DE2201242C3 - Monoazo pigments, processes for their production and their use - Google Patents

Description

couples, where R ¹ , R ² , R ³ , R ⁴ and η have the meanings given in claim ί

3. The use of the monoazo pigments according to claim 1 for coloring plastics Lacquers or printing inks.

m of R ^{1 is} hydrogen, methyl, methoxy, chlorine, cyano or methylsulfonyl, R ^{2 is} hydrogen, methyl, chlorine or methoxy, R ^{3 is} hydrogen, methyl, chlorine, bromine or methoxy, R ^{4 is} hydrogen, methyl, chlorine or methoxy and η 1 , Is 2 or 3.

2. A process for making monoazo pigments according to claim 1, characterized in that one

50 The invention relates to monoazo pigments of the formula I

a) a carboxylic acid halide of the general
formula O
π Ij H
O Λ Yy KJ Λ V I.
N N

R ¹
CONH -f I

R ² NHCO

COX

in which R ^{1 is} hydrogen, methyl, methoxy, chlorine, cyano in which X is chlorine or bromine, with an amine 55 or methylsulfonyl, R ^{2 is} hydrogen, methyl, chlorine

the general formula

NHCO

condensed or

or methoxy, R ³ hydrogen, methyl. Chlorine, bromine or methoxy, R ^{4 is} hydrogen, methyl, chlorine or methoxy and π is 1, 2 or 3, as well as the production of these monoazo pigments and their use. Furthermore, compounds are preferred which contain the halogens mentioned.

Compared to the closest comparable from the USA patents 30 79 376 and 33 31 832 known dyes have the dyes according to the invention Advantages in lightfastness and, in some cases, weatherfastness in the paint.

For the preparation of the dyes according to the invention one can

a carboxylic acid halide of the general formula U

(U)

COX

in which X is chlorine or bromine, with an amine of the general formula III

condense or

b) the diazonium compound of 1-aminoanthraquinone with a coupling component of general formula IV

OH

CONH

(IV)

J - ί /
R ² NHCO- <f Λ

TV (Cl) _n

couple, in which formulas R ¹ , R ² , R ³ , R ⁴ and η have the meanings given above.

The azo dye acids on which the azo carboxylic acid halides II are based are produced per se conventional manner by coupling the diazonium salt of 1-aminoanthraquinone with /> '- oxynaphthoic acid here.

The azo dye-carboxylic acids obtained in this way are transferred one into the corresponding acid halides 11 (chlorides or bromides) by treatment with phosphorus halides, such as phosphorus penic chloride or phosphorus pentabromide, phosphorus trichloride, phosphorus oxychloride or, preferably, thionyl chloride.

The reaction is expediently chlorinated in inert solvents such as nitrobenzene Benzenes, toluene, xylenes, dimethylformamide or N-methylpyrrolidone, carried out with an additive catalytic amounts of dimethylformamide or pyridine can be advantageous.

The condensation of the azocarboxylic acid halides »I with the amines III is advantageous in the anhydrous Medium, e.g. by heating the components in organic solvents such as nitrobenzene, o-dichlorobenzene, Trichlorobenzene, methyl benzoate, xylene, dimethylformamide, N-methylpyrrolidone, etc. carried out, with expediently an acidic

binding agent, such as sodium acetate or pyridine, or catalytic amounts of a compound that contains the Accelerated acylation reaction, such as collidine, dimethylformamide etc., can be added. An expedient embodiment of the condensation exists

z. B. in that the amines 111 before their addition in a just sufficient amount of solvent, preferably N-methylpyrrolidone or dimethylformamide, dissolves and to the submitted azocarboxylic acid halides II admits.

According to the second embodiment, the pigments I according to the invention are obtained if one diazotized 1-Aminoauthraquinone with the coupling components of the general formula IV on per se known way united.

The coupling components of the formula IV are obtained, for example, by condensation of 2-hydroxynaphthalene-3-carboxylic acid with an amine of the formula III in the presence of a chlorinating agent such as PCl ₃ .

The coupling is expediently carried out by combining the aqueous alkaline solution of the Coupling component IV (or a very finely divided suspension of coupling component IV in Water) optionally with the addition of an organic solvent with the acidic solution of the diazotized 1-Aminoanthraquinones made. A pH range of 4 to 7, which can be advantageously achieved by adding a Buffers, e.g. B. sodium acetate, and the addition of wetting or dispersing agents, for example Aralkyl sulfonates, facilitate the smooth course of the reaction.

The pigment dyes according to the invention are in this way in a very pure chemical state, but occasionally not in the optimal physical form for all purposes.

won. They can then be brought into the form adapted to the particular purpose by the usual measures, such as comminution, salt grinding or recrystallization.
The new pigments can be used for the dyeing of spinning pulp, for example viscose, for the production of colored printing pastes for letterpress or offset printing, for the production of colored varnishes, e.g. B. of nitrocellulose lacquers, acrylate lacquers, melamine resin lacquers or alkyd resins, for coloring Phe-

SS nol pastes or aminoplasts, from thermoplastics such as polystyrene, polyolefins or PVC, from rubber or silicone resins, used for dyeing laminate papers or sheets and for textile printing will.

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

Example 1

211 parts of the diazotized by coupling 1-Aminoanthraquinone with 2-hydroxy-naphthoic acid c-3 obtained dye with 950 parts

Nitrobenzene, 89 parts of thionyl chloride and 3 parts of dimethylformamide with stirring at 80 ° for 2 hours and then heated to 110 ° for 3 hours.

After the reaction mixture has cooled down, the uniformly crystalline azo dye monocarboxylic acid chloride becomes isolated by suction, with 500 parts of nitrobenzene, then 200 parts of benzene and finally 400 parts of cyclohexane washed. Obtained after drying at 80 ° under reduced pressure one pound 95 parts of a red crystal powder.

Analysis:

Calculated ... Cl 8.05%;
found Cl 8.1%.

15.8 parts of finely powdered amine of the formula

NHCO

'5

20th

are heated to 80 ° in 480 parts of nitrobenzene. 22.0 parts of the azo dye carboxylic acid chloride prepared as described above and 0.5 part of dimethylformamide are added. The mixture is then heated to 140 ° for 5 hours while stirring.
After cooling to 80 °, the sparingly soluble pigment which has precipitated is filtered off with suction, washed with a little nitrobenzene and then with methanol until the filtrate runs off clear. To obtain a water-moist paste, washing is also carried out with water.

To improve the pigment, it can (as a methanol-moist product) in methanol for a further 2 hours or another solvent or stirred out at room temperature.

After drying at 80 ° under reduced pressure, 32 parts of a red powder are obtained, which in is practically insoluble in the usual solvents.

Analysis:

Calculated ... N 7.8%;
found N 7.9%.

PVC foils and lacquers are characterized by brilliant red tones of the pigment and excellent light, Colored fastness to migration and varnishing.

Particularly noteworthy is the excellent coloration that can be achieved even with deep (full tone) colors Brilliance.

With the components of the table below one obtains further monoazo pigments if one 1 mol of the diazo compound of the amine mentioned in column 1 with 1 mol of 2-hydroxynaphthoic acid- (3) coupled, the resulting monoazo dye carboxylic acid converted into the acid halide and with 1 mol of des condensed in column II mentioned amine.

Column III designates the hue of a paint coating produced with the pigments obtained.

example I. © O
Il Y
H ₂ N 2 the same Y
O 3

111

the same

the same

bluish red

bluish red

bluish red

bluish tinge

the same

H, N Cl

NHCO- <O

Cl

bluish red

the same

H ₂ N- <O V-NHCO- <O V-Cl

bluestichiöroi

continuation

iispicl I

Η, Ν Ο

the same

the same

the same

the same

the same

the same

the same

the same

Cl Cl

Cl

H ₂ N-

Η, Ν-

Cl Cl

O> -NHCO- <O
Cl

Ci

• / o ^ -NHCO

Cl

Cl

NHCO ^^ C?)
Cl

Η, Ν

Cl
θ) - NHCO

Cl

Cl

CH ₃

H ₂ N

NHCO

Cl

CH ₃

NHCO

. α

H ₂ N

Η, Ν

Η, Ν— <O> —NHC0- < O λ-Cl red

Continuation of example I.

H ₁ N

the same

the same

the same

the same

the same

the same

the same

the same

the same

CN

πι

K O VCl red

CN

H ₂ N- / cT> - NHCO - / ÖV

Cl

CN

Cl

Cl

CN

Cl

Cl

OCH ₃

H ₂ N- / O

Cl

OCH,

Cl

NHCO

H ₂ N NHCO

ν /

Cl

Cl

Red

Red

Red

Brown

Brown

Red

yellowish red

Red

Red

continuation

example

30th

31

32

33

34

35

36

11th

the same

the same

the same

the same

viesgl.

the same

the same

the same

12th

Cl

H, N NHCO

Cl

H ₂ N

H, N

OCH ₃
NHCO

OCH ₃
NHCO

Cl

Cl

Cl

H ₃ C

H ₂ N NHCO

H ₃ C

H ₂ N

CH ₃

yellowish red

Red

Red

Red

Red

Red

Red

Red

Red

Red

Continued example

39

40 41 42

43 44

13th

O NH ₂

the same

O NH ₂

the same

the same

the same

the same

14th

NHCO-χΟ> - Cl

I o

Cl

CH ₃

Cl

NHCO

Cl

Cl

NHCO

Cl

H ₇ N

OCH ₃

NHCO - ^ > —Q \

Cl

CH ₃
NHCO

H, N

Cl

H ₂ N

NHCO-

Cl
NHCO-

-Cl

H ₁ N

Cl

CH ₃

II

Red

bluish red

bluish red

bluish red

bluish red

bluish red

bluish red

Red

use

Example 45
In paints

5 parts of the dye obtained according to Example 1 and 95 parts of stoving enamel mixture (e.g. 70% coconut alkyd resin, 60% in xylene and 30% melamine resin, about 55% in butanol / xylene) are rubbed in an atiritor. After application and a stoving time of 30 minutes at 120 °, brilliant full-tone finishes with very good lightfastness and fastness to overcoating are obtained. When adding z. B. TiO ₂ brilliant white highlights are achieved.

Example 46
In plastics

Strong, lightfast, but above all brilliant colors in soft PVC are obtained if, for example 0.05 part of that obtained in Example 1

Pigment in 50 parts of a soft PVC mixture, consisting of 65 parts of PVC powder, 35 parts of plasticizer and 2 parts of stabilizer, incorporated will. The coloring takes place on a heatable mixing roller mill at 140 ° within 8 to 10 mins.

_{Correspondingly, white blends can be achieved if, for example, 2.5 parts of TiO 2 are} admixed to 0.25 part of the dye obtained according to Example 1 and 50 parts of soft PVC mixture.

Example 47
In printing inks

5 parts of the dye obtained according to Example 1, 30 to 40 parts of resin (e.g. with phenol formaldehyde modified rosin resin) and 65 to 55 parts of toluene are intimately in a dispersing unit mixed. In this way, a toluene gravure printing ink of excellent lightfastness and excellent quality is obtained Brilliance.

609 620/203

Claims (1)

Patent claims:
1. Monoazo pigments of the general formula R ¹ CONH fll R ² NHCO b) the diazonium compound of 1-amino anthraquinone with a coupling component nent of the general formula