TW477791B - Phthalocyanine compound and use of the same as a colorant - Google Patents

Abstract

Compound formula, M is a divalent metal, oxo metal, halogenometal or hydroxymetal, or 2 hydrogen atoms, A is a radical or formula, which may be unsubstituted or substituted by phenoxy, naphthyloxy, phenylthio or by naphthylthio, X is a hetero atom selected from the group consisting of N, O, and S, m being the number a when X is O or S and the number 1 when X is N, V is any desired substituent that is inert towards alkylating reagents, Z is hydrogen, Z' or COOB, Z' is C2-C12alkylene-N(COOB)2, C2-C12alkylene-NHCOOB, C2-C12alkylene-OCOOB or C2-C12alkylene-SCOOB, x is a number from 1 to 4 and y is a number from 1 to 15, wherein the sum of x and y is a maximum of 16 and, optionally, a plurality of radicals X, V, Z and/or Z' may be identical or different, and B is an alkyl-, alkenyl-alkynyl-arakyl- or polyglycol- or polyamine-substituted alkylene group. The compound according to the invention is used as a colourant and a pigment precursor, especially in light-sensitive compositions for colour filters.

Description

477791 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（1 ) 本發明係有關新穎酞菁化合物和其作為著色劑的用途 Ο 長久以來，酞菁即以著色劑著稱，特別是作為藍色顏 料，如C.I顏料藍15和顏料藍16。利用取代基，可在某一 領域内影響基本構體的顏色，此時，被取代的產物，一般 而言，常是數種成份的難能確定的混合。此混合的組成和 顏色會依製備條件變化而有大大地不同。 1 惟，現代技術常要求具有更佳特性的著色劑。此等著 色劑的色度最好在各種不同條件下，亦能重複地被製備出 。此對於被加入到一良好的助溶形式，進而被轉換成其最 終顏料狀態的著色劑而言，更是特別重要。 目前已知被取代的欧菁並未能合意地滿足此等要求。 在W0 98/14520專利案中，揭示有甲醯化和乙醯化敌 菁的選擇性製備，以及由此衍生得的產物。 在EP 648 817專利案中揭示有，具直接或透過一^-Cfl’l-烯基-或磺基而與酞菁芯體相接合之具有烷氧碳醯 胺的欧菁。在WO98/32802專利中揭示有，其各種不同用 途的可能性。 WO98/32802描述有易溶性化合物如下式： 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 χ 297公釐） -------I-----· I — I ! I 訂---------線 (請先閱讀背面之注意事項再填寫本頁) 477791 五、發明說明（2 ) 經濟部智慧財產局員工消費合作社印製 A7 B7477791 Printed by A7 B7, Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs 5. Description of the invention (1) The present invention relates to novel phthalocyanine compounds and their use as colorants. 0 For a long time, phthalocyanines have been known as colorants, especially as Blue pigments, such as CI Pigment Blue 15 and Pigment Blue 16. The use of substituents can affect the color of the basic structure in a certain field. At this time, the substituted product is generally an indeterminate mixture of several components. The composition and color of this blend will vary greatly depending on the preparation conditions. 1 However, modern technology often requires colorants with better properties. The chromaticity of these toners can preferably be prepared repeatedly under various conditions. This is particularly important for colorants that are added to a good solubilizing form and are then converted to their final pigment state. The currently known substituted Eugen failed to satisfy these requirements desirably. In the WO 98/14520 patent, the selective preparation of formazan and acetocyanine and the products derived therefrom are disclosed. In EP 648 817, it is disclosed that cyanocyanine having an alkoxycarbamidine is bonded to a phthalocyanine core directly or through a ^ -Cfl'l-alkenyl- or sulfo group. The possibility of various uses is disclosed in the WO98 / 32802 patent. WO98 / 32802 describes soluble compounds with the following formula: The paper size is applicable to Chinese National Standard (CNS) A4 (21〇χ 297 mm) ------- I ----- · I — I! I Order --------- line (please read the precautions on the back before filling out this page) 477791 V. Description of the invention (2) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7

以及其熱分解。 惟令人訝異地，此等隱性酞菁在實際添加時，有造成 難以預料的困難情況出現。在其熱分解時，與其它隱性顏 料相較，會出現不欲見到的色染，而使色真無法達到令人 滿意的程度。此特別是在高價值應用，多色系統以及特別 是光敏性組成（阻劑）上是一問題。在該方面，譬如在濾色 鏡上， 高要求以及全然一定的色度是必須做到的。 US-3,972,904揭示水溶性織物染料，惟在_般高严 值，多色以及光敏性組成上不能被利用。 US-4,3 81，261的實施例8揭示下式化合物的製備·And its thermal decomposition. Surprisingly, when these recessive phthalocyanines are actually added, they cause unpredictable difficulties. When it is thermally decomposed, compared with other hidden pigments, unintended color stains may appear, making the color really unsatisfactory. This is a problem especially in high-value applications, multicolor systems, and especially photosensitive compositions (resistors). In this respect, for example, in color filters, high requirements and a certain chromaticity must be achieved. US-3,972,904 discloses water-soluble fabric dyes, but cannot be used for high stringency values, multi-colors, and photosensitive composition. Example 8 of US-4,3 81,261 discloses the preparation of compounds of the formula:

(請先閱讀背面之注意事項再填寫本頁)(Please read the notes on the back before filling this page)

477791 A7 B7 五、發明說明（477791 A7 B7 V. Description of the invention (

NN

NN

S02NH-C0NH(CH2)6NHC00CH ch2oocchch2 Ij-j-CHpOCCHCHj CH，OOCCHCK>S02NH-C0NH (CH2) 6NHC00CH ch2oocchch2 Ij-j-CHpOCCHCHj CH, OOCCHCK >

NN

N—Cu-"NN—Cu- " N

CH2〇OCCHCH2 S02NH-C0NH(CH2)eNHC00CHj"f-CH200CCHCH2 CH2OOCCHCH2 ch2oocchch2 *S02NH-CONH(CH2)6NHCOOCH24~CH2OOCCHCH2 ch2oocchch2 惟此化合物因其高黏度而無法在一般高價值，多色以 及光敏性組成上被利用。 US-4,000，158揭示有醇溶性和酮溶性酞菁化合物，此 等因其在顯影劑中過高的終溶性而無法在一般高價值，多 色以及光敏性組成上被利用。 令人§牙異地’此等問題可被依据本發明的化合物來解 決。 本發明係有關下式的化合物， (請先閱讀背面之注意事項再填寫本頁)CH2〇OCCHCH2 S02NH-C0NH (CH2) eNHC00CHj " f-CH200CCHCH2 CH2OOCCHCH2 ch2oocchch2 * S02NH-CONH (CH2) 6NHCOOCH24 ~ CH2OOCCHCH2 ch2oocchch2 However, this compound cannot be used in general because of its high viscosity and high photosensitivity. . US-4,000,158 discloses alcohol-soluble and ketone-soluble phthalocyanine compounds, which cannot be utilized for generally high-value, multicolor, and photosensitive compositions because of their too high final solubility in the developer. Such problems can be solved by the compounds according to the invention. This invention relates to compounds of the following formula, (Please read the precautions on the back before filling this page)

經濟部智慧財產局員工消費合作社印製 其中 /Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

A A ⑴· '(Y)y^lSO^(Z)mZ\ M代表兩價金屬，氧金屬，鹵金屬或羥金屬或2個盡 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公髮） 經濟部智慧財產局員工消費合作社印製 477791 A7 B7 — 五、發明說明（4 ) 原子， A代表一殘基二〕或，其係可為未被 取代，或被苯氧基，萘氧基，苯硫基或萘硫基所取代， X係代表一擇自由N，0和S所組成的族中的雜原子， 其中，當X等於0或S時，m為0，而當X等於N時，m為1， Y代表任意一不對烷化劑起反應的取代基， z代表氫，Z’或COOB， Z’ 代表 c2-c12 烷伸基-N(COOB)2，C2-C12 烷伸基-NHCOOB，C2-C12烧伸基-〇c〇〇B或C2-C12烧伸基-SCOOB， X係從1至4的一數目，而y係從〇至15的一數目， 其中X和y的總和最高是等於16,且視情況而定，X，γ，z 和/或Z’可越多越好，相同或互異，以及 B代表具下式的基；AA '·' (Y) y ^ lSO ^ (Z) mZ \ M stands for divalent metal, oxygen metal, halogen metal or hydroxy metal, or 2 paper sizes. Applicable to China National Standard (CNS) A4 (210 X 297) Issued by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative of the People's Republic of China 477791 A7 B7 — V. Description of the Invention (4) Atom, A represents one residue two] Or, it can be unsubstituted or phenoxy, naphthalene Substituted by oxy, phenylthio or naphthylthio, X represents a heteroatom in the group consisting of N, 0 and S, where m is 0 when X is equal to 0 or S, and when X is 0 When equal to N, m is 1, Y represents any substituent which does not react with the alkylating agent, z represents hydrogen, Z 'or COOB, Z' represents c2-c12 alkylene-N (COOB) 2, C2-C12 Alkylene-NHCOOB, C2-C12 alkylene-Oc00B or C2-C12 alkylene-SCOOB, X is a number from 1 to 4, and y is a number from 0 to 15, where The maximum sum of X and y is equal to 16, and as the case may be, the more X, γ, z, and / or Z 'can be, the same or different, and B represents a base with the following formula;

一，其中， R!是氫或C「C6烷基， R2和R3各自獨立地代表<：「<：6烷基 R4和各自獨立地代表crc6烷基，被o，s或nr12中斷 之(^-(：6烷基，未取代或被crc6_烷基，crc6_烷氧基，鹵基 ，氰基或氮基所取代的苯基或雙苯基， ^，:^和:^各自獨立地代表氫或匕-匕烷基， r9代表氫，c「c6烷基或下式的基： 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公髮） ----------------I--J--訂 d----I---· (請先閱讀背面之注意事項再填寫本頁) A7 、發明說明（One, where R! Is hydrogen or C, C6 alkyl, R2 and R3 each independently represent <: ": 6 alkyl R4 and each independently represent crc6 alkyl, interrupted by o, s or nr12 (^-(: 6 alkyl, unsubstituted or phenyl or bisphenyl substituted with crc6-alkyl, crc6-alkoxy, halo, cyano or nitrogen, each of ^,: ^ and: ^ Independently represents hydrogen or dagger-alkyl, r9 represents hydrogen, c "c6 alkyl or the following formula: This paper size applies to China National Standard (CNS) A4 specifications (210 X 297) ----- ----------- I--J--Order d ---- I --- · (Please read the notes on the back before filling out this page) A7 、 Invention description (

J-R 13J-R 13

或 II -GO—R15 η 經濟部智慧財產局員工消費合作社印製 和Ru各自獨立地代表氫，crc6烷基，crc6烷氧基， 齒基’氰基，氮基，N(R12)2，未被取代或被鹵基，氰基， 氮基，CrC6烷基或C「c6烷氧基所取代的笨基，Or II -GO—R15 η Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and Ru each independently represents hydrogen, crc6 alkyl, crc6 alkoxy, dentate 'cyano, nitrogen, N (R12) 2, not A phenyl group substituted or substituted by a halo group, a cyano group, a nitrogen group, a CrC6 alkyl group, or a C6 alkoxy group,

RuRu各代表crc6烷基，r14代表氫或(^-(^烷基以及 代表c^c：6烷基或未被取代或被c「c6烷基所取代的苯基 E代表未被取代或被(^-(^烷氧基，(:^匕烷硫基或c2_ Cu二烷胺基一次或多次取代之p，q_C2-C6伸烷基，其中p和q 是不同位置數目， X’代表一雜原子，其係選自由N，〇和S所組成之族中， 當X’等於0或S時，m’為0，而當X，等於N時，m，為1， 以及 1^和1^各自獨立地代表未被取代或被Crc6烷氧基，(：「 C6院硫基，C2-C12二烷胺基，c6-C12#氧基，C6-C12*硫基，c7-Cisi烧胺基或ci2-C24二芳胺基所一次或多次取代 烧基或[-(P’，q，_C2-C6伸烷基烷基，其中 是從1至1000的數目，p，和q，係不同位置數目，各個z，，係各 自獨立地代表雜原子〇，s或被CrCi2烷基所取代的N，以及 q-c：6伸烧基在其重複單位[_CrC6伸烷基-z，，_]中，係相同 或不同者， 以及L1和L2可為飽和或1 -至1 〇個不飽和，可不被中斷 或在在所欲位置被1至10個選自由_((：=〇>和(：：#4-所組成 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 9 --------------裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁} 477791 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 A7 ____m________五、發明說明（6 ) 的族的基團所中斷，以及可不帶有或帶有1至10個另選自 由鹵基，氰基和氮基所組成之族的取代基。 C2_C12伸烧基譬如是，ι，2-伸乙基，1,2-伸丙基，i，3-伸丙基，1，2-伸丁基，1,3-伸丁基，2,3-伸丁基，1，4-伸丁 基，2-曱基-1，2-伸丙基或伸戊基，伸己基，伸辛基，伸癸 基或十二烧基的一異構物。 cvc"芳氧基是〇-c6-c12芳基，譬如苯氧基或萘氧基 ，而又以苯氧基為佳。 cvc6烷硫基是s-crc6烷基，而以s-cvq烷基為佳。 q-Cu芳硫基是s-c6-c12芳基，譬如是苯硫基或萘硫 基，而以苯硫基為佳。 二烷基胺是N(烷基！）(烷基2)，其中在烷基1和烷 基2兩基團中碳原子的總數係從2至12 ,而以N(crc4烧基）-C「C4烧基為佳。 C7-C1S烷芳基胺是N(烷基〇(芳基2)，其中在烷基1和芳 基2兩基團中碳原子的總數係從7至18，而以甲苯基胺基或 乙本基胺基為佳。 Cu-C：24二芳基胺是N(芳基〇(芳基2)，其中在芳基】和 芳基2兩基團中碳原子的總數係從12至24，譬如是二苯基 胺基或苯萘基胺基，而以二苯基胺基為佳。 不對烷化劑起反應的取代基，可譬如是，在此後所給 的條件下，係不與焦碳酸酯起反應，譬如是那些不含羥基 ’胺基或魏基者。 取代基，S〇2(Z)mZ’和Y係可位在殘基A的任一個芳烴 本紙張尺度適用中國國家標準（CNS)A4規格（21() x 297公髮）~ -- 請 先 閱 讀 •背 面 之 注 意 事 項 再 填 寫 本 頁RuRu each represents a crc6 alkyl group, r14 represents hydrogen or (^-(^ alkyl) and c ^ c: 6 alkyl or unsubstituted or substituted by c "c6 alkyl phenyl E represents unsubstituted or substituted (^-(^ Alkoxy, (: ^ alkylthio or c2-Cu dialkylamino substituted p, q_C2-C6 alkylene, one or more times, where p and q are the number of different positions, X 'represents A heteroatom is selected from the group consisting of N, 0 and S. When X 'is equal to 0 or S, m' is 0, and when X is equal to N, m is 1, and 1 ^ and 1 ^ each independently represents an unsubstituted or Crc6 alkoxy group, (: "C6 thiol, C2-C12 dialkylamino, c6-C12 # oxy, C6-C12 * thio, c7-Cisi Amino or ci2-C24 diarylamino groups are substituted one or more times with alkyl or [-(P ', q, _C2-C6alkylenealkyl, where is the number from 1 to 1000, p, and q, Is the number of different positions, each z ,, each independently represents a heteroatom 0, s or N substituted by a CrCi2 alkyl group, and qc: 6 alkynyl in its repeating unit [_CrC6 alkynyl-z ,, ], Are the same or different, and L1 and L2 may be saturated or 1 to 10 unsaturated, may be Interrupted or 1 to 10 at the desired position selected from the group consisting of _ ((: = 〇 > and (:: # 4-) This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) ) 9 -------------- install -------- order --------- line (please read the precautions on the back before filling this page) 477791 A7 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ____m________ 5. The group of the family of invention description (6) is interrupted, and may be without or with 1 to 10 alternatives selected from halo, cyano and nitrogen The substituents of the group of the composition. C2_C12 alkylene is, for example, ι, 2-ethynyl, 1,2-propylidene, i, 3-propylidene, 1,2-butylidene, 1,3 -Butylene, 2,3-butylene, 1,4-butylene, 2-fluorenyl-1,2-propylene or pentylyl, hexyl, octyl, decyl or decyl The isomer of dialkyl. Cvc " Aryloxy is 0-c6-c12aryl, such as phenoxy or naphthyloxy, and phenoxy is preferred. Cvc6alkylthio is s-crc6alkane S-cvq alkyl is preferred. Q-Cu arylthio is s-c6-c12 aryl, such as phenylthio or naphthylthio, and phenylthio Dialkylamine is N (alkyl!) (Alkyl 2), in which the total number of carbon atoms in the two groups of alkyl 1 and alkyl 2 is from 2 to 12, and C4—C4 alkyl is preferred. C7-C1S alkylarylamines are N (alkyl0 (aryl2), where the total number of carbon atoms in both the alkyl1 and aryl2 groups is from 7 To 18, preferably tolylamino or ethylamino. Cu-C: 24 diarylamine is N (aryl0 (aryl2), where the total number of carbon atoms in both aryl] and aryl2 groups is from 12 to 24, such as diphenylamine Diphenylamino groups are preferred, and diphenylamino groups are preferred. Substituents that do not react with alkylating agents may, for example, not react with pyrocarbonates under the conditions given below, such as Those that do not contain a hydroxyl 'amino group or a Wei group. Substituents, S02 (Z) mZ' and Y are any aromatic hydrocarbons that may be located at residue A. The paper standards apply to Chinese National Standard (CNS) A4 specifications ( 21 () x 297 public hair) ~-Please read the notes on the back before filling in this page

訂 βOrder β

-10 - 477791 A7-10-477791 A7

訂 線 477791 A7 五、發明說明（ Y較佳是C1或Br。Z較佳是Η或COOB，而以COOB為更佳。Ζ’較佳是c2-c12伸烷基-NHCOOB或c2_cl2伸燒基· OCOOB，而以（：2-12伸烧基-OCOOB為更佳。 在Z中的c2_C12-伸烧基OCOOB以c2-C6•伸燒義 OCOOB為佳，而以c2_c4_伸烷基oc〇〇B為較佳，而又以 1，2 -伸乙基為最佳。Y以0或4至8為佳，而尤以〇為較佳。 X和y的總和較佳的是高至8。 B以具下式的族群為較佳， ㈣% 或一 E-X，、， 而以 i"，τπ； (Li)m R6或一Ε-Χ，\ 為更佳，尤其是 經濟部智慧財產局員工消費合作社印製 依族群B定義者之較佳者，且其在另一隱性著色劑上，譬如是在EP 742 255, EP 761 772或WO98/32802中被揭示為 較佳族群者。 Ri車父佳的是Cj-Ce院基。 式（I)的化合物可利用習知類似方法，譬如是由已知 的氯確化酜菁衍化來製備。橫化献菁本身可以習知方式經 由酞菁的氣磺化來製備。再者，它亦可如在Dyes andPigments ϋ_375(1997)中由 Κ· Sakamoto所發表以及 a (請先閱讀背面之注意事項再填寫本頁)Line 477791 A7 V. Description of the invention (Y is preferably C1 or Br. Z is preferably Η or COOB, and COOB is more preferred. Z ′ is preferably c2-c12 alkylene-NHCOOB or c2_cl2 alkylene · OCOOB, and (: 2-12 elongation-OCOOB is more preferred. C2_C12- elongation-based OCOOB in Z is preferably c2-C6 • elongation-synthetic OCOOB, and c2_c4_ealkylene oc. 〇B is preferred, and 1,2-ethylende is most preferred. Y is preferably 0 or 4 to 8, and particularly 0 is preferred. The sum of X and y is preferably as high as 8 B is better for ethnic groups with the following formula, ㈣% or -EX ,, and i ",τπ; (Li) m R6 or Ε-χ, \ is better, especially the Intellectual Property Bureau of the Ministry of Economic Affairs The employee consumer cooperative prints the better according to the definition of ethnic group B, and it is disclosed as the better ethnic group on another recessive colorant, such as in EP 742 255, EP 761 772 or WO98 / 32802. Che Fujia is a Cj-Ce compound. Compounds of formula (I) can be prepared by similar methods, such as derivatization with known chlorinated perylene cyanine. Transversal cyanine can itself be passed through phthalocyanine in a conventional manner. Gas sulfonation. Furthermore, it Also as published by K Sakamoto in Dyes and Pigments ϋ_375 (1997) and a (Please read the notes on the back before filling this page)

12 477791 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（9 )12 477791 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (9)

Hong 在 J. Phys. Chem. 21，2109(1987)所發表，藉由4-磺 基-酞酸的環化成酞菁-四磺酸，以及以五氣化磷進行接續 的氯化，或如在Houben-Weyl EM，725(1998-Georg Thieme Verlag Stuttgart)所公開之藉由被磺醯胺基所取代之酞二 賸的環化來獲得。需要時，亦可利用另一酞二胺的混合合 成來達成。被氣磺化的酞菁可接著利用醇，硫醇或胺將其 轉換成所欲的磺酸酯，以及磺醯胺。Hong in J. Phys. Chem. 21, 2109 (1987), cyclization of 4-sulfo-phthalic acid to phthalocyanine-tetrasulfonic acid, and subsequent chlorination with phosphorus pentafluoride, or as Obtained by Houben-Weyl EM, 725 (1998-Georg Thieme Verlag Stuttgart), obtained by cyclization of a phthalocyanine residue substituted with a sulfonamido group. If necessary, it can also be achieved by mixing and synthesizing another phthalodiamine. Gas sulfonated phthalocyanine can then be converted to the desired sulfonate, and sulfonamide by alcohol, thiol or amine.

1 較佳的是利用類似譬如在EP 648 770, EP 648 817, EP 654 71 1，EP 742 255, EP 761 772 和 WO98/32802 中所述的 方法來製備式（I)的化合物。 化學式為β、ΛΛ〆 焦碳酸二酯係在非質子有 機溶劑中，一作為催化劑之鹼的存在下，適當地在〇至12〇〇c 之間的溫度，最好是在10至100。(：之間的溫度，歷時2-80 小時進行轉換。 各別莫耳比率係依所添加殘基B來決定，此時，二碳 酸合適地係依理論所需的量還多的方式添加。 式⑴的酞菁，其中Z’代表C2-C12伸烷基-0扎(：2-(：12伸 院基-SH或C2-C12伸烧基-NH2，可依類似上述的方法，由 醜菁·氣化磺被伸烷基-二醇，CrCu伸烷基·二硫醇 伸烷基-二胺或羥基_C2-C12伸烷基-胺的轉換來製備 〇 依据本發明的式（I)的化合物特別適合團狀的高分子 有機物的著色。 可被依据本發明之式（I)的化合物所著色之合適的高 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 x 297公釐） -------------裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 13 477791 A7 五、發明說明（10 ) (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 分子有機物的例子有，乙烯基聚合物，諸如聚苯乙烯，聚 -α -甲基苯乙烯，聚-P-甲基苯乙烯，聚·ρ—羥基苯乙烯， 聚-Ρ-羥基苯基苯乙烯，聚（甲基丙烯酸酯）和聚（丙烯醯胺） 以及其對應的甲基丙烯醯基化合物，聚（甲基馬來酸酯）， 聚（丙烯胺），聚（甲基丙烯胺），聚（氯乙烯），聚（氟乙烯）， 聚（偏二氯乙烯），聚（偏二氟乙烯），聚（乙酸乙烯酯），聚 (甲基乙烯醚）和聚（丁基乙烯醚）；由crc6-醛，諸如甲醛 和乙醛等所衍生的酚醛清漆，以及雙環，最好是單環的酚 類，其需要時，係被一或多個CrC9-烷基，一或兩個鹵原 子或一苯環所取代，譬如是o-，m-或p-曱酚，二甲苯，P-特 -丁基盼，o-，m·或ρ -壬盼，p -氯盼或ρ -苯基紛，或一具 有多於一個酚基的化合物，諸如，間苯二酚，雙-(4-羥基 苯基）甲烷或2,2-雙-(4-羥苯基）丙烷；由馬來醯亞胺和/或 馬來酐所衍生的聚合物，諸如，馬來酐和苯乙烯所成的共 聚物；聚（乙烯基咣咯烷酮），生化聚合物和其衍生物， 諸如，纖維素，澱粉，殼質，殼聚糖，明膠，玉米朊，乙 基纖維素，硝基纖維素，乙酸纖維素酯以及丁酸纖維素酯 ，松香以及樹脂，諸如，橡膠，酪素，矽酮以及矽酮樹脂 ，ABS，腺-和蜜胺-曱醛樹脂，醇酸樹脂，酚樹脂，聚醯 胺，聚醯亞胺，聚醯胺/亞胺，聚颯，聚醚颯，聚苯醚， 聚胺基甲酸酯，聚脲，聚碳酸酯，聚芳烴，聚芳烴硫化物 ，聚環氧化物，聚烯烴，聚烷二烯。較佳的高分子有機物 是諸如，纖維素醚和酯，如乙基纖維素’硝基纖維素，乙 酸纖維素酯以及丁酸纖維素酯，松香以及樹脂’諸如聚合 14 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 發明說明（11 ) 或縮合的樹脂，諸如酚糊，聚碳酸酯，聚烯烴，聚笨乙烯 ，聚氯乙烯，聚醯胺，聚胺基甲酸酯，聚酯，ABS，聚苯 醚，橡膠，酪素，矽酮以及矽酮樹脂，單獨或混合存在。 前述高分子有機化合物可單獨或混合地作為塑性團物 ，，熔融或呈溶紡狀，清漆，塗料或印刷油墨使用。依使 用的目的，式（I)本發明若以調色劑或一製劑形式添加， 效果會更好。 式（I)本發明化合物特別合適於聚氯乙烯的大量著色 ，尤其是聚烯烴，如聚乙烯和聚丙烯，以及清漆，或粉末 清漆，印刷油墨和塗料。 以被著色的高分子有機物為基礎，式⑴本發明化合 物的添加用量係從0.01至30重量％，較佳的是從〇丨至1〇重 量％。 利用式（I)本發明化合物著色的高分子有機物質係以 如下方式來達成，即，需要時，式⑴化合物可利用輥輪 ，摻混或研磨裝置，以一主批次方式與此等基質混合。此 被著色的物料在此可依已知方法，如壓延，加壓，擠壓， 塗佈，模製或射出成型等，作成最後所欲的形狀。常常為 了製備不硬的模造體或減低其易碎性，在成型前，會在高 分子化合物中併入所謂的軟化劑。可作為軟化劑的有，譬 如疋，磷酸酯，醜酸或癸二酸。軟化劑可在式⑴本發明 化合物被併入到聚合物之前或之後，被納入進行加工步驟 ，依据獲致不同色調的需要性，可進一步在本發明化合物 之外’另將填充劑以及其它著色成份，如白色，彩色气零 477791 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（12 顏料#以所需的量加入到高分子有機物中。若欲對清 漆，塗料或印刷油墨著色時，高分子有機物和式⑴本發 明化合物，需要時，可一齊與添加物，如填充料，顏料， 速乾4或軟化劑等均句分散以及溶在一共同有機溶劑或混 合溶劑。此時，人們可以如下方式進行，即，將各別組份 抑或多種一齊分散或溶解，爾後才將所有組份加在一塊。 在譬如是聚氯乙烯或聚烯烴的著色，或在印刷油墨時 ，式（I)本發明化合物基於良佳的一般特性，如良好的抗 色移，耐光性以及耐候性等，而更是傑出。 極重要的疋，進入基質的本發明化合物轉變成式（I) 的對應化合物，其中，z，代表C2_Ci2伸烷基_〇H，c2_c^ 烷基-SH或（VCl2伸烷基-NH2。此可以最簡單的方式來達 成，即，經由含本發明化合物的固體，在有機或水性介質 中的溶液或分散液，聚合物溶液或熔融体的熱處理（在50 至25〇°C之間的溫度，最好是在100至200°C之間的溫度加 熱）來達成。在許多情況下，可經由一般普遍的***條件 ，立即達到所需要的轉變。 此使清漆，印刷油墨，合成材料，尤其是呈纖維形式 ,感熱記錄系統，喷墨印刷用的墨水，電子攝影記錄方法 用的調色劑，在平面或凸面受體上熱轉印用的色帶，以及 特別地亦在光敏性組成，如負或正阻配方等之著色時，具 有總括性較佳的特性，如清晰度，色調，色度，亮度，透 明度以及堅牢度，以及其在分析上有趣應用。 本發明的另一標的因而是，一高分子有機物含有一大 本紐尺度適用中國國家標準（CNS)A4規格（210 X 297公榮） " ------ --------------------:丨訂--------線赢 (請先閱讀背面之注意事項再填寫本頁) 16 4//791 A7 經濟部智慧財產局員工消費合作社印製 五、發明說明（η ) i在原地經由式⑴化合物熱分解產生式⑴的著色劑，a 中Z，代表C2-Cl2伸院基-〇H，c2_Ci2伸垸基_SH或c2_Ci2伸燒 基-nh2，以及是…熱·，光_或化學敏性記錄物質，喷墨 印刷用的墨水，電子攝影記錄方法用的調㈣，熱轉印用 的色帶’光敏性負或正阻劑組成等，其特徵在於，它含有 式⑴化合物。 喷墨印刷用的墨水，電子攝影記錄方法用的調色劑， 熱轉印用的色帶，熱光·或化學敏性記錄物f，以及光 敏性負或正阻劑組成均是業者所熟知者。 本發明化合物的-特別令人苛異的是，其加熱轉變可 生成-產物’其顏色對應光學應用所企求，惟目前以酞菁 尚無法達到的色調青綠（青綠色卜本發明化合物的熱解可 產生比現今化合物還高清晰度的產物。 多虧此改善的性質，使得本發明可溶性式⑴著色劑 在組成混合以製備構造性彩色相片或濾色片之應用時，特 別有利。應用可溶性顏料前驅物來製備構造性彩色相片或 ;慮色片已在EP 654 711被揭示。此等組成除了著色劑外， 尚匕3 s如疋正或負阻劑。包含阻劑配方的式⑴著色劑 可依所欲的圖案照射和顯影，在此，生成式⑴的著色劑 的熱轉變’其中z’代表c2_Ci2伸烧基-〇H，CrCi2伸烧基_SH 或cvc12伸絲侧2可即時在或緊接著照射或顯影後進行 。式（I)的化合物亦可經由喷墨印刷或熱感應擴散直接以 所欲的圖案在合適的受体層施用。此在EP 654 71 1公開的 方法亦甚適合用來製造濾光片。 Μ--------^---------^ (請先閱讀背面之注意事項再填寫本頁)1 It is preferred to prepare compounds of formula (I) by methods analogous to those described, for example, in EP 648 770, EP 648 817, EP 654 71 1, EP 742 255, EP 761 772 and WO98 / 32802. The chemical formula is β, ΛΛ〆 The pyrocarbonate diester is in an aprotic organic solvent, in the presence of a base as a catalyst, and suitably at a temperature between 0 and 1200c, preferably between 10 and 100. (: The temperature between 2 to 80 hours for conversion. The individual mole ratio is determined by the residue B added. At this time, the dicarbonic acid is suitably added in a manner that the theoretical amount is more. A phthalocyanine of the formula 其中, where Z ′ represents C2-C12 alkylene-0-Zr (: 2-(: 12 ethylenediyl-SH or C2-C12 alkylene-NH2, can be similar to the method described above, from Cyanide · Sulfurated alkylene-diol, CrCu alkylene · dithiol alkylene-diamine or hydroxy_C2-C12 alkylene-amine are prepared by conversion. According to the formula (I ) Compounds are particularly suitable for the coloring of macromolecular organic compounds. The appropriate high paper size that can be colored by the compound of formula (I) according to the present invention is applicable to the Chinese National Standard (CNS) A4 specification (21 × 297 mm) (Li) ------------- install -------- order --------- line (please read the precautions on the back before filling this page) 13 477791 A7 V. Description of Invention (10) (Please read the notes on the back before filling this page) Examples of molecular organic matter printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics are vinyl polymers such as polystyrene, poly -α-methylstyrene, poly-P-methylstyrene, poly · ρ-hydroxystyrene, poly-P-hydroxyphenylstyrene, poly (methacrylate) and poly (acrylamide) and Corresponding methacryl fluorenyl compounds, poly (methyl maleate), poly (acrylamine), poly (methacrylamine), poly (vinyl chloride), poly (fluoroethylene), poly (vinylidene) Vinyl chloride), poly (vinylidene fluoride), poly (vinyl acetate), poly (methyl vinyl ether), and poly (butyl vinyl ether); phenolic aldehydes derived from crc6-aldehydes, such as formaldehyde and acetaldehyde Varnishes, and bicyclic, preferably monocyclic phenols, are substituted with one or more CrC9-alkyl, one or two halogen atoms, or a benzene ring, such as o-, m- or p-fluorenol, xylene, p-tert-butylpan, o-, m · or ρ-nonpan, p-chloropan or ρ-phenyl, or a compound having more than one phenol group, such as , Resorcinol, bis- (4-hydroxyphenyl) methane or 2,2-bis- (4-hydroxyphenyl) propane; polymers derived from maleimide and / or maleic anhydride, Such as maleic anhydride and phenethyl Copolymers formed; poly (vinylpyrrolidone), biochemical polymers and their derivatives such as cellulose, starch, chitin, chitosan, gelatin, corn mash, ethyl cellulose, nitro Cellulose, cellulose acetate and cellulose butyrate, rosin and resins such as rubber, casein, silicone and silicone resin, ABS, gland- and melamine-acetaldehyde resins, alkyd resins, phenol resins , Polyfluorene, polyfluorene, polyamine / imine, polyfluorene, polyether, polyphenylene ether, polyurethane, polyurea, polycarbonate, polyarene, polyarene sulfide, Polyepoxide, polyolefin, polyalkadiene. Preferred high-molecular organic materials are, for example, cellulose ethers and esters, such as ethyl cellulose 'nitrocellulose, cellulose acetate and cellulose butyrate, rosin, and resin' such as polymerized. Standard (CNS) A4 (210 X 297 mm) Description of the invention (11) or condensation resin, such as phenol paste, polycarbonate, polyolefin, polyvinyl chloride, polyvinyl chloride, polyamide, polyamide Ester, polyester, ABS, polyphenylene ether, rubber, casein, silicone, and silicone resin, alone or in combination. The aforementioned polymer organic compounds can be used alone or in combination as plastic aggregates, melted or melt-spun, varnishes, coatings or printing inks. Depending on the purpose of use, the effect of the invention of formula (I) will be better if it is added in the form of a toner or a preparation. The compounds of the invention of formula (I) are particularly suitable for mass coloring of polyvinyl chloride, especially polyolefins such as polyethylene and polypropylene, and varnishes or powder varnishes, printing inks and coatings. Based on the colored polymer organic matter, the compound of the present invention is added in an amount of from 0.01 to 30% by weight, preferably from 0 to 10% by weight. The high-molecular organic substance colored with the compound of the present invention of the formula (I) is achieved in such a manner that, when necessary, the compound of the formula mixing. The colored material can be formed into the final desired shape here by known methods, such as calendering, pressing, pressing, coating, molding, or injection molding. Often, in order to prepare a non-hard molded body or reduce its fragility, a so-called softener is incorporated into a high-molecular compound before molding. Examples of softening agents include osmium, phosphate, ugly acid or sebacic acid. The softening agent can be incorporated into the processing step before or after the compound of the present invention is incorporated into the polymer. Depending on the need to obtain different shades, the filler can be further added to the compound of the present invention and other coloring ingredients. , Such as white, color gas zero 477791 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (12 Pigment # is added to the polymer organic matter in the required amount. At this time, the polymer organic compound and the compound of the present invention can be dispersed together with additives, such as fillers, pigments, quick-drying 4 or softeners, and dissolved in a common organic solvent or mixed solvent. People can do this by dispersing or dissolving the individual components or multiple types together, and then adding all the components together. For example, in the coloring of polyvinyl chloride or polyolefin, or when printing inks, the formula (I) The compounds of the present invention are even more outstanding based on good general characteristics, such as good color shift resistance, light resistance, and weather resistance. It is important that the compound of the present invention entering the matrix is transformed into the corresponding compound of formula (I), wherein z, represents C2_Ci2alkylene_OH, c2_c ^ alkyl-SH or (VCl2alkylene-NH2. This can The easiest way to achieve this is by heat treatment of a solid containing a compound of the invention, a solution or dispersion in an organic or aqueous medium, a polymer solution or a melt (temperature between 50 and 25 ° C, This is best achieved by heating at a temperature between 100 and 200 ° C. In many cases, the required transformation can be achieved immediately through the general insertion conditions. This makes varnishes, printing inks, synthetic materials, especially In the form of fibers, thermal recording systems, inks for inkjet printing, toners for electrophotographic recording methods, ribbons for thermal transfer on flat or convex receptors, and especially also photosensitive compositions such as When colored with negative or positive resistance formulas, it has better general characteristics such as sharpness, hue, chroma, brightness, transparency, and fastness, as well as its interesting application in analysis. Another object of the present invention is therefore Yes, a high-molecular organic substance contains a large standard applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 Gongrong) " ------ -------------- ------: 丨 Order -------- Line Win (Please read the notes on the back before filling out this page) 16 4 // 791 A7 Printed by the Employee Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Description of the invention (η) i generates a coloring agent of formula 经由 through thermal decomposition of a compound of formula 原 in situ, Z in a represents C2-Cl2 yenyl-OH, c2_Ci2 yenyl_SH or c2_Ci2 yenyl-nh2, And ... thermal, photo- or chemically-sensitive recording materials, inks for inkjet printing, toners for electrophotographic recording methods, ribbons for thermal transfer, 'photosensitive negative or positive resist composition, etc., which It is characterized in that it contains a compound of formula VII. Ink for inkjet printing, toner for electrophotographic recording method, ribbon for thermal transfer, thermo-optical or chemically sensitive recording material f, and composition of photosensitive negative or positive resist are well known to the industry By. The compound of the present invention is-particularly astounding-that its thermal transformation can produce a product-its color corresponds to that desired for optical applications, but currently has a shade of cyan-green (cyan-green) It can produce products with higher definition than today's compounds. Thanks to the improved properties, the soluble formula VII colorant of the present invention is particularly advantageous in applications where the composition is mixed to produce a structural color photograph or color filter. Soluble pigment precursors are used The color film has been disclosed in EP 654 711. In addition to the colorant, these compositions also have 3 s such as 疋 positive or negative resist. Formula ⑴ colorants containing resist formula can be Irradiate and develop according to the desired pattern. Here, the thermal transition of the toner of the production formula 'where z' represents c2_Ci2 elongation base-OH, CrCi2 elongation base_SH or cvc12 elongation side 2 can be immediately on or Immediately after irradiation or development. The compound of formula (I) can also be applied directly to the appropriate receptor layer in the desired pattern via inkjet printing or thermally induced diffusion. The method disclosed in EP 654 71 1 is also Suitable for the manufacture filters. Μ -------- ^ --------- ^ (Please read the notes and then fill in the back of this page)

五、發明說明（14 ) 、本發明因而亦有關構造性彩色相片或濾色片的製造方 法，其特徵在於，包含式⑴著色劑之正或負阻劑依圖案 照射和顯影及熱處理，其中，熱處理可在照射和顯影當時 或俟後發生，而熱轉變成式⑴的著色劑，其中Z，代表c2· Cl2伸烧基-〇H，C2_Cu伸烧基-SH或C2-Clj烧基顧2。 以下實例係用來說明本發明而非作範圍限制用（除非 另外特別註明，否則在此，，％，，均係指重量〇/0 : MAL:在備有kpg-攪拌器，迴流冷凝器，内置溫度 計，滴液漏斗以及N2·上方充注器的一 2·5升的燒瓶中，將 新鮮製備成的銅酞菁-四-磺化氣（依wo98/45756的實例i 製備，含30%銅酞菁-三·磺化氣）溶於丨升的四氟化氫THF 中。在1〇。(：下，將在100ml THF中的63 4g的乙醇胺滴加 到此藍色溶液中。此藍色懸浮液被攪拌3小時，然後迴流17 小時，其後在50°C及真空下，以旋轉揮發器濃縮溶解物。 殘留物再以1升的稀鹽酸（1M)懸浮之，並攪拌3〇分鐘。接 著過濾，以750 ml的水洗滌以及在50〇c/16〇 m巴過夜乾燥 。將獲得77g的藍色粉末。 經濟部智慧財產局員工消費合作社印製 元素分析[%] (C39 4H34 5N" 7On」s3 7Cu · 1.3H20) 理論值：C 44.85 H 3.54 N 15.53 S 11.25 求得值，C45.10 Η 3.83 N 15.46 S1123 利用W098/45756的實例1所述的方法，惟使用較少量 的氣磺酸，如此較易獲致具不同數目磺基之化合物的混合 物。由此，具1至3個磺基的化合物可依所需以一般分離方 法分離。此同質物或同質物混合物可替代銅酞菁_四_讀化 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 18 477791 A75. Description of the invention (14), and the present invention therefore also relates to a method for manufacturing a structural color photograph or color filter, characterized in that a positive or negative resist containing a formula ⑴ colorant is irradiated with a pattern and developed and heat-treated, wherein, The heat treatment can occur at the time of irradiation and development, or after dysprosium, and the heat is transformed into a toner of formula ⑴, where Z represents c2 · Cl2 eutectic-OH, C2_Cu eutectic-SH or C2-Clj eutectic Gu 2 . The following examples are intended to illustrate the present invention and are not intended to limit the scope (unless otherwise specifically noted, here,%, all refer to weight 0/0: MAL: with kpg-stirrer, reflux condenser, In a 2.5-liter flask with a built-in thermometer, a dropping funnel, and an N2 top-filler, freshly prepared copper phthalocyanine-tetra-sulfonated gas (prepared according to Example 98 of Wo98 / 45756, containing 30% Copper phthalocyanine-tri · sulfonated gas) was dissolved in liter of tetrahydrofluoride THF. At 10 ° (:, 63 4 g of ethanolamine in 100 ml of THF was added dropwise to this blue solution. This blue The suspension was stirred for 3 hours and then refluxed for 17 hours, after which the dissolved matter was concentrated with a rotary evaporator at 50 ° C under vacuum. The residue was suspended in 1 liter of dilute hydrochloric acid (1M) and stirred for 30 minutes. . Then filter, wash with 750 ml of water and dry overnight at 50c / 160m. 77g of blue powder will be obtained. Printed element analysis of employee cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [%] (C39 4H34 5N " 7On ″ s3 7Cu · 1.3H20) Theoretical value: C 44.85 H 3.54 N 15.53 S 11.25 Calculated value, C45.10 Η 3.8 3 N 15.46 S1123 uses the method described in Example 1 of W098 / 45756, but uses a smaller amount of gas sulfonic acid, so it is easier to obtain a mixture of compounds with different numbers of sulfo groups. Thus, there are 1 to 3 sulfo groups The compound can be separated by general separation methods as required. This homogeneous substance or mixture of homogeneous substances can replace copper phthalocyanine_ 四 _ 读 化 This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 18 477791 A7

經濟部智慧財產局員工消費合作社印製 五、發明說明（l5 ) 氯，作為起始物使用，而能獲可媲比的結果。 MA1·在備有kpg-攪拌器，迴流冷凝器，内置溫度 計’滴液漏斗以及Νπ上方充注器的一 1升的燒瓶中，將 83.4g的乙二胺溶於1〇〇毫升的thf中。將溶於28·0毫升的 THF中之17.36 mMol之新鮮製備成的銅酞菁-四_磺化氣（ 依W098/45756的實例1製備，含30%銅酞菁_三_磺化氣）。 在從20至25°C溫度下，滴加到黃色溶液内。此反應混合物 被擾拌2 %小時，然後在5〇〇c及真空下，以旋轉揮發器蒸 掉溶劑。濃稠藍綠懸浮液再混以7〇〇毫升的丙酮，並攪拌i 5 分鐘。接著過濾，並以丙酮洗滌直到濾液無色為止。濾餅 在50QC/160 m巴乾燥而獲得7g的藍色粉末。 元素分析[%] (C39 4H38 2N15 407 4S3 7Cu · 6H20) 理論值·· C 41.65 H 4.45 N 18.99 S 10.44 求得值；C 42.26 H 4.62 N18.il S 9.84 姓M :在備有KPG-攪拌器，内置溫度計，滴液漏斗 以及N2·上方充注器的一！升的燒瓶中，將122 5§的14•二 胺基·丁烧溶於100毫升的THF中。將溶於280毫升的THF 中之17.36 mMol之新鮮製備成的銅酞菁-四_磺化氣（依 W098/45756的實例1製備，含30%銅酞菁-三·績化氣）。在 從20至25QC溫度下，滴加到此溶液内。此反應混合物被授 拌2 %小時，然後在50°C及真空下，以旋轉揮發器蒸掉溶 劑。藍色油性殘留物再混以700毫升的丙酮，並授拌15分 鐘。接著過濾，並以丙酮洗滌直到濾液無色為止。濾餅在 50°C/160 m巴乾燥而獲得8.5g的藍色粉末。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------— — — — — — ·1111111 ^« — — — — — 1 — (請先閱讀背面之注意事項再填寫本頁) 19 477791 A7 B7 五、發明說明（16 ) 元素分析[%] (C46.8H53N15 4()7.483 7CU · 5H2〇) 理論值：C 45.92 Η 5.21 Ν 17.66 S 9.78 求得值；C 46.25 Η 4.78 Ν 16.45 S 9.61 例A4 ：在備有KPG-攪拌器，内置溫度計，滴液漏斗 以及N2-上方充注器的一 1升的燒瓶中，將i〇3.43g(0.89Mol) 的1·6-二胺基-己烷溶於300毫升的THF中。將溶於100毫升 的THF中之11·12 mMol之新鮮製備成的銅酞菁-四-磺化氣 (依W098/45756的實例1製備’含30%銅醜菁-三-確化氯） 。在從20至25°C内部溫度下，滴加到此懸浮液内。此反應 混合物被攪拌2½小時，然後在50。(：及真空下，以旋轉揮 發器蒸掉溶劑。藍色糊狀殘留物再混以700毫升的丙酮， 並攪掉15分鐘。接著過濾，並以丙酮洗滌直到濾液無色為 止。濾餅在50。(：/160 m巴乾燥而獲得2.3g的藍色粉末。 元素分析[%] (C54 8H67 8N15.407 4S3.7Cii · 6H20) 理論值：C 48.45 Η 5.99 Ν 16.05 S 8.83 求得值；C 47.94 Η 5.91 Ν 15.29 S 9.49 例Α5 •在備有迴流冷凝裔’内部溫度計，乱氣上方 充注為’ KPG稅摔為和輩狀加熱器的一 250毫升的多頸燒 瓶中，將在150 ml三氯苯的12.3g的4-磺基-酞酸，4.0g氣 化銅（II)，l，0gl，8-二氮雙環[5.4.0]十一-7-烯（DBU)和 30g 尿素加入。此反應溶液慢慢地在下加熱，接著迴流3 小時。此藍色懸浮液被冷卻到23。(：，過濾並以400 ml甲苯 洗務。遽餅在50QC/160 m巴乾燥，並立即在氬氣下，混以 65.lg五氯化碳，在150。(：下加熱，並在此溫度下授拌24小 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先M讀背面之注意事項再 丨裝--- 本頁) •線. 經濟部智慧財產局員工消費合作社印製 20 79 7 47 經濟部智慧財產局員工消費合作社印製 A7 __B7_ 五、發明説明（） 17 第88116202號專利申請案說明書修正頁 修正日期：90年8月 時。接著，多餘的五氣化磷在真空下，藉由蒸餾裝置在120 °C的水浴以及55 GC的頭餾溫度蒸掉，而承接容器以乾冰冷 卻。蒸餾殘留物再混以500 ml的水，過濾並以500 ml的水 洗滌。在備有迴流冷凝器，滴液漏斗，内部溫度計，氮氣 上方充注器，KPG攪拌器之500毫升的燒瓶中，將濾餅懸浮 於130毫升的THF中，且以滴流方式，混以在30毫升的THF 中之9.2g乙醇胺。濃稠的懸浮液再以100毫升的THF稀釋， 迴流加熱並攪拌20小時。接著，此藍色懸浮液在23Y下被 冷卻而溶劑被傾倒出。殘留物被混以200毫升的水，並攪拌 30分鐘。過遽懸浮液，並以200毫升的水洗蘇，以及在 50QC/160 m巴乾燥。而獲得6.3g的藍色粉末。 例A6 ：將105毫升的氯磺酸滴加到25.0g的銅酞菁中， 而冷卻的溫度係以最高為50QC的冰浴來維持。然後在45分 鐘内加熱到145QC。在3½小時後冷卻到80QC，接著，在25 分鐘内分批混以總量為32乃毫升的亞硫醯二氯。經過3 %小 時在80°-85°C下，以及在23°C下16小時後，反應混合物被 置入到4升的冰水。沉殿出的產物被過濾，以4升的冰水洗 滌並在空氣中乾燥30分鐘。 所得藍色糊狀物被溶於200毫升的四氫呋喃。60毫升的 乙醇胺溶液，在30QC冷卻下，45分鐘内，被滴加到200毫升 的四氫呋喃内。然後，反應混合物在迴流下加熱1 6小時， 並冷卻到230^，並在減壓下揮發。在加入1.5升的稀鹽酸 (0.5M)後，過濾沈澱，並以0.5升的稀鹽酸洗滌，並 本紙張尺度適用中國國家標準（CNS ) A4規格（210'乂 297公釐） I--------种本------、玎------線. (請先閱讀背面之注意事項再填寫本頁) 21 477791 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 A7 B7 五、發明說明（l8 ) 在95QC/130 m巴下揮發。如此可獲得42.0g之所欲的顏料 元素分析[%] (C4()H36N12012S4Cu · 4H20) 理論值：C 43.18 Η 3.70 N 15.11 S11.53 Cu5.71 H20 4.00 求得值；C 43.38 Η 3.64 N 14.65 S10.99 Cu5.65 H20 3.96 MAZ :進行類似例A6的程序，惟使用鈷酞菁以代替 銅欧菁。 例A8 :進行類似例A6的程序，惟使用鋅欧菁以代替 銅欧菁。 M-A9 :進行類似例A6的程序，惟使用銅萘酞菁以代 替銅酞菁。 M.A1Q :進行類似例A6的程序，惟使用五氣銅敌菁同 分異構物混合物以代替銅酜菁。 例All ：進行類似例A5的程序，惟使用3_苯氧基_醜 酸以代替 4-硫-酞酸。UV/VIS(CH2C12): Amax=^Unm 例A12 ：進行類似例A10的程序，惟使用3_(/5_萘氧笑 )-酞酸以代替3-苯氧基-酞酸。UV/VlS(cii Cl 3 2^a2/· A max =715nm MA12:進行類似例All的程序，惟使用3_苯硫基_酞 酸以代替3-苯氧基-酞酸。 例A14 ：進行類似例A12的程序，惟使用英辟美 )-敵酸以代替3-(/3-萘氧基）-献酸。 (請先閱讀背面之注意事項再填寫本頁) -------:—訂--------線秦 22 - 477791 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（I9 ) 例B1 :在備有滴流承接器，氮氣上方充注器的一 2,5 升的燒瓶中，將例A1所得之154g的化合物置入到1，5升的 THF中，並以KPG攪拌器攪拌19小時，接著分批將23 g60% 的氯化鈉加入並再次在23QC下攪拌24小時。接著，將在300 毫升的THF内的314,52g的二叔丁基二碳酸鹽滴加入，並 在23°C下攪拌此懸浮液24小時。令此溶液置放65小時。此 反應混合物接著被過濾器過濾，然後在40QC及真空下，以 旋轉揮發器濃縮濾出物。此藍色糊狀殘留物被懸浮在1升 的己烷中，過濾並以己烷洗滌殘留物。此粉狀濾餅被THF 所取走，並以此作為經過矽膠的洗液而過濾。在40QC及真 空下，濃縮濾出物而得藍色濕潤固体，被懸浮在1升的己 烷中，並以己烷洗滌再度過濾並在23°C/160 m巴過夜乾燥 。而獲得40g的藍色粉末。 元素分析[%] 理論值·· C 49.06 Η 4.67 N 11.44 S8.73 021.78Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (15) Chlorine is used as a starting material with comparable results. MA1 · In a 1 liter flask equipped with a kpg-stirrer, a reflux condenser, a built-in thermometer 'dropping funnel, and a top-filler Nπ, 83.4 g of ethylenediamine was dissolved in 100 ml of thf . Freshly prepared copper phthalocyanine-tetra-sulfonated gas (17.36 mMol) dissolved in 28.0 ml of THF (prepared according to Example 1 of W098 / 45756, containing 30% copper phthalocyanine_tri-sulfonated gas) . Add dropwise into the yellow solution at a temperature from 20 to 25 ° C. The reaction mixture was stirred for 2% hours, and then the solvent was distilled off at 500 ° C under a rotary evaporator. The thick blue-green suspension was mixed with 700 ml of acetone and stirred for 5 minutes. It was then filtered and washed with acetone until the filtrate was colorless. The filter cake was dried at 50 QC / 160 mbar to obtain 7 g of blue powder. Elemental analysis [%] (C39 4H38 2N15 407 4S3 7Cu · 6H20) Theoretical value · C 41.65 H 4.45 N 18.99 S 10.44 Calculated value; C 42.26 H 4.62 N18.il S 9.84 Surname M: KPG-Agitator is available , Built-in thermometer, dropping funnel and one of the N2 · top filler! In a 1 liter flask, 122 5 § of 14 · diamino · butane was dissolved in 100 ml of THF. Freshly prepared copper phthalocyanine-tetra-sulfonated gas (prepared according to Example 1 of W098 / 45756, containing 30% copper phthalocyanine-trifluorocarbon) was dissolved in 280 ml of 17.36 mMol in THF. Add dropwise to this solution at a temperature from 20 to 25 QC. The reaction mixture was stirred for 2% hours, then the solvent was evaporated off at 50 ° C under vacuum using a rotary volatilizer. The blue oily residue was mixed with 700 ml of acetone and mixed for 15 minutes. It was then filtered and washed with acetone until the filtrate was colorless. The filter cake was dried at 50 ° C / 160 mbar to obtain 8.5 g of a blue powder. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) --------- — — — — — 1111111 ^ «— — — — — 1 — (Please read the note on the back first Please fill in this page again for matters) 19 477791 A7 B7 V. Description of the invention (16) Elemental analysis [%] (C46.8H53N15 4 () 7.483 7CU · 5H2〇) Theoretical value: C 45.92 Η 5.21 Ν 17.66 S 9.78 Find the value; C 46.25 Η 4.78 Ν 16.45 S 9.61 Example A4: In a 1 liter flask equipped with KPG-stirrer, built-in thermometer, dropping funnel, and N2-upper filler, charge 〇3.43g (0.89Mol) of 1 · 6-diamino-hexane was dissolved in 300 ml of THF. A freshly prepared copper phthalocyanine-tetra-sulfonated gas (prepared according to Example 1 of W098 / 45756 'containing 30% copper cyanine-tri-confirmed chlorine) was prepared by dissolving 11 · 12 mMol in 100 ml of THF. Dropwise into this suspension at an internal temperature from 20 to 25 ° C. The reaction mixture was stirred for 2½ hours and then at 50 ° C. (: Under vacuum, use a rotary evaporator to evaporate the solvent. The blue paste residue was mixed with 700 ml of acetone and stirred for 15 minutes. Then filtered and washed with acetone until the filtrate was colorless. The filter cake was at 50 (:: / 160 m bar dried to obtain 2.3 g of blue powder. Elemental analysis [%] (C54 8H67 8N15.407 4S3.7Cii · 6H20) Theoretical value: C 48.45 Η 5.99 Ν 16.05 S 8.83 Calculated value; C 47.94 Η 5.91 Ν 15.29 S 9.49 Example A5 • In a 250-ml multi-necked flask equipped with a reflux condenser 'internal thermometer and turbulent gas, filled with' KPG tax 'and a multi-stage heater, will be placed in 150 ml 12.3 g of 4-sulfo-phthalic acid of trichlorobenzene, 4.0 g of copper (II) gasification, 1.0 g, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 30 g of urea Add. The reaction solution is slowly heated under reflux, followed by refluxing for 3 hours. The blue suspension is cooled to 23. (:, filtered and washed with 400 ml toluene. The cake is dried at 50QC / 160 mbar and immediately Under argon, mix with 65.lg of carbon pentachloride and heat at 150. (: and heat at this temperature for 24 hours. This paper size is applicable to Chinese national standards. (CNS) A4 size (210 X 297 mm) (Please read the precautions on the back before loading --- this page) • Line. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 20 79 7 47 Wisdom of the Ministry of Economic Affairs Printed by A7 __B7_ of the Consumer Cooperatives of the Property Bureau V. Invention Description (17) No. 88116202 Patent Application Specification Revised Page Revision Date: August 1990. Then, the excess phosphorus pentafluoride is under vacuum through a distillation device Evaporate in a 120 ° C water bath and a head distillation temperature of 55 GC, and the receiving container is cooled with dry ice. The distillation residue is mixed with 500 ml of water, filtered and washed with 500 ml of water. In a reflux condenser, Dropping funnel, internal thermometer, nitrogen top-filler, KPG stirrer in a 500 ml flask, the filter cake was suspended in 130 ml of THF, and in a trickle mode, mixed with 9.2 in 30 ml of THF g ethanolamine. The thick suspension was diluted with 100 ml of THF, heated at reflux and stirred for 20 hours. Then, the blue suspension was cooled at 23Y and the solvent was decanted. The residue was mixed with 200 ml of water And stir for 30 minutes. The suspension was washed with 200 ml of water and dried at 50 QC / 160 mbar. 6.3 g of blue powder was obtained. Example A6: 105 ml of chlorosulfonic acid was added dropwise to 25.0 g of copper phthalocyanine, The cooling temperature is maintained in an ice bath up to 50 QC. It is then heated to 145 QC in 45 minutes. After 3½ hours, it was cooled to 80 QC and then batchwise mixed with a total of 32 nanoliters of thionyl chloride in 25 minutes. After 3% hours at 80 ° -85 ° C and 16 hours at 23 ° C, the reaction mixture was placed in 4 liters of ice water. The product from Shen Dian was filtered, washed with 4 liters of ice water and dried in air for 30 minutes. The resulting blue paste was dissolved in 200 ml of tetrahydrofuran. 60 ml of ethanolamine solution was added dropwise to 200 ml of tetrahydrofuran within 45 minutes under 30QC cooling. Then, the reaction mixture was heated under reflux for 16 hours, cooled to 230 ° C, and evaporated under reduced pressure. After adding 1.5 liters of dilute hydrochloric acid (0.5M), filter the precipitate and wash with 0.5 liters of dilute hydrochloric acid. The paper size applies the Chinese National Standard (CNS) A4 specification (210 '乂 297 mm) I --- ----- Seeds ------, 玎 ------ line. (Please read the notes on the back before filling out this page) 21 477791 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (18) Volatile at 95QC / 130 mbar. In this way, 42.0g of the desired elemental analysis of the pigment can be obtained [%] (C4 () H36N12012S4Cu · 4H20) Theoretical value: C 43.18 Η 3.70 N 15.11 S11.53 Cu5.71 H20 4.00 Calculated value; C 43.38 Η 3.64 N 14.65 S10.99 Cu5.65 H20 3.96 MAZ: A procedure similar to that of Example A6 was performed, except that cobalt phthalocyanine was used instead of copper eucyanine. Example A8: A procedure similar to that of Example A6 was performed, except that zinc cyanine was used instead of copper cyanine. M-A9: A procedure similar to that of Example A6 was performed, except that copper naphthalocyanine was used instead of copper phthalocyanine. M.A1Q: A procedure similar to that of Example A6 was performed, except that a mixture of five gas copper dicyanine isomers was used instead of copper perylene. Example All: A procedure similar to that of Example A5 was performed, except that 3_phenoxy_ugly acid was used instead of 4-thio-phthalic acid. UV / VIS (CH2C12): Amax = ^ Unm Example A12: A procedure similar to that of Example A10 was performed, except that 3 _ (/ 5_naphthyloxy) -phthalic acid was used instead of 3-phenoxy-phthalic acid. UV / VlS (cii Cl 3 2 ^ a2 / · A max = 715 nm MA12: A procedure similar to that of All was performed, except that 3-phenylthio-phthalic acid was used instead of 3-phenoxy-phthalic acid. Example A14: Performed The procedure of Example A12 is similar, except that Inpremiex) -antimonylic acid is used instead of 3-(/ 3-naphthyloxy) -donate. (Please read the precautions on the back before filling this page) -------:-Order -------- Xin Qin 22-477791 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs Description of the Invention (I9) Example B1: In a 2,5 liter flask equipped with a drip receiver and a nitrogen overfiller, put 154 g of the compound obtained in Example A1 into 1,5 liters of THF. It was stirred with a KPG stirrer for 19 hours, then 23 g of 60% sodium chloride was added in portions and stirred again at 23QC for 24 hours. Next, 314,52 g of di-tert-butyl dicarbonate in 300 ml of THF was added dropwise, and the suspension was stirred at 23 ° C for 24 hours. This solution was allowed to stand for 65 hours. The reaction mixture was then filtered through a filter and the filtrate was concentrated on a rotary evaporator at 40 ° C and under vacuum. This blue paste-like residue was suspended in 1 liter of hexane, filtered and the residue was washed with hexane. This powdery cake was taken away by THF and filtered as a silicone washing lotion. At 40QC and vacuum, the filtrate was concentrated to give a blue moist solid, suspended in 1 liter of hexane, washed with hexane, filtered again, and dried overnight at 23 ° C / 160 mbar. 40 g of blue powder were obtained. Elemental analysis [%] Theoretical value · C 49.06 Η 4.67 N 11.44 S8.73 021.78

Cu4.33 求得值；C 49.57 Η 4.90 N 11.62 S8.19 Ο 21.02Cu4.33 Calculated value; C 49.57 Η 4.90 N 11.62 S8.19 Ο 21.02

Cu5.02 TGA(加熱速率10°C/Min):分解轉變點=160 °C ;它回 復到依例A1的產物。 UV/VIS(NMP): λ max=672nm9 ε = 178544. 例Β2 ··在一 250毫升的多頸燒瓶中，在氬氣下將例A2 所得之7g的化合物置入到100毫升的THF中，並攪拌24小 時，接著將〇,32g的N，N-二甲基-4-胺基苯胺（DMAP)加入以 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 23 — — — — — — — — — — — — — · I I I I I I I .1^ ·1111111· (請先閱讀背面之注意事項再填寫本頁) 477791 A7 B7 五、發明說明（20 ) (請先閱讀背面之注意事項再填寫本頁) 及在其後的5小時加入17,2g的二叔丁基二碳酸鹽，並在 23 QC下擾拌此懸浮液21小時。然後經過石夕藻土過濾，以thf 洗務，並在40°C及真空下，濃縮濾出物。此藍色殘留物被 溶於30毫升的二氣甲烧中，再混以15毫升的***並滴加到 300己烧，其後，將生成的懸浮液過濾，並以己烷洗滌。 此藍色濾餅被THF所溶解，並以此作為經過矽膠的洗液而 過濾。在40°C及真空下，以旋轉揮發器蒸掉此溶劑。藍色 殘留物，被懸浮在己烷中，過濾，並在23°C/160 m巴過夜 乾燥。而獲得2.8g的藍色粉末。 TGA(加熱速率i〇°c/Min):分解轉變點= 166 °C ;它回 復到依例A2的產物。 UV/VIS(NMP)： λ max=673nm? a = 88634. 經濟部智慧財產局員工消費合作社印製 M.B3 :在一 250毫升的多頸燒瓶中，在氬氣下將例A3 所得之8.5g的化合物置入到11〇毫升的THF中，並攪拌24 小時，接著將〇,35g的DMAP加入以及在其後的5小時加入 17,2g的二叔丁基二碳酸鹽，並在23°C下攪拌此懸浮液21 小時。然後經過矽藻土過濾，以THF洗滌，並在40QC及真 空下’濃縮濾、出物。此藍色殘留物被溶於3 0毫升的二氣甲 烷中，再混以15毫升的***並滴加到300毫升的己烷，其 後’將生成的懸浮液過濾、，並以己院洗務。此藍色濾、餅被 THF所溶解，並以此作為經過矽膠的洗液而過濾。在4〇〇C 及真空下，以旋轉揮發器蒸掉此溶劑。藍色殘留物被溶於 15毫升的二氯曱烧中，再混以7毫升的***並以滴加方式 加到200毫升的己烧中，其後，將生成的懸浮液過濾，並 24 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ♦ 經濟部智慧財產局員工消費合作社印製 477791 - A7 B7 五、發明說明（21 ) 以己烷洗滌。此濾餅在23°C/160 m巴下過夜乾燥。而獲得 1.3g的藍色粉末。 TGA(加熱速率10QC/Min):分解轉變點=166 °C ;它回 復到依例A3的產物。 ‘ UV/VIS(NMP): λ max=673nm9 ε = 89510. 例Β4 ：在一 250毫升的多頸燒瓶中，在氬氣下將例A4 所得之2.2g的化合物置入到30毫升的THF中，並攪拌8小 時，接著將83g的DMAP以及4,47g的二叔丁基二碳酸鹽加 入，並攪拌此懸浮液17小時。然後以THF作為洗液經過矽 藻土過濾，並在40QC及真空下，以旋轉揮發器蒸掉此溶劑 。。此藍色殘留物被溶於200毫升的己烷，過濾，並以己 烷洗滌。此濾餅在23QC/160 m巴下過夜乾燥。由於TGA被 稱為未純化物質，故此藍色粉末被溶於3毫升的二氣甲烷 中，再混以1.5毫升的***並以滴加方式加到30毫升的己 烷中，接著過濾，並在23°C/160 m巴下乾燥。而獲得0.4g 的藍色粉末。 元素分析[%] 理論值：C 54.03 Η 6·20 N 13.26 S7.59 求得值；C 53.08 Η 5·77 Ν 12.25 S7.38 TGA(加熱速率10°C/Min):分解轉變點=168 °C ;它回 復到依例A4的產物。 UV/VIS(NMP): λ max=672nm, ε =98871. 例Β5 ：在一備有攪拌器，溫度計和一氮氣入口之1·5 升的反應瓶中，在激烈的攪拌下，將例Α6所得之20.0g的 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 25 ------I------ 裝 — II 訂· — — — — —---線 (請先閱讀背面之注意事項再填寫本頁) 477791 A7 B7 五、發明說明（22 ) 化合物懸浮於2.7g的二甲基胺基苯胺，500毫升的四氫•吹 喃和40毫升的苯胺中。在23°C下，加入41，〇g的二叔丁基 焦碳酸鹽。此反應混合物進一步被擾拌20小時。接著，在 23QC/200 m巴下濃縮直到約50毫升的容積為止。藉著1升 的正己烧的加入，沉澱出一深藍色的沉澱。將此沉澱濾、出 並分批地以總量為1升的正己烷徹底洗滌。過濾後殘留物 被溶於600毫升的的四氫呋喃。此溶液經矽膠過濾，而矽 膠被再以500毫升的四氫呋喃沖洗。此濾出物在23°C/200 m 巴下被濃縮後，殘留物被500毫升的正己烧所收取並過渡 ，殘留物再以正己烷洗滌過濾。並在23QC/200 m巴下乾燥 。而獲得26.6g的純鈷藍色粉末，具有以下的推定式： (請先閱讀背面之注意事項再填寫本頁)Cu5.02 TGA (heating rate 10 ° C / Min): decomposition transition point = 160 ° C; it returns to the product according to Example A1. UV / VIS (NMP): λ max = 672nm9 ε = 178544. Example B2 · In a 250 ml multi-necked flask, put 7 g of the compound obtained in Example A2 into 100 ml of THF under argon, It was stirred for 24 hours, and then 0.32 g of N, N-dimethyl-4-aminoaniline (DMAP) was added to the Chinese paper standard (CNS) A4 (210 X 297 mm) at this paper scale. 23 — — — — — — — — — — — — — — IIIIIII .1 ^ · 1111111 · (Please read the notes on the back before filling this page) 477791 A7 B7 V. Description of the invention (20) (Please read the notes on the back first Please fill in this page again) and add 17.2 g of di-tert-butyl dicarbonate for the next 5 hours and stir the suspension for 21 hours at 23 QC. It was then filtered through celite, washed with thf, and the filtrate was concentrated under vacuum at 40 ° C. This blue residue was dissolved in 30 ml of dichloromethane, mixed with 15 ml of diethyl ether and added dropwise to 300 hexane, after which the resulting suspension was filtered and washed with hexane. This blue filter cake was dissolved in THF and filtered as a silica gel washing solution. At 40 ° C and under vacuum, the solvent was distilled off with a rotary evaporator. The blue residue was suspended in hexane, filtered and dried overnight at 23 ° C / 160 mbar. And 2.8 g of blue powder was obtained. TGA (heating rate i ° C / Min): decomposition transition point = 166 ° C; it reverts to the product according to Example A2. UV / VIS (NMP): λ max = 673nm? A = 88634. M.B3 printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs: In a 250 ml multi-necked flask, 8.5 obtained from Example A3 under argon g of the compound was put into 110 ml of THF and stirred for 24 hours, then 0.35 g of DMAP was added, and 17.2 g of di-tert-butyl dicarbonate was added 5 hours later, at 23 ° The suspension was stirred at C for 21 hours. It was then filtered through diatomaceous earth, washed with THF, and concentrated and filtered at 40QC under vacuum. This blue residue was dissolved in 30 ml of digas methane, mixed with 15 ml of diethyl ether and added dropwise to 300 ml of hexane, after which the resulting suspension was filtered and washed in the bath. Business. The blue filter and cake were dissolved in THF and filtered as a silica gel washing solution. The solvent was distilled off under a vacuum at 400 ° C with a rotary evaporator. The blue residue was dissolved in 15 ml of dichloromethane, and then mixed with 7 ml of diethyl ether and added dropwise to 200 ml of hexane. After that, the resulting suspension was filtered, and Paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) ♦ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 477791-A7 B7 V. Description of the invention (21) Wash with hexane. This filter cake was dried overnight at 23 ° C / 160 mbar. Instead, 1.3 g of a blue powder was obtained. TGA (heating rate 10QC / Min): decomposition transition point = 166 ° C; it returns to the product according to Example A3. 'UV / VIS (NMP): λ max = 673nm9 ε = 89510. Example B4: In a 250 ml multi-necked flask, put 2.2 g of the compound obtained in Example A4 into 30 ml of THF under argon. And stirred for 8 hours, then 83 g of DMAP and 4,47 g of di-tert-butyl dicarbonate were added, and the suspension was stirred for 17 hours. Then use THF as a washing solution to filter through diatomaceous earth, and evaporate the solvent with a rotary volatilizer under 40QC and vacuum. . This blue residue was dissolved in 200 ml of hexane, filtered, and washed with hexane. This filter cake was dried overnight at 23 QC / 160 mbar. Since TGA is called an unpurified substance, the blue powder was dissolved in 3 ml of digas methane, mixed with 1.5 ml of diethyl ether and added dropwise to 30 ml of hexane, followed by filtration, and Dry at 23 ° C / 160 m bar. 0.4 g of blue powder was obtained. Elemental analysis [%] Theoretical value: C 54.03 Η 6 · 20 N 13.26 S7.59 Calculated value; C 53.08 Η 5.77 Ν 12.25 S7.38 TGA (heating rate 10 ° C / Min): decomposition transition point = 168 ° C; it reverts to the product of Example A4. UV / VIS (NMP): λ max = 672nm, ε = 98871. Example B5: In a 1.5-liter reaction bottle equipped with a stirrer, thermometer, and a nitrogen inlet, under intense stirring, apply Example A6 The obtained paper size of 20.0g is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 25 ------ I ------ Packing — II order · — — — — —-- -Line (please read the precautions on the back before filling this page) 477791 A7 B7 V. Description of the invention (22) The compound is suspended in 2.7g of dimethylaminoaniline, 500ml of tetrahydro • bran and 40ml of In aniline. At 23 ° C, 41.0 g of di-tert-butyl pyrocarbonate was added. The reaction mixture was further stirred for 20 hours. Then, it was concentrated at 23 QC / 200 m bar until a volume of about 50 ml. With the addition of 1 liter of n-hexane, a dark blue precipitate precipitated. This precipitate was filtered, washed out and washed thoroughly in portions with a total of 1 liter of n-hexane. The residue after filtration was dissolved in 600 ml of tetrahydrofuran. This solution was filtered through silica gel, which was then rinsed with 500 ml of tetrahydrofuran. After the filtrate was concentrated at 23 ° C / 200 m bar, the residue was collected by 500 ml of n-hexane and transitioned. The residue was washed with n-hexane and filtered. And dried at 23QC / 200 m bar. And obtained 26.6g of pure cobalt blue powder, with the following inferred formula: (Please read the precautions on the back before filling this page)

經濟部智慧財產局員工消費合作社印製 例B6 :類似例B5的方式從依例A7的產物得到具有以 下構造式的產物： 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 26 477791 A7 B7The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed Example B6: A product similar to Example B5 was obtained from the product according to Example A7 with the following structural formula: This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ) 26 477791 A7 B7

五、發明說明（23 ) 元素分析[%] (c65h76n12o22s4c〇) 理論值：C 49.90 Η 4·90 N 10.74 S8.20 Co3.77 求得值；C 49.08 Η 4.66 N 11.20 S6.86 Co3.39 熱解重量分析（〇-400°C，10°C/Min) 理論值： 重量損失 32.0% 求得值； 重量損失 30.1% (最大值係在 158 °C) 例B7 :類似例B5的方式從依例A9的產物得到具有以 下構造式，而產量佳的產物： -------------裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁)V. Description of the invention (23) Elemental analysis [%] (c65h76n12o22s4c〇) Theoretical value: C 49.90 Η 4.90 N 10.74 S8.20 Co3.77 Calculated value; C 49.08 Η 4.66 N 11.20 S6.86 Co3.39 heat Solution weight analysis (0-400 ° C, 10 ° C / Min) Theoretical value: 32.0% of weight loss Calculated value; 30.1% of weight loss (maximum value is 158 ° C) Example B7: The method similar to Example B5 follows The product of Example A9 yields a product with the following structural formula and good yield: ------------- install -------- order --------- line ( (Please read the notes on the back before filling out this page)

本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 27 477791 A7 B7 五、發明說明（24 ) 熱解重量分析（0-400。(：，10°C/Min):最大值係在159This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 27 477791 A7 B7 V. Description of the invention (24) Pyrolysis weight analysis (0-400. (:, 10 ° C / Min): Max. Value is 159

°C 姓Μ :將例A6所得之5 .Og的化合物懸浮於140毫升的 四氫呋喃的懸浮液中被加入〇.66g的4-二曱基胺基苯胺和 U，4§的二叔丁基焦碳酸鹽。此反應混合物在23。(：下，被 擾拌16小時，並經由40g Hyflo Super-Cel®，接著再經由140 亳升的矽膠過濾。以600毫升的的四氫呋喃洗滌過濾器後 ，將溶液以減壓蒸餾蒸乾。以500毫升的正己烷沉澱出產 物，過濾，再以正己烷洗滌，並在20°C/130 m巴下乾燥。 而獲得7.4g的藍色粉末，其具有以下的構造式：° C Surname M: 5.0 g of the compound obtained in Example A6 was suspended in a suspension of 140 ml of tetrahydrofuran, and 0.66 g of 4-diamidinoaminoaniline and U, 4§ di-tert-butyl coke were added. Carbonate. This reaction mixture was at 23. (:, Stirred for 16 hours, filtered through 40g Hyflo Super-Cel®, and then filtered through 140 liters of silica gel. After washing the filter with 600 ml of tetrahydrofuran, the solution was distilled to dryness under reduced pressure. The product was precipitated from 500 ml of n-hexane, filtered, washed with n-hexane, and dried at 20 ° C / 130 m. To obtain 7.4 g of blue powder, which has the following structural formula:

so2n (請先閱讀背面之注意事項再填寫本頁) ο- 〇 元素分析[%] (C8GH1()()N12028S4Cu · 0·5Η2Ο) 經濟部智慧財產局員工消費合作社印製 理論值·· C 51.15 Η 5.42 Ν 8.95 S6.83 Cu3.38 H2〇 0.48 求得值；C 50.92 Η 5.04 Ν 9·66 S7.00 Cu3.59 Η2〇 0.48 UV/VIS(CH2C12): λ max=672nm( ε =140500). 熱解重量分析（0-400°C，10QC/Min) 理論值： 重量損失 42.8% 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 B7 五、 發明說明（25 求得值 177 〇〇 (最大值係在 具有以 MB9 ：類似例B8的方式從依例Aio的產物彳胃到 下構造式，而產量佳的產物： Q 〇so2n (Please read the notes on the back before filling this page) ο- 〇 Elemental analysis [%] (C8GH1 () () N12028S4Cu · 0 · 5Η2Ο) Theoretical value printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs · C 51.15 Η 5.42 Ν 8.95 S6.83 Cu3.38 H2〇0.48 Calculated value; C 50.92 Η 5.04 Ν 9.66 S7.00 Cu3.59 Η2 0.40 UV / VIS (CH2C12): λ max = 672nm (ε = 140500) Pyrolysis weight analysis (0-400 ° C, 10QC / Min) Theoretical value: Weight loss 42.8% This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) A7 B7 V. Description of the invention (25 Calculate a value of 177 〇〇 (The maximum value is obtained in the manner of MB9: similar to Example B8 from the stomach of the product of Example Aio to the lower structural formula, and the product with good yield: Q 〇

ό Ν αό Ν α

N— Cu—NN— Cu—N

Cu-Cu-

Ν X) ΟΝ X) Ο

Ο so2n ο J4 經濟部智慧財產局員工消費合作社印製Ο so2n ο J4 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

本紙張尺度適用中國國家標準（CNS)A4規格（21〇 χ 297公釐） 元素分析[%] (C79.4H10().5Cl5N15.4O29jSuCu · 1·6Η20) 理論值：C44.89 Η4·92 N10.15S5.58Cu2.99C1 8.34 Η20 1.6 求得值；C45.61 Η4.58 N10.29S6.72Cu3.15Cl 9.14 Η20 1.6 UV/VIS(CH2C12): λ max=676nm( ε =75363). M31〇 :類似例Β8的方式從依例A11的產物得到具有 以下構造式的產物（同質異構物混合物）： 29 477791 A7 ______B7 五、發明說明（26 ) °C.This paper size applies the Chinese National Standard (CNS) A4 specification (21〇χ 297 mm) Elemental analysis [%] (C79.4H10 (). 5Cl5N15.4O29jSuCu · 1. · 6Η20) Theoretical value: C44.89 Η4 · 92 N10 .15S5.58Cu2.99C1 8.34 Η20 1.6 Calculated value; C45.61 Η4.58 N10.29S6.72Cu3.15Cl 9.14 Η20 1.6 UV / VIS (CH2C12): λ max = 676nm (ε = 75363). M31〇: Similar The manner of Example B8 is obtained from the product according to Example A11 with the following structural formula (isomeric mixture): 29 477791 A7 ______B7 V. Description of the invention (26) ° C.

4 UV/VIS(CH2C12)： λ max=725nm( ε =59507). 熱解重量分析（0-400。<：，liTC/Min):最大值係在176 (請先閱讀背面之注意事項再填寫本頁) M.B 11 :類似例B10的方式從依例A12的產物得到具有 以下構造式的產物：4 UV / VIS (CH2C12): λ max = 725nm (ε = 59507). Pyrogravimetric analysis (0-400. ≪:, liTC / Min): The maximum value is 176 (please read the precautions on the back first) (Fill in this page) MB 11: A product similar to Example B10 is obtained from the product according to Example A12 with the following structural formula:

經濟部智慧財產局員工消費合作社印製Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

N> so2N > so2

UV/VIS(CH2C12): λ max=715nm( ε =32644). 熱解重量分析（〇-400°C，10°C/Min):最大值係在185 30 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 斗/7791 五、 A7 ___發明說明（27 ) 例B12 ：類似例B10的方式從依例A13的產物得到其對 應的的硫醚。 例B13 ：類似例B11的方式從依例A14的產物得到其對 應的的硫醚。 · 例B14 ：以類似例B8的方式，利用二叔戊基焦碳酸鹽 得到具有以下構造式及產量佳的產物：UV / VIS (CH2C12): λ max = 715nm (ε = 32644). Pyrogravimetric analysis (0-400 ° C, 10 ° C / Min): The maximum value is 185 30 This paper standard is applicable to Chinese national standard (CNS ) A4 specification (210 X 297 mm) Dou / 7791 V. A7 ___ Description of invention (27) Example B12: The corresponding thioether was obtained from the product according to Example A13 in a manner similar to Example B10. Example B13: A corresponding thioether was obtained from the product according to Example A14 in a manner similar to Example B11. Example B14: In a manner similar to Example B8, using di-tert-amylpyrocarbonate to obtain a product with the following structural formula and good yield:

〇· so2n UV/VIS(CH2C12): λ max=672nm( ε =110205)· V0· ο- ο 4 熱解重量分析（〇-400°C，HTC/Min):最大值係在177 )C. -------------裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 例B 15 :以類似例B8的方式，利用依實施例A8的產物 得到具有以下構造式及產量佳的產物： 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公髮） 31 477791 A7 B7 經濟部智慧財產局員工消費合作社印製〇 · so2n UV / VIS (CH2C12): λ max = 672nm (ε = 110205) · V0 ο- ο 4 Thermogravimetric analysis (〇-400 ° C, HTC / Min): The maximum value is 177) C. ------------- install -------- order --------- line (Please read the precautions on the back before filling this page) Example B 15: In a similar manner to Example B8, the product according to Example A8 is used to obtain a product with the following structural formula and good yield: Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with the Chinese National Standard (CNS) A4 specification (210 X Issued by 297) 31 477791 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

•so2n 五、發明說明（28 ) p-ο-ο 元素分析[%] (C8GH1()()N12028S4Zn) 理論值：C 50.86 Η 5.44 N 8.90 S 6·79 Ζη 3·46 H20 0.94 求得值：C 51.51 Η 5.19 N10.06 S 6.79 Ζη 3.02 H20 0.94 UV/VIS(CH2C12): λ max=674nm( £ =152876). 熱解重量分析（〇-400°C，10°C/Min):最大值係在177 °C. 例 Cl :藉由 1.24gTMPHM_C樹脂（Maruka Lyncur，Mw= 5300)，0.25gTMCymel 300(氰胺公司，雙重蒸德），〇.〇55gTM Triazine A(Produits Chimiques Auxiliaires et de Synthese, Longjumeau，）和0.5g依例B1的溶性顏料溶于7.5g的環戊酮 (™OMMHTR-2D9 Olin Micro-electronic Materials, Zwijndrecht, 比利時）中而製得一配方。在經由l_0/z m過濾器過濾後， 溶液被置於3.81x3.81 cm的大號玻璃板（Corning Typ 1737) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） --------.-------------:訂·---------線赢 (請先閱讀背面之注意事項再填寫本頁) 32 W7791• so2n V. Description of the invention (28) p-ο-ο Elemental analysis [%] (C8GH1 () () N12028S4Zn) Theoretical value: C 50.86 Η 5.44 N 8.90 S 6 · 79 Znη 3 · 46 H20 0.94 Find the value: C 51.51 Η 5.19 N10.06 S 6.79 Znη 3.02 H20 0.94 UV / VIS (CH2C12): λ max = 674nm (£ = 152876). Pyrogravimetric analysis (0-400 ° C, 10 ° C / Min): Maximum It is at 177 ° C. Example Cl: With 1.24gTMPHM_C resin (Maruka Lyncur, Mw = 5300), 0.25gTMCymel 300 (cyanamide company, double steam Germany), 0.055gTM Triazine A (Produits Chimiques Auxiliaires et de Synthese, Longjumeau,) and 0.5 g of the soluble pigment according to Example B1 were dissolved in 7.5 g of cyclopentanone (™ OMMHTR-2D9 Olin Micro-electronic Materials, Zwijndrecht, Belgium) to prepare a formulation. After filtering through a l_0 / zm filter, the solution was placed on a large glass plate (Corning Typ 1737) of 3.81x3.81 cm. The paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 public love)- ------.-------------: Order · --------- Line Win (Please read the notes on the back before filling this page) 32 W7791

經濟部智慧財產局員工消費合作社印製 五Λ發明說明（29) ，以1000U/min的轉速離心，接著在100°c的加熱板上乾 燥2分鐘。此層厚約1 ·5 // m。此膜層將透過一光罩’而利 用1^11又1^-502]\/[〇燈具（500111511丨〇)進行照相照射達06.75 之久（=100mJ/cm2)，接著在加熱板上在iOMC下加熱2分鐘 。其後，以含2.38重量％的羥化四甲銨，以及1重量％Triton ®X-100(FlukaChemie AG，Buchs，瑞士）之水性溶液進行 顯影25s，此時，膜層之先前曝光區維持原狀，而與之相 1 對的未曝光區則被溶掉。最後，構圖狀的玻璃板被水噴洗 2分鐘，以空氣乾燥並在200。(：下加熱5分鐘。而得一深藍 色圖樣的膜層構造。彩色座標，依標準光源F10測定，其數 值為：χ=0·209;"·326;Υ=46·5ο/〇。 例 C2 ：藉由 0.25gTMPHM-C樹脂（Maruka Lyncur，Mw= 5300)，0.06gTMCymel 300(氰胺公司，雙重蒸餾），〇.〇lgTM Triazine A(Produits Chimiques Auxiliaires et de Synthese， Longjumeau,)和0.10g依例B1的溶性顏料溶于〇.95g的環戊 丨酮（tmOMMHTR-2D，Olin Micro-electronic Materials, Zwijndrecht，比利時）中而製得一配方。在經由0.45 // m過 濾器過濾後，溶液被置於3.81x3.81 cm的大號玻璃板 (Corning Typ 1737)，以l〇〇〇U/min的轉速離心，接著在 100QC的加熱板上乾燥1分鐘。此膜層的最大吸收值（Amax) 為669nm。在200°C下五分鐘後，最大吸收值（λ max)為662nm 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 33 -------------裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the People's Republic of China (29), centrifuge at 1000U / min, and then dry on a heating plate at 100 ° C for 2 minutes. This layer is about 1 · 5 // m thick. This film will pass through a photomask 'and use 1 ^ 11 and 1 ^ -502] \ / [〇lamp (500111511 丨 〇) for photographic irradiation for a long time of 06.75 (= 100mJ / cm2), and then on a hot plate Heat at iOMC for 2 minutes. Thereafter, development was performed with an aqueous solution containing 2.38% by weight of tetramethylammonium hydroxide and 1% by weight of Triton ® X-100 (FlukaChemie AG, Buchs, Switzerland) for 25s. At this time, the previously exposed areas of the film layer remained intact. , And the unexposed area that is opposite to it is dissolved away. Finally, the patterned glass plate was spray-washed with water for 2 minutes, air-dried and dried at 200 ° C. (: Heating for 5 minutes. The film structure of a dark blue pattern is obtained. The color coordinates are measured according to the standard light source F10, and the value is: χ = 0.209; " · 326; Υ = 46 · 5ο / 〇. Example C2: With 0.25gTMPHM-C resin (Maruka Lyncur, Mw = 5300), 0.06gTMCymel 300 (cyanamide company, double distillation), 0.01gTM Triazine A (Produits Chimiques Auxiliaires et de Synthese, Longjumeau,) and 0.10 g A soluble pigment according to Example B1 was dissolved in 0.95 g of cyclopentanone (tmOMMHTR-2D, Olin Micro-electronic Materials, Zwijndrecht, Belgium) to prepare a formula. After filtering through a 0.45 // m filter, The solution was placed on a large glass plate (Corning Typ 1737) of 3.81 x 3.81 cm, centrifuged at 1000 U / min, and then dried on a hot plate at 100 QC for 1 minute. The maximum absorption value of this film (Amax) is 669nm. After five minutes at 200 ° C, the maximum absorption value (λ max) is 662nm. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 33 ------ ------- install -------- order --------- line (please read the precautions on the back before filling this page)

Claims (1)

477791 公告本六、申請專利範圍 A8 B8 C8 D8 W曰修正477791 Announcement VI. Scope of Patent Application A8 B8 C8 D8 W Amendment A (Y)y ISO^CZ)^ 第88116202號專利申請案申請專利範圍修正本 修正曰期：90年8月 1· 一種酞菁化合物，其具有下式 ⑴，其中 Μ代表兩價金屬，氧金屬，鹵金屬或羥金屬或2 個氫原子， Α代表一殘基或,其係可為未被取 代，或被苯氧基，萘氧基，苯硫基或萘硫基所取代， X係代表一擇自由N，〇和S所組成的族中的雜原 子，其中，當X等於0或S時，m為〇，而當X等於N時， m為1， Y代表任意一不對烷化劑起反應的取代基， Ζ代表氫，Ζ’或COOB， Ζ’代表c2-c12烧伸基-n(coob)2，c2_c12烷伸基 -NHCOOB，C2-C12 院伸基-OCOOB 或 C2-C12 烧伸基 -SCOOB， X係從1至4的一數目，而y係從〇至15的一數目， 其中X和y的總和最高是等於16，且視情況而定， 八， -----------裝-------，丨訂-----— (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 Y，Z和/或z’可越多越好，相同或互異，以及A (Y) y ISO ^ CZ) ^ Patent application No. 88116202 Amendment to the scope of patent application Amendment date: August 1990 1. A phthalocyanine compound having the following formula ⑴, where M represents a divalent metal, oxygen Metal, halogen metal or hydroxy metal or 2 hydrogen atoms, A represents a residue or, its system may be unsubstituted or substituted by phenoxy, naphthyloxy, phenylthio or naphthylthio, X Represents heteroatoms in a family of optional free N, 0 and S, where m is 0 when X is equal to 0 or S, and m is 1 when X is equal to N, Y represents any unpaired alkylation Substituents that react with the agent, Z represents hydrogen, Z 'or COOB, and Z' represents c2-c12 alkylene-n (coob) 2, c2-c12 alkylene-NHCOOB, C2-C12 alkenyl-OCOOB or C2- C12 Burning base-SCOOB, X is a number from 1 to 4, and y is a number from 0 to 15, where the sum of X and y is equal to 16 at the highest, and as the case may be, eight, --- -------- Install -------, 丨 Order ------ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, The more Z and / or z 'can be, the more Ok, same or different, and -34- 477791 A8 B8 C8 D8 六、申請專利範圍 B代表具下式的基； Γ /^Rl1 或 —E_X，-L2，其中， Rl是氫或CVC6烷基， R2和各自獨立地代表匕-匕烷基 114和118各自獨立地代表匕·：烷基，被o，s或nr12 中斷之CkG烷基，未取代或被Ci-Cr烷基，Ci-Cr烷氧 基’鹵基’氰基或硝基所取代的苯基或雙苯基， Rs，R6和r7各自獨立地代表氫或cKc6烷基， R9代表氫，CKC6烷基或下式的基： 13-34- 477791 A8 B8 C8 D8 VI. The scope of patent application B represents a group with the formula: Γ / ^ Rl1 or -E_X, -L2, where R1 is hydrogen or CVC6 alkyl, and R2 and R2 each independently represent- The alkyl groups 114 and 118 each independently represent a alkyl group: an alkyl group, a CkG alkyl group interrupted by o, s, or nr12, an unsubstituted or Ci-Cr alkyl group, and a Ci-Cr alkoxy 'halo' cyano group Or nitro substituted phenyl or biphenyl, Rs, R6 and r7 each independently represent hydrogen or cKc6 alkyl, R9 represents hydrogen, CKC6 alkyl or a group of the formula: 13 或 0II -CO—R 15 經濟部智慧財產局員工消費合作社印製 Rio和Ru各自獨立地代表氫，CVC6烷基，CVC6烷氧 基，li基，氰基，硝基，N(R12)2,未被取代或被鹵基， 氰基’硝基’ C「C6烷基或烷氧基所取代的苯基， RuRn各代表CVC6烧基，R14代表氫或CVC6烷基以 及1^5代表C「C6烷基或未被取代或被Cl_c6烷基所取代 的苯基， E代表未被取代或被（:广^烷氧基，〇1-€：6烷硫基或 CrCu二烷胺基一次或多次取代之p，q_c2-c6伸烷基，其 中P和q是不同位置數目， X’代表一雜原子，其係選自由N，0和S所組成之族 -----------裝-------Ί訂--------^9. (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） -35- 1 A8B8C8D8 經濟部智慧財產局員工消費合作社印製 六、申請專利範眉 中，田X等於〇或s時，m，為〇,而當X，等於N時，m，為i ，以及 Li和L2各自獨立地代表未被取代或被^-^^烷氧基 ，(VC6院硫基，q-c^2二燒胺基，C6_Ci2芳氧基，c6_Ci2芳 硫基，C7-cls芳烷胺基或Ci2_C24二芳胺基所一次或多次 取代之 Cl_C6烷基或[-(p，，q，-c2_c6伸烷基）-Z，，_]n-Cl-c6 烧基，其中，η疋從1至1000的數目，p，和q，係不同位置 數目，各個Z”係各自獨立地代表雜原子〇，s或被 烷基所取代的N，以及c：2-C6伸烷基在其重複單位 [-C2_C6伸烧基·ζ”_]中，係相同或不同者， 以及LjuL2可為飽和或1-至1〇個不飽和，可不被中 斷或在在所欲位置被1至1〇個選自由气c=〇)_*C6H4—所 組成的族的基團所中斷，以及可不帶有或帶有丨至1〇個 另選自由鹵基，氰基和硝基所組成之族的取代基。 2 ·依申請專利範圍第1項之化合物，具有下式：Or 0II-CO-R 15 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Rio and Ru each independently represent hydrogen, CVC6 alkyl, CVC6 alkoxy, li, cyano, nitro, N (R12) 2, Unsubstituted or halo, cyano 'nitro' C6 phenyl substituted by C6 alkyl or alkoxy, RuRn each represents CVC6 alkyl, R14 represents hydrogen or CVC6 alkyl and 1 ^ 5 represents C " C6 alkyl or phenyl which is unsubstituted or substituted by Cl_c6 alkyl, E represents unsubstituted or substituted (: ^ alkoxy, 〇1- €: 6 alkylthio or CrCu dialkylamino group once or Multiple substituted p, q_c2-c6 alkyl groups, where P and q are different numbers of positions, X 'represents a heteroatom, which is selected from the group consisting of N, 0 and S -------- --- Packing ------- ΊOrder -------- ^ 9. (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specifications ( 210 X 297 public love) -35- 1 A8B8C8D8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. In the patent application, when X is equal to 0 or s, m is 0, and when X is equal to N, m, i, and Li and L2 each Li stands for unsubstituted or ^-^^ alkoxy, (VC6 thiol, qc ^ 2 dialkylamino, C6_Ci2 aryloxy, c6_Ci2 arylthio, C7-cls aralkylamino or Ci2_C24 diaryl Cl_C6 alkyl or [-(p ,, q, -c2_c6alkyl) -Z ,, _] n-Cl-c6 alkyl substituted by amine groups one or more times, in which η 疋 is from 1 to 1000 Number, p, and q are the number of different positions, and each Z "is independently a heteroatom 0, s or N substituted by an alkyl group, and c: 2-C6 alkylene in its repeating unit [-C2_C6 In the case of elongation base ζ "_], it is the same or different, and LjuL2 may be saturated or 1 to 10 unsaturated, which may not be interrupted or 1 to 10 selected from the desired position in the desired position. = 〇) _ * C6H4—interrupted by the group of the group, and may be without or with 丨 to 10 substituents selected from the group consisting of halo, cyano and nitro. 2 · The compound according to item 1 of the scope of patent application has the following formula: 其中Μ、X、Y、Z、Z’、m、X及y如同申請專利範圍第 1項之定義。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------—丨 -----丨|丨訂/!|丨—！|^^|^· (請先閱讀背面之注意事項再填寫本頁) •36- 477791 A8 B8 C8 D8 、申請專利範圍 3.依申請專利範圍第1項之化合物，其中，a代表一 殘基 00 :: T 或Among them, M, X, Y, Z, Z ', m, X and y are the same as those defined in the first patent application. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ---------— 丨 ----- 丨 | 丨 Order /! | 丨 —! | ^^ | ^ · (Please read the notes on the back before filling out this page) • 36- 477791 A8 B8 C8 D8, patent application scope 3. Compound according to item 1 of patent application scope, where a represents a residue 00 :: T or ’其中’T代表苯氧基，萘氧基，苯硫基或萘硫基。 4·依申請專利範圍第3項之化合物，其中，a代表一殘基'Wherein' T represents phenoxy, naphthyloxy, phenylthio or naphthylthio. 4. The compound according to item 3 of the scope of patent application, wherein a represents a residue 或or 經濟部智慧財產局員工消費合作社印製 5·依申請專利範圍第1項之化合物，其中，X是n或〇，z， 是c2-c12伸烷基-NHC00B或cvc12伸烷基_0C00B，其 中B如同申請專利範圍第1項之定義。 6 ·依申请專利範圍第1項之化合物，其中，X是n，z是 C00B，Z是C2-C12伸烧基-0C00B，其中^如同申請專 利範圍第1項之定義。 7·依申請專利範圍第1項之化合物，其中，z，是C2_C6-伸 烧基-N(C00B)2、C2-C6-伸烧基-NHC00B、C2-C6-伸烧 基-0C00B，或C2-C6-伸烷基-SC00B，其中B如同申請 專利範圍第1項之定義。 8·依申請專利範圍第1項之化合物，其中， r2 ,Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The compound according to item 1 of the scope of patent application, where X is n or 0, z, which is c2-c12 alkylene-NHC00B or cvc12 alkylene_0C00B, where B is the same as the definition in item 1 of the scope of patent application. 6. The compound according to item 1 of the scope of patent application, wherein X is n, z is C00B, and Z is C2-C12 elongation group-0C00B, where ^ is the same as the definition of item 1 of the scope of patent application. 7. The compound according to item 1 of the scope of the patent application, wherein z is C2_C6-endenyl-N (C00B) 2, C2-C6-endenyl-NHC00B, C2-C6-endenyl-0C00B, or C2-C6-alkylene-SC00B, where B is the same as the definition in item 1 of the scope of patent application. 8. The compound according to item 1 of the scope of patent application, wherein r2, - Re 或（卜)m· R7 一 Έ-Χ、 其中Ε、k及m如同申請專利範圍第1項之定義 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝-------Ί訂··-------- (請先閱讀背面之注意事項再填寫本頁) -37- 477791 A8 B8 C8-Re or (bu) m · R7 aΈ-X, where E, k, and m are as defined in the scope of patent application No. 1 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm)- --------- Install ------- ΊOrder ·· -------- (Please read the precautions on the back before filling this page) -37- 477791 A8 B8 C8 六、申請專利範圍 9· 一含有大量之一在原地經由依申請專利範圍第丨項的式 (I)化合物熱分解所產生之依申請專利範圍第1項的式⑴ 著色劑之高分子有機物，其中z，代表C2_Ci2伸烷基 -OH，C2_•烷基-SH或C2-C12伸烷基-NH2。 ::_，:Λ,叫 10.—種熱或化學敏性記錄物質，喷墨印刷用的墨水 ，電子^記錄方法用的調色劑，熱轉印用的色帶，光 敏性負或正阻劑組成，其特徵在於，它含有式⑴化合 物。 11 · 一種構造性彩色相片或濾、色片的製造方法，其特徵在於 ，包含依申請專利範圍第1項的式⑴著色劑之正或負阻 劑，依圖案照射和顯影及熱處理，其中，熱處理可在照 射和顯影當時或俟後發生，而熱轉變成依申請專利範圍 第1項的式（I)的著色劑，其中Z’代表c2-c12伸院基-OH 、C2-C12伸烷基-SH或C2-C12伸烷基-NH2。 裂------->·訂··--- (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -38-6. Scope of patent application 9. A polymer organic substance containing a large amount of one of the formula ⑴ colorants according to item 1 of the patent application scope generated in situ by thermal decomposition of the compound of formula (I) according to item 丨 of the patent application scope, Among them, z, represents C2_Ci2 alkylene-OH, C2_ • alkyl-SH or C2-C12 alkylene-NH2. :: _ ,: Λ, called 10. —A kind of thermal or chemically sensitive recording substance, ink for inkjet printing, toner for electronic ^ recording method, ribbon for thermal transfer, negative or positive light sensitivity A resist composition, which is characterized in that it contains a compound of formula VII. 11 · A method for manufacturing a structural color photograph, filter, or color filter, characterized in that it comprises a positive or negative resist of the formula ⑴ colorant according to item 1 of the patent application scope, and is irradiated with a pattern and developed and heat-treated, wherein, The heat treatment can take place at the time of irradiation or development, or later, and the heat is transformed into the coloring agent of formula (I) according to item 1 of the scope of the patent application, where Z 'represents c2-c12 Extender-OH, C2-C12 alkane -SH or C2-C12 alkylene-NH2. --------- > · Order ·· --- (Please read the precautions on the back before filling out this page) Printed on paper standards of the Ministry of Economic Affairs and Intellectual Property Bureau Staff Consumer Cooperatives This paper applies Chinese National Standards (CNS) A4 size (210 X 297 mm) -38-