TW520373B - Process for the preparation of substituted amido phthalocyanine derivatives and substituted amido phthalocyanine derivatives - Google Patents

Abstract

A process for the preparation of substituted amido phthalocyanines having the general formula I: MPc-(CONR1R2)x, via the reaction of a phthalocyanine carboxamide having the formula MPc(CONH2)x II, wherein Pc is a Phthalocyanine ring; M is a hydrogen or a metal capable of forming a metal phthalocyanine such as Mg, Al, Ni, Fe, Zn, Pb, Sn or Cu and x is a number from 0.1 to 4.0, with an amine acid salt denoted by formula: III wherein R1 and R2 are independently selected from the group consisting of hydrogen; an alkyl group having 1-20 carbons; a cyclic alkyl group; an aryl group; an arylalkyl having 7-20 carbons; an alcohol group having 2-20 carbons; an alkyl amino alkyl group; an aliphatic amine having 1-20 carbons; an aliphatic amine acid salt having 1-20 carbons; polyoxyalkylene groups ranging in molecular weight 89-2000; polyoxyalkyleneamines ranging in molecular weight 148-4000; Z is the hydrogen sulphate or the hydrochloride salt of the amine.

Description

520373 A7 B7 V. Description of the Invention (1) Technical Field The present invention relates to a novel method for synthesizing substituted amidamine phthalocyanine and a novel substituted amidamine phthalocyanine derivative. Background The preparation of substituted amidophthalocyanine derivatives is well known and described in GB 844,419 and more recently EP 0519395. The multi-step prior art method for producing substituted amido phthalocyanine derivatives begins with the well-known phthalocyanine carboxyamidoamine. Phthalocyanine carboxyamidamine is made from a substituted phthalic acid derivative or anhydride derivative, such as trimellitic acid or anhydride. In the presence of high-boiling organic solvents such as nitrobenzene or o-nitrobenzene, or the use of excess urea as the solvent for the reaction, trimellitic acid and tartaric acid or anhydride are present in the presence of urea, copper salts and ammonium molybdate. Reaction in the presence. The ratio of trimellitic acid to osmic acid can be determined according to the desired degree of substitution of the phthalocyanine carboxyamidamine. The reaction mixture was heated at 18 0-2 50 C for about 4-20 hours. The reaction product thus obtained can be washed with a dilute aqueous acid solution or further purified with a general acid paste to obtain phthalocyanine carboxyamidamine, which is usually 90% pure. The next stage of preparation is to hydrolyze the formed amidine to an acid, and then react the acid group and the sulfoammonium chloride to generate a corresponding amidine gas. The final step in synthesizing amidine cyanine is to react the base gas with the relevant amine. EP 09153 95 describes many of these substituted amidoamines, where the maximum value of the amidine substitution is η equals 2 and it describes the manufacture of these derivatives and their use as phthalocyanine dyes by prior art, and their effect on optical The role of the recording element. Now it is found that the substituted amine g Taijing derivative can be applied to Chinese National Standard (CNS) A4 specifications (210 X 297 public love) from the basic paper size of Ugly Cyan. (Please read the precautions on the back before filling this page) | Install -------- Order --------

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 520373 A7 m 5. Description of the invention (prepared by the reaction of amidine and amine / acid salts. This novel method uses fewer steps and provides high yields than previous techniques Substituted amidoamine cyanine derivatives. Summary of the Invention 1 The present invention relates to a method for preparing a substituted acid amidocyanine having the general formula I:

MPc. (CONR1R2) x I is reacted via a phthalocyanine carboxyamidoamine having the molecular formula MPc (CONH2) x II with an amine salt represented by the general formula III, where ~ is a phthalocyanine ring 'Μ 疋 gas or 疋A metal that can form a metal cyanine, and X is a value from 0.1 to 40, preferably 1.0 to 3.0. /

FT where R1 and R2 are selected from hydrogen, alkyl groups containing 1-20 carbons, cycloalkyl, aryl, arylalkyl groups containing 1-20 carbons, alcohol groups containing 2-20 carbons, and amines. Base, aliphatic amines containing 1-20 carbons, aliphatic amines containing 1-20 carbon atoms, polyoxyalkylenes having a molecular weight range of 89-2000, polyoxyalkylenes having a molecular weight range of 148-4000 In the group consisting of alkylamines, z is the chlorosulfate or hydrochloride of the amine. It is an object of the present invention to provide a novel method for synthesizing a compound represented by the formula, which saves labor by the prior art method with many steps, and easily produces with high efficiency and purity using a relatively simple preparation and separation method . The aspects of this novel method with respect to reactants and conditions are described in this paper. The size of this paper applies to the Chinese National Standard (CNS) A4 (210 X 297 mm). (Please read the notes on the back first to write this page) 1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6 520373

5. Description of the invention (3) In the text. Another objective of the present invention is to provide novel substituted amidine / phthalocyanine derivatives. Description The method according to the present invention comprises the reaction of phthalocyanine carboxyamidoamine and an amine / acid salt to provide substituted amine g-toocyanine. The perylene cyanocarboxyamine material suitable for this method has the general formula MPc (CONH2) x, where M is hydrogen or a metal capable of forming a metal phthalocyanine and the value of X is from 0.1 to 4.0. Particularly suitable for use in the method of the present invention is copper cyanocyanine hydrochloride 'wherein the X value is from 1.0 to 3.0. The amine salt suitable for this method has the general formula ^-η · 2 m R2 where R1 and R2 are respectively from hydrogen, an alkyl group containing 120 carbons, a cycloalkyl group, an aryl group, and an aralkyl group containing 1-20 carbons. , Alcohol groups containing 2-20 carbons, alkylamines, aliphatic amines containing 1-20 carbons, aliphatic amines containing 1-20 carbons, polyoxygenated molecular weights ranging from 89-2000 The alkyl group is selected from polyoxyalkyleneamines having a molecular weight ranging from 148 to 4000, and z is a hydrogen sulfate or a hydrogenated gas salt of an amine. Examples of C! _C20 academies used herein include: methyl, propyl, butyl, hexyl, octyl, dodecyl, hexadecyl, octadecyl, tert-butyl, and oleyl. Preferred alkyl groups R2 and R2 are hydrogen and R2 is dodecyl, octadecyl, hexadecyl and oleyl. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) f installed -------- order-(Please read the precautions on the back before filling this page) 4 丨 Intellectual Property of the Ministry of Economic Affairs A7 printed by the Bureau ’s Consumer Cooperative: ^^ --------- V. Description of the Invention (4) Examples of qc ^ 2 cycloalkyl suitable for this include: cyclopentyl, cyclohexyl, and cyclooctyl, When Ri = hydrogen, cyclohexyl is preferred. (Please read the notes on the back before filling this page) "Examples of aralkyl groups suitable for this include: benzyl or naphthylmethyl 'when hydrogen, phenylfluorenyl is preferred. C6- suitable for this Examples of Cic aryl include: phenyl or naphthyl, and phenyl is preferred when Ri = hydrogen.-Cyclic substituents R1, R2 such as cycloalkyl, aralkyl and aryl substituents may contain one or Multiple substituents. Examples of suitable substituents include "C8 alkyl groups such as methyl, ethyl, η-propyl, n-butyl, and n-hexyl; C" C6 alkoxy groups such as methoxy, ethoxy , Η-propoxy, n-butoxy and n-hexyloxy; hydroxyl; nitro; and _ groups such as gas, bromine and iodo. Examples of CrC6 alkylamines suitable for use herein include: dimethylamine Ethyl, monomethylaminopropyl, and diethylaminopropylamine, and when R1 = hydrogen, diamidoaminopropyl is preferred. Examples of aliphatic amine groups suitable for this include: amineethyl , Aminepropyl, aminebutyl, aminepentyl, aminehexyl, amineheptyl, aminedecyl and amineoctyl. When R1 == hydrogen, the preferred aliphatic amines are aminehexyl, amineheptyl, amine Deca- and amine octyl. Ministry of Economic Affairs Examples of aliphatic amine acid salt bases printed by the Property Cooperative Consumer Cooperative are suitable for this purpose as hydrogenated hydrogen or hydrogen sulfate. The preferred amine salts when using dihydrogen are amine heptyl and amine dodecyl. And amine octyl hydrogenated hydrogen salts. Examples of C2 to Cm alcohol groups suitable for this include 2-Ethyl, 2-Ethyl-1, ^ dimethylethyl, 3-hydroxy-2,2-di Methylpropyl, 1-hydroxyhexyl, 1-hydroxypropyl, 1- ^ pentyl. When Rk hydrogen, the preferred group is 2 propyl, this paper size applies Chinese National Standard (CNS) A4 specifications ( (210 X 297 mm) 8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 520373 A7 B7 V. Description of the invention (5) Hexyl and 1-pentyl. Polyoxygenated bases suitable for this have a general structure:

—CHCH2- (OCHCH2) n-R where R = fluorenyl, and R can be hydrogen or methyl depending on whether ethylene oxide or propylene oxide is used for the polymerization reaction. Suitable polyoxyalkylene groups include polyoxyalkyleneamines having a general structure as follows: —CH2CH2〇CH2CH2OCH2CHrNH2 These materials are known as Jeffamine compounds and are available from Texaco Chemical Company to define the monoamine Jeffamine 89 (RTM) — Jeffamine M2070 (RTM) and the brand names of Jeffamine EDR 148 (RTM) -Jeffamine D400 (RTM) defining bisamines. The amine salts that are very suitable for use in the method of the present invention are the hydrochloride salts of the amines detailed previously. The phthalocyanine carboxyamidamine can react with an amine salt from an equal molar amount up to 100 times the excess molar number, preferably 5-20 times the molar number of the amine salt to 1 mol. This reaction can be carried out at a temperature in the range of 140 ° C-320 ° C, preferably 230-300 ° C. The reaction proceeds quickly between this temperature range, but to ensure that the reaction is complete, the reaction mixture should be heated for 0.5-20 hours, preferably 1-3 hours. As the high-boiling organic solvent, nitrobenzene, naphthalene, o-nitrotoluene, and mixtures thereof can be used. A preferred method is to use a melt of the amine salt as a solvent. This can be done because the boiling point of the amine salt is very high, which generally exceeds 250 ° C. Therefore, the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 4 -------- ^ — (Please read the notes on the back before filling this page) 9/3

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the scope and scope can be used to actually and successfully implement the solution. Separation of most obstructed products is achieved by separation and filtration tools, e.g. a wide range of amine salts used in the method of the invention are soluble in hot water. In most cases, excess amine salts can be removed by washing with hot water before or during filtration after the reactants have been formed. Use of other (water-insoluble) amine salts requires chloroform and ethanol to remove excess amine salts before filtering. When amine salts are not available commercially, they can be made from the parent amine and a suitable acid. The present invention further provides novel fluorene substituted cyanine derivatives of general formula I:

MPc-iCONR'R ^ x I where Pc is a cyanine ring; "is a metal that can form a metal phthalocyanine and X is a value from 0.1 to 4.0, preferably between 1.0 and 3.0; R1 and R2 is selected from hydrogen and polyoxyalkylene groups having a molecular weight range of 89-2000; polyoxyalkyleneamines having a molecular weight range of 148-4000. The following non-limiting examples further illustrate the Methods and products. Unless stated to the contrary, the reaction of carboxyamidamine and amine salt of phthalocyanine is complete. However, the final product shows the presence of phthalocyanine, which is derived from the production of carboxyamidamine, trimellitide The reaction of acetic acid (anhydride) and phthalic acid (anhydride). For the sake of completeness, the descriptions of the copper monophthalocyanine copper phthalocyanine CuPc ^ CONHJ! And the tetracarboxylic acid amidocyanoone CuPc (CONH2) 4 are included. Preparation of CuPciCONHJ 13g of copper chloride, 65g of arsenic acid, 27g of trimellitic acid and 0.4g of aluminum molybdate This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 4 ----- ----------- ^ ----- (Please read the notes on the back before filling this page) ^ 1. 10 520373 A7 Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Industrial and Commercial Cooperatives, and the description of the invention (the mixture is heated at about 180 ° C for 15 hours in the presence of 243g of urea. The reaction mixture is then allowed to cool and stirred to dissolve in 98% H2S04 at 60 ° C, then immersed in In an ice bath containing 500 g of ice and 3 liters of cold water, the green temperature is < 5 ° C. Then filtering and washing are performed to produce 53 g of CuPc ^ CONHA with a purity of about 88% as measured by sulfuric acid and thallium sulfate test. Preparation of CuPd_Ci) N.Hat A mixture of 13 g of copper vaporized, 122 g of trimellitic acid and 0.4 g of aluminum molybdate is heated in the presence of 243 g of urea at about 180 ° C. for 15 hours. The reaction mixture is then allowed to cool and Dissolve in 98% of 112304 with stirring at 60 ° C, then immerse it in an ice bath containing 500g of ice and 3 liters of cold water to ensure the temperature < 5.0. Then perform filtration and washing to produce sulfuric acid and tritium sulfate test stations. Measured 77g of CuPc (CONH2) 4 with a purity of about 88%. In the following examples, two starting materials, namely Cupc (CONH2) x and each compound of Formula I according to the present invention, are made into KBr circles. And its Fourier transform infrared spectrum is recorded between 4000 and 400 cm · 1 On a Philips PO 9800 FTIR spectrometer. This spectrum was used with compounds of the chemical formula to identify reaction efficiency and reaction products. F Example 1 Preparation of 5 g of copper cyanocyanine monocarboxyfluorene (88% purity) ) And 10 g of propylamine hydrochloride are manually mixed, and heated to about 280 ° C for about 1 hour with iso_mantle. The reaction mixture was allowed to cool to about 60 ° C and water was added to reslurry at about 800c. The slurry was filtered and further rinsed with about 80% of its water to remove excess amine gaseous hydrogen salt. The filtered, washed product was dried in an oven to produce 4.52 g of copper monopropylamidoamine phthalocyanine. Private paper size applies to China National Standard (CNS) A4 specifications_ (210 x 297 Public Love_ I ^ -------- Order ----- (Please read the precautions on the back before filling this page) 11 520373 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Five Ministry of Economic Affairs A7 ---- B7 ------- 、 Instructions for Invention (8)

The FTIR spectrum of the CuPc spermidine starting material is significantly different from that of the final product. Very strong peaks appeared in CuPc of propylamidine at 2900cnrl and 2850cnri but not in CuPc monocarboxyamidamine. This is strong evidence and very characteristic of alkyl stretching activities associated with propyl. Example 2 The use of copper dodecylamine phthalocyanine 19.4g of undecylamine was placed in a round bottom flask and a hydrogen chloride gas was continuously passed through the amine for about 1 hour and about 50 hours. (: Gentle heating to form dodecylamine gasified hydrogen salt. Then add 5g of CuPc monocarboxyamidoamine together and mix completely manually. The mixture is heated to about 280 ° C for about 2 hours. The reaction mixture is allowed to cool to room temperature. Warm, then repulp in the smallest amount of chloroform, and slowly add about 400ml of alcohol stirred by a magnetic stirrer. Filter and wash with alcohol to produce the product in an oven at 70%. The hydrazone was dried to obtain 4.69 g of monododecylamine CuPc.

The FTIR spectrum of CuPc benzylamine is significantly different from the final product. Dodecylamine CuPc showed very strong fluorene in MOOcnr1 and 2850 cm-i but not in CuPc monocarboxyfluorene. This is clear evidence and very characteristic of alkyl extension activities associated with dodecyl.

The MALDI-TOF mass spectrum of CuPc carboxyamidamine is also significantly different from that of the final product. The mass spectrum in the final product clearly shows the presence of monododecylamine CuPc by the peak at 7900/2. There is no corresponding peak for the starting material at these mass-to-charge ratios. f Example 3 A mono + octaamine copper phthalocyanine plate was prepared with 5 g of 88% purity phthalocyanine monocarboxyamidamine and 32 g of octadecylamine hydrochloride. Manually mixed well and heated to about 280 ° C with isomantle for about 2 hours This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) \ ----------------- (Please read the precautions on the back before filling this page) 12 52〇373 A7

V. Description of Invention (9) When printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. The reaction mixture was allowed to cool to room temperature and the product was separated in the same manner as in Example 2 to obtain 4.91 g of monooctadecylamine CuPc. The FTIR spectra of the starting and final products were significantly different. The products had very strong peaks at 2900 cm 1 and 2850 cm 1, but CuPc carboxyamidoamine did not. This is strong evidence and characteristics of the alkyl stretching activity associated with octadecyl. The Maldi-toff mass spectrum of the final product showed a strong peak at 874 m / z representing monooctadecylamine CuPc. The starting material has no corresponding peak at this mass-to-charge m / z ratio. Example 4 Preparation of indium tetrapropylammonium phthalocyanine indium 3.5 g of copper tetracarboxyammonium phthalocyanine and i8 g of hydrogen chloride propylamine were manually mixed and heated in an oil bath to about 18 ° C. for about 20 hours. This reaction mixture It was then allowed to cool to room temperature and reslurried with hot water at 80 ° C., then filtered and washed with hot water at about 80 C. The resulting filter cake was finally washed with acetone and dried in an oven at about 70 C. And 3g of tetraproxylamine CuPc was obtained. FTIR obviously showed that the propyl alkyl group in tetraproxylamine CuPc stretched at 2900cm · 1 and 2850cm · 1. Maldi mass spectrum also showed a statistically isomeric mixture of tetrasubstituted products, such as 794m / z Represents a mono-isomer, 839 m / z represents a di-isomer, 883 m / z represents a tri-isomer, and 925 m / z represents a tetra-isomer. Example 5 Monobenzidine amine phthalocyanine indium is rare. 2. g of copper weilamine phthalocyanine and 5.42 g of hydrogenated aniline were manually mixed in a test tube and heated to about 30 ° C with a Bunsen burner. The reaction mixture was allowed to cool to room temperature and Reslurry in hot water at about 800c to dissolve excess hydrogenated aniline. Filter and clean with hot water at about 80C. Then, use ethanol for final cleaning. The resulting filter cake is dried in an oven at about 70 ° C to obtain 1.98 g of monotoluidine CuPc. (Please read the precautions on the back before filling this page) ----- ^ --------- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 public love) 13 520373 C8 ----—_____ VI. Maldi mass spectrum of the products generated in the scope of patent application 1 Obviously, it corresponds to the strong peak of benzoxamine Cupc at 695 m / z, which is not present in the starting material. Example f- & Weylamine cyanine ketone was manually mixed with 6.62 g of phenethylamine hydrochloride in a test tube and heated using a Bunsen burner to about 300 t: about 30 minutes. This reaction mixture was allowed to cool to It was reslurried in hot water at about 80 ° C to dissolve excess hydrogenated phenethylamine. Filtration and washing were performed with hot water at about 80 ° C followed by final washing with ethanol. The resulting filter cake was About 70 ° C was dried in an oven to obtain 2.2 g of CuPc of monoacetophenamine. The FTIR spectrum of the product showed that the infrared activity of the secondary fluoramide was from 640 cm-i ' The activity of the primary amidine of the starting material was 1605 cm-1. However, the more conclusive Maldi mass spectrum of the product clearly showed a strong peak corresponding to monophenylacetamide CuPc at 724.2 m / z, which was not present in the starting material. (Please read the notes on the back before filling out this page) Printed clothing for the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 14 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

520373 Sixth, the scope of application for patents No. 881 14735 Application for amendments to the scope of patent applications April 19, 2011 1. A method for preparing substituted amidophthalocyanine having the following chemical formula: MPc-CCONR ^^ x I where M is hydrogen or a metal that can form a metal cyanine, Pc is a phthalocyanine group, X is a value from 0.1 to 4.0, R1 is hydrogen or R3, and R2 and R3 are selected from the following groups, Alkyl groups having 1-20 carbons; Cycloalkyl groups having 5-20 carbons; Aryl groups having 6-10 carbons; Aralkyl groups having 7-20 carbons; Hydroxyl groups having 2-20 carbons Alkyl; C4-C6 alkylamine alkyl or its acid salt; aliphatic amine alkyl or its acid salt with 1-20 carbons; aliphatic amine acid salt with 1-20 carbons; molecular weight range 89- Polyoxyalkylenes between 2000; and polyoxyalkyleneamines or their acid salts with molecular weights ranging from 148-4000, via a phthalocyanine carboxyamidoamine having the chemical formula MPc (CONH2) x II, (wherein; PC and M are as defined above) and are prepared by reacting with an amine salt represented by the following chemical formula: —η · zm H2 where R1 and R2 are as defined above, and Z is sulfuric acid or hydrochloric acid. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -15-A8 Declaring the scope of patents The method according to item 2, wherein M is hydrogen, magnesium, Shao, nickel, iron, zinc, lead, tin or copper. 3 | As in the method of claim 2 of the patent scope,] v [is copper and X is a value from 1.0 to 3.0. 4. The method according to any one of claims 1 to 3 in the patent scope, wherein R2 and R are (VCm alkyl groups; c5-C12 cycloalkyl groups; C7-C12 carbon aralkyl groups; CVC2〇 Hydroxyalkyl group; c6-C1 () aryl group; c4-c6 alkylamine group or its acid salt; C2-C2G aliphatic amine alkyl group or its acid salt; polymer with molecular weight range between 89-2000 Ethylene oxide or polypropylene oxide groups; polyoxyalkyleneamines or their acid salts with molecular weights in the range of 148-4000, 5. The method according to any one of claims 1 to 3, wherein With R3 as methyl, propyl, butyl, hexyl, heptyl, dodecyl, hexadecyl, octadecyl, third butyl, oleyl, cyclopentyl, cyclohexyl and cycloheptyl, Benzyl or naphthylmethyl, 2-hydroxyethyl, 2-hydroxy-1,1diethyl, 3-hydroxy-2,2-dimethylpropyl, 1-hydroxyheptyl, 2-hydroxypropyl , 1-hydroxypropyl, 1-hydroxypentyl, benzyl, naphthyl, dimethylaminoethyl, dimethylaminopropyl, diethylaminopropyl, amineethyl, aminepropyl, aminebutyl Group, aminepentyl, aminehexyl, amineheptyl, amineoctyl, aminedodecyl or -CH2CH2OCH2CH2OCH2CH2-NH2. 6. The method according to item 5 of the patent application, wherein R2 and R3 are dodecyl, octadecyl, hexadecyl, oleyl, 1-heptyl, 2-propyl, 1-pentyl Amine hexyl, amine heptyl, amine octyl, or amine dodecyl. 7. As in the method of applying for item 5 of the patent scope, where R1 is hydrogen and R2 is the paper standard applicable to China National Standard (CMS) A4 specifications (210X297 mm) -16- Scope of patent application Cyclohexyl, benzyl, 1-hydroxypentyl, phenyl, naphthyl, dimethylaminopropyl or -CH2CH2OCH2CH2OCH2CH2-NH2. 8. The method according to any one of claims 1 to 3, wherein z is gasified nitrogen. 9. The method according to item 1 of the scope of patent application, wherein the ratio of the amine salt having the chemical formula to the phthalocyanine carboxyamidine of the chemical formula II is between 1: 1 and 100: 1, 10 The method according to item 9 of the patent application range, wherein the molar ratio of the amine salt III to phthalocyanine carboxylamine II is from 5: 1 to 20: 1. 11 · The method according to item 1 of the patent application range, wherein the melting reaction temperature of the amine salt and the phthalocyanine carboxylic acid amine is from 14 ° C to 320 ° C. Ϊ2. The method according to item n of the patent application range, wherein the reaction temperature is from 230 ° C to 300 ° C. 13. The method of claim 1 in which the molten reaction mixture is heated for 0.5 to 20 hours. 14. The method according to claim 13 in which the molten reaction mixture is heated for 1 to 3 hours. 15 · —Amine phthalocyanine having the following chemical formula: MPcJCONR1! ^ I where M is hydrogen or a metal capable of forming a metal phthalocyanine, Pc is a phthalocyanine group, X is a value from 0.1 to 4.0, and R1 is hydrogen Or R3, and R2 and R3 are respectively selected from the following groups, polyoxyalkylene groups with molecular weights ranging from 89-2000; and molecular weights ranging from 148-4000 ^ Paper size applies Chinese National Standard (CNS) A4 specifications ( 210X297 mm)-^ 20373 Patented polyoxyalkyleneamine or its acid salt. 16. The amidamine phthalocyanine according to item 15 of the application, wherein% is hydrogen, magnesium, aluminum, nickel, iron, zinc, lead, tin < copper. 17. In the case of the amidoamine cyanocyanine according to item 16 of the patent application, μ is copper and X is a value from 1.0 to 3.0. 18. The amidophthalocyanine according to any one of claims 15 to 17, wherein R2 and R3 are CVC20 alkyl groups; C5-C12 cycloalkyl groups; c7-c12 carbon aralkyl groups; c2-c20 hydroxyalkyl; c6-c1 () aryl; c4-c6 amine alkyl or its acid salt, c2-c2G aliphatic amine alkyl or its acid salt; molecular weight range 89 Polyethylene oxide or polypropylene oxide groups between -2000; and polyoxyalkyleneamines or their acid salts with molecular weights ranging from 148-4000. 19. The amidamine phthalocyanine according to any one of claims 15 to 17, wherein R and R are fluorenyl, propyl, butyl, hexyl, heptyl, dodecyl, hexadecyl, ten Octyl, third butyl, oleyl, cyclopentyl, cyclohexyl and cycloheptyl, phenylfluorenyl or naphthylmethyl, 2-hydroxyethyl, 2-hydroxy-1,1dimethylethyl, 3-hydroxy -2,2-Dihydroxypropyl, 1-hydroxyheptyl, 2-hydroxypropyl, 1-hydroxypropyl, 1-hydroxypentyl, phenyl, naphthyl, dimethylaminoethyl, dimethyl Aminopropyl, diethylaminopropyl, amineethyl, aminepropyl, aminebutyl, aminepentyl, aminehexyl, amineheptyl, amineoctyl, aminedodecyl or -CH2CH2OCH2CH2OCH2CH2-NH2. 20. Amidamine phthalocyanine according to any one of claims 15 to 17, wherein R2 and R3 are dodecyl, octadecyl, hexadecyl, oleyl, heptyl, 2-hydroxypropyl Base, 1-hydroxypentyl, aminehexyl, amine heptyl, amine octyl, or amine The paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) 18 520373 8 8 8 8 AB c D 6. Apply for a patent Dodecyl, or where R1 is hydrogen and R2 is cyclohexyl, benzyl, 1-hydroxypentyl, phenyl, naphthyl, dimethylaminopropyl, or -CH2CH2OCH2CH2OCH2CH2-NH2. This paper size applies to China National Standard (CNS) A4 (210X297 mm) 19