DE1544578B1 - Monoazo pigments, processes for their production and their use - Google Patents

Description

The present invention relates to new monoazo pigments, a process for their preparation and their Use for pigmenting organic materials.

It has been found that a valuable monoazo pigment can be obtained by using the diazonium compound des4-chloro-3-aminobenzoic acid-2 ', 5-dichlorophenylamide with 2-hydroxynaphthalene-3-carboxylic acid phenylamide or 2-hydroxy-naphthalene-3-carboxylic acid (4'-methoxyphenyl) amide to give a compound of the following Formula couples

Cl Cl CONH

Cl

NH - CO

Cl

in which X denotes a hydrogen atom or the methoxy group, and optionally this compound by treatment with an organic compound that is liquid at the working temperature as a solvent at a temperature between 75 and 230 ° C, if necessary under pressure, in a particularly valuable physical Form transferred.

The 4-chloro-3-aminobenzoic acid-2 ', 5'-dichlorophenylamide used as a diazo component according to the invention is obtained by reacting 3-nitro-4-chloro-benzoyl chloride with 2,5-dichloroaniline according to methods known per se and subsequent reduction the nitro to the amino group. The diazotization of this amino compound is expedient in a mixture of glacial acetic acid and hydrochloric acid or in concentrated sulfuric acid.

The coupling of the diazonium compound of 4 - chloro - 3 - aminobenzoic acid - 2 ', 5' - dichlorophenylamide with the 2-hydroxynaphthalene-3-carboxylic acid phenylamides is usually carried out in an aqueous, preferably acidic solution, expediently at an elevated temperature, in particular at 30 to 80 ⁰ C, and optionally in the presence of an inert organic solvent and / or dispersant. Suitable organic solvents are e.g. B. the water-miscible, such as lower alcohols, z. B. methanol, ethanol, ethylene glycol monomethyl or ethyl ether, lower ketones such as acetone, or tertiary nitrogen bases such as pyridine or dimethylformamide, and also certain water-immiscible, such as optionally halogenated or nitrated hydrocarbons, z. B. toluene, xylene, chlorobenzene or nitrobenzene; Suitable dispersants are, for example, products of the action of a multiple stoichiometric amount of alkylene oxide, especially ethylene oxide, on fatty alcohols, phenols or fatty acids, or condensation products of naphthalenesulfonic acids with formaldehyde.

The new monoazo pigments precipitate out of the reaction mixture immediately after coupling. They can be processed into dry powders in the usual way, ie by filtering, washing and drying. They can be used even as a crude product for certain purposes where no particularly high requirements are placed on fastness properties - with the exception of light fastness. However, their special physical form, which is obtained by treating the crude product with an organic compound that is liquid at the working temperature as a solvent, at a temperature between 75 and 230 ^° C., preferably between 110 and 170 ^° C., is particularly valuable. Suitable solvents here are, for example, aromatic mononuclear or polynuclear hydrocarbons such as benzene, toluene, xylenes, diphenyl or naphthalene, methylnaphthalenes or tetrahydronaphthalene, or hydroaromatic hydrocarbons such as decahydronaphthalene, halogenated hydrocarbons, namely those of the aliphatic series such as carbon tetrachloride or carbon tetrachloride. or the aromatic series, such as chlorobenzene, 1,2-dichlorobenzene, trichlorobenzenes, chlorotoluenes or 1- or 2-chloronaphthalene, aromatic nitrohydrocarbons such as nitrobenzene, aromatic amines such as aniline, toluidines, xylidines, diphenylamine, Ν, Ν-dimethyl or N, N-diethylaniline, or heterocyclic amines, such as pyridine, isoquinoline, quinoline or morpholine, organic hydroxyl compounds, for example diols, such as ethylene glycol, diethylene glycol or 1,4-butanediol, their monoethers, for example ethylene glycol monomethyl or ethyl ether and their monoesters, e.g. Ethylene glycol monoacetate, or phenols, such as phenol o the o-, m- or p-cresol, also aromatic ethers, e.g. B. diphenyl ethers, aliphatic ketones whose alkyl radicals together have at least 5 carbon atoms, such as methyl isobutyl ketone, or amides of organic carboxylic acids, especially amides of lower fatty acids, such as formamide or dimethylformamide. Mixtures of such organic compounds can of course also be used. Preferred solvents are aromatic hydrocarbons such as toluene, xylenes, aromatic halogenated hydrocarbons, for example 1,2-dichlorobenzene and trichlorobenzenes, aromatic nitro hydrocarbons such as nitrobenzene, aromatic amines such as N, N-dimethylaniline and Ν, Ν-diethylaniline, or lower fatty acid amides z. B. dimethylformamide.

In this refined form, the new pigments have a higher opacity and stand out due to even better lightfastness, very good fastness to overcoating in stoving enamels, good fastness to migration in plasticized polyvinyl chloride, Rubbing fastness, heat fastness and fastness to many common organic solvents and water out.

To a similarly valuable physical modification of the new monoazo be obtained if the water-containing crude pigment in one of the above, at least 75 ° C, preferably boiling at at least 100 ⁰ C, is liquid at working temperature door and opposite the pigment and water chemically inert organic compound as Solvent heated at least until the water distills off from the aqueous pigment

BAO ORH3INAL

3 4

is, then the heating in the organic Pigments according to the invention stand out against-

Solvents under temperature increase up to highly comparable, from the French

at least. 230 ° C continued for a while and patent specification 1,328,646, example 4, and the German

finally the pigment from organic liquid patent specification 850 034, 4th table example, known filtered off. The advantage of this finishing method 5 pigments is characterized by better lightfastness.

Compared to the previously discussed consists in the way- Further details are from the following

case of drying the crude pigment. Examples can be seen. In this, parts mean, provided

The heating of the water-containing crude pigment is not otherwise expressly noted, parts by weight,

it is preferably carried out at a rate of 6 to 100 times. The temperatures are given in degrees Celsius. Amount (based on the weight of the anhydrous 10 parts by weight are related to parts by volume as

Pigments) of organic liquid compound. Gram to cubic centimeter. Here, the water is distilled with the organic

Solvent off. The organic liquid in the De-. -I ₁

Stillat is advantageously separated mechanically or, if it is necessary in Example 1, by fractional distillation of 6.31 parts of 4-chloro-3-aminobenzoic acid-2 ', 5'-di-

Water and leads it to the refining mixture chlorphenylamide are concentrated in 50 parts by volume.

again to. trated sulfuric acid dissolved at 22 to 24 °, whereupon

After all the water has been distilled off, the solution is heated to 10.4 parts by volume of a sulfuric acid

the pigment dispersion for a while in the nitrosylsulfuric acid mixture, which is 2.54 parts

organic liquid, preferably _{containing a further 20 HSO 4} NO, is added with stirring. After a

Temperature increase, in particular to 110 to 170 ⁰ C, the mixture in 1000 parts of water, the hour

if necessary under pressure. It is advisable to use 1 part of the product from 20 to 22 equivalents

the organic liquid, with which ethylene oxide contains octadecyl alcohol, is

the water is removed from the raw pigment beforehand, the temperature being increased to 50 °,

Has. 25 Adds to the diazonium compound thus prepared

The monoazo pigments according to the invention are a 90 ° hot solution of 5.42 parts while stirring

expedient for pigmenting organic oils with 2-hydroxynaphthalene-3-carboxylic acid phenylamide

Materials suitable: e.g. in printing inks for the gra- in 200 parts of water, 30 parts by volume of 2N sodium hydroxide solution

phical trades, in paints on oily base and 0.5 parts of Turkish red oil flow and increase

As in linseed oil paints, or on an aqueous base, the temperature rises to 70 ° in an hour. If the

situation, as in emulsion paints, in varnishes. Coupling has ended, the precipitate is

Those of the kind, such as nitro or stoving, washed neutral, vacuumed well, dried

paint. They can also be used for spin dyeing and pulverized.

of viscose or cellulose acetate, for pigmentation. The bright scarlet colored, very lightfast

of plastics, such as polyethylene, polystyrene, 35 pigment is used for certain purposes, where not particularly

Polyvinyl chloride, which the latter also plasticizers have high demands on fastness,

may contain, of cellulose esters, of curable z. B. for many graphic printing inks, well suited.

Resins or for pigmenting rubber as well as its special physi-

for the pulp coloring, for the production of kaiische form, which can be obtained by treating the

Laminate paper, for coating and padding 40 holding raw pigment with organic solution

for textiles and for pigmenting artificial leather at a higher temperature. To this

and use for pigment printing on textiles. The purpose is 6 parts of crude pigment in 150 parts by volume

The monoazo pigments according to the invention of the 1,2-dichlorobenzene slurried and given with stirring formula, in particular their valuable physical, heated to 143 to 145 ° for one hour. According to the Kaiische form, these materials produce pure, bright yellowish-tinged red pigmentations when the pigment is cooled to 50 °. Washed against with 1,2-dichlorobenzene, dried at 65 ° above previously known dyes with a similar constitution and pulverized. The scarlet pigment according to the invention has a greater covering power because of the fact that it has the much sought-after, brilliant color than the crude pigment and is characterized by an even scarlet or red hue with noticeably better light fastness, very good fastness to overcoat Fastness properties, especially high light in stoving enamels, good migration fastness in soft fastness, good to very good migration fastness in macher-containing polyvinyl chloride, thanks to good rubbing structures made from plasticized polyvinyl chloride, 'fastness, heat fastness and fastness to many excellent overcoating, rubbing and dry cleaning customary organic solvents and fastness to washing and good heat resistance.
unite. You also get the particularly valuable physical

What is particularly surprising is the fact that the pigment is in the kaiische form when the aqueous

these valuable properties in the coupling product of the raw pigment with 20 times the amount

product of diazotized 4-chloro-3-aminobenzoic acid-1,2-dichlorobenzene (based on the weight of the

2 ', 5'-dichlorophenylamide with an anhydrous pigment according to the invention) slowly while stirring

usable 2-hydroxy-naphthalene-3-carboxylic acid- 145 ° heated, water and organic solution

phenylamide occur, while previously known pigments can be distilled off, the latter is separated off and lukewarm

menie, which by coupling the same diazo compound returns to the pigment suspension. the

nente with 2-hydroxynaphthalene -3 -carboxylic acid- further processing of the pigment refined in this way

(2'-methyl-4'-chlorophenylamide) or with 2-hydroxy-65 happens as indicated in the previous paragraph.

naphthalene-3-carboxylic acid- (2'-naphthylamide) receives- With similar success, instead of 1,2-di-

Lich are, one or the other authenticity or chlorobenzene also nitrobenzene, 1-chloronaphthalene

lack the yellowish-red, pure shade. or Ν, Ν-dimethylaniline can be used.

BATH ORIGINAL

B ei s ρ i e 1 2

From 6.31 parts of 4-chloro-3-aminobenzoic acid-2 ', 5'-dichlorophenylamide a diazonium compound is prepared exactly as described in Example 1. To this end, a 90 ° hot solution of 6.04 parts of 2-hydroxynaphthalene-3-carboxylic acid (4'-methoxyphenyl) amide is left with stirring in 200 parts of water, 30 parts by volume of 2N sodium hydroxide solution and 0.5 parts of Turkish red oil flow in and increase the temperature to 70 ° in one hour. After the coupling is complete, this will be precipitated pigment is filtered off, washed neutral with water, filtered off with suction, dried at 65 ° and pulverized. Then you take it in 30 times the amount of 1,2-dichlorobenzene, based on the weight of the anhydrous azo pigment, and the mixture is heated with stirring for one hour 143 to 145 °. After cooling to 50 °, the pigment is filtered off, washed with 1,2-dichlorobenzene, dried at 65 ° and pulverized. The yellow-tinged red pigment produced in this way is suitable, for example for pigmenting graphic printing inks or stoving enamels, where its excellent lightfastness is noticeable. It is also very resistant to overpainting and heat and in many common uses practically insoluble in organic solvents.

Claims (4)

Patent claims: 1. Monoazo pigments of the formula Cl wherein X represents a hydrogen atom or the methoxy group. 2. Process for the preparation of monoazo pigments according to claim 1, characterized in that the diazonium compound of 4-chloro-3-aminobenzoic acid-2 ', 5 ^/ -dichlorophenylamide with 2-hydroxy-naphthalene-3-carboxylic acid phenylamide or 2-hydroxy-naphthalene -3-carboxylic acid- (4'-methoxyphenyl) -amide couples to a compound of the formula, NH - CO HO CONH- wherein X denotes a hydrogen atom or the methoxy group, and optionally this compound by treating with an organic compound that is liquid at the working temperature as Solvent at a temperature between 75 and 230 °, in a particularly valuable physical Form transferred. 3. The method according to claim 2, characterized in that the aftertreatment of the obtained monoazo pigments at a temperature between 110 and 170 °. 4. Use of the monoazo pigments of claim 1 for pigmenting organic Materials.