CH626114A5 - Process for preparing tetrazaporphin pigments - Google Patents

Description

The invention relates to the direct production of tetraza-porphin pigments.

It is known that copper phthalocyanines can be prepared by adding a metal phthalocyanine to the reaction mixture during the manufacturing process:

a) as a catalyst for accelerating phthalocyanine formation and for improving the yield,

b) as a seed material to obtain a certain crystal form of the copper phthalocyanine.

The addition of metal phthalocyanine derivatives as crystal growth inhibitors during manufacture is also known. However, in the processes described in the patent literature where a metal phthalocyanine is added during manufacture, the temperature is above 100 ° C.

Japanese Patent Application Laid-Open No. 83726/1974 describes the preparation of solvent-stable copper phthalocyanine pigments, characterized by the reaction of a phthalonitrile or indolenine compound with copper or a compound thereof, at a temperature of at most 100 ° C. in a hydrophilic organic solvent in the presence of an alkaline Substance and ground copper phthalocyanine with an average particle diameter of not more than 10 mu, the surface of the individual particles in the solvent-unstable form, but the core of which is in the solvent-stable form.

It has now surprisingly been found that if, in a process for the preparation of alpha, beta or gamma phthalocyanine, copper phthalocyanine in the usual pigment form is added from the start of the reaction at a temperature below 100 ° C., this influences the catalyst or crystalline form or both, with a greatly improved yield. Excellent quality pigments are obtained without the need for acid build-up or mechanical pulverization.

The invention relates to the method described in claim 1.

Examples of dinitriles are: aromatic dinitrile compounds such as phthalonitrile, halogenated dinitrile compounds such as mono-, di-, tri- or tetra-chlorophthalodinitrile and mono-, di-, tri- or tetra-bromophthalodinitrile, phthalodinitrile compounds substituted by sulphonic acid groups; Carboxy-substituted phthalonitrile compounds such as carboxyphthalodinitrile; phthalonitrile compounds substituted by nitro groups; phthalonitrile compounds substituted by amino groups; Alkyl substituted phthalonitrile compounds such as methylphthalodinitrile and ethylphthalodinitrile; Alkoxy or aryloxyphthalodinitrile compounds such as methoxyphthalodinitrile, phenoxyphthalodinitrile and ethoxyphthalodinitrile; and heterocyclic dinitrile compounds such as 2,3-dicyanopyridine. The dinitrile compounds can also be used as mixtures.

As copper compounds according to the present invention, for. B. copper (I) oxide, copper (II) oxide, copper (I) bromide, copper (II) bromide, copper sulfate, copper hydroxide and preferably copper (I) chloride, copper (II) chloride and copper acetate can be used. Copper is used in the form of copper powder.

The copper or copper compound is preferably used in an amount of one or more moles to four moles of the dinitrile compound.

Examples of alkaline substances used in the present invention are sodium oxide, sodium peroxide, sodium carbonate, potassium oxide, potassium peroxide, potassium hydroxide, potassium methoxide, potassium carbonate, magnesium oxide, magnesium hydroxide, calcium oxide, calcium peroxide, calcium hydroxide, barium oxide, barium hydroxide and preferably metallic sodium, sodium methoxide and sodium hydroxide .

The alkaline substances serve to keep the reaction medium alkaline and to make the reaction run evenly.

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The alkaline substances will advantageously be used in an amount that inhibits crystal growth and stabilizes

from up to two moles to one mole of dinitrile, but the effect achieved, even in the case of the alpha pigment. Examples

The amount of alkali, depending on the value of the etrazaporphinder, is:

applied copper salt and the valence of the metal of the I) chlorinated copper phthalocyanines, such as. B. mono-, di-

alkaline compound vary. If e.g. B. sodium hydroxide 5 or trichloro copper phthalocyanine.

is used and the copper is monovalent, one uses n) copper phthalocyanine sulfonic acids, eg. B. CuPc (S03H) n preferably 0.25 to 0.5 mol of NaOH per mol of the dinitrilever (where n = 1 to 4)

bond to and if the copper is divalent, it is preferred to use 0.5 to 0.75 mol of NaOH per mol of dinitrile compound. ] 0

The following hydrophilic aliphatic solvents with a hydroxyl group can be used in the process according to the invention: mono- or polyhydric hydrophilic alcohols, such as propanol, isopropanol, n-butanol, isobuta-

nol, secondary butanol, t-butanol or ethylene glycol, preferably methanol or ethanol, hydrophilic cellosolve products

("Cellosolve" is a registered trademark) such as B. up to 20 weight percent, preferably 1 to 10 weight percent

Methyl cellosolve, ethyl cellosolve and diethylene glycol ethyl cent, based on the weight of the pigment produced. The

These solvents can be used alone or in a mixture with a metal tetrazaporphine derivative at any point in time. 20 In the course of the manufacturing process or at the end of the same

The solvents can be added in any desired amount, or it can coexist with the copper tetraza.

be used if the reaction proceeds smoothly. Normal porphine pigment can be produced in situ.

The solvent is loaned in 2.0 to 15 times the amount of the condensation reaction according to the present invention

Dinitrile compound applied. is carried out at a temperature below 100 ° C and

The reaction in the reaction as catalyst and / or crystal form can vary depending on the solvent used.

copper tetrazaporphin used may be depending on the influencer. In particular, however,

good results for the desired pigment type in the alpha, beta or gamma at 70 ° C.

Form are used. The copper tetrazapor used. After the reaction has ended, a pigment with

The amount of phin can be from 0.5 to 200 percent by weight, based on the color and high color strength,

the pigment produced, vary, depending on an alpha, beta filtering, washing with water and drying of the or gamma pigment is desired. Obtained in the manufacture of the reaction product. If necessary, the pigment alpha or gamma copper tetrazaporphin is the amount before filtering and drying with dilute aqueous alpha or gamma copper tetra acid used for vaccination and / or dilute aqueous alkali aftertreated zaporphin 0.5 to 40 percent by weight and preferably 0 , 5 to be.

20% by weight for alpha pigments and 20 to 40%. 35 The copper tetrazaporphine pigments thus produced have

percent by weight for gamma pigments, based on the weight sen high color strength and pure color and they require the pigment produced. No special steps to reduce the particle size in the production of beta-Kup

Finished tetrazaporphin, on the other hand, is the size of the crystal shape, as is the case with the

flux / catalyst used amount of beta-copper tetra-pigment is the case.

zaporphin at least 40 percent by weight and preferably 40 if according to the preceding description of the invention

at least 51 percent by weight, in particular 100 to 150 genes in the reaction to form a complex with the copper

Percentage by weight, based on the pigment produced. In the case of a compound suitable for salt, for example dimethylglyoxime, a 100% beta pigment can be added to the reaction mixture in order to use such amounts, so that one element can be obtained directly in one step. If the selected tetrazaporphin pigment obtained in higher yield.

During the production process, the amount of beta-45 according to a further embodiment of the invention

Copper tetrazaporphin less than 40 weight percent was found to be a pigment with improved texture, gamma / beta blends are obtained instead of when using a hydrophilic organic solution

Obtain 100% beta pigment. The gamma / beta mixture is used and immediately after the reac-

by subsequent treatment with acid or ion, without prior isolation of the pigment, a small amount of a suitable aromatic organic solvent, 50 amount of acid is added with stirring.

for example toluene, xylene or diethylaniline, inorganic acids such as salt beta pigment are converted into 100% usable acids. acid, sulfuric acid, phosphonic acid; as well as organic acids

Another embodiment of the invention provides the veins such as acetic acid, propionic acid and oxalic acid.

Turning of one or more organic or inorganic compounds. If the acid is added to a stabilized alpha-pigment ammonium salt, in addition to the alkaline substance, or 55 ment or a beta pigment, the required acidity becomes. Examples of suitable inorganic or organic remainders, depending on the type of the hydrophilic organic ammonium salts, are ammonium chloride, ammonium sulfate, see solvent of different sizes, usually ammonium persulfate, ammonium orthophosphate, ammonium - but an amount of 0.5 to 75 percent by weight, preferably metaphosphate, Ammonium pyrophosphate, ammonium carbo- from 3 to 50 percent by weight, based on the weight of the nat, ammonium bicarbonate, ammonium formate, ammonium-60 hydrophilic organic solvent. This acetate and ammonium oxalate. The ammonium salts are pre-amount corresponds approximately to 0.015 to 2 times the structure-particulate in amounts of 0.1 to 10 weight percent, most preferred pigment, and it means a commercial evidence of 0.5 to 6 weight percent, based on the dinitrile - Part that uses the process with such a small amount of acid. can be carried out.

It has also been found that it is advantageous to use a reductant such as pyridine if the acid is added to a suspension of unstabilized agent such as sodium hydrosulfite and / or a nitrogenous alpha-pigment. ker mineral acid, e.g. B. 98% sulfuric acid or conc. If necessary, a metal tetrazaporphine derivative trated phosphoric acid, preferably 30 percent by weight

^ (S02NH.CH2.CII20H) 2

III) CuPc ^ 0 ^ and

(S03MI3.CH2C1I20H) 2

IV) l, 2,4-trichloro-3-phenoxy-copper phthalocyanine. The amount of tetrazaporphine derivative added is 1

626114

do not exceed; if organic acid is used, its amount should not exceed 40 percent by weight, in both cases based on the weight of the solvent.

The acid is best added dropwise and as soon as the mixture becomes more acidic, the pigment is filtered off, washed and dried. If necessary, the reaction mixture can be treated with a dilute aqueous alkaline solution after filtering. The acid can be satisfactorily removed from the pigment by filtering and washing with water.

The following Examples 1 to 3 illustrate the invention.

example 1

The following are added to 100 g of methanol: 0.9 g of dimethylglyoxim. After its dissolution, 6.2 g of copper (I) chloride are added.

The mixture is stirred until the formation of the dark brown complex has ended and then added: 32 g of phthalonitrile, 3.0 g of ammonium chloride, 3.0 g of beta copper phthalocyanine, 1.0 g of 1,2,4-tri-chloro-3- phenoxy copper phthalocyanine.

The mixture is stirred for one hour at room temperature and then slowly added: 5 g of sodium hydroxide, while slowly adding dropwise a solution of 1 g of pyridine in 10 ml of methanol. After the addition has ended, stir for Vi hour at room temperature; finally cook under reflux for 8 hours. After cooling to room temperature, 60 g of concentrated sulfuric acid (98%) are added dropwise. Stir for one hour at room temperature. The mixture is then neutralized by adding aqueous sodium hydroxide and then stirred for Vi hour at room temperature, whereupon 30 ml of diethylaniline are added. The mixture is refluxed for 1½ hours to obtain 100% beta-phthalocyanine.

50% hydrochloric acid is then added at room temperature until the pH is 1 to 2 and the mixture is stirred for an additional hour. The product is finally filtered off, washed first with methanol, then with hot dilute hydrochloric acid and then with hot dilute sodium hydroxide and dried at 50-60 ° C. The yield is 36 g.

Example 2

A similar procedure to that described in Example 1 is followed, but alpha-phthalocyanine is used in place of beta-phthalocyanine as the inoculant and, after 8 hours of refluxing, is cooled to room temperature, after which 60 g of 98% sulfuric acid are added dropwise. The mixture is stirred at room temperature for one hour and then under for half an hour

Reflux cooked. The mixture is finally filtered, washed with methanol, then with hot dilute hydrochloric acid and then with hot dilute sodium hydroxide, followed by drying at 50-60 ° C. The yield of alpha copper phthalocyanine pigment is 36 g.

Example 3

0.9 g of dimethylglyoxime are dissolved in 350 ml of methanol, 6.2 g of copper (I) chloride are added and the mixture is stirred until the dark brown complex has formed. The following are then added: 32 g of phthalonitrile, 3.0 g of ammonium chloride, 45 g of beta copper phthalocyanine and

1 g l, 2,4-trichloro-3-phenoxy copper phthalocyanine.

The mixture is stirred at room temperature for one hour, then 4 g of sodium metal are slowly added over the course of 40 minutes, with the simultaneous dropwise addition of 1 g of pyridine, dissolved in 10 ml of methanol. After the addition of sodium and pyridine has ended, the mixture is stirred for half an hour at room temperature.

After the mixture has been boiled under reflux for 8 hours, the mixture is filtered, washed with methanol and then with hot, dilute sodium hydroxide. After washing with water, stirring for one hour at 90-95 ° C in dilute aqueous hydrochloric acid, the product is filtered off, washed neutral and dried at 50 ° -60 ° C. The yield of beta copper phthalocyanine pigment is 77 g.

Comparative Example A

32 g of phthalonitrile (95% purity), 4.5 g of sodium hydroxide and 2 g of sodium carbonate are added to 100 g of methanol.

The mixture is stirred at room temperature and a solution or fine dispersion is obtained; then add: 1 g ammonium chloride,

2 g ammonium phosphate, 8.4 g copper (II) chloride.

Stir for one hour at room temperature and then reflux for 10 hours. Filter, wash with methanol, then with hot dilute hydrochloric acid and hot dilute sodium hydroxide. Wash neutral and dry at 50-60 ° C. The yield is 19.4 g.

Comparative Example B

32 g of phthalonitrile (95% purity) and 6.2 g of copper (I) chloride, 3.0 g of ammonium chloride are added to 100 g of methanol.

The mixture is stirred at room temperature for 1 hour and slowly added: 5 g of sodium hydroxide, stirred for 10 minutes, then 0.9 g of dimethylglyoxime are added. Stir at room temperature for half an hour, then reflux for 8 hours. Filter, wash with methanol, then with hot dilute hydrochloric acid and hot dilute sodium hydroxide. Wash neutral and dry at 50-60 ° C. The yield is 22 g.

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Claims (10)

626114 PATENT CLAIMS 1. Process for the preparation of alpha, beta or gamma copper tetrazaphorphin pigments, characterized in that an ortho-dinitrile compound of the general formula I -C CN r I A I ^ _ C CN in which A together with the carbon atoms to which it is attached forms an aryl or aromatic heterocyclic radical, X represents hydrogen or a halogen atom or a nitro, amino, carboxyl, alkyl, alkoxy or aryloxy group, and n represents an integer from 1 to 4; and copper or a copper compound capable of releasing the central metal atom of a tetrazaporphin pigment, at a temperature below 100 ° C in the presence of an alkaline substance in a hydrophilic aliphatic organic solvent containing one or more hydroxyl groups, and a copper at the start of the reaction -trazaporphin in the pigment form as a catalyst or crystal form influencer, or both. 2. The method according to claim 1, characterized in that the ortho-dinitrile means phthalonitrile. 3. The method according to claim 1 or 2, characterized in that the copper compound which can release the central metal atom of the tetrazaporphin pigment is either copper (I) chloride, copper (II) chloride or copper acetate. 4. The method according to any one of claims 1 to 3, characterized in that the copper or the copper compound is used in an amount of one or more moles to four moles of the dinitrile compound. 5. The method according to any one of claims 1 to 4, characterized in that sodium metal, sodium umoxid or sodium hydroxide is used as the alkaline substance. 6. The method according to any one of claims 1 to 5, characterized in that the alkaline substance is used in an amount of up to 2 moles to one mole of dinitrile. 7. The method according to any one of the preceding claims, characterized in that the hydrophilic hydroxy group-containing aliphatic solvent methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, secondary-butanol, t-butanol, ethylene glycol, ethylene glycol mono-methyl ether or ethylene glycol monoethyl ether is 8. The method according to any one of claims 1 to 7, characterized in that the amount by weight of the hydrophilic aliphatic solvent used is 2.0 to 15 times the amount of dinitrile. 9. The method according to claim 1 or 2, characterized in that the alpha, beta or gamma form is used as copper tetrazaporphin catalyst or crystal form influencer. 10. The method according to claim 9, characterized in that alpha-copper tetrazaporphin in an amount of 0.5 to 20% by weight, based on the weight of the pigmehts produced, is added.