201204683 六、發明說明： 【發明所屬之技術領域】 發明領域 本發明係關於一種使用熱固性塗 板之方法及如此所得之陶瓷基板。本 種用於陶瓷基板之塗覆組成物。 【先前技術】 發明背景 通常陶瓷基板諸如瓷磚或衛浴設 高度裝飾效果及耐刮性、耐磨性及溶 大量能源。 US 4143181係關於一種施用由底 之塗覆層至玻璃基板上之方法。底塗 衝擊而受損，該底塗層係呈包含由羥 熱固性連結劑之溶液而施用；該粉末 抗苛性蘇打之抗性，也包含由涇官能 性連結劑。 DE 1 974892 7係關於一種於耐熱 包含聚酯或聚胺基甲酸乙酯樹脂之熱 飾性或功能性塗層之方法。基板加熱 軟化點溫度。隨後粉末施用至已加熱 基板本身爲電絕緣。然後基板移至烤 末。舉例說明一種二塗層系統：第一 酯TGIC系統係以200微米厚度施用及拓 覆組成物塗覆陶瓷基 發明進一步係關於一 備係塗覆以釉質俾有 劑耐性。但上釉耗用 塗層及頂塗層所組成 層意圖保護基板免於 官能基聚酯所組成之 頂塗層係用來改良對 基聚酯所組成之熱固 性非金屬基板上獲得 固性組成物的耐刮裝 至高於欲施用塗層之 基板而未使用電場， 爐用以硬化熱固性粉 黑粉末塗層，亦即聚 I化10分鐘。隨後施用 201204683 含黃銅雪花片之相同聚酯TGIC系統所製成的第二透明 層，及又硬化1 〇分鐘來獲得高度裝飾性塗層。 US 6982 1 3 7係關於一種於瓷磚或玻璃上形成彩色影像 之方法，其中該基板首先以已硬化80 %至95 %之透明粉末聚 合物塗覆，然後施加靜電複印彩色影像，最終施用另一層 相同聚合物，然後系統經加熱而達成完全硬化。 此等先前技術塗層皆未獲得高裝飾性光整（finish)，不 具有傑出機械及化學效能，諸如耐刮性及耐化學性。 至目前爲止所提出的光整硬度並不足，特別極高硬度 (3 Η至4H)組合傑出溶劑耐性及熱震耐性構成一項技術挑 mh. 戦。 【發明内容】 發明槪要 發明人今日發現克服部分或全部前述缺點之塗層。因 此本發明係關於一種塗覆陶瓷基板之方法，該方法包含於 基板施用一種粉末塗覆組成物作爲底塗層，該組成物包含 具有羧-及/或羥-官能基之至少一種聚酯，及具有與該聚酯 官能基可起反應之官能基的至少一種硬化劑；硬化該所施 用之組成物；及又施用一層液體塗覆組成物，及藉暴露於 熱而硬化所施用之組成物。 用於此處「陶瓷基板」表示藉加熱作用無機非金屬材 料，諸如土族（earthy)原料所製造之產物。陶瓷基板典型地 主要包含含矽與其氧化物及錯合化合物稱作爲矽酸鹽之材 料。陶瓷基板較佳爲結構性黏土產物，諸如磚、瓷磚、赤 .201204683 土陶器或上釉建築磚。 以陶瓷瓷磚爲佳，特佳爲陶瓷壁磚及陶瓷地磚，尤其 爲陶瓷室內壁磚。 用於此處「藉暴露於熱而硬化」係指物理性乾燥、風 乾及烘乾。以風乾及特別以烘乾爲佳。「風乾」係指一種 自空氣擷取熱量之方法及其中樹脂之某些基團與來自空氣 之氧氣反應而交聯、硬化及乾燥。經常添加催化交聯之有 機金屬鹽或「乾燥劑」。可添加呈金屬錯合物形式之油乾 燥劑來加速乾燥。「烘乾」或「烤乾」或「烤爐烘烤」係 指於交聯劑或硬化劑存在下於中溫或升溫（特別高於9(TC ) 硬化。 「藉暴露於熱硬化」一詞特別排除「藉暴露於輻射硬 化」’藉此可使用熱來熔解樹脂，但需要暴露於光化輻射 及/或紫外光（選擇性地於另一種成分諸如光起始劑存在下） 及/或游離輻射（諸如電子束）用以硬化。 於根據本發明之方法中，液體塗覆組成物優異地係經 熱硬化。 用於本發明之粉末塗覆組成物係呈細粉形式存在，其 係施用在基板上及加熱時形成塗層於陶瓷基板上，於該處 理程序期間’來自該聚酯之至少部分官能基係與該硬化劑 之至少部分官能基反應。 本發明使用之聚酯通常係製自多酸組分，包含自70至 100莫耳％芳香族多羧酸及/或其酐，及自〇至3〇莫耳。/β脂芳 族或環脂族多酸及/或其酐；及製自多元醇組分，包含70至 201204683 100莫耳％脂肪族二醇’及自〇至30莫耳％環脂族二醇及/或 (環）脂族多元醇。「（環）脂族多元醇」表示載有多於兩個-0H 基之環脂族多元醇或脂肪族多元醇。 芳香族多羧酸較佳爲對苯二甲酸及間苯二甲酸及其混 合物。脂肪族二醇較佳係選自新戊二醇、丙二醇、2 -甲基 -1,3-丙二醇、2-乙基-2-丁基-1,3-丙二醇、乙二醇、二乙二 醇及其混合物。 用於本發明之聚酯可爲具有例如自15至100毫克KOH/ 克，較佳自30至70毫克KOH/克酸値（根據D0029300)之羧官 能基聚酯；或可爲具有例如自I5至300毫克KOH/克，較佳 自30至100毫克KOH/克羥値（根據D0067200)之羥官能基聚 酯。以羧官能基聚酯爲佳。聚酯較佳具有藉凝膠滲透層析 術（GPC)使用聚苯乙烯作爲標準品測量得之自600至1 5000 範圍之數目平均分子量（Μη)。較佳Μη爲至少1 1 00。較佳Μη 爲至多8500。 較佳聚酯具有藉差示掃描量熱術，根據ASTM D3418 使用每分鐘20°C之加熱梯度測得之自35°C至80°C之玻璃轉 化溫度（Tg)。可用於本發明之聚酯較佳具有大於50 °C之Tg。 聚酯較佳具有根據ASTM D4287-88之布汝克斐 (Brookfield)(錐/板）黏度係於I75t：測得之5 mPa.s至於 2 0 0 °C測得之1 5 0 0 〇 m P a . s之範圍。 用於本發明之聚酯爲先前技術已知且已經描述用於金 屬塗層。 當羧官能化聚酯係用於本發明時，包含可與此種聚酯 201204683 反應之反應性基團之硬化劑較佳係選自多環氧化合物、含 β-羥烷基醯胺之化合物及其混合物。較佳爲於室溫爲固體 且每分子含有至少兩個環氧基之多環氧化合物。以三縮水 甘油基異氰脲酸酯諸如市售商標名阿拉賴（Araldite) PT8 10、對苯二甲酸二縮水甘油酯與偏苯三酸三縮水甘油酯 之摻合物諸如市售商標名阿拉賴PT910或阿拉賴PT912，及 以雙酚A爲主之環氧樹脂諸如市售商標名阿拉賴GT 7 0 04或 D.E.R 692爲特佳。也可使用得自甲基丙烯酸縮水甘油酯及 /或丙烯酸縮水甘油酯及其它（甲基）丙烯酸單體及選擇性 地，其它烯屬單不飽和單體之含縮水甘油基丙烯酸系共聚 物。較佳丙烯酸系共聚物爲由伊士東化學公司（Estron Chemical Inc)出售及敘述於 WO 91/01748 之 GMA-300。 以含有至少一個，較佳兩個雙（β-羥烷基）醯胺基之β-羥烷基醯胺爲特佳。此等化合物業已說明於例如US 4,727,111 〇 前文敘述之硬化劑通常係以相對於每當量存在於硬化 劑之環氧基或β-羥烷基，自0.25至1.40，較佳自0.60至1.05 當量存在於聚酯之羧基之數量使用。 當使用羥官能化聚酯時，硬化劑較佳係選自嵌段異氰 酸酯交聯劑。嵌段異氰酸酯交聯劑之實例包括以下列成分 爲主者：異佛爾酮二異氰酸酯與ε-己內醯胺嵌段，市售維 它岡（VESTAGON)B 1 5 3 0 、盧可（R u c o ) N I - 2 及嘉吉 (0&以丨11)2400;或甲苯-2,4-二異氰酸酯與^己內醯胺嵌 段，即市售嘉吉24 5 0 ;及酚嵌段六亞甲基二異氰酸酯。 201204683 另一類可用的嵌段多異氰酸酯化合物爲異佛爾酮二異 氰酸酯之1,3-二吖咀-2,4-二酮二聚體與二醇之加合物，其 中該加合物形成中之NCO基對〇H基之比爲約1 : 0.5至1 : 0.9’二吖咀二酮對二醇之莫耳比爲自2: 1至6: 5，加合物 中自由態異氰酸基之含量係不大於8重量％，及加合物具有 約5 0 0至4 0 0 0之分子量及約7 0 °C至1 3 0。(：之熔點。此種加合 物於市面上係以商標名維它岡BF 1540獲得。 相對於每當量存在於硬化劑之（嵌段或非嵌段）異氰酸 基，硬化劑通常係以自0.3至1.4，較佳自0.7至1.2當量存在 於聚酯之羥基之數量使用。 用於本發明作爲底塗層之粉末塗覆組成物除了包含如 前文說明之一種或多種聚酯及一種或多種硬化劑之連結劑 外’可包含其它常用於粉末塗覆組成物的添加劑、塡充劑 及/或顏料。 本發明之較佳實施例中，該以粉末爲主之塗層係添加 顏料。用於根據本發明之方法之粉末塗覆組成物優異地進 ~步包含技藝界眾所周知之至少一種顔料及/或著色劑及/ 或塡充劑。也可於粉末塗覆組成物添加提供特殊效果的顏 料’諸如述於例如DE 19748927及WO 2008/09540之黃銅雪 花片' 金屬顏料及珠光顏料。金屬顏料之實例包括銅、鎳 及/或鋁顏料。另外粉末塗層可爲透明塗層。 用於根據本發明之方法之粉末塗覆組成物較佳包含自 3 0 %至9 7 %重量比聚酯，自3 %至5 0 %重量比硬化劑，自〇 % 至5 0 %，更佳自5 %至3 0 %重量比著色劑及/或顏料及/或塡充 201204683 劑，及自0%至1 0%重量比其它添加劑。 用於根據本發明之方法之粉末塗覆組成物之各組分可 於混合機或掺混機例如轉鼓混合器藉乾摻混混合。然後預 混物通常係於單螺桿或雙螺桿擠塑機內於自7 0 t至1 5 0 °C 範圍之溫度均化。擠塑物冷卻時被碾磨成粉末，較佳具有 自10微米至150微米之範圍之粒徑。 粉末塗覆組成物可藉任一種粉末塗覆法施用至陶瓷基 板。然後粉狀組成物可使用粉末槍諸如靜電電暈（CORONA) 槍或崔伯（TR IB Ο)槍沈積在陶瓷基板上。另一方面，可使用 眾所周知之粉末沈積方法諸如流化床技術。 於根據本發明之方法之較佳實施例中，陶瓷基板例如 瓷磚首先預熱至高於粉末塗覆組成物之玻璃轉化溫度，更 佳基板係預熱至60 °C至200 °C溫度。然後粉末塗覆組成物施 用至已預熱的基板，較佳未使用電場，及更佳確保基板爲 絕熱及絕電。沈積後，含有粉末塗覆組成物之陶瓷基板通 常係加熱至1 2 0 °C至3 0 0 °C間之溫度歷經1分鐘至6 0分鐘之 硬化時間’造成粒子流動與共同融結而於基板表面上形成 光滑均勻連續且無小凹坑之塗層。 於根據本發明之方法之較佳實施例中，施用本發明之 粉末塗覆組成物前，陶瓷基板例如瓷磚係以機械方式拋光 (例如，使用砂磨）。 通常無需化學前處理，除非例如陶瓷基板表面上存在 有油脂污物。 較佳使用的陶瓷基板爲未上釉，更特佳爲未上釉陶瓷 201204683 瓷磚。 於根據本發明之方法中’基板可以如前文描述之多於 一種粉末塗覆組成物塗覆。於此種情況下，塗覆組成物可 爲相同或相異。 於本發明之較佳實施例中，陶瓷基板可以單次粉末塗 覆而塗覆俾形成選擇性地添加顏料之單層底塗層。單層底 塗層選擇性地可包含i)(額外）羧或羥官能基聚酯與適當前 述硬化劑及/或u)高度羥官能基聚酯與酐硬化劑（諸如市售 得自賽德（Cytec)商標名貝寇帕（BECKp〇x) EH694)及/或前 述異氰酸酯硬化劑（諸如市售得自賽德公司商標名阿利妥 (ADDITOL) 932)及/或in)羧官能基丙烯酸系聚合物與雙酚 A衍生之環氧樹脂；及/或iv)熱硬化不飽和聚酯。 另一個本發明之較佳實施例中，陶瓷基板可循序以兩 種不同粉末塗覆物塗覆而形成兩層底塗層（其中任一層皆 可"選擇性地添加顏料）。各層可選擇性地包含如上單一底層 之實施例中所述的材料（i)、（ii)、（iii)及/或（iv)中之任一者。 月ί吏用之粉末塗覆組成物較佳係直接施用至陶瓷 基板上’而於施用粉末塗覆組成物前並未施用任何（其它） 底塗層。 包覆組成物之該層厚度通常於乾燥後係自25 微米至250微米。此層厚度較佳至少爲5〇微米，因而基板表 面上的任何缺陷變不可見。 根據本發明之方法中，施用液體塗覆組成物作爲額外 塗覆層0最佳液體層形成陶瓷基板例如陶瓷瓷磚外層。較 -10- 201204683 佳液體層形成頂塗層。 用於根據本發明之方法之液體塗覆組成物較佳包含選 自於由下列所組成之表單中之至少一種樹脂：（i)醇酸樹脂 或其雜混物；（i i)丙烯酸系樹脂或其雜混物；（i i i)聚酯樹脂 或其雜混物；（iv)聚胺基甲酸乙酯分散體或其雜混物；（v) 羥化多元醇；（vi)有機聚矽氧；（vii)酚系樹脂，可能與環氧 樹脂之組合物；及（viii)聚酯樹脂與丙烯酸系樹脂之組合。 較佳液體塗覆組成物包含下列樹脂中之至少一者：（i)丙烯 酸系樹脂或其雜混物；（ii)聚酯樹脂或其雜混物；（iii)聚胺 基甲酸乙酯分散體或其雜混物；（iv)羥化多元醇；或（v)有 機聚矽氧。 「雜混物」一詞係指樹脂藉反應之物理或化學改性。 適當雜混物爲技藝界眾所周知。雜混物之實例包括例如使 用丙烯酸系-聚胺基甲酸乙酯接枝共聚物之丙烯酸系-聚胺 基甲酸乙酯雜混物乳液或分散液。另一個實例構成芯殼技 術，例如使用醇酸樹脂芯及丙烯酸系殼來獲得最佳效能。 本發明之較佳實施例中，液體塗覆組成物包含至少一 種丙烯酸系樹脂及/或至少一種聚酯樹脂。最佳所使用的液 體塗覆組成物包含至少一種丙烯酸系樹脂及至聚酯樹脂。 前文中「丙烯酸系樹脂」一詞包括丙烯酸系樹脂雜混 物。同理「聚酯」一詞包括聚酯樹脂雜混物。 適當丙烯酸系樹脂雜混物之實例爲經以聚酯改性用以 改良薄膜撓曲性之丙烯酸系樹脂。適當聚酯雜混物之若干 實例提供如下。 -11 - 201204683 用於本發明之液體塗覆組成物之丙烯酸系樹脂選擇性 地爲羥化丙烯酸系樹脂。所使用之丙烯酸系樹脂可爲水 性，但較佳爲溶劑性。溶劑性丙烯酸系樹脂可爲熱塑性， 但較佳爲熱固性丙烯酸系樹脂。最佳所使用之丙烯酸系樹 脂爲溶劑性羥化丙烯酸系樹脂，其較佳爲熱固性。 丙烯酸系樹脂之較佳特徵爲固體質量分量高於50%， 更佳至少55%，最佳或至少60%(根據DIN EN ISO 3 2 5 1測 定）。較佳固體質量分量不超過99%。 丙烯酸系樹脂較佳具有其溶液之動態黏度（根據DIN ΕΝ ISO 3219於23 °C)爲50至40000 mPa.s。較佳黏度爲至少 500 mPa.s，更佳至少700 mPa.s。較佳黏度爲至多10000 mPa.s，更佳至多 SOOOmPa.s，最佳至多 6000 mPa.s。 較佳所使用的丙烯酸系樹脂具有固體樹脂上之羥（OH) 値（根據DIN ΕΝ ISO 4629)爲10至300毫克KOH/克。較佳羥 値爲至少35毫克KOH/克，更佳至少50毫克KOH/克。較佳羥 値爲至多200毫克KOH/克，更佳至多150毫克KOH/克。 用於本發明之液體塗覆組成物之聚酯可爲水性，但較 佳爲溶劑性。較佳該聚酯爲羥化聚酯，更特別爲溶劑性羥 化聚酯。 聚酯可爲線性、分支或略分支。以分支聚酯爲佳。 使用的聚酯較佳特徵爲具有至少60%固體質量分量’ 優異地至少70%，更佳至少7 5%(根據DIN EN ISO 3 25 1測 定）。較佳固體質量分量不超過99%。201204683 VI. Description of the Invention: [Technical Field of the Invention] Field of the Invention The present invention relates to a method of using a thermosetting coating and a ceramic substrate thus obtained. This is a coating composition for a ceramic substrate. [Prior Art] Background of the Invention Ceramic substrates such as ceramic tiles or sanitary ware are generally provided with a high decorative effect and scratch resistance, abrasion resistance and a large amount of energy. US 4,143,181 relates to a method of applying a coating layer from a bottom to a glass substrate. The primer is damaged by impact, and the undercoat layer is applied by a solution containing a hydroxy thermosetting binder; the powder is resistant to caustic soda and also contains a hydrazine functional linker. DE 1 974 892 7 relates to a process for the heat-resistant thermal or functional coating comprising a polyester or polyurethane resin. The substrate is heated to a softening point temperature. Subsequent application of the powder to the heated substrate itself is electrically insulating. The substrate is then moved to the roast. A two-coat system is exemplified: the first ester TGIC system is applied at a thickness of 200 microns and the topographical composition is coated with a ceramic matrix. The invention further relates to an enamel coating agent resistance. However, the glaze-consuming coating and the top coat layer are intended to protect the substrate from the top coat layer composed of the functional polyester to improve the obtained solid composition on the thermosetting non-metal substrate composed of the base polyester. The scratch resistance is higher than the substrate to which the coating is to be applied without using an electric field, and the furnace is used to harden the thermosetting powder black powder coating, that is, to form a polyimide for 10 minutes. A second clear layer of the same polyester TGIC system containing 201204683 brass flakes was then applied and hardened for another 1 minute to obtain a highly decorative coating. US 6982 1 3 7 relates to a method of forming a color image on a tile or glass, wherein the substrate is first coated with a 80% to 95% cured transparent powder polymer, then an electrophotographic color image is applied, and another layer is finally applied. The same polymer is then heated to achieve complete hardening. None of these prior art coatings have achieved high decorative finish, without outstanding mechanical and chemical properties such as scratch resistance and chemical resistance. The light dullness proposed so far is not sufficient, especially the extremely high hardness (3 Η to 4H) combination of outstanding solvent resistance and thermal shock resistance constitute a technical pick mh. SUMMARY OF THE INVENTION Summary of the Invention The inventors have found coatings that overcome some or all of the aforementioned disadvantages today. The present invention is therefore directed to a method of coating a ceramic substrate comprising applying a powder coating composition as a primer layer to a substrate, the composition comprising at least one polyester having a carboxy- and/or hydroxy-functional group, And at least one hardener having a functional group reactive with the polyester functional group; hardening the applied composition; and applying a liquid coating composition, and hardening the applied composition by exposure to heat . As used herein, "ceramic substrate" means a product produced by heating an inorganic non-metallic material such as an earthy raw material. The ceramic substrate typically comprises primarily a material comprising ruthenium and its oxide and a compound of the compound referred to as ruthenium. The ceramic substrate is preferably a structural clay product such as brick, tile, red. 201204683 earthenware or glazed building brick. Ceramic tiles are preferred, especially ceramic wall tiles and ceramic floor tiles, especially ceramic interior wall tiles. As used herein, "hardened by exposure to heat" means physical drying, air drying and drying. It is better to dry it and especially to dry it. "Air drying" refers to a method of extracting heat from air and reacting certain groups of the resin with oxygen from air to crosslink, harden and dry. Catalytic crosslinked organic metal salts or "desiccants" are often added. An oil desiccant in the form of a metal complex can be added to accelerate drying. "Drying" or "baked" or "baked oven" means medium temperature or elevated temperature in the presence of a crosslinking agent or hardener (especially higher than 9 (TC) hardening. "By exposure to heat hardening" The term specifically excludes "by exposure to radiation hardening", whereby heat can be used to melt the resin, but exposure to actinic radiation and/or ultraviolet light (optionally in the presence of another component such as a photoinitiator) and / Or free radiation (such as an electron beam) for hardening. In the method according to the invention, the liquid coating composition is excellently thermally hardened. The powder coating composition used in the present invention is present in the form of a fine powder, Applying a coating on the substrate and heating to form a coating on the ceramic substrate during which at least a portion of the functional groups from the polyester react with at least a portion of the functional groups of the curing agent. The polyesters used in the present invention are typically Based on a polyacid component comprising from 70 to 100 mole % of aromatic polycarboxylic acid and/or its anhydride, and from hydrazine to 3 Torr. /β aliphatic or cycloaliphatic polyacid and/or Its anhydride; and from the polyol component, including 70 to 201204683 100 Ear% aliphatic diol' and self-twisting to 30 mole% cycloaliphatic diol and/or (cyclo)aliphatic polyol. "(Cyclo)aliphatic polyol" means carrying more than two -0H groups The cycloaliphatic polyol or the aliphatic polyol. The aromatic polycarboxylic acid is preferably terephthalic acid and isophthalic acid and a mixture thereof. The aliphatic diol is preferably selected from neopentyl glycol, propylene glycol, 2 -methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, ethylene glycol, diethylene glycol, and mixtures thereof. The polyester used in the present invention may have, for example, self a carboxy-functional polyester of 15 to 100 mg KOH/g, preferably 30 to 70 mg KOH/g of acid hydrazine (according to D0029300); or may have, for example, from I5 to 300 mg KOH/g, preferably from 30 to a hydroxy-functional polyester of 100 mg KOH/g oxindole (according to D0067200). A carboxy-functional polyester is preferred. The polyester preferably has a polyether as a standard by gel permeation chromatography (GPC). The number average molecular weight (Μη) obtained from the range of 600 to 1 5000. Preferably, ηη is at least 1 00. Preferably, Μη is at most 8500. Preferred polyester has differential scanning calorimetry The glass transition temperature (Tg) from 35 ° C to 80 ° C measured according to ASTM D3418 using a heating gradient of 20 ° C per minute. The polyester useful in the present invention preferably has a Tg greater than 50 ° C. The ester preferably has a Brookfield (cone/plate) viscosity according to ASTM D4287-88 at I75t: 5 mPa.s measured to 500 ° C measured at 150 ° C. The range of s. The polyester used in the present invention is known in the prior art and has been described for metal coatings. When a carboxy-functionalized polyester is used in the present invention, it comprises a reaction with such polyester 201204683. The hardener of the reactive group is preferably selected from the group consisting of polyepoxides, compounds containing β-hydroxyalkylguanamine, and mixtures thereof. Preferred are polyepoxides which are solid at room temperature and contain at least two epoxy groups per molecule. Triglycidyl isocyanurate such as the trade name of Araldite PT8 10, diglycidyl terephthalate and triglycidyl trimellitate such as the commercial brand name Allah. Lai PT910 or Ala Lai PT912, and epoxy resin based on bisphenol A, such as the commercial brand name Allah GT 7 0 04 or DER 692 is particularly good. A glycidyl-based acrylic copolymer derived from glycidyl methacrylate and/or glycidyl acrylate and other (meth)acrylic monomers and, optionally, other ethylenically monounsaturated monomers may also be used. A preferred acrylic copolymer is GMA-300, sold by Easton Chemical Inc. and described in WO 91/01748. Particularly preferred is a β-hydroxyalkylguanamine containing at least one, preferably two, bis(β-hydroxyalkyl)guanamine groups. Such compounds have been described, for example, in U.S. Patent No. 4,727,111, the disclosure of which is incorporated herein by reference in its entirety in its entirety in the s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s Used in the amount of carboxyl groups of polyester. When a hydroxy-functional polyester is used, the hardener is preferably selected from the group consisting of blocked isocyanate crosslinkers. Examples of blocked isocyanate crosslinkers include the following components: isophorone diisocyanate and ε-caprolactam block, commercially available VEGAAGON B 1 5 3 0 , Luco (R Uco ) NI - 2 and Cargill (0& 丨 11) 2400; or toluene-2,4-diisocyanate and ^caprolactam block, ie commercially available Cargill 24 5 0 ; and phenolic block hexamethylene Diisocyanate. 201204683 Another useful block polyisocyanate compound is an adduct of a 1,3-dioxime-2,4-dione dimer of isophorone diisocyanate with a diol, wherein the adduct is formed The NCO group to 〇H group ratio is about 1:0.5 to 1: 0.9' diterpene diketone to diol molar ratio is from 2:1 to 6:5, free isocyanate in the adduct The content of the base is not more than 8% by weight, and the adduct has a molecular weight of from about 50,000 to 4,000 and from about 70 ° C to about 130. (: melting point. Such adducts are commercially available under the trade name Vitaoka BF 1540. The hardener is usually present relative to the (block or non-block) isocyanate groups present in the hardener per equivalent. It is used in an amount of from 0.3 to 1.4, preferably from 0.7 to 1.2 equivalents, of the hydroxyl group present in the polyester. The powder coating composition used as the undercoat layer of the present invention comprises, in addition to one or more polyesters and a kind as described above. The binder of the plurality of hardeners may comprise other additives, chelates and/or pigments commonly used in powder coating compositions. In a preferred embodiment of the invention, the powder-based coating is pigmented. The powder coating composition for use in the method according to the invention advantageously comprises at least one pigment and/or colorant and/or sputum agent well known in the art. It may also be provided in the powder coating composition. Effect pigments such as brass flakes 'metal pigments and pearlescent pigments as described, for example, in DE 19748927 and WO 2008/09540. Examples of metallic pigments include copper, nickel and/or aluminum pigments. Further powder coatings can be clear coatings . The powder coating composition for use in the process according to the invention preferably comprises from 30% to 97% by weight of polyester, from 3% to 5% by weight of hardener, from 〇% to 5%, more 5% to 30% by weight of colorant and/or pigment and/or hydrated 201204683 agent, and from 0% to 10% by weight of other additives. Powder coating composition for use in accordance with the method of the present invention The components can be blended by dry blending in a mixer or blender such as a tumbler mixer. The premix is then typically used in a single or twin screw extruder from 70 to 150 °C. The temperature of the range is homogenized. The extrudate is milled into a powder upon cooling, preferably having a particle size ranging from 10 microns to 150 microns. The powder coating composition can be applied to the ceramic substrate by any powder coating method. The powdered composition can then be deposited on a ceramic substrate using a powder gun such as a CORONA gun or a TR IB gun. On the other hand, well known powder deposition methods such as fluidized bed techniques can be used. In a preferred embodiment of the method according to the invention, the ceramic substrate, such as a ceramic tile, is first preheated above The glass transition temperature of the powder coating composition, preferably the substrate is preheated to a temperature of from 60 ° C to 200 ° C. The powder coating composition is then applied to the preheated substrate, preferably without an electric field, and more preferably The substrate is insulated and electrically insulated. After deposition, the ceramic substrate containing the powder coating composition is usually heated to a temperature between 1 20 ° C and 300 ° C for a hardening time of 1 minute to 60 minutes to cause particles. Flowing and co-melting to form a smooth, uniform continuous coating with no pits on the surface of the substrate. In a preferred embodiment of the method according to the invention, the ceramic substrate is applied, for example, prior to application of the powder coating composition of the invention. The tiles are mechanically polished (for example, using sanding). Chemical pretreatment is usually not required unless, for example, grease stains are present on the surface of the ceramic substrate. The preferred ceramic substrate is unglazed, and more preferably unglazed ceramic 201204683 tiles. In the method according to the invention, the substrate can be coated as more than one powder coating composition as previously described. In this case, the coating compositions may be the same or different. In a preferred embodiment of the invention, the ceramic substrate can be coated with a single powder to form a single layer of primer that selectively adds pigment. The single layer primer layer may optionally comprise i) (additional) carboxy or hydroxy functional polyesters with suitable foregoing hardeners and/or u) highly hydroxy functional polyesters and anhydride hardeners (such as commercially available from Sidel) (Cytec) under the trade name BECKP〇x EH694) and/or the aforementioned isocyanate hardener (such as commercially available from the Saide brand name ADDITOL 932) and/or in) carboxy-functional acrylics a polymer with a bisphenol A derived epoxy resin; and/or iv) a thermosetting unsaturated polyester. In another preferred embodiment of the invention, the ceramic substrate can be sequentially coated with two different powder coatings to form a two-layer primer layer (any of which can "selectively add pigments). Each layer may optionally comprise any of materials (i), (ii), (iii) and/or (iv) as described in the examples of a single underlayer as described above. The powder coating composition for the month is preferably applied directly to the ceramic substrate' and no (other) primer layer is applied prior to application of the powder coating composition. The thickness of the layer of the coating composition is typically from 25 microns to 250 microns after drying. The thickness of this layer is preferably at least 5 μm, so that any defects on the surface of the substrate become invisible. In the method according to the invention, the liquid coating composition is applied as an additional coating layer 0 to form a ceramic substrate such as a ceramic tile outer layer. Compared with -10- 201204683, the liquid layer forms a top coat. The liquid coating composition for use in the method according to the present invention preferably comprises at least one resin selected from the group consisting of: (i) an alkyd resin or a hybrid thereof; (ii) an acrylic resin or a heteromix thereof; (iii) a polyester resin or a hybrid thereof; (iv) a polyurethane urethane dispersion or a hybrid thereof; (v) a hydroxylated polyol; (vi) an organopolyfluorene; (vii) a phenolic resin, possibly a combination with an epoxy resin; and (viii) a combination of a polyester resin and an acrylic resin. Preferably, the liquid coating composition comprises at least one of the following resins: (i) an acrylic resin or a hybrid thereof; (ii) a polyester resin or a hybrid thereof; (iii) a dispersion of polyurethane Or a heteromix thereof; (iv) a hydroxylated polyol; or (v) an organopolyoxyl. The term "hybrid" refers to the physical or chemical modification of a resin by reaction. Suitable hybrids are well known in the art world. Examples of the hybrid mixture include, for example, an acrylic-polyurethane hybrid emulsion or dispersion using an acrylic-polyurethane graft copolymer. Another example constitutes a core shell technique, such as the use of an alkyd core and an acrylic shell for optimum performance. In a preferred embodiment of the invention, the liquid coating composition comprises at least one acrylic resin and/or at least one polyester resin. The liquid coating composition preferably used comprises at least one acrylic resin and to a polyester resin. The term "acrylic resin" as used herein includes an acrylic resin hybrid. Similarly, the term "polyester" includes polyester resin hybrids. An example of a suitable acrylic resin hybrid is an acrylic resin modified with a polyester to improve the flexibility of the film. Several examples of suitable polyester hybrids are provided below. -11 - 201204683 The acrylic resin used in the liquid coating composition of the present invention is selectively a hydroxylated acrylic resin. The acrylic resin to be used may be aqueous, but is preferably solvent. The solvent acrylic resin may be thermoplastic, but is preferably a thermosetting acrylic resin. The acrylic resin to be preferably used is a solvent-based hydroxylated acrylic resin, which is preferably thermosetting. The acrylic resin is preferably characterized by a solids mass fraction of more than 50%, more preferably at least 55%, most preferably at least 60% (as determined according to DIN EN ISO 3 2 5 1 ). Preferably, the solid mass component does not exceed 99%. The acrylic resin preferably has a dynamic viscosity of its solution (at 23 ° C according to DIN ΕΝ ISO 3219) of 50 to 40,000 mPa·s. Preferably, the viscosity is at least 500 mPa.s, more preferably at least 700 mPa.s. The preferred viscosity is at most 10,000 mPa.s, more preferably at most SOOOmPa.s, and optimally at most 6000 mPa.s. The acrylic resin preferably used has a hydroxyl (OH) oxime (according to DIN ΕΝ ISO 4629) of 10 to 300 mg KOH/g on a solid resin. Preferably, the hydroxyindole is at least 35 mg KOH/g, more preferably at least 50 mg KOH/g. Preferably, the hydroxyindole is at most 200 mg KOH/g, more preferably at most 150 mg KOH/g. The polyester used in the liquid coating composition of the present invention may be aqueous, but is preferably solvent. Preferably, the polyester is a hydroxylated polyester, more particularly a solvent-based hydroxylated polyester. The polyester can be linear, branched or slightly branched. Branched polyester is preferred. The polyester used is preferably characterized by having at least 60% solids mass fraction 'excellently at least 70%, more preferably at least 75% (measured according to DIN EN ISO 3 25 1). Preferably, the solid mass component does not exceed 99%.
聚酯溶液之較佳特徵爲動態黏度（根據DIN EN ISO -12- 201204683 3219於23 °C)爲50至35000 mPa.s。較佳黏度爲至少500 mPa.s，更佳至少1000 mPa.s，最佳至少1500 mPa.s。較佳 黏度爲至多30000mPa.s，更佳至少25000 mPa.s’最佳至多 20000 mPa.s 〇 較佳所使用的聚酯具有固體樹脂上之羥（〇H)値（根據 DIN EN ISO 4629)爲10至3 00毫克KOH/克。較佳羥値爲至少 80毫克KOH/克，更佳至少100毫克KOH/克，最佳至少150 毫克KOH/克。較佳羥値爲至多2 5 0毫克KOH/克。 特別適合的聚酯爲具有例如不大於2〇〇〇克/莫耳之重 量平均莫耳質量（Mw)之低莫耳質量聚酯多元醇，特別爲具 有自80至300毫克KOH/克之羥値及自5至35毫克KOH/克之 酸値者，描述於US 6,2 5 8,8 97及US 6087,469，其內容以引 用方式倂入此處。 此等聚酯較佳係得自反應混合物中下列物質分量之反 應：a)自1 %至4 5 %每分子具有至少二個羥基之脂肪族多環 多羥基化合物，b)自5 %至5 0 %分支脂肪族無環二羥基化合 物，c)自3 0%至50%脂肪族環狀多羧酸，d)自0%至30%每分 子具有三個或多個羥基之脂肪族無環或單環多羥基化合 物，及e)自0%至10%選自於脂肪族線性及單環二羥基化合 物、脂肪族線性及分支二羧酸、芳香族二羧酸 '芳香族羥 羧酸及每分子有三個或多個羧基之多羧酸之多官能化合 物，及f)自〇 %至1Ό %選自於一羧酸及一元醇之一官能化合 物。a)、b)、c)、d)、e)及f)各種情況下指示之物質分量優 異地加總至。 -13- 201204683 用於根據本發明之液體塗覆組成物之適當聚酯多元醇 之實例及該等聚酯多元醇之適當溶劑之實例可參考US 6,258,897及US 6087,469，其內容以引用方式倂入此處。 低莫耳質量聚酯多元醇例如可經由與異氰酸酯化合物 或包含環氧乙烷基之化合物反應而以化學或物理方式改 性。其它可能的改性包括摻混低莫耳質量脲衍生物。聚酯 多元醇也可爲（接枝其上之）丙烯酸酯聚合物基礎，諸如描 述於 US 6,258,897、EP 0776920 及 EP 0896991，其內容以引 用方式倂入此處。 本發明之較佳實施例中，液體塗覆組成物包含至少一 種丙烯酸系樹脂及至聚酯樹脂呈4: 1至2: 1，更佳3.5: 1 至2.5: 1，最佳3: 1至2.2: 1聚酯樹脂：丙烯酸系樹脂之比。 較佳用於根據本發明之方法之液體塗覆組成物進一步 包含至少一種硬化劑。適當硬化劑爲該技術領域眾所周知。 用於根據本發明之液體塗覆組成物之（選擇性羥化）聚 酯及/或（選擇性羥化）丙烯酸系樹脂可以任一種期望方式羥 化。可能的硬化劑（或交聯劑）包括（嵌段或非嵌段）多異氰酸 酯、胺樹脂、酚系樹脂、多羧酸類及其酐類（參考例如U S 6,258,897)。 呈非嵌段形式之多異氰酸酯可用於中溫或室溫固化。 用於升溫固化，額外適合使用嵌段多異氰酸酯及多羧酸類 及其酐類。 胺樹脂爲較佳硬化劑（或固化劑），更明確言之脲樹 脂、三聚氰胺樹脂及/或苯并胍樹脂。此等樹脂分別爲脲_、 • 14- 201204683 三聚氰胺-及/或苯并胍-甲醛縮合產物。特佳爲三聚氰胺樹 脂及尤其高固體甲基化三聚氰胺樹脂，諸如六甲氧甲基三 聚氰胺樹脂。 本文中，「高固體」係指至少7 0 %，特別至少7 5 %，較 佳至少9 5 %之固體質量分量。適當硬化劑爲例如具有固體 質量分量高於9 8 %之六甲氧甲基三聚氰胺樹脂。其它較佳 實例包括具有78%至82%範圍之固體質量分量之高胺樹脂。 較佳使用胺樹脂作爲硬化劑時添加酸催化劑。本發明 之實施例中使用的液體塗覆組成物進一步包含酸催化劑。 全然烷化胺樹脂經常要求強力酸催化劑諸如西凱 (CYC AT) 4045 ’而部分烷化及高亞胺樹月旨通常只需弱酸催 化劑。又，脲樹脂及甘脲樹脂對強酸催化劑的反應較佳。 可能的催化劑實例包括胺嵌段對甲苯磺酸（pTSA)、焦 磷酸二甲酯（DMAPP)、十二烷基苯磺酸（DDBSA)及二壬基 萘二磺酸（DNNDSA)。較佳催化劑爲胺嵌段對甲苯磺酸諸如 阿利妥VXK 6395及西凱4045。 較佳樹脂於液體塗覆組成物之質量分量爲10%至 9 0 %。較佳樹脂之質量分量爲至少2 0 %，更佳至少5 0 %。較 佳樹脂之質量分量至多8 5 %，更佳至多8 0 %。 較佳硬化劑於液體塗覆組成物之質量分量爲5 %至 70%。較佳硬化劑之質量分量爲至少1 0%，更佳至少1 2%。 較佳樹脂之質量分量至多40%，更佳至多25%。 樹脂與硬化劑之質量分量比較佳爲6 : 1至1 : 1，更特 佳爲5 : 1至2 : 1。 -15- 201204683 較佳於液體塗覆組成物中選擇性酸催化劑之質量分量 爲0%至1 0%，更特佳爲0.1 %至1 0%。較佳選擇性酸催化劑 之質量分量爲至少〇 . 3 %。較佳選擇性酸催化劑之質量分量 不超過8 %。 根據本發明之液體塗覆組成物可自於水的溶液或分散 液施用，但較佳係自於有機溶劑之溶液施用。 本發明之用於樹脂及特別較佳寡酯多元醇及/或丙烯 酸系樹脂的適當溶劑實例包括脂肪族、環脂族及芳香族烴 類，諸如二甲苯、甲苯；酯類諸如乙酸乙酯、乙酸丁酯、 具有長鏈醇殘基之乙酸酯類、丙酸丁酯、丙酸戊酯、乙酸 乙二醇一乙醚、相對應之乙酸甲醚，及乙酸丙二醇甲醚； 醚類諸如乙二醇乙醚、-一甲醚或-一 丁醚；二醇類；醇 類；酮類諸如甲基異戊基甲酮及甲基異丁基甲酮；內酯類， 及此等溶劑之混合物。其它有用之溶劑包括內酯類與二醇 類或醇類之反應產物。特佳爲二甲酯（例如DME-1，己二 酸、戊二酸及丁二酸之聖多索醇（santosol)二甲酯）與 S-100(得自華倫化學公司（HuaLun Chemistries)之芳香族烴 溶劑）之混合物。丁醇有助於塗料之安定儲存。 選擇性溶劑於該液體塗覆組成物之質量分量典型地爲 0%至50%。較佳選擇性溶劑之質量分量爲至少5%，更佳至 少1 0%。較佳選擇性溶劑之質量分量爲至多40%，更佳至多 3 0%。 用於本發明方法之液體塗覆組成物可進一步包含顏料 及/或著色劑及/或塡充劑。塡充劑之實例包括滑石、雲母、 -16 - 201204683 高嶺土、白堊、石英粉、頁岩粉、多種二氧化矽' 矽酸鹽 類等。選擇性顏料及/或著色劑及/或塡充劑於該液體塗覆 組成物之質量分量較佳爲〇%至50%，更佳爲2%至40%。 但較佳形成頂塗層之液體層爲實質上透明（澄清）亦即 實質上不含有色成分諸如顏料。用於根據本發明之方法之 液體塗覆組成物較佳爲不含著色劑及/或顏料及/或塡充劑 之透明塗層。 用於本發明之液體塗覆組成物也可含有尙未述及的其 它成分，例如塗覆技術習用之輔劑或添加劑。此等成分更 明確言之包括滑脫劑及均平劑；聚矽氧油類；添加劑諸如 纖維素酯類，尤其乙醯丁酸纖維素酯；塑化劑諸如磷酸酯 及苯二甲酸酯；黏度調節劑；流動改性劑；去光澤劑；紫 外光吸收劑及光安定劑、抗氧化劑及/或過氧化物清除劑； 消泡劑及/或濕潤劑；分散劑、活性稀釋劑/反應性稀釋劑 等。液體塗覆組成物之選擇性其它成分之質量分量較佳爲 0%至5%。較佳選擇性成分之質量分量爲至少0.2%。較佳選 擇性成分之質量分量爲至多2 %，更佳至多1 %。 本發明之較佳實施例使用的液體塗覆組成物包含自 50%至90%重量比樹脂；自10%至40%重量比硬化劑；選擇 性地，自5%至40 %重量比溶劑；選擇性地，自0%至8 %重量 比酸催化劑；選擇性地，自〇%至50%重量比著色劑及/或顏 料及/或塡充劑；及選擇性地，自〇%至2 %重量比額外成分。 液體塗覆組成物樹脂可藉任一種適當塗覆方法施用至 陶瓷基板。其實例爲刷塗、浸塗、流塗、輥塗或刀塗，但 俨、 5 -17- 201204683 特別爲噴塗。可加熱施用，及若有所需，可藉注入超臨界 流體（例如，二氧化碳）而形成方便施用形式。 於使用液體塗覆組成物塗覆基板後，基板經硬化。硬 化亦即交聯可藉熟諳技藝人士眾所周知之任一種適當手段 達成。爲了達成本發明之目的，液體塗覆組成物通常係在 自20°C至160°C，較佳自23°C至l4〇t之溫度範圍硬化5分鐘 至10日，更特別自15分鐘至120分鐘。 於根據本發明之方法中，基板可以如前文說明之多於 一種液體塗覆組成物塗覆。於此種情況下，液體塗覆組成 物可爲相同或相異。 包含液體塗覆組成物之該層厚度通常於硬化後係自1 微米至120微米，較佳自10微米至80微米，更佳自20微米至 70微米。 液體塗覆組成物可直接施用在粉末底塗層上，或一層 或多層中間層可施用在粉末底塗層與液體塗層（其較佳爲 液體頂塗層）間。 於較佳實施例中，本發明方法包含提供彩色影像至陶 瓷基板亦即瓷磚之額外步驟。「彩色影像」表示至少一色， 可能爲多色的影像、印刷或設計。「彩色」一詞包括特殊 色，例如金色、銀色、金屬色等。 較佳彩色影像係在以粉末底塗層塗覆陶瓷基板步驟之 後而在施用液體塗覆組成物作爲額外層之步驟之前施用。 較佳施用彩色影像前，陶瓷基板例如瓷磚首先以機械 方式拋光（例如，使用砂磨）。於根據本發明之方法之較佳 -18- 201204683 實施例中，陶瓷基板，更明確言之，塗覆以粉末底塗層之 陶瓷瓷磚係在施用彩色影像前，優異地係在施用粉末底塗 層後，可能也在施用粉末底塗層前經拋光。 本發明之較佳實施例中，彩色影像係使用例如印刷噴 墨昇華技術，更明確言之，染料昇華印刷而施用至陶瓷基 板，例如瓷磚。 提供彩色影像至陶瓷基板例如瓷磚之可能方式係藉熱 轉印。例如可使用該技術領域眾所周知之熱轉印紙。可使 用市售熱轉印紙，或使用電腦或彩色複印機印刷在適當紙 張上而形成專屬的設計。 於最簡單方式，轉寫紙朝向塗覆以粉末底塗層之陶瓷 基板加壓，及撕離背襯層。提供影像之一種方式係說明於 US 6982137，其內容以引用方式倂入此處。 適當設備例如熱轉印機器亦爲該技術領域眾所周知及 市售可得。典型地，已經施用至背襯片的靜電複印產生的 彩色影像係以例如約40 p si壓力加壓至粉末底塗層，使用例 如約180°C至220°C壓機溫度歷經約10分鐘至30分鐘，例如 允許材料冷卻，及施用額外液體層。也有且可使用其它用 以於陶瓷基板上，如陶瓷瓷碑形成影像之其它適當技術， 諸如紫外光光成像。 使用根·據本發明之方法可提供之設計或印刷之若干實 例：仿大理石、木紋、金屬色等。相反地，上釉瓷磚因烤 乾溫度高（大於1 200 °C )故經常無法滿足高度裝飾需求。 根據本發明之方法允許獲得陶瓷基板，尤其瓷磚’其 -19- 201204683 呈現高度裝飾光整以及傑出機械及化學效能，諸如耐刮 性、耐玷染性及化學品耐性。如此允許此等瓷磚例如適用 於浴室、廚房及需要高度耐性的其它環境。 特別耐玷染性'光澤度及彩度經常優於上釉瓷磚。比 較傳統上釉技術’本發明方法耗用較少能量且更環保友善。 本發明之構面係有關陶瓷基板尤其瓷磚，其可藉本發 明之方法獲得（或可得）。更明確言之，本發明係關於陶瓷 基板尤其瓷磚，包含得自粉末塗覆組成物之至少一基底塗 覆層（A)，該組成物係含具有羧-及/或羥-官能基之至少一種 聚酯，及具有與該聚酯官能基可起反應之官能基的至少一 種硬化劑；及得自如前文描述之液體塗覆組成物之至少又 一層（B)。 本發明之較佳實施例中，本發明之陶瓷基板尤其瓷磚 具有鉛筆硬度（根據Wolff Wilborn根據刮擦硬度測試器）至 少2H，較佳至少3H，更佳至少4H。使用本發明之方法甚至 可達成5H或6H之鉛筆硬度。 本發明之較佳實施例中，陶瓷基板上的底塗層係添加 顏料’直接設在此底塗層頂上的液體層爲透明塗層。另外， 液體層係添加顏料。 本發明之另一較佳實施例中，粉末塗層及液體塗層爲 透明塗層，施用液體塗層前彩色影像提供至瓷磚。另外， 底塗層係添加顏料，且對設置於其頂上之彩色影像提供背 景色彩（例如白色）。 較佳液體塗層（前述任一實施例）爲頂塗層。 -20- 201204683 顏料（前述任一者）可爲有機及/或無機。 本發明之另一構面係有關一種用於陶瓷基板之液體塗 覆組成物，包含U)至少一種丙烯酸系樹脂及/或至少一種聚 酯樹脂，及（b)至少一種胺樹脂’其較佳係爲三聚氰胺硬化 劑。適當丙烯酸系樹脂及聚酯樹脂已經如前文說明。較佳 丙烯酸系樹脂爲羥化丙烯酸系樹脂，及聚酯爲羥化聚酯。 用於液體塗覆組成物之選擇性的額外化合物及/或成分已 經如前文說明。 【實施方式】 下列實例將舉例說明本發明但非限制性。 製備例1:羧官能基聚酯PE1之合成 4 0 8.3 7克新戊二醇置於習知四頸圓底瓶，燒瓶裝配有 攪拌器、連結至水冷式冷凝器之蒸餾管柱、氮氣進氣口及 附接至調溫器的溫度計。燒瓶內容物經加熱同時於氮下攪 拌至約1 3 0 °C溫度，此時添加5 3 2 · 5 9克對苯二甲酸，5 9.1 8 克己二酸及2.00克三辛酸正丁錫。徐緩持續加熱至230 °C溫 度。自180 °C以上溫度，水自反應器蒸餾出。於大氣壓下蒸 餾停止時，徐緩施加50毫米汞柱（約6666 Pa)真空。於23 0 °C 及5 0毫米汞柱3小時後，獲得具有下列特性之聚酯：AN : 3 毫克KOH/克’ OHN : 42毫克KOH/克。然後反應混合物冷卻 至170 °C -190 °C，接著添加119.18克偏苯三酸酐。溫度維持 於〗80 °C直至該反應混合物變澄清。 獲得具有下列特性之羧官能基聚酯：AN = 72毫克KOH/ 克，OHN = 6毫克KOH/克，布汝克斐（175°C)黏度（錐/ -21 - 201204683 板）=1〇,〇〇〇 mPa.s ; Tg(DSC，20 K· /分）= 58°c。 製備例2:羧官能基聚酯PE2之合成 423.82克新戊二醇置於反應器內，於氮下加熱同時攪 拌至約l3〇°C溫度，此時添加720.34克間苯二甲酸及2.5克三 辛酸正丁錫。徐緩持續加熱至2 3 0 °C溫度。自1 8 0 °C以上溫 度，水自反應器蒸餾出。於大氣壓下蒸餾停止時，徐緩施 加50毫米汞柱真空。於230 °C及50毫米汞柱3小時後，獲得 具有下列特性之羧官能基聚酯：AN: 32毫克KOH/克，OHN : 2毫克KOH/克，布汝克斐（200°C)黏度（錐/板）·· 3,000 mPa.s ; Tg(DSC，20 K/分）：57°C。 製備例3 :羥官能基聚酯PE3之合成 439.94克新戊二醇與14.1 4克三羥甲基丙烷之混合物置 於反應器內，於氮下加熱同時攪拌至約130 °C溫度，此時添 加645.62克對苯二甲酸，33.98克己二酸及2.5克三辛酸正丁 錫。徐緩持續加熱至2 3 0 °C溫度。自1 8 0 °C以上溫度，水自反 應器蒸餾出。於大氣壓下蒸餾停止時，徐緩施加5 0毫米汞 柱真空。於2 3 0 °C及5 0毫米汞柱3小時後，獲得具有下列特 性之羥官能基聚酯：AN: 3毫克KOH/克，OHN: 32毫克KOH/ 克，布汝克斐（200 °C)黏度（錐 / 板）：7J00mPa.s; Tg(DSC， 2 0 K/分）：56〇C。 · 參考例1至3 : 製備例1至3之聚酯樹脂根據下列配方調配成黑色粉 末： -22- 201204683 表1 粉末組成物1 粉末組成物2 粉末組成物3 組成 數量(克） 組成 數量(克） 組成 數量(克） PE1 27.24 PE2 38.14 PE3 47.94 環氧硬化劑阿拉 賴 GT7004 27.24 環氧硬化劑阿 拉賴GT7004 16.34 硬化劑維它 岡 BF1530 6.54 炭黑FW2 1.06 炭黑FW2 1.06 炭黑FW2 1.06 白固(Blanc Fix)F 21.60 白固F 21.60 白固F 21.60 安息香 0.35 安息香 0.34 安息香 0.35 莫 拉 流 (Modaflow)P6000 0.99 莫拉流P6000 0.99 莫拉流 P6000 0.99 粉末組成物1至3之粉末分別施用至未經拋光之瓷磚 上。至目前爲止，瓷磚已經於200 °C預熱10分鐘，然後移至 木製撐體上俾便電絕緣。隨後使用吉瑪伏史（Gema Volstatic) PCG1以160微米層厚度噴霧粉末而未施用電 場。然後瓷磚移至對流烤爐，此處於200 °C硬化30分鐘。 製備例4:聚酯多元醇之合成 裝配有攪拌器、加熱器、水分離器及惰性氣體進氣口 之二升四頸瓶內進給2.45莫耳3(4)，8(9) -雙羥甲基-三環 -[5.2.1.02,6]癸烷，1.35莫耳新戊二醇，4.0莫耳六氫鄰苯二 甲酐及2.2莫耳三羥甲基丙烷。起始組分於氮下加熱至200 °C 及所形成之反應水連續移除。溫度徐緩升高至220 °C直至酸 値低於25毫克KOH/克。 隨後聚酯多元醇冷卻至120 °C及以乙酸丁酯稀釋及調 整至7 8 %固體質量分量（根據D IN E N I S 0 3 2 5 1測定）。終產 -23- 201204683 物爲透明且具有下列特徵：酸値2 1 .0毫克KOH/克，羥値2 1 9 毫克KOH/克，動態黏度（根據DIN EN ISO 3219測定）1 08 3 8 mPa.s，重量平均莫耳質量Mw爲1 3 1 5克/莫耳，及多分散性 U爲1.6，如上測定。 製備例5 :羥化丙烯酸系樹脂之合成 裝配有攪拌器、加熱與冷卻系統、惰性氣體進氣口及 進給裝置之二升四頸瓶內進給3 69克溶劑石腦油150/180 (具有自150°C至180°C之沸點範圍之烴混合物），及此進料使 用氮氣變成惰性及加熱至1 4 8 t。隨後以6小時時間透過滴 液漏斗，計量加入3 60克苯乙烯，3 2 5克丙烯酸丁酯，176 克甲基丙烯酸羥乙酯及18克丙烯酸之混合物。同時計量添 加2 6克過氧化二第三丁基溶解於8 8克溶劑石腦油（參見上 文）。6小時後，溫度維持於1 4 8 °C歷2小時。然後混合物冷 卻至120°C及以120克乙酸丁酯稀釋及調整至60%固體質量 分量（根據DIN EN ISO 3251測定）。終產物爲透明且具有下 列特徵：酸値17.0毫克KOH/克，羥値91毫克KOH/克，動態 黏度（根據DIN EN ISO 3219測定）1487 mPa.s，重量平均莫 耳質量Mw爲10460克/莫耳，及多分散性U = Mw/Mn爲4.0， 此處Μη爲數目平均莫耳質量，全部皆係使用聚苯乙烯標準 透過GPC測定。 調配物 實例4之樹脂係調配於實例6之塗覆調配物。 實例6 : 數量係以克數表示 -24- 201204683 組成物 A : 80.00 實 例 4之聚酯 7.50 甲 基 戊 基甲酮 1.85 乙 酸 丁 二醇酯 3.15 乙 酸 甲 氧丙酯 1.15 托 索 (Troysol)S 3 6 6 1) 1.06 美 塔 汀 (M e t a t i η) 7 1 2 / 1 % 於二甲苯 2) 0.55 帝 奴 文 (Tinuvin)292 3) 1.60 帝 奴 文 113 0 3) 1.90 甲 基 戊 基甲酮 0.44 乙 酸 丁 二醇酯 0.80 乙 酸 甲 氧丙酯 組成物 B : 47.30 迪 摩 律（D esm 〇dur)N 3 3 0 0 4) 18.90 甲 基 戊基甲酮 12.60 乙 酸 丁二醇酯 實例5之樹脂係調配於實例7之塗覆調配物。 實例7 : 數量係以克數表示 組成物A : 64.40 實例5之丙烯酸系 1 8.40 賽摩（C YMEL)MB-1 4-B 5) 1.60 正丁醇 1.60 乙酸丁二醇酯 -25- 201204683 6.90 乙酸異丁酯 2.00 托索S 366 1) 0.80 帝奴文2 9 2 3) 2.80 帝奴文1 1 3 0 3) 1.50 乙酸丁酯 組成物B : 26.20 溶劑石腦油1 5 0 /1 8 0 7.50 乙酸丁酯 實例4之聚酯與實例5之丙烯酸系之（3/1)摻合物係調配 於實例8之塗覆調配物。 實例8 :A preferred feature of the polyester solution is a dynamic viscosity (at 23 ° C according to DIN EN ISO -12-201204683 3219) of 50 to 35000 mPa.s. Preferably, the viscosity is at least 500 mPa.s, more preferably at least 1000 mPa.s, and most preferably at least 1500 mPa.s. Preferably, the viscosity is at most 30,000 mPa.s, more preferably at least 25,000 mPa.s' optimally at most 20,000 mPa.s. Preferably, the polyester used has a hydroxyl (〇H) 固体 on a solid resin (according to DIN EN ISO 4629) It is 10 to 300 mg KOH/g. Preferably, the oxindole is at least 80 mg KOH/g, more preferably at least 100 mg KOH/g, most preferably at least 150 mg KOH/g. Preferably, the oxindole is at most 2,500 mg KOH/g. Particularly suitable polyesters are low molar mass polyester polyols having a weight average molar mass (Mw) of, for example, not more than 2 gram per mole, particularly having from 0 to 300 mg KOH per gram of oxindole. And from 5 to 35 mg KOH/g of acid bismuth, as described in US Pat. No. 6,2,5,8,97, and US Pat. Preferably, the polyesters are derived from the reaction of the following components in the reaction mixture: a) from 1% to 45% of an aliphatic polycyclic polyhydroxy compound having at least two hydroxyl groups per molecule, b) from 5% to 5 0% branched aliphatic acyclic dihydroxy compound, c) from 30% to 50% aliphatic cyclic polycarboxylic acid, d) from 0% to 30% aliphatic acyclic with three or more hydroxyl groups per molecule Or a monocyclic polyhydroxy compound, and e) from 0% to 10% selected from aliphatic linear and monocyclic dihydroxy compounds, aliphatic linear and branched dicarboxylic acids, aromatic dicarboxylic acid 'aromatic hydroxycarboxylic acids and A polyfunctional compound having three or more carboxyl groups of a polycarboxylic acid per molecule, and f) from 〇% to 1% by weight selected from one of a monocarboxylic acid and a monohydric alcohol. The material components indicated in a), b), c), d), e) and f) are preferentially added to each other. -13- 201204683 Examples of suitable polyester polyols for use in the liquid coating compositions according to the invention and examples of suitable solvents for such polyester polyols are described in US Pat. No. 6,258,897 and US Pat. Please enter here. The low molar mass polyester polyol can be modified, for example, chemically or physically by reaction with an isocyanate compound or a compound containing an oxirane group. Other possible modifications include blending low molar mass urea derivatives. The polyester polyols can also be based on (grafted onto) acrylate polymer bases, such as those described in U.S. Patent No. 6,258,897, the disclosure of which is incorporated herein by reference. In a preferred embodiment of the invention, the liquid coating composition comprises at least one acrylic resin and to the polyester resin from 4:1 to 2:1, more preferably from 3.5:1 to 2.5:1, most preferably from 3:1 to 2.2. : 1 polyester resin: ratio of acrylic resin. The liquid coating composition preferably used in the method according to the present invention further comprises at least one hardener. Suitable hardeners are well known in the art. The (selective hydroxylated) polyester and/or (selective hydroxylated) acrylic resin used in the liquid coating composition according to the present invention may be hydroxylated in any desired manner. Possible hardeners (or crosslinkers) include (block or non-block) polyisocyanates, amine resins, phenolic resins, polycarboxylic acids and anhydrides thereof (see, for example, U S 6,258,897). Polyisocyanates in non-block form can be used for curing at medium or room temperature. For temperature curing, it is additionally suitable for use in block polyisocyanates and polycarboxylic acids and their anhydrides. The amine resin is a preferred hardener (or curing agent), more specifically urea resin, melamine resin and/or benzopyrene resin. These resins are respectively urea_, • 14-201204683 melamine- and/or benzofluorene-formaldehyde condensation products. Particularly preferred are melamine resins and especially high solids methylated melamine resins such as hexamethoxymethyl melamine resin. As used herein, "high solids" means at least 70%, especially at least 75%, preferably at least 9.55% by weight of solids. A suitable hardener is, for example, a hexamethoxymethyl melamine resin having a solid mass component of more than 98%. Other preferred examples include high amine resins having a solid mass component ranging from 78% to 82%. It is preferred to use an acid catalyst as an acid catalyst when an amine resin is used. The liquid coating composition used in the examples of the present invention further comprises an acid catalyst. Fully alkylated amine resins often require strong acid catalysts such as CYC AT 4045' and partial alkylation and high imine trees typically require only weak acid catalysts. Further, the urea resin and the glycoluril resin are preferred for the reaction with the strong acid catalyst. Examples of possible catalysts include amine block p-toluenesulfonic acid (pTSA), dimethyl pyrophosphate (DMAPP), dodecylbenzenesulfonic acid (DDBSA), and dinonylnaphthalenedisulfonic acid (DNNDSA). Preferred catalysts are the amine block p-toluenesulfonic acids such as Aldrich VXK 6395 and Xikai 4045. Preferably, the resin has a mass component of from 10% to 90% by weight of the liquid coating composition. Preferably, the mass component of the resin is at least 20%, more preferably at least 50%. The mass of the preferred resin is at most 85 %, more preferably at most 80%. Preferably, the hardener is present in the liquid coating composition in an amount of from 5% to 70% by mass. Preferably, the hardener has a mass component of at least 10%, more preferably at least 12%. Preferably, the mass component of the resin is at most 40%, more preferably at most 25%. The mass ratio of the resin to the hardener is preferably from 6:1 to 1:1, more preferably from 5:1 to 2:1. -15- 201204683 Preferably, the mass component of the selective acid catalyst in the liquid coating composition is from 0% to 10%, more preferably from 0.1% to 10%. Preferably, the mass component of the selective acid catalyst is at least 0.3%. Preferably, the mass component of the selective acid catalyst does not exceed 8%. The liquid coating composition according to the present invention may be applied from a solution or dispersion of water, but is preferably applied from a solution of an organic solvent. Examples of suitable solvents for the resin and particularly preferred oligoester polyols and/or acrylic resins of the present invention include aliphatic, cycloaliphatic and aromatic hydrocarbons such as xylene, toluene; esters such as ethyl acetate, Butyl acetate, acetate with long-chain alcohol residues, butyl propionate, amyl propionate, ethylene glycol monoethyl acetate, corresponding methyl acetate, and propylene glycol methyl ether; ethers such as ethylene Alcohol diethyl ether, monomethyl ether or monobutyl ether; glycols; alcohols; ketones such as methyl isoamyl ketone and methyl isobutyl ketone; lactones, and mixtures of such solvents. Other useful solvents include the reaction products of lactones with diols or alcohols. Particularly preferred are dimethyl esters (such as DME-1, adipic acid, glutaric acid and succinic acid santosol dimethyl ester) and S-100 (available from Hualun Chemical Company). A mixture of aromatic hydrocarbon solvents). Butanol helps to stabilize the storage of the coating. The mass component of the selective solvent to the liquid coating composition is typically from 0% to 50%. Preferably, the selective solvent has a mass component of at least 5%, more preferably at least 10%. Preferably, the mass component of the selective solvent is at most 40%, more preferably at most 30%. The liquid coating composition used in the method of the present invention may further comprise a pigment and/or a colorant and/or a chelating agent. Examples of the chelating agent include talc, mica, -16 - 201204683 kaolin, chalk, quartz powder, shale powder, and various cerium oxides - strontium salts. The mass component of the selective pigment and/or colorant and/or chelating agent to the liquid coating composition is preferably from 〇% to 50%, more preferably from 2% to 40%. Preferably, however, the liquid layer forming the topcoat layer is substantially transparent (clear), i.e., substantially free of color components such as pigments. The liquid coating composition for use in the process according to the invention is preferably a clear coating free of colorants and/or pigments and/or chelating agents. The liquid coating composition used in the present invention may also contain other ingredients not mentioned, such as adjuvants or additives for coating techniques. These ingredients more specifically include slip agents and leveling agents; polyoxyxides; additives such as cellulose esters, especially cellulose acetate butyrate; plasticizers such as phosphates and phthalates ; viscosity modifier; flow modifier; deluster; ultraviolet light absorber and light stabilizer, antioxidant and / or peroxide scavenger; defoamer and / or wetting agent; dispersant, reactive diluent / Reactive diluent and the like. The selectivity component of the liquid coating composition preferably has a mass component of from 0% to 5%. Preferably, the selective component has a mass component of at least 0.2%. Preferably, the mass component of the optional component is at most 2%, more preferably at most 1%. The liquid coating composition used in the preferred embodiment of the present invention comprises from 50% to 90% by weight of the resin; from 10% to 40% by weight of the hardener; alternatively, from 5% to 40% by weight of the solvent; Optionally, from 0% to 8% by weight of the acid catalyst; alternatively, from 〇% to 50% by weight of the colorant and/or pigment and/or sputum; and optionally, from 〇% to 2 % by weight of extra ingredients. The liquid coating composition resin can be applied to the ceramic substrate by any suitable coating method. Examples are brushing, dip coating, flow coating, roll coating or knife coating, but 俨, 5 -17- 201204683 is especially for spraying. It can be applied by heating and, if desired, by injecting a supercritical fluid (e.g., carbon dioxide) to form a convenient application form. After the substrate is coated with the liquid coating composition, the substrate is hardened. Hardening, that is, cross-linking, can be achieved by any suitable means known to those skilled in the art. For the purposes of the present invention, the liquid coating composition is typically cured at a temperature ranging from 20 ° C to 160 ° C, preferably from 23 ° C to 14 ° C for 5 minutes to 10 days, more particularly from 15 minutes to 120 minutes. In the method according to the invention, the substrate can be coated with more than one liquid coating composition as previously described. In this case, the liquid coating compositions may be the same or different. The thickness of the layer comprising the liquid coating composition is typically from 1 micron to 120 microns, preferably from 10 microns to 80 microns, more preferably from 20 microns to 70 microns, after hardening. The liquid coating composition can be applied directly to the powder basecoat, or one or more intermediate layers can be applied between the powder basecoat and the liquid coating, which is preferably a liquid topcoat. In a preferred embodiment, the method of the present invention includes the additional step of providing a color image to a ceramic substrate, i.e., a tile. "Color image" means at least one color, possibly multi-color image, print or design. The term "color" includes special colors such as gold, silver, metallic, and the like. Preferably, the color image is applied after the step of coating the ceramic substrate with the powder base coat and before the step of applying the liquid coating composition as an additional layer. Prior to the preferred application of the color image, the ceramic substrate, such as a tile, is first mechanically polished (e.g., using sanding). In the preferred embodiment of the method of the present invention, in the embodiment of -18-201204683, the ceramic substrate, more specifically, the ceramic tile coated with the powder undercoat is excellently applied to the application of the powder primer before applying the color image. After the layer, it may also be polished prior to application of the powder basecoat. In a preferred embodiment of the invention, the color image is applied to a ceramic substrate, such as a ceramic tile, using, for example, a printing ink sublimation technique, more specifically, dye sublimation printing. A possible way of providing a color image to a ceramic substrate such as a tile is by thermal transfer. For example, a thermal transfer paper well known in the art can be used. Commercially available thermal transfer paper can be used, or printed on a suitable paper using a computer or color copier to create a proprietary design. In the simplest manner, the transfer paper is pressed toward the ceramic substrate coated with the powder undercoat and the backing layer is peeled off. One way of providing an image is described in US 6,982, 137, the disclosure of which is incorporated herein by reference. Suitable equipment such as thermal transfer machines are also well known in the art and are commercially available. Typically, the color image produced by xerography that has been applied to the backing sheet is pressurized to the powder basecoat at a pressure of, for example, about 40 psi, using a press temperature of, for example, about 180 ° C to 220 ° C for about 10 minutes. For 30 minutes, for example, the material is allowed to cool, and an additional layer of liquid is applied. Other suitable techniques for forming images on ceramic substrates, such as ceramic porcelain, such as ultraviolet light imaging, are also available and can be used. A number of examples of design or printing that can be provided by the method according to the invention: imitation marble, wood grain, metallic color, and the like. Conversely, glazed tiles often fail to meet high decorative requirements due to high drying temperatures (greater than 1 200 °C). The method according to the invention allows the obtaining of ceramic substrates, in particular ceramic tiles, -19-201204683, which exhibit a high degree of decorative finishing and outstanding mechanical and chemical properties such as scratch resistance, stain resistance and chemical resistance. This allows such tiles to be used, for example, in bathrooms, kitchens, and other environments where high tolerance is required. Particularly resistant to staining, gloss and chroma are often superior to glazed tiles. Compared to conventional glazing techniques, the method of the invention consumes less energy and is more environmentally friendly. The facets of the present invention relate to ceramic substrates, particularly ceramic tiles, which are obtainable (or available) by the methods of the present invention. More specifically, the present invention relates to a ceramic substrate, particularly a ceramic tile, comprising at least one base coating layer (A) derived from a powder coating composition, the composition comprising at least a carboxy- and/or hydroxy-functional group. A polyester, and at least one hardener having a functional group reactive with the polyester functional group; and at least one further layer (B) derived from the liquid coating composition as hereinbefore described. In a preferred embodiment of the invention, the ceramic substrate, particularly the tile of the present invention, has a pencil hardness (according to Wolff Wilborn according to a scratch hardness tester) of at least 2H, preferably at least 3H, more preferably at least 4H. Even a pencil hardness of 5H or 6H can be achieved using the method of the present invention. In a preferred embodiment of the invention, the undercoat layer on the ceramic substrate is a pigmented coating. The liquid layer disposed directly on top of the undercoat layer is a clear coating. In addition, the liquid layer is added with a pigment. In another preferred embodiment of the invention, the powder coating and the liquid coating are clear coatings, and the color image is applied to the tile prior to application of the liquid coating. In addition, the undercoat layer is pigmented and provides a background color (e.g., white) to the color image disposed on top of it. A preferred liquid coating (any of the foregoing embodiments) is a topcoat. -20- 201204683 Pigments (any of the foregoing) may be organic and/or inorganic. Another aspect of the invention relates to a liquid coating composition for a ceramic substrate comprising U) at least one acrylic resin and/or at least one polyester resin, and (b) at least one amine resin' It is a melamine hardener. Suitable acrylic resins and polyester resins have been described above. Preferably, the acrylic resin is a hydroxylated acrylic resin, and the polyester is a hydroxylated polyester. Additional compounds and/or ingredients for the selectivity of the liquid coating composition have been previously described. [Examples] The following examples will illustrate the invention but are not limiting. Preparation Example 1: Synthesis of Carboxyl Functional Polyester PE1 4 0 8.3 7 g of neopentyl glycol was placed in a conventional four-necked round bottom flask equipped with a stirrer, a distillation column connected to a water-cooled condenser, and nitrogen gas. Air port and thermometer attached to the thermostat. The contents of the flask were heated while stirring under nitrogen to a temperature of about 130 ° C, at which time 5 3 2 · 5 9 g of terephthalic acid, 5 9.1 8 g of adipic acid and 2.00 g of n-butyltin trioctoate were added. Slowly heat up to 230 °C. Water is distilled from the reactor from a temperature above 180 °C. When the distillation was stopped at atmospheric pressure, a vacuum of 50 mmHg (about 6666 Pa) was slowly applied. After 3 hours at 23 ° C and 50 mm Hg, a polyester having the following properties was obtained: AN: 3 mg KOH / gram ' OHN : 42 mg KOH / gram. The reaction mixture was then cooled to 170 ° C - 190 ° C, followed by the addition of 119.18 g of trimellitic anhydride. The temperature was maintained at 80 ° C until the reaction mixture became clear. A carboxy-functional polyester having the following properties was obtained: AN = 72 mg KOH/g, OHN = 6 mg KOH/g, Brookfield (175 ° C) viscosity (cone / -21 - 201204683 plate) = 1 〇, 〇〇〇mPa.s ; Tg (DSC, 20 K· / min) = 58 ° c. Preparation Example 2: Synthesis of Carboxyl Functional Polyester PE2 423.82 g of neopentyl glycol was placed in a reactor, heated under nitrogen while stirring to a temperature of about 13 ° C, at which time 720.34 g of isophthalic acid and 2.5 g were added. N-butyl octanoate. Slowly heat up to 2 30 °C. Water is distilled from the reactor from a temperature above 180 °C. When distillation is stopped at atmospheric pressure, a vacuum of 50 mm Hg is applied slowly. After 3 hours at 230 ° C and 50 mm Hg, a carboxy-functional polyester having the following properties was obtained: AN: 32 mg KOH/g, OHN: 2 mg KOH/g, Brookfield (200 ° C) viscosity (cone/plate)·· 3,000 mPa.s; Tg (DSC, 20 K/min): 57 °C. Preparation Example 3: Synthesis of hydroxy-functional polyester PE3 A mixture of 439.94 g of neopentyl glycol and 14.1 g of trimethylolpropane was placed in a reactor and heated under nitrogen while stirring to a temperature of about 130 ° C. 645.62 grams of terephthalic acid, 33.98 grams of adipic acid, and 2.5 grams of n-butyltin trioctoate were added. Slowly heat up to 2 30 °C. From the temperature above 180 °C, water is distilled from the reactor. When the distillation was stopped at atmospheric pressure, a vacuum of 50 mm Hg was applied slowly. After 3 hours at 2300 ° C and 50 mm Hg, a hydroxy-functional polyester with the following properties was obtained: AN: 3 mg KOH/g, OHN: 32 mg KOH/g, Buchenkefe (200 °) C) Viscosity (cone/plate): 7 J00 mPa.s; Tg (DSC, 20 K/min): 56 〇C. Reference Examples 1 to 3: The polyester resins of Preparation Examples 1 to 3 were formulated into a black powder according to the following formulation: -22- 201204683 Table 1 Powder Composition 1 Powder Composition 2 Powder Composition 3 Composition Quantity (g) Composition Quantity (克) Composition quantity (g) PE1 27.24 PE2 38.14 PE3 47.94 Epoxy hardener Allah GT7004 27.24 Epoxy hardener Allah GT7004 16.34 Hardener Vitaoka BF1530 6.54 Carbon black FW2 1.06 Carbon black FW2 1.06 Carbon black FW2 1.06 White solid (Blanc Fix) F 21.60 White solid F 21.60 White solid F 21.60 Benzoin 0.35 Benzoin 0.34 Benzoin 0.35 Moura flow (Modaflow) P6000 0.99 Moura flow P6000 0.99 Mora flow P6000 0.99 Powder composition 1 to 3 powders are applied separately Polished tiles. Up to now, the tiles have been preheated at 200 °C for 10 minutes and then moved to the wooden support for electrical insulation. The powder was then sprayed with a thickness of 160 microns using Gema Volstatic PCG1 without applying an electric field. The tiles were then moved to a convection oven where they were allowed to harden at 200 °C for 30 minutes. Preparation Example 4: Synthesis of Polyester Polyols Two-liter four-necked bottles fed with a stirrer, heater, water separator and inert gas inlet were fed 2.45 m 3 (4), 8 (9) - double Hydroxymethyl-tricyclo-[5.2.1.02,6]decane, 1.35 moles of neopentyl glycol, 4.0 moles of hexahydrophthalic anhydride and 2.2 moles of trimethylolpropane. The starting component was heated to 200 ° C under nitrogen and the resulting reaction water was continuously removed. The temperature is slowly raised to 220 ° C until the acid enthalpy is less than 25 mg KOH / gram. The polyester polyol was then cooled to 120 ° C and diluted with butyl acetate and adjusted to 78% solids by mass (determined according to D IN E N I S 0 3 2 5 1). The final product -23- 201204683 is transparent and has the following characteristics: acid 値 2 1 .0 mg KOH / gram, oxindole 2 1 9 KOH KOH / gram, dynamic viscosity (determined according to DIN EN ISO 3219) 1 08 3 8 mPa .s, weight average molar mass Mw is 1 3 15 5 / mol, and polydispersity U is 1.6, as determined above. Preparation Example 5: Synthesis of a hydroxylated acrylic resin A two-liter four-necked flask equipped with a stirrer, a heating and cooling system, an inert gas inlet, and a feed device was fed with 3 69 g of solvent naphtha 150/180 ( A hydrocarbon mixture having a boiling range from 150 ° C to 180 ° C), and the feed was inerted with nitrogen and heated to 148 t. Subsequently, a mixture of 3 60 g of styrene, 325 g of butyl acrylate, 176 g of hydroxyethyl methacrylate and 18 g of acrylic acid was metered in through a dropping funnel over a period of 6 hours. At the same time, an addition of 26 g of dibutyl peroxide was dissolved in 8 8 g of solvent naphtha (see above). After 6 hours, the temperature was maintained at 1 48 ° C for 2 hours. The mixture was then cooled to 120 ° C and diluted with 120 g of butyl acetate and adjusted to 60% solids by mass (determined according to DIN EN ISO 3251). The final product is clear and has the following characteristics: acid sulphate 17.0 mg KOH/g, oxindole 91 mg KOH/g, dynamic viscosity (determined according to DIN EN ISO 3219) 1487 mPa.s, weight average molar mass Mw 10460 g/ Mohr, and polydispersity U = Mw / Mn is 4.0, where Μη is the number average molar mass, all measured by GPC using polystyrene standards. Formulation The resin of Example 4 was formulated in the coating formulation of Example 6. Example 6: Quantity is expressed in grams - 24 - 201204683 Composition A : 80.00 Polyester 7.50 of Example 4 1. Methyl amyl ketone 1.85 Butylene acetate 3.15 Methoxypropyl acetate 1.15 Toyso (S) 6 6 1) 1.06 Metatin η 7 1 2 / 1 % in xylene 2) 0.55 Tinuvin 292 3) 1.60 Emperor 113 0 3) 1.90 Methylpentyl ketone 0.44 Butylene acetate 0.80 methoxypropyl acetate composition B: 47.30 De sm 〇dur N 3 3 0 0 4) 18.90 Methyl amyl ketone 12.60 Butylene acetate Example 5 Resin system The coating formulation of Example 7 was formulated. Example 7: Quantity is expressed in grams. Composition A: 64.40 Example 5 Acrylic 1 8.40 Cyram (C YMEL) MB-1 4-B 5) 1.60 n-Butanol 1.60 Butylene Acetate-25- 201204683 6.90 Isobutyl acetate 2.00 Tosso S 366 1) 0.80 Dienvenir 2 9 2 3) 2.80 Dienvenir 1 1 3 0 3) 1.50 Butyl acetate composition B : 26.20 Solvent naphtha 1 5 0 /1 8 0 7.50 Butyl Acetate The polyester of Example 4 and the acrylic (3/1) blend of Example 5 were formulated in the coating formulation of Example 8. Example 8:
% 組成物A 38.3 實例4之聚酯 12.4 實例5之丙烯酸系 16.2 賽摩 3 62 9 2 莫拉流 9 2 0 0 ( 1 0 % ) 6) 2 B Y K 3 3 3 ( 1 0%) 7) 0.3 西凱 404 5 8 ) 6 正丁醇 6 DME-1 9) 16.8 S-100 10) 1) 滑脫劑及均平劑（特洛伊化學公司（1^(^<：1^111· Comp.)) 2) 催化劑（阿西瑪公司（Acima AG)) -26- 201204683 3) 紫外光吸收劑（汽巴嘉基公司（Ciba Geigy AG)) 4) 交聯劑（拜耳公司（Bayer AG)) 5) 交聯劑（賽德公司） 6) 流動改性劑（賽德公司） 7) 滑脫劑及濕潤劑（BYK化學公司） 8 )催化劑（賽德公司） 9) 己二酸、戊二酸及丁二酸之聖多索醇二甲酯（賽德公司） 10) 芳香烴溶劑（華倫公司） 前述塗覆組成物係以該技術領域人士眾所周知之方式 製備。 用於實例6、7及8之塗覆組成物，組成物A之組分首先 經徹底混合。用於實例6之塗覆組成物，組成物B係恰在處 理前添加，所得混合物之流動時間（噴霧黏度）係以額外稀 釋劑調整至流動杯（D IN 5 2 2 1 1，2 3 °C )爲2 1秒。用於實例7 之塗覆組成物，噴霧黏度係透過添加組成物B之溶劑混合物 而調整至流動杯爲2 1秒。 然後使用高體積低壓噴槍，具有1.8毫米噴嘴及0.7巴噴 嘴壓力，以約40微米乾膜層厚度噴霧。 測試結果 實例9 : 實例6之塗覆調配物係如前文說明噴霧至塗覆以粉末 組成物1之瓷磚上，於自室溫至80 °C之溫度放置。於80 °C硬 化3 0分鐘後，瓷磚冷卻用於評估。 實例〗〇 : •27- 201204683 實例7之塗覆調配物係如前文說明噴霧至塗覆以粉末 組成物3之瓷磚上，於室溫放置。施用塗層後1 0分鐘，溫度 升高至130°C。於130°C30分鐘後，瓷磚冷卻用於評估。 實例1 1 : 實例8之塗覆調配物係如前文說明噴霧至塗覆以粉末 組成物2之瓷磚上，於自室溫至180 °C之溫度放置。施用塗 層後溫度維持於180 °C30分鐘。然後瓷磚冷卻用於評估。 測試結果摘述於表2。 表中： 欄1 :指示根據I s Ο 1 5 1 8 4根據刮擦硬度測試器之錯筆 硬度 欄2:指示根據ASTMD523之60度光澤 欄3 :指示根據IS Ο 1 0 5 4 5 -1 1之耐龜裂性 欄4 :指示根據ISO 1 0545 - 1 3之耐化學性。下列爲其它 測試：對鹽酸（3%)及對KOH(30克/升）之耐性 欄5 :指示根據I S Ο 1 0 5 4 5 - 1 4之耐玷染性 欄6:指示根據IS〇l〇545-9之耐熱震性。材料係於15〇。〇 至1 5 °C測試1 5週期。 欄7:指示根據ISO 4582之耐候性 -28- w貧 201204683 表2 液體塗覆 組成物 硬度 光澤度 耐裂性 耐化學性 耐玷染性 耐熱震性 耐侯性 實例9 良好 優異 良好 優異 優異 優異 優異 實例10 優異 優異 良好 良好 良好 良好1 良好 實例11 優異 優異 優異 優異 優異 優異 優異 實例9至1 1所得瓷磚及參考例1至3所得瓷碍分別證實 極爲平滑光整而無任何凹坑及/或缺陷。 此表所得結果顯示藉本發明方法所得陶瓷瓷磚（實例9 至11)具有極佳耐裂性及耐熱震性以及優異光澤度及硬 度。以本發明之方法可獲得3H至4H或以上之鉛筆硬度。使 用本發明方法甚至可達5H或6H之鉛筆硬度。 只有粉末層之陶瓷瓷磚（參考例1至3)，或有液體底塗 層及粉末頂塗層之陶瓷瓷磚並未獲得期望性質。例如硬度 不足。 實例1 2 製備如表3所述之粉末塗覆組成物4。如此製備之粉末 塗覆組成物施用至經砂磨拋光的瓷磚上。瓷磚於2 0 (TC預熱 1 〇分鐘然後移至木製支架上俾便電絕緣。隨後使用吉瑪伏 史PCG1以200微米層厚度噴霧粉末而未施用電場。然後瓷 磚移至對流烤爐，此處於200°C硬化30分鐘。 隨後經聚酯塗覆之瓷磚經砂磨，接著爲使用熱轉印紙 (上海堤那攸旗幟工廠（Shanghai Tinayu Banner Factory))之 影像轉印設計步驟。紙張於瓷磚上覆蓋以粉末塗層及於 -29- 201204683 200 °C加熱20分鐘。此一步驟後，實例8之塗覆調配物如前 述噴霧至瓷磚上，於自室溫至180 °C之溫度放置。施用塗層 後溫度於18〇°C維持15分鐘。然後瓷磚冷卻用於評估。頂塗 層厚度：60微米。 表3 粉末組成物4 組成 數量（％) PE 1 25 環氧硬化劑D E R 6 6 3 U 25 二氧化矽粉末 40 莫拉流P 6000 1 安息香 0.5 西里達（Ceridust)391〇 1.5 R-706 6 耶羅賽（AEROXIDE) Alu C 0.3 DER663U爲得自陶氏化學公司（Dow Chemical)之環氧 硬化劑。西里達3 9 1 0爲得自克列里顏料及添加劑公司 (Clariant Pigments and Additives)之白色二硬脂基伸乙基 二醯胺。R-7 06表示得自杜邦公司（DuPont)之杜邦鈦純金紅 石二氧化鈦顔料。耶羅賽A丨u C爲得自德古莎-伊佛尼克公 司（Degussa-Evonik)之氧化鋁。 測試結果摘述於表4 : -30- 201204683 表4 液體塗覆組成物 硬度 光澤度 耐裂性 耐化學性 耐玷染性 耐熱震性 實例1 2 良好 優異 優異 優異 優異 優異 >3 Η 95 如上顯示使用本發明方法可獲得具有優異品質之高度 裝飾性光整。 【圖式簡單說明】 無。 【主要元件符號說明】 〇% Composition A 38.3 Example 4 Polyester 12.4 Example 5 Acrylic 16.2 Seymour 3 62 9 2 Moura Flow 9 2 0 0 ( 1 0 % ) 6) 2 BYK 3 3 3 ( 1 0%) 7) 0.3 Xikai 404 5 8 ) 6 n-butanol 6 DME-1 9) 16.8 S-100 10) 1) Slip agent and leveling agent (Troy Chemical Company (1^(^<:1^111· Comp.) 2) Catalyst (Acima AG) -26- 201204683 3) UV absorber (Ciba Geigy AG) 4) Crosslinker (Bayer AG) 5 Crosslinking agent (Side) 6) Flow modifier (Side) 7) Slip agent and wetting agent (BYK Chemical Company) 8) Catalyst (Side) 9) Adipic acid, glutaric acid And succinic acid succinol dimethyl ester (Side) 10) Aromatic hydrocarbon solvent (Warren) The aforementioned coating composition is prepared in a manner well known to those skilled in the art. For the coating compositions of Examples 6, 7, and 8, the components of Composition A were first thoroughly mixed. For the coating composition of Example 6, composition B was added just prior to treatment and the flow time (spray viscosity) of the resulting mixture was adjusted to the flow cup with additional diluent (D IN 5 2 2 1 1,2 3 ° C) is 2 1 second. For the coating composition of Example 7, the spray viscosity was adjusted to a flow cup for 21 seconds by adding a solvent mixture of Composition B. A high volume low pressure spray gun was then used, with a 1.8 mm nozzle and a 0.7 bar nozzle pressure, sprayed at a dry film thickness of about 40 microns. Test Results Example 9: The coating formulation of Example 6 was sprayed onto a tile coated with Powder Composition 1 as previously described and placed at a temperature from room temperature to 80 °C. After 30 minutes of hardening at 80 °C, the tiles were cooled for evaluation. EXAMPLES 〇: • 27-201204683 The coating formulation of Example 7 was sprayed onto a tile coated with Powder Composition 3 as previously described and placed at room temperature. Ten minutes after the application of the coating, the temperature was raised to 130 °C. After 30 minutes at 130 ° C, the tiles were cooled for evaluation. Example 1 1 : The coating formulation of Example 8 was sprayed onto a tile coated with Powder Composition 2 as previously described and placed at a temperature from room temperature to 180 °C. The temperature was maintained at 180 ° C for 30 minutes after application of the coating. The tiles are then cooled for evaluation. The test results are summarized in Table 2. In the table: Column 1: indicates according to I s Ο 1 5 1 8 4 according to the erroneous pen hardness of the scratch tester. Column 2: Indicates the 60 degree gloss bar according to ASTM D523. 3: Indicates according to IS Ο 1 0 5 4 5 -1 Resistance to cracking of column 1 : Indicates chemical resistance according to ISO 1 0545 - 13. The following are other tests: Resistance to hydrochloric acid (3%) and to KOH (30 g/L). Column 5: Indicates resistance to staining according to IS Ο 1 0 5 4 5 - 1 4 Column 6: Instructions according to IS〇l耐热 545-9 thermal shock resistance. The material is at 15 〇. 15 Test 1 5 cycles to 1 5 °C. Column 7: Indicates weather resistance according to ISO 4582 -28-w lean 201204683 Table 2 Liquid coating composition hardness Gloss crack resistance Chemical resistance Dye resistance Thermal shock resistance Example 9 Good Excellent Good Excellent Excellent Excellent Excellent Example 10 Excellent Excellent Good Good Good Good 1 Good Example 11 Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent Examples The ceramic tiles obtained in Examples 9 to 1 and the porcelain obtained in Reference Examples 1 to 3 were each confirmed to be extremely smooth and smooth without any pits and/or defects. The results obtained in this table show that the ceramic tiles obtained by the method of the present invention (Examples 9 to 11) have excellent crack resistance and thermal shock resistance as well as excellent gloss and hardness. A pencil hardness of 3H to 4H or more can be obtained by the method of the present invention. Even a pencil hardness of 5H or 6H can be achieved using the method of the invention. Only the ceramic tile of the powder layer (Reference Examples 1 to 3), or the ceramic tile having the liquid undercoat layer and the powder top coat layer did not obtain the desired properties. For example, the hardness is insufficient. Example 1 2 Powder coating composition 4 as described in Table 3 was prepared. The powder coating composition thus prepared is applied to a sanded polished tile. The tiles were preheated for 20 minutes (TC) and then moved to a wooden support for electrical insulation. The powder was then sprayed with a thickness of 200 microns using Gimma PCG1 without applying an electric field. The tiles were then moved to a convection oven. Hardened at 200 ° C for 30 minutes. The polyester-coated tiles were then sanded, followed by image transfer design steps using thermal transfer paper (Shanghai Tinayu Banner Factory). The upper cover was powder coated and heated at -29-201204683 at 200 ° C for 20 minutes. After this step, the coating formulation of Example 8 was sprayed onto the tile as previously described and placed at a temperature from room temperature to 180 ° C. The temperature after coating was maintained at 18 ° C for 15 minutes. The tile was then cooled for evaluation. Top coat thickness: 60 μm. Table 3 Powder composition 4 Composition number (%) PE 1 25 Epoxy hardener DER 6 6 3 U 25 cerium oxide powder 40 Moura flow P 6000 1 benzoin 0.5 Ceridust 391 〇 1.5 R-706 6 AEROXIDE Alu C 0.3 DER663U is a ring from Dow Chemical Oxygen hardener Up to 391 is a white distearyl extended ethyl bis-amine derived from Clariant Pigments and Additives. R-7 06 represents DuPont titanium pure rutile from DuPont Titanium dioxide pigment. Jerez A 丨u C is alumina from Degussa-Evonik. Test results are summarized in Table 4: -30- 201204683 Table 4 Hardness of liquid coating composition Gloss crack resistance Chemical resistance Dye resistance Thermal shock resistance 1 2 Excellent, excellent, excellent, excellent, excellent, excellent > 3 Η 95 As shown above, highly decorative finishing with excellent quality can be obtained by using the method of the present invention. Description] None. [Main component symbol description] 〇
/INN -31 -/INN -31 -