DE1644246A1 - Process for the production of disazo pigments - Google Patents

Description

Dr F Zumstein Sr. - Dr, E. Assmann

JR * Geigy AG-. _{Dr R} .Koenigsberger - Dipl.Phys.R. Holzbauer Z241 *

■ n * c α λ n * c η A-z Dr. F. Zumslein jun.

P 16 44 246.9-43 Patent attorneys:

- B Mönchen 2, Brä'uhausstrasse 4 / IU

New complete notification documents

Process for the production of disazo pigments,

The present invention relates to new disazo pigments, Process for their production, process for pigmenting polymers! organic material using this Pigments, as well as, as an industrial product, thatwith these new disazo pigments pigmented polymeric organic material.

It has been found that valuable bordeaux-colored Disazo pigments are obtained by adding 2 equivalents of the diazonium compound of 1-amino-2-methoxy-4-nitrobenzene or 1-amino-2 ^ ethoxy-4-nitrobenzene with 1 equivalent of 1, A-BIs- [2'-hydroxynaphthoyl- (3 ') -amino] -benzene to a Dlsazo pigment of

Formula I ~ ■ - ■ "■"

OR HO COKH-H ^ ^A r-NHOC OH RO

in the - _::

R 'denotes the methyl or ethyl group, "\ -

clutch. :

The coupling is expediently carried out by dropping an aqueous alkaline solution of the coupling component in the presence of the usual, the azo coupling promoting auxiliaries to the aqueous solution the diazonium compound carried out, whereby one by action of shredding forces, the average part size the poorly soluble in the acidic coupling mixture

component and the resulting dye keeps tinter 5μ .

These crushing forces are expedient by Friction generated, in particular by mechanical friction of the dispersion on solids. For the practical implementation of the Process is used as an apparatus for generating the necessary. Friction mainly ball or sand mills, anchor stirrers, high-speed stirrers, which are preferably equipped with rotors and stators, but also funnel mills with grinding disks, high-pressure mills or ultrasound machines.

There are auxiliary substances that promote the azo coupling

Wm particular chemically inert, non-ionic, anion-active or cation-active dispersing agent in question, for example, alkylaryl sulfonates, 'such as dodecylbenzene sulfonate, or Aralkylarylsulfonate such as alkali salts of products obtained by condensation of a mixture of naphthalenesulfonic acids and formaldehyde, or Polyalkylenoxydanlagerungsprodukte, for example, adducts of a multiple stoichiometric amount on alkylene oxides, especially ethylene oxide, and higher fatty alcohols or fatty acids; In addition, water-miscible inert organic materials

ik. Solvents such as lower aliphatic carboxylic acids e.g.

Acetic acid, lower alkanols, for example methanol, ethanol, isopropanol or ethylene glycol monomethyl or ethyl ether, Amides of lower fatty acids, such as dimethylformamide, or also non-coupling agents organic nitrogen bases, such as triethanolamine or pyridine, or then relatively small amounts of water-immiscible organic solvents, such as halogenated, if appropriate or nitrated aromatic hydrocarbons, e.g. benzene,

009844/1453

Toluene, xylenes, tetrahydronaphthalene, chlorobenzene, dichlorobenzenes or nitrobenzene, and certain aliphatic halogenated ones Hydrocarbons such as carbon tetrachloride or trichlorethylene.

The new pigments fall immediately after coupling out of the reaction mixture, you will go through in the usual way Filtering and washing, isolated and purified, - «Depending on the situation desired use can.man the raw pigment press cake dry and grind, process into watery doughs and pastes or flush in organic media, '

There is a modification of the method according to the invention in that a monoazo dye carboxylic acid halide is used in a molecular ratio of 2: 1 of formula II,

CQ-HaI _ ■■. ~ (II)

in the .

R denotes the methyl or ethyl group and Hal denotes bromine or, in particular, chlorine,.

with 1,4-diaminobenzene to form a disazo dye of the formula I | condensed. ,

The monoazo carboxylic acid halide which can be used as starting material of the formula II is conveniently obtained by treating the corresponding monoazo carboxylic acid with Halogenating agents such as phosphorus pentachloride, phosphorus oxychloride or thionyl chloride. The halogenation of the carboxylic acid to the acid halide is preferably carried out "in organic solution

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agents, as in optionally halogenated or nitrated Hydrocarbons, e.g. in benzene, toluene, xylenes or mono- and dichlorobenzenes or nitrobenzene.

The condensation of the acid halides of the formula II with 1,4-Diaminobenzene is expediently carried out using an excess of the former and advantageously in an organic one Solvent, e.g. in one of those mentioned in the previous section. Sometimes it is advisable to

- ■ - -

door in the presence of an acid-binding agent, e.g. a tertiary organic nitrogen base, such as pyridine, to condense-IP sate.

It is also possible to halogenate the monoazo carboxylic acid to the acid halide of the formula II and the Kon-r Densation of the latter with 1,4-diaminobenzene can be carried out in one operation without isolating the acid halide.

The new disazo pigments of the formula I are isolated in the usual way, in particular by filtration.

The new burgundy-colored pigments have good fastness properties and are characterized by high color strength .. For "- .. certain purposes the raw pigments can be used directly; they". but can also by methods known per se, for example by crystallization or extraction with organic solvents or by grinding with afterwards -removable grinding-. auxiliaries, e.g. salts, in their properties, especially in terms of purity and shape, still to be improved.

«- ■ The inventive disazo pigments of the formula I. are for pigmenting polymeric organic material "suitable,

00 98 44 / 1A53

- r

- primarily of printing inks for the graphic industry especially for paper printing, also in paints on an oily basis, such as linseed oil paints, or on an aqueous basis, as in emulsion paints, in varnishes of various types, such as nitro or stoving varnishes, or in alkyd resin varnishes. They can also be used for pigmenting plastics, such as polyethylene,., polystyrene, polyvinyl chloride, which the latter can also contain plasticizers, but in particular hard polyvinyl chloride, of cellulose esters., in particular for spin dyeing of viscose or acetate silk, of hard. resins, or for pigmenting rubber, as well as - for coloring paper pulp, for coating webs, e.g. during manufacture - of laminate paper .. or of synthetic leather, as well as for the Use pigment printing and textile padding.

The new disazo pigments color these materials in pure Bordeaux-colored, very strong and lightfast. Tones. They surpass that from Swiss patent specification No. 300.780 well-known, burgundy-colored pigment of the formula III

HO CQNH -tfjtyfrjy NHOC 'OH'

NV (^ \ - Έ - N__

^ ^W ' ⁽ⁱⁿ

with regard to their migration fastness in plasticized Polyvinyl chloride, what "considering the smaller molecular weight the connection according to the invention is surprising. They are also more light and varnished than the previously known Pigment of formula III. The aforementioned high color strength of the new

009844/1453

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Pigments allow the production of good flowing, more strongly colored Printing inks and relatively thin printing films.

The following examples illustrate the invention. Therein the temperatures are given in degrees Celsius.

009844/1453

■ Example 1

16.8 g of l-amino-2-methoxy-4-nitrobenzene are added to a mixture of 40 ml of IQ-η. Hydrochloric acid, 20 g of a 5% solution of the action product of 18-20 mol of ethylene oxide on stearyl alcohol and 50 ml of water and suspended for 1 to 2 hours. 350 ml of ice water are then added to the slurry and 22.2 g of a 33% aqueous flatrium nitrite solution are dispersed at about 0 °. As soon as a clear solution has formed, excess nitrous acid is decomposed by adding solid sulfamic acid, and the solution is added with 95 ml of 2N sodium acetate solution and 10 ml of xylene and a solution of 22.4 g of ₁ 4-bis (2 ^r -hydroxynaphthOyl-C3 ^l! ) - ainino] -benzene in 75 ml. 2N sodium hydroxide solution, 40 ml of ethanol and 500 ml of water »

After the addition of the coupling component is complete, it is removed the high-speed stirrer and then stirs the coupling mixture by means of a normal stirrer with anchor stirrer a few more Zr- \ t at room temperature until the coupling has ended, then filtered the disazo pigment formed was washed thoroughly with water and it dries at about 100 °,

38.6 g of a red-brown crude pigment (95.8% of theory) are obtained which is eminently suitable for pigmenting x ^r on, plasticizer-containing polyvinyl chloride in bordeaux-colored shades that are fast to migrate.

-, 8 - ■

20.0 g of this crude pigment are introduced into 360 g of dry nitrobenzoi for 2 to 3 hours at one temperature stirred from 200 ° and then at a temperature of 100 ° filtered, the suction filter is washed with warm nitrobenzoi until the drain is colorless, then the nitrobenzoi is displaced the filter cake with methanol and the pigment dries at about 100 °,.

18.2 g of a finely crystalline, grain-soft pigment are obtained (91.0% of the weight of the crude pigment). Refined with this Pigment preserved bordeaux-colored pigmentation j3n_ "Plasticized polyvinyl chloride has somewhat better fastness properties than those obtained with the raw pigment receives. - '

Example 2 . . ■

18.2 g of 1-amino-2-ethoxy-4-nitrobenzoi are dissolved in 250 ml of glacial acetic acid, with 150 ml of 2-n. Hydrochloric acid is added and at 8-1 = 2 ° with 105 ml of 1-n. Diazotized sodium nitrite solution. When the diazotization is complete, excess nitrous acid is decomposed by adding solid sulfamic acid, then 10 ml of xylene (mixture of isomers), 20 ml of a 5% aqueous solution of the adduct of 18-20 mol of ethylene oxide with stearyl alcohol and 95 ml of 2N are added to the solution. Sodium acetate solution and then added dropwise .. with vigorous stirring by means of a high-speed stirrer to the diazonium salt solution presented, a solution of 22.4 _{g of} 1,4-bis- [2'-hydroxynaphthoyl- (3 ') - aminolbenzene in 75 ml of 2-n. Sodium hydroxide solution, 40 ml of ethanol and 500 ml of water. . ■.

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After the addition of the coupling components, the High-speed stirrer and then stirred by means of a normal stirrer with anchor stirrer for some time at room temperature the clutch has ended. Thereupon the disazo pigment formed becomes filtered, washed thoroughly with water, dried at 50 ° and powdered.

A red-brown pigment is obtained which is excellent suitable for pigmenting plasticized polyvinyl chloride in burgundy-colored shades that are fast to migrate.

20 g of this crude pigment are refined as described in Example 1.

Achieved with this finely crystalline, grain-soft pigment Bordeaux-colored pigmentation of plasticized polyvinyl chloride have somewhat better fastness properties than those obtained with the raw pigment. "" ·.

Example 3 /

45.7 g of the coupling product.; Of diazotized 1-amino-2-methoxy-4-nitrobenzene and 2-hydroxy-3-naphthoic acid are suspended in 750 ml. chlorobenzene. Man-distilled to the full Dehydration 100 ml of chlorobenzene and are at 70 ° 18.8 g of distilled thionyl chloride within 5 minutes to the Suspension. The reaction mixture is then kept boiling for about 5 hours and filtered at the boiling point formed, precipitated monoazo dye carboxylic acid chloride off, wash it with a little chlorobenzene and dry it at 70 ° in a vacuum. -

0-0 9-8 UY U53

The carboxylic acid chloride mentioned is obtained in the form of greenish bronzing crystals with a melting point of 268 ° -269 ° (decomposition). ' After about 24 hours, a further fraction of the above acid chloride with a melting point of 269 ° -271 ° crystallizes from the mother liquor (Decomposition). .

15.7 g of this monoazo dye carboxylic acid chloride are suspended in 500 ml of dry toluene. At boiling point (110 °) 2.0 g of dry 1,4-diaminobenzene are in the suspension entered and rinsed with 80 ml of dry toluene. The condensation to the disazo pigment occurs immediately. Man W keeps the reaction mixture under reflux for 23 to 25 hours at the boiling point until the evolution of hydrochloric acid has ended, 'filters the crystallized pigment formed from the-' ■ While the suspension is still hot, it is washed with warm toluene until the run-off is colorless and it is dried at 70 ° in a vacuum.

A red-brown pigment powder is obtained which of example "1, section 3 is very similar.

If one uses instead of the 45.7 g of the coupling product ' of diazotized l-amino-2-methoxy-4-nitrobenzene and 2-hydroxy- ^ 3-naphthoic acid 46.7 ° g of the coupling product of diazotized l-amino-2-ethoxy-4-nitrobenzene and 2-hydroxy-3-naphthoic acid and if the rest of the procedure is as described in the example, a red-brown pigment powder is obtained that is practically that of the Example 2, section 3, corresponds.

9844/1453

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example A.

A stabilized mix of;

67 grams of polyvinyl chloride; (K-Werti ca * '7O) -, . 33 g dioctyl phthalate,

2 g dibutyltin dilaurate, '-. "." -...

0.3 g sodium barium organophosphate, e.g. * FERROCLERE '541 A (Pure Chemicals Ltd., Plastic Division England) as a light stabilizer,
2g titanium dipoxide and

0.65 g of bisazo pigment according to Example 1, From section 3,

is processed on a Misehvialzwerk at 160 ° and ansehlies-! | send pulled out to a sheet of 0.4 mm thickness. The pure, Bordeaux-red coloring is very good against migration, rubbing and rubbing heat resistant.

If, instead of the crude pigment obtained in accordance with Section 3 of Example 1, the refined pigment prepared in accordance with Section 5 of the same example is used, one obtains, with an-. otherwise the same. Procedure, pigments whose fastness properties are somewhat improved compared with those obtained with the boh pigment. - - '

If, instead of 0.65 g of disazo pigment according ^v Example 1, section 3.,. corresponding amounts of the disazo pigment according to Example 2, Section 3, \ ind procedure is otherwise v, ^r ie described in Example, one obtains burgundy-colored. Pigmentations with similar properties.

Example 5 - ''

A stoving enamel made of "... ..

20 g titanium dioxide (rutile),
40 g of a 60% solution of coconut alkyd resin (oil content ⁼

^; of the resin 32%) in xylene,

24 g of a 50% solution of melamine resin in butanol, 8- g xylene, -. ■ -. . _ ■ 7 g of ethylene glycol monomethyl ether and 1 g of disazopigraent according to Example 2, Section 3, is finely ground in a ball mill, on an aluminum -. Foil sprayed on, left to dry and finally baked for 30 minutes at 120 °. The pure, burgundy-red The coloring is very lightfast, varnishfast and heatfast.

If, instead of the 1 g of disazo pigment according to Example 2, Section 3, corresponding amounts of disazo pigment according to Example 1, section 3, then one obtains, otherwise the same Procedure, also a pure and strongly colored burgundy-red dyeing with similar fastness properties.

Example 6 .- ......

From 10 g disazo pigment according to Example 1

(raw or refined pigment), .- - - "

30 g alumina hydrate and "''

60 g printing varnish ".

a graphic printing ink is produced on a three-roll mill. Draw the prints obtained with the letterpress process with a beautiful Bordeaux l'uance and very good solvent and lightfastness. . ,

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Example 7 , -

1.0 g of the after. Example 2 produced pigment be with

4.0 g of printing varnish with the composition --.'_. 29.4 % ; linseed oil stand oil (300 poise), 67.2 % rental oil stand oil (20 poise), 2.1 % carbon oetoa.t- (8% Co) and 1.3 % lead octoate (24 ^ Pb). '■■ /' - '

finely ground on an Engelsmann grinding machine and

with the help of a cliché in the letterpress process with 1 g / m

printed on art paper. You get a strong ^

Bordeaux-colored print.

Example 8

A mixture of

25 parts by weight of a suspension polyvinyl chloride (K value approx. 70) (e.g. VESTOLIT B 7021 from Chemischen Werke Hüls, Germany),. 25 parts by weight of a suspension polyvinyl chloride ■ (K value approx. 80) (e.g. VESTOLIT E 8001 from Chemischen Ä

Werke Hüls, Germany), '
32 parts by weight of Dio _; ctylphthalate,

1 part by weight of dibutyltin dilaurate, 0.25 part by weight of sodium barium organophosphate

(e.g. FERROCLERE 541 A® from Pure Chemicals Ltd., Plastic Division, England) as a light stabilizer ', 6 parts by weight of chalk (finely ground),

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10, Γ75 parts by weight Sangajol (petrol hydrocarbon

Bp. 140-20O ⁰ C) and
0.5 part by weight of disazo pigment according to Example 1

(raw or refined pigment), is ground into a paste in a ball mill.

This paste is used to coat a linen fabric and then heats the tissue to around 160-180 °. These The procedure is repeated two more times.

A uniformly burgundy-colored artificial leather with good migration fastness of the pigmentation is obtained in this way.

009844/1453

Claims (1)

- ¹⁵ V Ί 644246 -. Patent claims 1, Process for the production of Dlsazoplgmenten, thereby characterized in that one has 2 equivalents of the diazonium compound of 'l-amino-2-methoxy-4-nitrobenzene or l-amino-2-ethoxy-4-nitrobenzene with 1st equivalent 1,4-bis- [2'-hydroxynaphthoyl- (3 ') ~ amino] benzene to a disazo pigment of the formula I, . OR -HO COWH- ^ jV-KHOC. OH RO - "■ CD in the . ™ R denotes the methyl or ethyl group, lcouples. 2. Process according to claim 1, characterized in that die.Kupplung is carried out by dropping an aqueous-alkaline solution of the coupling component onto the aqueous solution of the diazonium compound in the presence of customary auxiliaries which promote the azo coupling, the average particle size being obtained by the action of grinding forces g of the coupling component, which is sparingly soluble in the acidic coupling mixture, and the resulting dye below 5 μ . 3, modification of the method according to claim 1, characterized in that that in a molecular ratio of 2: 1 a monoazo dye carbonic acid halide of the formula II, / 1 453 ; 0H .0-shark CiD in which R is the methyl or ethyl group and Hal mean chlorine or bromine, with 1,4-diaminobenzbl to a DIsaz.opigment of the formula I. condensed. 4. Disazo pigments of the formula I, OR HO CONH-F ^N V-NHOC .OH / TV ° 2 ^W "W in which R is the methyl or ethyl group, 5. The disazo pigment of the formula I, in which R is the methyl group means. 6. The disazo pigment of the formula I, in which R is the ethyl group means. 7. A method for pigmenting polymeric organic material, characterized by the use of the disazo pigments of claim A. ■ 8 .. The polymeric pigmented using the disazo pigments of the claim? organic matter]. 0 Π 9 B U \ / BATH