DE2206611C2 - Dyes, processes for their production and their use as dispersants for the production of dispersions of pigments in organic liquids, for printing inks and coloring preparations - Google Patents

Description

The invention relates to dyes which contain a polyester radical and are used as dispersants for the ίο Production of pigment dispersions in organic solvents are suitable.

According to the invention, dyes of the formula

D- (Z-OOCR) _n
created, whereby

D represents the copper phthalocyanine residue,

Z stands for a methylene group and

R is the remainder of a polyester containing carboxyl end groups and having an acid number of 10-100 mg KOH / g of the formula RCOOH, which is different from the commercially available, smaller 12-hydroxystearic acid containing amounts of stearic acid and palmitic acid.

3. Process for the preparation of the dyes according to claim 1 or 2, characterized in that a dye compound of the formula

D- (ZY) _n

wherein D, Z and η have the meanings given in claim 1 and Y represents a chlorine or bromine atom, with one or more polyesters RCOOH which are derived from a hydroxycarboxylic acid of the formula

HO-X-COOH

wherein X is a divalent saturated or unsaturated aliphatic radical having at least 8 carbon atoms, with at least 4 carbon atoms between the hydroxyl and carboxylic acid group, or derived from a mixture of such a hydroxycarboxylic acid and a hydroxyl-free aliphatic carboxylic acid with 8-20 carbon atoms , is reacted in the presence of a quaternary ammonium or phosphonium compound and an acid-binding agent. D represents the residue of a dye attached to Z through a carbon atom of an aromatic ring present in D; Z represents a divalent bridging element; η represents a positive integer from 1 to 8 inclusive and

R represents the radical of a carboxyl-containing polyester of the formula RCOOH, which is of a hydroxycarboxylic acid of the formula

HO-X-COOH

wherein X is a divalent saturated or unsaturated aliphatic radical with at least 8 carbon atoms, with at least 4 carbon atoms between the hydroxy and carboxylic acid group are located, represents, or of a mixture of such a hydroxycarboxylic acid and one Hydroxy-free aliphatic carboxylic acid with 8-20 carbon atoms.

The dye radical D can be a residue of any known series of dyes, e.g. B. an azo or anthraquinone residue, be. However, D is preferably a phthalocyanine radical, in particular a copper phthalocyanine radical. The dye residue D is preferably free of strongly acidic groups, such as. B. carboxylic acid or sulfonic acid groups.

The type of divalent bridging element Z is not essential to the invention. As examples of such Bridging groups can be

-CH ₂ -, -NHCH ₂ CH ₂ -,
-NHCH ₂ CHOHCh ₂ -, -NHCOCH ₂ - and -SO ₂ NHCH ₂ CH ₂ -

mention. If D is a phthalocyanine radical, Z preferably represents the group -CH ₂ -.

According to a further feature of the invention is a method for producing the defined Proposed dyes according to the invention, which consists in that a dye compound of the formula

D- ^ ZY) _n

where D, Z and η have the meanings given above and Y is a chlorine or bromine atom, with one or more polyesters RCOOH which are derived from a hydroxycarboxylic acid of the formula

HO-X-COOH

wherein X is a divalent saturated or unsaturated aliphatic radical with at least 8 carbon atoms

men, with at least 4 carbon atoms between the hydroxyl and carboxylic acid group, represents, or of a mixture of such a hydroxycarboxylic acid and one of hydroxyl groups Derive free aliphatic carboxylic acid with 8-20 carbon atoms, in the presence of one Quaternary ammonium or phosphonium compound and an acid-binding agent implemented will.

The process according to the invention can expediently be implemented by stirring the reactants in an organic liquid the reaction at a temperature lying up to the boiling point of the reaction medium is carried out. The reaction is preferably carried out in the absence of water the reaction water is formed or a reactant contains water or in the form of an aqueous Solution is used, it is advisable to carry out the reaction at such a temperature that the water present evaporates from the reaction medium. At the end of the reaction, the organic Liquid z. B. removed by distillation. On the other hand, you can filter the mixture and the filtrate first extract with water to get the quaternary ammonium or phosphonium compound as well as about remove any inorganic salts present, and then perform an extraction with a solvent such as isobutanol to remove any unreacted polyester that may be present, and finally the organic liquid e.g. B. remove by distillation or evaporation.

If the quaternary ammonium or phosphonium compound is a quaternary ammonium hydroxide is used, it can - if sufficiently available - also serve as an acid-binding agent. The quaternary ammonium or phosphonium compound usually serves as a catalyst for the Reaction. Thus, the addition of stoichiometric amounts is possible, but not in fact required, and amounts in the range from 1 to 30 wt .-% - based on the dye compound - are sufficient.

The polyesters used in the process according to the invention can be prepared by heating the hydroxycarboxylic acid or a mixture of such acids or a mixture of such a hydroxycarboxylic acid and a carboxylic acid, optionally in the presence of an esterification catalyst, preferably to a temperature in the range from 160 ^° C. to 200 ^{° C.} C is heated until the desired molecular weight is achieved. The course of esterification can be followed by measuring the acid number of the product, the polyesters having an acid number in the range from 10 to 100 mg KOH / g, in particular from 20 to 50 mg KOH / g. The water formed during the esterification is removed from the reaction medium, which can conveniently be done by passing a nitrogen atom over it or, preferably, by carrying out the reaction in the presence of a solvent and distilling off the water immediately after it has been formed. B. toluene or xylene can be used. The polyesters obtained can be isolated in a customary manner.

In the hydroxycarboxylic acids mentioned, the radical X preferably contains 12 to 20 carbon atoms, with 8 to 14 carbon atoms preferably being located between the carboxylic acid group and the hydroxyl group. It is also preferred that the hydroxy group be a secondary hydroxy group

Specific examples of such hydroxycarboxylic acids can be ricinoleic acid, a mixture of 9- and 10-hydroxystearic acids (obtained by sulfation of oleic acid with subsequent hydrolysis) and 12-hydroxystearic acid and especially the commercially available hydrogenated castor oil fatty acid, which in addition to 12-hydroxystearic acid also has smaller amounts of it

ι ο contains stearic acid and palmitic acid.

As carboxylic acids, which are used together with the hydroxycarboxylic acids to produce the polyester can be, one uses saturated or unsaturated aliphatic carboxylic acids, especially alkyl or

is alkenyl carboxylic acids with a chain from 8 to 20 Carbon atoms. Examples of such acids can be lauric acid, pamitic acid, stearic acid and Mention oleic acid.

The dye compounds which can be used in the process of the present invention can be prepared according to the well-known Process for the introduction of groups of the form) -Z-Y in dye compounds. So z. B. chloromethyl or bromomethyl groups are introduced in that the corresponding Dye compound with formaldehyde or paraformaldehyde in the presence of hydrogen chloride, chlorosulfonic acid or hydrogen bromide is treated. y-chloro-jJ-hydroxypropylamino groups or y-bromo-j3-hydroxypropylamino groups can be introduced by the fact that the corresponding dye which contains an amino group with epichlorohydrin or epibromohydrin is reacted, and N- (chloro- or bromoalkyl) -sulfonamide groups can be introduced, by using the appropriate dye compound

) 5 treated chlorosulfonic acid and the sulfochloride obtained is reacted with a chloro- or bromoalkylamine.

As specific examples of the dye compounds mentioned with at least one reactive chlorine

4 (i or bromine atom one can mention the following:

Copper tris (chloromethyl) phthalocyanine,
i ^ -Bis-fy-chloro - ^ - hydroxypropylamino) -

anthraquinone,

2-methyl-4-N, N-di (/ I-hydroxyethyl) amino-4 '- (N-0-chloroethylsulfonamide) azobenzene,

l- (y-chloro- / miydroxypropylamino) -4- (4 '- /? - hydro-

xyäthoxy) phenylamino) anthraquinone,
Copper mono (chloromethyl) phthalocyanine and
Copper pentakis (chloromethyl) phthalocyanine.

As examples of acid-binding agents that can be used in the process according to the invention, one can mention sodium carbonate and sodium or potassium hydroxide.

As examples of organic liquids used in Process according to the invention can be used, one can use methyl isobutyl ketone, hydrocarbons such as petroleum fractions, toluene and xylene, as well as halogenated hydrocarbons with an unreactive one Halogen atom, e.g. B. chlorobenzene, mention.

The following can be mentioned as examples of quaternary ammonium or phosphonium compounds

nen:

Cetyltrimethylammonium bromide,
Tetraethylammonium hydroxide,
Dodecyltrimethylammonium bromide and
n-Hexadecyltri-n-propylphosphonium bromide.

The dyes according to the invention are suitable as dispersants for the preparation of dispersions of pigments in organic liquids, and such dispersions are also within the scope of the invention. It it has been found that it is not absolutely necessary in the preparation of the dispersions, absolutely to use pure dyes, since the dyes obtained according to the invention are initially still inorganic Salts, quaternary ammonium or phosphonium compounds as well as possibly unreacted polyester are just as suitable, because that Presence of such compounds does not affect the formation of the dispersions. As a result, the Dispersants are less expensive because they don't need to be cleaned if the dye is even in one corresponding organic liquid has been prepared, the solution of the dye in this can Liquid can be used directly for the preparation of the dispersion without ate the organic Liquid must be removed beforehand.

According to a further feature of the invention, finely divided dispersions of pigments are in Organic liquids created, whereby in the organic liquid a dye by definition is dissolved with at least one polyester residue.

These dispersions can be prepared by the customary and known methods for preparing dispersions be prepared. So can pigment, organic liquid and dye in any order mixed together and then mechanically processed to reduce the particle size of the pigment until the dispersion is created. Mechanical processing can be in a ball mill or a Mill can be done with pearls or gravel as a filling. Mechanical processing is preferred Carried out until the particle size of the pigment is below 20 μ and preferably below 10 μ. The dispersion can also contain other substances, such as e.g. B. zinc resinate, usually in dispersions of Pigments present in organic liquids contain.

But it is also possible to process the pigment to reduce its particle size to be carried out independently of or in admixture with either the organic liquid or the dye, whereupon the further component (s) is / are added and the desired dispersion is obtained by stirring. But you can also proceed so that a solution of the dye in the organic liquid with an aqueous medium to form an emulsion in a manner known per se, z. B. by rapid stirring, is mixed, in the presence of one or more surface-active Means after which the emulsion obtained is added to an aqueous slurry of the pigment and the organic liquid and water are separated by filtration and the residue is dried from pigment and dye. This residue can subsequently be converted into an organic Medium to be dispersed. Preparations obtained in this way and containing the pigment in finely divided form and containing the dye, form a further subject of the invention.

The amount of dye present in the dispersions preferably corresponds to 5 to 50% by weight, preferably 10 to 30% by weight, based on the pigment, the dispersions preferably 5 to 70% by weight Pigment, based on the dispersion.

Any inert organic liquid can be used as organic liquids for the dispersions in which the dyes are at least partially soluble (at normal temperature) and the at Use the dispersion to remain stable. Mixtures of two or more organic liquids can also be used be used. Preferred organic liquids are hydrocarbons and halogenated Hydrocarbons such as B. toluene, xylene, white spirit, ίο η-hexane, cyclohexane, chlorobenzene, carbon tetrachloride and perchlethylene. However, other organic liquids can also be used, such as. B. Esters such as alkyd resins and linseed oils thickened by heat, such as those used as lacquer binders for lithography Find use. It is especially preferred that the organic liquid is a predominantly aliphatic liquid Petroleum fraction is used. In general, the Choice of the organic liquid or the mixture of such liquids on the application purpose of the Dispersion from.

The pigments can be inorganic or organic in nature and belong to any of the recognized pigment classes belong. Inorganic pigments such. B. Titanium dioxide, soot, zinc oxide, Prussian blue, cadmium sulfide, Iron oxides, vermilion, ultramarine and chromium pigments, such as. B. lead, zinc-barium and calcium chromates, as well as the various mixtures and variations of such pigments as commercially available under the names chrome yellow lemon, lemon yellow, chrome yellow medium, chrome orange, molybdate red and Chrome red are available in question.

The following can be mentioned as examples of organic pigments: Pigments of the azo, thioindigo, Anthraquinones anthranthrone, isodibenzanthrone or triphenyldioxazine series, vat dye pigments,

Phthalocyanine pigments, such as. B. copper phthalocyanine and its derivatives halogenated in the core and Copper tetraphenyl and octaphenyl phthalocyanine, quinacridone pigments and color lakes of acidic, basic and mordant dyes. Such pigments are in z. B. Color Index, Volume 2, 2nd edition (1956) under the heading "Pigments" and in authorized supplements described. The preferred pigments are carbon black and especially copper phthalocyanine and its essentially halogenated derivatives. If the pigment is copper phthalocyanine in the j3 form, it can have the normal pigment form of copper phthalocyanine or a crude copper phthalocyanine.

The dyes according to the invention are particularly suitable for the production of pigment dispersions of copper phthalocyanine directly from crude copper phthalocyanine. A preferred class of dyes for the pigment dispersions consists of those dyes that are produced by the reaction of chloromethylated Copper phthalocyanine with the polyester, especially with a polyester that is different from 12-hydroxystearic acid optionally derived with smaller amounts of stearic and / or palmitic acid became.

The dispersions according to the invention are liquid or semi-liquid preparations that the pigment in fei η distributed and deflocculated form and are suitable for any purpose, to the dispersions of the solids concerned are commonly used. The dispersions are particularly suitable for the manufacture of printing inks by mixing the dispersions with the others, in the manufacture of such Colors common components are mixed. the

Dispersions are also suitable for the production of paints, the dispersions with conventional Alkyd or other resins are mixed. The dyes according to the invention can also be used as dispersants for the preparation of dispersions of other dyes, such as. B. acidic dyes, Disperse dyes and basic dyes, used in organic liquids, are such dispersions find use for the solvent dyeing of textiles.

The invention is explained in more detail below with the aid of examples, purely by way of example, the specified parts and percentages are based on weight.

The polyesters were made as follows:

Polyester A

A mixture of 348 parts of xylene and 3,350 parts of technical 12-hydroxystearic acid (with acid number 182 mg KOH / g and hydroxyl number 160 mg KOH / g) is stirred for 22 hours at 190 to 200 ° C, the water formed in the reaction>' om xylene is separated in the distillate, whereupon the distillate is returned to the reaction medium. A total of 152 parts of water are collected, whereupon the xylene is ^{evaporated off at 200 °} C. in a stream of nitrogen. The slightly golden yellow liquid obtained has an acid number of 33.0 mg KOH / g.

Polyester B

A mixture of 130 parts of xylene, 126 parts of stearic acid and 716 parts of 12-hydroxystearic acid is heated to 190 to 200 ° C. for 22 hours, the water formed in the reaction being separated off from the xylene in the distillate, whereupon the distillate is returned to the reaction medium. The xylene is then evaporated off by heating at 18O ⁰ C under reduced pressure. The liquid residue is cooled to 50 ° C, and an equal volume of a petroleum fraction with a boiling range of 100 to 120 ⁰ C is added. The mixture is ^{cooled to 10 °} C. and then filtered to separate off the stearic acid. The solvent is then distilled off at 10 (I ⁰ C and under reduced pressure to give the polyester in the form of a light golden yellow, viscous liquid having an acid number of 58.6 mg KOH / g is obtained.

Polyester C

A mixture of 65 parts of xylene and 500 parts of a technical ricinoleic 22 hours 190 to 200 ° C erhU7t _(wnhpi the ^CT ebildete water is distilled off continuously. The xylene is then concentrated under reduced pressure at 150 ° C distilled off The polyester obtained has an acid number of 13.7 mg KOH / g.

Polyester D

A mixture of 96 parts of xylene, 150 parts of oleic acid and 850 parts of ricinoleic acid is heated 22 hours at 190 to 200 ⁰ C wherein the water formed is distilled off continuously. The xylene is then distilled off under reduced pressure at 150 ° C. The polyester obtained has an acid number of 36.6 mg KOH / g.

example 1

A mixture of 443 parts of polyester A, 153 parts of a 25% strength aqueous solution of tetraethylammonium hydroxide, 6 parts of copper tris (chloromethyl) phthalocyanine and 72 parts of methyl isobutyl ketone is 16 hours under a reflux condenser with a water separator heated to boiling. The methyl isobutyl ketone is then distilled off under reduced pressure. The raw dye is thus obtained as a deep blue, viscous liquid.

Example 2

A mixture of 44.3 parts of polyester A, 9.5 parts of a technical grade cetyltrimethylammonium bromide, 72 Parts of methyl isobutyl ketone, 3.4 parts of a 32% strength aqueous sodium hydroxide solution and 6 parts Copper tris (chloromethyl) phthalocyanine is stored for 16 hours under a reflux condenser with a water separator ii stirred. The solvent is then deposited in a suction cup. Sumii you get that Raw product as a deep blue, viscous liquid.

Example 3

The procedure is as in Example 2, with the difference that only 1 part of the cetyltrimethylammonium bromide is used. A similar product is obtained.

Be i s ρ i e 1 4

A mixture of 44.3 parts of polyester A, 1 part of cetyltrimethylammonium bromide, 1.4 parts of sodium carbonate, 6 parts of copper tris-dichloromethyljphthalocy-

iii anin and 64 parts of a petroleum fraction with a boiling range of 100-120 ⁰ C is heated for 16 hours under a Rückflußkühier with water to boiling. The solution is then cooled and a small amount of solid is poured off. The solution

r, contains 47.9% crude dye.

Example 5

A mixture of 54 parts of polyester B, 2 parts of cetyltrimethylammonium bromide, 2.8 parts of sodium

4i) carbonate, 12 parts of copper tris- (chloromethyl) phthalocyanine and 64 parts of a petroleum fraction with the boiling range 100-120 ° C are ^{heated to 1H 0} C for 16 hours under a reflux condenser, the water formed being separated off via a separator. The solution obtained contains 54.0% crude dye and a trace of solid is poured off.

Example 6

A mixture of 53.5 parts of polyester C, 0.5 part of cetyltrimethylammonium amide, 0.7 part of sodium carbonate, 3 parts of copper-tris- (ch! Orniethy!) Phthalocyanine and 64 parts of a; Petroleum fraction with the boiling range 100-12O ⁰ C is stirred for 16 hours under a reflux condenser with water separator at the boil. The resulting solution with 533% crude dye is poured off from a trace of solid.

Example 7

A mixture of 40 parts Polyester D, 1 part of Cetyltrimethylammoniumbromids, 1.4 parts of sodium carbonate, 6 parts of copper-tris- {chloromethyl) phthalocyanine and 64 parts of a petroleum fraction with a boiling range of 100-120 ⁰ C for 16 hours under a reflux condenser with water at Stirred boiling The resulting solution with 47.7% crude dye is then poured off from a trace of solid.

Example 8

A mixture of 36.2 parts of a polyester made from technical 12-hydroxystearic acid with an acid number of 35.5 mg KOH / g, 0.76 parts of cetyltrimethylammonium bromide, 1.06 parts of sodium carbonate, 4.55 parts of copper tris (chloromethyl phthalocyanine) and 18 parts of a petroleum fraction having a boiling range of 100- 120 ⁰ C is stirred for 16 hours under a reflux condenser with water at the boiling point. The solution is then filtered to remove a trace of solids. The solution contains 69.6% crude dye.

Example 9

It will be like the example! 8 worked. After Filtration to remove the trace of solids, the filtrate is sequentially with a) water, b) acetone, c) Isobutanol (several times) and d) acetone extracted and then dried. The product obtained has the Shape of a dark blue tar.

The infrared absorption spectrum of the dye shows no absorption band at 2500 to 3500 cm- 'and 1712 cm- ¹ (for -COOH groups - clearly recognizable in the infrared absorption spectrum of the polyester used as the starting material) not even at 1600 cm- ¹ for -COO - groups; However, bands at 1730cm- ¹ and 1180cm- ¹ indicate the presence of ester groups.

Example 10

A mixture of 40 parts of the polyester according to Example 8. 0.8 parts of cetyltrimethylammonium bromide, 1.21 parts sodium carbonate, 10 parts 1 - (y-chloro - /? - hydroxypropylamino) -4- (4 '- (jJ-hydroxyethoxy) anilino ) -anthraquinone and 71 parts of a petroleum fraction with the boiling range 100 to 120 ⁰ C is stirred for 16 hours under a reflux condenser with water separator at the boil. The solvent is then removed by heating at 140 ⁰ C in a nitrogen stream, there remains the crude product as a dark blue viscose liquid.

Example 11

The procedure is as in Example 10, with the Deviation that instead of the anthraquinone compound used there, 10 parts of 2-methyl-4-N, N-di (0-

hydroxyethyl) amino-4 '- (N-0-chloroethylsulfonamide) azobenzene can be used. The product obtained is a dark brown viscous liquid

Example 12

The procedure is as in Example 10, with the Deviation that instead of the anthraquinone compound used there 10.7 parts 1- (J? -Hydroxyäthylamino) -

4- (2'-bromo-4 '- {N-ß-chloroethylsulfonamide) phenylazo) naphthalene can be used. The product is a deep red viscous liquid.

Example Π

A mixture of 18.2 parts of the polyester according to Example 8, 0.4 parts of Cetyltrimethylammoniumbromids, 0.55 parts of sodium carbonate, 6 parts of copper mono (chloromethyl) phthalocyanine and 35.5 parts of a petroleum fraction having a boiling range of 100-120 ⁰ C is 16 Stirred at the boil for hours under a reflux condenser with a water separator. The solvent will

ίο then removed in a stream of nitrogen and leaves behind a deep blue tar.

Example 14

A mixture of 36.3 parts of the polyester according to Example 8,0,76 parts of Cetyltrimethylammoniumbromids, 1.06 parts of sodium carbonate, 3.04 parts Kupfcrpentakis- (chloromethyl) phthalocyanine and 35.5 parts of a petroleum fraction having a boiling range of 100-120 ⁰ C is stirred at the boil for 16 hours under a reflux condenser with a water separator. The solvent is then removed in a stream of nitrogen, leaving a deep blue viscous liquid.

Usage example 15

A mixture of 3 parts of copper phthalocyanine in the 0 form, 0.6 parts of the dye according to Example 9 and

6.4 Dividing a petroleum fraction with the boiling range 100-120 ° C is 16 hours in a ball mill processed A finely divided, well deflocculated dispersion of the pigment is obtained, which can be used as a printing ink for the Gravure printing is suitable.

Similar finely divided, well deflocculated dispersions are obtained when the 0.6 parts of the dye according to Example 9 by in each case 0.6 parts of the dye according to Example 1, 2, 3 or 14 or by an amount of Dye solution according to Example 4, 5 or 8, which corresponds to 0.6 parts of crude dye, can be replaced.

Usage example 16

A mixture of 3 parts of copper phthalocyanine in the jS form, 1.5 parts of the dye according to Example 10 and

5.5 parts of a petroleum fraction having a boiling range of 100-120 ⁰ C is processed 16 hours in the ball mill, whereby a finely distributed, well deflocculated dispersion of the pigment is obtained which is suitable as an ink for gravure printing

The table below shows further examples of dispersions, each made by grinding of the pigment according to the 2nd column of the table together with the dye or the dye solution according to the 3rd column and the organic liquid according to the 4th column of the table. It will each time a finely divided, well deflocculated dispersion of the pigment in question is obtained.

Use application example

pigment

Dye or solution Org. Liquid

17 3 parts of the pigment that by

Coupling of tetraazotated 3,3'-dichlorobenzidine to Acetacetanflid is obtained.

14 parts of the dye according to Example 11

5.5 parts of a petroleum fraction with bp. 100-120 ⁰ C.

continuation

Ver pigment Dye or solution Org. Liquid whom- manic example

18th 3 parts of l- (2'-nitro-4'-methyl-
phenylazo) -2-naphthol 1.5 parts of the dye
according to example 12 19th 3 parts of copper phthalocyanine in
the ^ shape 1.5 parts of the dye
according to example 13 20th the same 2.8 parts of the dye solution
according to example 6 21 the same 3.1 parts of the dye solution
according to example 8 22nd 3 parts of indanthrone 0.9 parts of the dye solution
according to example 8 23 3 parts of a resin-coated CaI
cium tone of the l- (2'-sulfo-4'-
methylphenylazo) -2-naphthol-
3-carboxylic acid the same 24 3 parts lead sulfochromate the same 25th 3 parts of a nickel speaker of the
3- (4'-chlorophenylazo) quinoline
diol- (2.4) the same
the same 26th 3 parts Prussian blue the same 27 3 parts of an aluminum trickle

1,4-Dihydroxyanthraquinone-2-sulfonic acid varnish

28 3 parts TIOXIDE RCR (coated form of rutile titanium dioxide)

the same

the same.

4.2 parts of a petroleum fraction withSdp. 10Ü-120 ^and C

3.9 parts of a petroleum fraction withSdp. 100-120 ⁰ C.

6.1 parts of a petroleum fraction withSdp. 100-120 ⁰ C.

the same

the same

the same.

the same.

the same

29 3 parts of iron oxide the same the same 30th 3 parts of carbon black the same the same 31 3 parts copper-polychlor-
phthalocyanine the same the same 32 3 parts 4,10-dibromoanthrane
'.hron despl. the same 33 3 parts Phosphomoiybdowolf-
ramat Color Index Basic
Blue 7 (42595) the same the same 34 3 leiic copper phthalocyanine in
derjS form 1.5 parts of the dye
according to example 1 5.5 parts of n-hexane 35 the same the same 5.5 parts of cyclohexane 36 the same the same 5.5 parts of xylene

Usage example 37

A mixture of 60 parts of crude copper phthalocyanine, 15 parts of the dye according to Example 3 and 125 parts of a petroleum fraction with a boiling range of 100-120 ⁰ C in the ball mill processed Man erfailt a fiünigc, deflocculated dispersion of Kupferphthajoeyanins with no particles larger than 3 μ diameter . Most of the particles are less than 1 μm in size.

The dispersion is suitable for printing inks for gravure printing and shows increased color strength, improved

Finish and a greener shade opposite

customary dispersions of copper phthalocyanine in the 0 form.

Usage example

There are 25 parts of copper phthalocyanine in the 0 form, 5 parts of the dye according to Example 3 and Tefle of a petroleum fraction with the boiling range

Filled 260-290 ° C in a Baker-Perkins mixer and ground there for 60 minutes in a plastic state. Then 3.6 parts of the same petroleum fraction are added and the mixture is 15 minutes stirred. A homogeneous, viscous paste with a pigment content of 57.5% is obtained. The paste is suitable opt for printing inks for letterpress printing.

Usage example 39

60 parts of a furnace soot with a surface area of 80 mVg, 15.7 parts of the dye solution according to Example 4, 74.3 parts of a petroleum fraction with the boiling range 100-12O ⁰ C and 500 parts of steatite balls with a diameter of 6 mm are placed in a container, which is then rotated on a roller mill at 100 rpm for 24 hours. The contents of the container are then sieved to remove the balls. The product obtained is a flowable paste made from finely divided carbon black.

If this paste is coated with a gravure varnish, such as B. a solution of zinc / calcium resinate in one Hydrocarbon solvents, mixed, a black gravure ink with good gloss and is obtained coloristic properties in which the soot is finely divided.

Usage example 40

A mixture of 10 parts of 1,5-dihydroxy-4,8-diamino-2- (p-hydroxyphenyl) -6-hydroxymethylanthraquinone, 4.2 parts of the dye solution according to Example 4 and 160 Parts of perchlorethylene are processed in the ball mill for 16 hours. So you get a good Deflocculated dispersion of the anthraquinone dye, with the aromatic polyester fabrics by the solvent process can be colored.

Usage example 41

A mixture of 7.2 parts of the dye solution according to Example 8, 2.8 parts of perchlorethylene and 0.5 Share an adduct of a mixture of oleyl and Cetyl alcohol with 2.5 moles of ethylene oxide becomes a solution of 2 parts of an adduct of cetyl alcohol with 17 mol of ethylene oxide in 194 parts of water with 6 parts of sulfuric acid, whereupon the mixture is processed into an emulsion by rapid stirring.

5 parts of crude copper phthalocyanine is ground in the presence of a water-soluble inorganic salt. The salt is washed out and the copper phthalocyanine obtained in the form is heated in 100 parts of dilute sulfuric acid in order to dissolve metallic impurities. 42 parts of the above emulsion are added at 60 ^° C., the mixture is stirred for a further 15 minutes, the suspension is filtered, and the pigment is washed with water and then dried

A printing ink is prepared by adding 1.08 parts of the dried pigment to 0.92 parts of a synthetic letterpress varnish for lithography (viscous alkyl medium). These Printing ink is much less viscous than a control ink, which is analogously made from raw copper phthalocyanine but was made without adding the emulsion to the pigment slurry. With The print results obtained with this printing ink have the same color strength but a greater brightness than the print results achieved with the control color.

B e i s ρ i e 1 42

A mixture of 36.2 parts of the polyester according to Example, 8.0.76 parts of cetyltrimethylammonium bromide, 1.06 parts of sodium carbonate, 5.15 parts of a chloromethylated p, p'-di (6-methylbenzthiazol-2-yl) azobenzene with a chlorine content of 13.1% and 36 parts of a petroleum fraction with the boiling range 100-12O ⁰ C is stirred for 16 hours under a reflux condenser with ίο water separator at the boil. The solvent is then removed at 110 ⁰ C in a nitrogen stream, leaving the crude dye as a brown gum.

Usage example 43

A mixture of 3 parts of the pigment which was prepared by coupling tetraazotized 3,3'-dichloro-4,4'-diaminodiphenyl with acetacetanilide, 0.6 parts 2 "of the dye according to Example 42 and 6.4 parts of a petroleum fraction the boiling range 100-12O ⁰ C is processed in the ball mill for 16 hours. A finely divided, well deflocculated dispersion of the pigment is produced.

Example 44

A mixture of 36.3 parts of the polyester according to Example 8.0.76 parts of n-H exadecyl-tri-n-propylphospho-

In nium bromide, 1.06 parts of sodium carbonate, 4.55 parts of copper tris (chloromethyl) phthalocyanine and 36 parts of a petroleum fraction with the boiling range 100-120 ° C is stirred for 16 hours under a reflux condenser with a water separator at the boil. The solvent is then removed at 110 ⁰ C in a nitrogen stream, leaving behind a crude dye as a deep blue viscöse liquid.

Usage example 45

A mixture of 3 parts of copper phthalocyanine in the j9-form, 0.6 parts of the dye according to Example 44 and 6.4 parts of a petroleum fraction with a boiling range of 100-120 ⁰ C is processed 16 hours in the ball mill ■ '=>. A finely divided, well deflocculated dispersion of the pigment is thus obtained.

Usage example 46

So 96 parts of crude copper phthalocyanine 24 parts of the dye according to Example 3, 12.8 parts of zinc resinate and 167.2 parts of a petroleum fraction with the boiling range 100-120 "C are mixed in a stainless steel vessel, the vessel having a stirrer with three Discs (diameter 10 cm each, thickness 8 mm each) 1000 parts of glass beads with a diameter of 0.6 to 0.7 mm are added and the mixture is stirred for 60 minutes at a speed of 1880 rpm The dispersion does not have a significant number of pigment particles greater than 3 microns in diameter, with most pigment particles being less than 1 micron in size. The pigment dispersion is then separated from the glass beads
The dispersion obtained consists essentially of a dispersion of the pigment copper phthalocyanine in the 0 form and has a high color strength and shows a greenish, light hue when used in a gravure printing ink.

Usage example 47

A mixture of 64 parts of crude copper phthalocyanine, 16 parts of the dye according to Example 3, 12.8 Parts of zinc resinate and 107.2 parts of a petroleum fraction with a boiling range of 100-120 ° C are used in the Processed ball mill, whereby a liquid, deflocculated dispersion of the copper phthalocyanine is formed in the

no particles have a diameter greater than 3μ, while most of the particles have a diameter below Have 1 μ.

This dispersion is suitable for printing inks for gravure printing and gives printing inks with an increased Color strength, an improved finish and a greener shade compared to a conventional dispersion of copper phthalocyanine in the /? form.

230 222/84

Claims (1)

Patent claims:
1. The dyes of the formula D- (Z-OOCR) _n
characterized in that D represents the residue of a dye attached to Z via a carbon atom of one present in D aromatic ring is attached; Z represents a divalent bridging element; η represents a positive integer from 1 to 8 inclusive and R is the remainder of a polyester containing carboxyl end groups and having an acid number of 10-100 mg KOH / g of the formula RCOOH, which is derived from a hydroxycarboxylic acid the formula HO-X-COOH wherein X is a divalent saturated or unsaturated aliphatic radical with at least 8 carbon atoms, with at least 4 carbon atoms between the hydroxy and carboxylic acid group, or a mixture of such Hydroxycarboxylic acid and an aliphatic carboxylic acid free of hydroxyl groups 8-20 carbon atoms. 2. Dyes according to claim 1, characterized in that 4. Use of the dyes according to claim 1 or 2 as dispersants for the preparation of Dispersions of pigments in organic liquids, for printing inks and dye preparations.