DE2136767A1 - Process for the production of copper phthalocyanine pigments - Google Patents

Description

DR. MOLLER-IORi DIPL-PHYS. DR. MANITZ DtPL-CHEM. DR. DEUFIL DIPL.-IMß. PSMSTERWÄLD DiPL.-SN ©. -Q

CJ ijj <g (Q FJ if = »K)

gg. m where

v - S £ 300

Osaka / JlEiI

Process for production of copper © r = Phthalo crania-

pigments

Priority: -Japan -jojü 22 »July 197O ₉ JJr ₀ 64-6.

The invention relates to a new Yerfalirea for production

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(b) According to the sd.iiea process ^ in which phthalodinitrile and copper or its compounds are reacted with or without inert aromatic solvents with a ^ a high boiling point in the range from 170 ⁰ "to 100 ⁰ G»

However, these processes are industrially disadvantageous because the ^ reactions must be carried out at very high _{temperatures-s} and. the Eupferpfcthalocyanin obtained by these methods still weist- generally a "coarse particle size, so _r ds £ it vc'u low dispersion ability uad liartss, rough together is laid eggs Izais.e IFarb aft besitstc Tu ALSC SCLCL:.! © in crude [npferplstlialocyasiii as pigments do better a _s -E _T-iiiriEii irälich the Farbstärtts -verwendbar su "it was necessary that: ia.oh the procedures mentioned understanding received Hohprodiizt a treatment such as the so-called Säureanqueilverfal: Reindeer (acid pasting process ) or to subject it to the process of marrying salt with its pigmentation ο The pigmentation process was also necessary in the manufacture of halogen-containing copper phthalocyanines

² "" BAD ORIGINAL

109885/1740

In the former case, i.e., the acid dough process, a large amount of acid is required to prepare the crude copper phthalocyanine to solve, and furthermore there are disadvantages in that the acid must be removed from the pigment and the acid so removed "must be disposed of" therefore this procedure is at disadvantageous for industrial use »

In the latter, that is, when grinding with salt ₉ using mechanical forces, the process is complicated and a large amount of energy is required for a long time. In addition, the amount that can be handled per batch is small. Thus, the industrial application of this method is also disadvantageous

As mentioned above, the conventional methods of making copper phthaloeyanine pigments require the step of Production of the crude pigment and then the stage of Pigmentation. It is obvious that this procedure are disadvantageous when they are used industrially in comparison with a process that allows the pigments to produce in one stage in the pigment state. So became the development of processes for the production of the desired copper phthalocyanine pigments in one step in the pigment liid istrie longed for it impatiently.

Various proposals have already been made in this connection. For example, in the published Japanese Patent Application No. 16995/62 proposed a method according to which a crude copper phthalocyanine by baking of phthalonitrile and copper salts in the presence of inorganic Salts are prepared and milled without isolation with the addition of suitable solvents. Next will be published after the Japanese Patent Application No. 26913/65 substances capable of forming the phthalocyanine ring such as phthalic anhydride;

■ - 3 109885/1740

Phthalimide, phthalonitrile, etc., and a metal or compounds of this metal at low temperatures in the presence of organic or inorganic bodies, e.g. Kmu:!; - resins (e.g. polyethylene), synthetic rubber, titanium dioxide, barium sulfate, etc. in hydrophilic organic solvents heat treated. In the published Japanese Patent applications No. 7661/70 and No. 7662/70 finally became Process proposed in which in the course of the preparation of a copper phthalocyanine from phthalic acid or its Derivatives, the reaction system is stirred uniformly and vigorously in the presence of alkali metal salts.

According to the published Japanese patent application No. 16995/62, however, it is necessary to carry out the reaction at high temperatures above 200 ° C. In addition, these methods are only advantageous when connecting the isolation stage of the crude copper phthalocyanine, and on the other hand, the productivity of copper phthalocyanine considerably limited per batch. These methods are consequently not of advantage in industrial application.

According to the method of published Japanese patent application No. 26913/65 are substances such as synthetic resins (e.g. polyethylene), titanium dioxide or barium sulfate, i.e. cannot be removed with water, with which arise J '

Copper phthalocyanine mixed. The removal of such substances is impossible, and therefore the use of the product is very limited.

For that in the published Japanese patent applications No. 7661/70 and 7662/70 described process requires a reactor which has severe reaction conditions at bright Tejure doors can withstand 180 ° to 220 ° C, and for this reason oinJ these processes are not suitable for industrial use.

109885/1740 _BAD ORIGINAL

In the published Japanese patent applications 6706/70, fi ', X ^{: t} 8 / 7ü and 6709/70, methods are proposed according to which a copper phthalocyanine is produced by heating to react phthalonitrile with alkaline substances in hydrophilic solvents at low temperatures. However, if requested in small quantities, the yield is very good and the resulting pigment is not in a pigment range, but rather, for example, unequal in particle size and without 3 ? ar strength.

Further, it is an object of the invention to provide methods for easily industrial production of excellent copper phthaloeyane pigmentites in a pigment feed in one step and with a high yield . create.

According to the invention, processes for the production of copper phthalocyanine pigments in a pigmented state and free from impurities are created in one stage, which are calibrated in that a mixture of amino or Im: inoicoLvIo 1 emij derivatives and copper compounds with the addition oilier small amount of hydrophilic organic solvent mi ^ - emanier in the presence of a suitable amount of water-soluble -j / iorganischer salts at relatively low temperatures ■. / i high are reacted 50 ° C and 1 ^ O ⁰ C ' , whereby the Reaktiorisyumiecri is gematilen in a Reaktoj? with strong stirring or grinding device / .ijigen.

According to the invention, a fine pigment of high strength and color is obtained without the need for a further process of pi gm entization. In addition, this reaction is completed 3 "to 12 h no /; h after the start of the rise in temperature and the heat developed by daa milling sufficient to maintain a temperature of about 120 ⁰ C in. Thus, a large-sized heater not requ-Erlich. Furthermore, no by-product is created which could draw the equipment affected.

BATH

109885/1740

Therefore, the reaction system and the apparatus can be simplified and the desired product can be efficiently obtained in a short time and in a very high yield. Moreover, in the course of ordinary production of copper phthalocyanine from phthalic acid derivatives, it is an impurity unavoidable by chlorine. However, only according to the invention, if chlorine-free isoindolenine is used, completely chlorine-free copper phthalocyanine can be obtained.

The amino or iminoisoindolenine derivatives to be used according to the invention are represented by the following formula (I),

or X _n -4— N (I)

where X is a hydrogen, chlorine or bromine atom, η is an integer from 1 to 4-, P and P each lower alkoxy groups or together, men a hydroxy-lower alkyl group and P ^ an amino group, Di-lower-alkylamino group, lower-alkoxy group or hydroxyalkoxy group represent. In this context, alkyl and alkoxy groups fc with 1 to 5 carbon atoms are meant. Examples are 3-Amino-1-iminoisoindolenine (this compound is tautomeric with 1,3-diiminoisoindoline), i-imino-3-di-lower-alkylaminoisoindolenine, 1, i-di-lower alkoxy-3-ami.noisoindolenine, 3-lower alkoxy (or Hydroxy-lower alkoxy) -1-iminoisoindolenine, 1-hydroxy-lower alkylimino-3-aminoisoindolenine, 5 — chloro — 3 — amino-1-iminoisoindolenine, ^, ^, G ^ -Tetrachlor ^ -amino-i-iminoisoindolenine or 4> 5 »6,7-tetrabromo-3-amino-1-iminoisoindolenine or a mixture of this. Are 1-imino-3-di-lower alkylaminoisoindolenine, 1,1-di-lower alkoxy-3-aminoisoindolenine, 3-lower alkoxy (or Hydroxyni ederalkoxy) -1-iminoi soindolenine or 1-hydroxy-lower alkylimino-3-aminoisoindolenine used, arise during the reaction

- ⁶ - ORIGINAL BATHROOM

1 09885/1740

tion an amine, alcohol, glycol, or alkanolamine as a by-product, so that this should be taken into consideration when determining the amount to be added of the solvent prior to the reaction.

Copper compounds to be used according to the invention can Copper powder and various copper compounds such as hydroxides, Oxides, chlorides, sulfates, nitrates, acetates, etc. of copper can be named. Instead of the copper compounds mentioned, copper powder can also be used. The amount of copper or copper compounds to be used is preferably over 0.8 moles per 4 moles of amino or iminoisoindolenine derivatives, preferably at 0.8 to 1.5 moles, although the actual Amount is influenced by economic factors. To & z of a reducing agent in the reaction system makes the tone of the obtained pigment clearer.

As organic solvents to be used in the present invention, alcohols and polyols can be enumerated, such as, for example Methanol, ethanol, propanol, isopropanol, isobutanol, butanol, isoamyl alcohol, amyl alcohol, ethylene glycol, polyethylene glycol, Glycerin, diethylene glycol; Monoethers of polyols itfie, for example, methyl cellosolve, ethyl cellosolve, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; Formamide, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, Tetramethylene sulfone and mono-, di- and triethanolamine. A mixture of any two or more of these solvents can also be used.

The preferred amount of the solvents is between 0.01 and 0.5, preferably 0.04 and 0.3 parts by weight per part of the total weight the solid constituents in the reaction mixture.

BATH 109885/1740

Occasionally, in order to improve the grinding effect or maintain the crystal form, it is preferable to add one or more of the following compounds: aromatic hydrocarbons, halogenated hydrocarbons, aliphatic hydrocarbons, esters of organic carboxylic acids, ketones, nitrogen heterocycles and substituted benzenes. Specific examples of these additives are benzene, toluene, xylene, ethylbenzene, styrene, cumene, biphenyl, naphthalene, methylnaphthalene, ethylene tetralin, chlorobenzene, Brombenaol, chlorotoluene, chloronaphthalene, bromonaphthalene, carbon tetrachloride, tetrachloroethane, hexachloroethane, dichloro- Jk, trichlorethylene, Dibromäthylen, Tribromoethylene, perchlorethylene, cyclohexane, cycloheptane, η-hexane, n-heptane, isooctane, n-nonane, n-decane, n-undecane, n-dodecane, ethyl acetate, isopropyl acetate, propyl acetate, ethyl propionate, butyl acetate, isobutyl acetate, amylacetate , Methyl benzoate or ethyl benzoate, dimethyl or piäthylnaleate, ethylene glycol diacetate, diethyl malonate, di butyl phthalate, dioctyiphthalate, diethyl succinate, acetophenone, methyl isobutyl ketone, quinoline, - picoline, pyridine, nitrobenzene, anisole,. The "preferred addition amount of these compounds is between 0.05 and _3? 0 Gew.TIn. Per parts by weight of the AusgangsmateriaJs, for example, the amino or Jminoisoindolem.ne. At the test, an amount of 0.1 to 1.0 TIn. ^ Per part by weight of starting material If a material which leaves an amine, an alcohol or a glycol as a by-product in the reaction, the amount of solvent to be added initially can be reduced accordingly .

The Reaktionsteiüj.-oi ^ i-ar can hoi performing dei ¹ invention at 50 ° to 15> 0 ° C, preferably at 80 ° to 120 ⁰ C. The reaction time variiei't m depending on the particular SHAKE to be used Lösungnini and Kupi'ei'verbiiidungen, although 5 hours usually suffice to 12 to complete the reaction.

BATH ORIGINAL

109885/1740

The inorganic salts to be used according to the invention include anhydrous sodium or potassium sulfate, sodium or potassium chloride, -anhydrous calcium chloride, sodium or potassium carbonate, etc., obtained by washing with water during the subsequent Treatment stage can be removed. The appropriate one The amount of such inorganic salts is between 0.25 "to 10 times the weight of the amino or iminoisoindolenines, although usually an amount of 2 to 8 times by weight is effective is.

An apparatus with strong stirring or comminuting force is suitable as the reactor to be used according to the invention. Specific Examples are high-performance dispersion mixers of the double-arm type, which include those of the pressure type, e.g. the Banbury mixer, the dispersion mixer (Baker Perkins), the MS high-performance pressure kneader 'lyp D (from Moriyama Seisakusho), etc., as well as such with normal pressure, e.g. double arm kneader type S (from the company Moriyama Seisakusho), universal mixer (from Baker Perkins), intensive mixer (Inoue Seisakusho), etc.

The phthalocyanine pigment obtained in this way still contains inorganic pigments Salts. By removing such salts in the usual manner, a blue or green pigment having an excellent clear hue can be obtained can be obtained. If the product is treated with a dilute aqueous acidic and alkaline solution, a blue or green pigment with an even clearer shade can be obtained.

By suitable selection of the solvents, the copper phthalocyanine pigment can be obtained by the process according to the invention either in the form which is stable with respect to organic solvents or in a form which is unstable with respect to this, which does not require any further powdering, dissolution or pigmentation processes. Furthermore, polyhalogenated copper phthalocyanine with a green hue can also be obtained by using the halogenated 3-amino-i-iminoisoindolenines. These pigments are blue or green

~ ⁹ ~ ORIGINAL BATHROOM

109885/1740

Color with clear hue and have enough color strength as a pigment. Their color strength is 20 to 30 % higher than that of the usual, commercially available copper phthalocyanine pigments. Furthermore, the pigment properties required or desired for copper phthalocyanine pigments are comparable to those of the pigments obtained by conventional processes. Finally, since the pigment particles obtained in the present invention are soft, when the pigment is used as a color pigment of paints, printing inks or synthetic resins, the pigment is easily dispersed and needs only a short kneading time and a small amount of energy for satisfactory dispersion.

The following examples illustrate the invention without however, to limit them. In the examples, parts are parts by weight unless otherwise specified.

example 1

In an S-type double-arm kneader (manufactured by Moriyama Seisakusho), 145 TIe. -1-imino-3-aminoisoindolenine, 24.8 TIe. Copper (I) chloride, 700 teas. anhydrous sodium sulfate and 145 TIe. Brought ethylene glycol, and the temperature was increased to 100 ⁰ C with grinding. Thereafter, the temperature at 100 ° could be kept to 110 ⁰ C under Weitervermahlen. The temperature range was maintained for 3 hours and then the reaction product was discharged. The sodium sulfate was made from it by stirring the product in 3000 TIn. hot water at 95 ⁰ C removed over 30 min. Then the product was in 3000 TIn. 1% aqueous hydrochloric acid solution, then in 3000 TIn. 1% aqueous sodium hydroxide solution, in each case 30 min at 95 ° C., stirred. The filter compartment was washed with water until the washing water became neutral, and then dried. So were 136 TIe. Copper phthalocyanine obtained in a yield of 94.5 % . This copper phthalocyanine is the organic solvent unstable form and the average particle size

1 09885 / Ί 740

was "0.1" to 0.4u in diameter. It showed a clear blue Color and had enough tinting strength as a pigment to be used without further processing.

Example 2

The same procedure as in Example 1 was repeated, except that instead of 24.8 TIn. Copper (I) chloride 40 TIe. Copper (II) sulfate were used, and was the time for the temperature range of 100 to 11O ⁰ C 7 k. As a result, 130 TIe. Copper phthalocyanine (yield 90 %) of the type unstable to organic solvents was obtained. This product had excellent properties as a pigment.

Example 3

The same procedure as in Example 1 was repeated except that instead of 145 TIn. Ethylene glycol 116 TIe. Formamide were used. As a result, 135 TIe-. Obtain copper phthalocyanine (94 % yield) of the kind that is unstable to organic solvents! This product had excellent properties as a pigment.

Example 4

The same procedure as in Example 1 was repeated except that 116 TIe. Glycerin instead of 145 TIn. Ethylene glycol were used and the temperature was kept at 120 to 130 ⁰ C for 3 h with grinding. 137 TIe. Organic solvent unstable copper phthalocyanine was obtained (yield 95%). This product was excellent as a pigment.

Example 5

In one working at ordinary pressure intensive kneading (Inoue Soi F.akusho) 145 TIe were. i-Imino-3-aminoisoindclenine, 33.7 TIe. Copper (II) -chlond, 700 TIe. Sodium chloride and 116 TIe. Ethylene

- 11 -

109 8 8-5 / 17 40.

eingeblacht glycol, and the temperature was raised in 10 minutes, while mulling to 100 ⁰ C. After 100 ° C was reached, the external heating was stopped and the temperature for 3 hours only by the heat of milling at 100 to 110 ⁰ O kept. The reaction proceeded with the release of ammonia gas. Thereafter, the reaction mixture was discharged and stirred in hot water at 90 to 95 C to remove the ^Ü Natdumchlorids. After the product was further stirred in 1% aqueous hydrochloric acid solution at 90 to 95 ° C. and in 1 % aqueous sodium hydroxide solution at 90 to 95 ° C. for purification, it was filtered, washed with water and dried. So were 131 TIe. Copper phthalocyanine which is unstable to organic solvents (yield 91%) is obtained. This pigment had an average particle diameter of 0.1 to 0,4yU and excellent properties as a pigment.

Example 6

The same procedure as in Example 5 was repeated except that 109 TIe. Formamide instead of 116 TIn. Ethylene glycol were used. So 130 TIe. Copper phthalocyanine which is unstable to organic solvents is obtained (yield 90%). This product was excellent as a pigment.

Example 7

The same procedure as in Example 5 was repeated except that 116 Tie. Dimethyl sulfoxide instead of 116 TIn. Ethylene glycol were used. So were 132.5 TIe. Copper phthalocyanine which is unstable to organic solvents (92 % yield) is obtained. This product was excellent as a pigment.

- 12 -

109885/17 40

Example 8

In one working at ordinary pressure kneader 192 TIe were. 1,1-Dimetho ^ -3-aminoisoindolenine, 45.4 TIe. Copper (II) acetate, 580 TIe. anhydrous sodium sulfate and 1 ^ 5 TIe. Isobutyl alcohol introduced, and the temperature was increased to 100 ⁰ C while grinding. The temperature could then be kept between 100 ° and 110 ° C. without any external heating, with further grinding. The methanol which distilled out was recovered. After the above-mentioned temperature had been maintained for 3 k, the reaction product was recovered and post-treated in the same manner as in Example 1. So were 129 TIe. Organic solvent unstable type copper phthalocyanine obtained (yield 89.5%) · This product had an average particle diameter of 0.1 to 0.4 11 and was shown as a pigment even without further treatment.

At game 9

In a Banbury mixer were 136.3 TIe. 1-3nüno-3-diethyl aminoisoindolenine, 20.0 TIe. Copper hydroxide, 720 teas. anhydrous calcium chloride and 101.5 TIe. Dimethylformamide introduced, and the temperature was increased to 100 ⁰ C while grinding. The temperature wurd4 then 8 h at 100 ° to 110 ⁰ C. Thereafter, the product was treated in the same manner as in Example 1, with 88.3TIe. (Yield 92%) of organic solvent stable copper phthalocyanine having recorded properties as a pigment.

Example 1 0

In a kneader operating at ordinary pressure, 145 TIe. i-Imirio-iS-aniinoisoindolenine, 24.8 TIe. Copper (I) chlorifi, 7 <° 5 I ¹ Lo. anhydrous sodium sulfate and 101.5 TIe.

- 13 -

BATH ORIGINAL 109885 / 17A0

Dimethylformamide introduced, and the temperature was increased to 110 ⁰ C with grinding. The temperature was kept at 110 to 120 ° C. for 10 hours. Copper phthalocyanine was formed with liberation of ammonia gas. Then the product was treated in the same manner as in Example 1, using 134 parts (yield 93%) organic solvent-stable copper phthalocyanine having an average particle diameter of 0.04 to 0.1 η and excellent properties as a pigment were obtained.

Example 11

In one at. Kneaders working under normal pressure were 145 TIe. i-Imino-3-aminoisoindolenine, 24.8 TIe. Copper (I) chloride, 725 TIe. anhydrous sodium sulfate, 105 teas. Ethylene glycol and 43.5 TIe. Brought xylene, and the temperature was increased to 110 ° C with milling. Then this temperature became 9 h with further Maintain stirring. The product was then made in the same way treated as in Example 1, and 134-TIe. (9y% yield) versus organic solvent stable copper phthalocyanine with an average particle diameter of 0.02 to 0.06 µm and excellent pigment properties were obtained.

Example 12

W The same procedure as in Example 11 was repeated except that TIn instead of 105. Ethylene glycol and 43.5 TIn. Xylene, 105 TIa. Diethylene glycol monomethyl ether and 43.5 TIe. Diethyl succinate were used. So 130 TIe. (90% yield) to organic solvent stable copper phthalocyanine with excellent properties as a pigment.

Example 13

In a type D pressure kneader (from Moriyama Seisakusho) 145 TIe. 1,3-Diiminoisoindoline, 33.7 TIe. Copper (II) chloride,

- 14 109885 / 17AO

652 tie. Sodium chloride, 72.5 He. Dimethyl sulfoxide and 36.7 Tie. Introduced toluene, and the temperature was increased to 100 ° C with milling. The temperature was then ^{kept at 100 to 105 °} C. for 10 h. By treating the product in the same manner as in Example 1, 135 TIe. ( ^{Yield of 9 z} i % ) Organic solvent-stable type copper phthalocyanine having an average particle diameter of 0.02 to 0.06 η and excellent properties as a pigment was obtained.

Eg game 1 4-

In a Banbury mixer were 114.3 TIe. 3- (- Hydroxyethylimino) -1-iminoisoindoline, 16.3 TIe = copper (I) chloride, 760 TIe. Sodium sulfate and 50 teas. Entered formamide, and the temperature was increased to 100 ⁰ C while grinding. The temperature was then kept at 100 to 110 ° C. for 3 hours. 10 TIe = formamide were added to the mixture. The temperature was then kept at 100 to 110.degree. C. for 3 Ii. By treating the reaction product in the same manner as in Example 1, 7798 TIe. (90% yield) organic solvent unstable copper phthalocyanine having an average particle diameter of 0.02 to 0.06ai and excellent properties as a pigment.

Example 15

14-5 Tie »1,3-diiminoisomdoline, 24.8 TIe. Copper (I) chloride, 652 TIe. anhydrous sodium sulfate, 87 TIe. Isobutyl alcohol and 27 teas. Methyloaphthalene introduced, and the temperature was increased to 100 ° C with grinding. Then the temperature became 7 hours at the reflux temperature held. By treating the reaction product in the same manner as in Example 1, 121 TIe. versus organic

- 15 -

109.8 85/17 40 ^ßAD ORIG _INA L

Solvent stable copper phthalocyanine with excellent Properties retained as a pigment.

Example 16

In a kneader operating at normal pressure, 140 TIe. 5-chloro-1,3-diiminoisoindoline, 21.8 x TIe. Copper (I) chloride, 400 teas. anhydrous sodium sulfate, 320 teas. Sodium chloride, 56 TIe. Ethylene glycol and 84 TIe. Dimethylformamide introduced, and the temperature was increased to 100 ⁰ C while grinding. The temperature was kept 7 hours at 100 ° to 110 ⁰ C. Thereafter, the product was treated in the same manner as in Example 1. So were 125 TIe. (90% yield) obtained copper tetrachlorophthalocyanine of clear blue color and high color strength.

Example 17

The same procedure as in Example 16 was repeated except that 35.9 TIe. 5-chloro-1,3-diiminoisoindoline and 87 TIe. 1,3-diiminoisoindoline instead of 140 TIn. 5 ~ chloro-1,3-diiminoisoindoline were used. So were 113.5 TIe. (93% yield) blue copper phthalocyanine with one chlorine atom per molecule obtain.

Example 18

I4l, ^r i TIe, ^{Z |} '? 556,7-tetrachloro-3-amino-1-yininoisoindolenine, 13? 6 TIe. Copper ^ I) chloride, 710 TIe. anhydrous sodium sulfate, 113 TIe. Diethvienglykol -monomethyläther and 30 TIe. Brought xylene, and the temperature was increased to 120 ⁰ C and stirred at 120 to 150 ° 0, grinding was carried out for 12 h. The product was treated in the same manner as in Example 1 and 124 TIe. (88% aurbeute) copper hexadecachlorphthalocyanine with a clear green hue was obtained.

- 16 -

BAD ORIGfNAL

;. ·, - 109085/17 40

In this procedure, instead of 14-1.5 TIn. 4,5,6,7-tetrachloro-3-amino-i-iminoisoindolenine, 132.7 TIe. of this
and 4.6 TIe. 3-Amino-i-iminoisoindolenine is used. In this way, green copper phthalocyanine pigment was obtained which was substituted with 14.5 t> 15 chlorine atoms per molecule.

- patent claims -

1 0 98 8 ^{5/17 4 0 BAD 0R1G} ' ^NAU

Claims (1)

Claims 1. Process for the production of copper phthalocyanine pigments, characterized by reacting an amino- or imino-isoindolenine derivative of the formula: or X. Nile where X is a hydrogen, chlorine or bromine atom, η a whole 1 2
Number from 1 to 4-, P and P each represent a lower alkoxy group or together represent a hydroxy-lower alkylimino group and P 'represent an amino, di-lower alkylamino, lower alkoxy group or a hydroxyalkoxy group, with a copper compound in the presence of water-soluble inorganic salt and a small amount of a hydro; aid organic solvent in a reactor with powerful stirring or grinding devices. 2. The method according to claim 1, characterized in that the amino or imino-isoindolenine is 3-amino-1-iminoisoindolenine or its tautomer, i-imino-3-di-lower alkylaminoisoindolenine, 1, i-di-lower alkoxy-3-aminoiso indolenine, 3-lower alkoxy (or hydroxy-lower alkoxy) -1-iminoisoindolenine, 1-hydroxy-lower alkylimino-3-aminoisoindolenine, 5-chloro-3-amino-1-iminoisoindolenine, 4.5 ₅ 6.7-l ¹ etrachlor -3-amino-1-iminoisoindolenine or 4,5 »6,7-tetrabromo-3-amino-1-iminoisoindolenine or a mixture of these compounds is used. - 18 - BATH ORIGINAL 109885/1740 ό. Method according to claim 1, characterized in that one or more of the
Hydroxides, oxides, chlorides, sulphates and nitrates of copper
is or will be used. 4. The method according to claim 1, characterized in that one or more sulfates, chlorides and carbonates of sodium and as the water-soluble inorganic salt
Potassium and / or calcium chloride is or are used. 5- The method according to claim 1, characterized in that a hydrophilic organic solvent
or more alcohols, polyols, polyol monoesters, formamide,
Dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, tetramethylene sulfon and / or mono-, di- or triethanolamine is or are used. 6. The method according to claim 1 _5, characterized in that the reaction at a temperature of 50 to
150 ° C is carried out. 7. The method according to claim 1, characterized in that that the reaction is carried out for 3 to 12 hours. 8. The method according to claim 1, characterized in * - TL e t in that the copper compound is used in an amount of about 0.8 moles per mole of the 4-imino or amino isoindolenins we d. 9 · The method according to claim 1, characterized in that the water-soluble inorganic salt in a
0.25 to 10 times the amount by weight of the amino or iminoisoindolenine is used. - 19 - BATH ORIGINAL 10988 5/1740 JLO 10. The method according to claim 1, characterized in that that the hydrophilic organic solvent in an amount of 0.01 to 0.5 wt.TIn. per part total weight of solid constituents is used in the reaction mixture. 11. The method according to claim 1, characterized in that that the reactor is a high-performance dispersion mixer of the double arm type is used. 12. The method according to claim 1, characterized in that that the reaction continues in the presence of an organic solvent with a favorable crushing effect and is performed while maintaining a crystal form. 13. Copper phthalocyanine pigments prepared by the process according to claim 1. - 20 - 109885/17