DE2122521B2 - Modified diarylide pigment and process for its preparation - Google Patents

Description

a) a stoichiometric excess of the coupling component in relation to the tetrazotized benzidine, both of which are not water-soluble containing making groups, used, and a small proportion of a water-solubilizing groups having tetrazotized benzidine before coupling the tetrazotized benzidine or a part of the coupling component, both of which do not contain water-solubilizing groups, or the reaction mixture during or after its coupling or adds

b) a stoichiometric excess of the tetrazotized benzidine in relation to the coupling component, both of which did not contain any water-solubilizing groups, is used and a small portion of a coupling component having a water-solubilizing group, prior to coupling the coupling component, to a portion of the tetrazoiated benzidine, neither of which is water-solubilizing Contain groups, or the reaction mixture during or after its coupling admits, or

c) the dye before coupling to the tetrazotized benzidine or e.nem part of the coupling component, both of which contain no water-solubilizing groups, or the Reaction mixture is added during or after its coupling, or

d) the tetrazotized benzidine with the coupling component, both of which do not contain any water-solubilizing groups, in a solution of the dye couples

wherein the amount of the water-soluble dye, based on the diarylide pigment, is up to 25% by weight and one of the modifying agents mentioned in claim 1 is optionally also incorporated.

5. The method according to claim 4, characterized in that the modified diarylide pigment subjected during or after its preparation to the heat treatment with a solvent.

6. The method according to claim 5, characterized in that one is an aqueous paste or Suspension of the modified diarylide pigment with tetralin, dibenzyl ether or o-dichlorobenzene boils and then filtered off.

The present invention relates to a modified diarylide pigment which is different from the ordinary Diarylide pigment is distinguished by greater color strength, higher gloss and better transparency

The so-called benzidine yellow pigments are azo compounds that are tetrazotized by coupling a Benzidine, which can be substituted on the aromatic nucleus, with a coupling component, in particular an acetoacetarylamide. Usually 3,3'-dichlorobenzidine is used, however other substituted benzidines can also be used. B. Pigments made from tetrachlorobenzidines. examples for are

ν ·, acetoacetanilide,

Acetaacet-o-toluidid, Acetoacet-p-toluidide, Acetoacet-o-anisidide, Acetoacet-o-chloroanilide and Acetoacet-2,4-xyIidide.

The so-called Behzidin-Orange pigments are made prepared in an analogous manner by coupling tetrazotized 3,3'-dichlorobenzidine with a coupling component, in particular a 3-methyl-5-pyrazo-ion, which is in the 1-position by a phenyl substituent is substituted, which in turn has up to 5 substituents, such as alkyl, aryl or alkoxy groups or halogen atoms, may have

Other diarylide pigments can be made by coupling tetrazotified derivatives of non-chlorinated benzidines with coupling components. A Example of such a non-chlorinated benzidine, that can be coupled to form a pigment is dianisidine or 3,3'-dimethoxybenzidine.

It has now been found that the properties of the aforementioned diarylide pigments are considerably improved if a water-soluble diarylide dye is incorporated into the pigment. object the invention is thus a modified diarylide pigment, which consists of a pigment of a tetrazotized benzidine, coupled with an acetoacetarylide, an optionally substituted on the phenyl nucleus 1-phenyl-3-methyl-5-pyrazolone or 2-hydroxynaphthalene-3-carboxyanilide, and one incorporated therein water-soluble dye made from a tetrazotized benzidine coupled with an acetoacetarylide, a 1-Phenyl-3-methyl-5-pyrczolone or 2-hydroxy-naphthalene-3-carbosyanilkton which is optionally substituted on the phenyl nucleus, the dye content, based on the pigment, being up to 25% by weight and the modified pigment optionally also being a resin as an additional modifying agent Fatty alcohol or a diol or a polyol with 8 to 22 Carbon atoms, a fatty acid, a fatty acid ester or an aliphatic amine or amine salt with 1 contains up to 20 carbon atoms

The modified diarylide pigment is produced by both being used to produce the Diarylide pigment? as well as for the production of the water-soluble dye with a tetrazotized benzidine an acetoacetarylide otter an optionally substituted on the phenyl nucleus 1-phenyl-3-methyl-5-pyrazolone or 2-hydroxynaphthalene. -carboxyanilide as Coupling component couples, whereby one

a) a stoichiometric excess of the coupling component in relation to the tetrazotized Benzidine, both of which do not contain any water-solubilizing groups, and a small one Proportion of a tetrazotized benzidine having water-solubilizing groups before the Coupling the tetrazotized benzidine or part of the coupling component, both of which do not contain water-solubilizing groups, or the reaction mixture during or after it Domes admits, or

b) a stoichiometric excess of the tetrazotized benzidine in relation to the coupling component, neither of which is water-solubilizing Contain groups, used and a small proportion of a coupling component having water-solubilizing groups before coupling the coupling component or a part of tetrazotized benzidine, neither of which contain any water-solubilizing groups, or the reaction mixture is added during or after its coupling, or

c) the dye before coupling to the tetrazotized benzidine or part of the Küpplüngskornpönente, neither of which are water-solubilizing Contain groups, or add to the reaction mixture during or after its coupling, or

d) the tetrazotized benzidine with the coupling component, both of which are not water-solubilizing Groups contain coupling in a solution of the dye, the amount being ugly water-soluble Dyestuff, based on the diarylide pigment, is up to 25% by weight, and one optionally also incorporates one of the modifying agents mentioned in claim 1,

In the following, the terms "pigment benzidine" and "pigment coupling component" are used to describe the components that make up the pigment to be distinguished from those used to manufacture

ίο serve the dye.

The modified diarylide pigment can consist of a pigment benzidine and various coupling components together with the dye or also from various pigment benzidines and a cup bngskomponente herge together with the dye will be presented. The compositions according to the invention expediently contain up to 25% by weight of the soluble dye, based on the pigment content, but preferably 1 to 10% by weight.

- The reasons for the improvement in the properties of the benzidine pigment are not fully understood. It will believed that the soluble dye is adsorbed on the surface of the pigment particles, possibly causing the growth of the particles and influences their crystalline nature and thus changes or modifies the surface properties will.

The soluble dye can be obtained by coupling a water-solubilized tetrazotized benzidine with a coupling component that does not contain any water-solubilizing groups, or by coupling one tetrazotized benzidine with a coupling component that has water-solubilizing groups, or by coupling a tetrazotized benzidine and a coupling component, both of which have water-solubilizing groups. Groups which make water solubility are, for example, sulfonic acid and carboxylic acid groups and their water-soluble metal salts or, 'N.mino groups and their water-soluble salts. The free acids of the dyes can, for. B by boiling the sodium salts of the dyes obtained in the coupling reactions in hydrochloric acid. So z. B. that Pigment coupled with tetrazo-3,3'-dichlorobenzidine tes acetoacet-o-toluidide and the soluble dye Acetoacetanilide coupled with tetrazo-4,4'-diamino-2,2'-diphenyldisulfonic acid. On the other hand, it can Pigment acetoacet-m-xylidide with tetrazo-3 ^ '- dichlorobenzidine and the soluble dye acetoacet-m-xylidid be coupled with tetrazo-4,4'-diamino-2,2'-diphenyldisulfonic acid.

The adsorbed soluble dye can be made insoluble at a later stage in the preparation of the pigment preparation, e.g. B. through education insoluble salts with metals of groups IA, IB, HA, I IB, UIA, IHB and VIII of the periodic table. A very A suitable way to form the insoluble salts is a double conversion between the Sodium salt of the dye and a water-soluble one Salt of the metal at a pH of preferably 8 to 9. Typical soluble metal salts are zinc sulfate, magnesium sulfate, barium chloride, aluminum sulfate and Calcium chloride. It may be desirable to have the soluble dye in the pigment composition

To make μ insoluble if there is a risk that the dye will be washed out during the production of the pigment composition or into the reservoir solution that is used in the letterpress process or in the lithograph! -

see printing process is used, bleeds. Furthermore, a hydrophilic surface on the pigment can cause bleeding into the reservoir solution. The retention of the dye in the pigment composition imparts it as a water-soluble metal salt the pigment also have other advantages.

It has been found that the additional incorporation of a resin or a resinous material into the pigment compositions according to the invention Flow properties of the compositions in letterpress inks improves examples of such resins or resinous materials are wood resin and its derivatives such as hydrogenated wood resin and polyamide-type Resins such as those obtained by the condensation of phthalic anhydride with long chain amines will. Furthermore, the incorporation of surfactants, e.g. B. a naphthalene disulfonic acid / formaldehyde condensate the tinting strength of the compositions in letterpress inks; and the incorporation of non-ionic surfactants Agents such as condensates of long-chain alcohols and ethylene oxide, the gloss and texture in printing inks.

As indicated earlier, the modified diarylide pigment according to the present invention exhibits larger ones Color strength, higher gloss and better transparency in letterpress color media. The texture and the rheological However, properties of the pigment are not yet fully satisfactory.

Pigments that have a good texture and strong transparent letterpress inks with good ones Theological properties revealed are difficult to manufacture. It has been found that the Treatment of the pigment compositions of the invention with an organic solvent or by adding a long-chain fatty alcohol, diol or polyol containing at least 8 and preferably 8 contains up to 22 carbon atoms and may have ether or ester bonds, a pigment is obtained that not only the properties mentioned, but also particularly good flow properties in letterpress inks having

The fatty alcohols used for the treatment can be primary, secondary or tertiary alcohols and be saturated or unsaturated; the diols or polyols can be primary, secondary or tertiary hydroxyl groups and optionally be saturated or unsaturated. Examples of suitable materials are Cetyl alcohol, oleyl alcohol, behenyl alcohol, isooctanol and 2-ethylhexane -}, 3-diol. The amount of alcohol Glyol or diol may suitably be 0.1 to 30 % By weight, based on the dry weight of the pigment, with amounts of 0.1 to 10% by weight are preferred. If long-chain alcohols, i.e. alcohols with Cie-Ca chains, are used, analytical results show that more than 80% can remain in the final pigment compositions. The retained portion decreases as the chain length is shortened.

If the alcohol, diol or polyol is present during make-up or during make-up Reaction mixture is added, it is advantageous if a non-ionic surfactant such as an ethoxylated cetyl alcohol, is also present. It has been found that printing inks that result from this Formulated wisely produced pigments have better flow properties and higher gloss than those made from untreated pigment getting produced. It was also found advantageous to use a metal salt of a resin or the free one To add resin itself to the pigment which has been prepared or treated according to the invention, and that printing fluids made from this pigment have better color strength and flow properties than those made from untreated pigment. Similarly, it was found that the presence of resinous substances

ίο like hydrogenated resins, likewise the properties of Printing inks improved Resins or resinous materials can be present from the beginning or after be added to the coupling.

It has also been found that the presence of fatty acid such as oleic acid or stearic acid in the Pigment composition improves the hot and printing properties of printing inks. The acids can preferably be added in the form of their sodium salts during or after the coupling or present from the beginning:; a. You can in the pigment composition obtained by conversion insoluble in slightly soluble salts such as calcium and zinc salts. The present too of fatty acid esters is beneficial

It is known that Diaryüdpigmente with up to 25 % By weight, based on the pigment, to be treated with fatty amines of high molecular weight, whereby Result in products which exhibit excellent dispersibility in gravure inks. Such products however, have the disadvantage that the initially developed high color strength during storage of the Hydraulic fluid is not retained.

It has now surprisingly been found that when the production of the modified pigment with an amine treatment is combined. Products can be manufactured a which an excellent Have dispersibility as well as improved storage stability in hydraulic fluid, an important thing that It is surprising because it is not due to the individual effects of the two procedures was expected. According to a further embodiment of the production process, therefore, in the pigment composition a small proportion of an aliphatic amine or an amine salt which is 1 to 20 Contains carbon atoms, incorporated The products then have excellent theological properties in letterpress inks.

The exact constitution of the modified pigment obtained by incorporating a water-soluble dye

so obtained in a diarylide pigment and treating the composition with an amine depends from the dye, from the way in Jer die Process steps are carried out, and on the proportion of amine used. This share is in generally between 0.1 and 35%, based on & i Weight of pigment and dye. When a large amount of amine, e.g. B. more than 10% used when used in gravure inks, the products are stable to storage, while when used up to 10% the products have excellent transparency, color strength. Dispersibility and show theological properties in letterpress inks. The amine or amine salt can be used during of the coupling being present or prior to coupling to the tetrazole; »En pigment benzidine or to the pigment coupling agent are given.

When a large amount of amine is used, especially when the dye is reactive

21 22

Contains carbonyl group, an A / omcthinfarbstofl can be formed./. B. H> ei a pigment that a sulfonated benzicline dye of the formula

Ύ
Nile
ι SO ₁ II A "χ Y
Nile
I. I.
CO SO ₁ Il I.
co I.
(· 11 - N = N - <
I. «Ί ^ N - C 11
[ CO I.
(O
I. CH ₁ (Il

contains, an a / omethine dye can be formed which (in the presence of sodium ions) has the formula can have:

; ils monoazomethine or

as diazomethine.

In these formulas, R denotes an alkyl group having 1 to 20 carbon atoms, where RN H2 is im Manufacturing process used amine is depending on the pH and the amounts and of it Order of addition of the reactants can be dye-free amine or in the pigment Amine salt or a combination thereof may be present, or an amine salt of the dye, the Azomethine of the dye or the amine salt of the azomethine of the dye may be present.

The present invention is to be explained in more detail below with reference to four classes of diarylide pigments will.

Hcn / idin-Geih pigments

Name or color index number

Pigment yellow 12
(Color Index No. 21 OW)

Pigment yellow 13
(Color Index No. 21 KH)) Pigment Gelh 14
(Color Index No. 21 (WS)

Pigment (ielb 17
(Color Index No. 21 105)

Pigment yellow Nl

21 22

IO

(ichildel (lurch domes around

3, .V-Dichlorheii / idin and Acctoaeelanilid

3,3'-dichlorobeiiline and Acct < > acet-2.4-xv littici

3.3'-dichlorohenzidine and aeeloacet-o-toluidicl

3.3'-Di chlorine be η / id in and Aeeloacel-o-aniskliil

2,2'.5.5'-tetrachlorobenzene and Aeel <«ieet-2,4-xylidid

3,3'-l) ichlorben / idin and acetoacel-p-toliiidid

3.3'-dichlorobenzene and Acctoacet-o-diloranilidid

2. licn / idin-Rnt-Pmnientc

N, ime or C'olour index nunimer

Formed by domes of

Pigment cielb 37
(Cdlour-Indc.x No. 21 205)

Pigment yellow 41
(Color Index No. 21 200)

3,3'-dimoxybenzidine and lp-tolyl-3-meth.vl-5-p.vra / olone
3,3'-dimethoxydine and 1-phenyl-3-methyl-5-pyra / olone

3. Ikn / idin-Hlau pigments

Niime (Hler Color Index Niimnier

Pigment blue 20
(Dianisidine blue)

(iehildel by coupling of

3,3'-Dimethoxybenzidine and anilide of 2-naphthol-3-carboxylic acid

4. Tolidine yellow piumente

Name or color index number

Cie formed by domes of

Pigment yellow
(Color Index No. 21 135)

3,3'-dimethylbenzidine and acetoacet-c-toluidide

Examples 1 to 6 illustrate the preparation of the pigment and dye composition Examples 7 to 9 the additional treatment of the composition with a solvent and the Example! 0 the additional treatment of the composition with an amine.

The procedure used in Examples I to 6 is carried out in principle as follows:

A tetrazo solution is prepared in the usual way and held at 0 ° and the coupling component is dissolved in sodium hydroxide solution

The tetrazotized benzidine is conveniently obtained by either of the following two procedures Room temperature, coupled with the coupling component:

a) by reprecipitation of the coupling component with dilute acid in a coupling vessel and running the tetrazo solution in the course

, <> one hour at room temperature, the

pH value during coupling is 4 to 4.5, or
b) by running the tetrazo solution and the solution of the coupling component together into a coupling vessel at a pH of 4 to

5 "> 4.5.

After coupling, the slurry is brought to the boil and simmered for one hour held. Then the slurry is filtered to make the pigment composition free of inorganic salts washed and dried at 50 to 55 ° C.

The dye can be added in one of the four stages or prepared in one of these stages:

65 1. Before the clutch stage,

2. during the coupling stage,

3. after the coupling stage,

4. after the boiling point.

Il

The addition of metal salts in order to make the dyes water-insoluble is generally carried out either in levels 3 or 4.

B is ρ ie II
Solution I.

Tetrazo 3,3'-cl chlorbenzidin was Tetra / .otieren 26 parts 3,3'Dichlorbenzidin in 500 parts of water at 0 ⁰ C.

Suspension 2

Tetrazo-4,4'-diamino-2,2 '- (Iiphenyldisiilfonsaure was by tetrazotizing 2.0 parts of 4,4'-diamino-2,2'-diphenyidisulfonic acid made in 50 parts of water at O'C.

Solution 3

40.5 parts of acetoacetanilide were in 9.9 parts Sodium hydroxide dissolved in 900 parts of water Fim> A solution of 20 parts of sodium acetate in 200 parts of water was prepared in a coupling vessel. The pH was then adjusted to a value of 4.5 with dilute acetic acid.

5% of Solution 3 was added to the coupling jar and then added over 10 minutes the suspension 2 was added dropwise, making sure that at no time a substantial amount uncoupled tetrazo compound is present. Solutions I and 3 were then added over the course of I hour at the same time added dropwise to the vessel at room temperature, again no excess tetrazo compound was made possible, and the pH was, if necessary, by adding 10% sodium hydroxide solution held at a value of 4.5. Then the reaction mixture was brought to the boil and 30 Boiled minutes and the pigment composition filtered off, washed with water and kept at 50 to 55 ° C dried.

The pigment composition thus produced showed, when incorporated into a letterpress ink, better tinting strength and greater printing transparency than can be achieved with a pigment could, which had only been made by coupling 3.3'-dichlorobenzidine and acetoacetanilide.

Example 2

The same solutions and reaction conditions as indicated in Example 1 were used, however the process was changed by first mixing the solution I and the suspension 2 and then with the solution 3 were coupled. The pigment obtained was similar to that obtained in Example 1.

Example 3

The same solutions and reaction conditions as in Example 1 were used, but was the method changed in that the solution 1 was first coupled with the solution 3 and the Suspension 2 was then added to the reaction mixture. The pigment obtained was similar to that in Example 1 obtained.

Example 4
Solution 1

Tetrazo-3,3 "-d! Cniorbenzidine was replaced by tetrazoleren of 26 parts of 33'-dichlorobenzidine in 500 parts of water at 0 ° C.

Suspension 2

Tctrazo-4'-cliamino-2,2'biphenyldisulfonic acid was obtained by tetrazotizing 2.0 parts of 4,4'-diamino-2,2'-di-ι phenylsulfonic acid in 50 parts of water produced at OC.

Solution 3

40.5 parts of acetone acetanilide were in 9.9 parts

κι sodium hydroxide dissolved in 900 parts of water.

A solution of 20 parts of sodium acetate in 200 Parts of water were made up in a coupling vessel. Then the pH was diluted with fsigsäiire adjusted to a value of 4.5.

r> 5% of solution 3 was in the coupling vessel given and the suspension 2 was added dropwise over the course of 10 minutes, making sure that none Time a substantial amount of uncoupled tetrazo compound was present. The solutions ! and 3

- '(ι were then simultaneously added dropwise to the vessel in the course of 1 hour at room temperature, with again, at no time was an excess of the tetrazo compound allowed. The pH was if necessary, by adding 10% sodium hydroxide solution

. '"> solution kept at a value of 4.5. 2.4 parts of a Resin based on abietic acid dissolved in 6.0 parts of 10% sodium hydroxide solution then added to the pigment slurry. The slurry was then boiled for 1 hour,

! (i the pH using 10% sodium hydroxide solution adjusted to a value of 6 to 6.5, and then 1.7 parts of zinc sulfate was added. the The slurry was then filtered and the resulting pigment slurry was washed with water.

r> see and dried at 50 to 55 ⁰ C.

The pigment composition showed the same advantages and better flow properties than those after Example 1 obtained when the material was incorporated into a letterpress printing fluid.

4 (1.

Example 5

The procedure of Example 4 was repeated except that the resin was replaced by hydrogenated abietic acid was replaced. A pigment composition with similarly excellent properties was obtained.

Example 6

The procedure of Example 4 was repeated twice, but in one case the resin

> o by a resin made by reacting phthalic anhydride with dodecylamine, and in the other Case was replaced by a resin-modified cresylic acid. In each case, a pigment composition was obtained with similar excellent properties as the compositions prepared according to Example 4.

Example 7

5% solvent or fatty alcohol, diol or polyol, Based on the weight of the pigment, the pigment compositions described in Examples 1, 2 and 3 were incorporated after the coupling step but before boiling. The following were incorporated Materials used:

Cetyiaikohol,
Oleyl alcohol,
Isooctanol,

2-Ethytliexan-! , 2-diol.

Polyethylene glycol 600,

Xylene,

Dibenzyl ether,

Dipropylene glycol monolaural, o-dichlorobenzene,

Nitrobenzene,

Benzyl cyanide,

Quinoline.

The resulting compositions were tested in comparison with untreated pigment Ciclb 12, solvent-treated pigment (ielb 12 and with the compositions prepared exactly according to Examples I, 2 and 3. In each case, improved fluid properties and a better texture were found compared to that only pigment modified with the dyestuff and a superior color strength and transparency greener-green, nrm nj ^ ;; agile! "" pigment or compared to the pigment which had only been treated with solvent.

Example 8

1. A tetrazole solution was made from 26.0 parts 3.3'-dichlorobenzidine prepared in 500 parts of water.

2. A tetrazo suspension was made from 2.0 parts of 4,4'-diamino-2,2'-diphynyldisulfonic acid in 120 parts Water produced. 46.85 parts of acetoacet-m-xylidide were in 900 parts of water, the 9.15 parts of sodium hydroxide contained, solved. The acetoacet-m-xylidid was then added by adding a solution of 13.75 Parts of glacial acetic acid in 50 parts of water precipitated to form a slurry.

Then, over the course of P / 2 hours, the Tetrazo solution 1 to the slurry of the precipitated acetoacet-m-xylidide gel 1. The pH of the Reaction mixture was during the addition by a simultaneous addition of a 10% aqueous Sodium hydroxide solution held between 4.0 and 5.0.

The pH of the resulting yellow pigment slurry was then adjusted with 10% sodium hydroxide solution set to a value of 6.0. Then the tetrazo suspension became over 15 minutes 2 added to the slurry. The pH of the slurry was determined by the addition simultaneous addition of an aqueous 10% sodium hydroxide solution held between 5.5 and 6.0.

Then 4 parts of dibenzyl ether were added to the pigment slurry. The slurry was boiled for 1 hour and the pH was adjusted to a value of 8.0 to 9.0 with 10% sodium hydroxide solution. Then, the pigment by filtration, washing the filter cake through free of water soluble impurities and by drying at 50 ⁰ C was isolated

The pigment composition obtained according to this method was found when placed in a letterpress ink medium was incorporated, more glossy and more transparent prints with better color strength than with one Pigment composition could be achieved, which had only been treated with solvent (and which had not been treated with the dye). The theological properties of the hydraulic fluid were similar to those of a printing fluid made from the solvent-treated pigment

Example 9

I. A tetrazo solution was made from 27.4 parts of 3,3'-dichlorobenzidine in 500 parts of water.

ι 2. A tetrazo suspension was at'S !, 5 parts 4.4'-Diamino-2,2'-diphenyldisulfrnsäurc prepared in 100 parts of water.

49 parts of acetoacet-o-aniside were dissolved in 9.2 parts of sodium hydroxide in 900 parts of water, gelo. ,,.

κι The coupling component was then added of 14 parts of glacial acetic acid dissolved in 50 parts of water, under Precipitated formation of a slurry.

Then, in the course of 1 hour, the tetrazo solution 1 added to the slurry. The pH of the

ι> reaction mixture was through during the addition simultaneous addition of a 10% aqueous sodium hydroxide solution to a value between 4.0 and 4.5 held.

The pii-Weri u'oi eiii.iiienen geiben Pigmcntauf-

I was slurrying with 10% sodium hydroxide solution adf set a value from b.O to 7.0. Then the tetrazo suspension 2 became in the course of 15 Added to the slurry for minutes. The pH of the slurry became through during the addition

: "· The simultaneous addition of an IO% aqueous Sodium hydroxide solution maintained between 6.0 and 7.0.

A suspension of 4 parts of cetyl alcohol in 25 parts of water was added and the slurry

iii mung cooked for I hour. Then the slurry filtered, washed salt-free and dried at 50 to 55 ° C.

The pigment composition obtained showed when incorporated into a letterpress color medium

j-i was compared, improved theological properties with a pigment composition obtained by simply coupling acetoacet-o-anisidide with tetrazo-3,3'-dichlorobenzidine had been received. Compared to the untreated Pigmen; couldn't

• 40 remarkable loss of color strength observed will.

Example 10 Solution 1

67 parts of acetoacetanilide were in a solution of 28.2 parts of sodium hydroxide in 900 parts of water solved.

_ ₀ solution 2

43.5 parts of 3.3'-dichlorobenzidine were combined with 24.1 parts Sodium nitrite tetrazotized in 800 parts of water at 0 ° C.

Suspension 3

sulfonic acid were tetrazotized with 1.7 parts of sodium nitrite in 125 parts of water at 0 ⁰ C.

10% of the solution 1 was placed in a coupling vessel and the suspension 3 then in the course of Added for 10 minutes ensuring there was no substantial amount of uncoupled at any time Tetrazo component was present.

The remainder of Solution 1 and Solution 2 were then added to the reaction mixture simultaneously over the course of 1 hour. The reaction temperature was at or around room temperature and the pH is kept between 4.5 and 4.8, again no substantial

1β

Amount of uncoupled tetrazo components in any one Level was present.

28.2 parts of an amine mixture consisting essentially of palmityl, stearyl and oleyl amines dissolved in 17.0 parts of acetic acid in 1000 parts of water and then placed in the coupling vessel. The reaction mixture was then brought to the boil and 30 Boiled for minutes. Then the pH of the slurry reaction mixture was adjusted after boiling at a temperature of 70 ° C with a sodium hydroxide solution to a value of 10.0. Thereafter, the pigment composition was filtered off, washed with water and dried at 50 to 55 ° C

The pigment composition thus obtained was easily dispersible in rotogravure ink media, resulted in a storage-stable printing fluid that was stronger in terms of color strength and more transparent and led also results in a glossier product than the Benzidine Yellow pigment composition which merely by coupling Sp'-dichlorobenzide with acetoaceianilide had been prepared in the presence of the amine mixture. A pigment composition that without the use of the amine mixture or the like Amine or a combination of amines is not readily produced in rotogravure color media dispersible.

Example 11

A tetrazo solution was prepared from 50.6 parts of 100% strength 3,3'-dichlorobenzidine in the form of the hydrochloride in 1500 parts of water at 0 ^{° C.}

A suspension of 72 parts of 1-phenyl-3-methyl-5-pyrazolone in 1500 parts of water was 50 parts Buffered sodium acetate

Then the tetrazo solution was dripped into the pyrazolone suspension over 1 hour The pH of the solution was adjusted to a value of 4.0 to 4.5 held. After coupling, the slurry was divided into 5 parts

Part A

The slurry was filtered, the resulting pigment washed with water and kept at 50 ° C dried

part B

The slurry was boiled for 1 hour, filtered off and the resulting pigment was washed with water and kept at 50 "C dried

To the slurry was added 5%, based on the weight of the figure, of a dye obtained by coupling tetrazobenzidine-2 ^ '- disulfonic acid with p-sulfonated phenylethylpyrazolone . The resulting slurry was boiled for 1 hour, filtered, and the pigment composition was washed with water and dried at 50 to 55 ° C

Part D.

The slurry was heated to 90 ° C to held for 10 minutes at 90 ⁰ C. Damage was 5% of the same dye as it was in Tei

ίο C was added to the slurry and then the slurry was boiled for 3 <minutes mung filtered, the pigment composition was washed with water and kept at 50 to 55 ° C

is dried

Part E.

The slurry was boiled for 30 minutes to which 5% of the same dye was added then the slurry was filtered and the pigment composition washed free of salts and dried at 50 to 55 ° C

In letterpress inks, the pigment composition found in A was in terms of hue the transparency and the gloss are identical to the pigment composition resulting from C; the

The composition obtained according to B was identical to that obtained according to E, with both the composition Settlement B and E have poorer transparency and

had a gloss inferior to A; and the compositions obtained according to C and D had

Properties which were between the compositions obtained according to A and E. This illustrates the stabilization of the pigment by the dye at the stage at which the dye is added.

Example 12 Solution 1

Tetrazo-33'-diraethoxybenzidine was replaced by tetra-

quoting 303 parts of 100% 3,3'-dimethoxybene zidine with hydrochloric acid and 18.2 parts of sodium nitrite a temperature of CC, whereby one

Received final volume of 550 parts

Solution 2

A solution of 36 parts of sodium hydroxide and 8 parts of Turkish-Red-Ö! in 800 parts of water was on 70 ° C. Then * were slowly 69.7 with stirring Parts of 2-hydroxynaphthalene-3-carboxyanilide are added at a temperature of 25 ° C., whereby one Received final volume of 1200 parts

Solution 3 5 parts of the dye of the formula

CH ₅ NHCO

OH

CONHC «Hj

SOjNa

which is produced by coupling tetrazobenzidine-2,2'-disulfonic acid with 2-hydroxynaphthalene-3-carboxyanilide

030 182/37

were dissolved in a 10% sodium hydroxide solution

The solution 1 was added dropwise to the solution 2, the pH value being kept above 10.5 by suitable addition of 10 t sodium hydroxide solution. After the coupling had ended, the pH of the suspension was lowered to 5 [beta] and solution 3 was added. CMe slurry was made

then boiled for 1 hour and then the product filtered off, washed and stored at 50 to 55.degree dried

The pigment composition was unlike the product one in a letterpress ink similar method in which the dye was not added, superior gloss and one superior color strength.

Claims (4)

Patent claims: 1. Modified diarylide pigment, thereby characterized in that it consists of a pigment ί from a tetrazotized benzidine, coupled with an acetoacetarylide, an optionally substituted on the phenyl nucleus 1-phenyl-S-methyl-S-pyrazolone or 2-hydroxynaphthalene-3-carboxyaniIid, and a water-soluble dye incorporated therein consisting of a tetrazotized benzidine, coupled with an acetoacetarylide, an optionally substituted on the phenyl nucleus 1-phenyl-3-methyl-5-pyrazolone or 2-hydroxynaphthalene-3-carboxyanilide, the dye content being gene on the pigment, up to 25 wt .-% and wherein the modified pigment optionally as additional modifier or a resin, a fatty alcohol or a diol or a polyol with 8 up to 22 carbon atoms, a fatty acid, a fatty acid ester or an aliphatic «amine or Contains amine salt with 1 to 20 carbon atoms. 2. diarylide pigment according to claim 1, characterized in that the water-soluble diarylide dye sulfonic or carboxylic acid groups or having water-soluble metal sulfates or carbonates 3. diarylide pigment according to claim 1, characterized in that it is 1 to 10 wt .-% of one water-soluble dye, based on the pigment, contains 4. Process for the preparation of the modified diarylide pigment according to claim 1, characterized in that characterized in that both for the preparation of the diarylide pigment and for the preparation of the J> water-soluble dye couples a tetrazotized benzidine with an acetoacetarylide or an optionally substituted on the phenyl nucleus 1-phenyl-3-methyl-5-pyrazolone or 2-hydroxy-naphthaIin-3-carboxyanilide as coupling component, -in where one