TWI405822B - 強烈著色之紅色效應顏料 - Google Patents
強烈著色之紅色效應顏料 Download PDFInfo
- Publication number
- TWI405822B TWI405822B TW095101455A TW95101455A TWI405822B TW I405822 B TWI405822 B TW I405822B TW 095101455 A TW095101455 A TW 095101455A TW 95101455 A TW95101455 A TW 95101455A TW I405822 B TWI405822 B TW I405822B
- Authority
- TW
- Taiwan
- Prior art keywords
- thickness
- iron oxide
- sio
- pigment
- flakes
- Prior art date
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 108
- 230000000694 effects Effects 0.000 title claims abstract description 57
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 91
- 238000000576 coating method Methods 0.000 claims abstract description 45
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000002537 cosmetic Substances 0.000 claims description 11
- 239000004033 plastic Substances 0.000 claims description 10
- 229920003023 plastic Polymers 0.000 claims description 10
- 238000004040 coloring Methods 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 8
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- 239000000126 substance Substances 0.000 claims description 7
- -1 coatings Substances 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 5
- 229940079593 drug Drugs 0.000 claims description 5
- 239000000576 food coloring agent Substances 0.000 claims description 4
- 229910052595 hematite Inorganic materials 0.000 claims description 2
- 239000011019 hematite Substances 0.000 claims description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000013980 iron oxide Nutrition 0.000 description 25
- 239000002245 particle Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000009472 formulation Methods 0.000 description 7
- 239000010408 film Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000010445 mica Substances 0.000 description 5
- 229910052618 mica group Inorganic materials 0.000 description 5
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- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
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- 238000001354 calcination Methods 0.000 description 2
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000665112 Zonitoides nitidus Species 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
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- RGZSQWQPBWRIAQ-LSDHHAIUSA-N alpha-Bisabolol Natural products CC(C)=CCC[C@@](C)(O)[C@@H]1CCC(C)=CC1 RGZSQWQPBWRIAQ-LSDHHAIUSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
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- 238000000889 atomisation Methods 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229940093797 bioflavonoids Drugs 0.000 description 1
- 229940036350 bisabolol Drugs 0.000 description 1
- HHGZABIIYIWLGA-UHFFFAOYSA-N bisabolol Natural products CC1CCC(C(C)(O)CCC=C(C)C)CC1 HHGZABIIYIWLGA-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
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- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03F—SEWERS; CESSPOOLS
- E03F5/00—Sewerage structures
- E03F5/04—Gullies inlets, road sinks, floor drains with or without odour seals or sediment traps
- E03F5/0401—Gullies for use in roads or pavements
- E03F5/0405—Gullies for use in roads or pavements with an odour seal
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
-
- 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
-
- 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
- C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
-
- 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
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Description
本發明係關於一種強烈著色之紅色效應顏料，其包含經氧化鐵塗覆的SiO2
薄片，其中效應顏料的總厚度不大於500奈米(+/-30奈米)。本發明亦係關於用以製備這些顏料之方法，其中，SiO2
薄片經氧化鐵塗覆，其中所擇的SiO2
薄片和氧化鐵層的厚度為使得紅色效應顏料的總厚度不大於500奈米(+/-30奈米)者，本發明亦關於這些顏料於化粧品、塗漆、塗料、塑料、膜、保安印刷、文件和驗證書之保安特徵、用於種子著色、用於食物著色、或於藥物塗覆、及用於製備顏料組成物和乾燥製劑之用途。
紅色光澤或效應顏料的用途廣泛。此類型的顏料已為汽車塗漆、所有類型的裝飾性塗料和塑料著色、塗漆和印刷墨水及裝飾性化粧品應用不可或缺者。在環繞它們的基質中，這些顏料本身理想地平行於塗料表面排列並藉由干擾反射和吸收入射光之複雜的交互作用而具有其光學作用。明亮色彩和高光澤是多種應用感興趣的焦點。
此類型的顏料通常係藉由以金屬氧化物層(特別是氧化鐵層)塗覆薄片狀的雲母而製得。特別地，雲母具有底質厚度變化範圍大且無法明確地設定的缺點，此使得實質上無法控制於底質處的透光率和反射率，即使於透光底質
的情況中亦然，並因此而無法用於特定方式。
WO 93/08237揭示由二氧化矽基質構成並經氧化鐵層塗覆之薄片狀形式的紅色顏料作為底質。此處，基質可設定的範圍廣泛。WO93/08237中所述紅色顏料的缺點在於，當朝向平面視角時，它們具有棕色調，此為所不欲者。此外，對於具有純紅色調和高光澤之強烈紅色效應顏料有需求存在。此外，此底質厚度為500奈米，施用的層的厚度以20-250奈米為佳。總而言之，因此，得到總厚度相當大的顏料。但因為此顏料的應用性質被減弱，所以此不利於許多應用，其現象述於，如，P.Hoffmann,W.Duschek,New Effect Pigments,report volume DFG41,1999,50,123-132。在塗覆應用中，例如，厚顏料具有標的平行排列的問題。相當厚的顏料顆粒的不利形狀使得在黏合劑系統中更難以獲致所欲之平行於表面的排列。相當厚的顏料顆粒會以彼此呈角度的方式成列排列，因此，光線不再以最適方向反射且散射效應減低了定向的光澤。此外，引發應用的缺點，如，含有顏料之塗層的混濁效果提高(光澤霧化)和不良的影像辨視度(DOI)。此外，僅因為對相同質量而言，各顆粒的高質量意謂塗覆應用中的顏料顆粒數少得多，如此造成了顏色缺點。此對於掩飾力、光澤和總顏色表現有不利的影響。因此，對厚顏料顆粒而言，所欲性質是非常難以獲致的。
因此，此目的是要尋求具有改良之光學性質的紅色效應顏料，特別是具有純紅色調者，其可普遍地用於範圍非
常寬廣的應用上，且不具有施用缺點。
藉根據本發明之顏料達到前述目的。據此，本發明係關於強烈著色之紅色效應顏料，其包含經氧化鐵塗覆的SiO2
薄片，其中效應顏料的總厚度不大於500奈米(+/-30奈米)。
本發明亦關於用以製備這些顏料之方法，其中，SiO2
薄片經氧化鐵塗覆，其中所擇的SiO2
薄片和氧化鐵層的厚度為使得紅色效應顏料的總厚度不大於500奈米(+/-30奈米)者。
根據本發明之顏料的特點在於特別強烈和純粹的紅色效應。令人訝異地，此紅色效應顏料的色移情況非常輕微，或完全不具此效果，且沒有其他具氧化鐵層之紅色顏料之干擾的棕色。此外，根據本發明之顏料的優點在於它們的應用非常廣泛，它們具有改良的施用性質，例如，在塗覆應用中之減低的混濁效應和較佳的影像辨視度(DOI)或在化粧品調合物中之較佳的皮膚觸感。
因為此有利的性質，根據本發明之效應顏料普遍適用於類型非常廣泛的許多應用上。據此，本發明亦係關於這些顏料於化粧品、塗漆、塗料、塑料、膜、保安印刷、文件和驗證書之保安特徵、用於種子著色、用於食物著色、或於藥物塗覆、及用於製備顏料組成物和乾燥製劑之用途。
根據本發明之顏料係以合成的SiO2
薄片作為底質為基礎，此底質具有均勻的層厚度且以根據國際申請案WO93/08237，於連續輪帶上藉固化反應和水玻璃溶液之水解反應製得者為佳。此處的"均勻的層厚度"是指顆粒之總乾燥層厚度的層厚度誤差容許度由3至10%，以3至5%為佳。此薄片狀二氧化矽顆粒通常為非晶狀形式。此類型的合成薄片優於天然材料(如，雲母)，如，可視所須效果地調整層厚度及層厚度容許度受限。
底質的直徑通常介於1和250微米之間，以介於2和100微米之間為佳。它們的厚度介於250和400奈米之間並以330至350奈米為佳。薄片狀底質的平均縱橫比，即，平均長度測量值(此相當於平均直徑)與平均厚度測量值的比值通常由5至200，以20至150為佳，30至120特別佳。
根據本發明之顏料中的該底質經塗覆以氧化鐵層(特別是赤鐵礦層(α-Fe2
O3
))。各氧化鐵層的厚度介於30和150奈米之間，以50至130奈米為佳。基本上，就本發明而言，紅色效應顏料的總厚度不大於500奈米(+/-30奈米)。具有氧化鐵的SiO2
薄片之塗層可以僅存在於兩個最大的相對表面或以包覆方式存在；此SiO2
薄片以完全被氧化鐵所包覆為佳。在截面上，由此形成下列顏料結構：Fe2
O3
/SiO2
/Fe2
O3
三層的厚度總和必須不超過所要求的500奈米(+/-30奈米)。
為使所欲純粹紅色調最適化，底質和氧化鐵層的厚度精確地相配合較為有利。此處，特別佳的底質和各氧化鐵層的厚度分佈如下：
本發明的另一體系中，根據本發明之效應顏料可進一步被施以穩定用的有機塗層作為外層。此塗層的例子示於，如，EP 0 632 109、US 5,759,255、DE 43 17 019、DE 39 29 423、DE 32 35 017、EP 0 492 223、EP 0 342 533、EP 0 268 918、EP 0 141 174、EP 0 764 191、WO 98/13426或EP 0 465 805，茲將其中所揭示者列入參考。效應顏料包含有機塗層，如，有機矽烷或有機鈦酸鹽或有機鋯酸鹽，此外，除前述光學性質以外，對於天候影響(如，濕氣和光)具有較高的安定性，此為工業塗料和汽車領域特別感興趣者。額外塗層之無機組份可改良此安定性
。總之，額外安定性塗層的各比例應使得根據本發明之效應顏料的光學性質不會明顯受到影響。
本發明亦係關於這些顏料之製備，其中，SiO2
薄片經塗覆以氧化鐵，其中所擇的SiO2
薄片和氧化鐵層的厚度為使得紅色效應顏料的總厚度不大於500奈米(+/-30奈米)。底質厚度與施用的氧化鐵層厚度的個別相稱情況已述於前文中。
以氧化鐵層塗覆可藉濕式化學法和/或CVD或PVD法進行。
根據本發明之用以製備效應顏料之方法以濕式化學法為佳，其中可以使用發展用以製備珠光顏料之已知的濕式化學塗覆技巧，其述於，如，下列文獻中：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。
用於塗覆，SiO2
薄片懸浮於水中並藉由添加和沉積相關的無機金屬化合物而塗覆以氧化鐵，藉由同時添加酸或鹼而設定和維持氧化鐵沉澱所須的pH，之後自水性懸浮液分離經塗覆的底質，乾燥及選擇性鍛燒，以此方式設定各層的層厚度，於乾燥和選擇性鍛燒之後，顏料的厚度不大於500奈米(+/-30奈米)。
鍛燒溫度通常介於250和1000℃之間，特別是介於
350和900℃之間。
基本上，經氧化鐵塗覆顆粒之CVD或PVD法亦適用於製備根據本發明之顏料。此類型的方法述於，如，W.Ostertag.Nachr.Chem.Tech.Lab 1994,42
,849。此處，在蒸鍍法期間內，必須使底質維持均勻運動，以確保所有的顆粒表面具均勻塗層。
此外，在根據本發明之方法中，也可以另施用有機塗層作為外層。此類型塗覆法的例子特別見於EP 0 632 109、US 5,759,255、DE 43 17 019、DE 39 29 423、DE 32 35 017、EP 0 492 223、EP 0 342 533、EP 0 268 918、EP 0 141 174、EP 0 764 191、WO 98/13426或EP 0 465 805。有機塗層的例子和相關優點已於前文中述於本發明之顏料的結構中。施用有機塗層之程序步驟可直接接於根據本發明之方法的其他步驟之後。以顏料總重計，此處施用的物質的重量比僅0.1至5重量%，以0.5至3重量%為佳。
根據本發明之效應顏料可用於多種應用。據此，本發明亦關於根據本發明之顏料於化粧品、塗漆、塗料、塑料、膜、保安印刷、文件和驗證書之保安特徵、用於種子著色、用於食物著色、或於藥物塗覆、及用於製備顏料組成物和乾燥製劑之用途。
以化粧品為例，根據本發明之效應顏料特別適用於裝飾性化粧品產物和調合物，如，指甲油、著色粉末、唇膏或眼影、皂、牙膏..等。根據本發明之效應顏料當然亦可
與所有類型的化粧用原料和輔助劑合併。這些特別包括，油、脂、蠟、成膜物、防腐劑和通常決定應用性質之輔助劑(如，稠化劑)和流變添加劑(如，膨潤土、水輝石、二氧化矽、矽酸鈣、明膠、高分子量碳水化合物)和/或界面活性輔助劑..等。包含根據本發明之效應顏料之調合物可為親脂、親水或疏水型。以具有不連續的水和非水性之雜相調合物為例，根據本發明之顆粒可以僅存在於兩相之一之中或分佈於兩相之中。
水性調合物之pH可介於1和14之間，介於2和11之間較佳，介於5和8之間特別佳。根據本發明之效應顏料於調合物中之濃度不受限制。它們可視施用而定而介於0.001%(清洗性產品，例如，沐浴膠)和99%(例如，用於特別應用的光澤效應顆粒)之間。因此，根據本發明之效應顏料可以與化粧用活性成份合併。適當的活性成份有，如，驅蟲劑、UV A/BC保護用濾劑(如，OMC、B3、MBC)、抗老化活性成份、維生素和其衍生物(如，維生素A、C、E..等)、自身曬黑劑(特別是，如，DHA、赤藻酮糖)和其他化粧用活性成份(如，沒藥醇(bisabolol)、LPO、滲透壓調節因子(ectoine)、油柑、尿囊素、生物類黃酮和它們的衍生物)。
此效應顏料用於塗漆和塗料之用途上時，可以使用嫻於此技術者已知的所有應用範圍，例如，粉末塗料、汽車塗漆、用於照相凹版、橡皮版、網版或快乾印刷的印刷墨水，及戶外施用之塗料。此處之塗漆和塗料可以經，如，
射線固化，物理乾燥或化學固化。用以製備印刷墨水或液體塗料，多種黏合劑(如，以下列為底質者：丙烯酸酯、甲基丙烯酸酯、聚酯、聚胺基甲酸酯、硝基纖維素、乙基纖維素、聚醯胺、聚丁酸乙烯酯、酚醛樹脂、順-丁烯二酸系樹脂、澱粉或聚乙烯醇、胺基樹脂、醇酸樹脂、環氧樹脂、聚四氟乙烯、聚偏氟乙烯、聚氯乙烯或它們的混合物，特別是水溶性者)適用。此塗料可為粉末塗料或以水或溶劑為基礎的塗料，其中，塗料構份之選擇為嫻於此技術者所習知。常用於粉末塗料的聚合型黏合劑是，如，聚酯、環氧化物、聚胺基甲酸酯、丙烯酸酯或它們的混合物。
此外，根據本發明之效應顏料可用於薄膜和塑料，因此，例如，可用於農業用板、反射紅外光的膜和板、禮品包裝物、用於嫻於此技術者習知之所有應用的塑膠容器和模塑物。適合與根據本發明之效應顏料摻合的塑料是所有常見塑料，如，熱固物或熱塑物。可能的應用和適當的塑料、加工法和添加物之描述見於，RD 472005或R.Glausch,M.Kieser,R.Maisch,G.Pfaff,J.Weitzel,Perlglanzpigmente[Pearlescent Pigments],Curt R.Vincentz Verlag,1996,83ff，茲將其中所揭示者列入參考。
此外，根據本發明之效應顏料亦適用於保安相關範圍，如，防偽和驗證書(如，入場券、個人驗證卡、鈔票、支票和票卡)和用於其他防偽文件。此效應顏料除了可於
食品領域中用於食物之著色，亦在農業領域中用於種子和其他起始材料之著色。根據本發明之效應顏料亦可用於藥物(如，錠或藥丸)之塗層之著色。
在前述應用範圍中，根據本發明之效應顏料亦適合以與有機染料和/或顏料(如，透光和不透光的白色、彩色和黑色顏料)和與薄片狀氧化鐵、有機顏料、全像顏料、LCP(液晶聚合物)和慣用透光、彩色和黑色光澤顏料(以經金屬氧化物塗覆的雲母、Al2
O3
、Fe2
O3
、SiO2
..等為基礎)之混合物形式使用。根據本發明之效應顏料可以與市售顏料和填料以任何比例混合。
可提及的填料有，如，天然和合成雲母、尼龍粉末、純粹或經填充的蜜胺樹脂、滑石、玻璃、高嶺土、鋁、鎂、鈣、鋅之氧化物或氫氧化物、BiOCl、硫酸鋇、硫酸鈣、碳酸鈣、碳酸鎂、碳和這些物質的物理或化學組合。對於填料的顆粒形狀沒有任何限制。例如，根據需求，其可為薄片狀、球狀或針狀。
根據本發明之效應顏料適用以製造包含根據本發明之一或多種顆粒、黏合劑和選擇性的一或多種添加劑之可流動的顏料組成物和乾燥製劑。所謂"乾燥製劑"亦意謂包含0至8重量%，2至8重量%較佳，特別是3至6重量%，水和/或溶劑或溶劑混合物之製劑。此乾燥製劑以丸粒、顆粒、片、長圓形或錠形式且顆粒尺寸為0.2-80毫米為佳。此乾燥製劑特別用於製備印刷墨水和化粧用調合物。
茲將前述所有專利申請案和文獻全文列入此申請案作
為參考。
以下列實例更詳細地解釋本發明，但不欲以其限制本發明。
100克SiO2
薄片(厚度365奈米)於2升去礦質水中加熱至75℃。於攪拌時添加1120毫升FeCl3
溶液(相當於130% Fe2
O3
)。添加氫氧化鈉溶液(30%)，將此反應混合物的pH維持於3。添加FeCl3
溶液之後，使用氫氧化鈉溶液(30%)將pH提高至pH5。過濾此產物並以去礦質水清洗。於110℃乾燥之後，此產物於800℃鍛燒。
以此方式製得之顏料的顏色行為示於圖1(-▲-)。
100克SiO2
薄片(厚度445奈米)於1升去礦質水中加熱至75℃。於攪拌時添加237毫升FeCl3
溶液(相當於27.5% Fe2
O3
)。添加氫氧化鈉溶液(30%)，將此反應混合物維持於pH3。添加FeCl3
溶液之後，使用氫氧化鈉溶液(30%)將pH提高至pH5。過濾此產物並以去礦質水清洗。於110℃乾燥之後，此產物於800℃鍛燒。
以此方式製得之顏料的顏色行為示於圖1(-◆-)。
圖1顯示顏色位置，其與具有不同紅色調和不同色移行為的效應顏料比較。此處的顏色曲線顯示在a,b色系統
中之色值改變，此由含有此顏料的塗漆卡自垂直角度(90度平面視角)偏斜至180度(水平軸是a軸，自左=綠至右=紅)而得。
典型氧化鐵雲母顏料(-●-)的顏色較弱且無色移情況。偏斜時之典型的棕色調在曲線中不明顯。
如WO 93/08237中所述之具有氧化鐵塗層的典型SiO2
薄片顏料(-◆-)不具有初色調中的明亮紅色。偏斜時，發生強烈色移；實例中，其變為綠色。根據本發明之效應顏料之顏色(-▲-)顯現飽和的紅色，於偏斜時亦維持紅色。此顏色一直維持在a,b色系統的一個象限中，且色移非常小。
圖1表示根據本發明之顏料與得自先前技術者之紅色調之比較。
Claims (11)
- 一種強烈著色之紅色效應顏料，其包含經氧化鐵塗覆的SiO2 薄片，其中效應顏料的總厚度不大於500奈米(+/-30奈米)。
- 如申請專利範圍第1項之效應顏料，其中SiO2 薄片的直徑介於1和250微米之間，SiO2 薄片的厚度介於250和400奈米之間。
- 如申請專利範圍第1或2項之效應顏料，其中SiO2 薄片的厚度是250、300、350或400奈米。
- 如申請專利範圍第1或2項之效應顏料，其中氧化鐵是赤鐵礦(α-Fe2 O3 )。
- 如申請專利範圍第1或2項之效應顏料，其中氧化鐵層的厚度是由30至150奈米。
- 如申請專利範圍第1或2項之效應顏料，其中另將有機塗料施用於效應顏料。
- 一種製備如申請專利範圍第1項之效應顏料之方法，其特徵在於SiO2 薄片經氧化鐵塗覆，其中所擇的SiO2 薄片和氧化鐵層的厚度為使得紅色效應顏料的總厚度不大於500奈米(+/-30奈米)。
- 如申請專利範圍第7項之方法，其中氧化鐵的塗覆係以使得層厚度介於30和150奈米之間的方式進行。
- 如申請專利範圍第7或8項之方法，其中氧化鐵的塗覆係藉濕式化學法和/或CVD或PVD法進行。
- 一種如申請專利範圍第1項之效應顏料的用途， 其係用於化粧品、塗漆、塗料、塑料、膜、保安印刷、文件和驗證書之保安特徵、用於種子著色、用於食物著色、或用於藥物塗覆、及用於製備顏料組成物和乾燥製劑。
- 如申請專利範圍第1或2項之效應顏料，其包括：(1)一種總厚度為500 nm且包括厚度250 nm的SiO2 -薄片及二層厚度分別為125 nm的氧化鐵層之顏料；(2)一種總厚度為530 nm且包括厚度250 nm的SiO2 -薄片及二層厚度分別為140 nm的氧化鐵層之顏料；(3)一種總厚度為470 nm且包括厚度250 nm的SiO2 -薄片及二層厚度分別為110 nm的氧化鐵層之顏料；(4)一種總厚度為500 nm且包括厚度300 nm的SiO2 -薄片及二層厚度分別為100 nm的氧化鐵層之顏料；(5)一種總厚度為530 nm且包括厚度300 nm的SiO2 -薄片及二層厚度分別為115 nm的氧化鐵層之顏料；(6)一種總厚度為470 nm且包括厚度300 nm的SiO2 -薄片及二層厚度分別為85 nm的氧化鐵層之顏料；(7)一種總厚度為500 nm且包括厚度350 nm的SiO2 -薄片及二層厚度分別為75 nm的氧化鐵層之顏料；(8)一種總厚度為530 nm且包括厚度350 nm的SiO2 -薄片及二層厚度分別為90 nm的氧化鐵層之顏料；(9)一種總厚度為470 nm且包括厚度350 nm的SiO2 -薄片及二層厚度分別為60 nm的氧化鐵層之顏料；(10)一種總厚度為500 nm且包括厚度400 nm的SiO2 -薄 片及二層厚度分別為50 nm的氧化鐵層之顏料；(11)一種總厚度為530 nm且包括厚度400 nm的SiO2 -薄片及二層厚度分別為65 nm的氧化鐵層之顏料；或(12)一種總厚度為470 nm且包括厚度400 nm的SiO2 -薄片及二層厚度分別為35 nm的氧化鐵層之顏料。
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| US6875264B2 (en) * | 2003-01-17 | 2005-04-05 | Engelhard Corporation | Multi-layer effect pigment |
| DE102004045352A1 (de) * | 2003-10-01 | 2005-04-21 | Merck Patent Gmbh | Glänzende rote Interferenzpigmente |
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-
2005
- 2005-01-17 DE DE102005002124A patent/DE102005002124A1/de not_active Withdrawn
- 2005-12-22 EP EP05028172.4A patent/EP1681318B1/de active Active
- 2005-12-22 ES ES05028172T patent/ES2428502T3/es active Active
-
2006
- 2006-01-13 TW TW095101455A patent/TWI405822B/zh not_active IP Right Cessation
- 2006-01-13 US US11/331,449 patent/US7156913B2/en active Active
- 2006-01-16 JP JP2006007264A patent/JP2006199960A/ja active Pending
- 2006-01-16 CN CN2006100054721A patent/CN1814673B/zh active Active
- 2006-01-16 KR KR1020060004528A patent/KR101312172B1/ko active IP Right Grant
-
2013
- 2013-01-04 JP JP2013000226A patent/JP2013100524A/ja active Pending
- 2013-06-24 KR KR1020130072519A patent/KR20130081686A/ko not_active Application Discontinuation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004035693A1 (en) * | 2002-10-16 | 2004-04-29 | Ciba Specialty Chemicals Holding Inc. | Interference pigments on the basis of silicon oxides |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1814673A (zh) | 2006-08-09 |
| DE102005002124A1 (de) | 2006-07-27 |
| EP1681318B1 (de) | 2013-07-24 |
| CN1814673B (zh) | 2010-08-18 |
| EP1681318A3 (de) | 2007-09-12 |
| JP2006199960A (ja) | 2006-08-03 |
| KR20130081686A (ko) | 2013-07-17 |
| US20060156949A1 (en) | 2006-07-20 |
| US7156913B2 (en) | 2007-01-02 |
| KR20060083892A (ko) | 2006-07-21 |
| ES2428502T3 (es) | 2013-11-08 |
| TW200639221A (en) | 2006-11-16 |
| EP1681318A2 (de) | 2006-07-19 |
| JP2013100524A (ja) | 2013-05-23 |
| KR101312172B1 (ko) | 2013-09-26 |
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| MM4A | Annulment or lapse of patent due to non-payment of fees |