濕用的Byk 348(0.6%)潤濕並以22.9%的濃度摻入黏合劑中。
黏合劑:Koustom Kote 9000/USA,以水為底
此糊料以水稀釋直到以4毫米Erichsen杯於25℃測得的黏度為40秒。
自網紋陶瓷筒身(24 ccm/平方米),經由橡膠印刷板,此顏料印在無光澤的黑色塗料紙上。根據本發明之顏料具有高顯色強度。
得自使用例A至G之產物的特點在於其高光澤、高顯色強度及高色純度。
圖1表示圓形基材薄片的顯微照片。
圖2表示楕圓形基材薄片的顯微照片。
Claims (22)
- 一種以薄片形式基材為底的效果顏料,其特徵在於圓形形狀因子(circular form factor)(圓周2/標準化成圓形的面積)為1.2-2的該基材經至少一層折射指數n1.8的高折射指數層塗覆。
- 如申請專利範圍第1項之效果顏料,其中該基材的圓形形狀因子為1.2-1.8。
- 如申請專利範圍第1或2項之效果顏料,其中該基材的粒子尺寸為5-60微米。
- 如申請專利範圍第1項之效果顏料,其中該基材的厚度為0.2-0.6微米。
- 如申請專利範圍第1項之效果顏料,其中該薄片形式基材係選自人造雲母薄片、天然雲母薄片、SiO2薄片、Al2O3薄片、玻璃薄片、氧化鐵薄片、石墨薄片、TiO2薄片或彼等之混合物。
- 如申請專利範圍第5項之效果顏料,其中該薄片形式基材係雲母或玻璃薄片。
- 如申請專利範圍第5項之效果顏料,其中該薄片形式基材係天然雲母薄片。
- 如申請專利範圍第1項之效果顏料,其中該基材薄片經至少一層折射指數1.8的高折射指數層塗覆。
- 如申請專利範圍第1項之效果顏料,其中該高折射指數層係選自金屬氧化物、金屬硫化物、鈦酸鐵、水合氧化鐵、次氧化鈦、金屬、和所述化合物之混合物或混合 相。
- 如申請專利範圍第9項之效果顏料,其中該高折射指數層由TiO2、BiOCl、Ce2O3、Cr2O3、CoO、Co3O4、Fe2O3、Fe3O4、FeOOH、NiO、SnO2、VO2、V2O3、ZrO2、ZnO、CoAl2O4、BiVO4、鈦酸鐵、水合氧化鐵、Ti3O5、Ti2O3、TiO、Ce2S3、MoS2、鋁、鉻、鎳、銀、金、鈦、銅、或彼等的合金及所述化合物彼此之混合物或混合相所組成。
- 如申請專利範圍第9項之效果顏料,其中該高折射指數層由一或多種金屬氧化物所組成。
- 如申請專利範圍第1項之效果顏料,其中該基材經至少一層高折射指數層(n1.8)和至少一層低折射指數層(n<1.8)塗覆。
- 如申請專利範圍第12項之效果顏料,其中該低折射指數層係選自SiO2、Al2O3、AlO(OH)、MgF2。
- 如申請專利範圍第1項之效果顏料,其中該效果顏料的基材薄片上具有下列層序列基材薄片+TiO2(銳鈦)基材薄片+SnO2+TiO2(金紅石)基材薄片+TiO2+鈦酸鹼土金屬鹽基材薄片+SnO2+TiO2+鈦酸鹼土金屬鹽基材薄片+TiO2+Fe2O3基材薄片+SnO2+TiO2+Fe2O3基材薄片+TiO2+Fe3O4 基材薄片+SnO2+TiO2+Fe3O4基材薄片+TiO2+Cr2O3基材薄片+SnO2+TiO2+Cr2O3基材薄片+TiO2+胭脂紅(carmine red)基材薄片+SnO2+TiO2+胭脂紅基材薄片+TiO2+柏林藍(berlin blue)基材薄片+SnO2+TiO2+柏林藍基材薄片+TiO2/Fe2O3基材薄片+SnO2+TiO2/Fe2O3基材薄片+TiO2+SiO2+TiO2基材薄片+SnO2+TiO2+SiO2+SnO2+TiO2基材薄片+Fe2O3基材薄片+Fe3O4基材薄片+TiO2+SiO2+TiO2/Fe2O3基材薄片+SnO2+TiO2+SiO2+TiO2/Fe2O3基材薄片+TiO2+SiO2+TiO2+TiO2/Fe2O3基材薄片+SnO2+TiO2+SiO2+TiO2+TiO2/Fe2O3基材薄片+SnO2+TiO2+SiO2+SnO2+TiO2+TiO2/Fe2O3基材薄片+TiO2/Fe2O3+SiO2+TiO2+TiO2/Fe2O3基材薄片+TiO2/Fe2O3+SiO2+SnO2+TiO2+TiO2/Fe2O3基材薄片+TiO2/Fe2O3+SiO2+TiO2基材薄片+TiO2/Fe2O3+SiO2+SnO2+TiO2基材薄片+TiO2/Fe2O3+SiO2+TiO2/Fe2O3基材薄片+TiO2+SiO2+Fe3O4 基材薄片+TiO2+SiO2+Cr2O3基材薄片+Cr2O3基材薄片+Ag基材薄片+Au基材薄片+Fe2O3+SiO2+TiO2/Fe2O3基材薄片+SiO2+TiO2(銳鈦)基材薄片+SiO2+SnO2+TiO2(金紅石)基材薄片+SiO2+TiO2+鈦酸鹼土金屬鹽基材薄片+SiO2+SnO2+TiO2+鈦酸鹼土金屬鹽基材薄片+SiO2+TiO2+Fe2O3基材薄片+SiO2+SnO2+TiO2+Fe2O3基材薄片+SiO2+TiO2+Fe3O4基材薄片+SiO2+SnO2+TiO2+Fe3O4基材薄片+SiO2+TiO2+Cr2O3基材薄片+SiO2+SnO2+TiO2+Cr2O3基材薄片+SiO2+TiO2+胭脂紅基材薄片+SiO2+SnO2+TiO2+胭脂紅基材薄片+SiO2+TiO2+柏林藍基材薄片+SiO2+SnO2+TiO2+柏林藍基材薄片+SiO2+TiO2/Fe2O3基材薄片+SiO2+SnO2+TiO2/Fe2O3基材薄片+SiO2+TiO2+SiO2+TiO2基材薄片+SiO2+SnO2+TiO2+SiO2+SnO2+TiO2基材薄片+SiO2+Fe2O3 基材薄片+SiO2+Fe3O4基材薄片+SiO2+TiO2+SiO2+TiO2/Fe2O3基材薄片+SiO2+SnO2+TiO2+SiO2+TiO2/Fe2O3基材薄片+SiO2+TiO2+SiO2+TiO2+TiO2/Fe2O3基材薄片+SiO2+SnO2+TiO2+SiO2+TiO2+TiO2/Fe2O3基材薄片+SiO2+SnO2+TiO2+SiO2+SnO2+TiO2+TiO2/Fe2O3基材薄片+SiO2+TiO2/Fe2O3+SiO2+TiO2+TiO2/Fe2O3基材薄片+SiO2+TiO2/Fe2O3+SiO2+SnO2+TiO2+TiO2/Fe2O3基材薄片+SiO2+TiO2/Fe2O3+SiO2+TiO2基材薄片+SiO2+TiO2/Fe2O3+SiO2+SnO2+TiO2基材薄片+SiO2+TiO2/Fe2O3+SiO2+TiO2/Fe2O3基材薄片+SiO2+TiO2+SiO2+TiO2/Fe2O3基材薄片+SiO2+TiO2+SiO2+Fe3O4基材薄片+SiO2+TiO2+SiO2+Cr2O3基材薄片+SiO2+Cr2O3基材薄片+SiO2+Ag基材薄片+SiO2+Au基材薄片+SiO2+Fe2O3+SiO2+TiO2/Fe2O3基材薄片+TiO2(銳鈦)+SiO2基材薄片+SnO2+TiO2(金紅石)+SiO2。
- 如申請專利範圍第1至14項中任一項之效果顏料,其中該效果顏料另經有機和/或無機層進行後處理以 提高對光、水和氣候的安定性。
- 一種製造如申請專利範圍第1至15項中任一項之效果顏料的方法,其特徵在於相當大塊或粗薄片形式的基材先經研磨,之後將所形成之直徑為50-200微米的基材薄片引至粉碎機中,添加水和/或有機溶劑,以此方式形成的懸浮液在粉碎機中以機械處理數小時,該期間內,薄片表面同時被拋平,並選擇此步驟期間內基材粒子的機械載量,使得永久切變導致粒子的進一步和緩層離、及邊緣和表面的平滑,並藉由後續之多個沉降步驟形式的分級步驟達到窄的粒子尺寸分佈。
- 如申請專利範圍第16項之方法,其中該粒子尺寸分佈為5-60微米。
- 一種如申請專利範圍第1至15項中任一項之效果顏料的用途,其係用於塗漆、汽車塗漆、工業塗料、塗料、粉末塗料、印墨、塑料、按鈕膠(button pastes)、陶瓷材料、玻璃、用於種籽著色、作為塑料、玻璃、厚紙板和紙的雷射標記之吸收劑、作為塑料的雷射熔接之吸收劑、用於食物和醫藥產品的著色、用於食物和醫藥產品的塗料之著色、用於化妝品調合物、用於製造顏料組成物和無水製劑、及用於有價防偽文件。
- 一種調合物,其包含一或多種如申請專利範圍第1至15項中任一項之效果顏料。
- 如申請專利範圍第19項之調合物,其除了效果顏料以外,另外包含至少一種選自下列的組份:吸收劑、收 斂劑、抗菌物質、抗氧化劑、制汗劑、消泡劑、抗頭皮屑活性成分、抗靜電劑、黏合劑、生物添加劑、漂白劑、螯合劑、除臭劑、柔軟劑、乳化劑、乳液安定劑、染料、保濕劑、成膜劑、填料、氣味物質、調味物質、驅蟲劑、防腐劑、抗蝕劑、化妝油、溶劑、氧化劑、植物成分、緩衝物質、還原劑、界面活性劑、推進氣、遮光劑、UV濾光劑和UV吸收劑、變性劑、黏度調節劑、香料和維生素。
- 一種顏料組成物,其包含一或多種黏合劑、任意的一或多種添加劑、和如申請專利範圍第1至15項中任一項之效果顏料。
- 一種無水製劑,其包含如申請專利範圍第1至15項中任一項之效果顏料。
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DE102011121804A DE102011121804A1 (de) | 2011-12-21 | 2011-12-21 | Effektpigmente |
DE201210000887 DE102012000887A1 (de) | 2012-01-19 | 2012-01-19 | Effektpigmente |
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US (3) | US20130164356A1 (zh) |
EP (1) | EP2607432A1 (zh) |
JP (1) | JP6027431B2 (zh) |
KR (1) | KR102127779B1 (zh) |
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-
2012
- 2012-11-26 EP EP12007941.3A patent/EP2607432A1/de not_active Withdrawn
- 2012-11-29 GB GB1221551.3A patent/GB2498622B/en not_active Expired - Fee Related
- 2012-12-18 TW TW101148112A patent/TWI604020B/zh active
- 2012-12-20 JP JP2012278067A patent/JP6027431B2/ja active Active
- 2012-12-20 KR KR1020120149205A patent/KR102127779B1/ko active IP Right Grant
- 2012-12-20 US US13/721,212 patent/US20130164356A1/en not_active Abandoned
- 2012-12-20 CN CN2012105858382A patent/CN103183972A/zh active Pending
- 2012-12-20 CN CN201810262948.2A patent/CN108467608A/zh active Pending
-
2015
- 2015-09-08 US US14/847,726 patent/US20160068683A1/en not_active Abandoned
-
2020
- 2020-07-06 US US16/921,182 patent/US11773270B2/en active Active
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TWI804491B (zh) * | 2017-03-20 | 2023-06-11 | 德商麥克專利有限公司 | 顏料粉末及製造彼之方法 |
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GB2498622A (en) | 2013-07-24 |
KR102127779B1 (ko) | 2020-06-29 |
US20200339820A1 (en) | 2020-10-29 |
EP2607432A1 (de) | 2013-06-26 |
TWI604020B (zh) | 2017-11-01 |
GB2498622B (en) | 2016-07-20 |
CN108467608A (zh) | 2018-08-31 |
CN103183972A (zh) | 2013-07-03 |
KR20130072158A (ko) | 2013-07-01 |
JP2013129831A (ja) | 2013-07-04 |
JP6027431B2 (ja) | 2016-11-16 |
US11773270B2 (en) | 2023-10-03 |
US20130164356A1 (en) | 2013-06-27 |
US20160068683A1 (en) | 2016-03-10 |
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