201241103 六、發明說明： 22曰提交的歐洲專利申 出於所有的目的將該申請201241103 VI. Description of the invention: 22曰 Submitted European patent for all purposes
CuPc )以及製備它的方法 用於製備具有更好的可分 β並且經濟的方法，所述 顯示彩色圖像的濾光片， 同在其中結合了前述顏料 由於其優異的色強度和耐 何合成的有機顏料中最重 (約105)，並且其耐光 顏料。另外地，其合成從 、脲以及銅鹽）很容易地 的生產不但溫和而且經濟 或塑膠的一藍色染料來使 定的並且是更加所希望的 本申請要求於2010年12 J 請號EP 10196463.3的優先權， 的全部內容藉由引用結合在此。 【發明所屬之技術領域】 本發明總體上涉及銅酞青（ 。更具體地說，本發明涉及一種 散性的 CuPc顏料的新的有效I CuPc顏料尤其適合於製備用來 涉及由此製備的CuPc顏料，連 的液晶顯示裝置。 【先前技術】 銅酞青藍（C.I.顏料藍15 ) 久性而無例外地是當今生產的任 要的。它具有一高莫耳吸光係數 性和耐候性優於所有其他的有機 更低成本的材料（鄰苯二甲酸酐 進行，由此使得這種錯合物分子 。因此，它典型地作爲用於塗料 用。在顔料中，銅酞青係非常穩 ，因爲它具有多種不退色性。 銅酞青具有許多晶形。在該等晶形中，已知的具有實 201241103 際應用的那些包括銅酞青的α、β以及ε晶形。一普通的 慣例係使用β晶形來產生淡綠的藍顏色，而使用α晶形來 產生紅藍的顏色。另外，當需要比使用α晶形生產的顏色 更偏紅的藍色時，使用ε晶形。 銅酞青以三種晶形（即：α、β以及ε )可商購。該α 晶體（該晶體使用顏色指數命名法）被描述爲顔料藍15、 15 : 1以及15 : 2，並且是一透明的亮紅色調的藍色。該β 晶體被描述爲顏料藍15 : 3以及15 : 4，是一透明的綠色 調的藍色，並且重要的ε晶形係藍色的最偏紅的色調。其 鹵化的衍生物還被用作重要的綠色顏料。 典型地，該可商購的“粗製的”銅酞青顆粒包含不同的 晶形，其中大部分呈現β晶形。存在許多可供使用於將粗 製的銅酞青轉化成顏料形式的技術，例如藉由酸糊劑法以 產生100% α形式，或鹽硏磨法（涉及逐漸轉化成α形式 )。較佳的是它們藉由使用一酸糊劑法由呈現β晶形的銅 酞青顆粒製備。該β晶形銅酞青係從不同的公司（例如： 東洋油墨公司（Toyo Ink )(日本）、大日本油墨化學公 司（Dainippon Ink & Chemicals)(日本）等等）商購的 。該β晶形銅酞青藉由酸糊劑化法經受晶型轉化成爲α晶 形，這例如在烏爾曼工業化學百科全書，第五完整修訂版 ，1992，第Α20卷，第225-2 26頁中描述，將其藉由引用 結合在此。 呈現ε晶形的銅酞青（CuPc )顆粒典型地由作爲一起 始材料具有至少50 wt%的呈現α晶形的顆粒的CuPc顆粒 201241103 製備的。 已經提出了不同的方法用於生產一具有各個晶形的酞 青顏料。用於生產ε晶形銅酞青的一典型的方法係溶劑鹽 硏磨法，其中將呈現α晶形的銅酞青顆粒和呈現ε晶形的 銅酞青顆粒在一有機溶劑中硏磨。 例如，WO 200 9/037233揭露了一種方法，其中呈現α 晶形的CuPc顆粒在一溶劑中經受加熱（可隨意地使用硏 磨珠）用於到ε型的結晶的轉化。然後在該加熱後緊接著 —用於將該等ε型的CuPc顆粒微粉化的捏合過程。在WO 2 0 09/062995中，在從酸漿化法步驟中獲得α型的CuPc顆 粒後，將該等α型的CuPc顆粒在不同的溫度條件下進行 捏合。在該捏合的步驟過程中，按順序加入兩種CuPc衍 生物。 關於從β形銅酞青製備α形銅酞青的一方法，使用硫 酸（無機酸的一種）的著色法在本領域中是已知的。那就 是，使用一酸糊劑化法（acid pasting process)(當粗製 銅酞青溶解在大量濃硫酸中時將其進行處理）和一酸漿化 法（acid slurry process)(用大量具有不足以溶解該顏料 的濃度的硫酸處理粗製銅酞青以形成一種硫酸鹽）。 然而，由上述的方法獲得的該等產物以團聚體的形式 被生產’該等團聚體並沒有顯示所希望的性能特性。 爲了隨後達到最佳的應用特性，所謂的最終處理係在 例如溶劑中進行的，同時加入表面活性劑，如 GB 1096192A 和 GB 2039290 中所揭露的。EP 1580239A1 還 201241103 揭露了 一種用於生產ε晶形的銅酞青的方法，該方法包括 在一種路易士酸存在下在一有機溶劑（例如：叔戊苯、環 丁颯，等等）中加熱銅酞青。 WO 08/083 799Α揭露了 一種呈現ε晶形的銅酞青的顔 料組合物，該顏料組合物使用一濕硏磨方法（更具體地說 一鹽捏合操作）生產。 U S 4 2 3 9 6 8 5 Α揭露了用於從駄青的硫酸溶液的水解所 得到的一酞青壓製糊劑而製備酞青顏料的一種方法，其中 將少量的不溶于水的結晶的溶劑，在一非結晶的溶劑存在 或不存在下攪拌結合到所述壓製糊劑中，並且然後消除該 溶劑或該等溶劑並且乾燥該糊劑，並且因此收集所得到的 顔料》 US 3801591A揭露了由幾乎唯一的α I多晶型物組成 的金屬酞青顏料的生產，其中將粗製的金屬酞青在兩個階 段中經受受控的沉澱，接著在強烈攪拌下對所生成的發料 進行調節以產生一空氣/液體的介面並且因此有助於絮凝 ，因此過濾。 GB 1 4 1 1 8 8 0Α揭露了 一種用於以純的或實際上純的^ 改性的銅酞青的形式生產銅酞青的方法，該方法包括藉由 在一球磨機中進行硏磨將α -改性' γ -改性和/或δ _改性的 銅酞青轉化成α-/ε-改性的混合物、在—沒有或實質上沒 有該β -改性轉化發生的溫度（液體特異的限定的溫度（ liquid-specific limiting temperature ))下用一液體處理 該混合物以進行改性到ε-改性的轉化從而形成該液體與 -8 - 201241103 純的或實際上純的ε-改性的一混合物並且可隨意地對純的 或實際上純的ε-改性的銅酞青進行分離。 然而，上述的該等用於製備銅酞青顆粒的方法具有一 些問題，因爲該合成的CuPc顆粒仍然缺乏可分散性，這 導致了仍然要改進濾光片的顏料，例如關於該等由該等銅 酞青顆粒製備的濾光片的對比率。因此，在本領域中對開 發一種有效改進該等生成的銅酞青顆粒的可分散性的方法 以增加用於濾光片的最終顏料的性能（沒有上述的缺陷） 已經存在一種強烈的期望。 【發明內容】 本發明的目的在於解決常規的製備方法的問題，例如 :導致了來自生成的濾光片顏料的差對比率的相對低的可 分散性。 因此本發明涉及一種用於製備基於銅酞青（CuPc)顆 粒的產物的方法，所述方法包括在CuP c顆粒的製備過程 中或之後，向其中加入小於1 0重量％ C u P c顆粒之數量的 至少一種非極性溶劑。 本發明的諸位發明人確實已經發現了當在呈現ε晶形 的銅酞青顆粒的製備過程中或之後加入小於1 〇重量 %CuPc顆粒之量的一些非極性溶劑時，可以改進用於生產 藍色顏料的最終濾光片顏料的性能。 以下對本發明進行詳細描述。 本發明係針對開發一種用於製備基於銅酞青的產物的 -9 - 201241103 新的並且更有效的方法，該方法滿足了上述的特徵。 銅酞青（CuPc )典型地作爲一有效地用作LCD的濾 光片的藍色顏料被開發。該等濾光片必須是高度透明的、 均勻的並且在一具有均勻厚度的層中被製備。該等特徵由 幾個因素決定，包括銅酞青顆粒的化學純度、結晶純度、 初級粒徑以及粒徑分佈。在此方面，本揭露傳授了 一種製 備銅酞青的新的並且更有效的方法。 儘管在本發明的方法中可以使用本領域中已知的任何 類型的非極性溶劑，較佳的是使用選自脂環族的和芳香族 化合物的至少一種非極性溶劑。非極性溶劑的適合的例子 係選自由以下各項組成的群組的那些：正己烷、戊烷、環 戊烷、石油醚、環己烷、苯、萘、甲苯、或異丙苯，較佳 的是環己烷、苯或萘。 該非極性溶劑的量不受限制但是通常加入至少〇. 1重 量％，具體地至少0.5重量％，更具體地說至少1重量％之 數量的CuPc顆粒。該非極性溶劑加入的量値通常是小於 10%的量之數量的CuPc顆粒，具體地最大5重量％，更具 體地說最大3重量％。非極性溶劑加入的量値典型地可以 是從0.1重量％到小於10重量％的CuPc顆粒，較佳的是 從0.5重量％到5重量％，更佳的是從1重量％到3重量％ 〇 在本發明的一具體實施方式中，該至少一種非極性溶 劑可以與至少一種極性溶劑組合。該至少一種極性溶劑存 在的量値可以較佳的是從3.3重量％到2 0重量％的的C u p c •10, 201241103 顆粒，更佳的是從5重量％到1 0重量％，特別是從5重量 %到小於1 〇重量％。 在本發明的另一實施方式中’在本發明的方法中可以 加入一作爲分散劑起作用的表面活性劑，尤其在與該非極 性ί谷劑相问的處理步驟中。適合的表面活性劑包含有機竣 酸類或磺酸類、胺類或銨化合物 '或松香以及其衍生物類 ’例如：月桂酸、癸酸、檸檬酸、油酸、硬脂酸、十二院 基苯擴酸（DBSA)、對甲苯磺酸（pTSA)、月桂基胺、 苄胺、十六胺、十二烷胺、苯胺、6 -胺基己酸、4 -(胺甲基 )苯甲酸、十六烷基三甲基氯化銨、以及其組合，較佳的 是十六烷基三甲基氯化銨、松香以及其衍生物類、以及其 組合。 該等表面活性劑藉由與C u P c顆粒表面的相互作用被 認爲形成了一種雙電層’該雙電層藉由防止顆粒附聚作用 導致了所生成的分散體的更好的分散穩定性。該相互作用 可以是該表面活性劑分子與銅酞青顆粒的表面之間的離子 的或π-π-型相互作用。 在此術語“松香”被定義爲從松樹和一些其他的植物（ 主要地松柏類）中獲得的樹脂的一固體形式，該樹脂主要 由不同的樹脂酸（尤其松香酸）組成。可容易地獲得的並 且在自然界中存在的此種類的混合物包括，但不限於，妥 爾油松香、脂松松香或木松香。該等天然的混合物可以包 括除其他之外’不同量値的松香酸類型和/或海松酸類型 的松香酸，例如：松香酸、長葉松酸、新松香酸、左松脂 -11 - 201241103 酸' 海松酸、異海松酸或脫氫松香酸。除具有一個羧酸官 能度的松香酸之外’具有兩個或更多個羧酸官能度的松香 酸也被認爲是在本發明的意義中的松香酸。表述“松香衍 生物”被定義爲該松香的任何衍生物，例如：氫化的松香 、二聚的松香、聚淺色松香、由酯基取代的松香，等等。 當加入一表面活性劑時，其量値係不受限制的但總體 上是從〇. 1重量％到25重量％之數量的CuPc顆粒，較佳 的是從0.5重量％到20重量％，更佳的是1重量％到15重 量％。 在另一實施方式中，在該捏合步驟過程中和/或之後 可以加入至少一種驗金屬或鹼土金屬的鹽。該驗金屬鹽的 鹼金屬典型地是選自鈉、鉀以及鋰，特別是鈉。該鹼土金 屬鹽的鹼土金屬經常選自鈣以及鎂，最經常地鈣。該金屬 鹽有利地是一鹼土金屬鹽。適當的鹼金屬以及鹼土金屬鹽 的例子是鹼金屬以及鹼土金屬的氯化物，例如NaCl、KC1 ' LiCl、CaCl2、MgCl2;羧酸鹽類，例如 CH3COONa、 (CH3COO)2Ca;酸式鹽或驗式鹽，例如NaHC03、NaHS〇4 、Na2HP04、Ca(OH)Cl、Ba(OH)Cl，等等；尤其是 CaCl2 以及MgCl2。 當加入一鹼金屬或鹼土金屬鹽時，其量値不受限制， 但通常該鹽的加入量從0. 1重量％到25重量％的CuPc顆 粒’較佳的是從0 · 5重量％到2 0重量％，更佳的是從1重 量％到15重量％。 在本發明中，出人意料地已經發現了藉由以小於1 0 -12- 201241103 重量％的量加入該非極性溶劑，可以得到該等顏料顆粒的 更好的可分散性。還已經發現該等合成的顆粒呈現一更圓 的顆粒形狀。這導致了由該等顏料顆粒製備的生成物濾光 片的一改進的對比率，連同所述爐光片的一改進的亮度。 因此本發明還涉及具有圓形形狀的銅酞青（CuPc)顆 粒，尤其涉及表現從1 : 1到2 : 1的平均長徑比的CuPc 顆粒，較佳的是1 : 1到1 .5 : 1，更佳的是1 . 1到1 · 3 : 1 ’最佳的是大約1 : 1。在此該長徑比被定義爲一種顏料顆 粒的長度相對於其寬度。該長徑比通常由藉由透射電子顯 微術（TEM )或掃描電子顯微鏡術（SEM )所拍攝的照片 的圖像分析確定。該平均長度（L)可以藉由幾種方法而 確定，包括最大弗雷特直徑、可以***該顆粒的長方形的 長度或長度L的測量。同樣地，該等顆粒的平均寬度可以 根據等效的投影面積的一圓周的直徑、最小弗雷特直徑、 其中可以***該顆粒的長方形的寬度或該寬度1來確定。 因此，該長徑比（L/1 )對應于長度（L )和相關的寬度（1 )之間的比率，尤其最大弗雷特直徑比最小弗雷特直徑、 最大弗雷特直徑比等效投影面積的一圓周的直徑、其中可 以***該顆粒的長方形的長度比其中可以***該顆粒的長 方形的寬度或直接測量的長度比直接測量的寬度。一定數 量的顆粒的長徑比被定義爲平均每個顆粒的長徑比。在一 較佳的實施方式中，該長徑比係直接測量的顆粒的長度與 直接測量的顆粒的寬度的平均比率，所述長度和寬度藉由 T E Μ獲得的圖像測量的。 -13- 201241103 本發明的方法尤其適合於製備呈現ε晶形的CuPc顆 J/JL. 。 在本發明的一方面中，該產物（CuPc )顆粒呈現ε晶 形並且經添加至少一非極性溶劑的該等CuPc顆粒包括呈 現α晶形的C u P c顆粒。較佳的是，經添加至少一種非極 性溶劑的該等CuPc顆粒包括具有至少50 wt%的顆粒呈現 α晶形的CuPc顆粒。 在此方面的一具體實施方式中，將呈現ε晶形的銅酞 青顆粒（作爲種子顆粒）以相對於CuPc顆粒的總量從1 0 w t %到9 0 w t %、較佳的是從1 5 w t %到5 0 w t %的量加入到 經該添加至少一種非極性溶劑的該等CuPc顆粒中》 在一第一具體的實施方式中，呈現ε晶形的銅酞青顆 粒可以藉由在至少一種有機液體存在下將一種包括至少50 wt%的呈現α晶形的CuPc顆粒的起始材料在大於或等於 50°C的溫度下加熱並且可任地在珠粒的存在下進行硏磨 而製備。該有機液體例如可以選自由以下各項組成的群組 :N -甲基-2-吡咯烷酮，環丁颯，N，N -二甲基甲醯胺，二 醇類如丙二醇單甲醚乙酸酯，二乙二醇，醇類如二丙酮醇 ，乙腈，一氯苯，乙二醇丁醚，酮類以及喹啉類。如在此 定義的硏磨意思係一種方法，藉由該方法該等固體經受磨 損、硏磨等等以實現粒徑的減小。 在一第二具體實施方式中，ε CuPc顆粒可以藉由在至 少一種液體和至少一無機鹽存在下對包括至少5 0重量％呈 現α晶形的CuPc顆粒的一起始材料進行捏合來製備。該 14- 201241103 液體通常選自由以下各項組成的群組：N-甲基-2-吡咯烷 酮、環丁颯、N，N-二甲基甲醯胺、二乙二醇、二丙酮醇、 甘油、乙二醇、丙二醇、聚丙二醇、2 -丁氧基乙醇、伸甲 基二醇、二乙二醇單甲醚、三乙二醇單甲醚、二丙二醇單 甲醚' 1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、酮類以及唾 啉類。較佳的是’在溫度條件下進行捏合，從而溫度特徵 曲線作爲時間的函數顯示出至少兩個關於時間（d 77 d t )係 等於〇的溫度的導數。這兩個溫度與等於0的導數相關， 相差至少l〇°C。在另一實施方式中，捏合在一不變的或 逐步變化的溫度特徵曲線下進行。較佳的是，捏合在第一 溫度下進行並且然後在第二溫度下進行，其中該第一溫度 係80〇C-150°C (較佳的是1〇〇。<：-120。(：）並且該第二溫度 係30。〇-70°(：(較佳的是50°C-60°C)。此實施方式提供 了在捏合步驟過程中溫度的改變，藉由該步驟呈現α晶形 的CuPc顆粒被轉化成ε晶形並且它們的顆粒大小被顯著 地減小。 在國際專利申請 WO 2009/037233 以及 WO 2009/062995中描述了該捏合或加熱步驟（例如：持續時 間、珠粒、無機鹽，等等）的該等具體條件，將其所有內 容藉由引用以其全文結合在此。 在根據那些方法製備銅酞青之後，爲了除去副產物以 及前面的步驟中加入的添加劑，可以將所生成的混合物攪 拌一段時間，並且過濾。可以將濾餅藉由在蒸餾水中再漿 化若干次而洗滌，可隨意地在一有機溶劑存在下。 -15- 201241103 本發明的方法尤其還適合於製備CuPc顏料組合物， 該等組合物包括呈現ε晶形的C u P c顆粒。 在本發明的另一具體實施方式中，可以在製備一種包 括呈現ε晶形的CuPc顆粒的CuPc顏料組合物的過程中加 入該非極性溶劑。確切地，該非極性溶劑可以在一捏合步 驟或在一再漿化步驟中加入，其中對該捏合步驟之後獲得 的該濾餅在一溶劑（例如：水、一水混溶性溶劑或它們的 —混合物）中進行再漿化。在此實施方式中，藉由將該至 少一種非極性溶劑加入到呈現ε晶形的CuPc顆粒中，較 佳的是在一再漿化或捏合步驟過程中（尺寸減小），可以 獲得該等CuPc顆粒的一更圓的形狀。在一些進一步的具 體實施方式中，在該捏合步驟過程中可以加入一非極性溶 劑，並且隨後在該再漿化步驟過程中可以加入另一非極性 溶劑。因此本發明還涉及包括根據本發明的方法可獲得的 呈現ε晶形的CuPc顆粒的銅酞青（CuPc)顏料組合物。 本發明還涉及一種包括根據本發明的方法可獲得的呈現ε 晶形的銅酞青顆粒的濾光片。 本發明還涉及藉由本發明的方法可獲得的呈現ε晶形 的銅酞青CuPc顆粒。 鑒於以上內容，本發明的另一方面涉及使用按銅酞青 (CuPc)顆粒的小於1〇重量％CuPc顆粒之數量存在的至 少一種非極性溶劑製備一基於CuPc顆粒的產物的用途. 以下對本發明進行進一步說明，而並不將其範圍限制 於此。 -16- 201241103 若任何藉由引用結合在此的專利案、專利申請案以及 公開物中的揭露內容與本申請案的說明相衝突的程度至它 可能使一術語不清楚，則本說明應該優先。 【實施方式】 實例 實例1 ( β-CuPc到α-CuPc的轉化） 在一個2 L的玻璃燒杯將50 g的粗製的銅酞青加入到 500 g的95 wt%的硫酸中。此外，將生成物混合物在硫酸 中藉由一攪拌葉輪（特氟隆離心分離機，3 00 rpm的轉速 )在30°C下攪拌2小時以製備一硫酸鹽的懸浮液或溶液 。將該懸浮液或該溶液兩次倒入到5 L的水中以獲得一種 α晶形的銅酞青，然後將其在熱空氣下乾燥。在將產生的 固體粉碎之後，就結晶的產率而言幾乎定量地獲得了 α晶 形的銅酞青，這藉由XRD硏究證實。 實例2 (在環己院存在下α-CuPc到ε-CuPc的轉化） 將50 g在實例1中獲得的呈現a晶形的銅酞青顆粒 和12 g ε型銅酞青與3.0 g環己烷、80 g二乙二醇以及 400 g氯化鈉一起加入到一實驗室規模的捏合機中。將該 混合物在1 3 0 ° C下在的5 0 rpm轉速捏合6小時（第一階 段）’並且然後在80°C下在相同的轉速下捏合8小時（ 第二階段）。在捏合後’將生成物顆粒過濾並且用蒸餾水 洗滌幾次。 -17- 201241103 在去離子水中對該濕餅進行再成漿並且然後在保持攪 拌的同時加入10 g松香，並且獲得了一銅酞青組合物》 在完成該再成漿步驟後，藉由過濾對該漿料進行純化，並 且在80°C的溫度和104 Pa的壓力下進行乾燥。然後將該 乾燥的產物粉碎並且藉由透射電子顯微鏡（TEM )進行分 析。圖1展示了該等銅酞青顆粒的TEM圖像。 實例3 (在苯存在下α-CuPc到ε-CuPc的轉化） 以與實例2完全相同的方式獲得了呈現ε晶形的銅酞 青顆粒，除了在該捏合步驟過程中加入3.0 g苯之外。 實例4 (對比-沒有加入非極性溶劑和表面活性劑） 以與實例1和2完全相同的方式獲得了呈現ε晶形的 銅酞青顆粒，除了沒有加入非極性溶劑、表面活性劑以及 金屬鹽之外。根據使用透射電子顯微鏡（ΤΕΜ )對該等呈 現ε晶形的生成物銅酞青顆粒的一些乾燥的樣品的分析， 它們在圖像中顯示出呈現了更多的附聚作用（圖2)。 如圖1和2的該等ΤΕΜ圖像中所顯示的，根據本發 明的方法在一非極性溶劑的存在下（實例2)獲得的該等 ε-CuPc顆粒相對於根據實例在不加入一非極性溶劑的情況 下產生的該等ε-CuPc顆粒展現了更高的分散水平。此外 ，本發明的該等CuPc顆粒具有接近1 : 1的長徑比，該長 徑比對更高的對比率係有利的。 -18 - 201241103 實例5至7 (對比-沒有加入非極性溶劑） 以與實例2完全相同的方式獲得了呈現ε晶形的銅酞 青顆粒，除了在該再漿化步驟過程中分別加入0.5 g松香 和0.5 g氯化鈣、或1 .5 g松香和1 .5 g氯化鈣、或1〇.〇 g 松香之外。 實例8 (在環己烷存在下並且不加入表面活性劑a-CuPc 到ε - C u P c的轉化） 以與實例1和2完全相同的方式獲得了呈現ε晶形的 銅酞青顆粒，除了沒有加入表面活性劑以及金屬鹽之外。 與實例4的那些相比，然後將該乾燥的產物進行粉碎並且 該等顆粒的形狀更好。 濾光片中顆粒的測試 如在表1中所示，與實例4相比，使用來自根據實例 2和3製備的該等ε形銅酞青顏料顆粒的顏料製造的濾光 片在對比率上產生了分別大約8 %和1 0 %的改進。 在表1中，在其中加入了非極性溶劑以及可隨意地表 面活性劑的CuPc顔料展示了該濾光片顏料的硏磨料漿的 改進的對比率。這種改進可能是得自該等生成物CuPc顆 粒的更好的可分散性以及優化的形狀。 因此，這種增加的可分散性以及良好的顆粒形狀已經 導致了下游的濾光片的改進的對比率。 •19- 201241103 -_____表 1 實例 非極性溶劑/表面活件劑 對比率 實例2 ―別g噚匕院」g松香+ 〇.5 g CaCl2 8%改進 實例3 3.0 g 本 + 1〇·〇 g 松香 + 〇 5 e CaCl， 10%改進 實例4 1 (a.u.) 實例5 〇·5 g 松香 + 0.5 g CaCl, 3%改進 實例6 -.......】.5g 松香 +1.5gCaCl2 1%改進 實例7 10.0 g松番 1%改進 工業的應用 本領域普通技術人員將清楚的是，可對本發明做出不 同的變更和改變而不背離本發明的精神和範圍。因此，本 發明旨在涵蓋本發明的該等變更和變體，前提係它們在所 附申請專利範圍及其等效物的範圍之內。 【圖式簡單說明】 圖1係藉由根據實例2的方法製備的呈現ε晶相的銅 酞青顆粒的一透射電子顯微鏡（ΤΕΜ )圖像。 圖2係藉由根據實例4的方法製備的呈現ε晶相的銅 酞青顆粒的一ΤΕΜ的圖像。 若任何藉由引用結合在此的專利案、專利申請案以及 公開物中的揭露內容與本申請案的說明相衝突的程度至它 可能使一術語不清楚’則本說明應該優先。 -20-CuPc) and a method for preparing the same for preparing a method having a better separable β and economy, the filter for displaying a color image, in which the aforementioned pigment is combined due to its excellent color strength and resistance synthesis The most important organic pigment (about 105), and its light-resistant pigment. In addition, its synthesis from urea, copper salts and copper salts is easy to produce not only mild but also economical or plastic blue dye to make and is more desirable. This application claims in 2010 12 J. No. EP 10196463.3 The entire contents of the priority are hereby incorporated by reference. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention generally relates to copper indocyanine (more specifically, the present invention relates to a novel effective I CuPc pigment of a bulk CuPc pigment which is particularly suitable for preparation for the CuPc thus prepared. Pigment, connected liquid crystal display device. [Prior Art] Copper sapphire blue (CI Pigment Blue 15) is long-lasting and without exception, it is required for today's production. It has a high molar absorption coefficient and weather resistance. All other organic lower cost materials (phthalic anhydride are carried out, thereby making this complex molecule. Therefore, it is typically used as a coating. In pigments, the copper indigo is very stable because It has a variety of non-fading properties. Copper indocyanine has many crystal forms. Among these crystal forms, those known as real-time 201241103 applications include α, β and ε crystal forms of copper indocyanine. A common convention is to use β crystal form. To produce a light green blue color, and use the alpha crystal form to produce a red-blue color. In addition, when a blue color that is more reddish than the color produced using the alpha crystal form is required, the epsilon crystal form is used. Three crystal forms (i.e., α, β, and ε) are commercially available. The alpha crystal (which uses color index nomenclature) is described as Pigment Blue 15, 15:1, and 15:2, and is a transparent bright red tone. The blue crystal is described as pigment blue 15:3 and 15:4, which is a transparent greenish blue, and the important epsilon crystal is the most reddish hue of blue. Its halogenated derivative It is also used as an important green pigment. Typically, the commercially available "crude" copper indocyanine particles contain different crystal forms, most of which exhibit a beta crystal form. There are many available for converting crude copper indigo A technique in the form of a pigment, for example, by an acid paste method to produce a 100% alpha form, or a salt honing method (involving a gradual conversion to an alpha form). Preferably, they are rendered by the use of an acid paste process. Preparation of crystalline copper phthalocyanine particles from different companies (for example: Toyo Ink (Japan), Dainippon Ink & Chemicals (Japan), etc. Commercially available. Cyan is subjected to crystal form conversion to an alpha crystal form by acid paste, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Complete Revision, 1992, Vol. 20, pp. 225-2-26. This is incorporated herein by reference. The copper indocyanine (CuPc) particles exhibiting an epsilon crystal form are typically prepared from CuPc particles 201241103 having at least 50 wt% of particles exhibiting an alpha crystal form as a starting material. Different methods have been proposed. In the production of a phthalocyanine pigment having various crystal forms, a typical method for producing ε-formed copper phthalocyanine is a solvent salt honing method in which copper phthalocyanine particles having an alpha crystal form and copper phthalocyanine particles exhibiting an ε crystal form are formed. Honing in an organic solvent. For example, WO 200 9/037233 discloses a process in which CuPc particles exhibiting an alpha crystal form are subjected to heating in a solvent (optionally using beryllium beads) for conversion to ε-type crystals. This heating is then followed by a kneading process for micronizing the ε-type CuPc particles. In WO 2 0 09/062995, after α-type CuPc particles are obtained from the sizing step, the α-type CuPc particles are kneaded under different temperature conditions. During the kneading step, two CuPc derivatives were added in order. Regarding a method of preparing α-shaped copper indocyanine from β-shaped copper phthalocyanine, a coloring method using sulfuric acid (one of inorganic acids) is known in the art. That is, using an acid pasting process (when the crude copper phthalocyanine is dissolved in a large amount of concentrated sulfuric acid) and an acid slurry process (with a large amount of insufficient to dissolve) The concentration of the pigment is treated with sulfuric acid to treat the crude copper indigo to form a sulfate). However, the products obtained by the above process are produced in the form of agglomerates. The agglomerates do not exhibit the desired performance characteristics. In order to achieve the best application characteristics subsequently, the so-called final treatment is carried out, for example, in a solvent, together with the addition of surfactants, as disclosed in GB 1096192A and GB 2039290. EP 1580239 A1 also 201241103 discloses a process for producing copper indium in the epsilon crystal form, which comprises heating copper in an organic solvent (for example: tert-amylbenzene, cyclobutylhydrazine, etc.) in the presence of a Lewis acid. Indigo. WO 08/083 799 Α discloses a pigment composition which exhibits an epsilon crystal form of copper indigo which is produced using a wet honing method, more specifically a salt kneading operation. US 4 2 3 9 6 8 5 Α discloses a method for preparing an indigo pigment for use in a cyanine pressed paste obtained by hydrolysis of a sulfuric acid solution of indigo, wherein a small amount of a solvent insoluble in water is crystallized Agglomerating into the compressed paste in the presence or absence of a non-crystalline solvent, and then eliminating the solvent or the solvent and drying the paste, and thus collecting the resulting pigment. US 3801591A discloses Production of a metal indigo pigment consisting of almost the only alpha I polymorph, wherein the crude metal indigo is subjected to controlled precipitation in two stages, followed by conditioning of the resulting hair with vigorous agitation An air/liquid interface is created and thus contributes to flocculation and therefore filtration. GB 1 4 1 1 8 8 0 Α discloses a method for producing copper indocyanine in the form of pure or virtually pure modified copper indocyanine, which comprises a honing by means of a honing in a ball mill - modified ' γ - modified and / or δ _ modified copper phthalocyanine converted to α-/ε-modified mixture, at - no or substantially no temperature at which the β-modified conversion occurs (liquid specific Treatment of the mixture with a liquid at a liquid-specific limiting temperature for modification to ε-modified conversion to form the liquid with -8 - 201241103 pure or virtually pure ε-modification A mixture of and optionally free of pure or virtually pure ε-modified copper indigo. However, the above-described methods for preparing copper indocyanine particles have some problems because the synthesized CuPc particles still lack dispersibility, which leads to pigments which still need to improve the filter, for example, regarding such The contrast ratio of the filters prepared from the copper phthalocyanine particles. Accordingly, there has been a strong desire in the art to develop a method for effectively improving the dispersibility of such produced copper phthalocyanine particles to increase the properties of the final pigment for the filter (without the above-mentioned drawbacks). SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the conventional preparation method, for example, resulting in a relatively low dispersibility of the poor contrast ratio of the resulting filter pigment. The invention therefore relates to a process for the preparation of copper indigo (CuPc) particle-based products, which comprises adding less than 10% by weight of C u P c particles during or after the preparation of the CuP c particles A quantity of at least one non-polar solvent. The inventors of the present invention have indeed found that when a non-polar solvent is added in an amount of less than 1% by weight of CuPc particles during or after the preparation of the copper indigo particles exhibiting an epsilon crystal form, it can be improved for producing blue. The properties of the final filter pigment of the pigment. The invention is described in detail below. The present invention is directed to the development of a new and more efficient method for preparing a copper indocyanine-based product which satisfies the features described above. Copper indocyanine (CuPc) is typically developed as a blue pigment that is effectively used as a filter for LCDs. The filters must be highly transparent, uniform and prepared in a layer of uniform thickness. These characteristics are determined by several factors, including the chemical purity, crystal purity, primary particle size, and particle size distribution of the copper phthalocyanine particles. In this regard, the present disclosure teaches a new and more efficient method of preparing copper indocyanine. Although any type of non-polar solvent known in the art can be used in the process of the present invention, it is preferred to use at least one non-polar solvent selected from the group consisting of alicyclic and aromatic compounds. Suitable examples of non-polar solvents are those selected from the group consisting of n-hexane, pentane, cyclopentane, petroleum ether, cyclohexane, benzene, naphthalene, toluene, or cumene, preferably. It is cyclohexane, benzene or naphthalene. The amount of the non-polar solvent is not limited but usually at least 0.1% by weight, specifically at least 0.5% by weight, more specifically at least 1% by weight, of the CuPc particles are added. The amount of ruthenium added to the non-polar solvent is usually an amount of CuPc particles in an amount of less than 10%, specifically up to 5% by weight, more specifically up to 3% by weight. The amount of ruthenium added by the non-polar solvent may typically be from 0.1% by weight to less than 10% by weight of CuPc particles, preferably from 0.5% by weight to 5% by weight, more preferably from 1% by weight to 3% by weight. In a specific embodiment of the invention, the at least one non-polar solvent can be combined with at least one polar solvent. The amount of the at least one polar solvent present may preferably be from 3.3% to 20% by weight of Cupc® 10, 201241103 particles, more preferably from 5% by weight to 10% by weight, especially from 5 wt% to less than 1 wt%. In another embodiment of the invention, a surfactant acting as a dispersing agent can be added to the process of the invention, especially in the processing steps associated with the non-polar gluten. Suitable surfactants include organic tannins or sulfonic acids, amines or ammonium compounds 'or rosins and derivatives thereof' such as: lauric acid, capric acid, citric acid, oleic acid, stearic acid, twelfth benzene Acid expansion (DBSA), p-toluenesulfonic acid (pTSA), laurylamine, benzylamine, hexadecylamine, dodecylamine, aniline, 6-aminohexanoic acid, 4-(aminomethyl)benzoic acid, ten Hexyltrimethylammonium chloride, and combinations thereof, are preferably cetyltrimethylammonium chloride, rosin, and derivatives thereof, and combinations thereof. The surfactants are believed to form an electric double layer by interaction with the surface of the Cu P c particles. The electric double layer causes better dispersion of the resulting dispersion by preventing particle agglomeration. stability. The interaction may be an ionic or π-π-type interaction between the surfactant molecule and the surface of the copper indocyanine particles. The term "rosin" is defined herein as a solid form of a resin obtained from pine and some other plants (mainly conifers) which consists essentially of different resin acids (especially rosin acids). Mixtures of this type which are readily available and which are found in nature include, but are not limited to, tall oil rosin, gum rosin or wood rosin. Such natural mixtures may include, among other things, different amounts of rosin acid type and/or pimaric acid type rosin acid, for example: rosin acid, long-leaf acid, neo-abietic acid, left rosin-11 - 201241103 acid 'Pizaric acid, isopimaric acid or dehydroabietic acid. In addition to rosin acid having a carboxylic acid functionality, rosin having two or more carboxylic acid functionalities is also considered to be rosin acid in the sense of the present invention. The expression "rosin derivative" is defined as any derivative of the rosin, for example, hydrogenated rosin, dimeric rosin, poly light rosin, rosin substituted by an ester group, and the like. When a surfactant is added, the amount of the lanthanide is not limited, but is generally from 0.1% by weight to 25% by weight of the CuPc particles, preferably from 0.5% by weight to 20% by weight, more Preferably, it is from 1% by weight to 15% by weight. In another embodiment, at least one metal or alkaline earth metal salt may be added during and/or after the kneading step. The alkali metal of the metal salt is typically selected from the group consisting of sodium, potassium and lithium, especially sodium. The alkaline earth metal of the alkaline earth metal salt is often selected from the group consisting of calcium and magnesium, most often calcium. The metal salt is advantageously an alkaline earth metal salt. Examples of suitable alkali metal and alkaline earth metal salts are alkali metal and alkaline earth metal chlorides such as NaCl, KCl 'LiCl, CaCl 2 , MgCl 2 ; carboxylates such as CH 3 COONa, (CH 3 COO) 2 Ca; acid salts or assays Salts such as NaHC03, NaHS〇4, Na2HP04, Ca(OH)Cl, Ba(OH)Cl, etc.; especially CaCl2 and MgCl2. When the alkali metal or alkaline earth metal salt is added, the amount thereof is not limited, but usually the salt is added in an amount of from 0.1 to 25% by weight of the CuPc particles, preferably from 0.5 to 5% by weight. 20% by weight, more preferably from 1% by weight to 15% by weight. In the present invention, it has surprisingly been found that by adding the nonpolar solvent in an amount of less than 10-12 to 201241103% by weight, better dispersibility of the pigment particles can be obtained. It has also been found that the synthetic particles exhibit a more rounded particle shape. This results in an improved contrast ratio of the resultant filter prepared from the pigment particles, together with an improved brightness of the oven sheet. The present invention therefore also relates to copper indocyanine (CuPc) particles having a circular shape, and more particularly to CuPc particles exhibiting an average aspect ratio of from 1:1 to 2:1, preferably from 1:1 to 1.5: 1, better is 1. 1 to 1 · 3 : 1 'The best is about 1:1. Here, the aspect ratio is defined as the length of a pigment particle relative to its width. The aspect ratio is typically determined by image analysis of photographs taken by transmission electron microscopy (TEM) or scanning electron microscopy (SEM). The average length (L) can be determined by several methods, including the measurement of the maximum Frette diameter, the length of the rectangle into which the particle can be inserted, or the length L. Likewise, the average width of the particles can be determined based on the diameter of a circumference of the equivalent projected area, the minimum Frette diameter, the width of the rectangle into which the particle can be inserted, or the width 1. Therefore, the aspect ratio (L/1) corresponds to the ratio between the length (L) and the associated width (1), especially the maximum Frette diameter is equivalent to the minimum Frette diameter and the maximum Frette diameter ratio. The diameter of a circumference of the projected area, the length of the rectangle into which the particle can be inserted, is greater than the width of the rectangle in which the particle can be inserted or the directly measured length than the directly measured width. The aspect ratio of a certain number of particles is defined as the average aspect ratio of each particle. In a preferred embodiment, the aspect ratio is an average ratio of the length of the directly measured particles to the width of the directly measured particles, the length and width being measured by the image obtained by T E 。. -13- 201241103 The method of the present invention is particularly suitable for the preparation of CuPc particles J/JL. which exhibit an epsilon crystal form. In one aspect of the invention, the product (CuPc) particles exhibit an epsilon crystal form and the CuPc particles to which at least one non-polar solvent is added comprise Cu P c particles in the form of an alpha crystal. Preferably, the CuPc particles added with at least one non-polar solvent include CuPc particles having at least 50 wt% of the particles exhibiting an alpha crystal form. In a specific embodiment of this aspect, the copper phthalocyanine particles (as seed particles) having an epsilon crystal form are present from 10% by weight to 90% by weight, preferably from 1 5 to 5 % by weight relative to the total amount of CuPc particles. An amount of wt% to 50 wt% is added to the CuPc particles to which the at least one non-polar solvent is added. In a first specific embodiment, the copper indigo particles exhibiting an epsilon crystal form may be at least one A starting material comprising at least 50 wt% of CuPc particles exhibiting an alpha crystal form is heated at a temperature greater than or equal to 50 ° C in the presence of an organic liquid and optionally honed in the presence of beads. The organic liquid may, for example, be selected from the group consisting of N-methyl-2-pyrrolidone, cyclobutane, N,N-dimethylformamide, glycols such as propylene glycol monomethyl ether acetate , diethylene glycol, alcohols such as diacetone alcohol, acetonitrile, monochlorobenzene, ethylene glycol butyl ether, ketones and quinolines. A honing as defined herein is a method by which the solids are subjected to wear, honing, etc. to achieve a reduction in particle size. In a second embodiment, the ε CuPc particles can be prepared by kneading a starting material comprising at least 50% by weight of CuPc particles exhibiting an alpha crystal form in the presence of at least one liquid and at least one inorganic salt. The liquid of 14-201241103 is usually selected from the group consisting of N-methyl-2-pyrrolidone, cyclobutyl hydrazine, N,N-dimethylformamide, diethylene glycol, diacetone alcohol, glycerol , ethylene glycol, propylene glycol, polypropylene glycol, 2-butoxyethanol, methyl glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether ' 1-methoxy 2-propanol, 1-ethoxy-2-propanol, ketones and porphyrins. Preferably, the kneading is carried out under temperature conditions such that the temperature characteristic curve as a function of time shows at least two derivatives with respect to the time (d 77 d t ) which is equal to the temperature of 〇. These two temperatures are related to a derivative equal to zero, differing by at least l〇 °C. In another embodiment, the kneading is carried out under a constant or stepwise varying temperature profile. Preferably, the kneading is carried out at a first temperature and then at a second temperature, wherein the first temperature is 80 〇 C - 150 ° C (preferably 1 〇〇. <: -120. :) and the second temperature system 30. 〇-70° (: (preferably 50 ° C - 60 ° C). This embodiment provides a change in temperature during the kneading step, by which α is presented The crystalline CuPc particles are converted to the epsilon crystal form and their particle size is significantly reduced. The kneading or heating step (eg duration, beads, etc.) is described in the international patent applications WO 2009/037233 and WO 2009/062995. These specific conditions of inorganic salts, etc., are hereby incorporated by reference in their entirety. After the preparation of copper indigo according to those methods, in order to remove by-products and additives added in the previous step, The resulting mixture is stirred for a while and filtered. The filter cake can be washed by re-slurrying several times in distilled water, optionally in the presence of an organic solvent. -15- 201241103 The method of the invention is particularly suitable Preparation C uPc pigment composition, the composition comprising Cu P c particles exhibiting an epsilon crystal form. In another embodiment of the invention, a CuPc pigment composition comprising CuPc particles exhibiting an epsilon crystal form may be prepared. Adding the non-polar solvent. Specifically, the non-polar solvent may be added in a kneading step or in a re-pulping step, wherein the filter cake obtained after the kneading step is in a solvent (for example: water, a water-miscible solvent or Re-slurrying in their mixture. In this embodiment, by adding the at least one non-polar solvent to the CuPc particles exhibiting an epsilon crystal form, preferably during a repulping or kneading step ( A more rounded shape of the CuPc particles can be obtained. In some further embodiments, a non-polar solvent can be added during the kneading step and subsequently during the repulping step Another non-polar solvent may be added. The invention therefore also relates to a copper ruthenium comprising CuPc particles exhibiting an epsilon crystal form obtainable by the process according to the invention. Cyan (CuPc) pigment composition. The invention also relates to a filter comprising copper indigo particles exhibiting an epsilon crystal form obtainable by the method according to the invention. The invention also relates to an epsilon crystal form obtainable by the method of the invention The copper indocyanine CuPc particles. In view of the above, another aspect of the invention relates to the preparation of a CuPc-based particle using at least one non-polar solvent present in an amount of less than 1% by weight of CuPc particles of copper indocyanine (CuPc) particles. USE OF THE PRODUCT The following is a further description of the present invention and is not intended to limit the scope thereof. -16- 201241103 The disclosure of the patents, patent applications, and publications hereby The description of the case conflicts to the extent that it may make a term unclear, and this note should take precedence. [Examples] Example Example 1 (Conversion of β-CuPc to α-CuPc) 50 g of crude copper indigo was added to 500 g of 95 wt% sulfuric acid in a 2 L glass beaker. Further, the product mixture was stirred in sulfuric acid by a stirring impeller (Teflon centrifugal separator, 300 rpm) at 30 ° C for 2 hours to prepare a sulfate suspension or solution. This suspension or the solution was poured twice into 5 L of water to obtain a crystal form of copper indigo which was then dried under hot air. After the solid to be produced was pulverized, the α-crystal form of copper indocyanine was obtained almost quantitatively in terms of the yield of the crystal, which was confirmed by XRD study. Example 2 (Conversion of α-CuPc to ε-CuPc in the presence of Cycloheximide) 50 g of copper phthalocyanine particles in the form of a crystal obtained in Example 1 and 12 g of ε-type copper phthalocyanine and 3.0 g of cyclohexane 80 g of diethylene glycol and 400 g of sodium chloride were added together to a laboratory scale kneader. The mixture was kneaded at 50 ° C for 5 hours (first stage) at 1 30 ° C and then kneaded at 80 ° C for 8 hours at the same number of revolutions (second stage). The resultant particles were filtered after kneading and washed several times with distilled water. -17- 201241103 The wet cake is repulped in deionized water and then 10 g of rosin is added while maintaining agitation, and a copper indigo composition is obtained. After the completion of the repulping step, by filtration The slurry was purified and dried at a temperature of 80 ° C and a pressure of 104 Pa. The dried product was then pulverized and analyzed by transmission electron microscopy (TEM). Figure 1 shows a TEM image of the copper phthalocyanine particles. Example 3 (Conversion of α-CuPc to ε-CuPc in the presence of benzene) Copper phthalocyanine particles exhibiting an epsilon crystal form were obtained in exactly the same manner as in Example 2 except that 3.0 g of benzene was added during the kneading step. Example 4 (Comparative - no addition of a non-polar solvent and a surfactant) Copper indigo particles exhibiting an epsilon crystal form were obtained in exactly the same manner as in Examples 1 and 2 except that no non-polar solvent, surfactant and metal salt were added. outer. According to the analysis of some dried samples of the copper phthalocyanine particles which were obtained as the epsilon crystal form using a transmission electron microscope (ΤΕΜ), they showed more agglomeration in the image (Fig. 2). As shown in the enthalpy images of Figures 1 and 2, the ε-CuPc particles obtained in the presence of a non-polar solvent (Example 2) in accordance with the method of the present invention are not added to one according to the examples. The ε-CuPc particles produced in the case of polar solvents exhibit a higher level of dispersion. Furthermore, the CuPc particles of the present invention have an aspect ratio of approximately 1:1, which is advantageous for higher contrast ratios. -18 - 201241103 Examples 5 to 7 (Comparative - no addition of a non-polar solvent) Copper indigo particles exhibiting an epsilon crystal form were obtained in exactly the same manner as in Example 2 except that 0.5 g of rosin was separately added during the repulping step. And 0.5 g of calcium chloride, or 1.5 g of rosin and 1.5 g of calcium chloride, or 1 〇.〇g rosin. Example 8 (Conversion in the presence of cyclohexane and without the addition of surfactant a-CuPc to ε - C u P c ) Copper indigo particles exhibiting an epsilon crystal form were obtained in exactly the same manner as in Examples 1 and 2, except No surfactants or metal salts were added. The dried product was then pulverized and the shapes of the particles were better compared to those of Example 4. The test of the particles in the filter was as shown in Table 1, and the filter produced using the pigments from the ε-shaped copper phthalocyanine pigment particles prepared according to Examples 2 and 3 was compared to Example 4 on the contrast ratio. Improvements of approximately 8% and 10%, respectively, were produced. In Table 1, the CuPc pigment to which the non-polar solvent and optionally the surfactant were added exhibited an improved contrast ratio of the honing slurry of the filter pigment. This improvement may be due to the better dispersibility and optimized shape of the CuPc particles derived from such products. Therefore, this increased dispersibility and good particle shape have led to improved contrast ratios of downstream filters. •19- 201241103 -_____ Table 1 Example non-polar solvent / surface working agent contrast ratio example 2 - 别别 g噚匕院"g rosin + 〇.5 g CaCl2 8% improvement example 3 3.0 g this + 1 〇 · 〇 g rosin + 〇5 e CaCl, 10% improvement example 4 1 (au) Example 5 〇·5 g rosin + 0.5 g CaCl, 3% modified example 6 -.......]. 5g rosin + 1.5g CaCl2 1 % 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施Therefore, the present invention is intended to cover such modifications and variations of the present invention, and the scope of the appended claims and their equivalents. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a transmission electron microscope (ΤΕΜ) image of copper indigo particles exhibiting an epsilon crystal phase prepared by the method according to Example 2. Fig. 2 is an image of a crucible of copper indigo particles exhibiting an epsilon crystal phase prepared by the method according to Example 4. In the event that any disclosure of patents, patent applications, and publications incorporated by reference is inconsistent with the description of the present application to the extent that it may render the term unclear, the description should be preferred. -20-