DE2335121C3 - Monoazo pigments, process for their production and their use for pigmenting high molecular weight organic material - Google Patents

Description

C-N

N
H

wherein R _{1 is} a halogen atom, an alkyl or alkoxy group containing 1 to 4 carbon atoms, R _{2 is} a Η atom, an alkyl group containing 1 to 4 carbon atoms, or a phenyl group, X is an —NH or —CH ₂ O group , Y denotes an O or S atom or an imino group and Z denotes an O atom or an imino group.

2. Process for the preparation of Monoazopi lines of the formula

CO-NH

N = N-CH

C = Y

N
H

R ₁

C-N

! I I

ZR ₂

wherein R _{1 is} a halogen atom, an alkyl or alkoxy group containing 1 to 4 carbon atoms, R _{2 is} an H atom, an alkyl group containing 1 to 4 carbon atoms or a phenyl group, X dnc -NH- or -CH ₂ O- group , Y denotes an O or S atom or an imino group and Z denotes an O atom or an imino group, characterized in that a diazo or diazoamino compound of an amine of the formula

O = C

NH ₂

with a coupling component of the formula
CONH

/
CH,

C = Y

C-N

where R is a halogen atom, an alkyl or alkoxy group containing I to 4 carbon atoms, R _{1 is} a Η atom, an alkyl group containing I to 4 "carbon atoms, or a phenyl group, X is -NH- or - CH ₂ O group, Y is an O or S atom or an imino group and Z is an O atom or an imino group if one is a diazo or diazoumino compound of an amine of the formula

O = C

NH ₂

with a coupling component of the formula

CONH

CH ₂

C = Y

C-N

ZR ₂

clutch.

Since the dyes according to the invention

pigments are water-solubilizing groups, especially acidic water-solubilizing groups Groups such as sulfonic acid or carboxylic acid groups are of course excluded.

Dyes of the formula are of particular interest

CO-NH

N = N-CH CO

CO-NH

in which R ₁ and X have the meanings given, and in particular those of the formula

CO-NH

ZR ₂

clutch.

3. Process for pigmenting high molecular weight organic material, characterized through the use of the dyes according to claim 1.

O = C

N = N-CH

CO

CONH

in which R _{1 has} the meaning given, but is preferably an alkyl or alkoxy group containing from 1 to 4 carbon atoms.

The diazo component!) Is preferably used Amino-imidazolone of the formula

O = C

NH,

where Ri has the meaning given, preferably but an alkyl or alkoxy group. containing 1 to 4 carbon atoms.

The following diazo components are examples! called:

S-amino ^ -chloro-benzimidazolone, S-amino-o-bromo-benzimidazolon, 5-amino-6-methy) -benzimidazo! On,

S-amino-o-methoxy-benzimidazolone, - °

S-amino-o-ethoxy-benzimidazolone, S-amino-o-propoxy-benzimidazolone, S-amino-o-n-butoxy-benzimidazolone, 7-amino-6-chlorophenmorpholone- (3), 7-amino-6-methyl-phenmorpholone- (3), 7-Amino-6-methoxy-phenmorpholone- (3), 7-amino-6-ethoxy-phenmorpholone- (3).

These diazo components are known compounds.

Barbituric acid may be mentioned in particular as a coupling component; there are also theirs functional derivatives into consideration, for example N-methyl-, N-ethyl- or N-phenylbarbituric acid as well their thio and imino derivatives of the formulas

H, C

H ₂ C

CONH

CONH

CONH

CONH
CONH

C = S

C = NH

45

H ₂ C

C = NH

C NH

NH

55

These barbituric acid derivatives are known compounds.

The coupling expediently takes place by gradually adding the aqueous alkaline solution of the coupling component instead of the acidic solution of the diazonium salt. The coupling is expediently carried out at a pH of 4 to 6.

The pH is advantageously adjusted by adding a buffer. As a buffer z. B. the salts. especially alkali salts of formic acid, phosphoric acid or especially acetic acid. The alkaline solution of the coupling component expediently contains a wetting agent, dispersing agent or emulsifying agent, for example an aralkyl sulfonate, such as dodecylbenzenesulfonate or the sodium salt of IJ'-Naphlhylmelhansulfonsäure, polycondensation products of alkylene oxides, such as the action product of ethylene oxide of sulforicinoleates, for example n-butyl sulforicinoleate. The dispersion of the coupling component can also advantageously contain protective colloids, for example methyl cellulose or smaller amounts of inert organic solvents which are sparingly soluble or insoluble in water, for example optionally halogenated or nitrated aromatic hydrocarbons, such as benzene or toluene. Xylene, chlorobenzene, dichlorobenzene or nitrobenzene, and aliphatic ^ halogenated hydrocarbons, such as. B. carbon tetrachloride or trichlorethylene, also water-miscible organic solvents such as acetone, methyl ethyl ketone, methanol, ethanol or isopropanol. especially dimethylformamide.

Thanks to their insolubility, the pigments obtained can be filtered off from the reaction mixtures to be isolated. It proves to be advantageous, the pigments obtained with a preferably over 100 C boiling organic solvent to be aftertreated. Turn out to be particularly suitable benzenes substituted by halogen atoms, alkyl or nitro groups, such as xylenes, chlorobenzene, o-dichlorobenzene or nitrobenzene and pyridine bases. like pyridine. Picoline or quinoline, and also ketones, such as Cyclohexanone, ethers such as ethylene glycol monomethyl or monoethyl ether, amides such as dimethylformamide or N-methyl-pyrrolidone as well as sulfolane or dimethyl sulfoxide.

The aftertreatment is preferably carried out by heating the pigment in the solvent to 100 to 250 C, whereby in many cases a grain coarsening occurs, which has a positive effect on the lightfastness and migration fastness of the pigments obtained.

The coupling can also be carried out advantageously in such a way that an acidic solution of the Diazonium salt with an alkaline solution of the coupling component in a mixing nozzle continuously combined, with an immediate coupling of the components takes place. The resulting dye dispersion is continuously withdrawn from the mixing nozzle and the dye is separated off by filtration.

The corresponding diazoamino compounds can also be used instead of the diazonium salts. This is obtained by a known process by coupling an aryldiazonium salt with a primary one or preferably with a secondary amine. A wide variety are suitable for this purpose Amines, for example aliphatic amines, such as methylamine, ethylamine, ethanolamine, propylamine, Butylamine, hexylamine and especially dimethylamine. Diethylamine, diethanolamine, methylethanolamine. Dipropylamine or dibutylamine, aminoacetic acid, methylaminoacetic acid, butylaminoacetic acid, Aminoethanesulfonic acid, methylaminoethanesulfonic acid, guanylethanesulfonic acid, / Ϊ-aminoethylsulfuric acid, alicyclic amines such as cyclohexyiamine, N-methylcyclohexylamine, dicyclohexylamine, aromatic Amines, such as 4-aminobenzoic acid, sulfanilic acid, 4-sulfo - 2 - aminobenzoic acid, (4 - sulfophenyl) -guanidine, 4-N-methylaminobenzoic acid, 4-ethylaminobenzoic acid, I-aminonaphthalene-4-sulfonic acid, l-aminonaphthalene-2,4-disulfonic acid, heterocyclic

Amines such as piperidine, morpholine. Pyrrolidine. Dihy - '.' Roindole and finally also sodium cyanamide or dicyandiamide.

Usually the obtained are diazoamino compounds Slightly soluble in cold water and can optionally be in crystallized form after salting out are separated from the reaction medium. In many cases, the moist press cake for the further implementation can be used. In individual cases it can prove useful to use the diazoamides prior to the implementation to be dewatered by vacuum drying.

The coupling of the diazoamino compound with the coupling component takes place in an organic Solvents, for example chlorobenzene, o-dichlorobenzene, nitrobenzene, pyridine, ethylene glycol, ethylene glycol monoethyl or monomethyl ether. Dimethylformamide, formic acid or acetic acid. Using of solvents that are miscible with water, it is not necessary to use the diazoamino compounds to be used in anhydrous form. For example, the aqueous moist filter cake can be used will.

The coupling is expediently carried out in the heat, preferably at temperatures between 80 and 180 C. carried out in acidic medium and is generally very rapid and complete. If you use neutral solvents, so the addition of an acid, for example hydrogen chloride, sulfuric acid, formic acid or acetic acid is advantageous. Thanks to their insolubility, the pigments obtained can look the reaction mixture can be isolated by filtering off. Post-treatment with organic solvents as is necessary for pigments that are obtained by the aqueous coupling route, is therefore unnecessary in most cases.

Finally, the coupling can also be carried out in such a way that the amine to be diazotized with the Coupling component suspended in a molar ratio of 1: 1 in an organic solvent and with a diazotizing agent, especially an ester of nitrous acid, such as methyl, ethyl, Treated butyl, amyl or octyl nitrite.

The new dyes are valuable pigments which, in finely divided form, are used for pigmentation of high molecular weight organic material can be used, e.g. B. Cellulose and esters, such as ethyl cellulose, nitrocellulose, cellulose acetate, cellulose butyrate, natural resins or Synthetic resins such as polymerization resins or condensation resins, e.g. B. aminoplasts, in particular Urea and melamine formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters. Polyamides, Polyurethanes or polyesters, rubber. Casein, silicone and silicone resins, individually or in mixtures.

It does not matter whether the mentioned high molecular weight compounds are considered plastic masses. Melts or in the form of spinning solutions. Varnishes, paints or printing inks are present. Depending on Intended use proves to be advantageous, the new pigments as toners or in the form of preparations to use.

Compared to the dyes described in the examples of DT-OS 15 44 394, which have no substituents in the benzene-1 of the benzimidazolone other than the azo group, the invention p "pmcmc show a clearly bosseie Lich.ech.hei, 1 it _bcsscre accuracy.

IJZl Ä £ enoen examples mean the parts. Unless otherwise stated, parts by weight, percentages percentages by weight, and percentages are given in degrees.

example 1

• cn parts S-amino-o-ethoxy-benzimidazolone advertising ■ '· <u \ Vnliimtcilcn ice with 2.5 volumes of KaSäuÄzl and 2.5 volume 4 diazotized n-Namnitrillösung. The clear D.azo solution a ·, thin stream slowly to a solution of TSt i? En Bubhuric acid in ICO parts by volume Dime _h ; Fön amid, to which 1.5 parts of anhydrous Nari m · cetat are added, poured in. The mixture is stirred for 6 hours at normal temperature and then the pigment formed is washed off and washed with water and methanol. 3.2 parts of pigment are obtained ₁ -nuten in 75 parts by volume of N-methylpyrrolidone to the Sen. After repeated isolation and drying, you get 2.8 parts of the fragment of the formula

as a light red, soft powder. The pigment colors polyvinyl chloride In a very strong, yellow-red shade of excellent light and light fastness.

Examples 2 to 4

The following list includes other pigments which can be obtained in the given route. column S the diazo base coupled with barbituric acid will. The column II gives the nut to the P, gmenl obtained shade in polyvinyl chloride.

example 1
No.

I!

Orange Orange Red

2 5-amino-6-methyl-benzimidazolone

3 7-Amino-6-methyl-phenmorpholone- (3)

4 S-amino-6-methoxy-benzimidazoion

5 7-Amino-6-chlorophenmorpholone Orange

In the following table further pigments are described, which according to the method of the example can be obtained. Column I is the diazo base, column II is the coupling component and column III the shade obtained with the pigment in polyvinyl chloride.

example 5-amino Il III No. 6-ethoxy-benz- 6th imidazolone 2-imino-barbi- Red 5-amino turic acid c 6-methoxy- -I
I. benzimidazolone 2-imino-barbi- Yellowbrown 5-amino turic acid c 6-methyl-benz- 8th imidazolone 2-imino-barbi- Brown 7-amino turic acid 6-methyl-phen- 9 morpholone- (3) 2-lmino-barbi- GcIb 5-amino turic acid 6-chloro-benz- 10 imidazolone 2-lmino-barbi- orange 5-amino turic acid 6-ethoxy-benz- 11th imidazolone 2,4-diimino Gray- 7-amino barbituric acid violet 6-methyl-phen- 12th morpholone- (3) 2,4-diimino Red 5-amino barbituric acid c 6-methoxy-benz- 13th imidazolone 2,4-diimino Bordo 5-amino barbituric acid c 6-methyl-benz- 14th imidazolone 2,4-diimino Brown 5-amino barbituric acid c 6-chloro-benz- 15th imidazolone 2,4-diimino ocher 5-amino barbituric acid yellow 6-methoxy-benz- 16 imidazolone 2-thio-barbitur- violet 5-amino acid c 6-methyl-bcnz- 17th imidazolone 2-thio-barbitur- Blue red 5-ainino- acid 6-ethoxy-bcnz- IR imidazolone 2-thio-barbiUir- Blue red acid c

Example I.

No.

19 5-amino

6-chloro-benzimidazolone

20 7-A min o-

6-methyl-phen-

morpholone- (3)

21 5-Amino-6-methyl-benzimidazolone

22 7-amino

6-methoxy-phenmorpholone- (3)

2-thio-barbituric acid

1-phenyl-barbituric acid c

1-phenyl-barbituric acid c

in

Yellow Red

yellow

Red orange

Barbituric acid blue red

Example 23

• 65 parts of stabilized polyvinyl chloride, 35 parts of dioctyl phthalate and 0.2 parts of the dye obtained according to Example 1 are stirred together and then back on a two-roll calender for 7 minutes at 14O ⁰ C and hergewalzt. A yellow-red colored film of very good fastness to light and migration is obtained.

Example 24

1.00 g of the pigment obtained according to Example 9 is mixed with 4.00 g of the printing varnish of the composition

29.4% linseed oil stand oil (300 poise),
67.2% linseed oil stand oil (20 poise),

2.1% cobalt octoate (8% Co) and

1.3% lead octoate (24% 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 ² on art paper. A strong, pure yellow shade with good transparency and good gloss is obtained. In three- or four-color printing, very brilliant green tones can be produced 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.

Claims (1)

Patent claims:
1. Monoazo pigments of the sleeves CO-NH It has been found that valuable monoazo pigments can be obtained the formula O ■ - C = N-CH
\ C = Y