201107425 六、發明說明： 【發明所屬之技術領域】 本發明係關於綠色顏料、其製造方法、含其之著色劑及使 用其之物品的著色方法。更詳言之，係關於多鹵代鋅酞菁分 子與多_代非鋅金屬酞菁分子予以複合堆積的綠色顏料，含 其之綠色顏料組成物、其製造方法、含其之著色劑、使用其 之物品的著色方法以及已著色的物品。 【先前技術】 隨著最近資訊化機器的非常發展，以液晶彩色顯示器作為 資訊顯示構件，於個人電腦、移動式資訊機器、電視、投影 器、監視器、汽車衛星導航、行動電話、電子計算機和電子 字典之顯示晝面；資訊看板、指引看板、機能顯示板、標識 板等之顯示器；數位相機和錄影機之攝影晝面等所有資訊顯 示關連機器中已被多方面使用。伴隨於此使得液晶彩色顯示 器所搭載的彩色濾光片（以下，簡稱為「CF」）亦被要求高晝 質、寬廣的呈色色域、高精細性、色濃度、光穿透性、對比 性等之影像性能面更加優異之品質。關於該等液晶彩色顯示 器所搭載之CF綠色像素所使用的綠色顏料，先前使用C.I. 顏料綠36(以下，稱為「PG36」），但在期望高晝質、寬廣 的呈色色域的情況，比PG36更加呈現帶黃色之綠色的C.I. 顏料綠58(以下，稱為「PG58」被評估其色調和吸收波長的 敏銳度。 099118114 3 201107425 【發明内容】 (發明所欲解決之問題) PG58等之多溴基•多氯基鋅酞菁顏料’被使用作為塗料 和印刷油墨等之著色領域所通常使用之黃色、紅色、藍色、 黑色4原色之補足色表現的特定色。又’如上述，最近被利 用作為CF的綠色像素用顏料。但是，在塗料和印刷油墨等 有機溶劑系之著色劑製造階段和保存中、或者在著色加工和 製品化步驟中，更且在CF用彩色光阻和CF之製造步驟中， 根據使用條件易發生起因於必然且必要之耐溶劑性和耐熱 性等堅固性問題的色調變化和鮮明性惡化和安定性降低等 問題。於改良該等物性上之缺點，期望開發出鮮明且繼續保 持帶黃色之綠色色調，且物性優異的綠色顏料。 (解決問題之手段） 办本發明者等人，為了達成上述本發明之目的而重複致; ^之結果’發現將吩8分子、與具有類似其分子構造: 固的非鋅金屬顏料分子予以堆穑ν. 筚 積(taCkmg :堆積）所得:201107425 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a green pigment, a method for producing the same, a coloring agent containing the same, and a coloring method for an article using the same. More specifically, it relates to a green pigment in which a polyhalogenated zinc phthalocyanine molecule and a multi-generation non-zinc metal phthalocyanine molecule are compositely stacked, a green pigment composition containing the same, a method for producing the same, a coloring agent containing the same, and a use thereof The method of coloring the items and the colored items. [Prior Art] With the recent development of information machines, liquid crystal color displays are used as information display components in personal computers, mobile information machines, televisions, projectors, monitors, car satellite navigation, mobile phones, computers and The display of the electronic dictionary; the display of the information board, the guide board, the function display board, the sign board, etc.; all the information such as the digital camera and the video camera of the video recorder have been used in various aspects of the related machine. A color filter (hereinafter, abbreviated as "CF") mounted on a liquid crystal color display is also required to have a high quality, a wide color gamut, high definition, color density, light transmittance, and contrast. The image performance is superior to the quality. Regarding the green pigment used for the CF green pixels mounted on the liquid crystal color display, CI Pigment Green 36 (hereinafter referred to as "PG36") has been used, but in the case of high enamel and wide color gamut, PG36 further exhibits a yellowish green CI Pigment Green 58 (hereinafter, referred to as "PG58" is evaluated for its acuity and absorption wavelength acuity. 099118114 3 201107425 [Summary of the Invention] (Problems to be Solved by the Invention) PG58 and the like The bromine-polychlorinated zinc phthalocyanine pigment is used as a specific color for the complementary colors of the four primary colors of yellow, red, blue and black which are commonly used in the coloring field of paints and printing inks. It is used as a green pixel pigment for CF. However, in the coloring agent manufacturing stage and storage of organic solvents such as paints and printing inks, or in the coloring process and productization step, color resists and CFs for CF are used. In the manufacturing step, the color tone change and the deterioration of sharpness due to the inevitable and necessary problem such as solvent resistance and heat resistance are likely to occur depending on the use conditions. In order to achieve the above-mentioned problems, it is desired to develop a green pigment which is clear and continues to maintain a yellowish green hue and has excellent physical properties. (The means for solving the problem) The result of the present invention is repeated; ^ the result 'discovered that the pheno- 8 molecule, and a non-zinc metal pigment molecule having a similar molecular structure: solid are piled up 穑. hoarding (taCkmg: accumulation):
對於古W貝m續維持優異的色彩特性，j '有機溶劑和加熱賦予堅固性 達到完成本發明。 』解决上述問4,J 曹 即，若根據本發明之第―態 色顏料之特徵為平均, ，綠色顏料，且該 心與平，代絲代數為】2〜16數^2,之多齒代鋅 099118114 之多鹵代非鋅金屬酞菁 201107425 複合堆積物。 據本發明之其他祕，則提供上述綠色顏料之製 t代非辞方法之特徵為將上述多鹵基鋅敗菁與上述多 =:她太菁於介質中溶解，並由該溶液中使上述二個 刀子以複合堆積物型式共同析出。 =且^根據本發明之其他紐，則提供綠色顏料分散植 系或2綠色顏料分散組成物之特徵為含有有機溶劑系、水 '、3财'时機溶舰合溶織㈣媒體 聚物或聚合性單體所構成液 聚物或合成樹脂而成之樹㈣雜，視需要進_ 系分散劑或低分子分散輔助劑作為分散輔助劑。體 二=本發明之其他態樣，則提供著色劑 為在上述綠色顏料分散組成物中，進一人古 體、作為形成塗膜材料之熱可塑 ^有稀釋媒 反應性低聚物、聚合性單體及交聯；;^成反應性聚合體、 以上之材料，視嶋—步含有硬化觸㈣人=1種或 若根據本發明之再其他態樣，則提供使用上^成。 成物或著色劑將物品著色為其特徵之物品的著;= 分散組 經由其所形成的著色物品。 色方法，以及 (發明效果） 此綠色顏料為鮮明且繼續保 尤其是对熱性和耐溶船生等綠色色調，且物性 _ 口也優異’且特別有利使用 201107425 作為彩色濾光片的綠色像素用顏料。根據本發明之綠色顏料 的此種作用效果，將二種顏料混合使用並無法達成。根據本 發明之綠色顏料的此種優異的作用效果，預測構成此顏料之 二個顏料分子共同強力地堆積，經由分子間相互作用所增強 的新複合顏料構造而提供。尤其，二個分子彼此間以7Γ-7Γ 相互作用予以堆積，兩者分子複合且形成結晶，與各個原來 之顏料的結晶不同，認為形成新的顏料。但，以上之理論到 底為假設，本發明不被此種理論所限定。 【實施方式】 <定義〉 於本發明之記載中，將平均鹵代基取代數為12〜16之多鹵 代鋅酞菁以多（12〜16)鹵代鋅酞菁表示，平均鹵代基取代數 為12〜16之多鹵代非辞金屬酞菁以多（12〜16)鹵代非鋅金屬 酉太菁表示。即，該等表示中的「（12〜16)」，係表示各個顏料 分子中經取代的鹵代基的平均個數。又，於下列中，用語「鹵 代」、「溴基」、及「氯基」之前面刮號所示以及標示之數字， 同樣表示顏料分子中的「鹵代基」、「溴基」、及「氣基」之 取代基的平均個數。 又，於本說明書中，將多（12〜16)鹵代鋅酞菁及多（12〜16) 鹵代非鋅金屬酞菁以分子集合體顏料加以描述之情況中，分 別記述為多（12〜16)鹵代鋅酞菁顏料及多（12〜16)鹵代非鋅金 屬酞菁顏料，或簡述為A顏料及B顏料，更且以構成該等 099118114 6 201107425 顏料之分子加㈣述之情況中，分別Μ(ΐ2〜啊代辞醜 貴及多〇2〜I6)自代非鋅之) 為Α分子及Β分子。 或簡述 於本說明書中，所謂平均函代基取代數為12〜16之多自代 辞敝菁、與平_代絲代㈣12〜16之以麵鋅全2 权複合堆積物，意指其以分子程度堆積構成結晶的物質， 與该等二個顏料之共析物於實質上同義。 <製造方法> 本电明之綠色顏料，例如，根據下列方法調製。即，將多 (12,鹵代鋅酜顏料）、與多（12〜16)錢非辞^ 屬酿菁顏料(Β麟），於轉㈣料的介f巾轉，使a顏 料之A分子及B _之B奸兩好叫合堆積般共析取 得綠色顏料。作為溶解兩顏料之介質，使用酸、較佳為硫酸、 更佳為發煙硫酸或100%硫酸等。 作為本發明之綠色顏料的共析方法，使上述A分子與上 述B分子不會同時有溶解性，且A分子經由b分子堆積而 析出。例如必須迴避僅A分子析出，分子不析出的條 件。作為共析之方法，可列舉例如， (1) 於Α顏料與Β顏料溶解之酸溶液(較佳為高濃度酸溶液) 中，添加含水酸使酸濃度降低，析出兩分子的方法、 (2) 於溶解A顏料與B顏料之高濃度酸溶液中，吸收水分 使酸濃度降低且溶解度降低，析出兩分子的方法、 099118114 7 201107425 (3)將溶解A顏料與B顏料之高濃度酸溶液，注入劇烈攪 拌、或者喷流的大量水中或冰水中，瞬間使兩分子析出，堆 積的方法等。 於上述之(3)中，析出用的水或冰水亦可含有有機溶劑。 若根據本發明之較佳態樣，上述中以上述(3)之方法為佳。 特別，以吸引器、喷射器等之減壓吸引裝置將水以高速喷 流，並以此減壓作用將顏料的高濃度硫酸溶液吸引且與高速 喷流的水接觸，稀釋並析出顏料粒子的方法為佳。又，使用 溶解器、均質器等高速混合器，或者以「Max Blend」（商品 名、住友重機械工業公司製）等之具備高效率攪拌機的混合 槽，將析出用水劇烈攪拌，並於其中將顏料之酸溶液滴下、 流下或注入（以下，於包含滴下、流下意義中使用「注入」）， 於水中擴散析出顏料粒子的方法等亦可列舉作為較佳態樣。 若根據本發明之較佳態樣，於共析步驟中，或於共析步驟 後，作為顏料化處理（形成色素作用）步驟，進行將粗製顏料 中除去雜質以提高顏料純度的步驟、將顏料作成細微之步驟 及/或整理作為顏料之結晶的步驟等為佳。作為共析步驟中 之顏料化處理，可列舉在含有拒水性有機溶劑及/或親水性 有機溶劑之水和冰水中注入或者強制接觸，使其共析之同時 進行細微化、結晶調整化之顏料化處理的方法、或者在含有 共析物之處理水中添加該等有機溶劑並且接觸處理的方 法。又，於共析步驟後接著進行溶劑塗飾法等在有機溶劑， 099118114 8 201107425 例如於混合二甲苯中加熱處理，或者以混合二甲 熱處理等進行結晶化之公知的顏料化處理，視需要= 界面活_、減、各_賴、高好綠缺顏料J 物中之-種以上。I貞料之細微切可於共析步驟中進卜 又’於共析步雜料崎讀M H切料和踏丁 磨法在捏和機等之混練機中，與水溶性鹽、視需要盘水ς 有=共同混練、磨碎’並且細微化等之公知的顏料細微 化方法進行亦可。經細微化之顏料之初級粒子的平均粒 5〜130nm、較佳為 1〇〜11〇nm。 ”'、 <綠色顏料> 於構成本發明之綠色顏料的多自代辞醜菁顏料中，作 代基之鹵代基，意域基、料或此兩者基。特別由於多齒 代鋅酿菁㈣所期待之色調騎明之帶黃色的綠色，故以漠 基為主體㈣菁綠顏料為佳，且以導人漠基與氣基之(12以 上且未滿16、較佳為12〜15.9)演基·（超過0且4以下、較 佳為0.1 4)氣基舰菁㈣、及僅有絲(12〜16)之演基辞 酉太菁顏料為佳。更具體之較佳顏料為Μ%。 又:作為構成本發明之綠色顏料之外2〜⑹ 鹵代非鋅金 屬駄菁顏料之非鋅金屬，可列舉銅等之第I屬金属、紹等之 第II屬金屬、鎂等之第m屬金屬、鈦、錫等之第ιν屬金 屬ϋ卜鎳等之第νπι屬金屬所組成群中選出1種或 -以上之金屬。又，作為_代基，意指氣基、漠基或其兩者。 099118114 201107425 作為實現堅固性高之本發明之綠色顏料的較侄多（12〜16)鹵 代非鋅金屬酞菁，可列舉導入溴基和氣基的多（12以上且未 滿16、較佳為12〜15.9)溴基·（超過0且4以下、較佳為0.1〜4) 氯基非鋅金屬酜菁、僅有漠基之多（12〜16)溴基非鋅金屬酉太 菁、及僅有氯基之多（12〜16)氣基非鋅金屬酞菁，特佳為使 用（14〜16)溴基非辞金屬酞菁。 多溴基氣基鋅酞菁及多溴基氯基非鋅金屬酞菁，係將酞菁 顏料予以溴化之「後溴化法」而得。但是，一般無法迴避溴 化之同時引起氯化，並且難以完全控制鹵素之種類和取代 數，故由所得物質選取所欲之色調顏料，並且使用為佳。 於更加控制ii素之種類和取代數製造綠色顏料方面，期望 將已導入規定之取代個數的溴化、氯化或溴•氯化之酞酸 酐、酞醯亞胺、酞二腈類或胺基亞胺基異吲哚類使用作為原 料並且令其縮合反應，合成溴化或氯化、溴·氣化鋅或非鋅 金屬酞菁顏料。特別，取代基僅為溴基之多溴基鋅酞菁顏料 和多溴基非鋅金屬酞菁顏料，以三或四溴基酞酸酐、三或四 溴基酞醯亞胺、三或四溴基酞二腈類或三或四溴基胺基亞胺 基異吲哚類作為原料並與鋅鹽或非鋅金屬鹽共同縮合反應 之顏料的合成方法可較佳取得。 本發明之綠色顏料為财溶劑性和耐熱性等之堅固性優 異。本發明之綠色顏料於有機溶劑中的加熱、沸騰處理前後 之顏料粒子的粒徑不會大為伸長，且X射線繞射之繞射角 099118114 10 201107425 度及繞射強度於實質上亦無變化。作為確認其之方法，可列 舉在有機溶劑巾加熱處理之方法。若存在多齒代鋅献菁顏 料，則結晶粒子大為成長，且在粗大化之處理條件下，將本 發明之綠色顏料予以加熱處理。所得之處理顏料粒子的變 化’可根據電子顯微鏡^以麟粒子於針狀進—步粗大成 長之知序Μ確認H又，處理顏或由其分離之粗大 ’員料一Ρ刀的X射線繞射圖表，根據僅多鹵代辞狀菁顏料是 否於實質上未顯示或者顯示魏的肢繞射程度，可確認該 顏料粒子的混合存在程度。 <評估實驗> 準備⑽顏料、PG58顏料、及本發明之綠色顏料。又， 亦準備將作為比較之PG36顏料與PG58顏料作成甲醇膏料 混練之早純的顏料混合物。各個顏料於二甲苯_中添加、 加熱、飾_予以溶劑處理，調查處理顏料的粒徑及結 晶狀態的變化。 將溶劑處理前的脳顏料、PG58顏料、本發明之綠色 顏料、及單純之㈣混合物以6萬倍電子顯微鏡攝影。照片 不出顏料分別為大約30〜50nm(0.03〜0 〇5㈣大小之微粒子 狀或球狀者。 關於二曱苯_處理之顏料，首先，PG58之處理顏料為 結晶粒子非常成長且粗大化。其電子顯微_片，以倍率比 其他顏料下降1萬倍之倍钱影。於電顯W中未察見《立 099118114 201107425 子狀物質’全面僅為針狀或更粗的玻璃纖維狀結晶。此結晶 若以「長度χ橫寬」表示’則大約為1μ】ηχ〇 〇5pm至 7μπι><0·2μπι大小的針狀結晶’更且亦觀察到成長成其合體 的粗大結晶粒子。因此，顯示PG58顏料於溶劑中非常不安 定。PG36顏料、單純的顏料混合物及本發明之綠色顏料的 二曱苯沸騰處理顏料，以6萬倍攝影電子顯微鏡照片。pG36 之處理顏料之顏料粒子形狀顯示與處理前相同3〇〜7〇nm左 右的微粒子狀或球狀，且顯示於溶劑中安定。顏料與 P G 5 8顏料之混合物顯示微粒子狀粒子與針狀或玻璃纖維狀 的結晶粒子，且顯示兩顏料混合存在的照片。 本發明之綠色顏料，顯示與處理前相同3〇〜7〇nm 左右之 Μ粒子狀或球狀。但是，根據情況，察見些微橫寬大約 30nm、長度Ιμιη左右的細針狀結晶，推測有混合存在因堆 積化條件之模糊而認為未堆積的pG58。但是，將其使用作 為著色劑時，堅固性文其影響少，且於許多情況，實質上同 荨使用。 對於上述之二甲苯沸騰處理前和處理後之各顏料，測定X 射線繞射。表1及表2示出大約配合繞射角度之主要的繞射 波峰與相對強度。表中’「2Θ」表示繞射角度（。），「％」欄以 %表示繞射的相對強度’「形」欄表示繞射波峰的圖案，「s」 表示尖銳的圖案’「b」表示寬廣的圖案。 099118114 12 201107425 [表i] 一曱苯溶劑處理前之顏料之主要繞射波峰與相對強度 Ρ< 336 顏 i 14 P( 358顏料 複 '每 合堆積化 良色顏料 PG36顏料與 PG58顏料之混合物 2Θ % 形 2Θ % 形 20 % 形 2Θ % 形 16.6 57 S 16.8 43 b 16.8 49 S 16.6 47 S 17.6 42 S 17.5 36 b 17.8 33 b 22.3 61 S ---- . 22.4 55 S 22.3 57 S 25.0 100 b 25.0 100— 25.2 100 ——b— 25.0 27.1 100 83 S b~ 28.8 65 b 29.7 70 b 29.5 68 b 31.1 81 b 32.4 69 b 33.6 90 b 34.2 83 b 33.5 81 b ’ — [表2] ΐίίί劑沸騰試驗後之處理顏料之主要繞射波峰與 複合堆積化 綠色顏料 PG36顏料與 PG58顏料之混合物For the ancient W shell, the excellent color characteristics are maintained, and the 'organic solvent and heating impart a firmness to achieve the present invention. 』Solution of the above question 4, J Cao, that is, according to the invention, the characteristics of the first state color pigment are average, green pigment, and the heart and the flat, the generational algebra is [2 to 16 number ^ 2, the multi-tooth Polyhalogenated non-zinc metal phthalocyanine 201107425 composite deposit of zinc 099118114. According to another secret of the present invention, the method for providing the above-mentioned green pigment is characterized in that the above-mentioned polyhalogenated zinc phthalocyanine is dissolved in the medium and the above-mentioned poly-phthalic acid is dissolved in the medium, and the above is made from the solution. The two knives are co-precipitated in a composite deposit pattern. And according to the other invention of the present invention, the green pigment dispersion plant or the 2 green pigment dispersion composition is characterized by containing an organic solvent system, water ', 3 Choi' time machine-solving and weaving (four) media polymer or A polymer composed of a polymerizable monomer or a synthetic resin is used as a dispersing agent or a low molecular weight dispersing aid as a dispersing aid. Body 2 = other aspects of the present invention, the coloring agent is provided in the above-mentioned green pigment dispersion composition, into a human body, as a coating material, a thermoplastic resin, a diluent reactive oligomer, a polymerizable single And the cross-linking;; into a reactive polymer, the above materials, the step-by-step containing the hardened touch (four) human = 1 or, according to still another aspect of the present invention, provides the use of the above. An object or colorant that colors an item to the character of its character; = a colored item through which the dispersion group is formed. Color method, and (effect of the invention) This green pigment is vivid and continues to be protected, especially for green color such as heat and salt-resistant, and the physical property is excellent, and it is particularly advantageous to use 201107425 as a color filter for green pixel pigments. . According to the effect of the green pigment of the present invention, the mixing of the two pigments cannot be achieved. According to such an excellent effect of the green pigment of the present invention, it is predicted that two pigment molecules constituting the pigment are strongly piled together, and are provided by a new composite pigment structure enhanced by intermolecular interaction. In particular, the two molecules are deposited in a 7 Γ-7 相互作用 interaction with each other, and the two molecules recombine and form crystals, which are different from the crystals of the respective original pigments, and it is considered that a new pigment is formed. However, the above theory is assumed to be the assumption that the present invention is not limited by such theory. [Embodiment] <Definition> In the description of the present invention, a polyhalogenated zinc phthalocyanine having an average number of halo substituents of 12 to 16 is represented by poly(12~16)halogenated zinc phthalocyanine, and an average halogenation is given. A polyhalogenated non-metal phthalocyanine having a radical substitution number of 12 to 16 is represented by a poly(12-16) halogenated non-zinc metal ruthenium. That is, "(12~16)" in the above expressions indicates the average number of substituted halo groups in each pigment molecule. In the following, the terms "halogenated", "bromo-based", and "chlorine-based" are indicated by the scratches on the front and the numbers indicated, which also indicate "halo" and "bromo" in the pigment molecule. And the average number of substituents of "gas base". Further, in the present specification, in the case where a plurality of (12 to 16) halogenated zinc phthalocyanines and a plurality of (12 to 16) halogenated non-zinc metal phthalocyanines are described as molecular aggregate pigments, they are described as multiple (12). ~16) a halogenated zinc phthalocyanine pigment and a poly(12~16) halogenated non-zinc metal phthalocyanine pigment, or a brief description of the A pigment and the B pigment, and further comprising the molecular composition of the 099118114 6 201107425 pigment (4) In the case, Μ (ΐ2~ ah vain expensive and more 〇 2~I6) self-generation non-zinc) are Α molecules and Β molecules. Or briefly described in the present specification, the so-called average functional group substitution number is 12~16, and the self-generation phthalocyanine, and the flat-generation silk generation (four) 12~16 face zinc full-weight composite deposit, meaning The substance constituting the crystal is deposited at a molecular level, and is substantially synonymous with the eutectoids of the two pigments. <Production Method> The green pigment of the present invention is prepared, for example, according to the following method. That is, a plurality of (12, halogenated zinc ruthenium pigments) and a plurality of (12 to 16) money non-existing phthalocyanine pigments (unicorns) are transferred to the material of the (four) material to make the A molecule of the a pigment. And B _ of the B, two good and good, called the accumulation of green pigment. As the medium for dissolving the two pigments, an acid, preferably sulfuric acid, more preferably fuming sulfuric acid or 100% sulfuric acid or the like is used. In the eutectoid method of the green pigment of the present invention, the A molecule and the B molecule are not simultaneously soluble, and the A molecule is deposited by b molecule deposition. For example, it is necessary to avoid the condition in which only A molecules are precipitated and molecules are not precipitated. As a method of the eutectoid, for example, (1) a method of adding an aqueous acid to reduce the acid concentration in an acid solution (preferably a high-concentration acid solution) in which an anthraquinone pigment and an anthraquinone pigment are dissolved, and to precipitate two molecules, (2) In a high-concentration acid solution in which A pigment and B pigment are dissolved, water is absorbed to lower the acid concentration and solubility is lowered, and two molecules are precipitated, and 099118114 7 201107425 (3) dissolves the high-concentration acid solution of A pigment and B pigment. Injecting a large amount of water or ice water that is vigorously stirred or sprayed, and simultaneously depositing two molecules and stacking them. In the above (3), the water for precipitation or the ice water may contain an organic solvent. According to a preferred aspect of the present invention, the above method (3) is preferred. In particular, the water is sprayed at a high speed by a vacuum suction device such as a suction device or an ejector, and the high-concentration sulfuric acid solution of the pigment is attracted by the decompression and contacted with the water of the high-speed jet to dilute and precipitate the pigment particles. The method is better. In addition, a high-speed mixer such as a dissolver or a homogenizer, or a mixing tank equipped with a high-efficiency mixer such as "Max Blend" (trade name, manufactured by Sumitomo Heavy Industries, Ltd.), is used to vigorously stir the water for precipitation. A method in which the acid solution of the pigment is dropped, flowed or injected (hereinafter, "injection" is used in the sense of dropping or flowing down), and the pigment particles are diffused and precipitated in water is also preferable. According to a preferred embodiment of the present invention, in the eutectoidizing step or after the eutecting step, as a pigmentation treatment (forming pigmentation) step, a step of removing impurities in the crude pigment to improve the purity of the pigment, and a pigment are carried out. It is preferred to form a fine step and/or to arrange a step as a crystal of the pigment. The pigmentation treatment in the eutectoid step may be carried out by injecting or forcibly contacting water and ice water containing a water-repellent organic solvent and/or a hydrophilic organic solvent to carry out eutectoid precipitation while crystallizing and crystallizing. A method of treatment, or a method of adding such an organic solvent to the treated water containing the eutectoid and contacting the treatment. Further, after the eutectoid step, a solvent coating method or the like is carried out in an organic solvent, 099118114 8 201107425, for example, in a mixed xylene heat treatment, or a known pigmentation treatment in which crystallization is carried out by a mixed heat treatment such as dimethyl heat treatment, if necessary = interface Live _, subtraction, each _ _, high green deficiency pigment J in the species above. The fine cutting of the I material can be carried out in the eutectoid step and in the mixing machine of the MH cutting material and the tread grinding method in the kneading machine, and the water-soluble salt, as needed Water ς There is a well-known pigment finening method of = common kneading, grinding, and miniaturization. The primary particles of the finely divided pigment have an average particle size of 5 to 130 nm, preferably 1 to 11 nm. "', <Green Pigment> In the multi-self-expression ugly cyanine pigment constituting the green pigment of the present invention, a halogenated group, an Italian group, a material or both, which is a substituent, especially due to a multidentate The color of zinc phthalocyanine (4) is expected to be yellowish green, so the desert base is the main body. (4) The green pigment is preferred, and it is based on the guideline and the gas base (12 or more and less than 16, preferably 12). ~15.9) Acting base · (more than 0 and 4, preferably 0.1 4) gas-based warships (four), and only silk (12 ~ 16) based on the rhetoric of the phthalocyanine pigment is better. More specifically preferred pigment Further, as the non-zinc metal constituting the 2~(6) halogenated non-zinc metal phthalocyanine pigment other than the green pigment of the present invention, the first metal such as copper, the second metal of the group, and the magnesium may be mentioned. One or more metals selected from the group consisting of the νπι metal such as the metal of the mth metal, titanium, tin, etc., etc., etc. 099118114 201107425 More than (12~16) halogenated non-zinc metal phthalocyanines can be listed as green pigments of the invention with high robustness. Introducing a bromine group and a gas group (12 or more and less than 16, preferably 12 to 15.9) bromine group (more than 0 and 4 or less, preferably 0.1 to 4). Chloro-based non-zinc metal phthalocyanine, only desert More than (12~16) bromo-based non-zinc metal ruthenium phthalocyanine, and only chlorine-based (12~16) gas-based non-zinc metal phthalocyanine, especially for the use of (14~16) bromo-based non-metal Phthalocyanine. Polybrominated gas-based zinc phthalocyanine and polybrominated chlorine-based non-zinc metal phthalocyanine are obtained by post-bromination of phthalocyanine pigments by bromination. However, it is generally impossible to avoid chlorination while causing chlorination, and it is difficult to completely control the kind and substitution number of the halogen, so that the desired color pigment is selected from the obtained material, and it is preferably used. In order to control the type of ii and the number of substitutions to produce green pigments, it is desirable to introduce a predetermined number of substituted brominated, chlorinated or bromine-chlorinated phthalic anhydrides, quinones, sebaconitriles or amines. The imidoisoindole is used as a raw material and is subjected to a condensation reaction to synthesize a brominated or chlorinated, bromine-vaporized zinc or non-zinc metal phthalocyanine pigment. In particular, polybromozinc phthalocyanine pigments having a bromo group and polybrominated non-zinc metal phthalocyanine pigments, such as tri- or tetrabromophthalic anhydride, tri- or tetrabromo-imine, tri- or tetrabromo A method for synthesizing a pigment based on a dinitrile or a tris or tetrabromoaminoiminoisoindole as a raw material and co-condensed with a zinc salt or a non-zinc metal salt can be preferably obtained. The green pigment of the present invention is excellent in robustness such as solvent solubility and heat resistance. The particle size of the pigment particles before and after heating and boiling treatment of the green pigment of the present invention is not greatly elongated, and the diffraction angle of X-ray diffraction is 099118114 10 201107425 degrees and the diffraction intensity is substantially unchanged. . As a method of confirming the method, a method of heat-treating the organic solvent towel can be mentioned. If a multi-dentate zinc-donating pigment is present, the crystal particles are greatly grown, and the green pigment of the present invention is heat-treated under the conditions of coarsening. The obtained change of the treated pigment particles can be confirmed by an electron microscope, using the lining particles in the needle-like step-by-step growth process, and confirming the H-, and treating the face or the X-ray winding of the large-sized member. The graph was examined based on whether or not the polyhalogenated phthalocyanine pigment was substantially not shown or showed the degree of diffraction of the limbs of Wei, and the degree of mixing of the pigment particles was confirmed. <Evaluation Experiment> (10) Pigment, PG58 pigment, and green pigment of the present invention were prepared. Further, an early pure pigment mixture which is a mixture of PG36 pigment and PG58 pigment as a methanol paste is also prepared. Each of the pigments was added to xylene _, heated, and decorated with a solvent to investigate changes in the particle size and crystal state of the treated pigment. The ruthenium pigment before the solvent treatment, the PG58 pigment, the green pigment of the present invention, and the simple (4) mixture were photographed by a 60,000-fold electron microscope. The photographs are not in the form of fine particles or spheres of about 30 to 50 nm (0.03 to 0 〇 5 (four), respectively.) Regarding the pigment of the diphenylbenzene-treated pigment, first, the treated pigment of PG58 is very grown and coarsened. Electron microscopy _ film, the magnification is 10,000 times lower than other pigments. In the electric display W, it is not observed that the vertical 099118114 201107425 sub-materials are only needle-like or thicker glass fiber crystals. When the crystal is expressed by "length χ width", it is about 1 μ] η χ〇〇 5 pm to 7 μ π gt; < 0·2 μπι 针 针 晶 晶 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 It shows that the PG58 pigment is very unstable in the solvent. The PG36 pigment, the simple pigment mixture and the diphenyl benzene boiling treatment pigment of the green pigment of the present invention are shown by a 60,000-fold photographic electron micrograph. The pigment particle shape of the treated pigment of pG36 is displayed. It is the same as the microparticles or spheres of about 3〇~7〇nm before the treatment, and is shown to be stable in a solvent. The mixture of the pigment and the PG 5 8 pigment shows fine particles and needles or glass. The fibrous crystal particles show a photograph in which two pigments are mixed. The green pigment of the present invention exhibits a ruthenium particle shape or a spherical shape of about 3 〇 to 7 〇 nm before the treatment. However, depending on the situation, a slight cross is observed. The fine needle-like crystal having a width of about 30 nm and a length of about Ιμηη is presumed to be mixed with pG58 which is considered to be undeposited due to blurring of the deposition conditions. However, when it is used as a coloring agent, the influence of the solidity is small and many In the case of substantially the same use. X-ray diffraction is measured for each pigment before and after the above-mentioned xylene boiling treatment. Tables 1 and 2 show the main diffraction peaks and relative intensities approximately at the diffraction angle. In the table, '"2Θ" indicates the diffraction angle (.), the "%" column indicates the relative intensity of the diffraction in %. The "Shape" column indicates the pattern of the diffraction peak, and the "s" indicates the sharp pattern 'b'. Indicates a broad pattern. 099118114 12 201107425 [Table i] The main diffraction peaks and relative intensities of the pigment before the treatment with benzene solvent Ρ < 336 颜 i 14 P ( 358 pigment complex 'every stacking good color Mixture of PG36 pigment and PG58 pigment 2Θ % Shape 2Θ % Shape 20 % Shape 2Θ % Shape 16.6 57 S 16.8 43 b 16.8 49 S 16.6 47 S 17.6 42 S 17.5 36 b 17.8 33 b 22.3 61 S ---- . 22.4 55 S 22.3 57 S 25.0 100 b 25.0 100— 25.2 100 ——b—25.0 27.1 100 83 S b~ 28.8 65 b 29.7 70 b 29.5 68 b 31.1 81 b 32.4 69 b 33.6 90 b 34.2 83 b 33.5 81 b ' — [ Table 2] 主要ίίί The main diffraction peak of the treated pigment after the boiling test of the agent and the mixture of the composite stacked green pigment PG36 pigment and PG58 pigment
PG36顏料 PG58 i 2Θ % 形 2Θ % 16.6 59 s 16.6 69 17.7 40 s 17.8 42 23.3 64 s 22.4 77 25.0 100 s 24.9 95 27.1 78 29.8 70 s 29.9 68 31.0 76 s 31.0 87 33.6 90 s 33.6 10( 34.2 79 b 099118114 13 201107425 由上述結果顯示PG36顏料於處理前和後，於繞射角度和 相對強度幾乎完全未改變’結晶圖案呈現略微尖銳以外無改 變。另一方面，PG58顏料由X射線繞射亦許多繞射角度顯 不尖銳且大的繞射圖案’顯不顏料結晶大為成長，且整理面 間隔。又，PG36顏料、PG58顏料之混合物的繞射當然以兩 顏料之繞射的合算圖案表示。 本發明之綠色顏料顯示與上述混合物繞射完全不同的繞 射，顯示與混合物完全不同次元的結晶。若相比於PG36顏 料的繞射圖表，則溶劑處理前及處理後之圖表均包含繞射 角、相對強度’且顯示接近PG36顏料之繞射圖表的繞射圖 案。推測本發明之綠色顏料的繞射形狀大約寬廣且尖銳度察 見差異方面，顯示出非鋅顏料分子的堆積。 又，由本發明之綠色顏料的繞射圖案，若考察人顏料與B 顏料的堆積，則如下。即’本發明之綠色顏料相比於PG36 顏料、PG58顏料，於繞射形狀之尖銳度有差別，察見略微 寬廣者，但此3種顏料的全體繞射圖案類似，在各個繞射角 度大約一致處出現繞射，且其相對強度亦類似。由此情事推 測，PG36分子與PG58分子為分子構造上易於相互堆積的 分子。 本發明之綠色顏料，特別作為CF用之形成綠色像素用之 ^色顏料▼期待顯示出鮮明之帶黃色的綠色。此用途時， 物f生上於有機溶劑中之加熱處理前後顏料粒子的粒徑不會 099118114 201107425 大為伸長，且於χ射 化方面亦為有利。杯射<繞射角度及繞射強度無大變 未堆積之W代鋅㈣^綠㉞料，在喊些微混合存在 理條件或所㈣之用、/亦根據著色劑之配合處方和處 此混合存在。 造成影響之料中’允許 關於多鹵代辞酞菁斑夕 弁 /、夕_代非鋅金屬酞菁之莫耳比率，首 死以可保持、或不阻户 .Λ 礙夕鹵代鋅酞菁之優良性質之帶黃色 之綠色色調的範圍，且. ,两Γ ?文良多卣代鋅酞菁缺點之耐熱性 、冷s丨等期望可形成能帶來如上述性能、物性之構造的 、耳比率。又’耐熱性和耐溶劑性等可根據形成著色 劑時所 使用之溶劑種類、或者 了,、、、〖生為根據著色時之後處理的加熱 條件等’適當決定比率即可。 若根據本發明之較佳態樣，則多南代辞g太菁（XnMePc)與 多_代非鋅金屬@i^(XnMePe)的莫耳比率，以安定性為目 的之情況中，XnZnPc : XnMePC=3〇 : 70〜95 : 5、較佳為 4〇 : 6〇〜90: 1〇。特別於重視色調之情況中，以82: 18〜95:5 為佳。 <用途> 本發明之綠色顏料，作為著色劑，例如可使用於塗佈、印 刷版印刷、染色、捺染、文字記錄、描繪晝、噴墨印刷、電 子照片印刷、靜電印刷。又，除了形成CF像素用油墨以外， 可列舉作為以塗料之塗佈、使用樹脂著色劑之樹脂著色、印 099118114 15 201107425 刷油墨、染色劑、捺染劑等之著色劑、文具、緣圖具等之文 具類、喷墨用油墨、電子照片印刷用顯影劑或靜電印刷用顯 影劑等之資訊記錄材料等之者色成分的用途。 因此，若根據本發明之其他態樣，則提供含有本發明之綠 色顏料的著色劑。為了製造本發明之著色劑，準備顏料組成 物，且此顏料組成物亦可含有本發明之綠色顏料。因此，若 根據本發明之其他態樣，則又提供含有本發明之綠色顏料的 顏料分散組成物。此顏料分散組成物之形態，可為水性顏料 分散組成物、油性顏料分散組成物、樹脂分散型加工顏料、 或能量射線硬化性顏料分散組成物等。又，顏料濃度通常設 定高至10%〜50%，預先使顏料微分散，以輕易製造著色劑 之構成亦可。本發明之顏料組成物含有本發明之綠色顏料， 且含有作為介質之有機溶劑系、水系或水•親水性有機溶劑 混合溶劑系之適切的液體介質；聚合性低聚物、聚合性單體 等之聚合性液狀媒體、可塑劑、低聚物、合成樹脂等所構成 的樹脂介質；視需要作為分散輔助劑的聚合體系分散劑或低 分子分散辅助劑而成。 於本發明之顏料分散組成物中，進一步配合稀釋介質、作 用為形成塗膜材料之熱可塑性聚合體、反應性聚合體、反應 性低聚物、聚合性單體及交聯劑等中選出的適切材料等，且 視需要進一步添加硬化觸媒、聚合觸媒等，並且均勻混合、 分散，製造目的之著色劑。若根據本發明之一個態樣，則於 099118114 16 201107425 本發明之著色财’顏料(P)與形成塗膜材料(v)的配合質量 比，考慮用途、要求性能等而適#決定即可，—般為p: v=80:20〜1:99之範圍，較佳為70 m 於本發明之著色劑或顏料分散組成物中使顏料分散時，除 了形成皮膜性聚合體以外’加上視需要亦可添加公知的添加 劑。作為此種添加劑之例，可列舉作為顏料分散安定劑之公 矣離子n顏料衍生物及其對離子性之離子性聚合體系分散 劑、界面活性劑、消泡劑、平滑化劑、密合化劑、石浅偶合 劑等之各種添加劑等。 作為製造顏料为散組成物及著色劑所使用之顏料分散 機，可使用公知之分散機，例如球磨、砂磨、珠粒磨等之縱 型介質分散機、DYNO-MILL、橫型珠粒磨等之橫型介質分 散機、輥磨、超音波磨、高壓衝撞分散機等。使用上述一種 分散機予以數次分散處理之方法、或複合2種以上之分散機 之方法進行分散處理。平均粒徑通常為5〜130nm左右、較 佳為10〜llOnm。 作為本發明之著色劑所含之形成塗膜材料的樹脂，亦可使 用配合各種用途的公知樹脂成分。可列舉例如，合成橡膠樹 脂、丙烯酸樹脂、乙烯基樹脂、氯化橡膠樹脂、醇酸樹脂、 胺基曱酸酯樹脂、環氧系樹脂、矽樹脂、氟樹脂等之公知的 形成塗臈材料及紫外線硬化性樹脂系、電子射線硬化性樹脂 系等之能量射線硬化性之形成塗膜材料等。上述之形成被膜 099118114 17 201107425 材料亦可進一步具有反應性基，且作為反應性基，可列舉例 如，羥曱基、烷基羥曱基、異氰酸酯基、遮蔽性異氰酸酯基 (masked iS0Cyanate group)、環氧基等。又，根據用途使用 低聚物和單體，更且亦可併用交聯劑，例如，羥曱基三聚氰 胺系和異氰酸酯系、環氧系交聯劑。 本發明之著色劑為彩色濾光片用著色劑之情況，作為其形 成皮膜材料’可使用先前公知的任—種，且無特別限定。形 成像素用油墨為光刻顯影型之情況，使用總稱為形成感光性 像侧油墨的能量射線照射聚合型油墨。作為加成聚合或加 成又聯m ’可列舉熱聚合型、雷射熱線聚合型、紫外線 聚合型、光陽離子聚合型、電子射線聚合型等之加熱或能量 射線硬化性油墨等。其所使用之形成皮膜材料μ前公知之 :口成聚合，具有加成交聯性之不飽和雙鍵或具有聚合性環 ^基的早體、低聚物及/或聚合體、及視需要添加 起始劑、液體介質所構成 Τα 作為形成皮崎料技=絲合或加錢聯性固黏劑。 稀㈣「（甲細缔_ ^可列舉季戊四醇二(曱基)丙 二季戊四醇聚(4〜6)(曱表示丙烯酸醋甲基丙烯酸酉旨）、 基)丙稀綱之、雙_氧樹脂， _、(曱基㈣^笨(甲基)丙稀酸(共) 等；聚酯丙烯酸酯系樹 .▲丙烯酸共聚合體 甲酸醋丙_料樹//環氧丙烯酸料樹脂、聚胺基 099118114 日聚喊内烯酸酷系樹月皆、多元醇丙稀 201107425 系樹l等；感光性料、樹月旨、不飽和聚料樹脂等。其 可單獨使用，且亦可併用2種以上。 '、 又，作為光聚合起始劑，為公知的光聚合起始劑，可列舉 例如1，基·環己基苯基酉同、2遍基·2_甲基小苯基-丙院巧_ 二-二乙氧基乙酿笨、2，基修甲硫基)苯基)_2_咮淋 =’、2_节基-2佩二甲胺基)]她^ 專、、可單獨使用’且亦可併用2種以上。 使財發明之顏料分散組成物和使用其的著色劑，可將各 =;Lt。使用於形成彩色濾光片之綠色像素之情況，可 各%綠色彩色光阻併用公知的黃色頻料調製，並與 =、轉=、藍色光阻共⑽CF基板上以先前公知的光阻 ^轉:法、貼附法、喷墨印刷法、印刷法等方法形成綠色、 色工減光Γ像素、但麟蚊於此。例如，於絲上形成彩 〜之像素圖案之情況中，於基板上將該形成感光性像 素性油墨，例如，使用旋塗器'輥塗器、狹縫塗層器、印刷 機等進行全©塗敷，在職乾燥後密合鮮，㈣超高壓水 銀燈進行曝光並且供烤圖案。其次進行顯影及洗淨，視需要 進行後烘烤則可形成彩色濾光片的圖案。 於彩色濾'光片中，作為形成與綠色像素(G)共同使用之紅 色像素(R)、藍色像素⑻的顏料係使用先前公知的許多顏 料，如’❹不溶性偶氮系、溶性偶氮系、高分子量偶氮 系等之偶氮系顏料、喹吖酮紅系、喹吖酮紫紅等之喹吖酮系 099118114 201107425 =、二酮基料并料系顏料、㈣系顏料、花系顏料、 酞月^等之醜菁系顏料、異㈣琳酮系顏料、二啊紫等之 二啊系顏料”㈣并酞酮黃顏料、鎳偶氮黃等之鍺合物顏 料等。 作為牙透型R、G、B像素用之代表性顏料的具體例，於 紅色顏料為則7、PR242、PR254等，作為補色用或單獨 色用之黃色顏料為 ΡΥ83、ΡΥ138、ργΐ39、ργΐ5()、ργΐ85 等’作為藍色顏料為ΡΒ15 : 6、ρ諭等，作為補色用或單 獨色用之紫色顏料為PV23等，更且可列舉上述之紅色顏料 與黃色顏料之共沈顏料、及藍色顏料與紫色顏料之共沈顏 料、固溶體顏料或混晶顏料。 又，以上主要說明彩色濾光片的像素形成，但本發明之顏 料分散組成物及著色劑亦適合其他各種用途，例如，作為合 成或天然之樹脂、塗料、塑膠薄膜、各種紙、合成紙等之印 刷油墨、紙用之著色劑、織布用之捺染劑、筆記用油墨、彩 色衫印機5周色劑、喷墨用印表機油墨、熱轉印色帶用油墨等 之著色劑，分別提供優異之綠色的著色物品。 [實施例] 其次列舉具體的實施例進一步詳細說明本發明。另外，文 中的份及％只要無特別指明則為質量基準。又，以下之多填 基非鋅金屬酞菁之溴取代數’係表示縮合反應之裝入比率的 個數。 099118114 20 201107425 製造例1’8分子與16溴基酮酞菁分子的複合堆積綠色 顏料之製造） (1) 16演基銅酞菁顏料的合成 作為合成反應裝置，準備裝填攪拌裝置、逆流冷卻器、及 溫度計之反應容器及加熱裝置。準備作為原料之溴含有率為 69·〇%、每1分子之胁代個數為4.G的四祕㈣軒。對 於反應容器，添加反應介質之硝基苯14〇 〇份、上述之四溴 基駄酸酐46.4份、脲27,0份、四氯化鈦71份及氣化銅3 4 份。反應溫度由100°C慢慢升溫至17rc，就其原樣攪拌4 小時，繼續反應。反應終了前的反應溫度為195C>c。粗製顏 料之產量為44.8份，粗製顏料產率為97 4%。另外，配合 95%硫酸和20%發煙硫酸，調製100%硫酸。將所得之粗製 顏料10伤 >谷解於1 〇〇%硫酸1 〇〇份，並於7〇°C中授掉1小 時，於10倍之冰水中析出、過濾，並進行水洗（以下，稱為 「硫酸精製」）。其次以氫氧化鈉稀水溶液及乙醇及二甲基 曱醯胺洗淨。精製顏料之產率為94.9%。根據元素分析，銅 元素之含有率為3.44%(理論值：3.456%)、漠之含有率為 69.8%(理論值：69.52%)。由所得之16溴基酮酞菁綠顏料之 分析值所計算之每丨分子的平均溴取代個數為161，顯示酞 菁骨架完全經16個溴取代。以下，將其稱為「16溴基酮酞 菁粗粒子顏料」。 (2) PG58與16溴基酮酞菁分子的堆積化 099118114 201107425 將溴之平均取代數大約13個、氣之平均取代數大約3個 之PG58 16.39克(作為由平均取代基數之計算值為0 00960 莫耳、以下相同）、與上述之（1)合成反應所得之16溴基銅酞 菁粗粒子顏料3.61克(0.00196莫耳），於2〇%發煙硫酸140 克中溶解’並於70 C中搜拌2小時，放冷至室溫為止。以 吸引器將水以高速喷流，通過減壓的細管以吸引上述顏料的 發煙硫酸溶液，並與高速喷流的水接觸，稀釋析出顏料粒 子’並進行過遽及水洗。其次以二甲苯乳狀液法進行顏料 化，取得綠色顏料。以下，將其稱為「綠色堆積粗製顏料4」。 (3)以鹽研磨細微化處理調製複合堆積化綠色微粒子顏料 將上述(2)所得之綠色堆積粗製顏料_1 1〇〇份與氣化鈉 粉末600份及二乙二醇11〇份共同裝入裝配加壓蓋的捏和 機。於捏和機内預混合至均勻濕潤的塊為止，其次將加壓鍋 關閉並以壓力6kg/cm2按壓内容物並且進行混練及磨碎。一 邊將内容以92〜98°C之溫度管理，一邊進行2小時混練•磨 碎處理。將所得之磨碎物於80°C中加的3000份2%硫酸中 進行1小時之攪拌處理後’予以過濾及水洗除去氯化鈉及二 乙二醇，取得細微化之複合堆積化綠色顏料的加壓餅。為了 測定所得顏料之粒徑’於顏料加壓餅中添加相對於顏料 200%的非離子活性劑，並以水稀釋，予以超音波分散調製 顏料分散液，並以粒度測疋機器「Model N-4 | (Coalter公司 製）測定平均粒徑時’平均粒徑大約為25〜35nm。將加壓餅 099118114 22 201107425 乾燥、粉碎取得綠色顏料。所得之顏料即使於有機溶劑中加 熱處理，於顏料之粒徑及結晶狀態亦未察見實質的變化。以 下，將其稱為「綠色堆積顏料-1」。 製造例2 (PG58與16漠基酮酞菁分子之複合堆積綠色顏 料之製造） (1) PG58分子與16溴基酮酞菁分子的堆積化 將製造例1(2)所使用之PG58 16.81克(0.00985莫耳）、 與製造例1(1)之合成反應所得之16溴基銅酞菁粗粒子顏料 3.19克(0.00173莫耳）’溶解於20%發煙硫酸200克，並於 7〇°C中攪拌2小時，放冷至室溫後，注入馬克斯摻混攪拌槽 (住友重機械工業公司製）中裝入之含有1〇〇克丁基溶纖劑的 2000克冰水中，並進行過濾及水洗。將加壓餅乾燥、粉碎 取得綠色顏料。以下，將其稱為「綠色堆積顏料_2」。 製造例3 (PG58分子與PG36分子之複合堆積綠色顏料的 製造） (1) PG58分子與pG36分子的堆積化 同製造例2處理，將製造例1(2)所使用之PG58 18.00 克(0.01054莫耳）、和溴之平均取代數大約13個、氣之平均 取代數大約3個之卩〇36 2.0〇克(〇.〇〇117莫耳），溶解於2〇% 發煙硫酸200克，並於70°C攪拌2小時，放冷至室溫。以 吸引器將水以高速喷流，通過減壓的細管以吸引上述顏料的 杳煙硫酸溶液，並與高速喷流的水接觸，稀釋析出顏料粒 099Π8ΙΙ4 23 201107425 子，並進行過歧水洗。其切二？苯乳狀躲進行顏料 化，取得綠色顏料。以下，將其稱為「綠色堆積粗製顏料_3」。 (2)以鹽研磨細微化處理調製複合堆積化綠色微粒子_ 同製造例1(3)處理’將上述⑴所得之綠色堆積粗製顏料^ 100份與氣化鈉粉末_份及二乙二醇ιι〇份共同裳入裝配 加壓蓋的捏和機’同樣處理進行混練及磨碎。同樣處理於 2〇/。疏酸巾進行攪拌處理後，μ過敍水洗除去氣化納及 二乙二醇，取得細微化之複合堆積化綠色顏料的加壓餅。平 均粒徑大約為30nm。將加壓餅乾燥、粉碎取得綠色顏料。 所得之顏料即使於有機溶劑中加熱處理，於顏料之粒徑及結 晶狀怨亦未察見貫質的變化。以下’將其稱為「綠色堆積顏 料-3」。 製造例4(PG58分子與16溴基鋁酞菁分子之複合堆積綠色 顏科的製造） (1) 16溴基鋁酞菁顏料的合成 同製造例1(1)處理，於反應容器中裝入硝基苯、四溴基酞 酸酐、脲、及四氣化鉉之相同份數、而氣化銅改變成氯化鋁 3.34份。反應溫度由100°C升溫至175。(：並授拌5小時，最 終的反應溫度為200°C。粗製顏料之產量為4〇 〇份，粗製顏 料袤率為87.1%。將所得之粗製顏料同製造例1(1)處理予以 硫酸精製’並將顏料析出液過濾、水洗，並且乾燥、粉碎。 將如此所得之顏料’稱為「16溴基鋁酞菁顏料」。 099118114 24 201107425 (2) PG58分子與16溴基鋁酞菁分子的堆積化 同製造例1(2)處理，將PG58 14.75克(0.00864莫耳;)與 上述（1)之16溴基鋁酞菁顏料5.24克(0.00288莫耳）溶解於 20%發煙硫酸140克，於70°C中攪拌，放冷。使用吸引器將 上述顏料的發煙硫酸溶液吸引，並與高速喷流的水接觸，稀 釋析出顏料粒子。過濾'析出液，進行水洗，其次以二甲苯乳 狀液法進行顏料化’取得綠色顏料。以下，將其稱為「綠色 堆積粗製顏料-4」。 (3) 以鹽研磨細微化處理調製複合堆積化綠色微粒子顏料 同製造例1(3)處理’將上述(2)所得之綠色堆積粗製顏料_4 與氣化鈉粉末及一乙二醇共同裝入捏和機，預混合後，進行 混練•磨碎處理。所得之磨碎物於2%稀硫酸中進行攪拌處 理後，過濾及水洗，乾燥、粉碎取得綠色顏料。所得之顏料 即使於有機溶劑中加熱處理’於顏料之粒徑及結晶狀態亦未 察見實質的變化。以下，將其稱為「綠色堆積顏料_4」。 製造例5 (PG58分子與16漠基魏菁分子之複合堆積綠 色顏料的製造） (1) 16漠基鎂酜菁顏料的合成 同製造例！⑴處理，於反應容器中裝入石肖基苯、四漠基酉太 酸酐、脲、及四氣化鉉之相同份數’而氣化銅改變成氣化鎂 2.39份。反應溫度由10(rc升溫至17代並授摔4小時，最 終的反應溫度為195 C。粗製顏料產量為39 9份，粗製顏料 099118114 25 201107425 產率為88.7%。將所得之粗製顏料同製造例〗（！）處理予以硫 酸精製，並將顏料析出液過濾、水洗，並且乾燥、粉碎。將 如此所得之顏料，以下，稱為「16溴基鎂酞菁顏料」。 (1) PG58分子與16 >臭基鎂g太菁分子的堆積化 同製造例1(2)處理，將PG% 6.43克(0.00,377莫耳)與上 述（1)之16溴基鎂酞菁顏料13.57克(〇〇〇754莫耳）溶解於 20%發煙硫酸M0克，於7(TC中攪拌’放冷。使用吸引器將 上述顏料的發煙硫酸紐吸引，並與高速喷流的水接觸°，稀 釋析出顏·子。减析“，進行水洗，其:纽二甲苯乳 狀液法進行誠化’取得綠色顏料。以下，將其稱為「綠·^ 堆積粗製顏料-5」。 ⑶以鹽研磨細微化處理調製複合堆積化綠色微粒子 同製造例1(3)處理’將上述(2)所得之綠色堆積粗製顏心 與氣化鈉粉末及二乙二醇共同裝人捏和機，預混合後，進〜 混練•磨碎處理。所得之磨碎物於2%稀硫㈣進行_丁 理後’過渡及水洗，乾燥、粉碎取得綠色射卜所得二 即使於有機溶射加祕理，於顏料之粒徑及結晶狀態亦夫 察見實質的變化。以下’將其稱為「綠色堆積顏料_5」。 實施例1(綠色顏料高濃度分散液之調製） 預先，準備作為顏料分散液之_酸丁1笨乙1丙_ 經乙酿-甲基丙烯酸(質量比：5〇:15:1〇:25、平均分子旦夂 12,〇〇〇)共聚合體的30。/。丙：醇單f醚醋㈣（以下，簡稱為 099118114 26 201107425 「PGMA」）溶液。以下，稱為「樹脂分散劑PGMA溶液-1」。 配合製造例1 (3)所得之「綠色堆積顏料_ 1」19份、綠色顏 料石風化衍生物1份、陽離子性高分子系分散劑（聚酯醯胺化 ， 聚伸乙基亞胺、50%溶液）12份、上述所示之「樹脂分散劑 ' PGMA溶液-1」50份及PGMA 18份，並以溶解棒攪拌2小 時，確認無顏料塊後，於橫型環型珠粒磨分散機中使用氧化 結製珠粒（直徑0.65mm) ’以周速14m/s進行分散處理，取 得綠色之高濃度顏料分散液、「綠色堆積顏料高濃度分散液 • 1 j 〇 實施例2(各色顏料之高濃度分散液的調製） (1) 以細微化處理之各色微粒子顏料之調製 準備 PR254、PY138、PB15-6 及 PV23。根據製造例 1(3) 之複合堆積化綠色顏料之鹽研磨細微化處理，將各顏料粉末 與氣化鈉粉末及二乙二醇共同裝入裝配加壓蓋的捏和機，並 進行混練及磨碎。所得之磨碎物同樣以鹽、溶劑溶解、過濾 及水洗，取得各個細微化顏料的加壓餅。此各色細微化顏料 之平均粒徑為3〇〜4〇nm。將加壓餅乾燥、粉碎取得各顏料的 • 細微化粉末顏料。 (2) 顏料高濃度分散液的調製 同貫施例1處理，使用上述（1)所得之PR254、PY138、 PB15-6及pV23之微粒子顏料及各個公知的顏料砜化衍生 物，代替綠色堆積顏料-1及綠色顏料砜化衍生物，同樣配 099118114 27 201107425 合陽離子性高分子系分散劑、丙烯酸樹脂及PGMA，並以溶 解棒攪拌、解膠，以環型珠粒磨分散機進行分散處理，取得 各個顏料之高濃度分散液。以下，於「高濃度分散液-1」加 以各個色名表示。 (3)像素用形成像素性油墨的調製 為了於彩色濾光片之玻璃基板上形成RGB像素，根據下 述表3之配合，取得「綠色顏料感光性分散液-1」、「紅色顏 料感光性分散液-1」及「藍色顏料感光性分散液-1」。 [表3]形成RGB像素性油墨之調製 綠色顏料 感光性分散液-1 紅色顏料 感光性分散液-1 藍色顏料 感光性分散液-1 綠色高濃度分散液-1 63 紅色高濃度分散液-1 85 黃色高濃度分散液-1 37 15 藍色高濃度分散液-1 85 紫色高濃度分散液-1 15 感光性丙稀酸樹脂 清漆 50 50 50 TMPTA 10 10 10 HEMPA 2 2 2 DEAP 1 1 1 PGMA 37 37 37 合計 200 200 200 於上述中，TMPTA表示三羥曱基丙烷三丙烯酸酯， 1^]\/〇>八表示2-羥乙基-2-曱基丙酸，0£八？表示2,2-二乙氧 基乙醯苯。 實施例3(彩色濾光片之調製） 將進行矽烷偶合劑處理的玻璃基板安裝至旋塗器，並將上 099118114 28 201107425 述實施例2(3)之「紅色顏料感光性分散液-1」最初以300rpm5 秒鐘、其次以1200rpm 5秒鐘之條件旋塗。其次以80°C進 行10分鐘預烘烤，使具有鑲嵌狀圖案的光罩密合，並使用 超高壓水銀燈以100mJ/cm2的光量進行曝光。其次以專用顯 影液及專用潤洗進行顯影及洗淨，於玻璃基板上形成紅色之 鑲嵌狀圖案。 接著使用表3之「綠色顏料感光性分散液-1」及「藍色顏 料感光性分散液-1」根據上述方法進行塗佈及烘烤，形成綠 色鑲嵌狀圖案及藍色鑲嵌狀圖案，取得RGB的彩色濾光 片。所得之彩色濾光片具有優異的分光曲線特性，耐光性、 耐熱性等之堅固性優異，又，光穿透性亦具有優異之性質， 顯示作為液晶彩色顯示器用彩色濾光片之優異性質。 實施例4(彩色濾光片之調製） 使用製造例2〜5所得之綠色堆積顏料-2〜5代替上述實施 例1所使用之綠色堆積顏料-1，進行與上述實施例1及實施 例2同樣之操作，取得綠色顏料感光性分散液，並且同時使 用紅色顏料感光性分散液-1及藍色顏料感光性分散液-1，同 實施例3處理調製彩色濾光片，具有優異之分光曲線特性， 耐光性、耐熱性等之堅固性優異，又，光穿透性亦具有優異 之性質，取得液晶彩色顯示器用彩色濾光片。 實施例5(凹版油墨與凹版印刷） 將具有羧基之氯乙烯-醋酸乙烯酯-丙烯酸(89 : 6.7 : 4.3) 099118114 29 201107425 共聚合體（重量平均分子量為約3萬）12份溶解於醋酸丁酯- 甲基異丁基酮-二甲苯(43 : 20 : 20)混合溶劑68份，加入製 造例1(3)所得之綠色堆積顏料_丨5份並裝入球磨中且分散 16小時。添加3份二氧化石夕，再加入多分支型聚碳化二醯 亞胺系交聯劑（聚伸己基碳化二醯亞胺_二異氰酸酯與二季 戊四醇單月桂酸酯的反應生成物)2〇%甲苯溶液12份，混 合，作成黃綠色凹版油墨。作為鮮明之黃綠色特別色的凹版 油墨，將其他之紅色、藍色、黃色、茶色及黑色凹版油墨共 同與氯乙烯薄膜等進行凹版印刷，取得綺麗之多色印刷氯乙 烯等薄膜。 又，使用製造例2〜5所得之綠色堆積顏料_2〜5代替上述 使用的綠色堆積顏料-1，且同上述調製黃綠色凹版油墨，同 樣的薄膜進行凹版印刷’取得綺麗之多色印刷薄膜。 實施例6(塗料與塗佈） 加入具有羧基之曱基丙烯酸甲酯-曱基丙烯酸乙酯_曱基 丙烯酸辛酯·曱基丙烯酸羥乙酯-曱基丙烯酸(44 : 2〇 : 1〇 : 5) 共聚合體的醋酸乙酯溶液（固形份6〇%)45份、二甲苯19 9 份、製造例1(3)所得之綠色堆積顏料_丨5份及氧化鈦白色顏 料15份並裴入球磨且分散16小時。調製實施例5所使用之 多分支型聚碳化二酿亞胺系交聯劑薦溶液15份、及防止 分色劑0.1份之配合處方的黃綠色丙烯酸塗料。對行動電 話、個人電腦等之資訊關連製品、辦公室用品和家庭用品等 099118114 30 201107425 各種木製品、金屬製品、塑膠製品進行黃綠色之塗佈，可進 行财候性、耐久性、对水性等優異的塗佈。 又，使用製造例2〜5所得之綠色堆積顏料-2〜5代替上述 使用的綠色堆積顏料-1，且同上述調製黃綠色的丙烯酸塗 料，且同樣的各種構件進行塗佈，取得绮麗之黃綠色塗佈製 品。 099118114 31PG36 pigment PG58 i 2Θ % shape 2Θ % 16.6 59 s 16.6 69 17.7 40 s 17.8 42 23.3 64 s 22.4 77 25.0 100 s 24.9 95 27.1 78 29.8 70 s 29.9 68 31.0 76 s 31.0 87 33.6 90 s 33.6 10( 34.2 79 b 099118114 13 201107425 The above results show that the PG36 pigment has almost no change in the diffraction angle and the relative intensity before and after the treatment. The crystal pattern is slightly sharp except that it is slightly sharp. On the other hand, the PG58 pigment is also wound by X-ray diffraction. The diffraction pattern is not sharp and the diffraction pattern is large, and the pigment crystals are greatly grown, and the surface spacing is arranged. Moreover, the diffraction of the mixture of PG36 pigment and PG58 pigment is of course represented by a balanced pattern of diffraction of two pigments. The green pigment of the invention exhibits a completely different diffraction diffraction from the above mixture, showing crystals of completely different dimensions from the mixture. If compared to the diffraction diagram of the PG36 pigment, the graphs before and after solvent treatment contain diffraction angles. , relative intensity 'and showing a diffraction pattern close to the diffraction pattern of the PG36 pigment. It is presumed that the diffractive shape of the green pigment of the present invention is broad and sharp In view of the difference, it shows the accumulation of non-zinc pigment molecules. Further, from the diffraction pattern of the green pigment of the present invention, if the deposition of the human pigment and the B pigment is examined, the following is the case. [The green pigment of the present invention is compared to PG36. Pigment, PG58 pigment, the sharpness of the diffraction shape is different, see a slightly wider one, but the overall diffraction pattern of the three pigments is similar, the diffraction is about the same at each diffraction angle, and the relative intensity is also Similarly, it is speculated that the PG36 molecule and the PG58 molecule are molecules whose molecular structure is easy to accumulate with each other. The green pigment of the present invention, particularly as a color pigment for forming a green pixel for CF, is expected to exhibit a vivid yellowish color. Green. For this purpose, the particle size of the pigment particles before and after the heat treatment in the organic solvent is not extended to 099118114 201107425, and is also advantageous in terms of sputum irradiation. Cup shot < diffraction angle and winding W-generation zinc (four)^green 34 material with no change in the intensity of the shot, in the case of shuffling some micro-mixing conditions or (4), / also according to the formulation of the coloring agent and mixing In the material that affects, 'allows the molar ratio of polyhalogenated phthalocyanine 弁 、 /, 夕_代 non-zinc metal phthalocyanine, the first death can be maintained, or not blocked. 碍The range of the yellowish green hue of the excellent properties of zinc phthalocyanine, and the heat resistance, cold sputum, etc. of the disadvantages of the two kinds of zinc phthalocyanines are expected to form a structure capable of bringing the above properties and physical properties. , ear ratio. Further, the heat resistance, the solvent resistance, and the like may be appropriately determined depending on the type of the solvent to be used in forming the coloring agent, or the like, and the heating condition such as the treatment after the coloring. According to a preferred aspect of the present invention, the molar ratio of the polyxanthene (XnMePc) to the multi-generation non-zinc metal @i^(XnMePe), in the case of stability, XnZnPc: XnMePC=3〇: 70~95: 5, preferably 4〇: 6〇~90: 1〇. Especially in the case of paying attention to color tone, it is preferably 82: 18 to 95:5. <Use> The green pigment of the present invention can be used, for example, as a coloring agent for coating, printing, dyeing, dyeing, writing, drawing, inkjet printing, electrophotographic printing, or electrostatic printing. In addition to the ink for forming a CF pixel, a coloring agent such as a coating agent, a resin using a resin coloring agent, a printing ink, a dyeing agent, a dyeing agent, etc., a stationery, a stencil, etc. Uses of color components such as information recording materials such as stationery, inkjet ink, developer for electrophotographic printing, and developer for electrostatic printing. Therefore, according to another aspect of the present invention, a coloring agent containing the green pigment of the present invention is provided. In order to produce the color former of the present invention, a pigment composition is prepared, and the pigment composition may also contain the green pigment of the present invention. Therefore, according to another aspect of the present invention, a pigment dispersion composition containing the green pigment of the present invention is further provided. The form of the pigment dispersion composition may be an aqueous pigment dispersion composition, an oil pigment dispersion composition, a resin dispersion type processing pigment, or an energy ray curable pigment dispersion composition. Further, the pigment concentration is usually set to be as high as 10% to 50%, and the pigment may be finely dispersed in advance to easily form a coloring agent. The pigment composition of the present invention contains the green pigment of the present invention, and contains an organic solvent system as a medium, an aqueous liquid or a water/hydrophilic organic solvent mixed solvent, and a suitable liquid medium; a polymerizable oligomer, a polymerizable monomer, etc. A resin medium composed of a polymerizable liquid medium, a plasticizer, an oligomer, a synthetic resin, or the like; a polymerization system dispersing agent or a low molecular weight dispersing aid as a dispersing aid as needed. In the pigment dispersion composition of the present invention, a diluent medium, a thermoplastic polymer, a reactive polymer, a reactive oligomer, a polymerizable monomer, and a crosslinking agent which form a coating material are further blended. A coloring agent which is suitable for a material or the like and which is further added with a curing catalyst, a polymerization catalyst, etc., and uniformly mixed and dispersed to produce a purpose. According to an aspect of the present invention, in the case of 099118114 16 201107425, the color ratio of the pigment (P) of the present invention to the coating material (v) can be determined by considering the use, the required performance, and the like. Generally, it is a range of p: v=80:20 to 1:99, preferably 70 m. When the pigment is dispersed in the coloring agent or pigment dispersion composition of the present invention, in addition to forming a film-like polymer, It is also necessary to add a known additive. Examples of such an additive include a male argon ion pigment derivative as a pigment dispersion stabilizer, and an ionic ionic polymerization system dispersant, a surfactant, an antifoaming agent, a smoothing agent, and an adhesion agent. Various additives such as agents and stone coupling agents. As a pigment dispersing machine for producing a pigment as a bulk composition and a coloring agent, a known dispersing machine such as a vertical medium dispersing machine such as ball milling, sanding, bead grinding, DYNO-MILL, or a horizontal bead mill can be used. Such as horizontal media disperser, roller mill, ultrasonic mill, high-pressure collision disperser. The dispersion treatment is carried out by a method of dispersing a plurality of times using one of the above dispersing machines or a method of combining two or more types of dispersing machines. The average particle diameter is usually from about 5 to 130 nm, preferably from 10 to 11 nm. As the resin for forming the coating material contained in the coloring agent of the present invention, a known resin component for various applications can be used. For example, a known coating-forming material such as a synthetic rubber resin, an acrylic resin, a vinyl resin, a chlorinated rubber resin, an alkyd resin, an amino phthalate resin, an epoxy resin, an anthracene resin, or a fluororesin may be mentioned. A coating material for forming an energy ray-curable property such as an ultraviolet curable resin or an electron beam curable resin. The material for forming the above-mentioned film 099118114 17 201107425 may further have a reactive group, and examples of the reactive group include a hydroxymethyl group, an alkyl hydroxy group, an isocyanate group, a masked isocyanate group, and a ring. Oxyl and the like. Further, an oligomer and a monomer may be used depending on the use, and a crosslinking agent such as a hydroxydecyl melamine-based compound, an isocyanate-based or an epoxy-based crosslinking agent may be used in combination. In the case where the coloring agent of the present invention is a coloring agent for a color filter, any conventionally known one can be used as the material for forming the film, and is not particularly limited. In the case where the ink for forming a pixel is a photolithographic development type, a polymer ink is irradiated with energy rays collectively referred to as a photosensitive image side ink. Examples of the addition polymerization or the addition of m ' include a heat polymerization type, a laser heat polymerization type, an ultraviolet polymerization type, a photocation polymerization type, an electron beam polymerization type, and the like, and a heat or energy ray-curable ink. It is known before the formation of the film material μ: oral polymerization, an unsaturated double bond having a crosslinkability or an early body, an oligomer and/or a polymer having a polymerizable ring group, and optionally added The initiator and the liquid medium constitute Τα as a skin-forming or silk-adding cement. Rare (four) "(A fine _ _ can be listed as pentaerythritol di(indenyl) propylene dipentaerythritol poly (4 ~ 6) (曱 represents acrylic acid methacrylate methacrylate), base) acrylic, bis-oxygen resin, _, (曱基(四)^笨(methyl)acrylic acid (total), etc.; polyester acrylate tree. ▲ acrylic acid copolymer formic acid propylene _ tree / epoxy resin resin, polyamine 099118114 day The polyunic acid is a cool tree, the polyol propylene 201107425 is a tree, etc.; a photosensitive material, a tree, an unsaturated polymer resin, etc., which can be used alone or in combination of two or more. Further, as a photopolymerization initiator, a known photopolymerization initiator is exemplified by 1, for example, a cyclohexylphenyl fluorene, a 2 benzyl group, a methyl phenyl group, and a propyl group. -diethoxyethylene, stupid, 2, thiomethylthio)phenyl)_2_咮 = = ', 2 _ benzyl-2 dimethylamino)] she ^ special, can be used alone 'and Two or more types may be used in combination. The pigment dispersion composition of the invention and the coloring agent using the same may be used for each of the green color pixels of the color filter, and each of the green color photoresists may be used. It is prepared by using a known yellow frequency material, and is formed on the CF substrate by a known photo-resistance method, a pasting method, an inkjet printing method, a printing method, etc. on a CF substrate. For example, in the case where a pixel pattern of a color dot is formed on the wire, the photosensitive pixel ink is formed on the substrate, for example, using a spin coater's roll coater, The slit coater, the printing machine, etc. are coated with the full application, and are wetted after drying on the job. (4) The ultra-high pressure mercury lamp is exposed and baked, and then developed and washed, and then post-baked as needed to form a color. In the color filter 'light sheet, as the pigment forming the red pixel (R) and the blue pixel (8) used together with the green pixel (G), many previously known pigments such as '❹ insoluble couples are used. An azo-based pigment such as a nitrogen-based, a soluble azo-based or a high-molecular-weight azo-based quinone, a quinacridone red-based or a quinacridone-purple red quinacridone 099118114 201107425 =, a diketone-based binder pigment, (4) Ugly pigments, flower pigments, 酞月^, etc. Cyanine pigments, iso(tetra)linone pigments, two arsenic pigments, etc. (4) phthalocyanine yellow pigments, nickel azo yellow and the like. Specific examples of the representative pigments for the R, G, and B pixels of the tooth-permeable type include the red pigment: 7, PR242, PR254, etc., and the yellow pigments for complementary color or individual color are ΡΥ83, ΡΥ138, ργΐ39, ργΐ5 ( ), ργΐ85, etc. 'as a blue pigment, ΡΒ15: 6, ρ谕, etc., as a complementary color or a single color, the violet pigment is PV23, etc., and the co-sinking pigment of the above-mentioned red pigment and yellow pigment, and blue A co-precipitation pigment, a solid solution pigment or a mixed crystal pigment of a color pigment and a purple pigment. Further, the above mainly describes the pixel formation of the color filter, but the pigment dispersion composition and the color former of the present invention are also suitable for various other uses, for example, as synthetic or natural resins, paints, plastic films, various papers, synthetic papers, and the like. Printing ink, coloring agent for paper, dyeing agent for woven fabric, ink for note printing, coloring agent for color printing machine, ink for inkjet printer, ink for thermal transfer ribbon, etc. Provides excellent green colored items. [Examples] Next, the present invention will be described in further detail by way of specific examples. In addition, the parts and % in the text are the quality basis unless otherwise specified. Further, the number of bromine substitutions of the following multi-filled non-zinc metal phthalocyanines indicates the number of loading ratios of the condensation reaction. 099118114 20 201107425 Manufacture of composite green pigments of 1'8 molecule and 16 bromo ketone phthalocyanine molecule) (1) Synthesis of 16-based copper phthalocyanine pigment As a synthesis reaction device, a stirring device and a counter-current cooler are prepared. And the reaction vessel and heating device of the thermometer. The bromo content of the raw material is 69% 〇%, and the number of nucleus per molecule is 4.G. To the reaction vessel, 14 parts of nitrobenzene of the reaction medium, 46.4 parts of the above tetrabromophthalic anhydride, 27 parts of urea, 71 parts of titanium tetrachloride, and 34 parts of vaporized copper were added. The reaction temperature was gradually raised from a temperature of 100 ° C to 17 rc, and the mixture was stirred for 4 hours as it was, and the reaction was continued. The reaction temperature before the end of the reaction was 195 C > c. The yield of the crude pigment was 44.8 parts, and the yield of the crude pigment was 97 4%. Further, 100% sulfuric acid was prepared by mixing 95% sulfuric acid and 20% fuming sulfuric acid. The obtained crude pigment 10 was smashed into 1 〇〇% sulfuric acid 1 aliquot, and was allowed to stand at 7 ° C for 1 hour, precipitated in 10 times of ice water, filtered, and washed with water (hereinafter, It is called "refined sulfuric acid". Next, it was washed with a dilute aqueous solution of sodium hydroxide and ethanol and dimethyl decylamine. The yield of the refined pigment was 94.9%. According to the elemental analysis, the content of copper element was 3.44% (theoretical value: 3.456%), and the content of desert was 69.8% (theoretical value: 69.52%). The average number of bromine substitutions per molecule calculated from the analytical value of the obtained 16 bromo ketone phthalocyanine green pigment was 161, indicating that the phthalocyanine skeleton was completely substituted with 16 bromine groups. Hereinafter, this is referred to as "16 bromo ketone phthalocyanine coarse particle pigment". (2) Stacking of PG58 and 16 bromo ketone phthalocyanine molecules 099118114 201107425 The average number of substitutions of bromine is about 13 and the average number of substitutions of gas is about 3 PG58 16.39 g (as the calculated number of average substituents is 0) 00960 Mole, the same below), 16.1 g (0.00196 mol) of 16 bromo copper phthalocyanine coarse particle pigment obtained by the above-mentioned (1) synthesis reaction, dissolved in 2% by weight of sulphuric acid 140 g and at 70 Mix in C for 2 hours and let cool to room temperature. The water is sprayed at a high speed by a suction device, and the reduced pressure sulfuric acid solution is sucked through the reduced pressure capillary tube, and is contacted with the high-speed jet water to dilute the precipitated pigment particles and is subjected to hydrazine and water washing. Next, pigmentation was carried out by a xylene emulsion method to obtain a green pigment. Hereinafter, this is called "green stacked crude pigment 4". (3) Preparing the composite stacked green fine particle pigment by salt grinding and finening. The green stacked crude pigment_1 obtained in the above (2) is mixed with 600 parts of the gasified sodium powder and 11 parts of diethylene glycol. Put into the kneading machine that assembles the pressure cap. The mixture was pre-mixed in a kneader to a uniformly wet block, and then the pressure pot was closed and the contents were pressed at a pressure of 6 kg/cm 2 and kneaded and ground. The contents were managed at a temperature of 92 to 98 ° C while being kneaded and pulverized for 2 hours. The obtained ground product is stirred in 3000 parts of 2% sulfuric acid added at 80 ° C for 1 hour, and then filtered and washed with water to remove sodium chloride and diethylene glycol to obtain a fine composite stacked green pigment. Pressurized cake. In order to determine the particle size of the obtained pigment, 200% of the nonionic active agent relative to the pigment was added to the pigmented pressed cake, and diluted with water, ultrasonically dispersed to prepare a pigment dispersion, and the particle size measuring machine "Model N- 4 | (manufactured by Coaler) When the average particle diameter is measured, the average particle diameter is about 25 to 35 nm. The pressed cake 099118114 22 201107425 is dried and pulverized to obtain a green pigment. The obtained pigment is heat-treated in an organic solvent, and is pigmented. No substantial change was observed in the particle size and the crystal state. Hereinafter, it is referred to as "green stacked pigment-1". Production Example 2 (Production of composite green pigment of PG58 and 16-based ketone phthalocyanine molecules) (1) Stacking of PG58 molecule and 16-bromo ketone phthalocyanine molecule PG58 16.81 g used in Production Example 1 (2) (0.00985 mol), 16 bromo copper phthalocyanine coarse particle pigment obtained by the synthesis reaction of Production Example 1 (1) 3.19 g (0.00173 mol) was dissolved in 20% fuming sulfuric acid 200 g, and at 7 ° ° After stirring for 2 hours in C, the mixture was allowed to cool to room temperature, and then poured into 2000 g of ice water containing 1 g of butyl cellosolve, which was charged into a Max Mixing and Stirring Tank (manufactured by Sumitomo Heavy Industries, Ltd.), and filtered and washed. . The pressed cake was dried and pulverized to obtain a green pigment. Hereinafter, this is called "green stacked pigment_2". Production Example 3 (Production of composite green pigment of PG58 molecule and PG36 molecule) (1) Stacking of PG58 molecule and pG36 molecule was carried out in the same manner as in Production Example 2, and PG58 used in Production Example 1 (2) was 18.00 g (0.01054 m). The ear, and the average number of substitutions of bromine are about 13, the average number of substitutions of gas is about 3, 36 2.0 g (〇.〇〇117 m), dissolved in 2% of sulphuric acid 200 g, and Stir at 70 ° C for 2 hours and let cool to room temperature. The water is sprayed at a high speed by a suction device, and the reduced pressure sulfuric acid solution is sucked through the reduced pressure capillary tube, and is contacted with the high-speed jet water to dilute the precipitated pigment particles 099Π8ΙΙ4 23 201107425, and subjected to water washing. What is it? The phenyl emulsion is pigmented to obtain a green pigment. Hereinafter, this is called "green stacked crude pigment_3". (2) Preparation of composite stacked green fine particles by salt grinding fine treatment _ Same as Production Example 1 (3) Treatment 'The green stacked crude pigment obtained in the above (1) ^ 100 parts with sodium carbonate powder _ parts and diethylene glycol ιι The kneading machine that is commonly used in the assembly of the pressure cap is treated in the same manner for kneading and grinding. The same is handled at 2〇/. After the acid-repellent towel was stirred, the gasified sodium and diethylene glycol were removed by washing with water to obtain a pressed cake of the finely packed composite green pigment. The average particle size is about 30 nm. The pressed cake was dried and pulverized to obtain a green pigment. Even if the obtained pigment was heat-treated in an organic solvent, no change in the grain size and crystallinity of the pigment was observed. The following 'refers to it as 'green stacked pigment-3'. Production Example 4 (Production of PG58 molecule and 16 bromo aluminum phthalocyanine molecule composite green phthalocyanine) (1) Synthesis of 16 bromo aluminum phthalocyanine pigment was treated in the same manner as in Production Example 1 (1), and charged in a reaction vessel. The same number of parts of nitrobenzene, tetrabromophthalic anhydride, urea, and tetragas hydride were changed, and the vaporized copper was changed to 3.34 parts of aluminum chloride. The reaction temperature was raised from 100 ° C to 175. (: and the mixing was carried out for 5 hours, the final reaction temperature was 200 ° C. The yield of the crude pigment was 4 parts, and the crude pigment was 87.1%. The obtained crude pigment was treated with the production example 1 (1) to give sulfuric acid. Purification and filtration of the pigment precipitate, washing with water, drying and pulverization. The pigment thus obtained is referred to as "16 bromo aluminum phthalocyanine pigment". 099118114 24 201107425 (2) PG58 molecule and 16 bromo aluminum phthalocyanine molecule The stacking was carried out in the same manner as in Production Example 1 (2), and PG58 14.75 g (0.00864 mol;) and the above (1) 16 bromo aluminum phthalocyanine pigment 5.24 g (0.00288 mol) were dissolved in 20% fuming sulfuric acid 140. Gram, stir at 70 ° C, let cool. Use the aspirator to attract the fuming sulfuric acid solution of the above pigment, and contact with the high-speed jet of water to dilute the pigment particles. Filter the 'precipitate, wash with water, and secondly The pigmentation of the toluene emulsion method is carried out to obtain a green pigment. Hereinafter, it is referred to as "green-stacked crude pigment-4". (3) Preparation of composite deposited green fine particle pigment by salt polishing and finening treatment is the same as in Production Example 1 (3) Processing 'the green accumulation of the above (2) The crude pigment _4 is mixed with the gasified sodium powder and monoethylene glycol into a kneader, premixed, and then kneaded and pulverized. The obtained ground product is stirred in 2% dilute sulfuric acid, filtered, and The green pigment was obtained by washing with water, drying, and pulverization. The pigment obtained was heat-treated in an organic solvent, and no substantial change was observed in the particle size and crystal state of the pigment. Hereinafter, it is referred to as "green stacked pigment_4". Production Example 5 (Production of composite green pigment of PG58 molecule and 16-make-based Weijing molecule) (1) Synthesis of 16-glycol-based magnesium phthalocyanine pigment and production example! (1) Treatment, loading Shisaki benzene, four in a reaction vessel The same number of parts of the sulphuric acid anhydride, urea, and sulphuric acid sulphide and the gasification of copper changed to 2.39 parts of magnesium gasification. The reaction temperature was raised from 10 (rc to 17 generations and dropped for 4 hours, the final reaction temperature was 195 C. The yield of the crude pigment was 39 9 parts, and the yield of the crude pigment 099118114 25 201107425 was 88.7%. The obtained crude pigment was treated with the production example (!) for sulfuric acid purification, and the pigment precipitate was filtered, washed with water, and dried. ,powder The pigment thus obtained is hereinafter referred to as "16 bromo magnesium phthalocyanine pigment". (1) The deposition of PG58 molecule and 16 > odorant magnesium g phthalocyanine molecule is treated as in Production Example 1 (2). PG% 6.43 g (0.00,377 mol) and 13.57 g (〇〇〇754 mol) of the 16 bromo magnesium phthalocyanine pigment of the above (1) dissolved in 20% fuming sulfuric acid M0, stirred in 7 (TC) 'Let's cool. Use the aspirator to attract the fuming sulfuric acid of the above pigment, and contact with the high-speed jet of water to dilute the precipitate. The "green washing" was carried out to reduce the "water washing, and the neon xylene emulsion method was carried out". Hereinafter, it is referred to as "green · ^ stacked crude pigment-5". (3) Preparation of composite stacked green fine particles by salt grinding and finening treatment in the same manner as in Production Example 1 (3) 'The green stacked coarse skin center obtained by the above (2) and the gasified sodium powder and the diethylene glycol co-packing machine After pre-mixing, enter ~ mix and grind. The obtained ground material is subjected to 2% dilute sulfur (IV) after the transition and washing with water, drying and pulverizing to obtain a green jet. Even if the organic solution is added to the secret, the particle size and crystal state of the pigment are also observed. Substantial change. Hereinafter, it will be referred to as "green stacked pigment_5". Example 1 (Preparation of a green pigment high-concentration dispersion) In advance, as a pigment dispersion, _ acid butyl 1 stupyl 1 propyl _ _ ethoxy-methacrylic acid (mass ratio: 5 〇: 15:1 〇: 25) , average molecular denier 12, 〇〇〇) 30 of the copolymer. /. C: a solution of an alcohol mono-f-ether vinegar (iv) (hereinafter, abbreviated as 099118114 26 201107425 "PGMA"). Hereinafter, it is called "resin dispersing agent PGMA solution-1." 19 parts of "green-pigmented pigment _ 1" obtained in Production Example 1 (3), 1 part of green pigment stone weathering derivative, and cationic polymer-based dispersing agent (polyester amide, polyethylenimine, 50 12 parts, 12 parts of the above-mentioned "resin dispersant PGMA solution-1" and 50 parts of PGMA, and stirred with a dissolving rod for 2 hours, and after confirming that there is no pigment block, it was dispersed in a horizontal ring type bead mill. Oxidation-formed beads (diameter 0.65mm) were used in the machine to disperse at a peripheral speed of 14m/s to obtain a green high-concentration pigment dispersion, "green-stacked pigment high-concentration dispersion solution. 1 j 〇 Example 2 (various colors (Preparation of high-concentration dispersion of pigment) (1) Preparing PR254, PY138, PB15-6, and PV23 by preparation of finely divided fine particle pigments. The salt of the composite deposited green pigment according to Production Example 1 (3) is finely ground. The pigment powder is mixed with the gasified sodium powder and diethylene glycol into a kneading machine equipped with a pressure cap, and kneaded and ground. The obtained ground product is also dissolved in salt, solvent, and filtered. Washed with water to obtain pressure of each fine pigment The average particle diameter of the finely colored pigments is 3 〇 to 4 〇 nm. The pressed cake is dried and pulverized to obtain fine powder pigments of each pigment. (2) Modulation of pigment high-concentration dispersion is the same as in Example 1 The treatment, using the fine particles of PR254, PY138, PB15-6 and pV23 obtained in the above (1) and each of the known pigment sulfonated derivatives, instead of the green stacked pigment-1 and the green pigment sulfone derivative, are also equipped with 099118114 27 201107425 A cationic polymer dispersant, an acrylic resin, and PGMA are mixed, and the mixture is stirred and degummed with a dissolving rod, and dispersed by a ring-type bead mill disperser to obtain a high-concentration dispersion of each pigment. Dispersion-1" is indicated by each color name. (3) Preparation of Pixel Ink for Pixels In order to form RGB pixels on the glass substrate of the color filter, "green pigment photosensitive dispersion-1" and "red pigment sensitivity" were obtained according to the following Table 3. Dispersion-1" and "Blue Pigment Photosensitive Dispersion-1". [Table 3] Modulated green pigment photosensitive dispersion forming RGB pixilable ink-1 Red pigment photosensitive dispersion-1 Blue pigment photosensitive dispersion-1 Green high concentration dispersion-1 63 Red high concentration dispersion- 1 85 Yellow high concentration dispersion-1 37 15 Blue high concentration dispersion-1 85 Purple high concentration dispersion-1 15 Photosensitive acrylic resin varnish 50 50 50 TMPTA 10 10 10 HEMPA 2 2 2 DEAP 1 1 1 PGMA 37 37 37 Total 200 200 200 In the above, TMPTA stands for trishydroxypropyl propane triacrylate, 1^]\/〇>8 represents 2-hydroxyethyl-2-mercaptopropionic acid, 0£8? Represents 2,2-diethoxyethyl benzene. Example 3 (Preparation of color filter) A glass substrate subjected to a decane coupling agent was attached to a spin coater, and the "red pigment photosensitive dispersion-1" of Example 2 (3) was described in WO9911811428 201107425. It was initially spin-coated at 300 rpm for 5 seconds and then at 1200 rpm for 5 seconds. Next, prebaking was carried out at 80 ° C for 10 minutes, and a mask having a mosaic pattern was adhered, and exposure was performed using an ultrahigh pressure mercury lamp at a light amount of 100 mJ/cm 2 . Next, development and washing were carried out with a dedicated developing solution and a dedicated rinse to form a red mosaic pattern on the glass substrate. Then, using "green pigment photosensitive dispersion-1" and "blue pigment photosensitive dispersion-1" of Table 3, coating and baking were carried out according to the above method to form a green mosaic pattern and a blue mosaic pattern. RGB color filters. The obtained color filter has excellent spectral characteristics, excellent in light resistance such as light resistance and heat resistance, and excellent in light transmittance, and exhibits excellent properties as a color filter for liquid crystal color display. Example 4 (Preparation of color filter) The green deposited pigments -2 to 5 obtained in Production Examples 2 to 5 were used instead of the green deposited pigment-1 used in the above Example 1, and the above Example 1 and Example 2 were carried out. In the same operation, a green pigment photosensitive dispersion was obtained, and at the same time, a red pigment photosensitive dispersion-1 and a blue pigment photosensitive dispersion-1 were used, and the color filter was processed in the same manner as in Example 3, and the spectrum was excellent. It is excellent in properties such as light resistance and heat resistance, and excellent in light transmittance. It is a color filter for liquid crystal color displays. Example 5 (gravure ink and gravure printing) 12 parts of a vinyl chloride-vinyl acetate-acrylic acid (89: 6.7: 4.3) 099118114 29 201107425 copolymer (weight average molecular weight of about 30,000) having a carboxyl group was dissolved in butyl acetate. - 68 parts of a mixed solvent of methyl isobutyl ketone-xylene (43: 20: 20), 5 parts of the green deposited pigment obtained in Production Example 1 (3), and placed in a ball mill and dispersed for 16 hours. Adding 3 parts of sulfur dioxide, and adding a multi-branched polycarbodiimide cross-linking agent (reaction product of polyhexylcarbodiimide-diisocyanate and dipentaerythritol monolaurate) 2% 12 parts of toluene solution were mixed and made into a yellow-green gravure ink. As a gravure ink of a distinctive yellow-green color, other red, blue, yellow, brown, and black gravure inks are collectively printed on a vinyl chloride film to obtain a film of a multi-color printing vinyl chloride. Further, the green deposited pigments _2 to 5 obtained in Production Examples 2 to 5 were used instead of the above-mentioned green deposited pigment-1, and the same film was subjected to gravure printing as in the above-mentioned yellow-green intaglio printing ink. . Example 6 (Coating and Coating) Methyl methacrylate-ethyl methacrylate having carboxy group octyl methacrylate hydroxyethyl methacrylate-mercapto acrylate was added (44 : 2 〇: 1 〇: 5) 45 parts of an ethyl acetate solution (solid content: 6%) of a copolymer, 19 parts of xylene, 5 parts of a green deposited pigment obtained in Production Example 1 (3), and 15 parts of a titanium oxide white pigment, and infiltrated Milled and dispersed for 16 hours. The yellow-green acrylic paint having a multi-branched polycarbodiimide cross-linking agent recommended solution of Example 5 and a prescription for preventing the dispersing agent from 0.1 part was prepared. For related products such as mobile phones, personal computers, etc., related products, office supplies, and household goods, etc. 099118114 30 201107425 Various wood products, metal products, and plastic products are coated with yellow-green color, which can be excellent in terms of finance, durability, and water resistance. Coating. Further, the green deposited pigments -2 to 5 obtained in Production Examples 2 to 5 were used instead of the above-mentioned green deposited pigment-1, and the yellow-green acrylic paint was prepared as described above, and the same various members were coated to obtain a brilliant yellow. Green coated products. 099118114 31