DE1104688B - The coloring of plastic masses with pigment dyes - Google Patents

Description

GERMAN

It has been found that the perylene derivatives of the formula

(I)

wherein χ is hydrogen, chlorine, nitro, methyl, phenylamino, phenylazo or together with y a chain —CH ₂ —CH ₂ —CH ₂ —CH ₂ -, together with χ a chain —CH ₂ --- CH ₂ —CH ₂ - CH ₂ - ■ or y, if χ is methyl, hydrogen or methyl, if χ is hydrogen, hydrogen or together with ζ a chain —CH ₂ —CH ₂ —CH ₂ —CH ₂ - and, if χ is chlorine, Nitro, phenylamino or phenylazo, only hydrogen, and z, if χ is hydrogen, hydrogen or together with y a chain -CH ₂ -CH ₂ -CH ₂ -CH ₂ - and, if χ has another meaning, only hydrogen means, after being converted into finely divided form as pigments, very suitable for coloring paints, printing inks, plastics and polyester melts intended for spinning in the mass.

The materials dyed in this way have good lightfastness and good wetfastness. The dyes have some particularly interesting properties: ζ. Β. good fastness to overcoating in lacquers, good over-the-dyeing of plastic masses
with pigment dyes

Applicant:
Sandoz AG, Basel (Switzerland)

Representative: Dr. W. Schalk, Dipl.-Ing. P. Wirth,

Dipl.-Ing. G. E. M. Dannenberg

and Dr. V. Schmied-Kowarzik, patent attorneys,

Frankfurt / M., Große Eschenheimer Str. 39

Claimed priority;
Switzerland from December 24, 1957

Dr. Georg Geiger, Binningen (Switzerland),
has been named as the inventor

printing fastness in printing inks and high heat resistance in plastics in general, especially in polyester melts. In addition, the majority of these dyes have very good fastness to migration in polyvinyl chloride.
The pigment dyes of the formula (I) are prepared by heating perylene-S. ^ Q.lO-tetracarboxylic acid or its anhydride with the corresponding amines, e.g. B. according to German patent specification 386 057, optionally in the presence of solvents or diluents and possibly of reaction accelerators such as zinc chloride (see US Pat. No. 271S127) or in an aqueous medium (see US Pat. No. 2,543,747).

The dyes are brought into fine form before they are used, for example by reprecipitation from sulfuric acid or by grinding with grinding aids.

The following table lists some perylene derivatives which are suitable for dyeing in the mass are. They correspond to the formula (I) and are through the phenyl nucleus

109 540/430

as well as characterized by the hue of their coloring in polyvinyl chloride.

Pigment- Phenyl nucleus Phenyl hue dye 4-methylphenyl the coloring
in polyvinyl No. 4-chlorophenyl chloride 1 2,3-tetramethylene phenyl Red 2 3,4-tetramethylene phenyl Red 3 4-nitrophenyl Red 4th 4-phenylaminophenyl Red 5 4-phenylazo-phenyl Red 6th 3,4-dimethylphenyl Bordo 7th Bordo 8th Brownish red 9 Red

In the examples below, the parts are parts by weight, the percentages are percentages by weight and the temperatures are given in degrees Celsius.

example 1 Example 2

0.05 part of pigment no. 3 in the table is sealed with 100 parts of polystyrene granules Vessel shaken vigorously for 10 minutes. The mixture is on a rolling mill, one of which is on a roller 120 ° and the other roller is heated to 150 °, rolled, until the dye is homogeneously distributed. The colored mass is put on after cooling in a suitable mill a grain size of about 2 to 4 mm broken and then in an injection molding device at 160 to 240 ° injected any moldings. Red-colored compacts of good lightfastness are obtained.

Example 3 Example 4

30 parts of pigment No. 2 in the table are mixed with 5000 parts of terephthalic acid polyester fiber and fused in the usual way under a nitrogen atmosphere at about 285 °. After spinning the viscous mass obtained in this way becomes red-colored fibers with good light, peroxide bleach, Obtain blind vat and wet fastness properties, which are optionally stretched and / or puckered and shrink-set will.

Example 5

1 part of pigment No. 4 in the table and 5 parts Alumina hydrate are pasted on a three-roll mill with so much linseed oil varnish that a printing ink of the desired type Consistency arises. The printing ink produced in this way gives good red-colored prints on paper

ao light and overprint fastness.

Example 6

0.1 part of pigment no. 1 of the table is wetted with 1 part of dioctyl phthalate and with the Spatula pasted. To this end, 100 parts of a previously prepared mixture of 60 parts of polyvinyl chloride, 40 Share dioctyl phthalate and the usual stabilizers. The whole mixture is on one for 10 minutes Rolling mill gelatinized at 140 to 150 °. The mass obtained is placed in a press between polished plates pressed about 140 ° to form a film. A red-colored film of excellent lightfastness is obtained in this way.

When storing such a film between two white polyvinyl chloride films containing dioctyl phthalate, in which the ratio of polyvinyl chloride to dioctyl phthalate is 70:30, for 72 hours at 70 ° there is no migration of the dye into the white film.

100 parts of a commercially available nitro lacquer are colored with 2 parts of pigment no. 2 of the table. The lacquer gives red-colored spray and dip dyeings of excellent lightfastness and fastness to overcoating.

Example 7

1 part of the pigment dye no. 1 of the table, is dissolved in 10 to 20 parts of sulfuric acid of a concentration of 90 to 100 ° / _0, optionally with heating and then precipitated with vigorous stirring in 100 parts of water. The suspension obtained is filtered off, washed neutral with water and dried. The dye is obtained in a fine form, which in many cases is better or more quickly distributed in the media to be colored.

Example 8

1 part of pigment no.3 of the table is mixed with 10 parts of a solid grinding aid, such as common salt, Potassium chloride, calcium chloride or carbonate, urea, phthalic acid or similar in a ball mill for so long ground until the crystals of the red dye have essentially disappeared. The grist is then with water, with the addition of the necessary amounts of hydrochloric acid or sodium hydroxide solution, if an acid-soluble or alkali-soluble one Grinding aid was used, stirred and filtered and washed out of the grinding aid freed. The dye is obtained in a fine form, which in many cases is better or faster in the Media to be colored distributed.

0.05 parts of the pigment dye no. 9 of Table shaken vigorously with 100 parts polyethylene granulate in a ver _r closed vessel for 10 minutes. The mixture is rolled on a rolling mill, the rollers of which are heated to 120 or 150 °, until the dye is homogeneously distributed in the polyethylene. After cooling, the colored mass is broken in a suitable mill to a grain size of approximately 2 to 4 mm and then in the usual way, e.g. B. in an injection molding machine, processed into any desired moldings. Red-colored compacts with good fastness properties are obtained.

Example 9

0.1 part of pigment no. 7 of the table is wetted with 1 part of dioctyl phthalate and with the Pasted spatula To do this, mix 100 parts of a previously prepared mixture of 60 parts of polyvinyl chloride, 40 Share dioctyl phthalate and the usual stabilizers. The whole mixture is on one for 10 minutes Rolling mill gelatinized at 140 to 150 °. The mass obtained is placed in a press between polished plates pressed about 140 ° to form a film. A border-colored film with excellent light and light properties is obtained in this way Migration authenticity.

Claims (1)

Claim: Use of finely divided perylene pellets of the formula (I) wherein χ is hydrogen, chlorine, nitro, methyl, phenylamino, phenylazo, or together with y a chain —CH ₂ —CH ₂ —CH ₂ —CH ₂ - ■, together with χ a chain —CH ₂ —CH ₂ —CH ₂ - CH ₂ - or y, if χ is methyl, hydrogen or methyl, if χ is hydrogen, hydrogen or together with ζ a chain —CH ₂ —CH ₂ —CH ₂ —CH ₂ - · and, if χ is chlorine, Nitro, phenylamino or phenylazo, only hydrogen, and z, if χ is hydrogen, hydrogen or together with y a chain —CH ₂ —CH ₈ —CH ₂ —CH ₂ - · and, if χ has another meaning, only Hydrogen means as a pigment for plastic masses. Considered publications:
U.S. Patent No. 2,543,747. © 109 54Q / 430 4.61