1276620 九、發明說明： 【發明所屬之技術領域】 本發明係關於特別適合用 ;主覆陶瓷基材之塗料組合物 和方法。 【先前技術】 由食品和飲料卫業所用的玻璃和其它陶变容器通常塗有 簡的塗料和/或裝飾以資訊，例如容器的内容物或功能性 的仏不或其匕記號來標示產品和/或其來源。在許多國家 中飲料如皁酒和蘇打水是裝在可回收的玻璃瓶中銷售 、二在飲料消費後玻璃瓶回收讓飲料再填充。之後它們： 、肖f再填充、再貼上標籤、然後再銷售。印上去 的化樣和紙軚籤有許多缺點。如實例紙標籤和印上去的花 樣兩者都很昂貴、麻煩且容易在曝露於水或其它物質後消 ^此外，許多用在印上花樣的接著劑在瓶子清洗的過程 時變得很黏’而會使機器受到傷害或損耗之類。 為避免關於印上去的花樣和紙標籤之問題，更永久性的 裝飾物已被用於回收容器的玻璃表面。這些更永久性的裝 飾物是以糊劑形式來使用，其含有玻璃狀材料（或稱玻璃原 料混合物）、和載體典型地為揮發性有機溶劑或蠟（"v〇c”） 所精細研磨之粒j。在此糊劑以熱炫領印或其它應用的技 術用於玻璃表面後，此玻璃是在高溫下燒（如實例650。〇以 揮發和/或熱分解而驅除所有的載體，將玻璃狀的混合物熔 融，而將玻璃狀的混合物結合於玻璃表面。在熱熔絹印時， 玻璃狀混合物或其它要印刷的物質是用在所需的圖案上的 96457.doc 1276620 加熱阻隔物上。玻璃狀混合物熔融或軟化後經由擠壓器通 過阻隔物，而轉移至基材上燒。顏料對此高溫是沒有感覺 的其包含於糊劑中以提供組合物顏色。這些顏料典型地 各有重金屬，例如產生紅色的鎘、白色的鉛、和黃色的鉻。 關於此類裝飾方法之VOC和重金屬對環境是有危害的。高 溫燃燒的步驟需要相當的能量消耗且對工作者有傷害的危 機。 努力避免使用有機溶劑和重金屬於塗料中和/或裝飾的 π瓷谷益，而降低能源消耗涉及可硬化的有機黏合劑系統 之使用。傳統的有機顏料需要在可硬化的黏合劑系統中， 其以阻隔印刷的方法，在方法和溫度的條件下將其塗在陶 瓷表面上，而在此條件下任何硬化劑均沒有活性。熱硬化 的有機黏合劑，裝飾的容器在烘箱中加熱至_溫度使硬化 劑活化將黏合劑硬化，但並未使顏料降級，這使得黏合劑 與顏料附著至容器上。然而，如果需要使用第二層時，接 著的阻隔應用通f會讓前面戶斤塗的色層從容器上剝離下 來，或此色層會受到傷害，得到有缺陷的產品。如果第一 層在塗第二層前硬化或部分硬化時，則在接著塗一層時的 剝離或其它傷害就可避免’但明顯地損失了加工速度、效 率和/或能源的使用。 藉由紫外線輻射硬化黏合劑可以用來預製多層油墨設 計，其：避免塗下一層前’每層油墨硬化(或部分硬化時對 下層的傷害。然而’這需要在每個油墨塗覆配置後安裝紫 外線硬化裝置，增加設備的成本和複雜性。 /' 96457.doc 1276620 此種用於瓶子的塗料組合物通常是在嚴厲的物理和化學 環境特別地回收瓶子典型為在腐蝕性清潔溶液中重複清 冼循壞。下層的陶瓷基材易受此類腐蝕性清潔溶液分解， 軟化的下層基材可能引起其上的塗料組合物由基材上脫 離。對用為精細裝飾物之塗料組合物，例如在小尺寸上寫 下東西此問題使其更為惡化。精細的線條有時候被重複 的腐餘性清洗而損傷或除去，雖然大面積來看沒有顯著的 影響。 在製造玻璃容器時，一種，，熱封塗料，，通常用在新形成的 容器上，其在容器外層得到一種氧化錫的薄膜。氧化錫塗 料的存在，發現對有機農飾㉟耐重複腐颠性清洗之能力有 正面的影響。然而，氧化錫薄膜並不產生所需耐久性。 匕對用於塗復陶瓷容器的組合物和方法提供優越裝 倚效果Μ吏其成本具競爭性M吏能源消耗最小化和/或财粗 糙環境是有需要的。 【發明内容】 本發明係針對用於塗覆陶£基材之方法，其包括使用至 少-種有色的塗料組合物於至少_部分的基材上，而此組 合物至少含有一種可硬化的有機黏合劑和至少一種賦色 劑；使用—種實f上透明的塗频合物於至少-部分的基 材上’此組合物含有-種可硬化的有機黏合劑；且實質上 同時將在有色的塗料組合物和實質上透明的塗料組合物中 之黏合劑硬化；其中不論是有色的塗料或實質透明的塗料 均可詩第-次塗覆，且其中第—次使料塗料更含有許 96457.doc 1276620 多粒子。根據這些方法塗覆的基材亦包含於本發明的領 中。 … 【實施方式】 本發明一般係針對用於塗覆陶瓷基材之方法。π陶究，，來 照為一種廣泛的基材，一般特性為易碎、耐熱和/戋由一種 或多種非金屬礦物所形成者，包括但非限定有陶、土、黏 土、白陶、耐火磚土、瓷、玻璃陶瓷和玻璃。陶瓷基材可 上光油或不上光油，且可為任意形狀、大小或結構。 本發明有色的塗料組合物包括至少一種可硬化的有機黏 合劑和至少一種賦色劑。在此所用，，賦色劑”和相似的詞參 照為任何賦予顏色和/或其它不透明和/或其它對組合物的 視覺效果之物質，例如染料、顏料、染髮劑和其相似物。 賦色劑可包括如實例精細分割的固體粉劑，不可溶但在使 用的條件下可濕潤。賦予顏色之顏料為孰於此藝者所知， 且在美國專利第6,214,414號中可發現特別實例的名冊。單 獨的賦色劑或兩種或更多的賦色劑之混合物均可使用。耐 咼溫的顏料，例如玻璃狀混合物塗料和裝飾物且通常含有 重金屬所用者，均可使用，但因為在本發明中不需要高溫， I耐高溫的顏料亦可使用。因此，根據本發明可以避免I通 浜有骨的含重金屬顏料，而不犧牲外觀。本發明一個非限 定的具體實施例特別排除了重金屬包括鉻、鎘、鉛或鈷。 田使用時賦色劑可含本發明组合物之丨至65重量％ ,例如從 ⑽重量％或5至35重量％，重量％是以組合物的總重： 异。典型地用於塗料工業之任何顏料或染料均可使用，例 96457.doc 1276620 如二氧化鈦、碳黑、DPPB0紅、酞青綠或藍、氧化鐵、釩 酸鉍、萘酚AS、蒽醌、茈、鋁和喹脎啶酮。 其它在本發明中影響組合物外觀可用為賦色劑的物質包 括特別效果的顏料和/或特別效果的組合物，其產生一種或 多種效用，例如反射比、有珍珠光彩、金屬光澤、磷光、 赏光、光色性、熱色性、和角度色性。此類特別效用顏料/ 組合物一般賦予組合物顏色，而某些特別效用的顏料/組合 物並未賦予組合物可感受到的顏色，但其提供本發明組I 物其它可感受到的性質，例如視覺上的性質。 〇 實質上透明的塗料，如有色塗料亦含有至少一種可硬化 的有機黏合劑’其可與在有色塗料組合物中的可硬化有機 黏合劑相同或不同。"實質上透明的塗料"及其相似詞參照 為賦予底層基材或塗料一點或不賦予顏色之塗料。 如上所示，本發明是針對塗覆陶瓷基材之方法，包括使 用㈣塗料組合物於基材上，—種有色的塗料組合物和一 種實質上透明的塗料組合物。塗料可以用兩種順序，即有 色的再用透明的，或透明的再用有色的。第一次使用的塗 料’視狀況此塗料有時為第二次使用，其更含有許多"隔門 的”粒子。此粒子可為有機、無機或其組合，球狀、非球^ 或其組合。有機的粒子可為聚合的、非聚合的或其组人。 此粒子可為實心、中空、或其組合。適當的無機粒子為市 上可得，為鈍性的填充劑且可包含如實例玻璃，包括硼矽 酸鹽玻璃和納約玻璃、以及陶究。有機的粒子市上可得亦 很廣泛。適用於本發明的有機粒子可包括各式的聚合物種 96457.doc -10- 1276620 和其混合物；這些粒子在某些如下所述的具體實施例中可 顯不出所需的剛性和熱軟化性之組合。在某些具體實施例 中，某些有機粒子在達到所需的光澤度上特別有利，因為 其立即軟化而流動，得到平滑光澤的表面。適當的聚合物 ::包括聚醯胺、聚矽氧烷、聚丙烯酸酯、聚丙烯醯胺、 K苯乙烯、聚胺基甲酸酯和聚酯。適當的聚醯胺之非限定 實例包括聚醯胺12、聚醯胺11、和聚醯胺6/12。根據本發 明所用的塗料可以包括軟化的有機粒子和/或可以不經過 、下f哪的I人化性加工之有機粒子，和/或無機粒子。 古此：子在第—溫度或低於第—溫度時可為剛.生，且在較 南的第二溫度S低於第二溫度時軟化，於其時黏合劑硬 化’而在第一溫度時黏合劑並未硬化。因此粒子在所有相 關的：度下為剛性，即其在黏合劑硬化的溫度或低於此溫 2下亚不軟化，且在此所述的塗覆期間，基材會暴露於其 /皿度下’而不會有任何可感受的軟化。此"非軟化”的粒子 在達到如表面結構、摩擦餘、耐磨性和/或特別的反射性 的目的上可能是很有用的。此粒子在塗料組合物中可能存 在足夠顯示所需效果的量和比例。"剛性”和相似詞意謂粒 子亚不在指定的溫度下立即可麼縮，即粒子較未硬化的黏 合劑所含者具有較高的結構完整性。 更特別地，組合物所用的一種或多種成分是選擇使· 口 Μ為未硬化，而在有色組合物和/或實質上透明的塗料j 口物中的粒子在第一溫度下為剛性。第一溫度典型上為、彳 合物塗於基材上之溫度和/或為第二或接著的塗覆可能; 96457.doc 1276620 於基材上之溫度。這個溫度可能為室溫，或其可能在某些 升高的溫度下。在某些具體實施例中，在第二溫度下黏合 劑硬化且粒子軟化。”硬化"和相似詞參照為化學反應，其 使有機黏合劑的各種成分連接在一起形成熱固型的聚合 物。”軟化"和相似詞參照為在粒子中失去足夠的結構剛 性，使得粒子上發生變形和/或其它外形改變。如實例粒子 由本發明組合物表面突出，在第二溫度或低於其下時改變 外形，”炫融"或光滑化塗膜表Φ;因為此光滑化，當粒子 突出於塗膜表面為最少化若其未消失時，則光澤降低通常 二硯祭到。在其它的具體實施例中，一種或多種使用的組 粒子’其在第—和第二溫度下維持剛性和/或結構 的解Γ可以基於其在黏合劑和/或組合物 ’、、/合解度和/或可濕潤性選擇使用。過度溶解 於黏合劑中的粒子可能合名過度/合解 印刷m古 分解、膨潤或軟化，且在 表面外龠。石里』 次了此除此之外得到不需要的 上可能不需要兄刀濕潤，則在某些應用 月匕不而要的表面結構可能產生。 粒子可為球狀或非球狀之粒子。 擇將隔間功能最大化，和最 -尺寸和粒徑分佈選 不口取小化任何對外顴古 粒子大小根據需求 σ的效應。 π仗用者所需而變， 粒徑低於1微米。在某些非限定 ：:含有之平均 可為至少1微米，在立它 〃、“列中，平均粒徑 #匕非限定的且靜每 米’且發現在某些非限定的 ，^例中至少3微 ，、體只把例令滿足平均粒徑至 96457.doc 1276620 少為5微米。在某些具體實_中 塗料層沈澱時大約相同大小。 子大小典型地可為如 時，其無隔間的作用，且、。如果粒子相對於塗膜層太小 時可能由表面突出且降低塗寺其可能突出，或太多 在軟化後。當然此突出在列=物的最後光澤，即使 粒子大小和/或軟化性質可：；擇子:可能需要’在其例中 k擇適▲者。撰. 可以由用於熱熔頌印加工之網目大"L擇粒子大小亦 變成由粒子堵塞，其太大 ° 1«物可能 刷品質。 太大而不錢過，其結果為較差的印 2據本發明所料黏合劑可^自 I “貝上為液體狀態用在陶瓷基材上，之後 為耐久的硬化狀態。硬化可以由任何方法來 如加熱、紫外線輻射、 ^ 歹1 于束輻射或會使黏合劑硬化的一 ϋ匕形式的能量。在某些具體實施例中，黏合劑包括— y夕種有機成分’當用上硬化能量時其會進行硬化反 ”在某些非限定的具體實施例中’組合物可以包含環氧 樹脂和胺硬化劑（如f例雙氰胺）例如美國專㈣6 214 414 號中所揭示者，以及本發明中其它的非限定具體實施例， 黏合劑更可包括-種封閉的異氰酸醋硬化劑’例如美國專 =第6,214,414號中所揭示者併於此供參考。其他適當的樹 脂包括如實例含羥基或羧酸的丙烯酸系聚合物、含羥基或 羧酸的聚酯聚合物、異氰酸酯或含羥基的聚胺基曱酸酯聚 合物、含胺或異氰酸酯的聚脲酯，或任何其它的羥基、羧 96457.doc -13- 1276620 聚人：知二、胺基甲酸酯、異氰酸酯或環氧基官能性的 ♦2°適當的硬化劑可由熟於此藝者所決i且可包括 一種或多種胺基塑料、酚塑料、 氰酸醋、多元醇、： 乳化物、聚酸類、異 .s 夕兀胺、馱酐和碳化二亞胺。黏合劑和/ 或硬化劑的組合均可使用。 以 在一個非限定實例中，甲班 Λ衣虱基5能性的反應性有機樹 月曰可以使用；”聚環氧基官能立 月b陸思钟以數目平均分子量計 此樹:曰平均母莫耳含有超過一個環氧基，或平均每莫 :兩個L基或更多。在其它非限定的具體實施例中； 或電子束_輕射可用來起始黏合劑 為 :當調製含有反應性官能基，設計其暴露於韓射而熱固 ^包括各式自由基硬化的材料，例如丙稀酸醋、乙 、土 g月匕性材料、丙稀酸化的宣取仏i 的养承物和聚合物、以及乙烯 基醚與不飽和聚酯。 J 了為險離子起始的材料，例如環 脂族環氧基或乙烯基醚。滴a A 適§的自由基或陽離子光起始劑 一般使用紫外線硬化和視愔 况有EB硬化。自由基和陽離子 硬化的組合亦有可能，如势 戈I外線/電子束硬化加工與如上所 述之熱硬化組合物之組合。 在某些非限定的且體會# . ^ 灵％例中，用於本發明之黏合劑具 有或改變為具有黏度，適 ^於在6〇C至120°C下印刷；其它溫 度可以用在其它非限定的 Ί具體貫施例中。對熱硬化系統， 黏合劑的硬化機制是選擇 俘暴匕在弟二溫度前具有一點或沒 有活性，而至此溫度黏合劑才硬化。…免過度硬化， 96457.doc Ί4. 1276620 在第一和第二溫度之間的差異可為至少3(rc 為超過5(TC，雖然其它溫度差亦可用於本發 且更典型地 明中。 用於-種或多種有色塗料組合物中之可硬化有機黏合 劑，和用於實質上透明的塗料組合物中之可硬化有機黏合 ，可為相同或不同。類似地，如果有粒子用於兩種有色和 貝質上透明的塗料組合物中，其亦可為相同或不同。 在-些應用中，塗料以某種程度黏著於陶竟基材上，其 接近或達到-種永久的塗膜於基材上是f要的。此種高耐 久性塗料，對於要重複腐錄清洗（如實例在驗性溶液中） #谷@通常是需要的’其—般是由瓶裝業者於再填充前清 洗回收槪所用。瓶子可能在使用本發明組合物前以黏著的 促進劑處理，或黏合劑可能含有接著促進劑例如有機官能 性的矽烷、矽氧烷或鈦酸鹽。 在其它的制中’在有限次數的时至飲料瓶子業者後 塗料可以由容器上去除。如實例，季節或假期的裝飾物可 以在促銷期間置於瓶子上，並在結束促鎖期後去除。陶究 的基材可以在塗上塗料組合物前用增加剥離的組合物處 理。-個非限定的實例為用於處理陶竟基材之組合物，要 增強在腐錄清洗中本發明塗料組合物的剝離其為一種聚 乙稀組合物，例如聚乙烯乳液。增加剝離的組合物如實例 可用於冷的塗料加工上。 如上所示，併於本發明某些非限定具體實施例的組合物 中之粒子在第-溫度或低於第_溫度下時為剛性。此粒子 在此度下具有實質的結構剛性，此時組合物塗於表面 96457.doc -15- 1276620 上，在熱熔式的組合物時可以明顯地升高；在某些具體實 轭例中，在用來硬化黏合劑的溫度下，粒子會失去其結構 的特殊性。起初的剛性不需要排除所有的彈性或可塑性， 但足夠提供使用的塗料組合物未硬化時結構的完整性。此 釔構整性讓接下來在基材上的塗層不需要硬化每一層。 在此方法中，粒子的功能為”隔間”其維持塗料在實質所需 的位置上直到硬化。因為之前塗上的層或各層之完整性， 本發明讓兩層或更多層的塗膜，例如不同顏色的塗料或— 種或多種顏色的塗料，和一種或多種實質上透明的塗料， 可以使用而不需要在不同塗層間的硬化步驟。 在所有所需的各層均塗上後，可以使用硬化能量將所有 各層實質上同時實質上硬化。”實質上硬化”和相似詞意謂 黏合劑不只部分硬化。”實質上同時硬化”和相似詞參照為 在一個單一硬化步驟下實質上硬化所有塗層。 典型的市上瓶子裝飾加工使用熱熔絹印，溫度範圍從 它至120°(：，且硬化的溫度範圍從15〇它至22〇。(：，已發現聚 醯胺12的粒子特別適合。其它聚合物系統可能適合不同的 溫度範圍。 典型地黏合劑含有20至95重量％，重量％是以組合物總重 計算。如實例有色的塗料黏合劑可為35至65重量％，而實 質上透明的塗料黏合劑可能從50至95重量％，例如65至％ 重置％或75至95重量％。在某些非限定的具體實施例中，在 本發明塗料中所用相對較小尺寸和量的粒子不產生可見的 反射性。當使用粒子時，組合物的粒子含量典型地為5至5〇 96457.doc -16 - 1276620 重量％，或U)至35重量％，或15至3〇重量％，重量％是以組 合物總重計算。密度、粒子大小和粒子大小分佈會決定量 的適當度以達到滿足隔間功能和所需的薄膜外觀。如實例 可以發現較多重量％的粒子可能需要相對較密的粒子以達 到使用類似較少密度的粒子之效果。 反應性的蠟劑可以視情況地包含於本發明某些非限定的 具體實施例中。這些為長鍊脂肪族物質，其含有至少一個 具有活性氫之反應基，通常選自經基、胺基、亞脲基、胺 基甲酸、和胺基甲醯氧基，其具有物理特性—般與壤結合。 硬脂醇為經常使用的反應性壤之實例，但許多其它的化合 物：為技藝中所知。反應性的蠟可以視情況地構成高至二 重直％的組合物，例如從組合物的〇5至15重量〇/〇。 某些本發明的非限定具體實施例可能更含有實質上透明 和/或實質上無色的填充劑，且特別適於用在實質上透明的 ’、且口物中。廷些填充劑一般為精細分割的固體顆粒，其賦 予最終的塗料（為”實質上無色的"）—點或沒有賦予其顏 ，色，和/或吸收一點或沒有吸收有色光（為"實質上透明的 )。其可用來加入本發明之隔間粒子中。填充劑通常具有 取大的長度低於500奈米，例如低於1〇〇奈米，低於5〇奈米， 低於20奈米或在5至2時米的範圍中。在某些非限定的τ具體 實施例中’填充劑為疏水性。適當的疏水性填充劑之實例 包括AEROSIL煙燻的石夕土，其設計為R972, R974, r⑴ R812S’ R805(紐澤西Ridgefield park之以抑⑽公司卜當需 要日守-種實質上透明和/或無色的填充劑或兩種或多種實 96457.doc -17- 1276620 質上透明和/或無色的填充劑之混合物者 些有色組合物之具體實施例中時，實質上透明和 ^充劑典型地包含組合物的〇 〇1至2〇重量％，例如從丨至⑺ %或2至5%，而類似的量亦可以加入實質上透明的塗料 中’·為較高光澤的應用其可能要使無機添加劑最少化。 ^許多其它添加的物質亦可視情況用於本發明組合物中。 這些為抗氧化劑、除氣助劑和流動調整劑。這些僅為例證， 其它的需要時亦可使用。其它添加劑可能 :生、不透明性、耐久性、潤滑性、顏色亮度、和許；“ $於此藝者所知之功能。當存在時額外選用的材料可以用 白^上的s以達其習慣上之目的。典型地這些額外選用的 材料當存在時可以構成本發明塗料組合物的〇 〇1至丨5 %。 f 根據本發明，兩種或多種不同的塗料層用於基材上時， 至少一層為有色的，且至少一層實質上為透明的。一種"塗 料層，，或"裝飾層”一般參照為一層單獨_組合物。有色 =塗料層可以賦予標籤顏色或其它不透明性或給予基材視 =上的效果’I質上透明的塗料層可以賦予標籤透明的部 或可以用在貫貝上所有的基材上，給其下或之上的塗層 =者和基材本身提供保護和/或耐久性。當第二塗層用上 :夺’鄰接的和/或與第一塗層間隔者，在第一塗層中的粒子 精著隔間的功能維持未硬化第—層的完整性。因此，接著 在其上的、塗層，鄰接和/或與之前塗層間隔者並未干擾先前 96457.doc • 18 · 1276620 的塗層。最後塗上的塗層亦可以含有粒子，但因為其不面 對接下來嚴密的印刷作業，因此其不需要包括粒子。 在某些具體貫施例中，至少一種如上所述的有色塗料組 合物是用於陶瓷基材上。有色的塗料組合物可以用在至少 一部分的基材上或在至少一部分先前塗在基材的塗層上。 有色的塗料可以用不連接的字或設計用於基材上。實質上 透月的塗料可以用來做為透明的表面保護漆覆蓋在至少一 部分的有色層上。 在某些非限定的具體實施例中，一種或多種實質上透明 的塗層可以用來做為基材上的起始塗膜。當用為第一次塗 覆時，實質上透明的塗料更可以含有許多隔間的粒子。一 種或多種有色塗料可以再塗在所有或部分透明塗膜上。這 個安排亦可降低或減少有色塗料組合物的分解，因為下層 實質上透明的組合物可以扮演一種在陶瓷基材和有色塗膜 组合物之間的屏障。一種第二個實質上透明的塗料可以再 塗於所有或部分的一種或多種有色塗膜層上。第二個實質 上透明的塗料可與第一個實質上透明的塗料相同或不同。 在一具體貫施例中，隔間的粒子不在表面的保護塗層或最 上層組合物中，其為有色或透明，以便使其光澤和透明性 最大化。 實質上透明的塗料組合物特別適合用來改善有色塗料組 合物的耐久性，且可用在至少一部分的有色塗料組合物上 或在至少一部分有色塗料組合物之下，或兩者。如實例， 下層的有色塗料組合物含有隔間粒子可以用於陶瓷基材 96457.doc -19- 1276620 上且Λ貝上透明的塗料組合物是用於其上。被實質上透 明的塗料組合物所覆蓋的下層塗料組合物之範圍可能改 ^在—個具體實施財，實質上透明的塗料組合物覆蓋 實質上所有塗料塗到的物體上，如實例整個玻璃瓶。然而， 因為下層塗料組合物的分解基本上發生在下層塗料組合物 的邊緣（即在陶竟基材和下層塗料組合物之間的介面），實質 上透明的塗料組合物可以覆蓋下層塗料組合物的邊緣藉 此亦覆蓋鄰近陶究基材上的部分。對下層有色的塗料組合 物以精巧的細部例如以印刷或細線條的方式，其可用實質 上透明的塗料組合物較簡單地覆蓋整個下層的塗料组合 物。在這些具體實施例中實質上透明的塗料組合物是用於 物體的部分，低於5〇%的陶曼基材表面積，或低於25%的表 、在，、匕的例子中甚至低於陶莞基材表面積的1 〇% 均可能被實質上透明的塗料組合物覆蓋。實質上透明的塗 料組合物可以使用相同或不同技術塗在下層的塗料組合物 上。當任何有色層塗上基材之前，實質上透明的塗料對上 層任何有色層提供耐久性。在這些具體實施例中，實質上 明層提供在有色層和基材的介面之保護免於腐敍性的侵 裴。 物nr(有色的和實質上透明的）的順序視所需最終產 而定，包括任何用於其上的設計或其它指標，以 二貫貝上透明的塗料組合物對外在環境上所需保護的程 度0 96457.doc -20- 1276620 根據本發明，一種多色的有機裝飾物可以快速連續地以 口午多印刷的步驟塗於陶瓷基材上。每個塗層可為相同於或 不同於其它塗層。在所有的塗層塗過後，將經塗覆的基材 加熱至升高的溫度，以使所有塗層基本上同時硬化。在包 括封閉的異氰酸醋之組合物中硬化一種或多種經塗覆的塗 料組合物，其是在溫度足夠解除封閉的聚異氰酸酯下完成 的。以胺基硬化的環氧基為主之系統，硬化的溫度在典型 商業上瓶子裝飾之作業通常至少為15(rc，且可能到2〇〇它 同。硬化的溫度應不可高至引起不要的染色或其它使塗料 …、刀解。對其它樹脂系統或其它方法會使用不同的硬化溫 度。在某些非限定的具體實施例中，使用兩種或更多種如 在此所述的組合物到至少基材的一部分，且組合物實質上 同日守在溫度325°C或低於325°C下硬化。 如上所示，根據本發明的方法，塗料組合物可以用於未 衣飾的陶瓷基材上和/或用於已經有一次或多次先前塗覆 過的塗層上。在後者的狀況下，會察覺到接下來的塗層可 能直接塗於基材上，至少部分在一個或更多個其它塗層 上，或某些其組合上；”使用到至少一部分基材，，和相似詞 匕s所有這些替代，因為所有的裝飾層最終均用到基材 上。通常這些層是在升高的溫度下塗上，使得較冷的基材 之冷凝效果基本上會很快地將塗層固化。此種固化作用對 維持細線條的清晰度是有幫助的，在允許多層塗覆而不賦 予任何先⑷塗層之清晰度，和/或允許多層塗覆而沒有分別 將每一層硬化。在某些非限定的具體實施例中，對接下來 96457.doc -21 - 1276620 塗覆層之塗覆溫度較先前塗覆塗料會液化或過度軟化之溫 度為低是需要的。這增強先前塗覆的裝飾層之細線條清晰 度和解析度之維護。本方法特別適合將商標的標示塗覆於 - 玻璃瓶子上，或以任何其它的應用，其中在清晰度上特別 需要例如寫字。 ^ 根據本發明所用的組合物一般在塗覆後很快固化至接 觸。如那些可以有利地用於裝飾線條者，其在高速下作業， 其中瓶子或其它陶瓷物質後來均被塗覆。 、 在此本發明基本上敘述使用熱熔絹印之應用。要領會本 發明包括任何方法來使用塗料例如噴塗、窗簾塗覆、滾筒 塗覆、印刷或刷塗。 根據本發明塗覆的基材可為熱封閉的塗覆，在塗料組合 物下層形成氧化錫薄膜。然而可察覺的财久性是使用本發 月達到，即使當氧化錫薄膜的量低於一般認為最少的量時。 、根據本發明製造之物質亦可以為冷封閉塗覆，以有機潤 滑劑塗料例如聚乙烯來增強耐機械磨耗性。 如在此所用’除非另有明顯地特別指出，所有的數目例 如那些表示值、範圍、數量或％均可能讀為好像以文字”大 約”做為開端，即使這詞並不明確顯示。任何在此列舉的數 字範圍，是要包括在此所包圍之所有次範圍。複數包圍單 數且反之亦然。而且在此所用，，聚合物"一詞參照為預聚合 .物、寡聚物和均聚物及共聚物兩者；字頭”聚”參照為兩個 _ 或多個。 實例 96457.doc 22- 1276620 本發明更進一步以下列實例說明，其為說明而非限制， 且其中所有的部分均為重量比且所有的百分率均為重量 %，除非另有所指。下列的材料為實例中所用： EPON 880雙盼A二縮甘油基醚，德州休士頓Resolution Performance Product 〇 EPON 1001雙紛A二縮甘油基醚，德州休士頓Resolution Performance Product 〇 VESTAGON B1400，封閉的聚異氰酸酯，咸信為異弗爾 酮雙氰胺、1，1，1·三甲氧基丙烷之共聚物’和e ·己内醯胺 以3:1:3之莫耳比例，德國撾&1：1的〇681188&八0，塗料和賦色 劑。 ΤΙ-PURE R-706二氧化鈦顏料，達拉威州Wilmington之 E.I. du Pont de Nemours & Co. ΝΕΟ GEN DGH 矽酸鋁喬治亞州Dry Branch之Dry1276620 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to coating compositions and methods which are particularly suitable for use in a ceramic-coated substrate. [Prior Art] Glass and other ceramic containers used by the food and beverage industry are usually coated with a simple coating and/or decoration for information such as the contents or functional deficiencies of the container or its mark to indicate the product and / or its source. In many countries, beverages such as soap and soda are sold in recyclable glass bottles, and in the case of beverage consumption, glass bottles are recycled to refill the beverage. Then they:, Sha, then refill, label, and then sell. The printed samples and paper labels have many shortcomings. Both the example paper label and the printed pattern are expensive, cumbersome and easy to remove after exposure to water or other substances. In addition, many of the adhesives used to print the pattern become very sticky during the cleaning process of the bottle. It can cause damage or loss to the machine. To avoid problems with printed patterns and paper labels, more permanent decorations have been used to recover the glass surface of the container. These more permanent garnishes are used in the form of a paste containing a glassy material (or a mixture of glass materials) and a carrier which is typically a volatile organic solvent or wax ("v〇c") finely ground. After the paste is applied to the glass surface by a technique of hot flash or other application, the glass is fired at a high temperature (as in Example 650. The crucible is repelled and/or thermally decomposed to drive off all of the carriers, The glassy mixture is melted and the glassy mixture is bonded to the glass surface. At the time of hot melt printing, the glassy mixture or other material to be printed is 96457.doc 1276620 heating barrier used on the desired pattern. The glassy mixture is melted or softened and passed through a barrier through an extruder to be transferred to a substrate for burning. The pigment is not sensible to this high temperature and is included in the paste to provide the color of the composition. These pigments are typically each There are heavy metals such as red cadmium, white lead, and yellow chrome. VOCs and heavy metals in such decorative methods are hazardous to the environment. The energy consumption and the crisis of harm to workers. Efforts to avoid the use of organic solvents and heavy metals in paints and / or decorative π porcelain benefits, while reducing energy consumption involves the use of hardenable organic binder systems. Traditional organic The pigment needs to be in a hardenable binder system which is applied to the ceramic surface by means of a barrier printing method under the conditions of the method and temperature, under which any hardener is inactive. Thermosetting organic bonding The decorative container is heated in an oven to a temperature to activate the hardener to harden the adhesive, but does not degrade the pigment, which causes the binder and pigment to adhere to the container. However, if a second layer is required, then The barrier application will cause the color layer of the front smear to be peeled off from the container, or the color layer may be damaged to obtain a defective product. If the first layer is hardened or partially hardened before the second layer is applied, Peeling or other damage can then be avoided in the subsequent application of a layer 'but significantly loss of processing speed, efficiency and / or energy use. By UV Radiation-hardening adhesives can be used to pre-fabricate multi-layer ink designs: avoiding the need to apply a layer of ink before each layer of hardening (or partial hardening of the underlying layer. However) this requires the installation of an ultraviolet curing device after each ink coating configuration. , increasing the cost and complexity of the equipment. /' 96457.doc 1276620 Such coating compositions for bottles are typically recycled in a severe physical and chemical environment, typically in a corrosive cleaning solution. The underlying ceramic substrate is susceptible to decomposition by such corrosive cleaning solutions, and the softened underlying substrate may cause the coating composition thereon to be detached from the substrate. For coating compositions used as fine decorative materials, for example in small sizes This problem is exacerbated by writing down the problem. Fine lines are sometimes damaged or removed by repeated corrosion cleaning, although there is no significant impact on a large scale. In the manufacture of glass containers, a heat seal coating is typically used on newly formed containers which provide a film of tin oxide in the outer layer of the container. The presence of tin oxide coatings has been found to have a positive impact on the ability of organic agricultural products 35 to withstand repeated sacrificial cleaning. However, the tin oxide film does not produce the required durability.提供Provides superior suitability for compositions and methods for coating ceramic containers, and is costly to compete with M. Energy consumption is minimized and/or rough environments are needed. SUMMARY OF THE INVENTION The present invention is directed to a method for coating a substrate comprising using at least a colored coating composition on at least a portion of the substrate, and the composition contains at least one hardenable organic a binder and at least one coloring agent; using a transparent coating composition on at least a portion of the substrate - the composition contains a hardenable organic binder; and substantially simultaneously in the colored The coating composition and the adhesive in the substantially transparent coating composition are hardened; wherein the colored coating or the substantially transparent coating can be coated first, and wherein the first coating material contains more 96457 .doc 1276620 Multi-particles. Substrates coated according to these methods are also included in the present invention. [Embodiment] The present invention is generally directed to a method for coating a ceramic substrate. π 陶 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Earth, porcelain, glass ceramics and glass. The ceramic substrate can be varnished or varnished and can be of any shape, size or configuration. The colored coating composition of the present invention comprises at least one hardenable organic binder and at least one color former. As used herein, "color former" and similar terms are used to refer to any substance that imparts color and/or other opacity and/or other visual effects to the composition, such as dyes, pigments, hair dyes, and the like. The agent may comprise a solid powder which is finely divided as in the case, insoluble but wettable under the conditions of use. Color-imparting pigments are known to the art, and a list of special examples can be found in U.S. Patent No. 6,214,414. A separate coloring agent or a mixture of two or more coloring agents can be used. The temperature-resistant pigments, such as glassy mixture coatings and decorative materials, and usually used in heavy metals, can be used, but because of this In the invention, high temperature is not required, and a high temperature resistant pigment can also be used. Therefore, according to the present invention, it is possible to avoid the inclusion of heavy metal-containing pigments in the bone without sacrificing the appearance. A non-limiting embodiment of the present invention specifically excludes heavy metals. Including chromium, cadmium, lead or cobalt. When used in the field, the color former may comprise from 丨 to 65% by weight of the composition of the invention, for example from (10) by weight or from 5 to 35% by weight, by weight It is based on the total weight of the composition: Any pigment or dye that is typically used in the coatings industry can be used, for example, 96457.doc 1276620 such as titanium dioxide, carbon black, DPPB0 red, indocyanine green or blue, iron oxide, bismuth vanadate , naphthol AS, hydrazine, hydrazine, aluminum and quinacridone. Other substances which may be used as color formers in the present invention to affect the appearance of the composition include pigments and/or special effects of special effects, which produce a Or a variety of utilities, such as reflectance, pearl radiance, metallic luster, phosphorescence, light appreciation, photochromism, thermochromism, and angular chromaticity. Such special effect pigments/compositions generally impart color to the composition, while some special The useful pigment/composition does not impart a perceived color to the composition, but it provides other perceptible properties of the compositions of the present invention, such as visual properties. 〇 substantially transparent coatings, such as colored coatings, also At least one hardenable organic binder 'which may be the same or different from the hardenable organic binder in the pigmented coating composition. "Substantially transparent coating" A coating that imparts a little or no color to the underlying substrate or coating. As indicated above, the present invention is directed to a method of coating a ceramic substrate comprising using (iv) a coating composition on a substrate, a colored coating composition. And a substantially transparent coating composition. The coating can be used in two orders, that is, colored, transparent, or transparent, and colored. The first use of the coating, depending on the condition, is sometimes the second time. Used, it also contains a lot of "doors" particles. The particles can be organic, inorganic or a combination thereof, spherical, aspheric, or a combination thereof. The organic particles can be polymeric, non-polymeric or a group thereof. This particle can be solid, hollow, or a combination thereof. Suitable inorganic particles are commercially available, blunt fillers and may include, for example, glass, including borosilicate glass and saponin, and ceramics. Organic particles are also widely available in the market. Organic particles suitable for use in the present invention may include various types of polymer species 96457.doc -10- 1276620 and mixtures thereof; these particles may exhibit the desired rigidity and thermal softening properties in certain embodiments as described below. The combination. In some embodiments, certain organic particles are particularly advantageous in achieving the desired gloss because they soften and flow immediately, resulting in a smooth shiny surface. Suitable polymers :: include polyamines, polyoxyalkylenes, polyacrylates, polyacrylamides, K styrenes, polyurethanes and polyesters. Non-limiting examples of suitable polyamines include polyamido 12, polyamine 11, and polyamine 6/12. The coating material used in accordance with the present invention may comprise softened organic particles and/or organic particles which may be processed without treatment, and/or inorganic particles. This is the case: the child may be just at the first temperature or lower than the first temperature, and soften when the second temperature S is lower than the second temperature, at which time the adhesive hardens 'at the first temperature The adhesive did not harden. Thus the particles are rigid at all relevant degrees, i.e., they do not soften at or below the temperature at which the binder hardens, and the substrate will be exposed to it during the coating process described herein. Under 'nothing will have any sensible softening. This "non-softening" particle may be useful for purposes such as surface structure, frictional residual, abrasion resistance, and/or exceptional reflectivity. This particle may be sufficient to exhibit the desired effect in the coating composition. The amount and proportion. "rigidity" and similar terms mean that the particles are not immediately shrinkable at the specified temperature, ie the particles have a higher structural integrity than those contained in the uncured binder. More particularly, the one or more ingredients used in the composition are selected to be uncured, while the particles in the colored composition and/or substantially transparent coating are rigid at the first temperature. The first temperature is typically the temperature at which the ruthenium is applied to the substrate and/or the second or subsequent coating potential; 96457.doc 1276620 The temperature on the substrate. This temperature may be room temperature, or it may be at some elevated temperatures. In some embodiments, the binder hardens and the particles soften at the second temperature. "Hard hardening" and similar terms are referred to as chemical reactions that join the various components of the organic binder together to form a thermoset polymer. "Softening" and similar words refer to the loss of sufficient structural rigidity in the particles, Deformation and/or other shape changes occur on the particles. As the example particles protrude from the surface of the composition of the present invention, the shape is changed at or below the second temperature, "smoothing" or smoothing the film surface Φ; because of this smoothing, when the particles protrude from the surface of the coating film is the least If it does not disappear, the gloss is usually reduced to a second meal. In other embodiments, one or more of the used group particles 'maintain rigidity and/or structural relief at the first and second temperatures. It may be selected based on its ',//combination degree and/or wettability in the adhesive and/or composition. Particles that are excessively dissolved in the binder may be named excessively/disintegrated, decomposed, swollen or softened. And the surface is smashed outside. The stone is smashed. In addition to this, if it is not needed, it may not need to be wet by the brother knife. In some applications, the surface structure that is not required for the moon may be generated. The particles may be spherical or Non-spherical particles. Maximize the function of the compartment, and choose the most-size and particle size distribution to minimize the effect of any external particle size according to the demand σ. The diameter is less than 1 micron. Non-limiting:: The average can be at least 1 micron, in the column, "in the column, the average particle size #匕 is non-limiting and static per meter" and found in some non-limiting, ^ at least 3 micro , the body only orders to meet the average particle size to 96457.doc 1276620 less than 5 microns. In some concrete cases, the coating layer is about the same size when it is precipitated. The sub-size can typically be as such, it has no compartmental effect, and. If the particles are too small relative to the coating layer, they may protrude from the surface and may be less likely to protrude, or too much after softening. Of course this highlights the final luster of the column = matter, even if the particle size and / or softening properties can be:; choose: may need to 'in its case k choose the appropriate ▲. Written. The size of the mesh that can be used for hot-melt stencil processing is also changed to particle size, which is too large. It is too large and not too expensive, and the result is a poor printing. According to the invention, the adhesive can be used on a ceramic substrate in a liquid state, followed by a durable hardened state. Hardening can be performed by any method. For example, heating, ultraviolet radiation, 歹1 to beam radiation, or a form of energy that hardens the binder. In some embodiments, the binder includes - y 种 organic component 'when hardening energy is used When it is hardened, in some non-limiting embodiments, the composition may comprise an epoxy resin and an amine hardener (such as f dicyandiamide), such as those disclosed in U.S. Patent No. 4,214,414, In other non-limiting embodiments of the invention, the binder may further comprise a type of blocked isocyanate hardener, as disclosed in U.S. Patent No. 6,214,414, the disclosure of which is incorporated herein by reference. Other suitable resins include, for example, acrylic polymers containing hydroxyl or carboxylic acids, polyester polymers containing hydroxyl or carboxylic acids, isocyanates or hydroxyl-containing polyaminophthalate polymers, polyureas containing amines or isocyanates. Ester, or any other hydroxyl, carboxy 96457.doc -13 - 1276620 poly: bis, urethane, isocyanate or epoxy functional ♦ 2 ° appropriate hardener can be cooked by the artist And may include one or more of an amine based plastic, a phenolic plastic, a cyanate vinegar, a polyol, an emulsion, a polyacid, an isosylamine, a phthalic anhydride, and a carbodiimide. A combination of a binder and/or a hardener can be used. In a non-limiting example, a reactive organic tree can be used as a 5-functional group; "polyepoxy-functional Lieutenant b Lusi Zhong uses a number average molecular weight to calculate this tree: 曰 average mother mole Containing more than one epoxy group, or on average per mole: two L groups or more. In other non-limiting specific examples; or electron beam _ light shot can be used to initiate the binder: when the modulation contains reactive functionalities Base, designed to be exposed to the Korean shot and thermoset ^ including various types of free radical hardening materials, such as acrylic acid vinegar, B, earth glaude material, acrylic acidized 仏i's nutrient and polymerization And vinyl ethers and unsaturated polyesters. J is a starting material for hazardous ions, such as cycloaliphatic epoxy or vinyl ether. Drop a A suitable free radical or cationic photoinitiator is generally used UV hardening and depending on the condition are EB hardening. Combinations of free radical and cationic hardening are also possible, such as the combination of the exterior I/external beam hardening process and the thermosetting composition as described above. Experience # . ^ Ling% example, used in the present invention The adhesive has or has a viscosity, and is suitable for printing at 6 ° C to 120 ° C; other temperatures can be used in other non-limiting concrete examples. For the heat hardening system, the hardening mechanism of the adhesive is The choice of captive sputum has little or no activity before the temperature of the second two, and at this point the temperature adhesive hardens....to avoid excessive hardening, 96457.doc Ί4. 1276620 The difference between the first and second temperatures can be at least 3 ( Rc is more than 5 (TC, although other temperature differences can also be used in the present invention and more typically in the form of a hardenable organic binder for use in one or more pigmented coating compositions, and for substantially transparent coating combinations In the application, The coating adheres to the ceramic substrate to some extent, and it is close to or reaches a permanent coating film on the substrate. This high-durability coating is used for repeated cleaning (such as an example) In the solution) #谷@普通It is desirable that it is used by the bottler to clean the recovered mash before refilling. The bottle may be treated with an adhesion promoter prior to use of the composition of the invention, or the binder may contain a subsequent promoter such as an organofunctional decane. In other systems, the coating may be removed from the container after a limited number of times. For example, season or holiday decorations may be placed on the bottle during the promotion period. And removed after the end of the lock-up period. The base material of the ceramics can be treated with a composition that increases the peeling before the coating composition is applied. A non-limiting example is a composition for treating a ceramic substrate, which is to be enhanced. The peeling of the coating composition of the present invention in a rotting cleaning is a polyethylene composition such as a polyethylene emulsion. The composition for increasing the peeling can be used for cold coating processing as an example. As indicated above, and in the compositions of certain non-limiting embodiments of the invention, the particles are rigid at or below the first temperature. The particles have substantial structural rigidity at this degree, in which case the composition is applied to the surface 96457.doc -15-1276620, which can be significantly increased in the hot melt composition; in some specific yoke cases At the temperature used to harden the binder, the particles lose their structural specificity. The initial stiffness does not need to exclude all of the elasticity or plasticity, but is sufficient to provide structural integrity of the coating composition used without hardening. This 钇 structure makes it unnecessary for the coating on the substrate to harden each layer. In this method, the function of the particles is a "compartment" which maintains the coating in a substantially desired position until hardening. Because of the integrity of the previously applied layers or layers, the present invention allows for two or more layers of coating, such as paints of different colors or coatings of one or more colors, and one or more substantially transparent coatings, Use without the need for a hardening step between different coatings. After all of the desired layers have been applied, all of the layers can be substantially simultaneously substantially hardened using hardening energy. "Substantially hardening" and similar words mean that the adhesive is not only partially hardened. "Substantially hardening at the same time" and similar terms are used to substantially harden all coatings in a single hardening step. Typical municipal bottle decoration processes use hot melt stamping from a temperature range of 120° (:, and hardening temperatures range from 15 〇 to 22 〇. (:: Polyamide 12 particles have been found to be particularly suitable. Other polymer systems may be suitable for different temperature ranges. Typically the binder is present in an amount of from 20 to 95% by weight, based on the total weight of the composition. The example colored binder may be from 35 to 65 weight percent, while substantially The clear coating binder may range from 50 to 95% by weight, such as 65 to %, or 75 to 95% by weight. In certain non-limiting embodiments, the relatively small size and amount used in the coatings of the present invention. The particles do not produce visible reflectivity. When particles are used, the particle content of the composition is typically 5 to 5 〇 96457.doc -16 - 1276620% by weight, or U) to 35% by weight, or 15 to 3 〇 by weight. %, % by weight is calculated based on the total weight of the composition. The density, particle size and particle size distribution determine the appropriateness of the amount to achieve the function of the compartment and the desired appearance of the film. As an example, it can be found that more weight % of the particles may be need The effect of using denser particles to achieve the use of particles of similar density. Reactive waxes may optionally be included in certain non-limiting embodiments of the invention. These are long chain aliphatic materials containing At least one reactive group having an active hydrogen, usually selected from the group consisting of a trans-group, an amine group, a ureido group, an aminocarboxylic acid, and an aminomethyl methoxy group, which have physical properties and are generally combined with soil. Stearyl alcohol is frequently used. Examples of reactive soils, but many other compounds: are known in the art. Reactive waxes may optionally constitute up to twofold by weight of the composition, for example from 〇5 to 15 weights of the composition 〇/ Some non-limiting embodiments of the present invention may further comprise a substantially transparent and/or substantially colorless filler, and are particularly suitable for use in substantially transparent ', and in the mouth. For finely divided solid particles, which impart a final coating (for "substantially colorless") - or not imparting color, color, and/or absorption of little or no colored light (for "substantially transparent ) It can be used to add to the compartment particles of the present invention. Fillers typically have a large length of less than 500 nanometers, such as less than 1 nanometer, less than 5 nanometers, less than 20 nanometers or In the range of 5 to 2 hours. In some non-limiting specific embodiments, the 'filler is hydrophobic. Examples of suitable hydrophobic fillers include AEROSIL smoked Shixia, which is designed as R972, R974. , r(1) R812S' R805 (New Jersey Ridgefield park to suppress (10) company when needed to keep the day - a substantially transparent and / or colorless filler or two or more real 96457.doc -17 - 1276620 qualitatively transparent and / or a mixture of colorless fillers. In particular embodiments of the colored compositions, substantially transparent and filled typically comprise from 1 to 2% by weight of the composition, for example from hydrazine to (7) % or 2 Up to 5%, and similar amounts can be added to substantially transparent coatings'. For higher gloss applications, it may be desirable to minimize inorganic additives. ^ Many other added materials may also be used in the compositions of the invention as appropriate. These are antioxidants, degassing aids and flow regulators. These are examples only, and others can be used when needed. Other additives may: raw, opaque, durability, lubricity, color brightness, and Xu; "$ function known to the artist. When present, additional materials can be used to achieve the habit of white s The purpose of the above. Typically these additional materials, when present, may constitute from 〇〇1 to 丨5% of the coating composition of the present invention. f According to the present invention, when two or more different coating layers are applied to a substrate, At least one layer is colored and at least one layer is substantially transparent. A "coat layer, or "decorative layer" is generally referred to as a single layer of composition. Colored = paint layer can impart color or other opacity to the label or give the substrate a visual effect. 'Immediately transparent coating layer can impart a transparent portion to the label or can be used on all substrates on the St. The coating underneath or above and the substrate itself provide protection and/or durability. The function of the particle refining compartment in the first coating maintains the integrity of the uncured first layer when the second coating is contiguous and/or spaced from the first coating. Thus, the coating thereon, adjacent, and/or spaced from the previous coating does not interfere with the previous coating of 96457.doc • 18 · 1276620. The final applied coating may also contain particles, but since it does not face the next rigorous printing operation, it does not need to include particles. In some embodiments, at least one of the colored coating compositions described above is for use on a ceramic substrate. The colored coating composition can be applied to at least a portion of the substrate or to at least a portion of the coating previously applied to the substrate. Colored coatings can be applied to substrates using unconnected words or designs. Substantially translucent paint can be applied as a clear surface protective lacquer over at least a portion of the colored layer. In certain non-limiting embodiments, one or more substantially transparent coatings can be used as the starting coating film on the substrate. When used for the first application, substantially transparent coatings may contain particles of many compartments. One or more colored coatings can be applied to all or a portion of the clear coating film. This arrangement also reduces or reduces the decomposition of the pigmented coating composition because the underlying substantially transparent composition can act as a barrier between the ceramic substrate and the colored coating composition. A second substantially transparent coating can be applied to all or part of one or more of the colored coating layers. The second substantially transparent coating can be the same or different than the first substantially transparent coating. In a specific embodiment, the particles of the compartment are not in the protective coating or topmost composition of the surface, which is colored or transparent to maximize gloss and transparency. Substantially clear coating compositions are particularly suitable for improving the durability of the pigmented coating composition and can be used on at least a portion of the pigmented coating composition or under at least a portion of the pigmented coating composition, or both. As an example, the underlying colored coating composition containing the spacer particles can be used on a ceramic substrate 96457.doc -19-1266620 and the clear coating composition on the mussel is used thereon. The extent of the underlying coating composition that is covered by the substantially clear coating composition may be modified by a substantially transparent coating composition that covers substantially all of the coating applied to the object, such as an example glass bottle. . However, since the decomposition of the underlying coating composition substantially occurs at the edge of the underlying coating composition (ie, the interface between the ceramic substrate and the underlying coating composition), the substantially transparent coating composition can cover the underlying coating composition. The edge thus covers the portion of the adjacent ceramic substrate. The underlying colored coating composition can be used to cover the entire underlying coating composition with a substantially clear coating composition, such as in a printed or thin line. The substantially transparent coating composition in these embodiments is a portion for an object, less than 5% of the surface area of the Tauman substrate, or less than 25% of the surface, in the case of ruthenium, or even lower than the base of the ceramic. Any 1% of the surface area may be covered by a substantially transparent coating composition. The substantially transparent coating composition can be applied to the underlying coating composition using the same or different techniques. A substantially transparent coating provides durability to any colored layer of the upper layer before any colored layer is applied to the substrate. In these embodiments, the substantially clear layer provides protection from the nuisance of the interface between the colored layer and the substrate. The order of nr (colored and substantially transparent) depends on the desired final product, including any design or other indicators used thereon, to provide protection to the external environment from a transparent coating composition on the second pass. Degree of 0 96457.doc -20- 1276620 According to the present invention, a multi-colored organic decorative article can be applied to a ceramic substrate in a rapid and continuous step of printing in a noon and noon. Each coating can be the same or different from the other coatings. After all of the coating has been applied, the coated substrate is heated to an elevated temperature to allow all of the coating to harden substantially simultaneously. One or more of the coated coating compositions are cured in a composition comprising a blocked isocyanate which is carried out at a temperature sufficient to deblock the polyisocyanate. In the case of amine-based hardening epoxy-based systems, the hardening temperature is typically at least 15 (rc, and may be as high as 2 rc for typical bottle decoration operations. The hardening temperature should not be high enough to cause unwanted Dyeing or otherwise rendering the coating, knife. Different curing temperatures may be used for other resin systems or other methods. In certain non-limiting embodiments, two or more compositions as described herein are used. To at least a portion of the substrate, and the composition is substantially cured at the same temperature at 325 ° C or below 325 ° C. As indicated above, the coating composition can be used for uncoated ceramic substrates in accordance with the method of the present invention. On the material and/or on the coating that has been applied one or more times before. In the latter case, it is perceived that the next coating may be applied directly to the substrate, at least in part or more On a plurality of other coatings, or some combination thereof;" using at least a portion of the substrate, and similar words 匕s all of these substitutions, since all of the decorative layers are ultimately applied to the substrate. Usually these layers are At elevated temperatures This allows the condensation effect of the cooler substrate to substantially cure the coating very quickly. This curing is helpful in maintaining the sharpness of the fine lines, allowing multiple layers of coating without imparting any prior (4) coating. The clarity of the layers, and/or allows for multiple layers of coating without separately hardening each layer. In certain non-limiting embodiments, the coating temperature for the next 96457.doc -21 - 1276620 coating is earlier than the previous coating A low temperature at which the coating will liquefy or excessively soften is required. This enhances the maintenance of the fine line definition and resolution of the previously applied decorative layer. This method is particularly suitable for applying the logo of the trademark to the - glass bottle. Or in any other application, wherein in particular, for example, writing is required in terms of sharpness. ^ The compositions used according to the invention generally cure to contact quickly after application. As those which can be advantageously used for decorative lines, Work at high speeds where bottles or other ceramic materials are subsequently coated. The invention herein basically describes the use of hot melt stamping. It is to be understood that the invention includes any method to Coatings such as spray coating, curtain coating, roller coating, printing or brushing. The substrate coated according to the invention may be a heat-sealed coating which forms a tin oxide film under the coating composition. However, it is noticeable for a long time. Sexuality is achieved using the present month, even when the amount of tin oxide film is less than generally considered to be the least. The material made in accordance with the present invention may also be cold-sealed, with an organic lubricant coating such as polyethylene to enhance resistance. Mechanical wearability. As used herein, unless expressly stated otherwise, all numbers, such as those indicating values, ranges, quantities, or %, may be read as if the word "about" is used as the beginning, even if the word is not clear. Any range of numbers recited herein is intended to include all sub-ranges encompassed herein. The plural encompasses the singular and vice versa. Also, as used herein, the term "polymer" is pre-polymerized. Both the polymer and the homopolymer and the copolymer; the prefix "poly" refers to two or more. Examples 96457.doc 22- 1276620 The invention is further illustrated by the following examples, which are illustrative and not limiting, and all of which are by weight and all percentages are by weight unless otherwise indicated. The following materials are used in the examples: EPON 880 Double Hope A diglycidyl ether, Houston Houston Resolution Performance Product 〇 EPON 1001 Double A diglycidyl ether, Texas Houston Resolution Performance Product 〇VESTAGON B1400, closed Polyisocyanate, salt of isophorone dicyandiamide, copolymer of 1,1,1·trimethoxypropane and e · caprolactam in a molar ratio of 3:1:3, Germany &; 1:1 〇 681188 & eight, paint and coloring agent. ΤΙ-PURE R-706 Titanium Dioxide Pigment, E.I. du Pont de Nemours & Co. 达 GEN DGH, Aluminium Citrate, Georgia, Dry Branch, Dry Branch
Branch Kolin Co. SPHERICEL 110P8中空的硼矽酸鹽玻璃微球體，平均直 徑 11.7微米，賓州 Valley Forge之Potters Industries，Inc. MODAFLOW粉劑III流動調整劑，丙烯酸乙酯-丙烯酸異 辛酯共聚物含二氧化矽，密蘇里州聖路易士之Solutia Inc. UVITEX OB增白劑，2,2f-(2,5-蝽吩二基）雙[5-l，l-二甲基 乙基]]-苯并噁唑，瑞士Basil之汽巴特用化學品 BYK-405流變控制劑，聚羥基羧酸醯胺之溶液，德國 Wesel之BYK化學 96457.doc -23- 1276620 DYHARD 100M雙氰胺，98%微小化<40微米，德國 Trostberg之 SKW Trostberg AkiengesellschaftBranch Kolin Co. SPHERICEL 110P8 hollow borate glass microspheres, with an average diameter of 11.7 microns, Potters Industries, Inc., MODAFLOW Powder, Flow Conditioner, Valley Forge, Pennsylvania, Ethyl Acrylate-Isooctyl Acrylate Copolymer Cerium Oxide, Solutia Inc. UVITEX OB Brightener, 2,2f-(2,5- porphindiyl)bis[5-l,l-dimethylethyl]]-benzoate, St. Louis, Missouri Oxazole, Swiss Basil's steam bart chemical BYK-405 rheology control agent, polyhydroxy carboxylic acid guanamine solution, Germany Wesel's BYK chemistry 96457.doc -23- 1276620 DYHARD 100M dicyandiamide, 98% miniaturization <40 micron, SKW Trostberg Akiengesellschaft, Trostberg, Germany
AEROSIL R974疏水的煙燻石夕土，德國 Frankfort am Main 之 Degussa AG ORGASOL 1002 D NAT 1聚醯胺6之粉劑，平均粒徑20微 米，賓州費城 Atofina Chemicals ORGASOL 2001 UD NAT 1聚醯胺12之粉劑，平均粒徑5 微米，賓州費城Atofina ChemicalsAEROSIL R974 hydrophobic fumigation stone, Degussa AG ORGASOL 1002 D of Frankfort am Main, Germany, powder of 9 polyamide 6 with an average particle size of 20 μm, Philadelphia Atofina Chemicals ORGASOL 2001 UD NAT 1 Polyamide 12 Powder, average particle size 5 microns, Atofina Chemicals, Philadelphia, PA
VESTOSINT 2070聚醯胺12之粉劑，平均粒徑5微米，德 國 Marl之 Degussa AG DOVERPHOS S-680二硬月旨基異戊四醇二亞磷酸酯抗氧 化劑，來自俄亥俄州Dover之陶氏化學公司 FLUORAD含氟界面活性劑FC 4430非離子的聚合界面活 性劑，來自明尼蘇達州聖保羅之3M Specialty Materials INTERPROME 4049以偶氮為主的萘酚紅色著色劑，來自 中國的Sino INTERPROME 4047顏料，來自中國的Sino。 實例1 根據本發明一個具體實施例，使用有機粒子（VESTOSINT 2070聚醯胺12粉劑）製備一種白色裝飾組合物。將進料1的 材料在80°C至ll〇°C下混合直到均勻。將進料2的材料加入 進料1的混合物中，並在80°C至ll〇°C下混合得到白色均勻 的漿狀物。將所得的白色裝飾組合物倒入一容器中，並任 其冷卻至室溫，產生一種固態的塗料組合物。 96457.doc -24- 1276620 成分 重量，克 重量％ 進料1 EPON 880 50.00 25.08 EPON 1001F 60.00 30.10 硬脂醇 10.00 5.02 進料2 Ti〇2 32.00 16.05 藍色染料 0.1355 0.07 紫色染料 0.9184 0.46 DOVERPHOS S-680 1.01 0.51 VESTOSINT 2070 32.53 16.32 M0DAFL0W粉劑 III (65%) 4.00 2.01 UVITEX 0B 1.00 0.50 DYHARD 100M 7.73 3.88 實例2 根據本發明一個具體實施例，使用一種有機粒子 (VESTOSINT 2070聚醯胺12粉劑）和無機粒子（SPHERICEL 110P8玻璃珠）之混合物製備一種白色裝飾組合物。將進料1 的材料在80°C至110°C下混合直到均勻。將進料2的材料加 入進料1的混合物中，並在80°C至110°C下混合得到白色均 勻的漿狀物。將所得的白色裝飾組合物倒入一容器中，並 任其冷卻至室溫，產生一種固態的塗料組合物。 成分 重量，克 重量％ 進料1 EPON 880 45.00 21.72 EPON 1001F 65.00 31.37 96457.doc -25- 1276620 硬脂醇 20.00 9.65 進料2 Ti02 32.00 15.45 藍色染料 0.1350 0.07 紫色染料 0.9180 0.44 SPHERICEL 110P8 10.00 4.83 DOVERPHOS S-680 1.04 0.50 VESTOSINT 2070 20.71 10.00 MODAFLOW粉劑 III (65%) 4.00 1.93 UVITEX OB 1.00 0.48 DYHARD 100M 7.37 3.56 實例3 根據本發明一個具體實施例，使用有機粒子（ORGASOL 2001 UD NAT 1聚醯胺12粉劑）製備一種白色裝飾組合物。 將進料1的材料在80°C至ll〇°C下混合直到均勻。將進料2的 材料加入進料1的混合物中，並在80°C至110°C下混合得到 白色均勻的漿狀物。將所得的白色裝飾組合物倒入一容器 中，並任其冷卻至室溫，產生一種固態的塗料組合物。 成分 重量，克 重量％ 進料1 EPON 880 50.00 25.66 EPON 1001F 55.00 30.79 硬脂醇 10.00 5.13 進料2 Ti〇2 32.00 16.42 藍色染料 0.14 0.07 96457.doc -26- 1276620 紫色染料 0.92 0.47 DOVERPHOS S-680 0.98 0.50 ORGASOL 2001 UD NAT 1 28.12 14.43 MODAFLOW粉劑 III 4.00 2.05 (65%) UVITEX OB 1.00 0.51 DYHARD 100M 7.73 3.96 實例4 僅混合無機粒子（SPHERICEL 110P8中空玻璃珠）製備一 種白色裝飾組合物。將進料1的材料在80°C至ll〇°C下混合 直到均勻。將進料2的材料加入進料1的混合物中’並在8 0 °C至110°c下混合一小時，得到白色均句的漿狀物。將所得 的白色裝飾組合物倒入一容器中，並任其冷卻至室溫，產 生一種固態的塗料組合物。 成分 重量，克 重量％ 進料1 EPON 880 50.00 25.08 EPON 1001F 60.00 30.10 硬脂醇 10.00 5.02 進料2 Ti02 32.00 16.05 SPHERICEL 110P8 32.53 16.32 MODAFLOW 粉劑 4.00 2.01 III UVITEX OB 1.00 0.50 DYHARD 100M 7.73 3.88 DOVERPHOS S-680 1.01 0.51 96457.doc -27- 1276620 藍色染料 0.1355 0.07 紫色染料 0.9184 0.46 實例5 製備一種紅色裝飾組合物，其為用在實例1至4的裝飾物 上之表面印刷。此裝飾組合物不包括粒子，因其做為一種 接下來的裝飾層。將進料1的材料在80°C至110°C下混合直 到均勻。混合物更進一步在將80°C至11 〇°C下混合一小時以 製造一種紅色均勻的漿狀物。將所得的紅色裝飾組合物倒 入一容器中，並任其冷卻至室溫，產生一種固態的塗料組 合物。 成分 重量，克 重量％ 進料1 EPON 880 55.00 36.89 EPON 1001F 45.00 30.19 硬脂醇 10.00 6.71 VESTAGON B1400 10.00 6.71 進料2 INTERPROME 4049 4.00 2.69 INTERPROME 4047 8.00 5.36 Ti〇2 3.00 2.01 含氟界面活性劑FC 4430 0.50 0.34 MODAFLOW粉劑 III 3.00 2.01 DOVERPHOS S 680 0.74 0.50 BYK 405 0.56 0.38 DYHARD 100M 7.88 5.29 AEROSIL R974 1.40 0.94 96457.doc -28- 1276620 此紅色油墨成功地印在每個先前的白色油墨實例上，其 使用-種Strutzl5〇裝飾機器做為典型的多種油墨塗覆方^ 之部分。當以單一步驟硬化時在35〇ν下供烤45分鐘，所得 的瓶子裝飾物提供可接受的外觀和薄臈性能之性質。 實例6 光澤測量 將在實例1至4中製備之白色組合物，使用StnUz 〇1>_4半 自動一般目的裝飾機，以一種設計印在玻璃瓶上。使用一 種180網孔之不銹鋼篩網，並於8(rcs85£t的溫度範圍下將 白色裝飾組合物印出。印後的瓶子接著於強迫送風的烘箱 中在180 C硬化一個小時。裝飾物的表面光澤#N〇v〇_Curve 】區域光澤汁（來自英國East Sussex之Rhopoint Instmmentation Ltd·)測量，其使用ASTM D523之步驟並記 錄於表1中。本發明組合物（實例丨_3)的表面光澤較實例4 表1 實例 光澤，60° 1 43 — 2 34 3 37 4 23-28 製備如實例2中一種250網孔的白色裝飾組合物，其含有 有機粒子和無機粒子，具有下列成分： 實例7 96457.doc -29- Ϊ276620VESTOSINT 2070 Polyamide 12 powder with an average particle size of 5 μm, Degussa AG DOVERPHOS S-680, a hard-acting agent of Marl, Germany, from Dow Chemical Company, DLU, FLUORAD, Ohio Fluorinated surfactant FC 4430 nonionic polymeric surfactant, 3M Specialty Materials INTERPROME 4049 from St. Paul, Minnesota. Azo-based naphthol red colorant, Sino INTERPROME 4047 pigment from China, from Sino, China. Example 1 According to one embodiment of the invention, a white decorative composition was prepared using organic particles (VESTOSINT 2070 Polyamide 12 powder). The material of Feed 1 was mixed at 80 ° C to 11 ° C until uniform. The material of Feed 2 was added to the mixture of Feed 1 and mixed at 80 ° C to ll ° ° C to give a white homogeneous slurry. The resulting white decorative composition was poured into a container and allowed to cool to room temperature to produce a solid coating composition. 96457.doc -24- 1276620 Ingredient weight, gram weight % Feed 1 EPON 880 50.00 25.08 EPON 1001F 60.00 30.10 Stearyl alcohol 10.00 5.02 Feed 2 Ti〇2 32.00 16.05 Blue dye 0.1355 0.07 Purple dye 0.9184 0.46 DOVERPHOS S-680 1.01 0.51 VESTOSINT 2070 32.53 16.32 M0DAFL0W Powder III (65%) 4.00 2.01 UVITEX 0B 1.00 0.50 DYHARD 100M 7.73 3.88 Example 2 According to one embodiment of the invention, an organic particle (VESTOSINT 2070 Polyamide 12 powder) and inorganic particles are used ( A mixture of SPHERICEL 110P8 glass beads) prepared a white decorative composition. The material of Feed 1 was mixed at 80 ° C to 110 ° C until uniform. The material of Feed 2 was added to the mixture of Feed 1 and mixed at 80 ° C to 110 ° C to give a white homogeneous slurry. The resulting white decorative composition was poured into a container and allowed to cool to room temperature to produce a solid coating composition. Ingredient weight, gram weight % Feed 1 EPON 880 45.00 21.72 EPON 1001F 65.00 31.37 96457.doc -25- 1276620 Stearyl alcohol 20.00 9.65 Feed 2 Ti02 32.00 15.45 Blue dye 0.1350 0.07 Purple dye 0.9180 0.44 SPHERICEL 110P8 10.00 4.83 DOVERPHOS S - 680 1.04 0.50 VESTOSINT 2070 20.71 10.00 MODAFLOW Powder III (65%) 4.00 1.93 UVITEX OB 1.00 0.48 DYHARD 100M 7.37 3.56 Example 3 According to one embodiment of the invention, organic particles (ORGASOL 2001 UD NAT 1 Polyamide 12 powder) are used. A white decorative composition was prepared. The material of Feed 1 was mixed at 80 ° C to 11 ° C until uniform. The material of Feed 2 was added to the mixture of Feed 1 and mixed at 80 ° C to 110 ° C to give a white homogeneous slurry. The resulting white decorative composition was poured into a container and allowed to cool to room temperature to produce a solid coating composition. Ingredient weight, gram weight % Feed 1 EPON 880 50.00 25.66 EPON 1001F 55.00 30.79 Stearyl alcohol 10.00 5.13 Feed 2 Ti〇2 32.00 16.42 Blue dye 0.14 0.07 96457.doc -26- 1276620 Purple dye 0.92 0.47 DOVERPHOS S-680 0.98 0.50 ORGASOL 2001 UD NAT 1 28.12 14.43 MODAFLOW Powder III 4.00 2.05 (65%) UVITEX OB 1.00 0.51 DYHARD 100M 7.73 3.96 Example 4 Only inorganic particles (SPHERICEL 110P8 hollow glass beads) were mixed to prepare a white decorative composition. The material of Feed 1 was mixed at 80 ° C to 11 ° C until uniform. The material of Feed 2 was added to the mixture of Feed 1 ' and mixed at 80 ° C to 110 ° C for one hour to give a white uniform slurry. The resulting white decorative composition was poured into a container and allowed to cool to room temperature to produce a solid coating composition. Ingredient weight, gram weight % Feed 1 EPON 880 50.00 25.08 EPON 1001F 60.00 30.10 Stearyl alcohol 10.00 5.02 Feed 2 Ti02 32.00 16.05 SPHERICEL 110P8 32.53 16.32 MODAFLOW Powder 4.00 2.01 III UVITEX OB 1.00 0.50 DYHARD 100M 7.73 3.88 DOVERPHOS S-680 1.01 0.51 96457.doc -27- 1276620 Blue dye 0.1355 0.07 Purple dye 0.9184 0.46 Example 5 A red decorative composition was prepared which was surface printed on the decorative articles of Examples 1 to 4. This decorative composition does not include particles as a subsequent decorative layer. The material of Feed 1 was mixed at 80 ° C to 110 ° C until uniform. The mixture was further mixed at 80 ° C to 11 ° C for one hour to produce a red uniform slurry. The resulting red decorative composition was poured into a container and allowed to cool to room temperature to produce a solid coating composition. Ingredient weight, gram weight % Feed 1 EPON 880 55.00 36.89 EPON 1001F 45.00 30.19 Stearyl alcohol 10.00 6.71 VESTAGON B1400 10.00 6.71 Feed 2 INTERPROME 4049 4.00 2.69 INTERPROME 4047 8.00 5.36 Ti〇2 3.00 2.01 Fluorinated surfactant FC 4430 0.50 0.34 MODAFLOW Powder III 3.00 2.01 DOVERPHOS S 680 0.74 0.50 BYK 405 0.56 0.38 DYHARD 100M 7.88 5.29 AEROSIL R974 1.40 0.94 96457.doc -28- 1276620 This red ink was successfully printed on each of the previous white ink examples. The Strutzl 5〇 decorative machine is part of a typical range of ink coatings. When baked at 35 〇 ν for 45 minutes when hardened in a single step, the resulting bottle garnish provides acceptable appearance and properties of thinness properties. Example 6 Gloss measurement The white compositions prepared in Examples 1 to 4 were printed on a glass bottle in a design using a StnUz®1>_4 semi-automatic general purpose decorator. A 180 mesh stainless steel screen was used and the white decorative composition was printed at a temperature range of 8 (rcs 85 £t. The printed bottle was then hardened at 180 C for one hour in an forced air oven. Surface gloss #N〇v〇_Curve] Regional gloss juice (from Rhopoint Instmmentation Ltd., East Sussex, UK) measured using ASTM D523 and recorded in Table 1. Composition of the invention (Example 丨_3) Surface gloss compared to Example 4 Table 1 Example gloss, 60° 1 43 — 2 34 3 37 4 23-28 A 250-mesh white decorative composition as in Example 2 was prepared which contained organic particles and inorganic particles having the following composition: Example 7 96457.doc -29- Ϊ276620
將軟的飲料瓶子（250毫升容積）在325t下加熱7小時，以 移除任何事先存在的聚乙烯塗料。將所有加熱清潔後的空 瓶使用250網孔之不銹鋼篩網，以如實例5中之裝飾組合物 裝飾。一半的白色經裝飾瓶子使用250網孔之不銹鋼篩網， 96457.doc -30- 1276620 以實質上透明的塗料組合物塗覆在白色的油墨裝飾區域上 (’’透明塗膜”實例），而其餘一半並未得到一層透明塗膜（”控 制”實例）。如實例5中將兩個組合物以單一步驟烘烤而硬 化。每群瓶子的一半實質上以聚乙烯冷封閉塗料（，’含CEC，，) 噴塗，而其餘一半沒有得到冷封閉塗料（”無CEC”）。 讓經塗覆的瓶子受到加速的腐蝕性條件並測量如下列的 白色裝飾組合物之損失。將三支經塗覆的瓶子裝入冷水在 70°C攪拌的腐蝕性浴下（2·5重量％2NaOH、0.3重量％之 Diversylever防蝕刻劑和百萬分之50的CaC03)浸潰7分鐘。 將瓶子從浴中移去檢驗。任何小的印字之損失均視為是整 組的失敗。然後將瓶子倒空並再填充冷水，並再重複測試 循環直到觀察到失敗為止。記錄在表2中的數據說明白色裝 飾組合物的耐久性因使用實質上透明的塗料組合物之表面 塗覆，與裝飾白色組合物含或不含聚乙烯CEC之瓶子比較 明顯地增強。此數據亦指出塗在瓶子上的聚乙烯CEC含有 實質上透明的塗料組合物，其對白色裝飾組合物之耐久性 並無效果。 表2 試驗循環 控制無CEC 控制含CEC 透明塗膜無CEC 透明塗膜含CEC 1-9 通過通過通過 通過通過通過 通過通過通過 通過通過通過 10 通過通過失敗 通過通過通過 通過通過通過 通過通過通過 11-24 通過通過通過 通過通過通過 通過通過通過 25 通過通過失敗 通過通過通過 通過通過通過 26-45 通過通過通過 通過通過通過 46 通過通過通過 通過通過失敗 47 通過失敗失敗 96457.doc -31 - 1276620 雖然本發明已經以參考資料對其某些具體實施例之特別 細節敘述，這些細節並非要做為本發明領域之限制，除此 範圍外其均包含於附隨的申請專利範圍中。 96457.doc -32-A soft beverage bottle (250 ml volume) was heated at 325 t for 7 hours to remove any pre-existing polyethylene coating. All of the heated and cleaned empty bottles were decorated with a 250 mesh stainless steel screen to decorate as in the decorative composition of Example 5. Half of the white decorative bottle uses a 250 mesh stainless steel screen, 96457.doc -30-1266620 with a substantially clear coating composition applied to the white ink decorative area (''transparent coating' example)) The remaining half did not result in a clear coating ("Control" example). The two compositions were hardened in a single step as in Example 5. One half of each bottle was essentially a polyethylene cold seal coating (, 'included CEC,,) was sprayed while the remaining half did not receive a cold seal coating ("no CEC"). The coated bottles were subjected to accelerated corrosive conditions and the loss of white decorative compositions as follows was measured. The covered bottles were filled with cold water and immersed for 7 minutes under a corrosive bath (2. 5 wt% 2 NaOH, 0.3 wt% Diversylever anti-etching agent and 50 parts per million CaC03) stirred at 70 ° C. The test is removed. Any loss of small prints is considered a failure of the entire group. Then the bottle is emptied and refilled with cold water, and the test cycle is repeated until failure is observed. The data recorded in Table 2 indicates white. The durability of the decorative composition is significantly enhanced by the use of a surface coating of a substantially clear coating composition, as compared to a decorative white composition with or without a polyethylene CEC. This data also indicates the polyethylene applied to the bottle. CEC contains a substantially transparent coating composition which has no effect on the durability of the white decorative composition. Table 2 Test cycle control without CEC control CEC-containing clear coating film without CEC Clear coating film containing CEC 1-9 by passing Passing through through through through through 10 through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through through By passing 46 through by passing the failure 47 through the failure failure 96457.doc -31 - 1276620 although the invention has been described with particular reference to certain specific embodiments thereof, these details are not intended to be limiting of the scope of the invention Except for this range, it contains Accompanying patent scope. 96457.doc -32-