DE2739041A1 - PROCESS FOR PIGMENTING HIGH MOLECULAR ORGANIC MATERIAL - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann - Dr. R. Koenigsberger Dipl.-Phys. R. Holzbauer - Dipping. F. KUngseiden - Dr. F. Zumstein Jun.

TELEPHONE: SAMMELNR 22S341 β MÜNCHENS / JJU 4 I

TELEX S29979 BRÄUHAUSSTRASSE 4

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BANK ACCOUNT: BANKHAUS H AUFHÄUSER '

KTONR 397997. BLZ 70030600

Case 3-10685Λ

CIBA-GEIGT AG, CH-4002 Basel / Switzerland

Process for pigmenting high molecular weight organic material

j · It has been found that high molecular weight organic material produces excellent, true colorations If the pigments used are disazo compounds of the formula

OR
N = N-CHCOHN - / O} ~ NHCOCH-N = N

i Cl COCHo I COCHo Cl

used, where X is an H or chlorine atom, an alkyl or alkoxy group with 1-6 carbon atoms, a nitro or trifluorine ethyl group and R an alkyl group with 1-6 Means carbon atoms.

Those disazo compounds of the formula given in which R are ethyl groups and X are chlorine atoms are preferred mean.

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ORIGINAL INSPECTED

The disazo connection is of particular interest

the formula

COCH ₃

N = N-CHCONH

C ₂ H ₅

COCH.

NHCOCH-N = N

Cl

OC ₂ H ₅

Cl

In the disazo dyes to be used according to the invention are known compounds that are obtained by coupling the diazo compound of an amine of the formula

Cl.

NH,

with a bisacetoacetyl-phenylenediamine of the formula

OR CH ₃ COCH ₂ COl

NHCOCH ₂ COCh ₃

OR

obtained in a molar ratio of 2: 1.

As examples of the diazo components, there are the following Called diamines:

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2,3-dichloroaniline

2,4-dichloroaniline

2,5-dichloroaniline

2-methyl-3-chloroaniline 2-methyl-4-chloroaniline 2-methyl-5-chloroaniline 2-methyl-6-chloroaniline 3-methyl-2-chloroaniline 3-methyl-4-chloroaniline 3-methyl-5-chloroaniline 3-methyl-6-chloroaniline 4-Kethyl-2-chloroaniline 4-Methyl-3-chloroaniline 2-ethyl-5-chloroaniline 2-chloro-5-trifluoromethylaniline 2-chloro-4-nitroaniline

The coupling components are obtained by reaction

of a diamine of the formula

OR

where R has the meaning given, with diketene. The following diamines are examples:

2,5-diraethoxy-1,4-phenylenediamine 2,5-diethoxy-1,4-phenylenediamine 2,5-dipropoxy-1,4-phenylenediamine 2,5-diisopropoxy-1,4-phenylenediamine 2,5-dibutoxy-1,4-phenylenediamine 2,5-diisobutoxy-1,4-phenylenediamine 2,5-dipentoxy-1,4-phenylenediamine

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The coupling takes place preferably in a weakly acidic medium, expediently in the presence of customary agents which promote the coupling. Such dispersants may be mentioned in particular, for example aralkyl sulfonates such as dodecylbenzenesulfonate, or 1,1'-dinaphthylmethane-2,2 ^1- disulfonic acid or polycondensation products of alkylene oxides. The dispersion of the coupling component can also be advantageous

Protective colloids, for example methyl cellulose or smaller amounts of inert ones, which are sparingly soluble or insoluble in water contain organic solvents, for example optionally halogenated or nitrated aromatic hydrocarbons, such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene or nitrobenzene, as well as aliphatic halogenated hydrocarbons, such as carbon tetrachloride or trichlorethylene, furthermore water-miscible organic solvents such as acetone, Methyl ethyl ketone, methanol, ethanol or isopropanol.

The coupling can also advantageously be carried out in such a way that an acidic solution of the diazonium salt is used continuously combined with an alkaline solution of the coupling component in a mixing nozzle, with an immediate Coupling of the component takes place. Care must be taken, that diazo component and coupling component in squimolecular Quantities are present in the mixing nozzle, it proving to be advantageous, a small excess of the diazo component to use. The easiest way to do this is to control the pH of the liquid in the mixer nozzle. There is also a mixing nozzle in the mixing nozzle for a strong swirling of the to take care of both solutions. The resulting dye dispersion is withdrawn from the mixing nozzle and the dye is passed through Filtration separated.

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Finally, the coupling can also be carried out in such a way that the diazo component is mixed with the coupling component suspended in an organic solvent in a molar ratio of 2: 1 and with a diazotizing agent, in particular treated with an ester of nitric acid, such as methyl, ethyl, butyl, amyl or octyl nitrite.

The pigments obtained are usually already precipitated in the heat and can be filtered off and optionally can be isolated in pure form by washing with organic solvents.

The pigments obtained generally have a good texture and can mostly be used as raw products will. If necessary or desired, the raw products can be finely dispersed by grinding or kneading Form overpasses. It is useful to use grinding aids, such as inorganic and / or organic salts used in the presence or absence of organic solvents. To After grinding, auxiliaries are removed as usual, soluble inorganic salts e.g. with water and water-insoluble organic salts Auxiliaries, for example by steam distillation.

Boil also by treatment of the crude pigments with organic solvents, preferably such as about 10O ⁰ C, often can be an improvement of the properties he-.reicht. Benzenes substituted by halogen atoms, alkyl or nitro groups, such as xylenes, chlorobenzene, o-dichlorobenzene or nitrobenzene and pyridine bases such as pyridine, picoline or quinoline, and ketones such as cyclohexanone, ethers such as ethylene glycol monomethyl or monoethyl ether, amides, have proven particularly suitable. such as dimethylformamide or H-methyl-pyrrolidone, as well as dimethyl sulfoxide or water under pressure

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• ff '

The after-treatment is preferably carried out by heating the pigment in the solvent at 100 to 150 ⁰ C, in many cases a grain coarsening occurs, which affects gllnstig to light and migration fastness of the pigments obtained.

Synthetic resins such as cellulose ethers and esters, such as acetyl cellulose, nitrocellulose, and aminoplasts, in particular urea and melamine-formaldehyde resins, Alkyd resins, phenoplasts, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, Polyacrylonitrile, polyacrylic acid ester.

Of particular interest are paints, for example based on alkyd-melamine-formaldehyde, alkyd-urea-formaldehyde resins, as well as thermoplastic and thermosetting acrylic resins.

They are also according to the invention for printing inks to be used dyes of great interest.

The pigments to be used according to the invention have good dispersibility and thermal stability. The dyeings obtained are distinguished by good fastness to migration and exceptionally high fastness to light and weather. _x *

The disazo compounds to be used according to the invention are partly described in DT-PS 850-039. However, there is no indication of their use as pigments there.

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In CH-PS 557,407 similar disazo dyes are described which are used for pigmenting high molecular weight organic Material were used; however, the dyeings obtained therewith are less lightfast and weatherfast.

In the following examples, unless otherwise stated, parts are parts by weight and percentages Percentages by weight and temperatures are given in degrees Celsius.

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- a 11

For example

5.1 parts of 2,5-dichloroaniline are AO parts by volume Glacial acetic acid dissolved at room temperature. The brown solution is stirred with 8 parts by volume of concentrated hydrochloric acid, the resulting thick suspension (chlorohydrate) diluted with 16 parts of water, cooled to 5 °, during 15 minutes and at 5 ° with 8.3 parts by volume of AN sodium mitrite solution were added dropwise and the brown diazo solution obtained is clarified by filtration.

5.5 parts of 2,5-diethoxy-l, A-bisacetoacetylaminobenzene are then dissolved with 7.5 parts by volume of 30% sodium hydroxide solution in 60 parts v / water. The pale yellow solution is at 5 ° and the diazo solution is added dropwise over 15 minutes. An orange precipitate is formed. The received The suspension is brought to pH by the slow addition of 26 parts by volume of 30% strength aqueous sodium hydroxide solution set of 5. It is stirred for A hours at a temperature rising to 20 °, with AOO parts of water diluted, heated to 75 ° over the course of an hour and suction filtered while hot. The residue is washed free of salt and in vacuo dried at 60 °. 10. A parts, corresponding to 98% of theory, of a red powder of the formula are obtained

K = N

CH ₃ CO-CH-CONH

NHCO-CH-COCH,

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H 3 , 97 N 11 , 83 Cl 19th , 96% H 3 , 9 N 12th ,1 Cl 19th ,8th %

After treatment in N-methylpyrrolidone (1 hour at 162 °), with this pigment, rolled into polyvinyl chloride, true, orange colorations are obtained. Also polyester resins are colored with this pigment in pure and very real orange tones.

Analysis: Ber. C 50.72
Found C 50.5

The 2,5-diethoxy-1,4-bisacetoacetylaminobenzene can be used as follows getting produced:

9.8 parts of 2,5-diethoxy-1,4-phenylenediamine are heated to 40 ° in 100 parts by volume of glacial acetic acid. It arises a brown solution. 8.5 parts of diketene are added dropwise over 10 minutes. The temperature rises to 73 ° and it turns out a beige precipitate. The mixture is heated to 98 ° in 10 minutes and stirred at this temperature for 1 hour. lets cool to room temperature and sucks off the precipitate. The product is made with 40% acetic acid and then with washed in cold water. After drying, 14.9 parts (81% of theory) of a pale yellow powder with a melting point are obtained 214-216 °.

Analysis ; Calc .: C 59.33 H 6.64 N 7.69 % Found: C 59.2 H 6.6 N 7.7 X

The table below describes further pigments which are obtained by coupling in a molar ratio of 2: 1 of the diazotized bases the column I can be obtained with the bisacetoacetic arylides of the diamines of the column II. Column III gives the color the PVC film colored with 0.2% of these pigments.

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27390A1

E.g. I. II III 2 2-methyl-5-chloroaniline 2,5-dietoxy-1,4
pheny1end iamin yellow-orange 3 2,4-dichloroaniline Il brown orange 4th 2,6-dichloroaniline It yellow-orange 5 2-chloro-5-trifluoro-
methylaniline Il orange 6th 2-chloro-4-nitroaniline Il Brown 7th 2,5-dichloroaniline 2,5-dimethoxy
1,4-phenylenedi-
amine orange 8th 2-chloro-5-trifluoro-
methylaniline Il Il 9 2-methyl-3-chloroaniline Il Il 10 2-methyl-4-chloroaniline Il Il 11 2-methoxy-5-chloroaniline Il Il 12th 2-methyl-3-chloroaniline 2,5-DiSthoxy-1,4
phenylenediamine orange 13th 2-trifluoromethyl-4-
chloraniline Il It 14th 2-methoxy-5-chloroaniline Il It 15th 2,5-dichloroaniline 2,5-dipropoxy-1,4
phenylenediamine Il 16 2-methyl-5-chloroaniline Il yellow-orange 17th 2-chloro-5-trifluoro-
methylaniline H orange 18th 2-trifluoromethyl-4-
chloraniline It It L9 2,5-dichloroaniline 2,5-diisopropoxy
1,4-phenylenedi-
amine yellow 20th 2-methyl-5-chloroaniline Il green yellow 21 2-chloro-5-trifluoro-
methylaniline Il yellow η 2 -Tri fluorine thyl -4-
chloraniline It It 23 2,5-dichloroaniline 2,5-dibutoxy-1,4
phenylenediamine orange 809810/0 845

■ Ζ ¹ ·

Example 24

3.5 parts of 2,5-dichloroaniline and 3.6 parts of 2,5-diethoxy-l, 4-bis-acetoacetylamino-benzene are dissolved in 200 parts of ethylcellosolve and 20 parts of glacial acetic acid at 50 ⁰ C. After cooling to room temperature is allowed within 15 minutes, 2.5 part of tert-butyl nitrite in 100 parts of dichlorobenzene are added dropwise, the temperature rising to 40 ⁰ C and the pigment formation begins. The mixture is subsequently stirred for 2 hours at 40-50 ° C and 5 hours at 130-14O ⁰ C. The dye takes on a uniformly crystalline form. Under the microscope you can see orange crystalline aggregates with a length of 5-10 / 1. It is filtered at 140 ° C., washed with hot dichlorobenzene until the filtrate is colorless, then the dichlorobenzene is displaced by methanol and finally washed with hot water. After drying, 6 parts of an orange pigment are obtained.

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45 27390A1

Example 25

16.2 parts of 2,5-dichloro-aniline are dissolved in 50 parts by volume of glacial acetic acid at room temperature, 25 parts by volume of 30% hydrochloric acid are added, the mixture is stirred for 1 hour, cooled to 0-5 ° with ice and then mixed with 25% by volume Parts by volume of 4 / n sodium nitrite solution are added dropwise within 15 minutes. The diazo solution obtained is allowed to stir for 1 hour if the nitrite reaction is clearly positive. The diazo solution is then filtered clear and 3 parts of crystallized sodium acetate are added. 18.2 parts of 2,5-diaethoxy-1,4-bisacetoacetylaminobenzene are dissolved in 200 parts by volume of dimethylformamide at 120 °. The solution obtained is allowed to ^{cool to 70 p} and flow into the diazo solution so that the coupling temperature is a maximum of 20 ° (addition of ice). The pH value is approx. 2.0. This is now adjusted to 5.0 by adding 27 parts by volume of 30% strength sodium hydroxide solution, an orange pigment suspension being formed. The initially acidic reaction disappears by stirring the coupling suspension for 1-2 hours. The coupling compound is brought to the boiling point in a round bottom flask equipped with a stirrer, azeotrope separator (or descending cooler) and distillation is continued until the internal temperature is 105 °. (The pigment suspension is now quite viscous. 350 parts by volume of dimethylformamide are then added and the distillation continues until the internal temperature is 150 °. Stirring is then allowed to continue for 8 hours at 145-150 ° The temperature drops to 100 °, the pigment is filtered off, washed with hot dimethylformamide, then with hot water and dried in vacuo at 90-100 °.

20.4 parts of pigment are obtained in the form of an orange powder.

Rolled into polyvinyl chloride, this pigment gives real, orange colorations with excellent migration, light and and weather resistance.

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Example 26

0.2 g of the pigment prepared according to Example 1 and 100 g of polystyrene granulate are mixed and processed on the mixing mill at 130 ° until the color appears homogeneous. The mass is then chrome-plated between Panels pressed to form panels at 150 °. The orange color of the plates is lightfast. You can see the pigmentation in the extrusion press instead of on the mixing mill. It is also possible to use the homogeneously pigmented Granulate the mass and shape it in the injection molding machine.

Example 27

0.2 g of the pigment prepared according to Example 1, 1 g of titanium dioxide (rutile) and 100 g of polyethylene granules are used mixed in a drum and the mixture then processed on your mixing mill at 130 °. The mass gets hot pressed into sheets or shaped in an extrusion press. The plates show a beautiful orange hue of excellent Lightfastness.

Example 28

0.1 g of the pigment prepared according to Example 1, 0.5 g of titanium dioxide (rutile) and 100 g of polypropylene granules are mixed in a drum and the mixture

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then processed on the mixing mill at 130 ° until a homogeneously colored mixture is obtained. The crowd is pressed hot to form pelts of 1 millimeter. The pelts show a beautiful orange shade of good lightfastness.

Example 29

100 g of a powdery formaldehyde urea resin, which is suitable for molding compounds, 10 g of Lithopone and 1 g of the pigment prepared according to Example 1 are ground in a ball mill for 16 hours. After that, will the mass is pressed into molds at 140-160 °. The orange patterns have good light and heat resistance.

Example 30

24.5 g of an unesterified epoxy resin, 10.5 g of an oil-reactive alkylphenol resin, 35 g of xylene and 30 g Diacetone alcohol is processed into a lacquer and mixed with 4 g of the pigment prepared according to Example 1 in a ball mill Ground for 24 hours. After spraying onto aluminum foils and baking at 120 °, orange excesses of very good heat, varnish and light fastness.

Example 31 (acrylic resin stoving enamel)

4 parts of the finely divided pigment soaked Example 1 are stirred into 20 parts of solvent of the following composition: 50 parts of Solvesso 150 (mixture aromatic carbons), 15 parts of butyl acetate, 5 parts of Exkin II (leveling agent based on ketoxime), 25 parts of methyl

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Isobutyl ketone and 5 parts silicone oil (1% in Solvesso 150). After the complete fine distribution has been achieved (depending on according to the stirrer in approx. 15-60 minutes), the binders added, namely 48.3 parts of Baycryl L 530 (acrylic resin) (51% in xylene / butanol 3: 1) and 23.7 parts of Maprenal TTX (Melamine resin) (55% in butanol). After a short period of homogenization, the paint is applied using customary methods such as spraying and dipping or specifically for the continuous coating of metal sheets in the "coil coating" process and applied burned in (burn-in 30 min., 130 °). The orange paintwork obtained is characterized by very good flow, high gloss and excellent fine distribution of the pigment, as well as excellent weather resistance.

Example 32

4 g of the according to Example 1

obtained pigment, 35 g of a 60% solution of a urea-formaldehyde-modified alkyd resin in xylene-butanol 1: 1, 10 g turpentine oil and 5 g xylene are ground in a ball mill for 48 hours. After spraying the resulting colored lacquer onto an aluminum foil and baking it at 120 °, an orange coating of very good fastness to light, heat and varnish is obtained.

Example 33

80 g of an unsaturated, liquid polyester resin, 19.72 g of monostyrene and 0.28 g of a cobalt siccative containing 16% cobalt are mixed with 1 g of the pigment prepared according to Example 1 and 5 g of titanium dioxide (rutile) for 48 hours

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ground in a ball mill. Just before using this Lacquer is a mixture consisting of 4.15 g cumene hydroperoxide (70%), 2.52 g ethyl acetate and 13.33 g butyl acetate admitted. After peeling off this mixture on cardboard and drying in the air, you get an orange-colored Coating very good fastness to light, heat and varnish.

Example 34

67 g polyvinyl chloride powder (suspension polymer), 33 g of dioctyl phthalate, 2 g of dibutyltin dilaurate, 0.3 g of a phosphate-based stabilizer and 0.7 g of that according to the example 1 produced pigment are mixed and processed on the 160 ° hot mixing roll mill for 15 minutes. A sheet 0.4 mm thick is then produced on the calender. It is in a pure orange Colored shade. The coloring is heat-resistant and migration-fast. "·

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Claims (15)

Claims 1. A method for pigmenting high molecular weight organic material, characterized in that as Pigment is a disazo compound of the formula OR v ^ ¹ used, in which X is an H or chlorine atom, an alkyl or alkoxy group with 1-6 C atoms, a nitro or trifluoromethyl group and R is an alkyl group with 1-6 carbon atoms. 2. The method according to claim 1, characterized in that a disazo compound of the formula given is used wherein R is an ethyl group. 3. Process according to Claims 1 and 2, characterized in that a disazo compound of the specified Formula used in which X is a chlorine atom. 4. The method according to claim 1, characterized in »that one is a disazo compound of the formula COCH, I. N CHCONH COCH ₃ NHCOCH-N = N 809810/0845 ORIGINAL INSPECTED used in which X is a chlorine atom or a methyl group and R is an alkyl group having 1-3 C atoms. 5. The method according to claim 4, characterized in that that one has the disazo compound 'of the formula ei 9 ^c ? ^H s cocH, Ir ⁵ cocH-, N = N-CHCONH- <O) - NHCOCH-N = N Cl Cl OC ₂ H ₅ Cl used. 6. The method according to claim 1, characterized in that that you have a disazo compound of the formula Cl COCH ₃ N = N-CHCONH COCH ₃
NHCOCH-N = N used, where R is an alkyl group with 1-3 C atoms. 7. The method according to claim 1, characterized in that disazo compounds of the formula given are used which have been post-treated with organic solvents. 809810/0845 8. The method according to claim 7, characterized in that that the aftertreatment takes place at temperatures between 100-150 ° C. 9. The method according to claim 1, characterized in that the high molecular weight material is a plastic. 10. The method according to claim 1, characterized in that that the high molecular weight material is a lacquer. 11. The method according to claim 1, characterized in that the high molecular weight material is a printing ink. 12. High molecular weight organic material containing a disazo pigment of the formula given in claim 1. 13. Plastics containing a disazo pigment of the formula given in claim 1. 14. Paints containing a disazo pigment of the formula given in claim 1. 15. Printing inks containing a disazo pigment im
Claim 1 given formula. 809810/0845