CH623069A5 - Process for pigmenting high molecular-weight organic material - Google Patents

Description

623 069

2nd

PATENT CLAIMS 1. Process for pigmenting high molecular weight organic material, characterized in that a pigment is a disazo compound of the formula

ORCI coch3 J

N = N - Ìhc OHN— (Q

OR

COCH3 HCOCH -N = N '

used, wherein X is an H or chlorine atom, an alkyl or alkoxy group with 1-6 C atoms or a nitro or trifluoromethyl group and R is an alkyl group with 1-6 C atoms.

2. The method according to claim 1, characterized in that one uses a disazo compound of the formula given, wherein R represents an ethyl group.

3. The method according to claims 1 and 2, characterized

15 characterized in that one uses a disazo compound of the formula given, wherein X represents a chlorine atom.

4. The method according to claim 1, characterized in that the disazo compound of the formula

Cl OC0Hc

/ coch3 5

O / -N = N -CHCONH—

Cl

COCH3 NHCOCH-N = N

OC2H5

used.

5. The method according to claim 1, characterized in that disazo compounds of the formula given are used which have been aftertreated with organic solvents.

6. The method according to claims 1 and 5, characterized in that the after-treatment was carried out at temperatures between 100 and 150 ° C.

7. The method according to claim 1, characterized in that the high molecular material is a plastic.

8. The method according to claim 1, characterized in that the high molecular material is that of a lacquer.

9. The method according to claim 1, characterized in that the high molecular material is that of a printing ink.

10. Product of the method according to claim 1.

30th

40

45

It has been found that excellent coloring is obtained in high molecular weight organic material if disazo compounds according to claim 1 are used as pigments.

The disazo dyes to be used according to the invention are known compounds which are obtained by coupling the diazo compound of an amine of the formula

Cl

■ NEL

55

with a bisacetoacetyl-phenylenediamine of the formula

OR

ch3coch2cohn-Y0Y-nhcoch2coch3

OR

can be obtained in a molar ratio of 2: 1.

The pigments obtained generally have a good texture and can mostly be used as raw products. If necessary or desired, the raw products can be converted into a finely dispersed form by grinding or kneading. It is useful to use grinding aids such as inorganic and / or organic salts in the presence or absence of organic solvents. After grinding, auxiliary agents are removed as usual, soluble inorganic salts e.g. with water and water-insoluble organic auxiliaries, for example by steam distillation.

The properties can often also be improved by treating the crude pigments with organic solvents, preferably those which boil above 100 ° C. Particularly suitable have been found to be benzenes substituted by halogen atoms, alkyl or nitro groups, such as xylenes, chlorobenzene, o-dichlorobenzene or nitrobenzene, and pyridine bases, such as pyridine, picoline or quinoline, and also ketones, such as cyclohexanone, ether, such as ethylene glycol monomethyl or monoethyl ether, amides such as dimethylformamide or N-methyl-pyrrolidone, and dimethyl sulfoxide or water under pressure.

The aftertreatment is preferably carried out by heating the pigment in the solvent to from 100 to 150 ° C., in many cases coarsening of the grain occurring, which has a favorable effect on the light and migration fastness of the pigments obtained.

Synthetic resins are preferably mentioned as high molecular weight organic material, e.g. Cellulose ethers and esters, such as acetyl cellulose, nitrocellulose, also aminoplasts, in particular urea and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters.

Of particular interest are coatings, for example based on alkyd-melamine-formaldehyde, alkyd-urea-formaldehyde resins, and thermoplastic and thermosetting acrylic resins.

The dyes to be used according to the invention are also of great interest for printing inks.

3rd

623 069

The pigments to be used according to the invention have good dispersibility and thermal stability. The dyeings obtained are characterized by good fastness to migration and exceptionally high light and weather fastness.

In CH-PS 557 407 similar disazo dyes are described which have been used for pigmenting high molecular weight organic material; however, the dyeings thus obtained are less fast to light and weather.

Unless otherwise stated, the parts in the examples below mean parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

example 1

5.1 parts of 2,5-dichloroaniline are dissolved in 40 parts by volume of glacial acetic acid at room temperature. The brown solution is stirred with 8 parts by volume of concentrated hydrochloric acid, the resulting thick suspension (chlorohydrate) diluted with 16 parts of water, cooled to 5 °, for 15 minutes and at 5 ° with 8.3 parts by volume of 4N sodium nitrite solution added dropwise and the brown diazo solution obtained was filtered clear.

5

5.5 parts of 2,5-diethoxy-1,4-bis-acetoacetylaminobenzene are then dissolved in 7.5 parts by volume of 30% sodium hydroxide solution in 60 parts of water. The pale yellow solution is added dropwise to the diazo solution at 5 ° and in 15 minutes. An orange precipitate is formed. The suspension obtained is adjusted to a pH of 5 by slowly adding 26 parts by volume of 30% strength aqueous sodium hydroxide solution. It is stirred for 4 hours at a temperature rising to 20 °, diluted with 400 parts of water, heated to 75 ° in the course of 15 hours and suction filtered under hot conditions. The residue is washed free of salt and dried in vacuo at 60 °. 10.4 parts, corresponding to 98% of theory, of a red powder of the formula are obtained

H = nh (0

ch3co-ch-conh

OC2H5

After-treatment in N-methylpyrrolidone (1 hour at 162 °) gives this pigment, rolled in polyvinyl chloride, real, orange colorations. Polyester resins are also colored with this pigment in pure and very real orange tones.

The table below describes further pigments which are obtained by coupling in a molar ratio of 2: 1 of the diazotized bases of the collones I with the bisacetoaceticarylides of the diamines of the column II. Column III indicates the color of the PVC film colored with 0.2% of these pigments. Ex. I «m

35

2 2-methyl-5-chloroaniline

3 2,4-dichloroaniline

4 2,6-dichloroaniline

5 2-chloro-5-trifluoromethylaniline

6 2-chloro-4-nitro-aniline

7 2,5-dichloroaniline

2,5-diethoxy-1,4-

phenylenediamine do.

do.

do.

do.

yellow orange brown orange yellow orange orange brown

2,5-dimethoxy-orange

1,4-phenylenedi-

amine

8th

2-chloro-5-trifluoro

do.

do.

methylaniline

9

2-methyl-3-chloro-aniline do.

do.

10th

2-methyl-4-chloro-aniline do.

do.

11

2-methoxy-5-chloro-aniline do.

do.

45

Example 12

67 g of polyvinyl chloride powder (suspension polymer), 33 g of dioctyl phthalate, 2 g of dibutyltin dilaurate, 0.3 g of a phosphate-based stabilizer and 0.7 g of the pigment prepared according to Example 1 are mixed and processed on the 160 ° hot mixing mill for 15 minutes. A film with a thickness of 0.4 mm is then produced on the calender. It is colored in a pure orange shade. The coloring is heat-resistant and migration-resistant.

Example 13

0.2 g of the pigment prepared according to Example 1 and 100 g of polystyrene granules are mixed and processed on the mixing roll mill at 130 ° until the color appears homogeneous. The mass is then pressed between chrome-plated plates at 150 ° to plates. The orange color of the plates is lightfast. The pigmentation can also be carried out in the extrusion press instead of on the mixing mill. It is also possible to granulate the homogeneously pigmented mass and to deform it in the injection molding machine.

50

Example 14

0.2 g of the pigment produced according to Example 1, 1 g of titanium dioxide (rutile) and 100 g of polyethylene granules are mixed in a 55 drum and the mixture is then processed on the mixing roll mill at 130 °. The mass is hot pressed into sheets or shaped in the extrusion press. The plates show a beautiful orange color with excellent lightfastness.

60

Example 15

0.1 g of the pigment produced according to Example 1, 0.5 g of titanium dioxide (rutile) and 100 g of polypropylene granules are mixed in a drum and the mixture is then processed on the mixing roller mill at 130 ° until a homogeneously colored mixture is obtained. The mass is hot pressed into skins of 1 millimeter. The skins show a nice orange shade of good light fastness.

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Example 16

100 g of a powdered formaldehyde-urea resin which is suitable for molding compounds, 10 g of lithopone and 1 g of the pigment prepared according to Example 1 are ground in a ball mill for 16 hours. The mass is then pressed into molds at 1.4-160 °. The orange patterns have good light and heat resistance.

Example 17

24.5 g of an unesterified epoxy resin, 10.5 g of an oil-active alkylphenol resin, 35 g of xylene and 30 g of diacetone alcohol are processed to a lacquer and ground with 4 g of the pigment prepared according to Example 1 in a ball mill for 24 hours. After spraying on aluminum foils and baking at 120 °, orange coatings of very good heat, overcoating and light fastness are obtained.

Example 18 (acrylic enamel)

4 parts of the finely divided pigment according to Example 1 are stirred into 20 parts of solvent of the following composition: 50 parts of Solvesso 150 (mixture of aromatic carbons), 15 parts of butyl acetate, 5 parts of Exkin II (leveling agent based on ketoxime), 25 parts of methyl isobutyl ketone and 5 Parts of silicone oil (1% in Solvesso 150). After the complete fine distribution is reached (depending on the type of stirrer in about 15-60 minutes), the binders are added, namely 48.3 parts BaycrylL 530 (acrylic resin) (51% in xylene / butanol 3: 1) and 23.7 Parts of Maprenal TTX (melamine resin) (55% in butanol). After a short period of homogenization, the paint is applied in the usual way

Methods such as spraying and dipping or specially for the continuous coating of metal sheets are applied and baked in the “coil coating” process (baking in 30 minutes, 130 °). The orange varnishes obtained are characterized by a very good flow, high gloss and excellent fine distribution of the pigment, as well as excellent weather fastness.

Example 19

4 g of the pigment obtained according to Example 1, 35 g of a 60% strength solution of an alkyd resin modified with urea-formaldehyde in xylene-butanol 1: 1, 10 g of turpentine oil and 5 g of xylene are ground in a ball mill for 48 hours. After spraying the resulting, colored varnish on an aluminum foil and baking at 120 °, an orange coating of very good light, heat and overlap resistance is obtained.

Example 20

20 80 g of an unsaturated, liquid polyester resin, 19.72 g of monostyrene and 0.28 g of a cobalt siccative, which contains 16% cobalt, are mixed with 1 g of the pigment prepared according to Example 1 and 5 g of titanium dioxide (rutile) for 48 hours ground in a ball mill. Shortly before using this lacquer 25, a mixture consisting of 4.15 g of cumene hydroperoxide (70%), 2.52 g of ethyl acetate and 13.33 g of butyl acetate is added. After peeling off this mixture on cardboard and drying in the air, an orange-colored coating is obtained with very good fastness to light, heat and overcoating.

C.