DE1959308A1 - Dye salts of the phthaloxyanine series - Google Patents

Description

Badisehe Anilin- & Soda-labrik AG

Our reference: OZ 26 492 Hee / Hu
6700 Ludwigshafen, Nov. 25. 1969

Dye salts of the phthalocyanine series

This invention relates to new phthalocyanine series dye salts and their use.

The new dyes have the general formula

in the Pc the remainder of a metal-containing phthalocyanine,
X a basic dye,

Y is an aliphatic amine with at least 4 carbon atoms,

1 2

which contains at least one ether group, R and R hydrogen atoms, aliphatic ^ hydrocarbon radicals, the hydroxy and /
or ether groups, or together with the nitrogen atom of the sulfonamide group common members of a heterocyclic ring,

m 1,2 or 3 »η 0, 1, 2 or 3, ρ 0, 1, 2 or 3,
η + ρ 1, 2 or 3 and m + η + ρ 2, 3 or 4 mean.

The dye salts according to the invention are derived from metal-containing phthalocyanines, for example from iron, cobalt,
Nickel, but especially from copper phthalocyanine.

The new dye salts contain, for example, xanthene dyes, such as rhodamine dyes, or di- or triarylmethane dyes, such as malachite green, diamond green, rhodulin dyes, methyl, ethyl or crystal violet, victoria dyes and fuchsine as basic dyes. Of particular technical interest
are the new dye salts that contain xanthene dyes as basic dyes.
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As aliphatic ^ amines with at least 4 carbon atoms and The new dye salts can contain at least one ether group e.g. straight-chain or branched, primary, secondary or tertiary amines with up to 30 carbon atoms and 1 to 3 ether groups contain. Of these amines, the saturated amines having an alkoxy group are preferred. Examples are the ethylamines or propylamines, the ß- or ^ -position alkoxy groups with 1 to 18 carbon atoms, such as ethoxy, propoxy, Butoxy, pentoxy, hexoxy, octoxy, nonoxy, decyloxy, dodecyloxy or trideoyloxy groups, including the isomers Members such as isopentoxy, 2-ethylhexoxy, isononoxy or isotridecyloxy groups contain, as well as their N-methyl or U, Ii-dimethyl derivatives, such as Ν, ΙΙ-dimethyl-isopentoxy- or -2-ethylhexoxypropylamine.

As substituents of the sulfonamide group (R and R) there are e.g. alkyl radicals substituted by hydroxyl and / or ether groups with up to 6 carbon atoms, such as hydroxyethyl, propyl, Isopropyl, 2- or 3-hydroxypropyl, methyl, ethyl, butyl, Isobutyl, 3-hydroxybutyl, 1,3-dihydroxyisobutyl, methoxyethyl, Methoxypropyl-, ethoxypropyl-, eth- or hydroxethoxy-

1 2

ethyl residues into consideration. The substituents R and R are members of a heterocycle, they form, for example, a morpholine ring.

Of the new dye salts, the compounds are particularly valuable the formula

CuPc

in which CuPc a copper phthalocyanine st, Z a dye of the rhodamine series, preferably rhodamine B, R a straight-chain or branched aliphatic radical with 2 to 18 carbon atoms, preferably the radical -CH ₂ -GH- (CH ₂ ) ₅ -CH ₃ ,

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R ^ is a hydroxyalkyl radical with 2 to = 6 carbon atoms, Έ? a hydrogen atom, an alkyl residue 1 to 3 carbon atoms or the radical R,
q, s and t are 1 or 2 and q + s + t are 3 or 4.

The new dye salts of the formula I are prepared, for example, by reacting phthalocyanine derivatives of the formula

m + n

(SO ₉ -N - '*

1 . III,

with the basic dyes (m.X) and, in the event that η does not represent 0, with the amines (n.Y) advantageous in this Order. The sulfonic acid groups of the phthalocyanine derivatives can be used also exist in the form of the alkali or ammonium salts and the basic dyes and amines also in salt form, e.g. as formates, acetates, hydrochlorides or nitrates. The conversion to the formation of the dye salts decreases for economic reasons it is expedient to use an aqueous medium. But you can also, e.g. sparingly soluble or insoluble in water React starting materials j in organic solvents, e.g. in alcohols.

Depending on the choice of the basic dye, the greenish blue shade of the phthalocyanine derivative used as the starting compound becomes of formula III shifted more or less to yellow or red. Because of their pure reddish shade of blue the new dye salts containing rhodamine dyes from special coloristic interest.

The dye salts according to the invention are acidic to neutral Water sparingly to insoluble. However, they dissolve in organic Solvents, preferably those based on alcohol. Through a suitable combination of sulfonamide residues with sulfonic amine groups can reduce the solubility of the final dyes especially influenced by alcoholic agents, which can be determined by possible preliminary tests.

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The new dye salts are suitable for the production of printing inks, Ballpoint pen pastes, carbonless paper, hectopaper, stamp inks, inks and transparent varnishes. You get with them prints, varnishes or lettering with improved Water fastness in comparison to the correspondingly used dye salts, which are made exclusively from phthalocyanine sulfonic acids and basic dyes.

The parts and percentages given in the examples are parts by weight and percentages by weight.

example 1

A solution of 100 parts of copper phthalocyanine in- 600 parts of chlorosulfonic acid is gradually heated to 130 to 135 ⁰ G held for about 5 hours at this temperature * is then added at about 80 ⁰ C under stirring, with 100 parts of thionyl chloride and pouring the mixture after two hours Dwell time on ice. After filtering off with suction and washing with ice water, the copper phthalocyanine 3 »3 ', 3V'» 3 * '' - tetrasulfoGhlorid is made into a paste with ice, neutralized with a little 10 percent aqueous sodium hydroxide solution and mixed with a solution of 18 parts 1,3-propanolamine in 200 parts of water are stirred. The suspension is kept weakly alkaline by adding a dilute sodium bicarbonate or sodium hydroxide solution dropwise. After completion of the SuIfamidierung residual sulfonyl chloride groups is for saponification heated under optional addition of sodium hydroxide solution at about 65 ⁰ C until a clear solution. A solution of 83 parts of rhodamine B (CI. 45 170) in 1000 parts of warm water is added to this solution or to a solution obtained by acidification, suction of the precipitated phthalocyanine derivative and redissolving in water with the addition of dilute sodium hydroxide solution. The mixture is adjusted to a pH of about 5 with dilute formic acid and a solution of 60 parts of 3- (2 ^1- ethylhexoxy) propylamine and 16 parts of formic acid in 600 parts of water is added dropwise. The mixture is stirred for a few hours at room temperature and then for 3 hours at 35 to 40 ^° C., suctioned off warm, washed with water and dried in a steam cabinet. 280 parts of a dye are obtained which have a violet-blue color

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Dissolves very well in 80 or 99 percent alcohol, ethyl glycol or diethylene glycol. The dye consists of a mixture of two compounds of the formula II, in which R is the radical -CH ₂ -CH (C ₂ H ₅ ) - (CH ₂ ), - CH ,, R ^{4 is} a hydrogen atom, R ^{5 is} 3-hydroxypropyl, Z denotes rhodamine B and q = 1, and s denotes 2 or 1 and t denotes 1 or 2.

Similar blue-violet to violet-blue dye salts are obtained if rhodamine B is replaced by equivalent amounts of other basic Dyes, such as Rhodamine 6G- (CI. 45 I60), the corresponding Methyl ester compound, crystal violet (CI. 42 555) or methyl violet (CI. 42 535) replaced. The use of equivalent Quantities of diamond green G- (CI. 42 040) or malachite green B (CI. 42 000) leads to green-blue coloring salts.

Example 2

2000 parts of a solution containing 98 parts of copper phthalocyanine 3,3 ', 3' ¹ , 3 '''- di-hydroxyäthylsulfamido-disulfonic acid is adjusted to a pH of 10.5 with 10 percent sodium hydroxide solution and with a Solution of 48 parts of Rhodamine B (CI.45 170) in 1000 parts of water. After 3 hours' residence percent 3-acetic acid, the pH is lowered to 4.5 by dropwise addition of, stirred for 5 hours at 45 ⁰ C and 25 ⁰ C, a solution of 19 parts of 3- (2'-Äthylhexoxy) -propylamine and 6 parts of glacial acetic acid in 200 parts of water were added. The mixture is heated to 40 ^° C. for a short time, then the dyestuff is filtered off with suction while warm and dried ^{at 80 ° C. under reduced pressure.} The dye obtained dissolves in pure or water-containing ethyl alcohol with a violet-blue color. It corresponds to the formula II, in which Z rhodamine B, R ^{3 is} the radical -CH ₀ -CH (C ₀ Hc) - (GH _o ), - CH ,, R ⁴ "is a hydrogen

c c- c. 0 c. D J?

atom, R ß-hydroxyethyl, q and s each mean 1 and t 2.

Instead of the copper phthalocyanine derivative, the corresponding Compound of nickel or cobalt phthalocyanine can be implemented with a similar result.

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Example 3

63 parts of copper phthalocyanine-3, 3 ^! , 3 '. ·, 3 "· - or 4,4', 4", 4 " ^! - hydroxyethylsulfamido-trisulfonic acid are dissolved in 1500 parts of water and mixed with a solution of 32 parts of rhodamine B in 500 parts of water The pH value is kept at about 10 for 3 hours by adding dilute sodium hydroxide solution and then lowered with highly dilute formic acid to 4. After stirring for 4 hours at 50 ^° C., one of the solutions becomes at room temperature

a) 19 parts of isopentoxypropylamine »

b) 21 parts of hexoxypropylamine

c) 25 parts of isooctoxypropylamine

d) 27 parts of isononoxypropylamine

e) 28 parts of decyloxypropylamine

f) 32 parts of dodecyloxypropylamine

g) 34 parts of isotridecyloxypropylamine

in.einem mixture of 300 parts of water and 3 parts of formic acid added dropwise. After suctioning off, washing with water and drying, a violet-blue in each case is obtained, in alcoholic Medium soluble dye.

The dye has the formula I, in which X is rhodamine B, Y is the

1 2

called amine, R a hydrogen atom, R hydroxyethyl, m = 1, η = 2 and ρ = 1 mean.

Example 4

A neutral solution of 30 parts of copper phthalocyanine-4,4 ^1> 4 '''4''' - tetrasulfonic in 50Ό parts of water, water is gradually added at 5O ⁰ G with a warm solution of 16 parts of Rhodamine B in 300 parts. After several hours of stirring, 20 parts of 3- (2'-Äthylhexoxy] -propylamine and 7 parts of glacial acetic acid at room temperature dissolved in 100 parts of water was added dropwise. Then I hour at 40 ⁰ C is heated, suction filtered hot, washed with 200 parts of water and under reduced . pressure at 8O ⁰ G dried to 62 parts receives a violet blue dye of the dye has the formula II in which Z rhodanine B, R ³ is -CH ₂ -GH (C ₂ H ₅₎ -.. (CH ₂ V ₃ - CH ₅ , q = I, s = 3 and t = 0.

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Instead of 16 parts of rhodamine B (a) 24, (b) 32 are used or (c) 48 parts of this basic dye, this also gives dyes soluble in spirits and glycol half-ethers, which are clearly shifted in color to the redder side and have the following composition

(away)
Mixture of

(c)

q. 1 2 2 3 S. 3 2 2 1

Other dyes are obtained when in a corresponding manner, 27 parts of copper phthalocyanine-3,3 ^1, 3 '' - trisulfonic acid with (d) or 16 (e) 32 parts of Rhodamine B, and (d) 13 or (e) 7 parts Reacts 2-ethylhexoxypropylamine. These dyes have the composition

U)

(e)

q 1 2 S. 2 ' 1

Example 5

52 parts of copper phthalocyanine-hydroxyisobutylsulfamido-trisulfonic acid, obtained from copper phthalocyanine tetrasulfochloride and 3-aminobutano1-1, are dissolved in 2000 parts of water with the addition of dilute sodium hydroxide solution at a pH of 11.2. After adding a warm solution of 24 parts of rhodamine B in 500 parts of water, the mixture is stirred for 3 hours and then the pH is lowered to 4.5 by the gradual dropwise addition of 3 percent acetic acid. The suspension thus obtained is heated for 2 hours at 40 ⁰ G and, after cooling to 20 ⁰ O-with 250 parts of a 10 percent Isooctoxy-propylaminformiat solution in small proportions added. After a longer residence time, the dye is isolated and dried. It corresponds to the formula, I, in the X

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1 2

Rhodamine, Y the amine mentioned, R hydrogen, R hydroxyisobutyl, in = 1, η = 2 and p = 1.

If the amount of rhodamine is increased to 40 to 48 parts, the result reddish blue-violet dyes in the shade.

Example 6

30 parts of cobalt phthalocyanine hydroxyethoxyethylsulfamidodisulfonic acid, obtained from cobalt phthalocyanine 3.3 ", 3" - trisulfonic acid monochloride and aminoethyl glycol ether, are dissolved neutrally in 1000 parts of water and, with stirring, with a warm solution of 16 parts of rhodamine B in 40 parts of water and then after two hours Residence time with a solution of 7 parts of 3- (2 ^! -Lthylhexoxy) -propylamine and 2 parts of glacial acetic acid in 50 parts of water, giving a petrol-soluble reddish blue dye of the formula I with m == 1, η-1 ,: ρ = 1.

Example 7

A solution, heated to 130 to 132 ^° C. for 4 hours, of 100 parts of copper phthalocyanine in 800 parts of chlorosulfonic acid is poured cold onto ice. After filtering off with suction and washing with ice water, the sulfochlorinated copper phthalocyanine obtained is stirred with 18 parts of a cold 25 percent strength aqueous ammonia solution and a solution of 25 parts of sodium carbonate in 200 parts of water for 20 hours. The isolated reaction product, which is predominantly a mixture of copper phthalocyanine trisulfamidomonosulfonic acid and copper phthalocyanine disulfoimido monosulfonic acid in addition to copper phthalocyanine disulfamido disulfonic acid and monosulfamido disulfonic acid, is dissolved in water at a pH value of 10 to 11 and with a solution of 100 Parts of rhodamine B in 2000 parts of water are added. After a short residence time at 40 to 50 ° C., a pH of 4 to 5 is set by adding dropwise dilute formic acid and, after 3 hours, the precipitate is filtered off with suction and dried. A mixture of four dyes of the formula I is obtained, in which η = 0 and m and η have the following meanings:

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O.Z. 26 492

m 1 1 2 2 P. 3 2 2 1

If, instead of ammonia, appropriate amounts of hydroxyethylamine, di-methyl- or N-ethyl-hydroxyethylamine, diethanolamine, 2-amino-2-methyl-1,3-dihydroxypropane, morpholine or dimethylmorpholine, and if the rest of the procedure is as indicated, in this way dye mixtures with similar properties are obtained.

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Claims (4)

Claims in the Pc the remainder of a metal-containing phthalocyanine, X a basic dye, Y is an aliphatic amine with at least 4 carbon atoms, ■ - '' ■ χ ■ ■ -..- ■ ■ · ■■ \ "2 '■ · - ■■■■"''"' - ' ■■■■ which contains at least one ether group, R and R hydrogen atoms, aliphatic ^ hydrocarbon radicals, the hydroxy and / or ether groups, or common members together with the nitrogen atom of the sulfonamide group a heterocyclic ring, m 1, 2 or 3, η 0, 1, 2 or 3, ρ 0, 1, 2 or 3, η + ρ 1, 2 or 3 and m + η + ρ 2, 3 or 4 mean. 2. Dye salts of the formula CuPc - (SO ₃ H ₊ H ₂ N - (- CH ₂ ) ^ 0-R ³ ) in the CuPc a copper phthalocyanine residue, Z a dye the rhodamine series, R is a straight-chain or branched aliphatic radical with 2 to 18 carbon atoms, R is a hydroxyalkyl radical with 2 to 6 carbon atoms, R is a hydrogen atom, an alkyl radical with 1 to 3 carbon atoms or the radical R,
q, s and t are 1 or 2 and q + s + t are 3 or 4. 3. Dye salts of the formula - 11 - 109823/1 969; : O.Z. 26 492 CuPc (SO ₅ H + H ₂ N (C. -R "R ' 1 4 5 in which Z denotes rhodamine B and R _t R, q and t have the meaning given in claim 2. 4. The use of the dyes according to claims 1 to 3 for the production of printing inks, ballpoint pen pastes, Carbonless papers, hectopaper, stamp inks, inks and transparent varnishes. Badische Anilin- & Soda-Fabrik AG 10982 3/1969