CH618209A5 - Process for the preparation of novel dyestuffs of the perylene-3,4,9,10-dicarboximide series - Google Patents

Description

The invention relates to a process for the preparation of new dyes of the perylene-3,4,9,10-tetracarboxylic acid diimide series and their use for dyeing varnishes, resins, printing inks, printing pastes and plastics in bulk.

Perylene tetracarboxylic acid diimides are known from the following publications: DE-ASn 1569 615.1 720 618 and 1916 169; DE-PS1130 099; CH-PS 372163; U.S. Patent Nos. 2,794,805 and 3554776.

The new dyes have the formula I.

Z-:

N-Z

in which Z stands for -CH2-CH2-OR or -CH2-CH2-CH2-OR, R for alkyl with 1 to 8 C atoms, X for chlorine or bromine and n for a number between 0 and 3 and the radicals R can be the same or different. They are obtained by condensation of the corresponding perylene-3,4,9,10-tetracarboxylic acid or of its dianhydride with primary aliphatic amines in the heat, if ether amines of the formula are used as primary amines

Z-NHz or mixtures of these amines are used, where Z has the meaning given above. The dyes are distinguished by very good fastness properties.

For R as alkyl in particular z. For example: methyl, ethyl, n-propyl, iso-propyl, butyl, iso-butyl, 2-butyl, pentyl, hexyl, octyl, 2-ethylhexyl. Lower alkyl radicals having 1 to 4 carbon atoms are preferably suitable as alkyl radicals for R. Of the alkyl radicals mentioned, n-butyl, isobutyl, 2-butyl, n-propyl, isopropyl and especially methyl or ethyl are preferred for reasons of color and application technology. The radicals R can be the same or different.

The perylene radical can carry 1 to 3 chlorine or bromine atoms, preferably n = 0.

The condensation of the perylene tetracarboxylic acid or of its dianhydride with the aliphatic ether amines is conveniently carried out in inert solvents or diluents such as alcohols, for. B. isobutanol or 2-ethylhexanol, glycols, in a large excess of the primary amines in question, which serve as solvents, or preferably in water at higher temperatures such as 80 to 200 ° C, preferably at 130 to 180 ° C, optionally under pressure

The process products are isolated from the reaction mixture in a conventional manner, for. B. by filtration. If necessary, the reaction mixture can be diluted beforehand at temperatures between room temperature and 100 ° C. with inert solvents. Suitable inert solvents are preferably water or alcohols such as methanol or ethanol

To remove any traces of perylene tetracarboxylic acid that may still be present, the dyes can be treated with dilute, warm soda solution, sodium or potassium hydroxide solution. If desired, the dyes can be further purified by reprecipitation from sulfuric acid or by recrystallization.

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Ais ether amines of the formulas H2N- (CH2) 2-OR (II) and H2N- In DT-PS 1 130 099 fluorescent dyes

(CH2) j-OR (III) are described for the reaction with perylenetetra-, which are formed by condensation of primary aliphatic

carboxylic acid z. B. into consideration: 2-Pentoxyäthylamin, 2-Hexox> - see or cycloaliphatic amines with 4 and more C-Ato-

ethylamine, 2- (2'-ethylhexoxy) ethylamine, 2-n-propoxyethyl with perylenetetracarboxylic acid, its anhydride or its amine, 2-n-butoxyethylamine, 2-methoxyethylamine, 2-ethoxy- 5 derivatives are obtained. In contrast, the

Ethylamine and mixtures of these amines, or 3-n-propoxypropyl- new ether group-containing dyes by a better amine, 3-iso-propoxypropylamine, 3-butoxypropylamine, 3-pentoxy-distributability in the plastics. In addition, the propylamine, 3-hexoxypropylamine, 3-ß-ethylhexoxypropylamine, dyes have advantages in the synthesis. This is because of the

3-ethoxypropylamine, 3-methoxypropylamine or also Gemi- water solubility of the ether amines used in particular see these amines. 10 two dyes with lower alkoxy, such as the

Of the ether amines (II) mentioned, economic ethoxy, propoxy and isopropoxy compounds of (I) are used. For reasons of color and color, 2-n-propoxyethylamine, very easy to distribute (dispersibility), the color

2-n-butoxyethylamine and especially 2-methoxyethylamine and. 3-Ethoxypropylamine material is particularly preferred.

2-Ethoxyethylamine is particularly preferred. From the same The dye (I) with Z = - (CI-h) 3-OR and R = ethyl has the

Reasons are occurring from the ether amines (III) 3-ethoxypropyl 15 property in two different modifications,

amine and 3-methoxypropylamine preferred. which differ in the X-ray diffraction pattern: in one

The dyes are excellently suitable for the mass-colored blue-red diamond-shaped to prism-like crystallizing form A.

Exercise of synthetic plastics, in particular of ther- and in an orange spindle-shaped crystallizing form B.

moplastic plastics such as polyethylene, polycarbonates, Form A is preferably formed at reaction temperatures

Polyvinyl chloride, especially hard polyvinyl chloride, 20 up to 160 ° C, while at higher reaction temperatures

Polystyrene and its copolymers. With dyes, e.g. B. Form B is formed at 170 ° C. Both forms can be converted into Z 3-alkoxypropyl residues with more than 2 carbon atoms in alkoxy: by heating form A in higher, you get very clear, bright yellow-orange colorations, boiling organic liquids, e.g. B. Diglycol, which in particular in transparent colorations fluoresce the form B. By heating the form B in DMF you get and still have a very good lightfastness. 25 form A. When coloring plastics, they behave

Dyes in which Z is 2-alkoxyethyl radicals give approximately the same in both forms.

Polyvinyl chloride or polyethylene strongly bluish red color. The parts mentioned in the examples are parts by weight, exercises. In plastics that require higher temperatures for processing, e.g. B. polystyrene or polycarbonates, receives Example 1

on the other hand, bright orange colorations, which are transparent 30 parts in water, 120 parts of perylene tetracarbonate

annuity coloring fluoresce and high light fastness acid anhydride and 74 parts of y-ethoxypropylamine mixed and have. heated under pressure to 130 to 135 ° C. Stir for about 5 hours

Dyes which, as Z alkoxyethyl or 3-methoxy, do not contain any free perylene t-pyl radical at this temperature until a sample is used, are excellent for dyeing tracarboxylic acid. After cooling and varnishing, resins, printing inks or printing pastes. These color spans are diluted with water, filtered, washed neutral and substances can be over-dried in pigment preparations for this purpose. Yield: 170 parts of perylene tetracarboxylic acid bis- <Y- leads, which are used as such for further coloring (ethoxypropylimide) in the form of a bluish red diamond-shaped. The dye with Z = 3-methoxypropyl ger platelets (form A).

lightfast black coloring. The new dyes, especially those as Z 2-alkoxyethyl residues or the 3-methoxypropyl residue, 40 Example 2

hold, have high solvent, varnish and soft- In 400 parts of ethylene glycol, 110 parts of perylene tetra

Making rights as they are required for lacquer and soft polyvinyl chlorocarboxylic acid anhydride and 76 parts of Y-ethoxypropylamine under coloration. This applies especially to the dyeing stirring heated to 155 to 160 ° C and for as long as

substances in which Z represents 2-methoxyethyl, 2-ethoxyethyl, 3-temperature until there is no more free perylenetetracarboxylic acid, thoxypropyl or 3-ethoxypropyl. These dyes 45 can be detected. This is the case after about 1 hour. Colorings or varnishes are given with very good to let cool to about 80 ° C, diluted with 300 parts of metha-

recorded authenticity properties. noi, filtered at around 40 ° C, washes the filter cake with

The solubility of the dyes (I) in plastics becomes ethyl alcohol, then with water and dried. Yield: 161 parts determined by the alkoxy radical; dyes with perylene tetracarboxylic acid bis (Y-ethoxypropylimide) are in the form

Alkoxypropyl residues usually in synthetic plastics 50 from bluish-red, diamond-shaped platelets (Form A). more soluble than the corresponding ones with the alkoxyethyl

most. Example 3

Thus, the dyes (I) with R = methyl and ethyl pig. If the procedure is as in Example 2, but the material heated to 170 to 175 ° C. for 2 hours at temperatures of 280 condensation is obtained release after up to 290 ° C. In contrast, the 2- or 3-alcohols are processed 157 parts of the same dye in the form of xyderivate with 3 and more carbon atoms in the alkoxy even with 180 orange-red spindle-shaped crystal platelets (form B).

dissolved up to 200 ° C; d. H. you get bright orange colors with them. Example 4

50 parts of the dye obtained according to Example Î (Form A)

The pigment dyes obtained in the synthesis can be used in 150 parts of ethylene glycol for about 1 hour with 195 to 90% crude dyes in many cases. Stirred 200 ° C. After working up, you get with quantitative

Advantageously, however, the raw dyestuffs will be obtained by yielding the dye in the form of orange-red spindles

Finishing measures, e.g. B. by transfer into a fine ver (form B).

divided form, such as by reprecipitation from sulfuric acid or by The same result is obtained with the dye of the

Grinding and subsequent recrystallization in water in 65 games 2.

organic solvents or mixtures thereof at a higher temperature in a manner known per se in particular example 5

Transfer finish forms. 5 parts of the dye of Example 3 (Form B) are in

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300 parts of dimethylformamide held at boiling temperature for 15 minutes. After cooling to normal temperature, uniform crystal prisms of shape A are obtained.

The same result is obtained with the dye from Example 4.

Example 6

120 parts of perylene tetracarbonic anhydride and 84 parts of y-isopropoxypropylamine are stirred in 360 parts of water and heated to 130 to 135 ° C. under pressure. The mixture is stirred at this temperature for about 5 hours until a sample no longer shows any free perylene tetracarboxylic acid. After cooling and releasing the pressure, the mixture is diluted with water, filtered, washed neutral and dried. Yield: 173 parts of the perylene tetracarbonic acid {bis-y-isopropoxypropylimide) in the form red crystals.

Example 7

0.05 part of the dye obtained in Example 1 is dry-mixed in a drum mixer with 100 parts of ground polystyrene block polymer. The mixture is melted and homogenized on a screw press at a cylinder temperature of 200 to 250 ° C. The colored plastic mass is granulated by hot knocking off the nozzle head or by pulling threads with cooling. The granules obtained in this way are then injected into moldings in an injection molding apparatus at 200 to 250 ° C. and pressed onto any desired bodies on presses. You get bright yellow-orange moldings with very good lightfastness, which fluoresce in a similar color.

Instead of polystyrene block polymer, a polystyrene emulsion or suspension polymer or copolymers with butadiene and acrylonitrile or acrylic esters can also be used.

If, instead of the dye of Example 1, the dyes of Examples 2, 3 or 6 are used, very similar colorations are obtained.

Example 8

0.1 part of the dye of Example 1 is mixed with 100 parts of ground polystyrene block polymer and 1 part of titanium dioxide, as indicated in Example 2. The mixture is melted, homogenized and granulated. The granules obtained in this way are injected or pressed into shaped bodies (processing temperature 200 to 250 ° C.). Bright orange molded or pressed parts with very good fastness properties are obtained.

If, instead of the dye of Example 1, the same amount of the dye of Example 6 is used, very similar colorations are obtained.

Example 9

0.1 part of the dye obtained in Example 1 is homogenized with 100 parts of polyvinyl chloride powder (suspension or emulsion product) and 2 parts of hexyl dibutyl-tin-bis-thioglycolate on a mixing roll mill at 150 to 160 ° C (approx. 8 minutes) . The rolled skins obtained are pressed on a plate press at 140 ° C with approx. 0.4 kg / cm2. Transparent, bright orange compacts are obtained.

If, instead of the dye of Example 1, the dye of Example 6 is used, very similar colorations are obtained.

Example 10

0.1 part of the dye obtained in Example 1 is homogenized with 100 parts of polyvinyl chloride powder (suspension or emulsion product), 1 part of titanium dioxide (rutile product) and 2 parts of dibutyl-tin-bis-thioglycolic acid hexyl ester on a mixing mill as described in Example 8 and then to

Pressed plates. Clear orange pellets are obtained.

If, instead of the dye of Example 1, the dye of Example 6 is used, very similar colorations are obtained.

Example 11

In 800 parts of ethylene glycol, 110 parts of perylene tetracarboxylic anhydride and 138 parts of y- (2-ethylhexoxy) propylamine are heated to 140 ° to 145 ° C. with stirring and held at this temperature until no more perylene tetracarboxylic acid can be detected 1 hour the case. It is allowed to cool to 80 ° C., diluted with 500 parts of methanol, filtered at about 40 ° C., the filter cake is washed with methanol and water. After drying, 190 parts of perylene-tetracarboxylic acid bis (y-ethyhexoxypropylimide) are obtained in the form of red crystals.

Example 12

The procedure is as described in Example 2, but 119 parts of monochloroperylenetetracarboxylic anhydride are used instead of 11 parts by weight of perylene tetracarboxylic anhydride, and a very similar dye is obtained.

The monochloroperylenetetracarboxylic acid or its anhydride is produced in the following way:

100 parts of perylene tetracarboxylic anhydride in 700 parts of nitrobenzene with 12 parts of iodine and 390 parts of sulfuryl chloride are heated to 65 to 70 ° C. and stirred at this temperature for 2 hours. The mixture is further heated to 80 to 85 ° C. and kept at this temperature for 7 hours. After cooling to ordinary temperature, the mixture is filtered off, washed with nitrobenzene, methanol and water and dried. A perylene tetracarboxylic anhydride with a chlorine content of 8.9% is obtained in very good yield. This corresponds to a monochloroperylenetetracarboxylic anhydride.

Example 13

120 parts of perylene tetracarbonic anhydride and 55 parts of 2-methoxyethylamine are stirred in 360 parts of water and heated to 130 to 135 ° C. under pressure. The mixture is stirred at this temperature for about 10 hours until a sample no longer shows any free perylene tetracarboxylic acid. After cooling and relaxing, the reaction mixture is diluted with water, filtered, washed with a 1% aqueous warm sodium carbonate solution until the effluent is clear, washed neutral and dried. 153 parts of perylene tetracarboxylic acid bis (β-methoxyethylimide) are obtained in the form of a red dye powder.

Analysis: C30H22O6N2 (507)

calc. 71.1% C 4.4% H 19.0% O 5.5% N

found 71.5% C 4.5% H 19.1% O 5.6% N

Example 14

In 800 parts of ethylene glycol, 110 parts of perylene tetracarboxylic anhydride and 56 parts of 2-methoxyethylamine are heated to 170 to 175 ° C. with stirring and kept at this temperature until no more perylene tetracarboxylic acid can be detected. This is the case after about 1 hour. The mixture is allowed to cool to about 150 ° C., diluted with 200 parts of dimethylformamide, filtered at about 40 ° C., the filter material is washed with 100 parts of dimethylformamide, then with water and dried. 125 parts of perylene tetracarboxylic acid bis (β-methoxyethylimide) are obtained as a red powder.

Analysis: C30H22O6N2 (507)

calc. 71.1% C 4.4% H 19.0% O 5.5% N

found 69.7% C 4.8% H 19.9% O 5.8% N

Example 15

The procedure is as described in Example 1, but is used

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Instead of 55 parts of 2-methoxyethylamine, 64 parts of 2-ethoxyethylamine and 1 part of an alkyd resin modified with soybean oil and 2 parts and holding for 5 hours at 130 to 135 ° C., after working up with an alkyd resin modified with synthetic fatty acid), 161 parts of perylene tetracarboxylic acid are worked up -bis- (ß-ethoxy-. with 30 parts of titanium dioxide (rutile), 22 parts of an ethylimide) in the form of a red dye powder, solvent-free melamine resin and 6 parts of a colloidal

"s len silicon dioxide on the three-roll mill at 80 atm with 6 example 16 • passages to a 30 percent white paste.

In 400 parts of ethylene glycol, 11.0 parts of perylene tetra. ...; -

carboxylic anhydride and 67 parts of 2-ethoxyethylamine. untec: b) paint paste

Stirring heated to 155 to 160 ° C and as long as this tem-; ; ' 0.5 parts of the full-tone paste (30 percent) from Example 19a)

held until no more perylene tetracarboxylic acid io and 10 parts of white paste (30 percent) a) are on a phone

must be demonstrated. This is the case after about 1 hour. One rubs and rubs.

allows to cool to 80 ° C, diluted with 300 parts of methanol, fil-

triert at about 40 ° C, washes the filter material with a little methanol, c) performing the coloring then with water and drying. 140 parts of perylene are obtained. With a film-pulling device, the coating paste b) with a tracarboxylic acid bis- (β-ethoxyethylimide) as a red powder. i s layer thickness of 100 p. applied to cardboard and 45 minutes

Analysis: C32H26O6N2 (535) baked in a drying cabinet at 120 ° C. Bluish

calc. 7.1.9% C 4.9% H 5.2% N red tints with excellent light and very good results. 71.4% C 4.9% H 5.2% N Weatherfastness preserved.

If, instead of the dye of Example 13, Example 17 20 dye of Example 15 is used, a very similar color is obtained.

If one proceeds as described in Example 2, exercise is used.

however, instead of 56 parts of 2-methoxyethylamine, 72 parts of 2-n-propoxyethylamine. The reaction mixture is with metha- Example 21

noi (instead of dimethylformamide) diluted. After the baked-on coating (white waste 1:20, from dye paste), 155 parts of perylenetetracarboxylic acid bis (β-n-25 a) 69 parts are obtained, one by redissolving the dye of the propoxy-ethylimide) as a red powder. game 14 finely divided aqueous 29 percent dye dough obtained from concentrated sulfuric acid are modified with 64 Example 18 parts of a solvent-free soybean oil

The procedure is as described in Example 5, but alkyd resin and 16 parts of bis-ethyl-hexylphthalate are used on a 82-part 3-n-butoxyethyl-30 three-roll mill with 6 passages at 60 atm by flushing to amine instead of 72 parts of 2-n-propoxyethylamine. this gives 157 parts of perylene tetracarboxylic acid bis- (ß-n- a solid paste processed.

butoxy-ethylimide) as a red powder. b) 66 parts of binder obtained by mixing 70

Parts of solvent-free soybean oil-modified alkyd resin, Example 19 17.5 parts of bis-ethyl-hexylphthalate and 12.5 parts of one

Full-tone stove enamel (1 percent) 35 solvent-free melamine resin, with 30 parts

Titanium dioxide (rutile) and 4 parts of a colloidal silicon dioxide on the three-roll mill at 60 atm with 6 passages to a) full-tone paste (30 percent) of a titanium dioxide paste.

3 parts of dye from Example 13 are mixed with 7 parts of a) 0.4 part of the full-tone paste produced according to a) and 5 varnish-like binders (= Grinding Base 100 S from. 40 parts of the titanium dioxide paste produced according to b) are available from Lawter Chemicals Inc. , Chicago) on a three-roller mill. A plate grinder mixed and ground. With this, with 6 passages at 80 atm to a 30 percent full-tone paste, color paste is processed as in Example 7 c). that is baked at 120 ° C for 45 minutes. A strong bluish-red coloration with very good light fastness is obtained.

b) Full-tone paint paste (10%) is used instead of a dough of the dye of

2 parts of solid paste a) are mixed with 4 parts of a binder with Example 14, 71.5 parts of a correspondingly prepared 28 percent mixture consisting of 1 part of a dough from Example 16 modified with soybean oil, thus giving a very similar alkyd resin, 2 parts of a coloring with synthetic fatty acid.

modified alkyd resin and 3 parts of a solvent-free melamine resin mixed. Example 22

Soft PVC (0.1% transparent coloring):

0.05 part of the dye obtained in Example 13 is carried out by c) carrying out the dyeing 50 parts of a mixture of 65 parts of polyvinyl chloride powder,

The lacquer paste b) is applied to cardboard in a 55 35 parts of diethylhexyl phthalate and 2 parts of dibutyl-tin up to a layer thickness of 100 | x using a film-pulling device, and thioglycolic acid hexyl ester is baked on a mixing mill at 150 at 120 ° C. for 45 minutes. This gives a very opaque, homogenized up to 160 ° C (duration: approx. 8 minutes), bluish-tinged red coloring with excellent light and very rolled and smoothed on a calender mill. Good weather fastness. receives blue-red colored skins with excellent light and

If the <> 0 plasticizer fastness is used instead of the dye of Example 13.

Dye of Example 15, you get a very similar color. Example 23

Soft PVC (white blend 1:10)

Example 20 0.25 parts of dye obtained in Example 13 are also

Stove enamelling (white waste 1:20) m 2.5 parts titanium dioxide (rutile) and 50 parts one

Mixture of 65 parts of polyvinyl chloride powder, 36 parts of di-a) white paste (30 percent) ethylhexyl phthalate and 2 parts of dibutyl-tin-bis-thioglycolic acid.

42 parts of a binder (obtained by mixing rehexyl ester on a mixing roll mill at 150 to 160 ° C

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homogenized (duration: approx. 8 minutes), rolled into skins and smoothed on a calender mill. Blue-red colored skins are obtained with excellent light and softening properties.

Example 24 Soft PVC (full tone)

If the procedure is as in Example 23, but using 0.5 part instead of 0.25 part of dye and 0.25 part instead of 2.5 part of titanium dioxide, strong blue-red colored skins are obtained with excellent light and softening properties.

Example 25

Hard PVC (0.1 percent transparent coloring)

0.1 part of the dye obtained in Example 13 is homogenized with 100 parts of polyvinyl chloride powder (suspension or emulsion product) and 2 parts of dibutyl-tin-bis-thioglycolic acid hexyl ester on a mixing roll mill at 150 to 160 ° C. (duration: approx. 8 minutes ). The rolled skins obtained are pressed on a plate press at 140 ° C. at about 0.4 kg / cm 2 to give blue-red compacts with excellent lightfastness

If, instead of the dye of Example 13, the dyes of Examples 15, 17 or 18 are used, very similar colorations are obtained.

Example 26 Rigid PVC (full tone)

1 part of the dye obtained in Example 13 is homogenized with 100 parts of polyvinyl chloride powder (suspension or emulsion product), 0.5 part of titanium dioxide (rutile product) and 2 parts of dibutyl-tin-bis-thioglycolic acid hexyl ester on a mixing roll mill at 150 to 160 ° C ( Duration: approx. 8 minutes). The rolled skins obtained are pressed on a plate press at 140 ° C with approx. 0.4 kg / cm2. Strong blue-red colored compacts with excellent lightfastness are obtained.

If the dyes of Examples 15, 17 or 18 are used, very similar colorations are obtained.

Example 27

Polyethylene (0.05 percent transparent coloring)

0.05 part of dye, obtained according to Example 13, is dry-mixed in a drum mixer with 100 parts of polyethylene powder (high-pressure product). The mixture is melted and homogenized on a screw press at a cylinder temperature of 160 to 200 ° C. The colored plastic mass is obtained by hot cutting on Granulated nozzle head or by pulling threads with cooling The granules obtained in this way are then injected into moldings in an injection molding apparatus at 200 ° C. or pressed onto any desired body on presses. A yellowish-blue-red compact with excellent lightfastness is obtained.

Example 28

Polyethylene (white blend 1:10)

0.1 part of the dye of Example 13 is mixed with 100 parts of polyethylene powder (high-pressure product) and 1 part of titanium dioxide (rutile product) as indicated in Example 15 and processed to give moldings. Blue-red compacts with very good light fastness are obtained.

Example 29

Polystyrene (0.05 percent transparent coloring)

0.05 part of the dye, obtained according to Example 16, is dry-mixed in a drum mixer with 100 parts of ground polystyrene block polymer. The mixture is melted and homogenized on a screw press at a cylinder temperature of 200 to 250 ° C. The colored plastic mass is granulated by hot knocking on the nozzle head or by pulling threads with cooling. The granules obtained in this way are then injected into moldings in an injection molding device at 200 to 250 ° C. or pressed to any desired body on 5 presses. Bright orange moldings with excellent light fastness are obtained which fluoresce in a similar color.

Instead of polystyrene block polymer, a polystyrene emulsion polymer or suspension polymer io or mixed polymer with butadiene and acrylonitrile or acrylic esters can also be used.

If one uses instead of the dye of Example 16. Dyes of Examples 15, 17 or 18, very similar colorations are obtained.

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Example 30

Polystyrene (white blend 1:10)

0.1 part of the dye of Example 16 is mixed with 100 parts of ground polystyrene block polymer and 1 part of titanium di-20 oxide, as indicated in Example 17. The mixture is melted, homogenized and granulated. The granules obtained in this way are injected or pressed into shaped articles (processing temperature 200 to 250 ° C.). Bright orange colored molded or pressed parts with very good light fastness are obtained

If, instead of the dye of Example 4, the dyes of Examples 15, 17 or 18 are used, very similar colorations are obtained.

3o Example 31

If the procedure is as described in Example 16, but instead of 110 parts of perylene tetracarboxylic anhydride, 119 parts of monochloroperylene tetracarboxylic anhydride are used, a very similar dye is obtained. 35 The monochloroperylenetetracarboxylic acid or its anhydride is produced in the following way:

100 parts of perylenetetracarboxylic anhydride are heated to 65 to 70 ° C. in 700 parts of nitrobenzene with 12 parts of iodine and 390 parts of sulfuryl chloride, and the mixture is stirred at this temperature for two hours. The mixture is heated further to 80 to 85 ° C. and held at this temperature for 7 hours. After cooling to room temperature, the mixture is filtered, the filter cake washed with nitrobenzene, methanol and water and dried. A chloroperylenetetracarboxylic acid 45 anhydride with a chlorine content of 8.9%, corresponding to the monochloroperylene tetracarboxylic anhydride, is obtained in very good yield.

Example 32

120 parts of perylene tetracarbon-5o acid anhydride and 64 parts of y-methoxypropylamine are stirred in 360 parts of water and heated to 130 to 135 ° C. in a pressure-tightly sealed reaction vessel. The mixture is stirred at this temperature for about 5 hours until a sample no longer shows any free perylene tetracarboxylic acid. After cooling and relaxing, the reaction mixture is diluted with water, filtered and the filter material is washed neutral and dried. 162 parts of the perylene tetracarboxylic acid bis (Y-methoxypropylimide) are obtained as a black powder. Brownish-black crystals can be seen under the microscope.

bo analysis: C32H260sN2 (535)

calc. 71.9% C 4.9% H 18.0% O 5.2% N

found 70.8% C 4.7% H 18.1% O 5.6% N

Example 33

65 In 400 parts of ethylene glycol, 110 parts of perylene tetra-carboxylic anhydride and 66 parts of y-methoxypropylamine are heated to 170 to 175 ° C with stirring and kept at this temperature until no more perylene tetracarboxylic acid

must be demonstrated. This is the case after about 1 hour. The mixture is allowed to cool to about 150 ° C., diluted with 200 parts of dimethylformamide and filtered at about 40 ° C. The filter residue is washed with 100 parts of dimethylformamide, then with water and dried. 140 parts of the perylenetetracarbonic acid-bis ^ y-methoxypropylimide) are obtained as a black powder. Brownish-black crystals can be seen under the microscope.

Analysis: C32H26O6N2 (535)

calc. 71.9% C 4.9% H 18.0% O 5.2% N

found 71.4% C 5.0% H 18.2% O 5.5% N

Example 34

10% full-color stove enamel a) Full-tone paste (30%)

3 parts of dye of Example 32 are processed with 7 parts of a varnish-like binder (= Grinding Base 100 S from Lawter Chemicals Inc., Chicago) on a three-roll mill with 6 passages at 80 atm to a 30 percent solid paste.

b) The solid color paste used for the coloring (10%)

2 parts of solid paste a) are mixed with 4 parts of a binder mixture consisting of 1 part of an alkyd resin modified with soybean oil, 2 parts of an alkyd resin modified with synthetic fatty acid and 3 parts of a solvent-free melamine resin. C) Coloring is carried out

The lacquer paste b) is applied to cardboard in a layer thickness of 100 | i using a film puller and baked at 120 ° C. for 45 minutes. A black color is obtained with excellent light and weather fastness.

Example 35

Stove enamelling (white waste 1:20)

a) White paste (30 percent)

42 parts of a binder obtained by mixing 1 part of an alkyd resin modified with soybean oil and 2 parts of an alkyd resin modified with synthetic fatty acid are mixed with 30 parts of titanium dioxide (rutile material), 22 parts of a solvent-free melamine resin and 6 parts of a colloidal silicon dioxide on a three-roll mill at 80 rubbed with 6 passages to a 30 percent white paste.

b) paint paste

0.5 part of solid paste (30 percent) from Example 34 a) and 10 parts of white paste (30 percent) a) are mixed and triturated on a plate grater.

c) performing the coloring

The lacquer paste b) is applied to cardboard with a layer thickness of 100 n using a film-pulling device and baked for 45 minutes at 120 ° C. Gray colorations with excellent light and weather fastness are obtained.

Example 36

0.1 part of the dye obtained in Example 32 is homogenized with 100 parts of polyvinyl chloride powder (emulsion product) and 2 parts of dibutyl-tin-bis-thioglycolic acid hexyl ester on a mixing roll mill at 150 to 160 ° C. (duration: approx. 8 minutes). The rolled skins obtained are pressed on a plate press at 140 ° C with approx. 0.4 kg / cm2. Olive-colored compacts with excellent lightfastness are obtained.

The same result is obtained with polyvinyl chloride, which has been prepared by suspension polymerization.

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Example 37

0.1 part of the dye obtained in Example 32 is homogenized with 100 parts of polyvinyl chloride powder (suspension product), 1 part of titanium dioxide (rutile product) and 2 parts of dibutyl-tin-bis-thioglycolic acid hexyl ester on a mixing mill as described in Example 5 and then added Pressed plates. One obtains red-tinged gray compacts with excellent light fastness.

If 1 part is used instead of 0.1 part of dye and 0.5 part instead of 1 part of titanium dioxide, black compacts with excellent lightfastness are obtained.

The same results are obtained with polyvinyl chloride which has been obtained by emulsion polymerization.

Example 38

0.05 part of dye, obtained according to Example 32, is dry-mixed in a drum mixer with 100 parts of ground polystyrene block polymer. The mixture is melted and homogenized on a screw press at a cylinder temperature of 200 to 250 ° C. The colored plastic mass is granulated by hot knocking off the nozzle head or by pulling threads with cooling. The granules obtained in this way are then injected into moldings in an injection molding apparatus at 200 to 250 ° C. or pressed onto any desired body on presses. Bright yellow-orange molded parts with excellent lightfastness, which fluoresce in a similar color, are obtained.

Instead of polystyrene block polymer, a polystyrene emulsion polymer or suspension polymer or a copolymer with butadiene and acrylonitrile or acrylic esters can also be used.

Example 39

0.1 part of the dye of Example 32 is mixed with 100 parts of ground polystyrene block polymer and 1 part of titanium dioxide, as indicated in Example 38. The mixture is melted, homogenized and granulated. The granules obtained in this way are injected or pressed into shaped articles (processing temperature 200 to 250 ° C.). Bright orange molded or pressed parts with very good light fastness are obtained.

Example 40

0.05 part of the dye obtained in Example 32 is homogenized with 50 parts of a mixture of 65 parts of polyvinyl chloride powder, 35 parts of di-ethylhexyl phthalate and 2 parts of dibutyl-tin-bis-thioglycolic acid hexyl ester on a mixing mill at 150 to 160 ° C ( Duration: approx. 8 minutes), rolled into skins and smoothed on a calender mill. Olive-colored skins with excellent lightfastness are obtained.

Example 41

0.25 part of the dye obtained in Example 32 is obtained with 2.5 parts of titanium dioxide (rutile material) and 50 parts of a mixture of 65 parts of polyvinyl chloride powder, 35 parts of diethylhexyl phthalate and 2 parts of dibutyl-tin-bis-thioglycolic acid rehexyl ester on a mixing roll mill homogenized at 150 to 160 ° C (approx. 8 minutes), rolled into skins and smoothed on a calender mill. Gray-colored skins with excellent light fastness are obtained.

If instead of 0.25 part of dye 0.5 parts and instead of 2.5 parts of titanium dioxide 0.25 part are used, black skins with excellent light fastness are obtained.

Example 42

0.05 part of dye, obtained according to Example 32, is dry-mixed in a drum mixer with 100 parts of polyethylene powder (high-pressure product). The mixture is on

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a screw press at a cylinder temperature of 160 compacts with excellent lightfastness.

melted and homogenized up to 200 ° C. The colored piasti example 43

see mass is granulated by hot knocking on the nozzle head or 0.1 part of the dye of Example 32 is granulated with 100 parts by pulling out threads with cooling. The polyethylene powder (high-pressure product) and 1 part of titanium dioxide obtained in this way are then mixed in an injection molding machine (rutile product) as indicated in Example 42 and sprayed to shape at 200 ° C. or molded on pressed moldings pressed to any body you get black-gray good lightfastness

Claims (13)

618209 PATENT CLAIMS 1. Process for the preparation of new dyes of the perylene-3,4,9,10-tetracarboxylic acid diimide series of the formula I -Z Z- in which Z stands for -CH2-CH2-OR or -CH2-CH2-CH2-OR, R for alkyl with 1 to 8 C atoms, X for chlorine or bromine and n for a number between 0 and 3 and the radicals R can be identical or different, by condensation of the corresponding perylenetetracarboxylic acid or of its dianhydride with primary aliphatic amines in the heat, characterized in that ether amines of the formula as primary amines Z - NH2 or mixtures of these amines, where Z has the meaning given above. 2. The method according to claim 1, characterized in that dyes are prepared in which n = 0. 3. The method according to claim 1, characterized in that dyes are prepared in which R represents the same or different alkyl having 1 to 4 carbon atoms. 4. The method according to claim 1, characterized in that dyes are prepared in which R is n-butyl, isobutyl, 2-butyl, n-propyl, isopropyl, ethyl or methyl. 5. The method according to claim 1, characterized in that dyes are prepared in which R is methyl or ethyl and n = 0 (zero) 6. The method according to claim 1, characterized in that dyes are prepared in which Z = -CH2-CH2-CH2-OCH3 and n = 0. 7. The method according to claim 1, characterized in that dyes are prepared in which Z = -CH2-CH2-OCH3 or -CH2-CH2-OC2HS and n = 0. 8. The method according to claim 1, characterized in that one carries out the condensation at temperatures between 80 and 200 ° C. 9. The method according to claim 1, characterized in that one carries out the condensation at temperatures between 130 and 180 ° C. 10. The method according to claim 1, characterized in that one carries out the condensation in a large excess of the ether amine 11. The method according to claim 1, characterized in that one carries out the condensation in inert solvents or diluents. 12. The method according to claim 1, characterized in that one carries out the condensation in alcohols, glycols or water as inert diluents or solvents 13. Use of the process products obtained by the process according to claim 1 for dyeing lacquers, resins, printing inks for non-textile purposes, glue colors or for coloring plastics in bulk.