DE2847661A1 - NEW MODIFICATION OF A DISAZOPIGMENT - Google Patents

Description

Dr. F. Zumstein Sr. - Cr. E-. Assmai in - Ci. R. Koenigsberger Dipl.-Pbys. R. Holzbauer - Dip: .- ing. F. Klingse-sen - Dr. F. ZumstekvjurH _Λ

PATENT LAWYERS 78 ^ »7F6 1

8OOO Munich 2 ■ Bräuhausstrasse 4 - Telephone collection no. 22 53 41 Telegrams Zumpat - Telex 529979

k. ■

Oasis 3-114-26 / =

CIBA-GEIGY AG, CH-4-002 Basel /. Switzerland

New modification of a disazo pigment

The present invention relates to the new brown β-modification of a disazo pigment. While on the Areas of blue, green and red pigments organic pigments were found relatively early that met the highest requirements for fastness it took a long time to produce high-quality organic brown pigments. This succeeded, for example from the two CH-PS No. 434 520 and No. 561 258, by using diazotized nitrochloro- or trichloroanilines as diazo components. Such in themselves undoubtedly However, high-quality pigments have a major impact on the currently applicable environmental protection regulations falling disadvantage stemming from their manufacture: nitrochloric and trichloroanilines can only be used if they are used are diazotized by nitrosylsulfuric acid or glacial acetic acid, which is associated with significant ecological difficulties which are difficult and costly to deal with.

can be sided. In addition, those with nitrochlorani-

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linen produced pigments to fizzle out when grinding.

In DT-OS No. 2,361,433, Example 1 describes the production of a reddish-brown disazo pigment of the formula (I)

by condensation of the azocarboxylic acid chloride of the formula (II)

(II)

COCl

in a molar ratio of 2: 1 with 1,5-diaminonaphthalene in o-dichlorobenzene, the 1,5-diaminonaphthalene dissolved in o-dichlorobenzene being added to a solution of the carboxylic acid chloride of the formula (II) in o-dichlorobenzene at 110 ° C. and the mixture is then heated ^{to 145 ° C. for 18 hours.} The dye obtained, in the production of which the above-mentioned ecological difficulties do not occur, has good fastness properties, but is of little colouration because of its dull shade.

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"C"

ristic interest. The X-ray diffraction diagram of this pigment, which we will refer to as the α-modification in the following, is characterized by the following lines:

Interplanar spacing or intensity of the line

d-value in A

10.8 very strong

9.5 medium

6.9 medium

4.99 strong

4.74 medium

4.32 strong D *

4.09 'medium D *

3.67 medium

3.23 very strong

3.14 medium

* D = diffuse

• where further weak lines appear in the range from 11.0 to 3.1 A, namely with the following d-values: 7.8 4.0 3.95 3.87 3.73 3.63 3.33 and 3.17 &.

It has now been found that, surprisingly, a new, valuable, strongly colored, neutral brown can be obtained Crystal modification of the dye of the formula (I), called ß-modification, reaches its X-ray diffraction spectrum is characterized by the following lines:

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Lattice level spacing or d-value in A

Intensity of the line

10.5
6.5
6.2
5.24 4.78 4.33 4.14 3.67 3.45 3.38 3.30 3.26 3.16

very strong

middle

very strong

middle

middle

middle

middle

strong

strong

strong

very strong

middle

middle

further weak lines appear in the range 11.0 to 3.1 A, namely with the following d-values:

17.2 3.5 and 3.22 &,

if you have undissolved 1,5-diaminonaphthalene optionally together with a catalytic amount of a tertiary amine, especially pyridine at room temperature one The suspension of the carboxylic acid chloride of the formula (II) in an inert organic solvent is added, the mixture thus obtained is heated and the condensation at increased Temperature complete.

The addition of catalytic amounts of pyridine improves the fastness to migration.

It has also been found that, surprisingly, to the same new one called β-modification Crystal modification arrives when one uses the α modification

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of the pigment of the formula (I) heated in an inert high-boiling organic solvent. Preference is given to ^{organic solvents boiling above 200 °} C., in particular nitro

benzene. .... ". -

The X-ray diffraction diagrams were obtained by a conventional powder method, with the diffraction pattern was registered on films. A Guinier-DeWolff No. 2 camera with CuKa radiation was used for recording (γ = 1.5418 Å). The calibration substance used was α-quartz with d values from ASTM File No. 5-0490 is used. The intensities were visually estimated and divided into four levels: very strong / strong / medium / weak.

The new pigment modification is suitable in finely divided form for coloring high-molecular organic Material of natural or artificial origin. It can e.g. natural resins, drying oils or rubber. But it can also be modified natural substances act, for example chlorinated rubber, oil-modified alkyd resins or viscose or cellulose derivatives such as acetyl cellulose and nitrocellulose, and especially fully synthetic organic polyplasts, i.e. plastics, which are produced by polymerization, polycondensation and polyaddition. From the class of these plastics the following are particularly mentioned: polyethylene, polypropylene, polyisobutylene, polystyrene, polyvinyl chloride, polyvinyl acetate, Polyacrylonitrile, polyacrylic acid and polymethacrylic acid esters j polyester, especially high molecular weight Esters of aromatic polycarboxylic acids with polyfunctional alcohols; Polyamides; the condensation products of

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Formaldehyde with phenols, the so-called phenoplasts, and the condensation products of formaldehyde with urea, Thiourea and melamine, the so-called aminoplasts; the polyester used as coating resins, both saturated, such as alkyd resins, as well as unsaturated, such as maleate resins, and also those among the Hamen "epoxy resins" known polyaddition or polycondensation products of epichlorohydrin with polyols or polyphenols; also the so-called thermoplastics, i.e. the non-hardenable polyplasts. It should be emphasized that not only the uniform compounds, but also mixtures of polyplasts, as well as mixed condensates and mixed polymers, such as those based on butadiene, with the inventive Pigment modification can be pigmented.

It does not matter whether the high molecular weight compounds mentioned as plastic masses, melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending on the intended use it proves to be advantageous to use the pigment modification according to the invention as a toner or in the form of preparations to use.

The pigment modification according to the invention is characterized by its color strength, by good heat, light, Weather, overcoating, rubbing, solvent and migration fastness as well as good dispersibility.

In the examples below, the parts, unless otherwise indicated, mean parts by weight, the Percentages by weight and the temperatures are given in degrees Celsius.

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For example

72.2 parts of the azo dye, which is obtained by coupling diazotized 1-amino-2,5-dichlorobenzene with 2,3-hydroxynaphthoic acid, are finely dispersed in a mixture with 520 parts of o-dichlorobenzene and heated to 85 ° with stirring. Then leave the. 32.7 parts of thionyl chloride are added dropwise over the course of 10 minutes at 80-90 °. The reaction mixture is heated further and kept at 115-120 ° for 60 minutes. After cooling to 20 °, the azo dye carboxylic acid chloride which has precipitated in crystalline form is isolated by filtration, washed with a little cold o-dichlorobenzene, then with petroleum ether and dried in vacuo at 70 °.

37.95 parts of the azo dye carboxylic acid chloride thus obtained are mixed with 650 parts of dry o-dichlorobenzene at 20-25 ° for 15 minutes. 2.5 parts of pyridine and 7.9 parts of 1,5-naphthylenediamine are added to the fine suspension. The mixture is heated and stirred at 140-145 ° for 15 hours. The precipitated condensation product is filtered off at 100 °, washed first with 100 ° warm o-dichlorobenzene, then with 20 ° warm methanol and then with 80 ° warm water. Finally, it is dried in vacuo at 100 °. 39.4 parts (93.4% of theory) of the pigment of the formula (I), whose X-ray diffraction spectrum is identical to that which characterizes the β-modification in the description, are obtained. The β-modification pigment obtained is a brown powder which is very sparingly soluble in organic solvents. It dyes PVC and paints in neutral, deep brown shades of very good resistance to migration, light, weather, overcoating and heat.

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Elemental analysis of the pigment obtained.

C H Cl N 0

% Found: 62.3 3.2 17.0 9.8 7.5% Calculated: 62.5 3.1 16.8 9.9 7.6

Example 2 (direct method)

36.1 parts of the azo dye, which one through Coupling of diazotized ^ l-amino-2,5-dichlorobenzene with 2,3-hydroxynaphthoic acid is finely divided heated in a mixture with 700 parts of dry o-dichlorobenzene with stirring to 85 °. Then leave the Course of 10 minutes at 80-90 °. 16.4 parts of thionyl chloride are added dropwise. The reaction mixture is heated and during Held at 115-120 ° for 60 minutes. Then the excess of thionyl chloride together with 50 parts of o-dichlorobenzene distilled off under a weak vacuum. The azo dye carboxylic acid chloride formed is cooled to 20 ° and then gives equal to 2.5 parts of pyridine and 7.9 parts of 1,5-naphthylenediamine to. The red suspension is heated and stirred at 140-145 ° for 15 hours. The educated brown The pigment is filtered off at 100 ° and worked up as described in Example 1. 40.3 parts are obtained (95.6% of theory) of the pigment of the formula (I), which has the same β-modification (characterized by the X-ray diffraction spectrum), the same shade and the same fastness properties as the pigment of Example 1 has.

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Example 3 Conversion of the α-modification into the β-modification

5 parts of the according to Example 1 of German Offenlegungsschrift No. 2 361 433 by condensation of the Azo dye carboxylic acid chlorides obtained in a molar ratio of 2.2: 1 with 1,5-naphthylenediamine in o-dichlorobenzene Disazopigtnentes are boiled in 180 parts of nitrobenzene with stirring for 3 hours. After cooling down 100 ° the pigment is filtered off, washed first with a little 100 ° warm nitrobenzene, then with 20 ° warm methanol and dried in vacuo at 100 °. 4.6 parts of a brown, soft pigment powder are obtained, which is the corresponds to β modification. By grinding or kneading salt the pigment is brought into a form that is favorable in terms of application, which polyvinyl chloride films in brown tones colors; it has the properties mentioned in Example 1. One prolonged treatment with nitrobenzene does not change the modification. The β modification is therefore stable. For conversion In the β-form, other solvents boiling above 200 °, such as 1-chloronaphthalene, can also be used.

Example 4

65 parts of polyvinyl chloride, 35 T _e ile dioctyl phthalate and 0.2 parts of the pigment obtained according to Example 1 are mixed together and then back on a two-roll calender for 7 minutes at 140 ° and hergewalzt. A neutral brown colored film of strong hue and very good fastness to light, weather, migration and varnish is obtained.

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Example 5

In a rod mill, 40 parts of a nitrocellulose lacquer, 2.375 parts of titanium dioxide and 0.125 Parts of the pigment obtained in Example 1 were ground for 16 hours. The paint obtained is applied to an aluminum foil applied in a thin layer. A neutral brown varnish with excellent fastness properties is obtained,

Example 6

A mixture of 25 parts of the pigment obtained in Example 1, 25 parts of acetyl cellulose (34.5 % bound acetic acid), 100 parts of sodium chloride and 50 parts of diacetone alcohol is treated in a kneader with cooling until the pigment has the desired degree of fineness. Then add 25 parts of water and knead until a fine-grained mass is formed. This is placed on a suction filter and washed with water until no more chlorine ions can be detected in the filtrate. It is dried in vacuo at 85 ° and then ground in a hammer mill.

• To an acetate silk dope consisting of 100 parts of acetyl cellulose and 376 parts of acetone is added 1.33 parts of the pigment preparation obtained. The mixture is stirred for 3 hours, resulting in complete distribution of the dye leads. The thread obtained from this mass in the usual way after the drying process has a neutral color brown color, which has very good fastness properties.

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Example7

0.25 parts of the dye according to Example 1 are mixed with 40 parts of an alkyd melamine stoving varnish, which contains 50% dye and 4.75 parts of titanium dioxide, ground in a rod mill for 24 hours. The received Varnish is applied to an aluminum foil in a thin layer pulled out and baked for one hour at 120 °. A brown paint finish with good light and color is obtained Weather resistance.

Example 8

4.8 parts of the dye according to Example 1 who are ground with 4.8 parts of the sodium salt of 1,1'-dinaphthylmethane-2,2'-disulfonic acid and 22.1 parts of water in one of the customary colloid mills until all pigment particles less than 1 p. are. The pigment suspension obtained in this way has a pigment content of approx.

If this aqueous suspension is added to the viscose spinning mass, it is obtained by the usual spinning process a neutral brown dyed cellulose thread with very good fastness properties.

Example 9

A stabilized mixture of 100 g of a suspension polyvinyl chloride ("Hostalit C 260", Farbwerke Hoechst AG, K value = 60), 1.5 g of a complex of barium and cadmium salts of higher fatty acids, complexing agents and

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Antioxidants as stabilizers ("Advastab BC 26", CIBA-Geigy AG ₅ Basel), 0.5 g of a costabilizer based on organic phosphite compounds ("Advastab CH 300", CIBA-GEIGY AG, Basel), 3.0 g of an epoxidized Soybean oils ("Advaplast 29", CIBA-GEIGY AG, Basel), 0.5 g of a lubricant ("E-wax", BASF AG, Ludwigshafen), 2.0 g of titanium dioxide ("Titanium dioxide KRONOS Cl 220", Titangesellschaft GmbH, Leverkusen) and 0.1 g of the pigment according to Example 1 is processed for 8 minutes at 180 ° on a mixing roller mill with a roller speed of 20:24 (friction 1: 1.2) and a roller gap of 0.3 mm and then at a Temperature of 180 ° pressed to a plastic of 1 mm. The brown color of the rigid polyvinyl chloride plate obtained in this way is extremely resistant to rubbing, heat, migration, light and weathering.

Example 10

From 10 g of the pigment according to Example 1, 30 g of alumina hydrate and 60 g of one produced on a linseed oil stand oil base Printing varnish is used to produce a graphic printing ink on a three-roll mill.

The prints obtained therewith in the letterpress process are distinguished by a beautiful brown shade of excellent Lightfastness and very good fastness to solvents and varnishes.

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Example 11

A stabilized mixture of 65 g of an emulsion polyvinyl chloride with a K value of 72-74 ("Lonza GD ", Lonza AG, Basel), 32 g of dioctyl phthalate, 3 g of an epoxidized soybean oil as a plasticizer (" Advaplast 39 ", Ciba-Geigy AG, Basel), 1.5 g of a complex of fatty acid barium and cadmium salts, complexing agents and antioxidants as a stabilizer ("Advastab B C 26", CIBA-GEIGY AG, Basel), 0.5 g of a costabilizer based on organic phosphite compounds ("Advastab CH 300", Ciba-Geigy AG, Basel), 5 g of titanium dioxide ("Titanium dioxide KRONOS RN 56 ", Titangesellschaft GmbH, Leverkusen) and 0.5 g of the pigment according to Example 1 for 8 minutes at 160 ° on a mixing roller mill with a roller speed of 20:24 (friction 1: 1.2) and a roller spacing processed by 0.3 mm. The brown color of the soft polyvinyl chloride film obtained in this way is very good Migration, rubbing, heat and light fastness.

Example 12

A stoving enamel made of 20 g of titanium dioxide (e.g. "Titanium dioxide KRONOS RN 57" from Titangesellschaft GmbH, Leverkusen), 40 g of a 60% solution of a coconut alkyd resin (mixed polycondensate of coconut oil fatty acid, phthalic acid and Pentaerythritol) in xylene, 24 g "of a 50% solution of a Melamine resin (e.g. "Superbeckamin 852" from ReichhoId-Chemie, Hamburg) in butanol, 8 g of xylene, 7 g of ethylene glycol non-thy lather and 1 g of the pigment according to Example 1 is finely ground in a ball mill, on an aluminum foil sprayed on, left to dry and then baked for 30 minutes at 120 °. The brown color is very good

weatherproof, varnishproof and heatproof.

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Claims (10)

Claims Disazo pigment of the formula Cl O) -NHOC (D in its new β-modification, characterized by an X-ray diffraction diagram, which shows lines of very strong intensity on a lattice plane spacing of 3.30, 6.2 and 10.5 A, lines of strong intensity at 3.38, 3.45 and 3.67 Ά lines , at 3.16, 3.26, 4.14, 4.33, 4.78, 5.24 and 6.5 £ lines of medium intensity and at 3.22, 3.50 and 17.2 S lines of weak intensity having. 2. Process for the preparation of the new β-modification des Disazo pigments of the formula (I) by condensation of a carboxylic acid halide the formula Cl. (II) COHaI 909819/0799 78476S1 wherein Hal represents a halogen atom with 1,5-diaminonaphthalene in a molar ratio of 2: 1, characterized in that the undissolved 1,5-diaminonaphthalene optionally together with a catalytic amount of a tertiary amine, especially pyridine at room temperature of a suspension of the Acid chloride of the formula (II) was added in an inert organic solvent, and the mixture thus obtained was heated and the condensation is completed at an elevated temperature. 3. The method according to claim 2, characterized in that one is used as the inert organic solvent chlorinated benzene is used. 4. The method according to claim 3, characterized in that that one uses o-dichlorobenzene. 5. The method according to claim 2, characterized in that that the condensation is completed at temperatures between 100 and 180 ΐ. 6. Process for the preparation of the β-modification of the Disazo pigments of the formula (I) according to claim 1, characterized in that the α-modification of the pigment of formula (I) heated in an inert high-boiling organic solvent. 7. The method according to claim 6, characterized in that that an organic solvent boiling above 200 ° C. is used as the high-boiling organic solvent. 8. The method according to claim 7, characterized in that the organic solvent used is nitrobenzene used. 909819/0799 -JtS - 9. A method for pigmenting high molecular weight organic material, characterized by the use the β-modification of the disazo pigment of the formula (I). 10. Colored high molecular weight organic material containing the β-modification of the disazo pigment as pigment of formula (I). 9G 3819/0799