DE3712946A1 - Monoazo pigments - Google Patents

Abstract

Laked azopigments of the formula I <IMAGE> in which R1 and R2 independently of one another are hydrogen, halogen, C1-4-alkyl, C1-4-alkoxy or nitro, R3 is hydrogen or halogen, R4 is halogen and Me is a divalent metal, are extremely well-suited for dyeing plastics compositions. <IMAGE>

Description

It was found that the lacquered azo pigments of the formula I

wherein
R ₁ and R ₂ independently of one another are hydrogen, halogen, C _1-4 -alkyl, C _1-4 -alkoxy or nitro,
R _{3 is} hydrogen or halogen,
R ₄ halogen and
Me mean a divalent metal
excellent for coloring plastic materials and varnishes.

In preferred compounds of formula I mean
R ₁ and R ₂ independently of one another are hydrogen, chlorine, bromine, methyl, methoxy, ethoxy or nitro,
R ₃ and R _{4 are} chlorine or bromine, preferably chlorine and
Me Co, Ca, Sr, Ba, Mg or Mn.

In particularly preferred pigments of the formula I mean
R ₁ and R ₂ independently of one another are hydrogen, chlorine, methyl, methoxy or nitro, especially hydrogen,
R ₃ and R ₄ chlorine and
Me cobalt or manganese.

In preferred dyes of the formula I, the SO ₃ ^- group is bonded in the ortho or para position to the azo group.

The production of the new pigments is characterized in that to produce an azo compound of the formula II

with the salt of a divalent metal, preferably a Co, Ca, Sr, Ba, Mg or Mn salt, lacquered.

The compounds of formula II are from known starting compounds by diazotization and coupling, in analogy to known methods, easy to manufacture. The reaction of a compound of formula II with the salt of a divalent metal is preferably found in aqueous Solution or suspension, at temperatures between 60 and 90 ° C, in particular 75 to 85 ° C instead.

The pigments of the formula I according to the invention are particularly suitable for coloring plastic masses or varnishes, including solvent-free and solvent-based masses of plastics or Synthetic resins can be understood (in paints on oily or watery Basis, in varnishes of various types, for spin dyeing viscose or cellulose acetate, for pigmenting polyethylene, polystyrene, Polyvinyl chloride, rubber and synthetic leather). You can also in Printing inks for the graphic industry, for pulp dyeing, for coating textiles or for pigment printing Find.

The dyeings obtained are distinguished by their excellent Fastness to heat, light and weather, chemical resistance, their migration, Efflorescence, overcoating and solvent fastness, their color strength and the very good application properties, e.g. B. fastness to flocculation, Fastness to crystallization and fastness to dispersion.

In the following examples, parts are by weight and Percentages by weight. The temperatures are given in degrees Celsius. A part by volume corresponds to the volume of a part by weight Water.

example 1

24.2 parts of 4-amino-2,5-dichlorobenzenesulfonic acid are at 20 to 22 ° Stirred for 1 hour in 30 parts of water and 30 parts by volume of hydrochloric acid, the temperature is then reduced to 0 to 5 ° by external cooling, adds 7.1 parts of sodium nitrite dissolved in 21 over 15 minutes Add water, keeping the temperature at 0 to 5 °. Man stir for an hour at about 5 ° and then destroy the excess Sodium nitrite with 0.2 parts of aminosulfonic acid.

20.4 parts of 1-phenylpyrazolone-3-carboxylic acid in 100 parts of water of 50 ° and 4.0 parts of sodium hydroxide dissolved by very slow addition to a mixture of 10 parts by volume of glacial acetic acid, 40 parts Sodium acetate, 150 parts water and 150 parts ice again (to one fine suspension) precipitated and the whole, with cooling to 0 to 5 °, slowly mixed with the suspension of the diazonium salt. The resulting one orange suspension is still 4 hours at 0 to 5 ° and stirred for a further 2 hours at room temperature.

One adds the azo dye suspension very slowly, with stirring Solution of 15.8 parts of manganese sulfate in 100 parts of water, heated to approx. 80 °, stir for 2 hours at 80 to 85 °, filter hot and wash the pigment with hot water until the filtrate runs free of chloride. The press cake obtained is dried and ground.

Instead of the manganese sulfate solution, the equivalent amount can also be used Magnesium, calcium, strontium or barium chloride for lacquering used, the pigments thus obtained are in their properties very similar to the manganese complex.  

The following Table 1 shows further dyes according to the invention, which were produced analogously to the first example. The The coupling component is always 1-phenylpyrazolone-3-carboxylic acid. All dyes from Table 1 and Table 2 are incorporated into PVC a yellow shade.

Table 1

In the following Table 2 with other according to the Example 1 producible dyes are the substituents Formula I specified.

Table 2

Application example 1

0.05 part of the dye according to Example 1 (Mn salt) is mixed with 50 Share a mixture of 65% polyvinyl chloride and 35% diethylhexyl phthalate and 2 parts hexyl dibutyltin bis-thioglycolate homogenized in a mixing mill at 150 to 160 ° for about 8 minutes rolled on a skin and smoothed on a calender mill. The received transparent yellow fur is characterized by a very good Lightfastness.

Example of use 2

4 parts of the manganese complex pigment according to Example 1 are mixed with 96 parts of a mixture
50 parts of a 60% solution of coconut aldehyde melamine resin with 32% fat content in xylene,
30 parts of a 50% melamine resin solution in butanol,
10 parts of xylene and
10 parts of ethylene glycol monoethyl ether
Milled in a ball mill for 24 hours. The dispersion obtained is sprayed onto aluminum sheet, left to air dry for 30 minutes and then baked at 120 ° for 30 minutes. You get a brilliant yellow film with excellent light and weather fastness.

According to the two application examples, all the others can also be used in the Examples 1 to 21 specified pigments can be used.

Claims (5)

1. Laked azo pigments of the formula I wherein
R ₁ and R ₂ independently of one another are hydrogen, halogen, C _1-4 -alkyl, C _1-4 -alkoxy or nitro,
R _{3 is} hydrogen or halogen,
R ₄ halogen and
Me mean a divalent metal. 2. Laked azo pigments of formula I according to claim 1,
wherein
R ₁ and R ₂ independently of one another are hydrogen, chlorine, bromine, methyl, methoxy, ethoxy or nitro
R ₃ and R _{4 are} chlorine or bromine, preferably chlorine and
Me mean Co, Ca, Sr, Ba, Mg or Mn. 3. Laked azo pigments of the formula I according to claim 1
wherein
R ₁ and R ₂ independently of one another are hydrogen, chlorine, methyl, methoxy or nitro, preferably hydrogen,
R ₃ and R ₄ chlorine and
Me mean Co or Mn. 4. A process for the preparation of compounds of formula I according to claim 1, characterized in that an azo compound of formula II lacquered with the salt of a divalent metal, preferably a Co, Ca, Sr, Ba, Mg or Mn salt. 5. Use of the compounds of formula I as pigments for coloring of plastic masses.