DE1233521B - Process for the preparation of phthalocyanine dyes - Google Patents

Description

DESREPUBLIC OF GERMANY

CZECH

PATENT OFFICE

EDITORIAL

Int. Cl .:

C09b

C09B 4 7/08.

German class: 22 e- 7/02

Number:
File number:
Registration day:
Display day:

1233 521
J227611Vc / 22e
3rd December 1962
2nd February 1967

The invention relates to the production of new phthalocyanine compounds, in particular new compounds of the copper phthalocyanine series, which are used as reactive dyes are valuable.

An important property of one that reacts with cellulose As is known, dye consists in the fact that, after the dyeing or printing process, the part the dye on or in the material that is not chemically bound to the cellulose molecule, must wash out of the material. This is especially the case when it comes to printed fabrics otherwise the white parts of the fabric will be discolored during normal washing will. A number of phthalocyanine reactive dyes have been put on the market, the typical ones to provide bright greenish-blue colors that are characteristic of this chromophore, however, all of which, to some extent, have the disadvantage that adjacent material during post-wash treatments becomes discolored.

It has now been found that valuable reactive dyes are obtained which do not have this disadvantage if a copper phthalocyanine polysulfonic acid chloride optionally containing sulfonic acid groups with ammonia, piperazine and a 1,3,5-triazine containing at least 2 halogen atoms or a pyrimidine bearing at least 3 halogen atoms to form a mixture of compounds of general formula

(SO ₃ H) ₁

CH ₂ -C

CH ₂ -CH ₂

~ ^R

in which CuPc is the copper phthalocyanine nucleus, χ and ν each have the value 0.1 or 2, r has the value 1 or 2, the sum of .v, y and r is at most 4 and R is a halo-1,3.5 -triazine- or a pyrimidine group bearing at least 2 halogen atoms means, condensed in such proportions that one has an apparent value for χ from 0.5 to 2, for y from 0.5 to 1.5 and for - from 1 to 1.5 receives. R is, for example, a 2,4-dibromo or, preferably, 2,4-dichloro-1,3,5-triazinyl and also a 2-bromo or 2-chloro-1,3,5-triazine group which contains a group which is bonded via a nitrogen, oxygen or sulfur atom, e.g. B. an amino or substituted amino group, an etherified hydroxyl or etherified mercapto group. Examples of substituted processes for the production of
Phthalocyanine dyes

Applicant:

Imperial Chemical Industries Limited, London

Representative:

Dr.-Ing. H. Fincke, Dipl.-Ing. H. Bohr
and Dipl.-Ing. S. Staeger, patent attorneys,
Munich 5, Müllerstr. 31

Named as inventor:

Victor David Poole,

Manchester, Lancashire (UK)

Claimed priority:

Great Britain 4 December 1961 (43 242)

Amino, etherified hydroxyl or etherified mercapto groups are alkylamino groups, especially low molecular weight alkylamino groups, such as methylamino, Ethylamino, propylaraino, dimethylamine, diethylamino or N-methyl-N-propyJarainogruppen, substituted alkylamino groups, e.g. B. substituted low molecular weight alkylamino groups, like ß-Hydroxyäthylamino-, Di - (/} - hydroxyäthy)) - araino- and benzylamino groups, cycloalkylamino groups such as cyclohexylamino groups, arylamino groups, such as phenylamino, naphthylamine, chlorophenylamino, Methoxyphenylamino, tolylamino and nitrophenylamino groups, N-alkyl-N-arylamino groups, like N-methyl-N-phenylamino-, N-methyl-N-sulfophenylamino- and N- / 5-hydroxyethyl-N-tolylamino groups, and heterocyclic amino groups, such as piperidyl and morpholino groups, especially substituted amino groups, the one Contain hydroxyl, carboxyl or sulfonic acid groups, such as sulfophenylamino, carboxyphenylamino, disulfophenylamino, sulfonaphthylamino, sulfoäthylamino- and sulfatoethylamino groups, alkoxy groups, especially low molecular weight alkoxy groups, such as Methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy groups, residues of phenols, such as Phenols, such as phenoxy, p-tolyloxy, p-sulfophenoxy, p-chlorophenoxy, p-carboxyphenoxy and 2'-nitro-4'-sulfophenoxy radicals, aliphatic thio groups, such as

709 501/357

3 4

Methylthio-, ethylthio-, ß-hydroxyethyltbio-, ß-Cavb- of cyanuric chloride and cyanuric bromide with ammonia

oxyäthylthio and carboxymethylthio groups, and or an organic primary or secondary,

the residues of thiophenols, such as phenylthio, p-chloro-amine or a hydroxy or mercapto compound,

phenylthio, p-nitrophenylthio and p-sulfophenyl such as methylamine, ethylamine, / S-hydroxyethylamine,

thioreste. 5 dimethylamine, di - (/ 9-hydroxyethyl) amine, cyclo-

Examples of at least two halogen aioms ent- hexylamine, benzylamine, aniline, o-, m- and p-chlorine

holding pyrimidine groups R are 2,4-dibromo or aniline, o-, nv and p-anisidine, o-, in- and p-toluidine,

l ^ -Dichlor-o-pyrimidyl-, 4,6-dibromo- or 4,6-di- o-aminobenzenesulfonic acid, m-aminobenzenesulfone-

chloro-2-pyrimidyl, 2,4,5-tribromo or 2,4,5-tri acid, p-aminobenzenesulfonic acid, anthranilic acid,

chloro-6-pyrimidyl, 4,5,6-tribromo or 4,5,6-TYi-io aniline-2,5-disulfonic acid, / I-naphthylamine, 2-naph-

chloro-2-pyrimidyl, 2,4-dibromo- or 2,4-dichloroethylamine-6-aulphone acid, 2-naphthylamine-3,6-disulphone

5-cyano-6-pyrimidyl, 2,4-dibromo or 2,4-dichloric acid, piperidine and morpholine, methanol, phenol,

S-carbomethoxy-O-pyrimidyl- and 2,4-dibromo-P-nitrothiophenol, p-chlorothiophenol, benzyl mer-

or 2,4-dichloro-5-caΓboxy-6-pyrimidyl groups. captan, methyl mercaptan, thioglycol or thio-

The preferred mixtures of compounds of glycolic acid.

general formula are those of compounds The compounds of the general formula in which of this general formula, in which the substituents R is a 1,3,5-triazine radical which is a single halogen the 3 'positions of the phthalocyanine nucleus are atom and contains a group that and R is a 4-chloro-1,3,5-triazin-2-yl radical, in which a substance atom is bonded, can according to the invention the carbon atom in the 6-position of the triazine nucleus also by converting a cyanuric halide in legs Chlorine, amino, sulfo-N-methylanilino, phen- any order with a) one mole of ammonia oxy-, / I-hydroxy-ätbylamino-, sulfoanilino-, tolylthio- or a primary or secondary amine or or in particular carries a methoxy radical. b) with one mole of piperazine and implementation of the

The new phthalocyanine compounds can after holding the condensation product with a copper

of the invention by condensation of a copper 25 phthalocyanine, the four sulfonic acid chloride or three

phthalocyanine tetrasulfonic acid chloride of a copper sulfonic acid chloride and a sulfonic acid group or

phthalocyanine trisulfonic acid chloride - monosulfonic acid two sulfonic acid chloride and two sulfonic acid groups

or a copper phthalocyanine disulfonic acid chloride or mixtures thereof in the presence of Am-

disulfonic acid or a mixture of these compounds can be obtained. These connections can

fertilize in an aqueous medium with a monoacyl 30 according to the invention also by condensation of the

piperazine in the presence of ammonia, splitting off compounds of the general formula in which R is a

of the acyl group by hydrolysis, and subsequent 2,4-dichloro-1,3,5-triazine radical, with 1 mol of ammonia

Obtained condensation of the product obtained with a or a primary or secondary amine

Moles of one containing at least two halogen atoms.

1,3,5-triazine compound or at least three 35 The novel Pbthalo-

Halogen atom c-containing pyrimidine compound per cyano compounds are valuable for coloring

present Suü'opiperazidgruppe can be obtained. Textile goods, especially cellulose textiles, such as tree

The two condensations can suitably be wool, linen and rayon. According to the invention

by stirring the reaction partners in a dyes that can be prepared are preferably on

liquid means are carried out, the preferably 40 textile material together with an acid-binding agent

a solvent for at least one of the reaction applied, which is applied to the textile before, during

participant is. Preferably, water is used or applied after the dyes have been applied

or a mixture of water and one with water. Examples of acid binding agents are

miscible solvents, such as acetone, and works with sodium carbonate, sodium hydroxide, sodium meta-

at a temperature of 0 to about 50 ⁰ C or in 45 silicate and trisodium phosphate. There can also be

in some cases even higher. Optionally, bonds such as sodium bicarbonate can be used

to neutralize the liberated and trichloroacetic acid sodium, which is

Heat an acid-binding agent to heat hydrogen halide and split off an acid-binding agent. These

set. Fabrics can be applied to textile goods after a dyeing, padding

The hydrolysis is expediently applied by heating or pressure processes. The for

the product obtained in the first condensation dyeing or padding used aqueous solutions

in a strongly acidic aqueous medium with boiling or the dyes, any of the usual dyeing auxiliaries

carried out close to the boiling point. contain agents such as sodium chloride, sodium sulfate,

The sulfonic acid chloride groups and sulfonic acid sodium alginate, sodium dibenzyl sulfanilate, urea groups in the starting compounds can form ^{soluble and} water-soluble alkyl ethers of cellulose. If the dyes are not applied to the textile material either in the 3 'positions or in the 4' positions after a printing process or in the two mentioned positions of the phthalo drive, the printing paste containing the cyanine nucleus can stand. Examples of triazines and pyrimidines that can be used in those processes of the invention that are normally added to printing pastes, such as urea, ethanol and sodium m-nitrones, are 2,4,6-tribromopyrimidine , 2,4,6-trichlorobenzenesulfonate. Thickeners for use with the pyrimidine, 2,4,5,6-tetrachloropyrimidine, 2,4,5,6-tetra- new dyes are alginates such as sodium alginate. brompyrimidiivSCyan ^ Aö-tricMorpyrirrudin.S-Cyan- The dyes that can be prepared according to the invention can also be used for coloring natural proteins, such as wool, pyrimidine, 5- Carboxy-2,4,6-tribronipyrimidine, 5-car- 65 silk and leather, as well as synthetic polyamides and boniethoxy-2,4,6-trichloropyrimidine, 5-carbometh-polyacrylonitrile, can be used. Green oxy-2,4,6-tribromopyrimidine, cyanuric bromide, cyanuric blue shades with high fastness to washing, anuric chloride and the primary condensation products are obtained by treating these materials in a slightly alkaline,

5 6

treated with a neutral or acidic solution of the dye. temperature for a period of one hour at 6O ⁰ C

The dyeing of wool is preferably increased.

Presence of a canonical surfactant add 250 parts of concentrated hydrochloric acid

Compound, such as stearylamide methylpyridinium chloride, added and the mixture at 90 to 3 hours

Cetylpyridinium bromide or cetyltrimethylam- 5 95'C stirred. After cooling down to 20 ° C

Monium bromide and preferably also in counter-the crystals are filtered off with 10% aqueous hydrochloric acid

was a nonionic surfactant - washed and dried.

binding through, such as the polyaducts of ethylene oxide Analysis of this mixture shows that 11.3 nitrogen

with fatty alcohols, alkylphenols and long-chain substance atoms per copper atom. This shows that

Alkylamines. io 1.3 sulfonamide groups and 1.0 sulfopipsrazide groups

In this form of application, the copper atoms present according to the invention result in a bright greenish color according to the dyes that can be produced. ■ \ i blue dyeings having excellent resistance e ι s ρ ι e to light and wet treatments such as washing and 9.6 parts of the Example 1 using the mixture hypochlorite bleach. They have an excellent coloring power of copper phthalocyanine-N-3-sulfopiperazide-sulfone and can produce strong color tones. Amide-sulfonic acids are warped with 700 parts of water. They differ not only in the fact that they are stirred and mixed with a sodium hydroxide solution, the property mentioned above, namely in that until a clear solution is obtained. After the dyeing or loading, the solution is cooled to 5 ° C. and unreacted dye is washed out with a solution of 1.9 parts of print, but rather that of the cyanuric chloride in 50 parts of acetone is added. The dyestuff separated from the fabric also does not cause any deterioration. The pH value of the mixture is produced and retained between 6.0 and 6.5. As soon as the implementation is finished, you will get exceptionally bright colors. 15 parts of 4N solution of ammonia was added and the GeGegenüber heats the reactive dyes of the phthalocyanine 25 mixed to 35 to 4O ⁰ C and stirred for 1 hour, series of Examples 2 and 23 of the French The mixture is cooled to, with 150 parts of Patent 1,270,859 If the dyestuffs produced according to the Er salt added and the precipitated dyestuff is filtered off, the advantage is that they, if dried, do not bleed out so severely. The analysis of this product gives a value of

The parts and proportions given in the examples are 3.3% saponifiable chlorine; this value corresponds to 1.0

percentages relate to weight. reactive groups in the molecule.

τ. ■ ■ ι λ example3

Example I 1 ^v

3.5 parts of N-methyl-m-aminobenzenesulfonic acid are

9.6 parts of a mixture of which the following 35 is stirred with 50 parts of water and the copper phthalocyanine pH of 7 obtained in a manner described with 1 η sodium hydroxide solution. The Lö-N-3-aulfopiperazid-sulfonamide-sulfonic acids are ^{cooled to 0} ° C. and stirred with a solution of 700 parts of water and a 4% strength of 3.5 parts of cyanuric chloride in 50 parts of acetone-sodium hydroxide solution is added, until a clear solution is found. The pH of the mixture is maintained by entering. A solution of the corresponding addition of 1N sodium hydroxide solution between 2 parts of 2,4-dichloro-6-methoxy-1,3-triazine in 50 parts of 6 and 6.5 is then kept at 20 to 25 ° C. As soon as the reaction has ended, acetone is added. The temperature is raised slowly to a solution of 3.6 parts Piperazinhydrat at 35 ^c C and the pH-value added by the addition of 30 parts of water so that the pH of the! -Natronlauge between 6.0 and 6.5 held. As soon as the mixture is kept between 7.0 and 7.5. After the reaction has ended, 150 parts of salt are added, after the addition is complete, 18 parts of 1N sodium hydroxide solution are added, the precipitated dye is filtered off and the solution is dried, and the clear solution becomes one. stirred suspension of copper phthalooyanine sulfo-

Analysis of this product reveals a chloride content (obtained from 7.2 parts of copper phthalocyanine

hydrolyzable to 3.2 ° / ₀ chlorine. This value corresponds to the one described in the second section of example 1

1.0 reactive groups in the molecule. 50 benen method) added in 400 parts of ice water.

The mixture of copper phthalocyanine-N-3-sulfo- The mixture is ^{heated to 50 0} C for 1 hour while

piperazide-sulfonamide-sulfonic acids can be found as follows to determine the pH of the mixture by corresponding

be made: addition of 4n-N-ammonia solution at 8 holds. As soon

57.6 parts of copper phthalocyanine are slowly completed in the reaction, the solution is introduced to 2O ⁰ C, 270 parts of chlorosulfonic acid, and the Ge 55 is cooled, mixed with 120 parts of salt and the mixture is stirred at 135 to 143 ° C for 3 hours . The precipitated dye was filtered off and dried. Mixture is cooled to 80 C and ^c within an analysis of this product gives a value hour with 50 parts of thionyl chloride. Then 3.7% saponifiable chlorine. This value corresponds, the mixture is stirred for 2 hours at 85 to 9O ⁰ C. 1.5 reactive groups per copper atom. The mixture is cooled to 2O ⁰ C, on ice overall 6 _"Q. poured off and the precipitated sulfonyl chloride B e s 1 e ρ 1 I e b 1 s 4 filtered and 6 with 600 parts of l% aqueous hydrochloric acid The procedures of Examples 1, 2 and 3 are washed at 0 ⁰ C. repeated, but instead of the mixture, the in

The sulfonic acid chloride is in 800 parts of ice - these examples used copper phthalocyanine

suspended in water and with 18.4 parts of monoacetyl- «5 N-3-sulfopiperazide-sulfonamide-sulfonic acid in each

piperazine hydrochloride added. The pH of the trap the mixture of copper phthalocyanine-3,4 ', 4 ",

Mixture is used by adding 4n-ammonia- 4 "'- sulfopiperazide-sulfonamide-sulfonic acids,

solution kept at pH-8, while the tempe- ration of 93 parts of the potassium salt

Example 12

of copper phthalocyanine tri-'l-sulfonic acid in place of 57.6 parts of copper phthalocyanine is obtained.

Analysis of this mixture shows that it contains 11.3 nitrogen atoms per copper atom. This shows, that 1.3 sulfonamide groups and 1.0 sulfopiperazide groups present per copper atom. The end products have 1.0, 1.0 to 1.5 reactive groups each Copper atom.

Example 7

If the 2,4-dichloro-6-methoxy-1,3,5-triazine used in Example 1 against 2.7 parts of 2,4-dichloro-6-phenoxy-1,3,5-triazine replaced, a 2.9% saponifiable chlorine is obtained (corresponding to 1.0 reactive Groups per copper atom) containing product.

Example 8

If the ammonia solution used in Example 2 is replaced by 1.2 parts of monoethanolamine one containing 3.1% saponifiable chlorine (corresponding to 1.0 reactive group per copper atom) Product.

Example 9

If you use the N-methylm-aminobenzenesulfonic acid used in Example 3 Replaced by 3.3 parts of m-aminobenzenesulfonic acid, a 3.7% saponifiable acid is obtained Product containing chlorine (corresponding to 1.5 reactive groups per copper atom). at Using 4.8 parts of aniline-3,5-disulfonic acid, a chlorine containing 3.3% saponifiable is obtained Product.

Example 10

If you use the ammonia solution used in Example 2 against a solution of 1.3 parts of p-thiocresol Replaced in 10 parts of sodium hydroxide solution, a 2.9% saponifiable chlorine is obtained (corresponding to a reactive Group per copper atom) containing product.

do

Example 11

9.6 parts of a mixture of copper phthalocyanine-3-sulfopiperazide-sulfonamide-sulfonic acids, prepared according to Example 1, are stirred with 700 parts of water and a 4% sodium hydroxide solution is added until a clear solution is obtained. Then a solution of 1.9 parts of cyanuric chloride is added in 50 parts of acetone at 5 to 1O ⁰ C. The pH of the mixture is kept at 6.0 to 6.5 by adding 1N sodium hydroxide solution. As soon as the reaction has ended, 150 parts of salt are added, and the precipitated dye is filtered off and acetone is added, and the mixture is heated to 55.degree. The pH of the mixture is kept at 6.5 by adding 1N sodium hydroxide solution. As soon as the reaction has ended, 80 parts of salt are added, the precipitated dye is filtered off and dried.

Example 13

In the method of Example 12, 2.4 parts of 2,4,5,6-tetrachloropyrimidine be used in place of 2,4,6-trichloropyrimidine, and it is carried out at a temperature of 45 ⁰ C in place of 55 ⁰ C. A similar product is obtained.

Example 14

In the method of Example 12, 2.1 parts of 5-cyano-2,4,6-trichloropyrimidine used in place of 2,4,6-trichloropyrimidine, and it is at an operating temperature of 20 to 25 ° C instead of 55 ⁰ C worked. A similar product is obtained.

Claims (3)

Patent claims: 1. Process for the preparation of phthalocyanine dyes ^ characterized in that one optionally contains sulfonic acid groups containing copper phthalocyanine polysulfonic acid chloride with ammonia, piperazine uod a 1,3,5-triazine containing at least 2 halogen atoms or at least 3 halogen atoms containing pyrimidine to a mixture of compounds of the general formula CuPc- (SO ₂ NH ₈ ) S, ,, CH ₃ -CH _2x 2 \ :No CH ₂ -CH ₂ ' dries. It contains 5.9% saponifiable chlorine, accordingly
atom. 1.0 reactive group per copper 55 8.7 parts of a mixture of copper phthalocyanine-N-3-sulfopiperazide-sulfonamide-sulfonic acids, prepared according to Example 1, are stirred with 400 parts of water and a 4% strength sodium hydroxide solution is added until a clear solution is obtained. This is followed by a solution of 2.0 parts of 2,4,6-tricblorpyrimidine in 40 parts in which CuPc is the copper phthalocyanine nucleus, R is a halogen-1,3,5-triazine or a pyrimidine group containing at least 2 halogen atoms, χ and y each have the value 0, 1 or 2, ζ has the value 1 or 2 and the sum of x, y and ζ is at most 4, condensed in such proportions that an apparent value for .v of 0.5 to 2, for y from 0.5 to 1.5 and for ζ from 1 to 1.5. 2. Modification of the method according to claim 1, characterized in that in place of the Piperazins uses a monoacylpiperazine and the acyl group by hydrolysis before condensation with the triazine or pyrimidine starting compound. 3. Further development of the method according to claim 1 or 2, characterized in that the phthalocyanine dye in which R is a Dichloro-1,3,5-triazine radical, further condensed with ammonia or a primary or secondary amine, Considered publications:
French Patent No. 1 270 859. When the registration was announced, 1 coloring table with explanations was laid out. 709 507/557 1.67 © Bundesdruckerei Berlin