DE2206611A1 - Dyes and processes for their preparation - Google Patents

Description

PATENT LAWYERS DR.-INO. H. FINCKE

DIPl.-ING. H DRILL ^ r ™ DIPL.-ING. S. STAEGER

MÖNCHEN 5 MULLCRSTR. 31

Imperial Chemical Industries Limited, London, Great Britain

Dyes and processes for their preparation

The invention relates to dyes which contain a polyester residue and which can be used as a dispersion

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suitable for the production of pigment dispersions in organic solvents.

According to the invention, dyes of the formula D— ZO.OCR) _n

created, whereby

D represents the radical of a dye attached to Z via a carbon atom of one present in D.

aromatic ring is bonded; Z represents a divalent bridging element; η is a positive integer from i up to and including

8 represents and
R represents the radical of a carboxyl-containing polyester of the formula RGOOH, which is different 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, where there are at least 4 carbon atoms are located between the hydroxyl and carboxylic acid group, represents, or a mixture of derived from such a hydroxycarboxylic acid and a carboxylic acid free of hydroxyl groups.

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The dye off radical D can be a radical; anyone known series of dyes, e.g. an azo or anthraquinone radical. Preferably D is however, a phthalocyanine radical, particularly a radical of copper phthalocyanine. The radical D is preferably free from strongly acidic groups such as ZoB. Carboxylic acid or sulfonic acid groups.

The type of divalent bridging link Z
is not critical. As examples of such
Bridging groups can be -CH ₂ -, -1
-NHCh ₂ CHOHCH ₂ -, -HHCOCH ₂ - and - £
mention. If D is a phthalocyanine radical, Z preferably represents the group -CHp-.

According to a further feature of the invention proposed a process for the preparation of the dyes defined according to the invention, the is that a dye compound of the formula

where D, Z and η have the meanings given above and Γ represents a chlorine or bromine atom, with one or more polyesters RCOOH, which differ from a hydroxycarboxylic acid of the formula

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HO-X-CCX) H

wherein X is a divalent saturated or unsaturated aliphatic radical with at least 8 carbon atoms, with at least H -carbon atoms between the hydroxy and Oarbonsaüregruppe, or derived from a mixture of such a hydroxycarboxylic acid and a carboxylic acid free of hydroxyl groups, in the presence of one Quaternary ammonium or phosphonium compound and an acid-binding agent is implemented.

The method according to the invention can expediently be implemented by stirring the reactants in an organic liquid be, the reaction at a temperature lying up to the boiling point of the reaction medium Temperature is carried out. The reaction is preferably carried out with the exclusion of water carried out «If water is formed during the reaction is or a reactant contains water or used in the form of an aqueous solution is, it is advisable to carry out the reaction at such a temperature that the existing Water evaporated from the reaction medium Am

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At the end of the reaction, the organic liquid can ZoB. removed by distillation. On the other hand, the mixture can be filtered and the filtrate first extracted with water in order to remove the quaternary ammonium or phosphonium compound and any inorganic salts present, and then an extraction with a solvent such as isobutanol can be carried out to remove any unreacted polyester that may be present, and finally remove the organic liquid ζ.B _{0 by} distillation or by evaporation.

If as a quaternary ammonium or phosphonium compound a quaternary ammonium hydroxide is used, it can - if sufficient present - also serve as an acid-binding agent. The quaternary ammonium or phosphonium compound but normally serves as a catalyst for the reaction. Thus the addition of Although stoichiometric amounts are possible, they are in fact not 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 produced in that the hydroxycarboxylic acid or a mixture of such

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Acids or a mixture of such a hydroxycarboxylic acid and a carboxylic acid is optionally heated in the presence of an esterification catalyst, preferably at a temperature in the range of 160 ° C to 200 ⁰ C, until the desired molecular weight is reached. 0er esterification. The course can be followed by measuring the acid number of the product, the preferred 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 stream of nitrogen over it or preferably by carrying out the reaction in the presence of a solvent and distilling off the water immediately after its formation, the solvent ZoB. 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, preferably with 8 to 14 carbon atoms between the carboxylic acid group and the hydroxyl group are located. It is also preferred that the Ifydr Oxy group is a secondary Ifydr Oxy group.

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Αΐε certain examples of such Bydro: xycarboxylic acids one can use ricinoleic acid, a mixture of 9 ~ and 10-hydroxy stearic acids (obtained by Sulphation of oleic acid with subsequent hydrolysis) and i2% droxystearic acid as well in particular the commercially available hydrogenated castor oil fatty acid, which in addition to 12-Bydro: xyBtearic acid also contains smaller amounts of stearic acid and palmitic acid.

As carboxylic acids, which together old the hydroxycarboxylic acids used for the production of the polyester can be, one preferably uses saturated or unsaturated aliphatic carboxylic acids ,, in particular alkyl or alkenyl carboxylic acids with a chain of 8 to 20 carbon atoms, a. Examples of such acids are lauric acid, pamitic acid and stearic acid and mention oleic acid.

Those that can be used in the method according to the invention Dye compounds can be made according to the well-known Process for the introduction of groups of the formula -Z-Y in dye compounds will. For example, chloromethyl or bromomethyl groups can be introduced by the corresponding dye compound with formal

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-8- 2206811

dehyde or paraformaldehyde in the presence of
Hydrogen chloride, chlorosulfonic acid or hydrogen bromide is treated. Y-chloro-ß-hydroxypropylamino groups or Y-bromo-ß-hydroxypropylamino groups can be introduced by reacting the corresponding dye, which contains an amino group, with epichlorohydrin or epibromohydrin, and N- (chloro- or bromoalkyl) sulfonamide groups can be introduced by using the appropriate dye compound
Treated chlorosulfonic acid and the obtained
Sulfochloride is reacted with a chloro- or bromoalkylamine.

The following can be mentioned as specific examples of the dye compounds mentioned with at least one reactive chlorine or bromine atom: copper tris (chloromethyl) phthalocyanine, 1 _$ 4 ~ bis (T-chloro β-hydroxypropylamino) anthraquinone, 2-methyl 1 ~ H- = 1 $ _{T /} N-di (ß-hydro3-quarthyl) amino-4 '- (N-ß-chloroethylsulfonamide) = azobenzene, 1- (Y-chloro-ß-hydroxypropylamino) -4- (4'-ß-hydroayethoxy) phenylamino ) anthraquinone, copper mono (chloromethyl) phthalocyanine and copper pentakis chloromethyl) phthalocyanine.

As examples of acid-binding agents that are used in

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can be used according to the invention, sodium carbonate and sodium · = or mention potassium hydroxide.

As examples of organic liquids that are used in the process according to the invention, can, one can use methyl isobutyl ketone, hydrocarbons such as petroleum fractions, toluene and xylene, and halogenated hydrocarbons with an unreactive halogen atom such as chlorobenzene.

The following can be mentioned as examples of quaternary ammonium or phosphonium compounds: 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 has been found that it it is not absolutely necessary to use absolutely pure dyes in the preparation of the dispersions use, since the color obtained according to the invention

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substances that initially contain inorganic salts, quaternary ammonium or phosphonium compounds as well as possibly containing unreacted polyester, are just as suitable because the presence such compounds do not adversely affect the formation of the dispersions. Thereby are the dispersants are less expensive because they do not need to be cleaned. When the dye has even been prepared in an appropriate organic liquid, the solution of The dye in this liquid can be used directly for the preparation of the dispersion, without the organic liquid having to be removed beforehand.

According to a further feature of the invention finely divided dispersions of pigments in organic liquids created, in which organic liquid dissolved a dye as defined with at least one polyester residue is.

These dispersions can be prepared by the customary and known methods for preparing dispersions be prepared. Pigments, organic liquids and dyes can be used in any order.

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followed mixed together and then mechanically to reduce the particle size of the pigment processed until the dispersion is created. Mechanical processing can be done in a ball mill or a mill with pearls or gravel as a filling. Preferably the mechanical processing is 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 zinc resinate, which are commonly used in dispersions contained in pigments present in organic liquids

However, it is also possible to process the pigment to reduce its particle size independently of or in a mixture with either the organic liquid or the dye, whereupon the further component (s) is or are added and the desired dispersion is carried out stirring is obtained. Han but also kan so moved that a solution of the dye in the organic liquid with an aqueous medium to form an emulsion in manner known per se _t, for example by rapid stirring, mixed

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is, in the presence of one or more surface-active agents, whereupon the obtained Emulsion is added to an aqueous slurry of the pigment and the organic Liquid and water are separated by filtration and the residue consists of pigment and Dye is dried. This residue can subsequently be dispersed in an organic medium are «preparations that are obtained in this way and the pigment in finely divided form as well contain 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, where the dispersions preferably contain 5 to 70% by weight of 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 boron temperature) and the at Use the dispersion to remain stable. Mixtures of two or more organic compounds can also be used Liquids are used. Preferred organizational

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Niche liquids are hydrocarbons and halogenated hydrocarbons "such as toluene, Xylene, white spirit, η-hexane, cyclohexane, chlorobenzene, carbon tetrachloride and perchlorethylene. However, other organic liquids can also be used, such as, for example, esters such as alkyd resins and linseed oils thickened by heat, such as those used as lacquer binders for lithography Find. It is particularly preferred that the organic liquid is a predominantly aliphatic « Petroleum fraction is used · In general, the number of organic liquid or · the Mixing of such liquids depends on the application of the dispersion.

The pigments can be inorganic or organic in nature and belong to any of the recognized pigment classes include · As inorganic pigments, for example. Titanium dioxide »soot, zinc oxide, Prussian blue, Cadmium sulfide, elsenic oxide, vermilion, ultramarine and chrome pigments such as ZoB. Lead, zinc barium and calcium chromates, as well as the various mixtures and modifications of such pigments, such as they are commercially available under the names chrome yellow lemon, lemon yellow, chrome yellow medium, chrome orange, Molybdate Red and Chrome Red are available, in question

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The following can be mentioned as examples of organic pigments: Pigments of the azo, thioindigo, Anthraquinone, anthranthrone, isodibenzanthrone or triphenyldioxazine series, vat pigments, Phthalocyanine pigments such as 2.B. Copper phthalocyanine and its core halogenated »derivatives and copper * tetraphenyl and octaphenyl phthalocyanine, Quinacridone pigments and color lakes of the acidic, basic and mordant dyes «Such Pigments are in e.g. Color Index, Volume 2, 2nd edition (1956) under the heading "Pigments" as well described in authorized supplements. Thieves·"- Preferred pigments are Buss and especially copper phthalocyanine and its core halogenated Derivatives. If the pigment copper phthalocyanine is in the ß-form, it can be the normal pigment form of copper phthalocyanine or a crude copper phthalocyanine.

The dyes according to the invention are suitable especially for the production of pigment dispersions of copper phthalocyanine directly from raw copper phthalocyanine. There is a preferred coloring class for the pigment dispersions from such dyes, which are produced by the implementation of

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chloromethylated copper phthalocyanine with the Polyester, in particular with a polyester which is equal to 12-hydroxystearic acid, if appropriate old smaller amounts of stearic and / or palmitic acid derived.

The dispersions according to the invention are liquid or semi-liquid preparations that contain the pigment in finely divided and deflocculated form and are suitable for any purpose, for which dispersions of the solids in question are usually used. Thus the dispersions are particularly suitable for the production of Printing inks, however, the dispersions with the others, in the production of such inks common components are mixed. The dispersions are also suitable for manufacture of paints, the dispersions being mixed with common alkyd or other resins will. The dyes according to the invention can also be used as dispersants for the preparation of Dispersions of other dyes, such as acid dyes, disperse dyes and basic dyes, are used in organic liquids, such dispersions for The use of solvent dyeing of textiles Find.

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The invention is illustrated below with reference to Examples are explained in more detail purely by way of example, the specified parts and percentages being based on the Weight based on bind.

The polyesters were made as follows:

Polyester A

A mixture of 348 parts of xylene and 3350 parts of technical 12 Hydroxy8tearin8äure (acid number 182 ag KOH / g and flydroxylzahl 160 mg KO ^ g) is stirred for 22 hours at 190 to 200 ⁰ C, the water formed in the reaction of 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 nitrogen atom. 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 ^ -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 will then

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evaporated by heating to 180 ° 0 under reduced pressure. The liquid residue is ^{cooled to ^ 0 °} C. and an equal volume of a petroleum fraction with the boiling range 100 to 120 ^° C. is added. The mixture is cooled to 10 * 0 and then filtered to separate off the stearic acid. The solvent is then ^{distilled off at 100 °} C., specifically under reduced pressure, the polyester being obtained in the form of a slightly golden yellow, viscous liquid with an acid number of 58.6 mg KOH / g. '

Polyester C

A mixture of 65 ropes of xylene and 500 parts of technical ricinoleic acid is heated to 190 to 200 ° C. for 22 hours, the water formed being continuously distilled off. The xylene is then distilled off under reduced pressure at 15O ⁰ C, "The obtained polyester has an acid number of 13.7 mg

Polyester D

A mixture of 96 parts of xylene, 150 parts of oleic acid and 850 parts of ricinoleic acid is heated to 190 to 200 ° 0 for 22 hours, the water formed is continuously distilled off. The xylene will then

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distilled off ^{at 15O 0} G under reduced pressure. The polyester obtained has an acid number of 36.6 mg KOH / g.

example 1

A mixture of 44.3 ropes of polyester A, 15.3 parts a 25% aqueous solution of Tetraäthylaamoniumhydroxyd, 6 parts of copper tris (chloromethylphthalocyanine and 72 parts Methyl isobutyl ketone is 16 hours under a The reflux condenser is heated to the boil with a water separator. 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 of copper tris (chloromethyl) phthalocyanine is stirred for 16 hours under a reflux condenser with a water separator. The solvent will then evaporated in a stream of nitrogen. Consequently the crude product is obtained as a deep blue, viscous one

Liquid·

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Example 3

The procedure is as in Example 2, with the difference that only 1 part of the oetyltrimethyl « ammonium bromide is used. Wan receives one Similar product.

Example 4

A mixture of 44.3 parts Polyester A, 1 part of Cetyltrimethylammoniumbromids, 1.4 parts of sodium carbonate, 6 parts of copper-tris (chloromethyl) phthalocyanine and 64 parts of a Erdolfraktion having a boiling range of 100-120 ⁰ C for 16 hours under a reflux condenser heated to boiling with water separator. The solution is then cooled and a small amount of solid is poured off. The solution contains 47.9% crude dye.

Example 5

A mixture of 54 parts Polyester B, 2 parts of Cetyltrimethylammoniumbromide, 2.8 parts H atriumcarbonat, 12 parts of copper = "tris- (chlormethylphthalocyanin and 64 parts of a petroleum" fraction having a boiling range of 100-120 ⁰ C for 16 hours under a reflux condenser heated to 111 ° 0, the water formed over a

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Separator is separated. The solution obtained contains 54 »0% crude dye and is from one Trace of solid poured off.

Example 6

A mixture of 53.5 parts of polyester C, 0.5 part Cetyltrimethylammonium bromide, 0.7 parts of sodium » carbonate, 3 parts of copper tris (chloromethyl) phthalocyanine and 64 parts of a petroleum fraction with the boiling range 100-120 ° C is 16 hours under a reflux condenser with a water separator stirred at the boil · The resulting solution with 53.9% crude dye is poured off from a trace of solid.

Example 7

A mixture of 40 parts of polyester D, 1 part of the Cetyltrimethylammonium bromide, 1.4 parts of sodium carbonate, 6 parts of copper tris (chloromethyl) phthalocyanine and 64 parts of a petroleum fraction with the boiling range 100-120 ° C is 16 hours under a reflux condenser with a water separator stirred at the boil. The solution obtained with 47.7% Crude dye is then poured off from a trace of solid.

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Example 8

A mixture of 36.2 parts of a polyester made from technical 12-Hydro ^ ystearic 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 -Cchloromethyl phthalocyanine and 18 parts of a petroleum fraction with the boiling range 100-12O ⁰ C is stirred for hours under a reflux condenser with water separator at the boil. The solution is then filtered to remove a trace of solids. The solution contains 69.6% crude dye.

Example 9

The procedure is as in Example 8. After filtration to remove the trace, solid becomes but the filtrate in turn 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 2,500 to 3,500

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cm "" ¹ and 1,712 cm " ¹ (for -COOH groups - clearly recognizable in the infrared absorption spectrum of the polyester used as the starting material) not even at 1,600 cm" ¹ for -C00 ""groups; However, bands at 1,730 cm "" ¹ and 1,180 cm ** 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 cetyltrietbylammonium bromide, 1.2 parts of sodium carbonate, 10 parts of 1- (Y-Cblor-ß-hydroraypropylamino) - ^ - ^ · - (ß-hydroacyäthaxy) anilino) anthraquinone and 71 parts of a petroleum fraction with a boiling range of 100 to 120 ⁰ G is stirred for 16 hours under a reflux condenser with water at boiling · Bas solvent is then dried by heating to 140 ° 0 in a nitrogen stream removed. The crude product remains as a dark blue viscous liquid

Example 11 The procedure is as in Example 10, with the Deviation that instead of the one used there Anthraquinone compound 10 parts 2-methyl-4-lT _f lf-

di (ß-hy dr oxy ethyl) amino-4 - (H-ß-chloroethylsulfonamide) asobensol can be used · The product obtained

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Is a dark brown viscous liquid.

Example 12

The procedure is as in Example 10, with the

Deviation that instead of the one used there

Anthraquinone compound 10.7 parts 1- (ß-Bördroxy-

ätbylamino) -4- (2 ^f -bromo - ^ '- (K-ß-chloroethylsulfonamide) -phenylazo) naphthalene can be used. The product

is a deep red viscous liquid

example

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 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 tar.

example

A mixture of 36.3 parts of the polyester according to Example 8, 0.76 parts of the cetyltrimethylammonium bromide, 1.06 parts sodium carbonate, 3.04 parts

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Copper pentakis (chlormethylphthalocyanin and 35.5 parts of a petroleum fraction? Iit a boiling range of 100-120 ⁰ C is stirred for 16 hours under fester reflux condenser with water at the boiling point. Bas solvent is then removed in a nitrogen stream and leaves a deep blue viscose liquid.

Example 15

A mixture of 3 parts of copper phthalocyanine in the β-form, 0.6 parts of the dye according to Example 9 and 6.4 parts of a petroleum fraction with the boiling range 100-12O ⁰ C is processed in a ball mill for 16 hours. A finely divided, well deflocculated dispersion of the pigment is obtained, which is suitable as a printing ink for gravure printing

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 one Amount of the dye solution according to Example 4, 5 or 8, which denies 0.6 parts of raw dye £, is replaced will.

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Example 16

A mixture of 3 parts of Kupferpathalocyanin in the ß-form, 1.5 parts of the dye according to Example 10 and 5.5 parts of a petroleum fraction with the boiling range 100-12O ° O is 16 hours in processed in the ball mill, a finely divided, well deflocculated dispersion of the pigment which is suitable as a printing ink for gravure printing

The following table are further examples for dispersions to be found in each case, by kahlening the pigment according to the 2nd column of Table together with the dye or the dye solution according to the 3 · column and the organic liquid according to the 4 "column of the Table will be generated · A finely divided, well deflocculated dispersion of the pigment in question.

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example

Figment dye or solution

Org. Liquid

17th

18th

19 20

21 22 23

24 25

3 parts of the pigment, the 3,3'-dichlorobenzidine tetraazotized by coupling on Acetacetanllid is obtained

3 parts i- ^ '

phenylazo) -2-naphthol

3 parts of copper phthalocyanine in the ß-form

dto.

dto.

3 parts of indanthrone

3 parts of a resinized calcium toner of 1- (2'-sulfo-4'-methylghenylazo) -2-naphthol-3-carboxylic acid

3 parts lead sulfochromate

3 parts of a nickel clay des

(-ChlorphenylaJ5o) quinoline ~ (2) 1.5 _## parts of the dye according to Example 11

1.5 _M parts of the dye according to Example 12

1.5 parts of the dye according to Example 13

2 _A 8 parts of the dye solution according to Example 6

3 _A 1 parts of the dye solution according to Example 8

Ο _λ 9 parts of the dye solution according to Example 8

dto ·

dto ·
dto.

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

dto.

dto.

4.2 parts of a Erd- ι olfraktion with Sdp. 100-120 * 0

2.9 parts of an earth "oil fraction with bp. 100-120 ⁰ C

6.1 parts of a Erdolfraktion with bp * · 100-120 ⁰ C

dtO

dto «, dto.

example

Pigment dye or solution

Org. Liquid

<o co co

ro

03

3 parts Freussisch blue

3 parts of an aluminum color lacquer of 1,4-dibydroxyantnrachinon ~ 2-8ulfoic acid

3 parts TIOXIDE HOR (coated form of rutile titanium dioxide)

3 parts of iron oxide 3 parts of carbon black

3 parts of Xupfer polychlorophthalocyanine

3 parts of 4,10-dibromanthranthrone

3 parts of phosphomolybdotungstate Color Index Basic Blue (42595)

28

29 30 31

32

33

35 36 0 _A 9 parts of the dye solution according to Example 8

dto. dt o.

dto. dto. dto.

dt o.

dto «

3 parts of copper phthalocyanine in 1.5% of the dye the ß-form according to example 1

dto dto ο dto. dto.

6.1 parts of an oil · fraction with bp. 100-120 ⁰ C

dto.

dto.

dto. ro dto. I. dto «, dtO O dto.

5.5 parts of n-hexane

5.5 parts cyclohexane 5.5 parts xylene

N3 fO O

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 the boiling range 100-120 ° C is processed in the ball mill. A liquid, deflocculated dispersion of copper phthalocyanine with no particles larger than 3 \ is obtained l diameter. Most of the particles are less than 1 μ in size.

The dispersion is suitable for printing inks for gravure printing and shows increased color strength, improved Finish and a greener shade compared to conventional dispersions of copper phthalocyanine in the p-form.

Example 38

There are 25 parts of copper phthalocyanine in the beta form, 5 parts of the dye according to Example 3 and 10 parts of a petroleum fraction having a boiling range of 260-290 ⁰ C are introduced in a Baker-Perkins mixer, where 60 Hinuten in a plastic state milled "Then Another 3 _{tons of} 6 parts of the same petroleum fraction are added and the mixture is boiled for 15 minutes. Han receives a homogeneous, viscous paste with a pigment content of 57 »5% · The paste is suitable for printing inks for letterpress printing.

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Example 39

60 parts of an oven soot with a surface area of 80 m 2 / g, 15.7 parts of the dye solution according to FIG Example 4, 74.3 parts of a petroleum fraction with the boiling range 100-120 ° C and 500 parts of steatite balls with a diameter of 6 mm are placed in a container, which is then 24 hours at 100 U / Hin is rotated on a roller mill. The contents of the container are then used to remove the balls sifted. The product obtained is a flowable paste made from finely divided soot.

If this paste is coated with a gravure varnish, e.g. a solution of zinc / calcium resinate in a coal » hydrogen solvent, mixed, one obtains a black gravure ink with good gloss and coloristic properties in which the soot is finely divided.

Example 40

A mixture of 10 parts of 1,5-dihydroxy-4,8-diamino-2- (p-hydroxyphenyl) -e-hydroxymethylanthraquinone, 4.2 parts of the dye solution according to Example 4 and 160 parts of perchlorethylene is 16 hours in the Ball mill processed. Thus, a well deflocculated dispersion of the anthraquinone dye is obtained the aromatic polyester fabrics according to the

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Solvent processes can be colored. Example 41

A mixture of 7.2 parts of the dye solution according to Example 8, 2.8 parts of perchlorethylene and 0.5 part of an adduct of a mixture of oleyl and cetyl alcohol with 2.5 parts of ethylene oxide becomes a solution of 2 parts of an adduct clay cetyl alcohol with 17 mol Ethylene oxide in 194 parts of water with 6 parts of sulfuric acid is added, 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 obtained α-form copper phthalocyanine is heated in 100 parts of dilute sulfuric acid to dissolve metallic impurities. 4-2 parts of the above emulsion at 60 ⁰ C was added thereto, the mixture is nachgerpuhrt for 15 minutes, the slurry is filtered and the pigment is washed with water and then dried.

A printing ink is produced in that 1.08 Parts of the dried pigment with 0.92 parts of a synthetic letterpress varnish for lithography (viscous alkyd medium). This pressure «

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color is much less viscous than a control color, the analogue from the crude copper phthalocyanine but without adding the emulsion to the pigment slurry · The print results obtained with this printing ink show the same color strength but a higher brightness than the print results achieved with the control color

Example 42

A mixture of 36.3 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) α20-benzene 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 Vaeser separator at the boil · The solvent is then ^{removed at 110 0} C in a nitrogen stream and leaves the crude dye in the form of a brown rubber.

Example 45

A mixture of 3 parts of the pigment which was prepared by coupling tetraazotlertem 3t3'-dichloro-4.4 ^l diaminodiphenyl with acetacetanilide, 0.6 part of the dye according to Example 42 and 6.4 parts of a petroleum fraction with the boiling range

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100-120 ° C is processed in the ball mill for 16 hours. The result is a finely divided, well deflocculated dispersion of the pigment «

Example 44

A mixture of 36.3 parts of the polyester according to Example 8, 0.76 parts of n-hexadecyl-tri-n-propylphosphonium bromide, 1.06 parts of sodium carbonate, 4.55 parts of copper-tris-chloromethylphthalocyanine and parts of a petroleum fraction with a boiling range of 100 -120 ⁰ C is stirred for 16 hours under a reflux "condenser with water at the boiling point. The solvent is then removed at 110 ° C. in a stream of nitrogen and leaves a crude dye as a deep blue viscous liquid.

Example 45

A mixture of 3 parts of copper phthalocyanine in the beta-form, 0.6 parts of Farbstoffa 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 obtained "Thus, a finely distributed, well deflocculated dispersion of the pigment.

Example 46

96 parts of crude copper phthalocyanine. 24 parts of the

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Dye according to Example 3, 12.8 parts of zinc resinate iXQd 167.2 parts of a petroleum fraction having a boiling range of 100-120 ⁰ C are mixed in a stainless steel vessel, wherein the Gefass with a stirrer having three discs (diameter 10 cm, thickness 8 mm each). 1,000 parts of glass beads 0.6 to 0.7 in diameter are added and the mixture is stirred for 60 minutes at a speed of 1,880 rpm. According to this, the dispersion does not have a substantial number of pigment particles with a diameter of more than 3 V, with most of the pigment particles having a size below 1 μ 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 ß-form and has a high color strength and shows a greenish, light hue Use in a gravure ink

Example »7

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 the boiling range 100-120 ⁰ C is in the

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Processed ball mill, resulting in a liquid, deflocculated dispersion of copper phthalocyanine, in which no! Particles have a diameter of more than 3 μ, while most of the particles have a diameter of less than 1 μ.

This dispersion is particularly suitable for printing inks for gravure printing and produces printing inks with increased color strength, an improved finish and a greener hue compared to a conventional dispersion of copper phthalocyanine in the

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209835/1184

Claims (2)

Claims D represents the radical of a dye attached to Z via a carbon atom of one present in D aromatic ring is bonded; Z represents a divalent bridging member; η represents a positive integer from 1 to 8 inclusive and R is the remainder of a terminal containing carboxyl groups Represents polyester of the formula ROOOH, which is different 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 hydroxy and carboxylic acid group are _t represents _t or a mixture of such a hydroxycarboxylic acid and derives a free of hydroxy carboxylic acid * - 36 - 209835/1184 2. Substances, characterized in that they are made of a finely divided dispersion of a pigment in an organic liquid, in which a dye according to claim 1 is solved exist. MTtNTAN) M-Ui CMt-ΙΝβ. H. hhCUt, Om.-tN <i. M. DWL.- im «, s. 209835/1184