DE2122521A1 - Pigment compositions - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann Dr. R. Koenlgsberger - Dlpl.-Phys. R. Holzbauer - Dr. F. Zumstein Jun.

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CIBA-GEIGY A.G., Basel / Switzerland

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Pigment compositions

The present invention relates to pigment compositions and, more particularly, to the preparation of diarylide pigment compositions. Diarylide pigments are also known as benzidine pigments, however the former nomenclature is according to one more recent practice preferred.

The so-called benzidine yellow pigments are azo compounds, that by coupling tetrazotized 3,3'-dichlorobenzidine itself or a tetrazotized benzidine that has further substituents on the aromatic nucleus, with a coupling agent which is an acetoacetarylamide. Usually 3,3'-dichlorobenzidine itself is used, however, other substituted benzidines can also be used, e.g. pigments were made from tetrachlorobenzidines manufactured. Examples of coupling agents that have been used are acetoacetanilide, acetoacet-o-toluidid, acetoacet-p-toluidid, Acetoacet-o-anisidide, acetoacet-o-chloranilide and acetoacet-2,4-xylidide.

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The so-called benzidine orange pigments are produced in an analogous manner by coupling tetrazotized 3,3 »-dichlorobenzidine with a coupling agent which is a 3-methyl-5-pyrazolone, which is additionally in the 1-position with a phenyl substituent is substituted, which in turn carry up to 5 substituents, such as alkyl, aryl, alkoxy groups or halogen atoms can.

Other diarylide pigments can be made by coupling tetrazotized derivatives of non-chlorinated benzidines with coupling agents. An example of such a non-chlorinated benzidine that couples to form a pigment is dianisidine, 3,3'-dimethoxybenzidine.

A process has now been found for the production of diarylide pigment compositions which have better color strengths and transparency properties compared to conventional diarylide pigments when they are incorporated into printing fluids. In accordance with the present invention, diarylide pigment compositions are made by coupling a tetrazotized pigment benzidine with a pigment coupling agent and incorporating a water-soluble dye into the pigment. Usually this dye is a coupled diarylide dye, but other classes of dyes such as monoazo dyes or even dyes other than azo dyes such as diphenylchrysoin can be used. The terms "pigment benzidine" and "pigment coupling ^{agent 1} '" used in the present specification have been used only to distinguish the compounds which form the pigment from the compounds from those compounds which are used to prepare the dye.

The incorporation of the dye can be done in a variety of ways Procedures take place. In one procedure, a stoichioraetric Excess of the pigment coupling agent used in relation to the tetrazotized pigment benzidine and a small proportion of one or more tetrazotized

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sulfonated benzidines or tetrazotized carboxylated benzidines prior to coupling to the tetrazotized pigment benzidine or before coupling to a portion of the pigment coupling agent or during or after coupling to the reaction mixture, preferably before isolating and drying the Pigment added

• In another process, a stoichiometric excess of the tetrazotized pigment benzidine via the pigment coupling agent may be used, and a small proportion of one or more coupling agents that are water-solubilizing containing functional groups may be to the pigment coupling agent before coupling or to a part of the tetrazotized Pigment benzidine can be added before coupling or to the reaction mixture during or after coupling.

¹ He desired change in the properties of the diarylide pigments can also be achieved according to the invention by adding one or more soluble dyes before coupling to the tetrazotized pigment benzidine or before coupling to a part of the pigment coupling agent or during or after coupling to the reaction mixture or the previously prepared Diarylide pigment, or by coupling the pigment in a solution of such a soluble dye. In such cases the coupling agent of the dye need not be the same as the coupling agent of the pigment itself, nor do the corresponding tetrazotized benzidines need to be the same. The dye need not have a structure similar to that of the pigment that is to be modified.

The soluble dye can be prepared by coupling one suitably water-solubilized tetrazotized benzidine with a coupling agent that does not contain water-solubilizing groups contains, or by coupling a tetrazotized benzidine with a coupling agent, the water-solubilizing groups or by coupling a tetrazotized benzidine and a coupling agent, both of which are water soluble

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making groups included. Under water soluble Making groups is understood to mean groups such as sulfonic acid and carboxylic acid groups and water-soluble metal salts thereof, amino groups and water-soluble salts of amino groups such as those with aliphatic acids are formed. The free acids of the dyes can be obtained, for example, by boiling the sodium salts of the dyes that are used in the Coupling reactions obtained in hydrochloric acid. For example, the pigment can be a tetrazo-3,3 dichlorobenzidine coupled acetoacet-o-toluidide, and the soluble dye could be acetoacetanilide coupled with Tetrazo-4,4'-diamino-2,2'-biphenyldisulfonic acid; alternatively the pigment acetoacet-m-xylidide could be coupled with tetrazo-3,3'-dichlorobenzidine and the soluble dye acetoacet-m-xylidide coupled with tetrazo-4,4-diamino-2,2'-diphenyl di sulfonic acid. Mixtures of soluble dyes can be used.

The sulfonated or carboxylated benzidines according to the invention used can be mono- or disubstituted or can have more than two acid groups. Very suitable benzidines are disubstituted, i.e. they are those compounds which have a sulfonic acid group or a carboxylic acid group as substituents on each aromatic nucleus.

The exact mechanism by which the improvement of the Benz— idinpigments is not entirely clear. It is believed, however, that certain active compounds are most likely the soluble dye itself, is adsorbed on the surface of the pigment particles, possibly causing the Affects the growth of the particles and their crystalline nature, thereby modifying the final surface properties will. If desired, the adsorbed soluble dye can be made insoluble at a later stage in the manufacture of the pigment, e.g., by making it insoluble Salts with metals of groups IA, IB, HA, HB, IHA, IHB and VIII of the periodic table. A very suitable way to form the insoluble salts consists in a double conversion

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Zung reaction between the sodium salt of the dye and a water soluble salt of the selected metal at an alkaline _pH value, as in einem'p "value 8 to 9 Typical soluble metal salts are zinc sulfate, magnesium sulfate, barium chloride, aluminum sulfate and calcium chloride. It may be desirable to make the soluble dye component insoluble in the pigment in this manner if there is a risk that the dye will be washed out during the leaching step in the preparation of the treated pigment, or if there is a risk that it will Dye bleeds into the reservoir solution used in the letterpress (letterpress) process or the lithographic printing process. Furthermore, a hydrophilic surface on a pigment can cause bleeding into a reservoir solution. The retention of the dye in the final pigment composition as a water-insoluble metal salt also gives the pigment other benefits.

The present invention also relates to the diarylide pigment compositions and mixtures prepared in this manner of two or more such compositions. The compositions can consist of a single pigment benzidine and various coupling agents along with the dye or made from various pigment benzidines and a single coupling agent together with the dye. In general, the compositions contain up to 25% by weight of the soluble dye, based on the pigment, but preferably 1 to 10% by weight.

If the soluble dye is prepared in situ, a stoichiometric excess of one or another pigment coupling agent will be used used in relation to the tetrazotized pigment benzidine. A suitable excess is that the theoretical amount of constituents is present that is required for a complete stoichiometric coupling to provide both the pigment and the soluble dye, or an amount in which a slight excess of the coupling agent over this stoichiometric amount, e.g.

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up to 5% by weight, based on the others to be coupled Components, is present.

The sulfonated or carboxylated benzidines which can be used in the process of the invention include the acids themselves and their soluble metal salts. The amount of sulfonated or carboxylated benzidine can be up to 25% by weight of the pigment benzidine, but it is preferred not to use more than 10 % . There is no significant improvement when larger proportions are used.

"It was found that the additional incorporation of a resin or a resinous material in the pigment compositions of the invention improves the flow properties of the compositions in letterpress inks. Examples of such Marches or resinous materials are wood resin and its Derivatives such as hydrogenated wood resin and polyamide type resins such as those obtained by condensation of phthalic anhydride can be obtained with long-chain amines. Furthermore, the incorporation of surfactants, e.g. Naphthalenedisulphonic acid / formaldehyde condensate, which is sold under the trade name Belloid SF, the coloring power of the compositions in letterpress inks, and the incorporation

fc of non-ionic surfactants such as condensates of long-chain alcohols and Xthylenoxyd, in particular a '*' * ■ -.? that, "ubrol W is Icohol / ethylene oxide condensate sold under the i ^ aiiii available, improves the gloss and the texture in hydraulic fluids.

As already indicated, the products manufactured according to the present invention, pigment compositions products give high color strength _s high gloss and good transparency when incorporated into letterpress inks media. However, the texture and rheological properties of the compositions are not entirely satisfactory.

1 0 9 "8 4 9/1 6 5 5

Solvent treatment of pigments is known. Such treatment generally leads to pigments that have a weak color strength, give matte prints and have a low gloss, but which flow well Printing fluids result if si% * in letterpress fluid media be incorporated. On the other hand, the texture of the pigment is again poor.

It is also known to treat azo pigments with fatty acids, in order to obtain products with good coloring strengths and pure brilliant tones, and that the products have the advantage. have that they can be more easily filtered from finely dispersed suspensions to be used in the dry state to become. However, nothing is said about the texture of the pigment.

Pigments that have a good texture and the letterpress fluids good color strength, good transparency and good rheological properties are actually very good difficult to manufacture. It has now surprisingly been found that if the preparation of the pigment compositions according to the invention with a conventional solvent treatment or combined with the addition of long-chain fatty alcohols, diols or polyols, a pigment is obtained which not only has desirable properties in letterpress fluids, but also particularly good flow properties and has transparency, facts that could not be predicted with knowledge of the effects of any process alone. According to another embodiment of the present invention, therefore, the pigment composition becomes a common one Solvent treatment or additionally with a fatty alcohol, a diol or polyol, which is at least 8 and preferably contains 8 to 22 carbon atoms and the Xther or ester bonds may have, offset.

It would be expected that two opposing mechanisms (the dye, which inhibits crystallite growth, and

1 0 9 8 U 9/1 6 5 5

the solvent that promotes this growth) to one Compromise product would result because of the flow properties normally related to transparency - the more opaque or opaque, the better the flow properties. However, it has been found that the best results in terms of transparency and flow properties can be achieved with both treatments.

The simple solvent treatment of pigments leads to compositions which have good flow properties (at low shear forces), and these compositions produce opaque, opaque prints in printing fluids. W For multi-color printing processes it is important that the printing fluids are deposited as a transparent film. It is therefore very important to obtain both a good transparency of the print and a well-flowing printing fluid.

A special example of a pigment, its properties Can be greatly improved in this way is a benzidine yellow pigment that can be obtained by coupling acetoacet-oanisidid and tetrazotized 3,3'-dichlorobenzidine. Compared with the pigment prepared in the usual way, the pigment, in which a water-soluble coupled diarylide * Dye is incorporated, improved rheological properties and almost equal tint strength in letterpress ink media, and a pigment that undergoes solvent treatment in the absence of the dye has been subjected to, has improved rheological properties and a lower color strength and gives more opaque prints in letterpress ink media. A pigment treated by both procedures has improved rheological properties, almost retains color strength, the gloss and transparency of untreated pigment and shows an improved texture.

It has been found that the surface properties are more desirable Way can be modified if certain

1 0 9 8 A 9/1 6 5 5

specific alcohols present during the manufacture of the pigment or when the pigment is treated with these alcohols after it has been prepared in a conventional manner.

When making an azo pigment by coupling a diazotized one Amino compound with a coupling agent becomes a minor proportion of a fatty alcohol or diol or polyol, the Contains 8 to 22 and preferably at least 12 carbon atoms, to the coupling agent prior to coupling, or to the amino compound before or after the diazotization and before the coupling, or to the reaction mixture during the coupling, or to the pigment slurry resulting from coupling ' given. The pigment is then worked up in the usual way. It was also found that it is possible to adjust the surface properties a preformed azo pigment by adding small amounts of these alcohols, diols or polyols modify, e.g., by preparing the pigment in an aqueous slurry, the alcohol, the diol or the polyol with stirring to the slurry, the whole is heated and the pigment is filtered off, washed and dried.

If the alcohol, diol or polyol is added to one or the other of the starting materials used in the manufacture of the pigment or is added to the reaction mixture during coupling, the schedules of the various coupling steps and the temperatures used do not have to be significantly changed. When the alcohol, diol or polyol is added to a pigment slurry, it has been found that the time necessary to achieve the desired effect, ie, before the pigment is filtered off, washed and dried, is not critical and is of course not a few minutes up to 2 to 3 hours. The preparation of azo pigments normally involves a step in which a pigment slurry is heated or boiled before the pigment is filtered off, and it is advantageous if the alcohol, diol or polyol is present at least during the heating step.

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However, this is not essential and good results can be obtained at temperatures from 0 to 100 ° C.

The fatty alcohols used in the process according to the invention can be primary, secondary or tertiary alcohols and can be saturated or unsaturated; the diols or polyols can contain primary, secondary or tertiary hydroxyl groups and can likewise be saturated or unsaturated. Examples of suitable materials are cetyl alcohol, oleyl alcohol, behenyl alcohol, isooctanol and 2-ethylhexane-1,3-diol. The amount of alcohol, polyol or diol can suitably be 0.1 to 30% by weight, based on the dry weight of the pigment to be produced or treated, with amounts of 0.1 to 10% by weight being preferred. When long chain alcohols, ie alcohols with Cig to Cpp 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. However, this is predictable based on knowledge of the solubilities of fatty alcohols in water.

If the alcohol, diol, or polyol is present during coupling or is added to the reaction mixture during coupling, it is advantageous to use a nonionic surfactant such as an ethoxylated cetyl alcohol condensate sold under the trade name Lubrol W is available, is also available. It has been found that oil pressure fluids formulated from pigment produced in this way have better flow properties and higher gloss than pressure fluids produced from untreated pigment. It has also been found advantageous to add a metal salt of a resin or the free resin itself to the pigment prepared or treated according to the invention, and it has been found that printing fluids made from this pigment have better color strength and flow properties than is the case with hydraulic fluids that of untreated Pig "

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ment. Similarly, it was found that the presence of resinous substances such as hydrogenated resins also affect the printing properties of printing fluids improved. Resins or resinous materials can be present initially or can be present after the coupling step of the process.

It has also been found that the presence of fatty acid such as oleic acid or stearic acid in the pigment composition the flow and pressure properties of hydraulic fluids are improved. The acids can preferably be in the form of their Sodium salts can be added during or after the coupling step or can be present from the start. You can insoluble in the final pigment composition by converting to slightly soluble salts such as calcium and zinc salts be made. The presence of fatty acid esters is equally valuable.

It is known to use diarylide pigments with up to 25% by weight, based on the pigment, with fatty amines of high molecular weight to treat, resulting in products that show excellent dispersibility in gravure inks. However, such products have the disadvantage that the initially developed high color strength during storage of the Hydraulic fluid is not retained.

It has now been found, surprisingly, that if the erfindungsgeroässer If pigment production is combined with an amine treatment, products can be produced that have a have excellent dispersibility as well as improved storage stability in hydraulic fluids, a fact which is surprising since it was not to be expected based on the effects of the two approaches alone. According to In a further embodiment of the present invention, therefore, a small proportion is included in the pigment composition an aliphatic amine, the amine salt or the amine oxide containing 1 to 20 carbon atoms, incorporated, and the

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Products then have excellent rheological properties in letterpress fluids.

The exact constitution of the pi gm en tz us amine composition obtained by incorporating a water-soluble coupled diarylide dye into a pigment and treating the composition with an amine depends on the dye and the manner in which the process steps are carried out , and on the amount of amine or amine oxide used. This proportion is generally between 0.1 and 35%, based on the weight of the pigment and the dye. When a large amount of amine, for example more than 10%, is used, the products, when used in gravure ink liquids, are stable to storage, while when used up to 10 % , the products are excellent in transparency, color strength, dispersibility and exhibit rheological properties in letterpress color media. The amine or amine oxide can be present during coupling or can be added to the tetrazotized pigment benzidine or to the pigment coupling agent prior to coupling, and can also be added to a preformed pigment in various ways.

If a large amount of amine is used, especially if the dye contains a reactive carbonyl group, it may an azomethine dye can be formed. For example, in the case of a pigment containing a sulfonated benzidine dye of the formula

SO H SO ₃ JI CH ₃

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contains, an azomethine dye can be formed, which (in the presence of sodium ions) the following formula can be assigned:

N-N-CH

SO well

SO ₃ Na

(the monoazomethine) or

- N = N - CH

C = NO

(the diazomethine).

In these formulas, R denotes an alkyl group having 1 to 20 carbon atoms, RNH _{2 being} the amine used in the process according to the invention. Depending on the p "value and the quantities and the order in which the ingredients are added

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Actors can be present in the pigment, or dye-free amine or amine salt, or a combination thereof it can also be an amine salt of the dye, the azomethine of the dye or the amine salt of the azomethine of the dye to be available.

When a tetrazotized pigment benzidine in the presence of dye is coupled with a pigment coupling agent, an amine salt is added after coupling, which p "on a Value of 10 is made alkaline and the slurry is boiled and sodium or another alkali metal is the only one If the metallic cation is present, it is found that the dye in the pigment product is in the form of its metal salt is present and no amine salt and no azomethine are present.

Alternatively, the slurry may first be cooked and then mixed with the amine salt and then the p "- be increased value or the amine salt can be added to the slurry before the slurry is boiled and the _pH value can be increased later In any case, it can be expected that the dye will be adsorbed onto the freshly precipitated particles during coupling and thereby stabilize the crystallite size of the pigment. There is no chemical reaction between the dye and the pigment. The amine salt is added and is also partially adsorbed on the pigment particles, and the excess amine

-, flocculated as free amine on the pigment surface. The pigment thus formed, which is dispersed in gravure ink media, is found to be upon storage is stable and has better color strengths than a pigment which has only been treated with an amine in the usual way is. The pigment nevertheless retains excellent dispersibility which is a property of amine-treated pigments.

If so, the procedure described first is slightly modified will j that the pigment is initially in the presence of the dye is coupled, then the slurry again e.g.

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to a p _H - is made alkaline value of 10, then the amine salt is added to the alkaline AufschlMmmung and the slurry is then boiled, showing the analytical examination of the pigment, that the metal content of the pigment is decreased to a value below the theoretical amount, that is required to form the metal color & cofxsalses and that the free amine and amine salt of the color are present. Pigment which has been formed in this way and is dispersed in gravure printing ink media is stable on storage and has a better coloring strength than a pigment which has merely been treated with an amine in the usual way. The printing fluids also have excellent rheological properties which, as can be shown, are a result of the presence of the amine salt of the dye.

Oise's last-described procedure can be modified slightly with the same results by adding the The slurry is made alkaline and then boiled before the amine salt is added, or the slurry can be boiled are then made alkaline and then mixed with the amine salt. In any case, the product is that same.

When the pigment is coupled in the presence of dye, keeping the slurry acidic then adding amine salt and the slurry is boiled, it is found that in the pigroent product amine salt itself is present. The same result is obtained if the slurry is kept acidic, boiled and then the amine salt is added.

Another method by which the process of the present invention can be carried out involves incorporating the dye into the pigment, forming the metal salt of the dye, and then adding the amine. The adsorbed soluble dye can be made insoluble by forming an insoluble salt with a metal of Groups IA, IB, HA, HB, IHA, IHB and VIII of the Periodic Table. A

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■ - 16 -

a very suitable way of forming the insoluble salt is a double decomposition reaction between the sodium salt of the dye and the water-soluble salt of the selected metal at an alkaline ρ ,, value, such as a p “value from 8 to 9. Typical soluble metal salts are zinc sulfate, magnesium sulfate, barium chloride, aluminum sulfate and Calcium chloride.

The studies carried out in these processes suggest that an adsorbed layer of dye occurs during pigment manufacture is being built. The addition of amine salts causes further adsorption on the pigment surface,

W because the amine group is attracted to the acid groups of the dye. The combined effect of this double adsorbed layer is to protect the pigment particles during cooking and drying. It is believed that the dye oil treatment in turn controls the size of the primary pigment particles, but does not provide any protection against cementation (aggregation) or agglomeration of the primary particles during the boiling and drying stages. The resulting pigment cannot be easily dispersed in pigment vehicles, ie it has a poor texture. However, in the amine treatment, the particles are better against the centering during the boiling and drying processes.

k protects, and products with better texture are formed. The theological properties of the products in letterpress inks are considerably enhanced by this combined dye / Amine treatment improves and are better than those Properties of pigments that have only been subjected to dye treatment and better than the properties of conventional pigments that have been treated with amines.

The amines to be used according to the invention can be primary, be secondary or tertiary amines. Examples of amines are primary amines, such as the product sold under the trade name Armies T in the trade is * essentially stearylamine, resin amine, such as amine derivatives of wood resin and related compounds

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fertilize, which is available under the trade name Rosin Amin D.
are, N-long chain alkylalkylenediamines, such as those that do
are available under the trade name Duomeen, polyamines,
such as N-coconut trimethylenediamine-N'-propylamine, polyamide / polyamine derivatives, such as those available under the trade name Merginamide, β-amines, such as those under the trade name Armeen L 11
and Duomeen L 15 available, ethoxylated fatty amines and fatty diamines, which are available under the trade names Ethomeen and Ethoduomeen
available, and derivatives of these compounds. Other specific amines are those given later in the Examples, e.g. in Table IX.

As already stated, the process of the invention leads to pigments which can contain one or more dyes, free amines, amine salts, amine salts of dyes and azomethine compounds of dyes, the formation of the latter two types of compounds being natural
depend on the presence of acid groups on the dye.
Amine salts of water-soluble coupled diarylide dyes are novel compounds per se. When dispersed in gravure ink liquid media, the salts provide desirable coloring properties with obvious advantages in terms of tinting strength and their partial solubility in the medium.

Good results are also achieved in accordance with the invention when the pigment composition is subjected to both a conventional solvent treatment and a. small proportion of an aliphatic amine, an amine salt or an amine oxide with 1
up to 20 carbon atoms is incorporated.

The present invention is intended to be further illustrated with five classes of diarylide pigments which are given below
will.

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1. Benzidine Yellow Pieces

Name or color index number

Pigment Yellow 12 (Color Index No 21090

Pigment Yellow 13 (Color Index No.21100)

Pigment Yellow 14 (Color Index No. 21095)

Pigment Yellow 17 (Color Index No. 21105)

Pigment yellow 81

Formed by domes of

3,3 · dichlorobenzidine and acetoacetanilide

3,3'-dichlorobenzidine and Acetoacet-2,4-xylidide

3,3'-dichlorobenzidine, and acetoacet-o-toluidide

3,3 · -dichlorobenzidine and acetoacet-o-anisidide

2,2 · _r 5,5'-tetrachlorobenzidine and acetoacet-2,4-xylidide

3,3'-dichlorobenzidine and acetoacet-p-toluidide

3,3 * -dichlorobenzidine and acetoacet-o-chloroanilidide

2. Benzidine Orange Piqmente

Name or color index number

Pigment Orange 15 (Color Index No.21130)

Pigment Orange 34 (Color Index No.21115) Formed by domes of

- 3,3 · -dichlorobenzidine and 1-phenyl-3-methyl-5-pyrazolone

3,3'-dichlorobenzidine and 1-p-Tolyl-3-methyl-5-pyrazolone

3. Benzidine Red Pieces

Warn or color "' - lobster

Pigment red 37
(Color Index No. 21205)

Pigment red 41
(Color Index No.21200) Formed by coupling

3,3'-dimethoxybenzidine and 1-p-Tolyl-3-methyl-5-pyrazolone

3,3 · -Dimethoxybenzidine and 1-phenyl-3-methyl-5-pyrazolone

4. Benzidine Blue Pieces

Urine or color indax no.

Formed by domes of

Pigment blue 20 COiai; isidin ~ blue) 3,3'-dimethoxybenzidine and anilide of 2-naphthol-3-carboxylic acid

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5. Tolidine Yellow Pieces

Pigment Yellow 3,3'-Dimethylbenzindin and

(Color Index No. 21135) Acetoacet-o-toluidide

Examples 1 to 6 7 explain in more detail the treatment of pigment with dye, Examples 68 to 78 illustrate this Treatment of the pigment with dye and solvent, and Examples 79 to 129 illustrate treatment of the pigment with dye and an amine or amine oxide.

If no further details are given, this is in the
Examples 1 through 67 essentially used the following procedures:

Eint tetrazo solution is prepared in the usual way and kept at 0 °, ui
solution solved.

0 ° held, and a coupling agent is in sodium hydroxide

The tetrazotized benzidine is prepared by one of two procedures, normally at room temperature, coupled with the coupling agent:

a) by reprecipitation of the coupling agent with dilute acid in a coupling vessel and running in the
Tetrazo solution over the course of an hour, normally room temperature being used. The p "value during coupling is normally 4 to 4.5;

b) the tetrazo solution and the solution of the coupling agent are allowed to run together into a coupling vessel which contains sodium acetate buffer. The p "value is again like
specified under a).

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

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

1. before the clutch stage

2. during the clutch stage

3. after the coupling stage

4. after the boiling point.

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

Example 1

Solution 1: Tetrazo-3,3'-dichlorobenzidine was obtained by tetrazotizing of 26 part egg

manufactured.

of 26 parts of 3,3 · dichlorobenzidine in 500 parts of water at ⁰ ° C.

Suspension 2: Tetrazo-4,4'-diamino-2,2'-diphenyldisulfonic acid ψ was prepared by tetrazotizing 2.0 parts of 4,4'-diamino-2,2'-diphenyldisulfonic acid ^{in 50 parts of water at 0 ° C.}

Solution 3: 40.5 parts of acetoacetanilide were added to 9.9 parts of sodium hydroxide dissolved in 900 parts of water.

A solution of 20 parts of sodium acetate in 200 parts of water was prepared in a coupling vessel. The _pH value was then adjusted with dilute acetic acid to a value of 4.5.

5 % of solution 3 was added to the coupling vessel, and then suspension 2 was added in the course of 10 minutes .

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dripping, making sure that at no time any substantial amount of uncoupled tetrazo compound is present. Solutions 1 and 3 were then used over the course of 1 hour at the same time added dropwise to the vessel at room temperature, again not allowing an excess of tetrazo compound was, and the p "value was, if necessary, by adding 10% sodium hydroxide solution kept at a value of 4.5. Then the reaction mixture was brought to the boil and boiled for 30 minutes, then the pigment composition was filtered off, washed with water and dried at 50 to 55 C.

The pigment composition thus prepared showed better tinting strength when incorporated into a letterpress ink and greater print transparency than could be achieved with a pigment obtained by coupling only of 3,3'-dichlorobenzidine and acetoacetanilide was.

Example 2

The same solutions and reaction conditions as given in Example 1 were used, but the procedure was followed changed in that the solution 1 and the suspension 2 were first mixed and then coupled with the solution 3. 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 the procedure was thereby changed that the solution 1 was first coupled with the solution 3 and the reaction mixture then with the suspension was moved. The pigment obtained was similar to that obtained in Example 1.

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Example 4

Solution 1: Tetrazo-3,3'-dichlorobenzidine was obtained by tetrazotizing of 26 parts

manufactured.

of 26 parts of 3,3 · dichlorobenzidine in 500 parts of water at ⁰ ° C.

Suspension 2: tetrazo 4,4'-diamino-2, 2 '-biphenyldisulfonsaure was tetrazotizing of 2.0 parts 4,4-diamino-2,2'-· diphenyldisulphonic in 50 parts of water at O ⁰ C prepared.

Solution 3: 40.5 parts of acetoacetanilide were added to 9.9 parts of sodium hydroxide dissolved in 900 parts of water.

^ A solution of 20 parts of sodium acetate in 200 parts of water was prepared in a coupling vessel. Then, the _pH value was adjusted with diluted acetic acid to a value of 4.5.

5 % of the solution 3 was added to the coupling vessel, and then the suspension 2 was added dropwise over the course of 10 minutes, making sure that at no time a substantial amount of uncoupled TeCrazo compound was present. Solutions 1 and 3 were then simultaneously added dropwise to the vessel over the course of 1 hour at room temperature, again not allowing an excess of the tetrazo compound at any time, and the p n value was increased, if necessary, by adding 10% strength ™ Sodium Hydroxide Solution Maintained at 4.5. 2.4 parts of an abietic acid based resin available under the trade name Mark WW Rosin dissolved in 6.0 parts of 109% sodium hydroxide solution were then added to the pigment slurry. The slurry was then boiled for 1 hour, the p _H value was adjusted using 10% sodium hydroxide solution to a value of 6 to 6.5 '■, and then 1.7 parts of zinc sulphate. The slurry was then filtered, and the pigment slurry thus obtained was washed with water and dried at 50 to 55 ° C.

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The pigment composition was similar to that obtained in Example 1 with the same advantages and better flow properties if the material is incorporated into a letterpress liquid became.

Example 5

The procedure of Example 4 was repeated except that the resin (WW Rosin) was sold under the trade name Hydrogenated abietic acid available from Staybelite Resin has been replaced. A pigment composition with similar was obtained excellent properties.

Example 6

The procedure of Example 4 was repeated twice, but in one case the resin (WW Rosin) was replaced by a resin, produced by reacting phthalic anhydride with dodecylamine, and in the other case it was replaced by a resin-modified cresylic acid (Beckacite 1624). In any case, received a pigment composition having excellent properties similar to that prepared according to Example 4 is obtained S a s ings.

A number of dyes of the following general formula I with the corresponding ones given in Table I below Substituents were identified in Pigment Yellow 12, Color Index No. 21090 for each of the four possible ones given before Example 1 above Manufacturing stages incorporated, taking them in the form of a aqueous solution or a slurry or prepared in situ.

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HCr-N = ^ i

OC
I.

Table I.

example
No. X I. Z η 7th Cl H '1-SO ₃ Na 1 δ H SO ₃ Na. . ^ -SO ₃ Na 1 9
10 CH ₃
CH ₃ SO ₃ Na
SO ₃ Na H
'1-SO ₃ Na 1
1 11 H CO ₂ Na H 1 12th Cl ■; H 4- CO ₂ Na 1 13th H SO ₃ (Ca) * H 1 14th H SO ₃ (Ba) I. H , 1 i 15 Cl H P-NH ₂ 1

In each case, there were advantages in terms of application technology, such as those already produced above for that prepared according to Example 1 Product have been described.

Example 16

Solution 1, tetrazo-3,3'-dichlorobenzidine, was prepared by tetrazotizing 26 parts of 3,3'-dichlorobenzidine in 500 parts of water at ⁰ ° C.

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Suspension 2, tetrazo-4,4'-diamino-2,2'-diphenyldisulfonic acid, was prepared by tetrazotizing 2.0 parts of 4.4 ^l -diamino-2,2 · -diphenyldisulfonic acid in 50 parts of water at 0 ° C.

Solution 3, 46.9 parts of acetoacet-m-xylidide, was in 9.9 parts Sodium hydroxide dissolved in 900 parts of water.

A solution of 20 parts of sodium acetate in 200 parts of water was prepared in a coupling vessel. Then, the _pH value was adjusted with diluted acetic acid to a value of 4.5.

5 % of Solution 3 was added to the coupling vessel and then Suspension 2 was added dropwise over 10 minutes, making sure that there was no substantial amount of uncoupled tetrazo compound present at any time. Solutions 1 and 3 were then simultaneously added dropwise to the vessel at room temperature over the course of 1 hour, again at no time an excess of tetrazo compound was present, and the p n value was, if necessary, by adding a 10% Sodium hydroxide solution kept at a value of 4.5. The reaction mixture was then heated to the boil and boiled for 30 minutes, after which the pigment composition was filtered off:
became.

filtered off, washed with water and dried at 50 to 55 ° C

The pigment composition thus prepared showed better tinting strength when incorporated into a letterpress ink and greater print transparency than was possible with a pigment obtained by simply coupling 3,3'-dichlorobenzidine and acetoacet-m-xylidide had been prepared.

Example 17

The same solutions and reaction conditions as in Example 16 were used, but this made the procedure somewhat modified so that the solution 1 and the suspension 2 were first mixed and then coupled with the solution 3. That

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pigment obtained was similar to that obtained in Example 16.

Example 18

The same solutions and reaction conditions were used as in Example 16, but the procedure was thereby changed somewhat that solution 1 was first coupled with solution 3 and then solution 2 became the reaction mixture given. The pigment obtained was similar to that obtained in Example 16.

Example 19

1. A tetrazo solution was made from 28.0 parts of 3,3'-dichlorobenzidine made in 500 parts of water.

2. 46.85 parts of acetoacet-m-xylidide were in 900 parts of water dissolved, which contained 9.15 parts of sodium hydroxide.

A solution of 20 parts of sodium acetate in 200 parts of water was prepared in a coupling vessel. The ρ ,, value was then adjusted to a value of 4.5 with dilute acetic acid. 5 parts of the sodium salt of the dye obtained by coupling tetrazo-4,4'-diamino-2,2'-diphenyldisulfonic acid and acetoacet-m-xylidide, dissolved in dilute sodium hydroxide solution, were added to the coupling vessel given.

Solutions 1 and 2 were performed at room temperature., Af 1 hour added dropwise to the vessel simultaneously, ex At no time was a surplus allowed to tetrazo compound, and the p "value was as necessary to the extent that by adding a 10 % sodium hydroxide solution adjusted to a value of 4.5. The reaction mixture was then heated to the boil and kept boiling for 30 minutes. Then the pigment composition was filtered off, washed with water and dried at 50 to 55 ° C.

The pigment composition produced in this way had the same advantages over untreated pigments as found in the pigment

1 0 9 8 A 9/1685

ment composition of Example 16 was shown.

Example 20

The procedure of Example 16 was repeated to the point that all solutions were coupled together. The p "value was then increased to a value of 8 to 8.5 with the aid of dilute sodium hydroxide solution, and it became 2 parts Barium chloride, dissolved in 50 parts of water, was added. The reaction mixture was then boiled and filtered. The separated The pigment was washed as indicated in Example 16, and dried.

The pigment obtained was similar to that obtained according to the procedure from Example 16.

Bui soi el 21

The procedure of Example 16 was repeated again to the point where all solutions were coupled together. The p "value was then measured with dilute hydrochloric acid lowered to a value of 1 to 2, and the reaction mixture was brought to the boil and filtered off. The separated pigment was, as indicated in Example 16, washed and dried.

The pigment obtained was similar to that according to the procedure of Example 16 received.

Examples 22, 23 and 24

The same solutions and reaction conditions of Examples 16, 17 and 18 were used with the exception that 5,5'-dimethyl-4,4 ^l -diamino-2,2'-diphenyldisulfonic acid (2 parts) the 4,4 ' -Diamino-2.2 ^l -diphenyldisulfonic acid replace. As in Example 16, the pigment compositions formed had advantages over untreated pigments.

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Examples 25, 26 and 27

The same solutions and reaction conditions were used as in Examples 16, 17 and 18, respectively, with the exception that 4,4'-diamino-3,3'-diphenyldicarboxylic acid (1.9 parts) replaced 4,4'-diamino-2,2'-diphenyldisulfonic acid. The educated As indicated in Example 16, pigment compositions showed advantages over untreated pigments.

Example 28

The same solutions and reaction conditions were used as in Example 19, with the exception that that by coupling of tetrazo-4,4'-diamino-2,2'-diphenyldisulfonic acid and acetacetm-xylidide . produced dye was replaced by a dye obtained by coupling tetrazo-4,4 · -diamino-2,2'-diphenyldisulfonic acid and acetoacetanilide had been produced. The pigment obtained was similar to that obtained in Example 16.

Example 29

The same solutions and reaction conditions as given in Example 19 were used, with the exception that the through Coupling of tetrazo-4,4'-diamino-2,2'-diphenyldisulfonic acid and Acetoacet-m-xylidide produced by the dye produced under the trade name Diphenyl Chrysoin 3 G, Color Index Direct Yellow available dye was replaced. The pigment obtained was similar to that obtained in Example 16 and had similar advantages.

Example 30

The same solutions and reaction conditions were used as given in Example 19, except that the dye obtained by coupling tetrazo-3,3'-dichlorobenzidine and acetoacetanilide-4-sulfonic acid (sodium salt) was replaced with the dye used in Example 19. The pigment obtained had excellent properties.

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Example 31

The same solutions and reaction conditions were used as in Example 19, with the exception that that by coupling of tetrazo-3,3-dichlorobenzidine and acetoacetanilide-4-carboxylic acid The dye produced was substituted for the dye used in Example 19. The pigment obtained was excellent Properties.

Example 32

The same solutions and reaction conditions were used as in Example 19, with the exception that that by coupling of tetrazo-3,3'-dichlorobenzidine and acetoacet-4-aminoanilide as the acetate salt prepared in Example 19 replaced the dye used. A product similar to that made in Example '16 was obtained.

Example 33

The procedure given in Example 16 was repeated, except that the calcium salt of the dye was used in place of the sodium salt. The pigment composition obtained showed excellent properties similar to that in FIG
Pigment composition obtained in Example 16.

Example 34

The same solutions and reaction conditions were used as in Example 19, except that the dye used in Example 19, which was prepared by coupling tetrazo-4,4 · -diaminodiphenyl-2,2'-disulfonic acid and acetoacet-m-xylidide was replaced by the dye that
by coupling tetrazotized 4,4 ^l -diamino-2,2'-diphenyldisulfonic acid with acetoacetanilide-4-sulfonic acid sodium salt
had been made.

Examples 35, 36 and 37

The same solutions and reaction conditions were used as in Examples 16, 17 and 18, respectively, with the exception that

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the acetoacet-m-xylidide by 43.7 parts of acetoacet-o-toluidide was replaced.

Compared to the preparation of the same pigment without the treatment, these products showed an improvement Color strength and print transparency.

Example 38

Solution 1, tetrazo 3,3'-dichlorobenzidine was prepared by tetrazotising 26 parts 3,3 ^f -dichlorobenzidine in 500 parts of water at ⁰ ° C.

Suspension 2, tetrazo-4.4 ^l -diamino-2.2 ^l -diphenyldisulphonic acid, was obtained by tetrazotizing 2.0 parts of 4,4'-diamino-2,2'-diphenyl disulphonic acid in 50 parts of water at ^{0 0} C manufactured.

Solution 3, 2.5 parts of acetoacetanilide, was dissolved in 0.6 part of sodium hydroxide in 50 parts of water. This solution was added to a solution of 20 parts of sodium acetate in 200 parts of water in the coupling vessel. The p _H was adjusted using dilute acetic acid to a value of 6.5.

Suspension 2 was added to the coupling vessel over the course of 10 minutes, making sure that at no time a substantial amount of uncoupled tetrazo compound was present.

Li .- ..: / 4, 41.5 parts of acetoacet-o-toluidide, was dissolved in 915 parts of sodium hydroxide in 900 parts of water. 5 % of this solution was added dropwise to the coupling vessel. Solutions 1 and 4 were then added to the coupling vessel over the course of 1 hour, again not allowing an excess of tetrazo compound at any time, and the p n value was increased to the extent necessary by adding 10% sodium hydroxide solution kept a value of 4.5.

The reaction mixture was then brought to the boil, Pig's 09 8 49 / 16-55

Filtered off ment composition, washed with water and dried at 50 to 55 ° C.

There were improvements in transparency, color strength and gloss in bookdrack colors compared to an untreated pigment can be found.

Example 39

The procedure given in Example 38 was followed except that that by coupling acetoacetanilide with Aniline-2,5-disulfonic acid was used. The pigment composition obtained showed similar advantages versus untreated pigment like the pigment composition from Example 38.

Bfci ,, ο isle 40 to 48

M ■ - f «JfJ» .- »ll III ■■■! ■» Il Μ ———

A number of dyes of the general formula I with the particular substituents indicated in the table below have been used in Pigment Yellow 14, Color Index No. 21095, incorporated in each of the four possible production stages given before Example 1 and in the form of an aqueous slurry / solution to the Reaction mixture added or prepared in situ.

Table II

example
No. X I. Z η 40 Cl II 4- SO ₃ Ka 1 41 H SO Ka h- SO ₃ Ka 1 42 CH ₃ SO ₃ Ka H 1 43 CH ₃ SO Ka 2- CIL 1

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In each case, as already stated above, application advantages could be achieved.

The general procedures described were carried out with benzidine yellow pigments and the dyes listed in Table III below. The dye had again the formula X defined above.

Table III

Ex
No. iel
pigment X Y Z η 44 Pigment yellow M H SO ₃ Na 2-0CII- 1 45. Pigment yellow 81 Cl Cl 4-SO-Na 1 46 Dichlcrobenzidin coupled.
with acetoacet-p-toluidide H SO ₃ Na P-CH ₃ 1 47)
■)
48)
) Pichlorobenzidime coupled,
with acetoacet-o-
chloranilide H
CH ₃ SO ₃ Na
SO ₃ Na o-Cl
o-Cl 1
1

In any case, it was possible to achieve application advantages, as already indicated above.

Example 49

A tetrazo solution was made from 50.6 parts of 100% 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-S-methyl-S-pyrazolone in 1500 parts of water was buffered with 50 parts of sodium acetate »

Then the tetrazo solution was dripped into the pyrazolone suspension over 1 hour. The _pH value of the solution was adjusted to

1098A9 / 1 655

held at a value of 4.0 to 4.5. After coupling, the slurry was divided into 5 parts.

Part A The slurry was filtered, the resulting pigment washed with water and dried at 50.degree.

Part B The slurry was boiled for 1 hour, filtered off, and the resulting pigment washed with water and dried at 50 ° C.

Part C To the slurry was added 5 % , based on pigment weight, of a dye obtained by coupling tetrazobenzidine-2,2'-disulfonic acid with p-sulfonated phenylmethylpyrazolone. 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. and ^{held at 90 °} C. for 10 minutes. Then 5 % of the same dye as added in Part C was added to the slurry and then the slurry was boiled for 30 minutes. The slurry was then filtered, the pigment composition was washed with water and dried at 50 to 55 ° C.

Part E The slurry was boiled for 30 minutes, 5 % of the same dye was added, the slurry was filtered and the pigment composition washed free of salts and dried at 50-55 ° C.

In letterpress inks, the pigment composition that resulted in A was in terms of hue, transparency and des Gloss was identical to the pigment composition obtained according to C; the composition obtained according to B was identical with that obtained according to E, wherein both compositions B and E have a poorer transparency and a poorer one Had gloss as A, and the compositions obtained according to C and D had properties intermediate between those according to A and B obtained compositions were. This explains the stability

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lization of the pigment by the dye at the stage at to which the dye is added.

Examples 50 to 54

A series of dyes of the following general formulas II and III which are those given in Table IV below Substituents had, in Pigment Orange 15, Color Index No. 21130, in each of those described immediately before Example 1 added four possible stages, and they were added in the form of an aqueous solution / slurry or in situ manufactured.

COONa

CH-K = ^ i

C ti

III

Table IV

\ = X

at
game
No- Color
material
formula ( X Ϊ Z η 50 II ( H • SO ₃ Na H 1 51 < Cl H 4-SO ₃ Na 1 52 III ( H SO ₃ CaI H 1 53
5'i H
H H
H II
3- NH ₂ 1
1

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As described above, application technology could be used in each Pall Advantages are found.

Example 55

Solution 1, tetrazo-3,3'-dichlorobenzidine, was prepared by tetrazotizing 77.1 parts of 3,3'-dichlorobenzidine in 1500 parts of water at ⁰ ° C.

Suspension 2, tetrazo 4,4'-diamino-2,2'-diphenyldisulphonic was prepared by tetrazotising 5.35 parts of 4,4'-diamino-2,2'-diphenyldisulphonic in 100 parts of water at 0 ⁰ C.

Solution 1 and suspension 2 were mixed to give the suspension 4. Solution 3, 126 parts of l-p-tolyl-S-methyl-S-pyrazolone, were dissolved in 37.8 parts of sodium hydroxide in 900 parts of water.

A solution of 7.2 parts of sodium acetate in 2000 parts of water was then made up in the coupling vessel. The p "value was brought to 5.0 with dilute hydrochloric acid, and the Solution 3 and suspension 4 were simultaneously dropped in at room temperature over 30 minutes, ensuring It was found that at no time was there any substantial amount of uncoupled tetrazo compound present.

The resulting slurry was then heated to 90 ° C and held at that temperature for 30 minutes. The pigment composition was then filtered off, washed with water and dried at 50 to 55 ° C.

The pigment composition thus prepared had improved tinting strength, improved gloss and better Transparency, when incorporated into letterpress ink, compared to a pigment obtained by simply coupling 3,3'-dichlorobenzidine prepared with l-p-tolyl-3-methyl-5-pyrazolone had been.

1 0 9-849 / 1 655

Example 56

Solution 1, tetrazo-3,3'-dichlorobenzidine, was prepared by tetrazotizing 50.6 parts of 3,3'-dichlorobenzidine in 1000 parts of water at ⁰ ° C.

Solution 2, 77.0 parts of 1-p-tolyl-S-methyl-S-pyrazolone, was added dissolved in 23.0 parts of sodium hydroxide in 500 parts of water.

A solution of 5.5 parts of sodium acetate in 1500 parts of water was then prepared in a coupling vessel I. The solutions 1 and 2 were added dropwise at the same time at room temperature over the course of 30 minutes, ensuring that that at no time a substantial amount of uncoupled Tetrazo compound was present. This resulted in slurry I «

Solution 3, tetrazo 3,3'-dichlorobenzidine was prepared by tetrazotising of 2.1 parts of 3,3 ^f -dichlorobenzidine in 50 parts of water at O ⁰ C.

Solution 4, 4.4 parts of 1-p-suifophenyl-3-methyl-5-pyrazolone, was made dissolved in 1.5 parts of sodium hydroxide in 500 parts of water.

A solution of 2.0 parts of sodium acetate in 200 parts of water was then prepared in a coupling vessel II. The solutions 3 and 4 were dropped simultaneously at room temperature over 10 minutes, making sure that none Time a substantial amount of uncoupled tetrazo compound was present. This made slurry II.

The slurry II was then added to the slurry I, and the mixture was heated to 90 ⁰ C, filtered, washed with water and dried at 50 ° C.

The advantages of this pigment composition over merely coupling 3,3'-dichlorobenzidine with 1-p-tolyl-3-methyl-5-pyrazolone The untreated pigment produced are similar to those of the pigments produced according to Example 55 together.

1 098A9 / 1655

settlement.

Example 57

Solution 1, tetrazo-3,3'-dichlorobenzidine, was tetrazotized of 77.1 parts of 3,3'-dichlorobenzidine in 1500 parts of water manufactured at 0 ° C.

Suspension 2, tetrazo 4,4'-diamino-2,2'-diphenyldisulfonsaure was prepared by tetrazotising 5.35 parts of 4,4'-diamino-2,2'-diphenyldisulfonsaure in water at 0 ⁰ C.

Solution 3: 126 parts of l-p ~ tolyl-3-methyl-5-pyrazolone were dissolved in 37.8 parts of sodium hydroxide dissolved in 900 parts of water.

A solution of 7.2 parts of sodium acetate in 2000 parts of water was then made up in a coupling vessel. The p "became adjusted to 5.0 with dilute hydrochloric acid, and solutions 1 and 3 were simultaneously im Added dropwise over the course of 30 minutes, ensuring that at no time a substantial excess of uncoupled Tetrazo compound was present.

The suspension 2 was then added in the course of 10 minutes to the reaction mixture obtained from the solutions 1 and 3, and the resulting reaction mixture was heated ^{to 90 ° C. for 30 minutes.} The pigment was then filtered off, washed with water and dried at 50 to 55 ° C.

The pigment produced in this way had superior tinting strength when incorporated into a letterpress ink, compared to the pigment made by simply coupling 3,3'-dichlorobenzidine with l-p-tolyl-3-methyl-5-pyrazolone had been.

Example 58

Suspension 1: tetrazo-4,4-diamino-2,2'-diphenyldisulfonic acid was obtained by tetrazotizing 2.6 parts of 4,4'-diamino-2,2'-di-

1098-9 / 1655

- 38 phenyl disulfonic acid at 0 ⁰ C produced.

Solution 2: 3.9 parts of 1-p-sulfophenyl-S-methyl-S-pyrazolone were added dissolved in 1.4 parts of sodium hydroxide in 50 parts of water.

Solution 3: 3.3 · -dichlorobenzidine tetrazo was prepared by tetrazotising 50.6 parts of 3,3'-dichlorobenzidine in 1000 parts of water at 0 ⁰ C.

Solution 4: 77.0 parts of 1-p-tolyl-S-methyl-S-pyrazolone were in 23.0 parts of sodium hydroxide dissolved in 500 parts of water.

A solution of 5.5 parts of sodium acetate in 1500 parts of water was then made up in a coupling vessel.

The suspension 1 and the solution 2 were then added dropwise at the same time at Kctum temperature in the course of 10 minutes, ensured It was found that at no time was there a substantial amount of uncoupled tetrazo compound present.

After that, solutions 3 and 4 were simultaneously at room temperature dripped in over 30 minutes, ensuring that at no time a substantial amount of uncoupled Tetrazo compound was present.

The resulting slurry was then heated to 90 ⁰ C, for 30 minutes at 90 ° C maintained, then filtered off, and the pigment composition was washed with water and finally dried at 50 ° C.

The benefits of this pigment composition were similar to those of the Example 55 composition.

Example 59

Solution 1: tetrazo 3,3'-dichlorobenzidine was prepared by tetrazotising of 77.1 parts 3,3 · -dichlorobenzidine in 1500 parts of water at 0 ⁰ C.

10 9 8 4 9/1655

Suspension 2: tetrazo-4,4'-diamino-2,2'-diphenyldisulfonic acid was obtained by tetrazotizing 5.35 parts of 4,4'-diamino-2,2 · - diphenyldisulfonic acid prepared in water at 0C.

Solution 3: 6.2 parts of acetoacetanilide were added to 2 parts of sodium hydroxide dissolved in 50 parts of water. This was added to a solution of 7.2 parts of sodium acetate in 2000 parts of water a coupling vessel. The suspension 2 was added dropwise to the coupling vessel over the course of 10 minutes, ensuring it was found that there was no excess of the tetrazo compound.

Solution 4: 120 parts of 1-p-tolyl-3-methyl-5-pyrazolone were dissolved in 36.0 parts of sodium hydroxide in 900 parts of water. 5 % of this solution was added to the coupling vessel.

Solutions 1 and 4 were then simultaneously added dropwise to the coupling vessel over a period of 30 minutes, making sure that no excess tetrazo compound was present at any time. The p n value during coupling was kept at a value of 4.5 by adding the required amount of 10% sodium hydroxide solution during the coupling process.

The slurry was heated to 90 ⁰ C, filtered off, and the pigment composition was washed with water and dried at 50 to 55 ° C.

The pigment composition so prepared had superior tinting strength when incorporated into letterpress ink, compared to the pigment made by simply coupling 3,3'-dichlorobenzidine and 1-p-tolyl-3-methyl-5-pyrazolone had been.

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Example 60

The conditions for this preparation were identical to those used in Example 58 except that 5% of the formaldehyde condensate was used with naphthalenedisulfonic acid, which is available under the trade name Belloid SFD, before the coupling stages was added to the coupling vessel.

It was found that the pigment composition incorporated in letterpress ink has a greater color strength than that of Example 58.

Examples 61 to 64

Further dyes were, as in the following table V an = given, incorporated into Pigment Orange 34 at each of the possible manufacturing stages indicated above, whereby they are in the form an i ^ aqe solution / slurry were added or in situ. The dyes were as indicated above Formula II.

Table ¥

at
game X · I. 2 a 61 H SOjNa H 1 62
63 ■ a
H 3 "I.
SO ₃ Ka ■ H
^h - ~ SO Ka 1
■ 2 . Gk Cl H ** - SO well.
i

O H ΰ I I Das «

In each case, advantages in terms of application technology, as already stated, could be achieved.

Examples 65 and 66

Two benzidine red pigments were mixed with dyes of the above Formula II, the meanings of which are given in the following Table VI, treated.

Tabel pigment X VI Y Z η Pigment red 37
Pigment red 41 H
H SO ₃ Ka
SO ^ Well k-S0 "Well
4-3CLNa 1
1 at
game 65
66

The pigment compositions prepared according to these two examples showed excellent transparency in letterpress ink.

Example 67

The yellow pigment, Color Index No. 21135, was mixed with the dye of in each of the above four preparation steps following formula

SO ₃ Ka SO Na

CO

treated.

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Example 68

Solution 1: Tetrazo-3,3'-dimethoxybenzidine was obtained by diazotizing 30.5 parts of 100% 3,3'-dimethoxybenzidine with hydrochloric acid and 18.2 parts of sodium nitrite to give a final volume of 550 parts at one temperature manufactured from 0 ⁰ C.

Solution 2: A solution of 36 parts of sodium hydroxide and 8 parts of Turkish red oil in 800 parts of water was heated to 70.degree. Then 69.7 parts of naphthol AS (2-hydroxynaphthalene-3-carboxyanilide) were slowly added with stirring added at a temperature of 25 ° C, so that a final volume of 1200 parts was obtained.

Solution 3: 5 parts of the dye of the formula

PhNlICO OH

- N = N-

S0, Na SO-Ka

COX ¹ IlFh

that by coupling tetrazobenzidine-2,2'-disulfonic acid with Naphthol AS had been made in a 10% strength Dissolved sodium hydroxide solution.

Solution 1 was added dropwise to solution 2, the p n value being kept above 10.5 by suitable addition of 10% sodium hydroxide solution. After completion of coupling, the _pH value was lowered to 5.0 to the suspension, and the solution 3 was added. The slurry was then boiled for 1 hour and then the product was filtered off, washed and dried at 50-55 ° C.

The pigment composition was in a letterpress ink Compared to the product of a similar process in which

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the dye was not added, superior gloss and color strength.

Examples 69 to 70 illustrate the inventive treatment of pigment / dye compositions with solvents, Fatty acids or fatty acid esters, fatty alcohols, diols or polyols. These can be used at any of the four production stages the pigment composition to which the dye can be added.

Example 69

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

Cetyl alcohol, oleyl alcohol, isooctanol, 2-ethylhexane-1,2-diol, polyethylene glycol 600, xylene, dibenzyl ether, dipropylene glycol _{monolarate 5} <~ -dichlorobenzene, nitrobenzene, benzylcyanici, ^{/ = v} ^. >, 11 ;;.

The resulting compositions were compared with untreated Pigment Yellow 12, treated with solvent, Pigment Yellow 12 and with exactly the same as in Examples 1, 2 and 3 Prepared compositions examined. In each case, improved flow properties and a better texture were found compared to the pigment treated only with the dye and superior in color strength and transparency to the untreated pigment or versus the pigment that was only treated with solvent.

Example 70

1. A tetrazo solution was made from 26.0 parts of 3,3'-dichlorobenzidine made in 500 parts of water.

2. A tetrazo suspension was prepared from 2.0 parts of 4,4'-diamino-2,2 ·· diphenyldisulfonic acid in 120 parts of water.

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46.85 parts of acetoacet-m-xylidide were in 900 parts of water, which contained 9.15 parts of sodium hydroxide, dissolved. Acetoacet-m-xylidide was then added by adding a solution of 13.75 parts of glacial acetic acid in 50 parts of water to form a slurry failed.

Then the tetrazo solution 1 was added to the slurry of the precipitated acetoacet-m-xylidide in the course of 1 1/2 hours. The _pH value of the reaction mixture was kept during the addition by simultaneously adding a 10% aqueous sodium hydroxide solution between 4.0 and 4.5.

The p "fourth of the yellow pigment slurry obtained was then adjusted to a value of 6.0 with 10% sodium hydroxide solution. Then the tetrazo suspension 2 was added to the slurry over 15 minutes. Der p "value of the slurry was maintained by simultaneous addition of an aqueous 10% NatriurahydroxydlÖsung between 5.5 and 6.0 during ^rf he addition.

Then 4 parts of dibenzyl ether were added to the pigment slurry given. The slurry was boiled for 1 hour, and the p "value was reduced to one with 10% sodium hydroxide solution Value set from 8.0 to 9.0. The pigment was then dissolved by filtration, by washing the filter cake free of water borrowed impurities and isolated by drying at 50 C.

The pigment composition obtained according to this process gave if it has been incorporated into a letterpress ink medium, glossier and more transparent prints with better color strength than could be achieved with a pigment composition, which had been treated with solvent only (and which had not been treated with the dye). The rheological Properties of the hydraulic fluid were similar to those a print made from the solvent-treated pigment

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Example 71

The procedure described in Example 10 was repeated with the difference that 4 parts of o-dichlorobenzene were used instead of 4 parts of dibenzyl ether. The resulting pigment composition had similar properties to the pigment obtained in Example 69.

Example 72

a) The procedure given in Example 16 was used, with the difference that 5 % cetyl alcohol, based on the pigment, was added before the pigment suspension was boiled and filtered.

b) The procedure described in Example 16 was used, with the difference that 5 % oleic acid, based on the pigment weight, was added before the pigment suspension was boiled and filtered.

In each case, the product had superior flow properties and texture compared to the product of Example 16, while the desirable transparency has been largely retained. Similar results were obtained in both cases if the addition was made before or during coupling.

Example 73

The procedure described in Example 35 was followed ', with the difference that 5%, based on the weight of the pigment,

a) cetyl alcohol

b) tetralin

c) polyethylene glycol 600

were added before the pigment suspension was boiled and filtered became. In each case the product had superior flow properties, compared with the pigment obtained in Example 35, while the advantages of color strength and transparency the pigment composition were generally retained.

109849/1655

Similar results were obtained when the addition was made before or during coupling.

Example 74

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

2. A tetrazo suspension was prepared from 1.5 parts of 4,4'-diamino-2,2 ^l -diphenyldisulfonic acid in 100 parts of water «

49 parts of acetoacet-o-anisidide were dissolved in 9.2 parts of sodium hydroxide, dissolved in 900 parts of water. The coupling agent was then dissolved by adding 14 parts of glacial acetic acid in 50 parts of water, precipitated to form a slurry.

Then, over 1 hour, the tetrazo solution 1 became the slurry given. The p n value of the reaction mixture was determined during the addition by simultaneous addition of a 10% aqueous sodium hydroxide solution to a value between 4.0 and 4.5 held.

The p n value of the yellow pigment slurry obtained was then adjusted to a value of 6.0 to 7.0 with 10% strength sodium hydroxide solution. Then the tetrazo suspension 2 was added to the slurry over 15 minutes. The _pH value of the slurry was maintained at a value between 6.0 and 7.0 during the addition by the simultaneous addition of a 10% aqueous sodium hydroxide solution.

A suspension of 4 parts of cetyl alcohol in 25 parts of water was added and the slurry was boiled for 1 hour. Then the slurry was filtered, washed salt free and dried at 50 to 55 ° C.

The pigment composition obtained showed, when in a Letterpress ink medium was incorporated, improved rheological

109849/1665

gical properties compared to a pigment composition, which was obtained by simply coupling acetoacet-o-anisidide with tetrazo-3,3'-dichlorobenzidine. Opposite to no noticeable loss in color strength could be observed with the untreated pigment.

Example 75

The procedure described in Example 74 was used, with the difference that, based on the weight of the pigment,

a) tetralin

b) oleic acid

were added before the pigment suspension was boiled and filtered became. The resulting pigments showed excellent flow properties and transparencies.

Similar results are obtained when the additions are made at an earlier stage of manufacture.

Example 76

The procedure described in Example 47 was carried out, with the difference that 5%, based on the pigment weight,

a) cetyl alcohol

b) tetralin

c) polyethylene glycol 600

were incorporated before the pigment suspension was boiled and filtered. The products obtained according to these treatments showed better flow properties and better transparencies.

Example 77

The procedure described in Example 49, Part C was used, with the difference that 5%, based on the pigment weight, tetralin was added before the pigment suspension was cooked. The resulting pigment composition possessed

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drawn flow properties and transparency.

Example 78

Solution 1 - tetrazo 3,3'-dichlorobenzidine was prepared by tetrazotising 3,3'-dichlorobenzidine of 77.10 parts in 1500 parts of water 'ser at 0 ⁰ C.

Suspension 2 - tetrazo-4,4'diamino-2,2'-diphenyldisulfonic acid was obtained by tetrazotizing 5.35 parts of 4 _? 4'-diamino-2,2'-diphenyldisulfonic acid in water at 0 ⁰ C produced.

Solution 3 - 126 parts of l-p-tolyl-S-methyl-S-pyrasolone were in 37.8 parts of sodium hydroxide dissolved in 900 parts of water »

A solution of 7.2 parts of sodium acetate in 2000 parts of water was then prepared in a coupling vessel. The p "value was adjusted to a value of 5.0 with dilute hydrochloric acid, and solutions 1 and 3 were mixed simultaneously at room temperature over the course of added dropwise 30 minutes _s wherein it was ensured that at any time a substantial amount of uncoupled tetrazo compound "was present then i-jyr ~ de the suspension 2 added over 10 minutes to the obtained from the solutions 1 and 3 of the reaction mixture ,,

Then 5 parts of cetyl alcohol, suspended in 50 parts of mass, were added to the reaction mixture. The resulting reaction mixture was heated to 90 ° C. and kept at this temperature for 30 minutes. The pigment was then filtered off, _{washed 5} ″ with water and dried at 50 to 55 ° C. When the pigment produced in this way was incorporated into a letterpress ink, it showed up to 15 % greater color strength than the pigment which was only obtained by coupling 3, 3'-dichlorobensidine had been produced with l ~ p-TQlyl-3-methyl-5-pyrazGlOn - the rheological properties of letterpress inks are "- was better than those of a similar _{printing fluid 9} which were produced with an untreated pigment .

10 9-8 49/1665

Example 79

The procedure described in Example 78 was repeated, with the difference that, based on the pigment weight, 5% Tetralin replaced the cetyl alcohol used there.

The properties of the pigment obtained after this treatment were similar to those of the pigment obtained in Example 78.

Examples 80 to 130 illustrate the inventive treatment of pigment compositions with amines or amine oxides. The amine or the amine oxide can be added in any of the four production stages of the pigment composition in which the dye can be added. The examples are divided into two groups, Nos. 80 to 100 and Nos. 101 to 130. The first group shows the addition of more than 10 % of an amine or amine oxide for gravure inks, while the second group explains the addition of 5% of an amine or amine oxide for letterpress inks.

Example 80

Solution 1: 67 parts of acetoacetanilide were dissolved in a solution of 28.2 parts of sodium hydroxide in 900 parts of water.

Solution 2; 43.5 parts of 3,3'-dichlorobenzidine were mixed with 24.1 parts of sodium
animals.

Sodium nitrite in 800 parts of water at 0 C tetrazo-

Suspension 3: 4.1 parts of 5,5'-dimethyl-4,4'-diamino-2,2'-diphenyldisulfonic acid were tetrazotized ^{with 1.7 parts of sodium nitrite in 125 parts of water at 0 ° C.}

10 % of Solution 1 was placed in a coupling vessel and Suspension 3 was then added over 10 minutes, ensuring that no substantial amount of uncoupled tetrazo compound was present at any time.

The remainder of Solution 1 and Solution 2 were then added to the reaction mixture simultaneously over the course of 1 hour. the

10984 9 / 16SS

-. 50 -

The reaction temperature was at or around room temperature and the p "~ Value held between 4.5 and 4.8, again not a substantial amount of uncoupled tetrazo compound to any Time was available.

28.2 parts of the amine mixture available under the trade name Armeen T (which is believed to consist essentially of palmityl, stearyl and oleyl amines) were dissolved in 17.0 parts of glacial acetic acid in 1000 parts of water and then added to the coupling vessel . The reaction mixture was then brought to the boil and boiled for 30 minutes. Then the p n value of the reaction mixture present in the form of a slurry was ^{adjusted to a value of 10.0 after boiling at a temperature of 70 °} C. with a sodium hydroxide solution. The pigment composition was then filtered off, washed with water and dried at 50 to 55 ° C.

The pigment composition obtained in this way was easily dispersible in rotogravure ink media, produced a storage-stable printing fluid, and was stronger and more transparent in terms of color and color. Eventually a more glossy product than the eenzidine yellow pigment composition, which was made for coupling 3,3'-dichlorobenzidine with acetoacetanilide in the presence of Armeen T only. A pigment composition made without the use of Armeen T or a similar amine or combination of amines is not readily dispersible in rotogravure ink media.

Example 81

As in Example 79, solutions 1 and 2 and a suspension 3, and a solution of Armeen T as set forth in Example 80 was also made. The whole The amount of solution 1 was added to the coupling vessel and the Pjj value was reduced to below with dilute acid 7.0, and then Solution 2 and Suspension 3 were mixed and added to the jar, followed by the Addition of the Armeen T. The reaction mixture was then prepared as in

109849/1555

• Example 80 given, worked up, and the pigment obtained was similar to that obtained in Example 80 in showing the same desirable properties when in printing fluid media was dispersed, which was shown in a storage-stable printing fluid.

Example 82

The same solutions and reaction conditions as in Example 80 were used, but this made the procedure somewhat modified that the solution 2 was first coupled with the solution 1 and then the suspension 3 to the reaction mixture was given. The pigment compositions obtained were similar to that obtained in Example 80 and gave storage-stable properties Gravure inks.

Examples 83 to 85

The procedures outlined in Examples 80 through 82 were repeated, with armies T represented by an equal weight of Duomeen T was replaced. The pigment compositions obtained had excellent properties similar to those of the compositions of Examples 80 to 52, and those made from them Gravure inks were stable on storage.

Examples 86 to 88

The procedures described in Examples 80 to 82 were repeated, but instead of 4,4'-diamino-5,5'-dimethyl-2,2'-diphenyldisulfonic acid an equivalent amount of 4,4'-diamino-2,2'-diphenyldisulfonic acid was used. the The pigment compositions obtained were stronger and more transparent than the pigment obtained by simply coupling 3,3'-dichlorobenzidine with acetoacetanilide, with advantages similar to those obtained in Examples 80-82 Products obtained from these pigment compositions The rotogravure inks produced were stable on storage.

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Examples 89 to 91

The procedures described in Examples 86-88 were repeated with the amine armies T by an equal weight Duomeen T was replaced. The pigment compositions obtained showed excellent properties similar to those in FIG Examples 86 to 88 obtained pigment compositions, and in addition, those prepared from these pigment compositions Rotogravure printing inks have a long shelf life.

Examples 92 to 94

• Pigment Yellow 12, Color Index No. 21090, was used with the dye of the formula I defined above and the particular substituents indicated in Table VII below "in an amount of 5%, based on the pigment weight, and treated with 5% amine, based on the pigment weight:

Table VII

at
game X ϊ Z η Used
Amines 92 H SO ₃ Na H 1 (Armies L15
(lAiOiiioen. LI5 93 Cl H 1 (Armies T
(Buo ::: c? On ϊ 9h II SO ₃ Ka '' -SO ₃ Na 1

In each case, excellent pigment compositions were obtained which were stable in gravure inks on storage.

Examples 95 to 97

The procedures described in Examples 80 to 82 were repeated, except that 72.5 parts of acetoacet-o-toluidide were used instead of the 67 parts of acetoacet _a nilide. The pigment compositions obtained were superior to those

109849/18 5 5

which can only be achieved by coupling 3,3'-dichlorobenzidine with acetoacet-o-toluidide were obtained, and the gravure inks made from these pigment compositions were stable on storage and had similarly good properties as the pigment compositions, obtained in Examples 80-82.

Examples 98 and 99

Pigment Yellow 14, Color Index 21095, was, as indicated in the following Table VIII, with the dye and. the amine treated. The dye had the formula I given above.

X Table VIII i Z η Used.
Amines II
H SO ₃ Na
SO ₃ Na U
h -SO ₃ Na 1
1 (Armies Ϊ
(Aaoineen T at
game 99

In each case, excellent pigment compositions were obtained which gave storage-stable gravure inks.

Example 100

The pigment composition described in Example 47 was made with Armeen T or Duomeen at each of the four stages of manufacture T treated in an amount of 15% based on the pigment weight. Excellent pigment compositions were obtained which were stable on storage in gravure printing inks.

Examples 101-105

Pigment Yellow 12, Color Index 21090, has been made with a variety of dyes and a number of amines or amine oxides treated, the proportion of amine or amine oxide in each case 5%, based on the pigment weight, so that one Pigment composition obtained for letterpress ink applications

10 9 8 Λ 9/1 6BS

«.122521

is very suitable. The dye was as defined above Formula I and the particular substituents are given in Table IX below.

Table IX.

at
game • X ϊ Z η Amines used (Armies ϊ 101 H SO ₃ Na H 1 ((primary amine) (jDuoiüC-en ϊ (U-langkefc (term alkylalkylene (diaiain 102 Cl H 4-SO-Ka 1 (Arir.een 2HT (secondary (res amine) (Armies J) MCD ((tertiary amine 103 CLL SO well .4-SO-Na 1 (Mereinarriicl · ;; L275 ((Polyoaia ./Po Iy am in) (iiosin amines]) ((Harz arnin) 104 H SO ₃ Na 4-SO-Ka 1 (Aiorneen L15 (ß-amine) (Army T / Aromox C / 12Λ ' ((priirä-resAain / Amin- (K-oxide) 105 H SO-Caj II 1 (? thor? ecn T 12 (ethox- (ylated amine) \ Casaniine C (1-Ατ \ χη (ät) iyl-2-alUyIi r.dda z ~ (oil in) (cyclic) V N- (3-aninopropyl - (cycl ohexylainin) ν (cyclic)

In each case the compositions produced showed improved results Flow properties, better dispersibility and texture, if incorporated into letterpress color media. 'The rheological properties of the hydraulic fluids can controlled to some extent by the type of amine used; Treatment with Rosin Amine D, Duomeen T and Armeen T result in well-flowing products and a certain increase in coverage. However, Merginamide L 275 retains the transparency more easily Dye treatments and results in only a slight improvement in the flow properties. The best results

1098A9 / 16BS

nits are achieved with regard to the application properties, when the dyes are added before the coupling step and the amine treatment after the coupling or Koch steps he follows.

Example 106

1. A tetrazo solution was made from 26.00 parts of 3,3'-dichlorobenzidine made in 500 parts of water.

2. A tetrazo suspension was made from 2.00 parts of 4,4'-diamino-2,2'-diphenyldisulfonic acid made in 120 parts of water.

46.85 parts of acetoacet-m-xylidide were dissolved in 900 parts of water / water, which contained 9.15 parts of sodium hydroxide. Then the acetoacet-m-xylidide by adding a solution of 13.75 Part glacial acetic acid in 50 parts water to form a slurry failed.

Then, the tetrazo solution 1 was added to the precipitated acetoacet-m-xylidide slurry over 1 1/2 hours. The p, value of the reaction mixture was determined during the addition by the simultaneous addition of a 10% strength aqueous sodium hydroxide solution held at a value between 4.0 and 4.5.

The p n value of the yellow pigment slurry obtained became then with 10% sodium hydroxide solution to a value of 6.0 set. Then, in the course of 15 minutes, the tetrazo suspension 2 was added to the slurry, the p “value of the slurry during the addition by a simultaneous Addition of a 10% aqueous sodium hydroxide solution was kept at a value between 5.5 and 6.0.

A solution of 3.5 parts Armeen T in 250 parts water containing 2.1 grams of glacial acetic acid then became the pigment slurry given. The slurry was boiled for 1 hour and the p "value was reduced to one with 10% sodium hydroxide solution Value set from 8.0 to 9.0. Then the pigment was put together

109849/1655

Settlement by filtering, by washing the filter cloth free isolated from water soluble impurities and by drying at 50 ° C.

The pigment obtained in this way was mixed with the pigment obtained only by coupling the pigment gasoline with the coupling agent without sulfonated benzidine and without subsequent amine treatment, and with the pigment that by Coupling in the presence of the sulfonated benzidine, but without subsequent amine treatment, was compared. The pigment according to the invention resulted in a standard letterpress ink medium in an amount of 28.6% (weight / weight) a hydraulic fluid with the best rheological properties, Color strengths, transparency and gloss.

Examples 107-109

The procedure described in Example 105 was repeated, with the difference that Armeen T was replaced by 3.5 parts Duorneen T or by 3.5 parts of Merginamide L 275 or by 3.5 parts of Rosin Amine D. Similar results were obtained.

Examples 110 to 112

Pigment Yellow 13, Color Index No. 21100, has been treated with a variety of dyes and a number of amines or amino oxides, the proportion of amine or amine oxide in each case 5%, based on the pigment weight, and with a pigment ment composition suitable for use in letterpress inks is very suitable. The dye had the formula I already defined above, with the particular substituents are given in Table X below.

109849 / - 1,655

_ 57 -

Table X

At- ; χ ϊ Z η Amines used . .game...", . (Armies ϊ ((priiiiires amine) (Duomeen T (X-langket- (term alkylalkylol - no ■ H SO ₃ Xa 2, h (CIL) ₂ '2 (diwnine) (Armson 2KT (secondary (Armies DMCD ((tertiary amine) ν Me ig ina; R iii c » h J ( ? SO well (iiosin amines Ώ 111 CH ₃ 2 ) 'Harzamiri) (Duoween L15 (β-Ατ.ΐη) (Armies ϊ / Arorr.ox C / i2'.i ((prirra'res Amir / ajr.in « (K-oxide) (Kihonmen Tl 2 (ethox- (ylated amine) SO well (Casa; nine C (1-anino- 112 II H · 1 (ethyl-2-alkyliniclaz- (olin) (cyclic) (1 \ ^T - (3-Aiainopr opyl— (cyclohexylamine) ((cyclic) (Methylamine (Cyclohexylamine '

In each case the compositions produced showed improved results Flow properties, improved dispersibility and Texture when incorporated into letterpress color media.

Examples 113-118

Pigment Yellow 14, Color Index No. 21095, has been treated with a variety of dyes and a number of amines, the amount of amine in each case being 5% based on the pigment weight, and pigment compositions were obtained which were very suitable for letterpress applications. The dye had the formula I already given above, where the special substituents in Table XI below

. 1 0 9 8 A 9 / 16SS

22521

given are.

Table XI

at
game X Y Z η Amines used 113. Cl H 4-SO Ne 1 (Armies T
I ■ 114 H SO ₃ Na H 1 (Duomccn T 115 / ■ «tr
CL ₃ SO ₃ Na H 1 V.
(Rosin Amino D 116 H SU Well 2-CH ₃ 1 117 CH ₃ SO ₃ Na 2-CH ₃ 1 118 H SO ₃ Ka 4-SO Well 1

The compositions obtained showed an improvement in transparency, gloss and color strength when incorporated into letterpress color media.

Examples 119 to 121

The procedure used in Examples 45, 47 and 48 was repeated with the difference that, based on the pigment weight, 5 %

a) armies T

b) Duomeen T

c) raisin amines D

were added before the pigment suspension was boiled and filtered became. Pigment compositions were obtained which exhibited excellent properties when used in letterpress printing. color media have been incorporated.

Examples 122 to 124

Pigment Orange 15, Color Index No. 21130, has been used with a variety of dyes and a number of amines, the proportion of dye and atnin in each case being 5%

109849 / 1BBS

on pigment weight, made up and where pigment compositions that were manufactured for letterpress ink applications were very suitable. The dye had the formula II already given above, the particular substituents in the Table XII below.

X Tabel XII Z Amines used H
H
Cl II
¹ I-SO Ka
'1-SO ₃ Ka (Armies T
(
(Riomeen T
(
(Rosin Amine D example X 122
123
124 Su ₃ Ka
SO ₃ Na
H

Products with exceptional color strength, transparency and gloss were obtained.

Example 125

Solution 1: Tetrazo-3,3'-dichlorobenzidine was prepared by tetrazotizing 77.10 parts of 3,3'-dichlorobenzidine in 1500 parts of water at 0.degree.

Suspension 2; Tetrazo-4,4'-diamino-2,2'-diphenyldisulfonic acid was prepared by tetrazotizing 5.35 parts of 4,4'-diamino-2,2'-diphenyldisulfonic acid in water at 0.degree.

Solution 3: 126 parts of 1-p-tolyl-3-methyl-5-pyrazolone were dissolved in 37.8 parts of sodium hydroxide, dissolved in 900 parts of water.

A solution of 7.2 parts of sodium acetate in 2000 parts of water was prepared in a coupling vessel. The _pH value was washed with dilute hydrochloric acid to a value of 5.0

109849/1655

set, and solutions 1 and 3 were added simultaneously at room temperature over 30 minutes, ensuring It was found that at no time was there a substantial amount of uncoupled tetrazo compound present. The suspension was then added to the reaction mixture resulting from Solutions 1 and 3 over 10 minutes.

Then 5 parts of Armeen T dissolved in dilute acetic acid were added to the reaction mixture. The resulting reaction mixture was heated to 90 ⁰ C and held for 30 minutes at 90 ° C. The pigment was then filtered off, washed with water and dried at 50 to 55.degree.

If you put the pigment so produced in a letterpress ink medium incorporated, the result was a better color strength than was possible with an untreated pigment, and at the same time good rheological properties and adequate Texture have been achieved.

Examples 126 and 127

Pigment Orange 34, Color Index No. 21115, has been assigned a variety treated by dyes and a number of amines, the proportion of amine in each case 5%, based on the pigment weight, and a pigment composition was obtained which is very suitable for use in letterpress applications suitable is. The dye had the formula II given above, the particular substituents in the following Table XIII are specified.

Table XIII

example X I. Z Amines used 126
127 H
Cl SO ₃ Na
H II -
'1-SO ₃ Na (Armies T
(Dvjomeen T
(Rosin Amine D

109849/1655

Products with exceptional color strength and transparency were obtained and shine.

Examples 128 to 130

The procedures described in Examples 65, 66 and 68 were repeated with the exception that, based on the pigment weight, 5 %

a) Duomeen T

b) raisin amines D

• were incorporated before the pigment suspension was boiled and was filtered. The products showed advantages in terms of flow properties, texture and dispersibility in letterpress color media.

The following example is intended to illustrate the preparation of an amine salt of a dye.

Example 131

10 parts of the dye obtained by coupling tetrazobenzidine-2,2'-disulfonic acid with acetoacetanilide were dissolved in 200 parts of hot water. The p "value of this Solution was made using a 10% sodium hydroxide solution increased to a value of 9 to 10. Then a solution of 5.5 parts of stearylamine in the form of the acetate salt was added, and the precipitated amine salt was filtered and dried. In a typical aromatic gravure ink system gave the product an interesting yellow hue.

The following example is intended to show the incorporation of resin into a explain pigment composition according to the invention.

Example 132

The procedure described in Example 16 was repeated, with the difference that, based on the pigment weight, 25% by weight of the magnesium salt of wood resin to the coupling vessel

109849 / 16GS

_Ä 1 2 2 5 2 1

were given before the coupling took place.

The pigment composition was compared to the equivalent resin treated pigment that was not compared to the dye had been treated. In letterpress inks, the dye-treated pigment obtained showed a more transparent, stronger pressure in terms of color than was the case with the other pigment.

The following example is intended to illustrate solvent treatment and the incorporation of an amine into a pigment.

Example 133

The procedure described in Example 70 was followed by the preparation the pigment / dye slurry is repeated. Then 5 parts (based on the weight of the Pigments related) given cetyl alcohol instead of the dibenzyl ether. The slurry was boiled for 1 hour with cold water cooled to 70 ° C. and then 6 parts by weight of Rosin Amine D and 6 parts by weight of acetic acid in water were added. Of the The p "value of the slurry was determined with 10% sodium hydroxide solution increased to a p "value of 9-10. The slurry was then filtered, washed and dried at 50.degree.

This product had greater color strength, gloss and transparency in a letterpress ink medium, than was the case with the untreated pigment.

The following two examples are intended to treat the dye with explain mixed coupling.

Example 134

Tetrazo-3,3'-dichlorobenzidine was converted from 54.8 in the usual manner Parts made 100% 3,3'-dichlorobenzidine.

47.0 parts of acetoacet-m-xylidide and 40.6 parts of acetoacetanilide were dissolved in 27 parts of sodium hydroxide in 1300 parts of water.

109849/1655

50 parts of sodium acetate were dissolved in 500 parts of water in a coupling vessel. Then 10 % of the coupling component solution was added and the p "value of the solution was adjusted to a value below 7.0 with dilute hydrochloric acid,

Then both the solutions of the coupling component and the tetrazo compounds were simultaneously at the same rate added dropwise over 1 hour at room temperature.

After coupling, the slurry was divided into four equal parts divided up

A. This part 1 hour, boiled, filtered, and the pigment is washed and dried at 50 ⁰ C.

B. The second part was admixed with 5% , based on the weight of the pigment, of the dye prepared by coupling tetrazobenzidine-2,2-disulfonic acid with an equimolar mixture of acetoacetanilide and acetoacet-m-xylidide. The dye had previously been dissolved in hot water.

The slurry was then boiled for 1 hour, filtered, and dried then the pigment was washed and dried at 50 ° C.

C. To the third part was added 5% of the dye used in B (dissolved in hot water) and the slurry was stirred for 5 minutes. Then 5%, based on the pigment weight, of Rson Amine D, dissolved in dilute hot acetic acid, was added. The slurry was then cooked for 1 hour filtered off and the pigment was washed and dried at -50 ⁰ C.

D. To the fourth part was added 5 % of the dye used in Part B (dissolved in hot water). Then 5% cetyl alcohol based on pigment weight was added and the slurry was boiled for 1 hour, then filtered, and the pigment was washed and dried at 50 ° C.

1098A9 / 16B5

The pigment compositions prepared according to Sections B, C and D. showed advantages over ink strength and transparency in letterpress ink media comparison A, the composition obtained according to B still having advantages in terms of gloss. Both the According to C and the compositions obtained according to D showed better flow and dispersibility properties than the product obtained according to B.

Example 135

Tetrazo-3,3'-dichlorobenzidine was obtained by tetrazotizing 25.3 parts of 3,3'-dichlorobenzidine prepared.

This connection was made through a simultaneous process with a mixture of 17.4 parts of 1-phenyl-S-methyl-S-pyrazolone and 18.8 parts of 1-p-tolyl-S-methyl-S-pyrazolone a ρ value of 4.5 to 5.0 at room temperature. A solution of 5% was then added to the pigment slurry. of a dye, based on the pigment weight, added by coupling tetrazobenzidine-2,2'sulfonic acid with an equimolar mixture of 1-phenyl-3-methyl-5-pyrazolone and 1-p-tolyl-3-methyl-5-pyrazolone was obtained. Then the slurry was heated to 90 ° C and over 30 minutes held at this temperature. The pigment composition was then filtered, washed and dried at 50 ° C.

At a. Comparison of the properties of this pigment composition with a pigment composition that was not treated with dye during manufacture show that a letterpress ink has advantages in terms of transparency and gloss.

If both dye and amine treatments are used in the mixed coupling processes are used show advantages over simple dye treatments in terms of the flow and dispersibility properties.

109849/16 S 5

Claims (35)

Claims 1.) Process for the preparation of a diarylide pigment composition, characterized in that a tetrazotized pigment benzidine is coupled with a pigment coupling agent and incorporates a water-soluble dye into the pigment. 2 ..) Process for the preparation of a diarylide pigment composition, characterized in that a tetrazotized pigment benzidine is coupled with a pigment coupling agent and incorporating a water-soluble coupled diarylide dye into the pigment. 3.) Process according to claim 2, characterized in that a stoichiometric excess of the pigment coupling agent is used in the coupling compared to the tetrazotized pigment benzidine used and a lower proportion of a tetrazotized sulfonated benzidine or tetrazotized carboxylated benzidine prior to coupling to the tetrazotized one Pigment benzidine or part of the pigment coupling agent before coupling or during or after coupling the reaction mixture gives. 4.) The method according to claim 2, characterized in that a water-soluble coupled diarylide dye prior to coupling to the tetrazotized pigment benzidine or to a portion of the pigment coupling agent before or during coupling or added to the reaction mixture after coupling. 5.) Method according to Amspruch 2, characterized in that a water-soluble coupled diarylide dye is added to a previously prepared diarylide pigment. 6.) The method according to claim 2, characterized in that the coupling of the pigment in a water-soluble coupled Diarylide dye takes place. 109849/1655 7.) The method according to claim 2, characterized in that a resin or a resinous material in the composition is incorporated. 8.) The method according to claim 2, characterized in that a surfactant is included in the composition ii is being worked on. 9.) Diarylide pigment composition, characterized in that it is a coupled diarylide pigment and a water-soluble one contains coupled diarylide dye. 10.) Composition according to claim 9, characterized in that the diarylide pigment is a benzidine yellow or a benzidine orange is. 11.) Composition according to claim 9 or 10, characterized in that that it contains 1 to 10% by weight of dye, based on the pigment. 12.) The method according to claim 2, characterized in that the pigment composition of a conventional solvent treatment is subjected or additionally with a fatty alcohol, a diol or a polyol with 8 to 22 carbon atoms is moved. 13.) Method according to claim 12, characterized in that an aqueous paste or an aqueous suspension of the pigment composition boiled with tetralin, dibenzyl ether or o-dichlorobenzene and then the pigment composition is filtered off. 14.) The method according to claim 12, characterized in that a small amount of a fatty alcohol, a diol or Polyol with 8 to 22 carbon atoms before coupling to the pigment coupling agent or before or after the diazptation and before coupling to the pigment benzidine or 109849/1665 added to the reaction mixture during or after coupling will. 15.) Method according to claim 12, characterized in that the diarylide pigment composition is in an aqueous slurry is formed, a small proportion of a fatty alcohol, a diol or polyol having 8 to 22 carbon atoms is added to the slurry with stirring and heating, and then the pigment composition is filtered off, washed and dried. 16) The method according to claim 14 or 15, characterized _r net that 0.1 to 10% by weight of the alcohol, diol or polyol, based on the dry pigment composition which is prepared or treated to be used gekennzeich '. 17.) Method according to one of claims 13, 15 and 16, characterized in that the alcohol, the diol or polyol is present during coupling or is added to the reaction mixture during coupling and during a non-ionic surfactant is also present in the coupling. 18.) Method according to one of claims 12 to 17, characterized characterized in that a metal salt of a resin or the free resin itself is added to the pigment composition will. 19.) The method according to claim 2, characterized in that a fatty acid or a fatty acid ester in the pigment composition is incorporated. 20.) Diarylide pigment composition, characterized in that it is a coupled diarylide pigment and a water-soluble one coupled diarylide dye together with an alcohol, a diol or a polyol having 8 to 22 carbon atoms contains. 109849 / 16B5 21.) Process according to claim 2, characterized in that an aliphatic amine, an amine salt or an amine oxide having 1 to 20 carbon atoms in the pigment composition is incorporated. 22.) The method according to claim 21, characterized in that a salt of an amine which contains 1 to 20 carbon atoms, is added to an acidic aqueous slurry of the pigment composition and the p "value is then alkaline is made and the slurry is boiled. 23.) The method according to claim 21, characterized in that an acidic aqueous slurry of the pigment composition cooked with the salt of an amine containing 1 to 20 carbon contains atoms, added and then the p "value is alkaline is made. 24.) The method according to claim 21, characterized in that a salt of an amine containing 1 to 20 carbon atoms, to an acidic aqueous slurry of the pigment composition is added, the slurry is then boiled and the p "value made alkaline. 25.) The method according to claim 21, characterized in that an acidic aqueous slurry of the pigment composition made alkaline with the salt of an amine, the 1
contains up to 20 carbon atoms, is added and then boiled. 26.) The method according to claim 21, characterized in that an acidic aqueous slurry of the pigment composition is made alkaline, the slurry is then boiled and then a salt of an amine containing 1 to 20 carbon atoms is added. 27.) The method according to claim 21, characterized in that an acidic aqueous slurry of the pigment composition 655 The mixture is boiled, the slurry is then made alkaline and then a salt of an amine containing 1 to 20 carbon atoms is added. 28.) The method according to claim 21, characterized in that a salt of an amine which contains 1 to 20 carbon atoms, is added to an acidic aqueous slurry of the pigment composition and then the slurry is cooked. 29.) The method according to claim 4, characterized in that an acidic aqueous slurry of the pigment composition is boiled and then a salt of an amine containing 1 to 20 carbon atoms is added. 30.) Method according to claim 21, characterized in that the amine or amine oxide is present during coupling or prior to coupling to the tetrazotized pigment benzidine or added to the pigment coupling agent. 31.) Diarylide pigment composition, characterized in that it is a coupled diarylide pigment and a water-soluble one coupled diarylide dye together with an aliphatic amine, an amine salt or amine oxide with 1 to Contains 20 carbon atoms. 32.) Diarylide pigment composition according to claim 31, characterized in that it contains one or more dyes, free amines, amine salts, amine salts of dyes, azo-Ti ^ titanium compounds of dyes and amine salts of azomethine compounds of dyes contains. 33.) Diarylide pigment composition according to claim 31, characterized in that it contains 0.1 to 10% by weight of the amine, of the amine salt or the amine oxide, based on the composition. 10 9 8 4 9/1655 - το- ", 22521 34.) Diarylide pigment composition according to claim 31, characterized in that it contains more than 10% by weight of the amine, of the amine salt or the amine oxide, based on the composition, contains. 35.) Process according to claims 12 and 21, characterized in that the pigment composition of a customary
Is subjected to solvent treatment and with a small amount of an aliphatic amine, an amine salt
or amine oxides with 1 to 20 carbon atoms added
will. 10 9 8 4 9/1655