TWI248949B - Plastics stabilized with zinc oxide-containing, abrasion-resistant multilayers - Google Patents
Plastics stabilized with zinc oxide-containing, abrasion-resistant multilayers Download PDFInfo
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- TWI248949B TWI248949B TW90108223A TW90108223A TWI248949B TW I248949 B TWI248949 B TW I248949B TW 90108223 A TW90108223 A TW 90108223A TW 90108223 A TW90108223 A TW 90108223A TW I248949 B TWI248949 B TW I248949B
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- zinc oxide
- layer
- coating
- resistant
- sol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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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
- 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
- C09D183/00—Coating 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
- C09D183/14—Coating 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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
- C09C1/04—Compounds of zinc
- C09C1/043—Zinc oxide
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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
- 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
- C09D183/00—Coating 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
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31765—Inorganic-containing or next to inorganic-containing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Wrappers (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
經濟部智慧財產局員工消費合作社印製 Ϊ248949 A7 ^---------- 五、發明說明(1 ) 本發明涉及採用含氧化鋅的对磨多層穩定的塑料。 許多塑料為了在戶外使用必須採用適宜的紫外線 (UV )吸收劑進行防護以防降解。實施該項措施的方 法,可以採用,例如,將UV吸收劑加到整個塑料材料 5中。還能夠採用含UV吸收劑的塗層來防護塑料,該塗層 例如可以借助於共擠出或者採用濕化學方法來塗布。 一般說,塑料可以通過使用有機UV吸收劑有效地來 防護。但是,在經受很長時間的UV幅射(如陽光)時, 有機UV吸收劑本身會緩慢降解,因此失去其防護作用。 10另外,氣候的作用(受潮,高溫以使UV吸收劑受到 損失,這是因為滲移和浸出而引起的。 另一方面,無機uv吸收劑,例如氧化鋅,沒有上述 有機UV吸收劑的缺點。而且,如果所用的氧化鋅(納米 Zn〇)的粒度足夠小,那末可以自此產生高透明層。這種 、 I5 氣化鋅鈉米粒子的製造敛述在,例如’德國專利申請DE 19907704.5 。 如果塑料材料除了需要uv、輻射方面的防護之外,還 需要抗機械磨損方面的防護,那末這可通過施塗抗磨塗層 來貫現。特別是在用諸如聚碳酸g旨之類的塑料代替玻璃 20時,就需要極其耐磨。以前敘述過一些塗層,它們能夠滿 足這些嚴格的技術要求。其實例可見述於US — A 5677410、DE —A 196 03 241、WO 98/52992、EP - A 947520、DE-A 45 38 361 和 EP —A 0 263 428。然而,將 氧化鋅加入這些塗層之中常常會引起一些問題,因為這會 -3 _ 本紙張尺度適用中國國家標準(CNS)A4規格(210 x 297公爱)~yui(JTS " ' -------It--------- (請先閲讀背面之注意事項再填寫本頁) f 1248949
經濟部智慧財產局員工消費合作社印製 使耐磨性下降。另外,相容性不適當也會引起塗層中的氧 化鋅納米粒子發生聚集或附聚,這樣會引起塑^發生混 濁。如果塗料溶液含有酸性催化劑(在採用溶膠〜凝膠溶 液的情況下),氧化鋅就會溶解,不再起uv防護作用。 5 本發明的目的是提供一種具有耐久UV輻射防護性能 和耐磨表面的塑料,其中不發生在生產塗層中所遇S的2 述缺點。 現在々人I異地發現,採用一種多層結構,复含有至 少一層含ZnO的層和至少一層耐磨層,能夠製造出具有 10 上述性能的塑料。 本發明涉及一種具有塗層的塑料製品,所述塗層含有 至少一層含氧化鋅的層,和至少一層耐磨外層。
採用粒度<30nm的ZnO納米粒子作氧化鋅原料。所 優選的ZnO納米粒子制劑是可以與塗覆溶液和/或塗覆溶 15液的至少一種組分直接混合的、而且不發生絮凝或其它分 離現象的制劑。特別優選使用德國專利申請DE 一 A 1990770 4.5所敘述的ZnO納米粒子。 在本發明範圍内,耐磨塗層是達到下述標準的塗層, 在採用泰伯爾氏耐磨試驗機(IS0 3537 , 1〇〇〇周期,每輪 20負荷5〇〇g,CS—10一F磨蝕介質)劃痕之後,在劃痕痕跡 上的散射光(按ASTM D 1003)顯示為20%以下,優選 10%以下,更優選5%以下。相比之下,市售聚碳酸酯 (Makrolon,由Bayer公司出品)。在泰伯爾氏耐磨試驗 機試驗僅100周期之後,在劃痕痕跡上的散射光大於3〇 -4- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) --------------------訂---------線 (請先閲讀背面之注意事項再填寫本頁) 1248949 A7 五、發明說明( 10 15 20 耐磨塗層的例子是,特別應提及,熱或輻射固化溶膠 一凝膠材料。該溶膠一凝膠材料一般以低分子量有機烷氧 基矽烷和/或有機矽烷醇的縮合物為基礎,這些縮合物在 基材上可以通過進一步縮合和/或聚合(在不飽和或環氧 官能有機甲矽烷基殘餘物的情況下)而固化,從而產生高 耐磨塗層。這些溶膠一凝膠材料反覆見述於文獻中,例2 US-A 5677410、DE-A 196 03 241、w〇 98/52992、Ep -A 947 520、DE-A 45 38 361 和 EP~ A 0 263 428。 、在本發明範圍之中,含有氧化辞的塗料,除了適宜的 基料之外’優選含有粒彳$主要為丨—槪㈤的氧化辞粒子, 這樣在可見光範圍中觀察塗層就沒有值得注意的散射或吸 收特別適於氧化鋅的基料是僅僅稱微呈現或者沒有 化分解趨勢者。塗料含有卜5Qwt%氧化辞。 按照本發明的在塑料上的最簡單的多層結構含有含 化鋅的層和财磨外層。然而,也可以施塗另外的層。 在本發明的-個實施方案中,含有氧化辞的和耐 樣得到的’先將含氧化鋅的層塗布在基材上,快 速揮备成分如溶料任縣發除去。然後 、 進行或不進行進—步固化,最後進行熱綠射固化科, =布含氧化辞的層,以便改善枯合性。然而i能 夠使用偶聯劑本身作氧化鋅粒子的枯合劑,如此不再需要 閱 訂 | -5- 本紙張尺度適用中國格⑵。χ 經濟部智慧財產局員工消費合作社印製 1248949 A7 __ B7 五、發明說明(4) 另外的塗層步驟。 另外還能夠以純無機層或者主要是無機層的形式,以 氣相沉積按照本發明的多層結構的财磨層。無機層可以含 有諸如Si〇2、Ti〇2、Al2〇3或者其混合物。以這種方式, 5可以進一步增加耐磨性,和/或,可以改善減反射作用。 能夠採用各種有機矽烷實現水分散體中的納米結晶氧 化鋅的表面改性。有機矽烧必須含有至少一種縮合交聯殘 基。這些殘基的例子是烷氧基殘基,特別是曱氧基或乙氧 基殘基,矽烷醇或乙醯氧基殘基。有機矽烷的有機殘基可 10以是脂族的,芳族的或任選脂族或芳族取代的。這些有機 矽烷的例子包括曱基三乙氧基矽烷或3一環氧丙氧基丙基 三曱氧基矽烷。 在本發明的一個實施方案中,水分散體中的納米氧化 鋅的表面改性,通過加入有機矽烷(純的或者溶於適宜溶 15劑中)以及在15°C和100°C之間的溫度下攪拌反應混合物 來進行。為了防止附聚,優選也可以在超聲波存在下進行 反應。 在固化塗層中有機矽烷和納米氧化鋅的比通常以達到 這種程度為準,即,在塗布到諸如塑料、破璃、陶瓷材 20料、金屬等基材上,經乾燥/固化之後,能夠得到透明塗 層。上述比例為納米氧化鋅1 —50wt%,有機石夕烧為5 — 90wt% 〇 特別優選的基材是透明基材。 含有氧化鋅的、耐磨層可以通過所有常用方法進行塗 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公g ) --------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 1248949 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(5) 布,包括離心塗布、喷塗、浸塗、流塗、刮塗或刷塗。 可以施加按照本發明的多層結構的基材的例子是塑 料,例如聚醯胺、聚乙烯、聚丙烯、聚甲基丙烯酸曱酯、 聚苯乙烯、聚乙烯基環己烷及其共聚物、丙類腈/丁二烯/ 5苯乙烯共聚物(ABS)、聚氯乙烯、聚碳酸醋或其共混 物。 按照本發明的具有耐UV和耐磨塗層的透明塑料可以 用作,例如玻璃的替代品,用於玻璃鑲嵌建築或車輛(小 汽車、公共汽車、卡車、火車) ίο 财劃痕塗料1 : 耐劃痕塗料由溶膠一凝膠溶液製造,其組成為6.8% 環一{Si〇CH3〔(CH2)2Si(CH3)2OH〕}4,32.1%原硅酸四乙 醋,9·6%2—丁醇鋁,5.1%乙醯乙酸酯,12.6%水,32.8 % 1 —甲氧基一2 —丙醇和1%光穩定劑(Tinuvin 384, 15 ciba公司出品)。製造方法見述於EP-A 947520。環一 {SiOCH3〔(CH2)2Si(CH3)2〇H〕}4 的製造如 US-A5 880 305 所述。下文稱環一 {SiOCH3〔(CH2)2Si(CH3)2〇H〕}4 為 〇4 —石夕炫醇。 耐劃痕塗料2 · 2〇 將l〇g四乙氧基矽烷(TEOS)溶於5.5g 1—甲氧基— 2一丙醇中,與l.Og 0.1N對曱苯磺酸混合,同時攪拌, 再授雜另外30min。然後再加入另外l.Og 〇.IN對甲苯石黃 酸,與攪拌另外60min (預水解)。3.〇g仲丁醇鋁溶解在 l.Og 1—甲氧基一 2 —丙醇中,與1.6g乙醯乙酸酯混合, 太紙張尺庶谪用Τϋ家標準(CN^A4規格(21〇 X 297公釐) --------------------- 訂---------線 (請先閱讀背面之注意事項再填寫本頁) . 1248949 A7 B7 五、發明說明(6) 同時用冰冷卻,在5。〇下加入到預水解物中。一旦加完, 加入另外2.〇g 〇1N對甲苯磺酸和24g —矽烷醇溶 解在3.8gl甲氧基~2—丙醇中的溶液,再授拌6〇min。 借助於離心塗布各層,其中在各種情況下,總指出最 5兩轉速(單位:rPm)和最高轉速下的保持時間(以秒為 單位)。 採用泰伯爾氏耐磨試驗機試驗偵測耐磨性(ISO 3537 ’ 1000周期,每輪500g,CS—10 — F磨蝕介質)和 隨後測定散射光(ASTM D 1003 )。塗層的 Makrolon 10 3103的耐受性通過按照astM G 154 — 97 (周期4)的 QUV — A和按照din 53 384的QUV-B天然老化進行測 定。如同聚碳酸酯的汜黃測定一樣,氾黃指數b*通過mN 6174反射進行測定。離心步驟用實驗室離心機(Heraeus 製造,VariofugeRE),採用半徑20,4cm的轉筒。 15 多層塗層的一個實施方案如下: 經濟部智慧財產局員工消費合作社印製 耐劃痕層_ 含ZnO層_ 偶聯劑(底層) 聚碳酸酉旨 --------------------訂---------線 (請先閲讀背面之注意事項再填寫本頁) 在獲得含ZnO層與聚碳酸酯的足夠的粘合性時,可 以免除偶聯劑(底層)。另外,也能夠應用偶聯劑作Zn〇 20 粒子的基料,從而有如下層結構: 太紙張尺唐i®用中國國家標準(CNQA4梘格(210 X 297公釐) 1248949 A7 B7
非表面改性的納米氧化鋅的製造 將59〇g醋酸辞脫水物 2〇〇〇α 隹6L燒瓶中室溫下攪拌入 ⑼刀析級Me0Ii中。西法缺从 時,在A;g[7 φ •曰次鋅沒有完全溶解。與此同 5 10 15 經濟部智慧財產局員工消費合作社印製 20 八㈣L衣造296·1§分析級刪(86·6%)在100他 斤e〇H中的K0H溶液。然後將U)_ KOH溶液加 入到《鋅料巾。在以前未_的醋_接著被溶解。 二後加入其餘K〇H溶液。立即出現鬆散白色沉殿,在授 拌、力7〇mm之後成為半透明狀。然後加熱所得溶膠25min 至沸點,此後切斷熱源。在靜置過夜之後,形成白色沉殿 物。攪拌之後’離心分離出該沉殿物(3Qmin,5刪 rpm曰)。_ 295.9g凝膠狀殘渣,χ—射線衍射作為唯一 結晶相的所得氧化辞。使凝膠狀殘渣與439.3g二氯甲烷混 口,進行振蕩直至沉澱完全分散。所得分散體是半透明 的,沉降穩定幾個月。 實例2 非表面改性納米氧化鋅的製造,適用於採用有機矽烷 在水分散體中進行表面改性。 將590g醋酸鋅脫水物在6L燒瓶中懸浮在2〇〇〇g分 析級MeOH中,並加熱至60°C。醋酸鋅被溶解。與此同 時,在冷卻下製造302g分析級KOH (8屯7%)在1〇〇〇g 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1248949 A7 B7 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 五、發明說明(8) 分析級MeOH中的KOH溶液。然後在60°c下將KOH溶 液加入醋酸鋅溶液中。立即出現鬆散白色沉澱,在約5min 之後成為半透明的。在60°C下攪拌另外80min,在攪拌時 間結束時,該批料為乳白色。除去熱源之後,進行攪拌另 5外210min。靜置過夜之後,排出3243g,並用l〇〇〇g分析 級MeOH補充。然後攪拌溶膠2〇min。沉降時間達45min 後’排出768g上層清液,補充入500g分析級MeOH。再 攪拌30min溶膠,沉降40min之後,再排出745g上層清 液,補充入500g分析級Me0H。接著最後攪拌溶膠30min ’然後離心分離(3〇min,5000 rpm),得到潷析出 的253.15g凝膠狀殘渣,χ_射線衍射研究顯示為作為唯 一結晶相的所得氧化鋅。 實例3 採用自實例1的非表面改性的納米氧化鋅的雙層結構 ,仲丁醇紹溶解在5.9g 甲氧基—2二醇 ,至下加入155g乙醯乙酸醋,該溶液加熱至 cj所得溶液中滴加17.3§ D4_魏醇和3 — 、=—2—丙醇,同時進行授拌。在加完之後,將所得 浴液在60t下再授拌此(銘/m石夕貌前 ^付 =’將58.〇g四乙氧基石夕院(聰)溶於5。;= (預水解)。隨後,預水解物在授 y祝拌此 倾-錢醇前體混合,再授拌所得溶液^ =室溫的紹 94.8§按照實例1製造的纟 ·'、'後,加入 4减鋅分散體(25 wt% 10 15 20
1248949 經濟部智慧財產局員工消費合作社印製 樣品 No. oh 250h 500h 750h ΤδοοϊΓ HFC 528-1 2.9 X X X x ^ HFC 528-2 2.8 1.8 X X x '^ HFC 528-3 3.2 X 2.1 X X HFC 528-4 2.5 X X 1.9 x ^ HFC 528-5 2.9 X X X —— 2.7 A7 B7 五、發明說明()
Zn0)、5.〇g去離子水和另外20.7g在38.1g 1—曱氧基 一2—丙醇中的d4一矽烷醇,在室溫下攪拌反應混合物另 外 lhr 〇 為改善枯合性’通過旋轉塗布(⑻rpm,2〇sec), 5採用羥曱基三乙氧基矽烷(HMTS,在乙醇中含50 wt /^) 塗布5塊聚碳酸醋板(Makrolon Bayer公司出 口口)。並在130 C下加熱處理lhr。然後,把含有氧化辞 的塗料溶液喷塗到以上述方法預處理過的板上;在固化 (lhr,130°C )之後,所得板進行quV — A天然老化試 10 驗。 表1茱總了 QUV —A天然老化結果,並以圖示出。 15 實例4 採用3—環氧丙氧基丙基三曱氧基矽烷在水分散體中 進行自貫例2的納米氧化鋅的表面改性 將l〇g按照貫例2製造的納米氧化鋅凝膠(含有約μ -11 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) -------------------ί 訂---------線 (請先閱讀背面之注意事項再填寫本頁) 1248949 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(10) wt%氧化辞和約40 wt% MeOH,蒸餾水,無機鹽)與 9〇g条餘水混合,劇烈攪拌,直至得到半透明的分散體。 然後’ l〇g 3 —環氧丙氧基丙基三甲氧基矽烷加入其中, 在70°C下於超聲波浴中進行;然後再加熱反應混合物經 5 30mm至70°C同時用超聲波處理(反應容器不密封,使產 生的甲醇逸出)。在冷卻之後,得到無色/乳狀的分散體/ 乳狀液。 實例5 具有表面改性納米氧化鋅的三層結構(採用泰伯爾氏 10 财磨5式驗測定耐磨性) 為改善枯合性,在每種情況下,第一 Makrolon板 (l〇X 10cm)先用3—氨基丙基三甲氧基矽烷(AMMO, 200 ipm,20 sec)塗布,第二塊板用羥基甲基三乙氧基矽 院(HMTS,在乙醇中含50 wt%,1000 rpm,20 sec)塗 15布,均在UOt:下熱處理30min。然後,採用薄膜流延機 (隙高30μηι)向兩塊Makrolon板上塗布按照實例4製造 的納米氧化鋅分散體,並在n〇ac下固化30min。最後再 塗布耐劃痕塗層2 ( 500 rpm,20 sec),在80°C下固化 lhr’然後在i3〇°c下固化ihr。在泰伯爾氏耐磨機劃痕之 20後’發現散射光增量4.0 % ( AMMO )和3.5 % (HMTS )。 與其比較,市售具有劃痕塗層的聚碳酸酯(如 MargardMRlO)散射光增量約12%。 實例6 -12- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公楚) I--I----I-----------訂---------線 <請先閱讀背面之注意事項再填寫本頁) 1248949 A7 5
ο IX —— __— B7_______發明說明(11 ) 具有表面改性納米氧化辞的雙層結構(採用quv—b 天然老化測定耐UV性) ^為改善粘合性,先採用羥基甲基三乙氧基矽烷(在乙 醇中含 50 wt%,1000 rpm,20 sec)塗布 Makr〇1〇n 板 (7.5X15cm),然後在13(TC下加熱處理lhr。然後,採 用旋轉塗布(400 rpm,20 sec)塗布按照實例4製造的納 米氧化鋅分散體,在130°C下固化ihr之後,最後還塗布 耐劃痕塗層2,在80°C下固化ihr,在13(rc下lhr。然後 採用QUV — B天然老化試驗測定耐uv性和耐天然老化 性。象測定聚碳酸酯氾黃那樣,測定氾黃指數b*。與其比較,未塗層聚碳酸酯(Makrolon 3103, Bayer公司出品)氾黃指數b*在5〇〇hr之後為18·5。在表2中彙總了 QUV—B天然老化結果。 , (請先閱讀背面之注意事項再填寫本頁) -----
5 IX 訂---------線. 經濟部智慧財產局員工消費合作社印製 20 樣品 oh 250h 500h Makrolon 3103 採用納米ZnO 1.3 1.4 2.5 Makrolon 3103 11.2 18.5 實例7 具有實例1的未表面改性的納米氧化鋅的三層結構 (採用泰伯爾氏耐磨試驗測定耐劃痕性) 首先,將29.5g仲丁醇鋁溶解在5.9g 1—曱氧基一2 -13 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1248949 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(12) 一丙醇中,鱼 1 ς e • g乙酿乙酸自旨混合,並加熱。向所得溶 解中滴加17.3g在3l.8g 1-甲氧基-2—丙醇中的D4 — 夕烧醇叫授拌。在加完之後,纟60°C下再進行授拌 lhr (鋁/D4—矽烷醇前體)。 5 f此同時,將5&〇g TEOS溶解在50·3§ ! 一丁醇 中/、5 〇g 〇·1ΪΝί對甲苯磺酸混合,同時進行授拌,再 授拌6〇mm (财解)。然後雜/ΙΜ —魏_體和預水 解物/心並再授拌60min。最後,力口入94.8g ΖηΟ溶 膠⑶wt%,在二氯甲烷中,自實例1製造)和5你去 1〇離子水,然後再加入20·%在38.1g 1-甲氧基_2_丙 醇的D4一石夕烷醇。接著,再授拌所得溶液60min,然後進 行塗布。 為改善所得氧化鋅塗料溶液對聚碳酸醋的枯合性,通 過旋轉塗布(i_rpm,2Gsee),採㈣基甲基三乙氧 I5基矽烷(HMTS,在乙醇中含5〇 wt % )塗布5塊
Makrdon 板(100 mmX1〇〇 mm),在 13〇。〇下熱處理 lhr 〇 然而,可以採用其它化合物作偶聯劑,如丙烯酸酯' 丙稀酸醋烧氧基石夕烧、甲基丙稀酸醋、甲基丙稀酸醋烧氧 20基矽院、氧基矽烧或甚至聚氨酯。 在塗布偶聯劑(底層)之後,通過旋轉塗布(2〇〇〇 ipm,20 sec)將氧化鋅塗料溶液塗布到Makr〇1〇n板上, 然後在130 C下熱固化30min。 然後通過旋轉塗布(_ rpm,20 sec)塗布耐劃痕塗 -14- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公复)------ --------訂---------線 (請先閱讀背面之注意事項再填寫本頁)
Claims (1)
1248949 年/5 補充 B8 C8 D8 六、申請專利範圍 專利申請案第90108223號 ROC Patent Appln. No.90108223 修正之申請專利範圍中文本-附件(一) Amended Claims in Chinese - Enel. (Ϊ) 5 (民國94年8月io日送呈) (Submitted on August 3〇 ,2005) 1· 一種具有塗層的塑料製品,所述塗層含有至少一層含 氧化鋅的層和至少一層耐磨之含溶膠-凝膠材料的外 10 層,其特徵在於該溶膠-凝膠材料係以低分子量有機烷 氧基石夕烧及/或有機石夕烧醇的縮合物為基礎,且氧化鋅 具有主要粒度為1 — 30 nm。 2·如申請專利範圍第1項的塑料製品,其中氧化鋅粒子 採用3—環氧丙氧基丙基三曱氧基矽烷進行表面改 15 性。 3 · —種塑料製品’含有透明塑料和塗層,所述塑料選自 聚醯胺、聚乙烯、聚丙烯、聚甲基丙烯酸甲酯、聚苯 乙烯、聚乙烯基環己烷及其共聚物、丙烯腈/丁二烯/苯 乙烯共聚物(ABS)、聚氣乙烯、聚碳酸酯及其共混 20 物,所述塗層含有至少一層含氧化鋅的層和至少一層 經濟部智慧財產局員工消費合作社印製 耐磨外層,其中耐磨塗層含溶膠一凝膠物料且含氧化 辞的層含有粒度主要為1 一3Onm的氧化辞粒子。 4·如申請專利範圍第3項的塑料製品,其中氧化鋅粒子 採用3 —環氧丙氧基丙基三甲氧基矽烷(3_ 25 glycidoxypropyltrimethoxysilane)進行表面改性。 -16 - 90101B-接 2 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公爱)
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DE2000118429 DE10018429A1 (de) | 2000-04-14 | 2000-04-14 | Kunststoffe die mit zinkoxidhaltigen, abriebfesten Multischichten stabilisiert sind |
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DE10102739A1 (de) * | 2001-01-23 | 2002-07-25 | Bayer Ag | Verfahren zur Herstellung von Sol-Gel-Kondensaten auf Basis polyfunktioneller Organosilane sowie deren Verwendung |
DE10212121A1 (de) * | 2002-03-15 | 2003-09-25 | Bayer Ag | Verfahren zur Herstellung von nano-Zinkoxid-Dispersionen stabilisiert durch hydroxylgruppenhaltige anorganische Polymere |
DE10244212A1 (de) * | 2002-09-23 | 2004-03-25 | Bayer Aktiengesellschaft | Zinkoxiddispersionen in halogen- und wasserfreien Dispersionsmedien |
DE10324305A1 (de) * | 2003-05-30 | 2004-12-16 | Bayer Ag | Verfahren zur Herstellung sphärischer Zinkoxidpartikel |
DE102005056622A1 (de) * | 2005-11-25 | 2007-05-31 | Merck Patent Gmbh | Nanopartikel |
BRPI1014426A2 (pt) * | 2009-06-24 | 2016-04-12 | Basf Se | processo para a preparacao de nanoparticulas de oxido de zinco modificadas, nanoparticula de oxido de zinco, formulacao liquida ou solida, materiais organicos inanimados, usos de corpos moldados, e de nanoparticulas de oxido de zinco modificadas, e, processo para estabilizar materiais organicos inanimados contra o efeito da luz, radicais livres ou calor |
CN102875956B (zh) * | 2012-09-20 | 2014-04-23 | 吴江市天源塑胶有限公司 | 一种高耐磨工程塑料 |
TR201617722A2 (tr) * | 2016-12-02 | 2017-02-21 | Tuerkiye Sise Ve Cam Fabrikalari Anonim Sirketi | Anorgani̇k nanoparti̇küller i̇çeren saydam uv koruyucu sert kaplama ve kaplamali cam |
CN109134903B (zh) * | 2018-08-14 | 2021-06-18 | 安徽久升户外用品有限公司 | 一种电瓶车防雨遮阳蓬用金刚石微粉-二氧化钛填充制备改性聚碳酸酯板材的方法 |
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US5693422A (en) * | 1990-10-02 | 1997-12-02 | Ppg Industries, Inc. | Silica-free UV-absorbing abrasion resistant coatings |
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US5747152A (en) * | 1993-12-02 | 1998-05-05 | Dai Nippon Printing Co., Ltd. | Transparent functional membrane containing functional ultrafine particles, transparent functional film, and process for producing the same |
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US5677410A (en) | 1995-05-16 | 1997-10-14 | Bayer Ag | Carbosilane-dendrimers, carbosilane-hybrid materials, methods for manufacturing them and a method for manufacturing coatings from the carbosilane-dendrimers |
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DE19711650C1 (de) | 1997-03-20 | 1998-06-10 | Bayer Ag | Verfahren zur Herstellung SiOH-funktioneller Carbosilan-Dendrimere |
JPH11179837A (ja) * | 1997-12-24 | 1999-07-06 | Asahi Glass Co Ltd | 被覆成形板およびその製造方法 |
US6319594B1 (en) * | 1998-03-17 | 2001-11-20 | Dai Nippon Printing Co., Ltd. | Low reflective antistatic hardcoat film |
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US6261694B1 (en) * | 1999-03-17 | 2001-07-17 | General Electric Company | Infrared reflecting coatings |
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PT1146069E (pt) | 2007-12-20 |
CZ20011350A3 (cs) | 2001-12-12 |
DE10018429A1 (de) | 2001-10-18 |
JP2002012685A (ja) | 2002-01-15 |
ES2292504T3 (es) | 2008-03-16 |
KR20010100900A (ko) | 2001-11-14 |
CA2343626A1 (en) | 2001-10-14 |
MXPA01003700A (es) | 2002-06-04 |
EP1146069A2 (de) | 2001-10-17 |
PL203808B1 (pl) | 2009-11-30 |
EP1146069B1 (de) | 2007-09-12 |
US20010044020A1 (en) | 2001-11-22 |
HK1042717A1 (en) | 2002-08-23 |
CN1328075A (zh) | 2001-12-26 |
CA2343626C (en) | 2008-07-29 |
DE50112983D1 (de) | 2007-10-25 |
ATE373038T1 (de) | 2007-09-15 |
PL347050A1 (en) | 2001-10-22 |
US6884501B2 (en) | 2005-04-26 |
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