DE1644244C - Monoazo pigment dye, process for its preparation and its use - Google Patents

Description

The present invention relates to a new monoazo pigment, a process for its preparation and its use for pigmenting high molecular weight organic material.
The need for strong, brilliant, lightfast yellow pigments, especially for the production of printing inks for graphic multicolor printing, is well known. In particular, as is evident from the proposed standard CEI12-64 of the European color scale for letterpress printing, pure, greenish yellows are sought which, in combination or by overprinting with blue pigments, allow brilliant green tones to be produced. In addition, the pigments should show good flow properties in printing inks, even with a high pigment content, and should show gloss and transparency in the prints.

A monoazo pigment has now been found which largely meets these requirements This pigment is obtained by converting the diazonium compound of l-amino-2-methoxy-4-nitrobenzene with a compound of formula I.

CH ₃

CO

CH ₁
CO

NH

»3

(I)

-OH,

Cl-

35

coupled to a monoazo pigment of formula II:

CH ₁
OCH _{1 co}

, - 'L i

O ₁ N- <> -N = N-CH

45

CO

NH

(II)

-OCH ₁

/ V

Cl

SS

The coupling is expediently carried out in an aqueous, preferably weakly acidic, in particular acetic acidic solution or suspension. To accelerate the coupling or to influence the shape of the pigments formed, auxiliaries known per se can be added to the coupling mixture, for example inert organic solvents which are miscible with water, such as lower alkenols, e.g. B. methanol, ethanol, Ethyleneglykoknono-methyl or -tthylether, lower aliphatic ^ acids, such as formic acid, vinegar · «β • lure, lower fatty acid amides such as dimethylformamide or certain tertiary nitrogen bases, 2. B, tri-ethanolamine or pyridine, furthermore small amounts of water-immiscible organic solvents, such as optionally halogenated or nitrated aromatic hydrocarbons, e.g. B. benzene, toluene, chlorobenzene, nitrobenzene or tetrahydronaphthalene, and also nonionic, anionic or cationic dispersants - as such, adducts of a multiple stoichiometric amount of alkylene oxide, especially ethylene oxide, on fatty alcohols or fatty acids, and also condensation products of naphthalenesulfonic acids are particularly suitable -, also resins or resin soaps, protective colloids such as casein or methyl cellulose, also UIe, plasticizers or solid colorless substrates such as barium sulfate or alumina hydrate

The new monoazo pigment precipitates out of the reaction mixture immediately after coupling. It Is isolated and cleaned in the usual way by filtering and washing, depending on the intended use the raw pigment press cake can be dried and ground, processed into aqueous doughs and pastes or in organic media flush. The pigment can also be converted into granular or powdery preparations with auxiliaries such as carrier resins process.

If desired, the new pigment can be used to improve the color strength and / or change the hue can also be produced in a mixture with other pigments. So you can, for example up to 30% of the diazo component or the coupling component of the formula I by another Diazo component of the nitroaniline series or another coupling component of the acetoacetanilide series substitute.

The monoazo pigment according to the invention is for pigmenting high molecular weight organic materials Suitable primarily for printing inks for the graphic industry, especially for paper printing. The pigment can also be used for other purposes in which similar monoazo pigments of the Acetoacetanilid series come into consideration, can be used, for. B. in paints on an oily basis, as in linseed oil paints, or on an aqueous basis, as in emulsion paints, in varnishes of various types Kind, as for example in nitro, alkyd resin or stove enamels, for the production of wallpapers and fijntpapier, for pulp coloring, for paper laminates, also for pigmenting plastics such as polyethylene, polystyrene, polyvinyl chloride, in particular hard polyvinyl chloride, as well as curable Resins, of cellulose esters, especially for spin dyeing of viscose or acetate silk, as well as for pigment printing and padding of textiles, among others. m.

The new pigment colors these materials in pure, pale yellow, very strong and lightfast shades. The oil and solvent fastness of the new yellow pigment is good for a pigment of this class. When used for graphic printing, the good flowability of the printing inks produced with them should also be mentioned. The prints with the pigment, which can be obtained in particular when rosin is also used in the coupling, are also distinguished by a beautiful gloss and transparency. Transparency is particularly desirable in multi-color printing and in spin dyeing of rayon. The aforementioned high color strength of the new pigment allows the production of good flowing, strong color printing inks and relatively thin printing films.

Particularly surprising is the fact that all immediately afterwards, by adding a solution of 2.49 g of acetoacet (2-methoxy-based coupling product) in 50 ml Methanol is allowed to drip into the pigments known from Piazonium of one or the other authenticity, salt solution. The resulting pigment of good flowability in binders or the green suspension is thereupon for a further 5 minutes to 56 bis • lack a pale yellow shade. Heated to 58 °, filtered off on a suction filter, the back of the benzene was washed neutral with water for the important yellow pigments; at 50 ° getrockidin range, the new pigment has the advantage of being net and pulverized.

that its production is harmless because the pigment produced in this way is excellently suited

noxious 3,3'-dichlorobenzidine dispensed io for the production of ve ?, good flowing printing inks for

can be. Compared to the US patent - the graphic industry and results in very strong, pure,

Font 3 032 546 described pigment from diazotized greenish yellow prints of good gloss and T / ans-

tem l-amino-2-methoxy-4-nitrobenzene and acetoacet parenz and very good lightfastness. In combination

(2-methoxyanilide) it has the advantage of a green with blue printing inks are z. B. in multicolor

pungent yellow shade and corresponds to practically 15 printing very pure green shades available,

the above-mentioned CEI standards, without any loss.

Mixtures made with other pigments Example 2

Need to become. This allowed to be used in combination with 8.40 g of l-amino-2-methoxy-4-nitrobenzene

suitable blue pigments, the production of pure fine powder in 75 ml of 2 η-hydrochloric acid with stirring

Green tones, while interspersed with the above-cited ao and continued for 2 hours at 25 ° Compared to pigment that is only significantly more cloudy, stirred. Then 60 g of marked

rather against olive green tones. Add the small ice and diazotize the amine at 0 to

The new pigment surpasses the well-known 2 ° by adding 10.35 g of 33.3% sodium *

Yellow from diazotized 1-amino-2-nitro-4-chlorobenzene nitrite solution for about an hour.

and acetoacet- (2-chloroanilide) of the USA patent specification as On the other hand, 12.65 g of acetoacet- (2-meth-

1 059 599 with regard to its multiple over-oxy-5-chloranilide) in 400 g water and 37.5 ml 2N Na-

lay color f 'Irke (for example in printing inks). tron lye at 20 °, gives another 25 ml of 2 n-nattium

This previously known MonoazoDigment therefore has the acetate solution, 1.25 g of an addition product of

major disadvantage that it is the production of free flowing 20 moles of ethylene oxide and stearyl alcohol and 150 g

yellow printing inks with deep color strengths do not add ice to the solution and ultimately leave it under

permitted. The pigment according to the invention is furthermore constant stirring at 3 to 5 ° 45 ml of 2N acetic acid

Interpreting üchtechtei as that from the USA.-Patent for this mixture.

1,051,565 known pigment from l-amino-2-methoxy- To the fine suspension of the

4-nitrobenzene and acetoacet- (2-chloroanilide). Similar coupling components are allowed within 30 minutes

Monoazo pigments from the isomeric l-amino-2-nitro- 35 grooves the cleared, cold diazonium salt-

4-methoxybenzoI solution according to the German patent and then increases the temperature

461 499 show comparatively fewer requested red - within an hour to 40 \ Then that will

pungent yellow tones. More yellow from acetoacet- (2-mith- formed pigment filtered off on a suction filter, new-

oxy-5-chloro-4-nitroanilide) washed according to the German patent tral, dried at 50 ° and pulverized,

402 869 require a much higher effort 40 It results in printing inks similarly strong and pure,

in the production and are also much worse greenish yellow prints like the one obtained in Example 1

lightfast and weaker in color as the tene pigment according to the invention.

new pigment. If you add 4.0 g of a 45% colophony, a pure greenish soap (sodium salt), dissolved in 40 ml of water, to the alkaline solution of the coupling and works Yellow tone, very good lightfastness, otherwise the same for printing inks as indicated in the example Satisfactory fastness to solvents and varnish, one is a yellow pigment with which prints with low oil absorption and very good flow behavior; especially good transparency and beautiful gloss, the prints made with it let you aim, nice balance and good transparency. These 50 B e i s ρ i e I 3 Combination of valuable properties is also

surprising because a yellow pigment made from dia- 168 g of l-amino-2-methoxy-4-nitrobenzene are used as

zotierterl-Amino-i-methoxy ^ nitrobenzolundAceto- fine powder with stirring in a mixture of

Acet- (3-cliloraniIid) weakly colored and very poorly light- 300 ml of 10 η-hydrochloric acid and 1200 ml of water.

is real. SS wear and stir overnight. One admits to this

The following examples illustrate the invention of the mixture 1200 g of crushed ice and diazotized

manure. In it, the temperatures in degrees Celsius are the amine at 0 to 5 ° by running in

specified. 207.0 g of 33.3% sodium nitrite solution for about

If ο ie I 1 ^{10 minutes} · Be 'weakly positive nitrite reaction becomes

^p 60 was stirred for a further hour while cold.

1.68 g of l-amino-2-methoxy-4-nitrobenzene are dissolved in On the other hand, 256 g of acetoacet- (2-methoxy

50 ml of glacial acetic acid are dissolved, whereupon 5-chloroanilide is added to the solution in 4500 ml of water and 200 g of sodium bicarbonate.

12 ml of 10 η hydrochloric acid are added. To this mixture caustic (30%) at 20 ', the solution is mixed with 85 g

If a solution of sodium acetate (crystalline) and 25 g of an additive

of 0.76 g of sodium nitrate in 190 g of water, stirs the 6 products "from 20 mol of ethylene oxide to stearyl alcohol,

thus obtained diazonium salt solution at room temperature dissolved in 250 ml of water, diluted with 2000 g of ice and temperature for another 3 minutes, this mixture is finally left with constant stirring at 0 to 5 "in COmI 2 N sodium acetate solution is added and 135 g of acetic acid (80%) run in for 10 minutes.

The fine suspension of the coupling component produced in this way is then immediately added to the clarified cold suspension within 30 minutes while stirring Diazonium salt solution flow in, the temperature being kept below 10 ° by adding more ice. On that the pigment suspension formed is heated to 40 ° within 2 hours by blowing in steam. If the diazonium compound is still detectable a little coupling component, dissolved in dilute sodium hydroxide solution, is added until the diazo reaction is negative.

The pigment is then filtered off, washed neutral, dried at 60 ° and then pulverized.

The pigment produced in this way allows the production of free flowing, very strong printing inks for the graphic trade, with which one can produce pure and strong greenish-yellow prints of very good lightfastness, good gloss and beautiful transparency.

Substituting the alkaline solution of the coupling component still 80 g of a 45 ° / ₀ sodium rosin soap (sodium salt) dissolved in 800 ml of water, and treated as indicated above is otherwise the same, one obtains a particularly transparent in the photographic printing and glossy yellow pigment, which in combination with blue printing inks z. B. in multi-color printing is very suitable for producing particularly pure green tones.

Example 4

1.00 g of the pigment prepared according to Example 3, Sections 1 to 4, is mixed with 4.00 g of the printing varnish of the composition

29.4 ° / ₀ linseed oil stand oil (300 poise), 67.2 ⁰ Z ₀ linseed oil stand oil (20 poise),

2.1 _^0/0 of cobalt octoate (8 ° / ₀ Co), and

l, 3 _^0/0 lead octoate (24 _^0/0 Pb)

finely rubbed on an Engelsmann rubbing machine and then printed with the help of a cliché in the letterpress process with 1 g / m * on art paper. A strong, pure, greenish shade of yellow with good transparency and good gloss is obtained. In three- or four-color printing, very brilliant green tones can be created by overprinting on blue. The pigment is also suitable for other printing processes, such as gravure printing. Offset printing, flexographic printing, and also gives very good results here.

Example p

3.2 g of the pigment prepared according to Example 3, Sections 1 to 4, are mixed with 0.8 g of copper phthalocyanine anin («-form), 36.0 g of alumina hydrate and 60.0 g of printing varnish rubbed into a printing ink, which is printed on white synthetic paper with the help of a gelatin roller. A very strong, pure green color print is obtained.

Claims (3)

Patent claims: 1. Monoazo pigment dye of the formula I: OCH ₃ O ₁ N- CH, CO = N-CH 'j CO NH - OCH, Cl 2. Process for the preparation of the monoazo pigment of the formula I, characterized in that the diazonium compound of l-Amino-2-methoxy-4-nitrobenzene with a compound of the formula II CH ₃ CO CH ₁ CO NH α-11 r ~ OCH ₃ clutch. 3. Process for pigmenting high molecular weight organic material, characterized through the use of the monoazo pigment dye of claim 1.