TW201625753A - 製造結構化塗料之方法 - Google Patents

製造結構化塗料之方法 Download PDF

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TW201625753A
TW201625753A TW104129777A TW104129777A TW201625753A TW 201625753 A TW201625753 A TW 201625753A TW 104129777 A TW104129777 A TW 104129777A TW 104129777 A TW104129777 A TW 104129777A TW 201625753 A TW201625753 A TW 201625753A
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coating
oxide
pigment
photoresist
acid
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TW104129777A
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TWI671369B (zh
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洛夫 艾森曼
克利斯汀 布林
爾恩 霍普
索尼婭 梅洛夫
格哈德 雷納
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贏創德固賽有限責任公司
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001General methods for coating; Devices therefor
    • C03C17/002General methods for coating; Devices therefor for flat glass, e.g. float glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
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    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208Oxides, e.g. ceramics
    • C23C18/1212Zeolites, glasses
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    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/122Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125Process of deposition of the inorganic material
    • C23C18/1254Sol or sol-gel processing
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    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125Process of deposition of the inorganic material
    • C23C18/1262Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
    • C23C18/127Preformed particles
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    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
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    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16Coating processes; Apparatus therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16Coating processes; Apparatus therefor
    • G03F7/162Coating on a rotating support, e.g. using a whirler or a spinner
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    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16Coating processes; Apparatus therefor
    • G03F7/168Finishing the coated layer, e.g. drying, baking, soaking
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    • G03F7/20Exposure; Apparatus therefor
    • G03F7/2002Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
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    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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    • G03F7/42Stripping or agents therefor
    • G03F7/422Stripping or agents therefor using liquids only
    • G03F7/426Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00Processes for applying liquids or other fluent materials
    • B05D1/32Processes for applying liquids or other fluent materials using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
    • B05D1/322Removable films used as masks
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    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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Abstract

本發明係關於一種製造結構化塗料的方法,其中將包含至少一種無機黏合劑、至少一氧化物顏料(其基於1克物質,於標準條件下,在添加由15毫升之1M草酸和15毫升之20%之水性氫氯酸構成的混合物之後,導致溫度提升至少4℃)及至少一溶劑的塗料組成物施加至基材,以光阻至少部份地塗覆所得之塗料組成物膜且以酸處理該塗料組成物和該光阻塗覆之基材,關於藉由該方法可得之結構化層及關於彼之用途。

Description

製造結構化塗料之方法
本發明係關於一種製造結構化塗料的方法。本發明尤其是關於一種製造光學稠密、熱穩定、非傳導性結構化塗料之方法。本發明同樣地係關於可藉由根據本發明之方法製造之結構化塗料。
結構化塗料對於很多應用技術領域具有重要性。光學稠密、非傳導性結構化塗料對於在半導體技術中之很多應用是必要的。尤其對於顯示器之製造,光學稠密之非傳導性塗料是需要的,以框住該顯示器邊緣,使電子組件避光及/或用於濾色器之像素分離。達成以上目的之塗料,因為彼常產生黑色塗料,係稱為黑色基質。然而,彼等原則上可能具有任何想要的顏色。較佳地,然而,黑色基質是黑色或白色。
該先前技術揭示多種製造結構化塗料之方法,尤其是製造黑色基質者。
EP 0 762 996 A1揭示一種製造結構化塗料之方法, 其中該結構化係藉由壓紋工具製造。然而,此方法不適用於精細結構化塗料,例如在半導體技術中所要求者。
例如,黑色基質也可藉由鉻之沉積,尤其是利用濺鍍製造(EP 0 740 183 A1)。然而,此方法具有之缺點是:對應之方法在設備方面極複雜且需要大的建構,且整合於製造顯示器之方法中是極複雜的。使用鉻之另一缺點是:彼是重金屬且因此對環境有害,且處置是極昂貴的。
結構化塗料或黑色基質原則上也可經由有機染料之著色而製造(EP 0 740 183 A1)。然而,包含有機染料之塗料組成物對於獲得具有高彩色深度和均勻彩色分配的結構化塗料並不適合。黑色塗料尤其不能利用這些溶液來製造,因為迄今並沒有導致深黑色塗料的有機染料。包含不同染料之混合物的塗料組成物也具有導致不恰當之彩色深度的缺點。另一結果是不利的不均勻著色。包含有機染料之塗料也不能耐受如在顯示器製造時所用之溫度。因這理由,包含有機染料之溶液迄今在顯示器製造中尚未有任何商業用途。
迄今還不能使用慣用之印刷方法(其使用包含非有機染料之著色劑的塗料組成物)以製造足夠精細之結構化塗料及尤其沒有足夠鮮明邊界之黑色基質。製造黑色基質之措施是基於例如包含黏合劑和無機顏料之塗料組成物的使用(EP 0 740 183 A1)。使用之顏料可以是碳黑(亦即顏料黑)。然而,碳黑是不利的,因為對應之塗料可變為傳導性的。或者,也可以使用金屬氧化物(尤其是尖晶石彩 色顏料)。在這些之間,特佳是尖晶石彩色顏料,因為彼也可被使用以由包含高顏料濃度之塗料組成物製造非傳導性塗料。此外,顏料黑和很多其它顏料僅可困難地被分散且具有凝聚傾向而再次對該黑色基質層品質有不良影響。最終,尖晶石顏料是極熱穩定的,且與顏料黑及非尖晶石顏料不同地,在一些情況中,甚至可能不被形成直至彼係在該固化之塗料內(Silva et al.,Journal of Magnetism and Magnetic Materials,272-276(2004)e1851-e1853)。該彩色顏料也可以經表面處理(參考例如DE 40 14 928 C1和US 6,136,083 A)。然而,還不可能藉由使用金屬氧化物顏料且迄今已知的方法以製造足夠精細之結構化塗料。
最後,結構化塗料或黑色基質也可藉由包含黑色顏料(例如碳黑)之光敏性塗料組成物的選擇性轉化而製造。然而,此方法也導致較差之塗料,尤其是因為在高顏料含量下不完全的轉化。EP 0 740 183 A1揭示一種製造結構化塗料之方法,其中將包含黑色化合物氧化物顏料(包含至少二種金屬氧化物、無機黏合劑和光敏性樹脂)的塗料組成物施加至基材,且經施加之塗料組成物係透過光罩以汞蒸氣燈照射,顯影、清洗且隨意地進一步經後加熱。然而,基於有機系統之光敏性樹脂之使用具有之缺點是使用彼等所製造之層不能曝於在顯示器製造時有利地被使用之高溫。
本文件所解決之問題因此是避免該先前技術之缺點的問題。更特別地,本文件中所解決之問題是提供一種製造結構化塗料的方法的問題,利用此方法可獲得極精細之結構化塗料且此方法使用不含有機染料、黏合劑及光敏性樹脂的著色用塗料組成物。
此目的係藉由製造結構化塗料之方法達成,其中將包含至少一種無機黏合劑、至少一種氧化物顏料(其基於1克物質,於標準條件(SATP:25℃,1.013巴)下,在添加由15毫升之1M草酸和15毫升之20%之水性氫氯酸構成的混合物之後,導致溫度提升至少4℃)和至少一溶劑的塗料組成物施加至基材,所得之塗料組成物膜部份地以光阻塗覆且以該塗料組成物及該光阻塗覆之基材係以酸處理。
根據本發明之製造結構化塗料的方法原則上適合製造任何想要之結構化塗料。較佳地,然而,藉此可製造之塗料是來自半導體技術領域之結構化塗料。更佳地,根據本發明之方法是製造結構化黑色基質之方法。令人驚訝地已發現:因此可能製造極精細之結構(具有寬度<10μm)。此外,根據本發明之方法具有之優點是彼還可以相對弱酸來操作。因此可以避免使用毒性蝕刻劑,例如氫氟酸。
在根據本發明之方法中,將塗料組成物施加至基材。原則上,任何想要之基材對於根據本發明之方法是合適的。然而,對於隨後用在半導體技術中,較佳是選自玻璃、矽、二氧化矽、金屬氧化物或過渡金屬氧化物、金屬 或聚合物材料(尤其是PI、PEN、PEEK、PC或PET)的基材。該基材也可未經處理或經處理。"經處理之基材"一詞另外不僅包括用以產生所要之表面性質的處理,也包括用以產生所要之技術性質的處理(尤其是用以產生想要之電子性質,例如用於施加顯示器結構(例如像素)的處理)。
經施加至該基材的塗料組成物包含至少一種無機黏合劑、至少一種氧化物顏料及至少一種溶劑。彼因此可能還具有另外的組成構份。較佳地,然而,本發明之塗料組成物僅由一或多種黏合劑、一或多種氧化物顏料及一或多種溶劑組成。為了要製造具有良好高溫應用適合性之結構化塗料,根據本發明之方法使用僅由一或多種無機黏合劑、一或多種氧化物顏料及一或多種溶劑組成之塗料組成物。
該塗料組成物較佳是在標準條件(SATP:25℃、1.013巴)下為液態之塗料組成物,其具有特別容易施加及獲得特別精細結構的優點。
使用之塗料組成物包含至少一種無機黏合劑。較佳地,該至少一種無機黏合劑是一種在正式意義上為隨意經烷基化之烷氧基矽烷的縮合產物的黏合劑。
較佳之有機黏合劑具有通式SiaR1 bOc(OR2)d,其中a≧2、b≧0、c≧1、d≧5且R1和R2=有機基團。
對應之無機黏合劑(形式上是氧基烷氧基矽烷化合物或經烷基化之氧基烷氧基矽烷化合物)是烷氧基矽烷類和隨意經烷基化之烷氧基矽烷類的縮合產物且可在酸或酸酯 催化作用下由此被製備。使用之反應物較佳可以是通式Si(OR2)4之烷氧基矽烷類(其中R2=有機基團)和通式SiR1(OR2)3之經烷基化的烷氧基矽烷類(其中R1和R2=有機基團)。對應之反應可以在水中特別有效率地進行。該反應可利用磷酸酯(較佳地利用磷酸單甲酯類)特別有效率地進行。使用之反應物較佳可以是通式Si(OR2)4之烷氧基矽烷類和經烷基化的烷氧基矽烷類SiR1(OR2)3,其中R1或R2=-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2。即使該反應係在水之存在下進行,通常令人滿意的是:在反應完成後,亦即在黏合劑形成後,水僅極小比例地存在,以該塗料組成物之總質量為基準計,一般是<5重量%,尤其是<2重量%,更特別是<1重量%的情況。
另外較佳之無機黏合劑因此具有通式SiaR1 bOc(OR2)d,其中R1和R2=-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2,較佳地R1和R2=-CH3及/或-CH2CH3,a≧2、b≧0、c≧1且d≧5。
可以獲得顯出特別低脆性之特別良好的塗料,當使用SiCH3(OCH2CH3)3和Si(OCH2CH3)4之混合物。所得之黏合劑對應地具有R1=-CH3及R2基團=-CH2CH3
對於製造具有特別均質並低的表面粗糙度的層的可精細結構化的黑色基質,具有特別良好適合性的是另外之包含對應黏合劑的塗料組成物,其中a=5至150,較佳地a=20至100,較佳地a=30至80個矽原子。
b+d之和的最大值,尤其是在低的a值的情況中,係 接近4.a。c值是至少1且與a、b和d之值的關係是4.a=b+2.c+d。較佳地,對於達成所得之層的特別良好性質,c對a的比率平均是1.1至2.0,另外較佳是1.15至1.8,最佳是1.2至1.5。
較佳地,本發明之塗料組成物另外基本上沒有有機黏合劑(亦即以黏合劑之總質量為基準計,有機黏合劑之比例低於或等於5重量%,較佳低於或等於2重量%,另外較佳是0重量%),因為在可用於至高800℃之加熱步驟的情況中彼具有大優點。
再者,該無機黏合劑係用在根據本發明之方法中以用於達成塗料組成物之特別良好結果,以該塗料之總質量為基準計,其比例是5重量%至75重量%,另外較佳地10重量%至45重量%。
在根據本發明之方法中使用之塗料組成物另外包括至少一種氧化物顏料,其基於1克物質,於標準條件(SATP:25℃,1.013巴)下,在添加由15毫升之1M草酸和15毫升之20%之水性氫氯酸構成的混合物之後,導致溫度提升至少4℃。
在添加具有30毫升體積(15毫升之1M草酸和15毫升之20%之水性氫氯酸(HCl))之混合物至1克氧化物顏料(其在SATP下添加且隨後在200rpm攪拌後60秒,對於根據本發明可用之氧化物顏料而言,相對其它氧化物顏料,具有提升至少29℃之溫度的特別特徵)之後,此放熱反應是對反應性及因此對應之各別混合型氧化 物顏料的適合性的指標。
對應之氧化物顏料可被了解意思是i)以氧化態為1之(半)金屬的氧化物為底質的顏料,ii)以氧化態大於1之(半)金屬的混合型氧化物((半)金屬之混合價氧化物,例如氧化鐵Fe3O4)為底質的顏料及iii)以氧化態各為1或更大之至少二種(半)金屬的混合型氧化物為底質的顏料(混合相氧化物顏料)。"(半)金屬"一詞包含等量之金屬和半金屬。
較佳地,該至少一種氧化物顏料是以氧化態大於1之(半)金屬的混合型氧化物(例如氧化鐵Fe3O4)為底質的顏料及/或以氧化態各為1或更大之至少二種(半)金屬的混合型氧化物為底質的顏料(即混合相氧化物顏料)。另外較佳地,該顏料是以氧化態各再次為1或更大之至少二種(半)金屬之混合型氧化物為底質的顏料。最佳地,該顏料是以至少二種金屬之混合型氧化物為底質的顏料,其中至少二種金屬有不同氧化態(混合價氧化物)。對應之化合物是氧化物及/或混合型氧化物且可具有例如尖晶石結構或逆尖晶石結構(且因此是單相混合相顏料),或者為不同結晶相之混合物形式。
特別良好之結果係利用混合型鐵-錳氧化物顏料達成。另外,特佳是含氧化銅之混合型鐵-錳氧化物,利用彼可以達成極特別良好之結果。對應之"混合型氧化物"顏料據了解意思是單相及多相混合型晶體氧化物二者。極特佳之含氧化銅的混合型鐵-錳氧化物是那些可藉由氧化錳 (II)(MnO)、氧化錳(III)(Mn2O3)、氧化鐵(II)(FeO)、氧化鐵(III)(Fe2O3)和氧化銅(II)(CuO)的煅燒獲得者。對應之混合型氧化物也藉由Colour Index(簡稱為C.I.)稱為"Pigment Black 26"。C.I.是從1925即存在之對於所有常用之著色劑和以染料為底質之化學品的參考著作且是在顏料和染料化學領域中的標準著作。Colour Index是由the British Society of Dyers and Colourists and the American Association of Textile Chemists and Colorists所出版的。
對應之特佳顏料是可由The Shepherd Color Company,USA獲得之Black 444,由Dainichiseika Color & Chemicals Mfg.Co.,Ltd.,Japan獲得之Daipyroxide Black 9550,由Kremer Pigmente GmbH und Co.KG,Germany獲得之Spinel Black 47400及由Ferro GmbH,Germany獲得之PS 24-3060。即使這些特佳顏料係稱為錳-鐵黑色尖晶石,並不確定這些顏料僅具有或到底有無尖晶石結構。
除了經提及之氧化物顏料之外,也可能有另外之彩色顏料存在於該組成物中,尤其是氧化鈦、鋅白、尖晶石藍、鋅鋇白、硫酸鋇、氧化鋅、碳酸鈣、白矽石或高嶺土。較佳地,然而,本發明之組成物僅含有上述氧化物顏料,其導致所述之溫度提升。
此外,用於獲得具有特別良好非傳導性之塗料的組成物較佳是不含碳的,意思就是彼不含有任何比例之碳同素異形體諸如碳黑、石墨、活性碳、碳塵、富勒烯、石墨烯 及類似者。"不具有任何比例之碳同素異形體"據了解意思是碳同素異形體比例不多於0.5重量%,較佳不多於0.2重量%,最佳不多於0.1重量%,此係以所秤出之顏料組成物的總質量為基準計。
在該組成物中具有所述性質的氧化物顏料的比例,以該組成物之總質量為基準計,較佳是10重量%至50重量%,另較佳是15重量%至40重量%且更佳是15重量%至35重量%。
該組成物還包含至少一種溶劑。原則上,可想到有機溶劑和水二者作為溶劑。然而,當該至少一種溶劑是有機溶劑或有機溶劑混合物時獲得特別良好的塗料。較佳地,該有機溶劑是醇、烷基酯、烷氧基醇及/或烷氧基烷基酯。最佳地,該至少一種溶劑是1-甲氧基-2-丙醇、乳酸乙酯、乙酸丁酯、苯甲酸乙酯、丙二醇單甲基醚乙酸酯、三(乙二醇)單乙基醚(乙基三乙二醇,TGEE)、乙醇、異丙醇及/或丁醇。
通常,該溶劑之比例,以該塗料之總質量為基準計,較佳是20重量%-80重量%,進一步較佳是35重量%-70重量%。
該組成物除了必要成分無機黏合劑、溶劑和氧化物顏料之外,也還可另外包括進一步之添加物和添加劑。例如,除了該至少一種氧化物顏料之外,該組成物還可包括另外的顏料或染料。較佳地,然而,本發明之組成物僅包含氧化物顏料作為顏料成份。此外,該組成物可包括至少 一種潤溼用添加劑、分散用添加劑及/或勻染用添加劑作為達成正面性質之添加劑。特佳之添加劑是以胺甲酸酯共聚物或例如以矽氧烷類改質之聚醚類為底質之添加劑。特佳之添加劑是名為TEGO Dispers 656和TEGO Glide 450(各得自Evonik Goldschmidt GmbH)和BYK 111(得自Byk Chemie GmbH)之市售產品。還可能添加顆粒狀SiOx作為本發明之塗料組成物的填料以獲得有利的性質。
較佳地,為要獲得特別良好之塗覆性、印刷性和可噴霧性,在根據本發明之方法中使用之組成物具有黏度是1mPa.s至10Pa.s,尤其是1mPa.s至100mPa.s,其係根據DIN 53019之第1和2部份測定且在20℃下測量。對應之黏度可藉由添加聚合物、纖維素衍生物、或SiO2(以商品名為Aerosil所得者)而建立,且尤其佳是利用PMMA、聚乙烯醇、胺甲酸酯增稠劑或聚丙烯酸酯增稠劑。
添加物或添加劑若真存在,則一般使用比例,以該組成物之總質量為基準計,係不多於10重量%,較佳不多於3重量%。使用之塗料組成物可以極有效率地被結構化,尤其是當對無機黏合劑、氧化物顏料和溶劑所描述之一或多個較佳具體例被選擇時。此外,所述之塗料組成物具有之優點是:彼等甚至可利用弱酸或弱酸混合物成功地被極精細地結構化,且因此無須經由例如高技術之真空方法(例如在乾蝕刻的情況中)或利用強酸或對健康或環境有高度破壞之酸(諸如氫氟酸)的蝕刻。
當用在根據本發明之方法中,所述之塗料組成物不僅導致所要之優點,另外也令人意外地導致所得塗料的特高光學密度。
該塗料組成物對該基材之施加可在全面積上進行或以結構化方式進行。當該塗料組成物係施加在全面積上,該方法可以特簡單且因此有利的方式進行。
本發明之塗料組成物原則上可以任何想要方式被施加至該基材。
較佳地,該塗料組成物係藉由選自印刷方法(尤其是柔版印刷/凹版印刷、噴墨印刷(最佳是連續熱或壓力噴墨印刷)、平版印刷、數位平版印刷及網版印刷)、噴霧方法、旋轉塗覆方法、浸漬塗覆方法的塗覆方法、和選自彎月面(meniscus)塗覆、狹縫塗覆、槽模(slot-die)塗覆及幕式塗覆的方法被施加至該基材。最佳地,該塗料組成物利用印刷方法或旋轉塗覆方法被施加。尤其適合之印刷方法是噴墨及液態染色劑方法(例如HP Indigo),因為這些方法特別適合印刷材料之結構化施加。最佳地,根據本發明之方法是旋轉塗覆方法,因為因此可能以特別簡單方式達成全面積塗覆。
若該液態塗料組成物係藉由旋轉塗覆被施加,此較佳以在100與5000rpm之間的速度進行。較佳地,塗覆首先係在100至1000rpm的低速進行5秒至30秒之時間,然後該旋轉速度再次增至1500至5000rpm以進行10秒至120秒。
原則上,當選擇合適之性質,可能在施加該塗料組成物後立即施加該光阻。
較佳地,然而,在施加該液態塗料組成物後,該溶劑係在施加該光阻之前藉由乾燥被移除。此外,此防止在稍後固化步驟中層之龜裂且改良該塗料組成物在該基材上之黏合性。該乾燥較佳在標準壓力下、於50與150℃之間的溫度、在30秒與1小時之間的乾燥時間內加熱地進行。另外較佳地,該乾燥係利用加熱至90-120℃(在1013毫巴)進行5-10分鐘之時間。對應之隨意的乾燥步驟也可被稱為"預先退火"。
在具有隨後乾燥之該塗料組成物的施加後,所得之膜部份地以光阻塗覆。此可藉由施加該塗料在全面積上且之後選擇地將其結構化(例如利用罩方法且隨後移除所要之部位)或藉由光阻之結構化施加(例如經由印刷方法)而完成。進行方式和措施對此技術中之技術人員係已知的,如各別市售光阻之合適性。特佳之商品是得自MicroChemicals GmbH的光阻AZ 1514H。
在部份施加該光阻後,獲得經塗覆之基材,其顯現出經施加在全面積上或在結構中之塗料膜,其轉而部份地被結構化光阻層覆蓋。以結構化光阻覆蓋之塗料膜的部位對應於想要之經著色的塗料,例如對應於該黑色基質。
在部份施加光阻後,以該塗料組成物和該光阻塗覆之基材係以酸處理。令人驚訝地,已發現顯現出所提及之溫度提升的顏料可由未被光阻覆蓋之塗料組成物膜滲出。以 酸處理因此使預先施加之塗料透明。
在本發明背景中之酸據了解意思是無機酸或有機酸。這些是在水溶液中形成質子(H+離子)且具有低於7.0之pH的化學化合物。較佳可用之酸具有pH在1與6之間,另外較佳在1與3之間。較佳可用之酸是氫氯酸、硫酸、磷酸、硝酸、氫氟酸、矽酸、碳酸、乙酸、檸檬酸及苯甲酸。較佳可用之酸是濃度0.3至2.5mol/l之水性草酸和3.0-12.0mol/l之水性氫氯酸(後者對應於10重量%-35重量%)。也可能使用上述之酸的混合物。極特別良好之結果係藉由比率為1:2至2:1(體積份)的1M水性草酸和6M水性HCl的混合物達成。
以酸之處理可用任何想要之方式進行。較佳地,經塗覆之基材係浸漬於合適之浸漬槽中。較佳之處理時間或浸漬時間是1至15分鐘,另外較佳是3至5分鐘。以酸之處理另外較佳在標準條件(SATP:25℃,1.013巴)下進行。
該酸處理導致所述之氧化物顏料由該塗料滲出(參考圖1)。此在合適位置上留下以該無機黏合劑為底質之酸不可溶的塗料。其稍微多孔性的表面優先地適合另外塗料(特別是抗反射或抗指紋塗料)的施加。
為獲得對應較佳之具有無色無機塗料的經塗覆基材,該光阻因此在酸處理後被移除且其餘之塗料被固化。較佳地,該光阻可藉由溶解在有機溶劑中而移除。更佳地,該光阻可利用溶劑(例如丙酮)移除。
然而,特別平滑且因此同樣較佳之層是當在該酸處理後已經清除顏料的塗料被部份地或完全地(較佳是完全地)被移除時的結果。該不含顏料的無機塗料較佳可利用鹼移除。
在本發明背景中之鹼包含在水溶液中形成氫氧離子(OH-離子)且具有pH大於7.00之化學化合物。較佳可用之鹼具有pH在8與14之間,另外較佳在11與14之間。較佳使用之鹼是濃度0.02至1.0M之水性NaOH。
以鹼之處理可用任何想要之方法進行。較佳地,該經塗覆之基材浸漬於合適浸漬槽中。較佳之處理時間或浸漬時間是10秒至5分鐘,另外較佳是10至90秒。該以鹼之處理另外較佳係在標準條件下進行。
在本發明之同樣較佳的具體例中,在該酸處理後,該不含顏料之塗料部份地(參考圖2)或完全地(參考圖3)移除,然後該光阻被移除且最後其餘塗料被固化。特別平滑且因此特別較佳之塗料是當該不含顏料之塗料被完全移除後的結果。
隨後之固化被進行,不管該不含顏料之塗料是否被部份地或完全地移除,較佳地係在1013毫巴壓力,於200℃至800℃之溫度經1分鐘至1小時之時間,較佳地,在300-400℃之溫度經1-10分鐘之時間。
本發明另外提供可藉由根據本發明之方法製造之結構化層。
本發明另外提供可藉由根據本發明之方法製造之層在 電子組件及汽車建構中的用途。
圖1:由塗料之氧化物顏料的酸滲出。
圖2:不含顏料之塗料的部份移除。
圖3:不含顏料之塗料的完全移除。
實例 實例1:構成該溶膠-凝膠基質
‧TEOS(15.44wt%)及MTES(66.18wt%)被混合。
‧隨後添加的是去礦質化之H2O(9.18wt%)和Hordaphos CCMS磷酸酯(0.02wt%)。
‧該混合物在攪拌器板上攪拌過夜。
‧然後,再次添加去礦質化之H2O(9.18wt%)。
‧該溶膠-凝膠混合物熟成2天(伴隨攪拌)。
實例2:分散液之製造
‧起初饋入1-甲氧基-2-丙醇溶劑(57.85wt%),以稀釋該溶膠-凝膠混合物至合適固體濃度。
‧然後,添加15.03wt%之該溶膠-凝膠混合物。
‧添加TEGO Dispers 710分散及潤溼用添加劑(2.10wt%)。
‧最後,添加得自Kremer Pigmente GmbH & Co.KG之尖晶石黑"最深黑(Fe,Mn)(Fe,Mn)2O4"(量25.02wt%)。
‧為供利用經攪拌之混合器(Scandex)的分散,添加約30克之氧化鋯研磨用珠(大小為0.4至0.6mm)。
‧該分散混合物在該經攪拌之混合器中被分散至少2小時,但較好是10小時。
‧在該分散後,該研磨用珠係藉由沉積或過濾移除。
實例3:基材塗覆
‧使用玻璃基材以作為待塗覆之基材。
‧在塗覆之前,該玻璃基材以有機溶劑(異丙醇)清潔,以DI水沖洗,然後以氮吹乾。
‧該分散液係利用具有以下參數之旋轉塗覆施加:在500rpm 10秒,在2000rpm 30秒。
‧該結構化之前是預烘乾步驟,以逐漸移除該溶劑且防止層之龜裂(在該熱板上於100℃ 10分鐘)。
實例4:光阻之施加;UV曝光
‧利用旋轉塗覆方法,將得自MicroChemicals GmbH之光阻AZ 1514H施加至經塗覆的玻璃基材,其具有下列參數:在2000rpm 30秒。
‧該固化係在該熱板上於180℃進行80秒。
‧在該固化後,該基材係在光罩對準曝光機中,透過 光罩,曝於UV光10秒。
實例5:顯影
‧該經曝光之玻璃基材在含有得自MicroChem GmbH之AZ Developer之浴中顯影2.5分鐘。
‧之後,該玻璃基材係以DI水沖洗且以氮吹乾。
實例6:結構化
‧在第一步驟中該玻璃基材係於由1M草酸和20%之水性氫氯酸(1:1)組成的浴中處理5分鐘。
‧之後,該玻璃基材係以DI水沖洗且以氮吹乾。
‧在第二步驟中該玻璃基材係於由0.5M氫氧化鈉溶液組成之浴中處理40秒。
‧之後,該玻璃基材係以DI水沖洗且以氮吹乾。
實例7:固化
‧固化係在熱板上於350℃進行5分鐘。

Claims (14)

  1. 一種結構化塗料的製造方法,其中a.將包含下列物質之塗料組成物施加至基材:i.至少一種無機黏合劑,ii.至少一氧化物顏料,其基於1克物質,於標準條件下,在添加由15毫升之1M草酸和15毫升之20%之水性氫氯酸構成的混合物之後,導致溫度提升至少4℃,及iii.至少一溶劑,b.以光阻至少部份地塗覆所得之塗料組成物膜且c.以酸處理以該塗料組成物和該光阻塗覆之該基材。
  2. 如申請專利範圍第1項之方法,其中該無機黏合劑具有通式SiaR1 bOc(OR2)d,其中a≧2、b≧0、c≧1、d≧5且R1和R2=有機基團。
  3. 如申請專利範圍第1或2項之方法,其中該顏料是以氧化態大於1之(半)金屬之混合型氧化物為底質之顏料及/或以氧化態各為1或更大之至少二種(半)金屬的至少二種混合型氧化物為底質的顏料。
  4. 如申請專利範圍第3項之方法,其中彼是混合型鐵-錳氧化物。
  5. 如申請專利範圍第4項之方法,其中彼是含銅之混合型鐵-錳氧化物。
  6. 如申請專利範圍第5項之方法,其中該混合型鐵-錳氧化物可經由煅燒氧化錳(II)、氧化錳(III)、氧化鐵(II)和氧化鐵(III)和氧化銅(II)獲得。
  7. 如申請專利範圍第6項之方法,其中該顏料係指定為具有Colour Index名稱Pigment Black 26之顏料群。
  8. 如申請專利範圍第1項之方法,其中該氧化物顏料之比例以該組成物之總質量為基準計是10重量%-50重量%。
  9. 如申請專利範圍第1項之方法,其中該至少一種溶劑係選自醇、烷基酯、烷氧基醇及/或烷氧基烷基酯。
  10. 如申請專利範圍第1項之方法,其中使用之該酸是濃度0.3至2.5mol/l之水性草酸、3.0至12.0mol/l之水性氫氯酸或具有1M水性草酸與6M水性HCl之體積比率為1:2至2:1的比例的混合物。
  11. 如申請專利範圍第1項之方法,其中在該酸處理後a.移除該光阻且b.固化殘餘之塗料。
  12. 如申請專利範圍第1項之方法,其中在該酸處理後a.部份地或完全地移除不含顏料之塗料,b.移除該光阻且c.固化殘餘之塗料。
  13. 一種結構化塗料,其可藉由如申請專利範圍第1至12項中之任一項的方法獲得。
  14. 一種如申請專利範圍第13項之結構化塗料於電子組件或汽車建構中的用途。
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EP3191422A1 (de) 2017-07-19
KR20170053627A (ko) 2017-05-16
JP6560747B2 (ja) 2019-08-14
TWI671369B (zh) 2019-09-11
WO2016037887A1 (de) 2016-03-17
RU2660664C1 (ru) 2018-07-09
DE102014218300B3 (de) 2016-01-07
CN106687618A (zh) 2017-05-17
US10479722B2 (en) 2019-11-19
EP3191422B1 (de) 2018-06-20
US20170305784A1 (en) 2017-10-26

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