DE1569841C - Pigments and processes for their manufacture - Google Patents

Description

The invention relates to pigment dyes from the series of condensation products of perylene-3,4,9, 10-tetracarboxylic acid and a process for its preparation.

Vat dyes of the perylene series have been used for dyeing textiles for a long time. The good lightfastness properties of these dyes have led to them also being perylene derivatives Use pigment dyes. In particular, there were very special condensation products of Perylene - 3,4,9,10 - tetracarboxylic acid selected, which are particularly suitable as pigments and improved Properties, especially with regard to their resistance to solvents.

Processes are also known which improve the fastness properties of pigment dyes Achieve in such a way that in the production of these dyes an enlargement of the molecule is made. In a process of this type, the molecule is enlarged by acid imide formation it acts. In this process, dyes or dye intermediates that one or contain several pairs of carboxyl groups in ortho- or peri-position and to form cyclic ones Acid imides are capable of working with ammonia or with any mono- or diamines or their substitution products implemented.

It has been shown that the range of previously known, dyes built up from condensation products of perylene-3,4,9,10-tetracarboxylic acid in can be expanded in a progressive manner that according to the invention perylene-3,4,9,10-tetracarboxylic acid either in free form or in the form of their anhydride or mixtures of the compounds mentioned with amines of the general formula,

H ₂ N

R - N

R,

in which R is a phenylene _{radical, a diphenylene radical or a 3,3'-dimethyldiphenylene radical and R 1 is} the radical of phthalic acid, naphthalic acid or 3-nitronaphthalic acid, condensed in a manner known per se in a liquid reaction medium, optionally in the presence of a condensing agent being, pigment dyes of the general formula

CO _x ■

Ν —RN R ₁

CO ⁷ \ oc /

arise, in which R and R _{1 have} the meaning given above.

Since the amines which can be used according to the invention are very easily mixed with perylenetetracarboxylic acid or its anhydride are condensable, the starting components are used when carrying out the process according to the invention preferably used in an equivalent ratio. The amine can of course also be used in excess.

Among the applicable amines have N, N - naphthalylbenzidine, 3 - nitronaphthalic acid-N- (4-aminophenylimide), N, N-naphthalyl- (3,3'-dimethylbenzidine) and phthalic acid-N- (4-aminophenylimide) Proven to be particularly advantageous.

Although the condensation reaction by all customary methods, for example under increased or reduced pressure, at temperatures between 50 and 200 ° C and using ketones and water can be carried out as the reaction medium, the process according to the invention is preferred carried out so that the starting products in a high-boiling organic liquid as Reaction medium and heated in the presence of a condensing agent.

The high-boiling organic liquid is advantageously nitrobenzene or ortho-dichlorobenzene and as a condensing agent, the compounds customary for this purpose, e.g. B. zinc chloride, hydrogen chloride or Glacial acetic acid, used.

The obtainable by the process of the invention products are red to bordorote compounds which are after conversion into finely divided form valuable pigments and for dyeing ⁶ S synthetic or natural high molecular materials such as PVC, polystyrene, polyethylene, polyester or rubber are well suited. The new pigments can also be used for coloring paints, e.g. B. Use nitro and stove enamels, printing inks or for mass coloring paper or viscose very well.

The above-mentioned fine distribution of those obtained by the process carried out according to the invention Perylene derivatives in a form usable as a color pigment can be used with comparable success on the done in a variety of ways. So z. B. a reprecipitation from sulfuric acid, a grinding with or without grinding aids, sources in sulfuric acid or organic solvents such as aromatic hydrocarbons, chlorinated aromatic hydrocarbons, nitro hydrocarbons or dimethylformamide, good usable results.

The percentages given in the examples are percentages by weight.

example 1

9.8 g of 3,4,9,10-perylenetetracarboxylic dianhydride are first distilled anhydrous together with 2.65 g of zinc chloride and 2.65 g of sodium acetate in 150 ecm of nitrobenzene. After cooling to 180 ° C., a solution of 32.0 g of N, N-naphthalenylbenzidine in 150 ecm of nitrobenzene is added and the mixture is heated to the boil for 15 hours with stirring and reflux. The reaction product is filtered off while still hot, washed with hot nitrobenzene until no more amine can be detected, and washed out with ethanol and water. To possibly unreacted perylenetetracarboxylic to remove the crude product is repeatedly boiled in about 5 "/ _o i ^ he potassium carbonate, to leak on the filter paper - no fluorescence is visible after aspiration - especially when viewed under the UV lamp. Neutral washing and drying gives you one

bluish-tinged red pigment dye with very good lightfastness and excellent migrationfastness.

Example..2

9.8 g of 3,4,9,10-perylenetetracarboxylic dianhydride are first distilled anhydrous together with 2.65 g of zinc chloride and 2.65 g of sodium acetate in 150 ml of nitrobenzene. After cooling to 180 ^° C., a solution of 18.2 g of Ν, Ν-naphthalenylbenzidine in 150 ml of nitrobenzene is added and the mixture is refluxed for 15 hours with stirring. After working up as indicated in Example 1, the same pigment with the same fastness properties is obtained in the same yield.

Example 3

9.8 g of 3,4,9,10-perylenetetracarboxylic dianhydride are first distilled anhydrous together with 2.65 g of zinc chloride and 2.65 g of sodium acetate in 150 ecm of nitrobenzene. After cooling to 180 ^° C., a solution of 29.1 g of 3-nitronaphthalic acid-N - (4-aminophenylimide) in 150 ecm of nitrobenzene is added and the mixture is heated to the boil for 15 hours with stirring and reflux. After working up as indicated in Example 1, a bluish-tinged red pigment dye with excellent migration and lightfastness is obtained.

Example 4

9.8 g of 3,4,9,10-perylenetetracarboxylic dianhydride are first distilled anhydrous together with 2.65 g of zinc chloride and 2.65 g of sodium acetate in 150 ecm of nitrobenzene. After cooling to 180 ⁰ C are rrjan

ίο a solution of 34.3 g of N, N-naphthalyl- (3,3-dimethylbenzidine) in 150 ecm nitrobenzene and heated to boiling for 15 hours with stirring and reflux. After working up as indicated in Example 1, a bright red pigment dye is obtained very good migration fastness.

E xample 1 5

9.8 g of 3,4,9,10-perylenetetracarboxylic acid dianhydride are first anhydrous together with 2.65 g of zinc chloride and 2.65 g of sodium acetate in 150 ecm of nitrobenzene distilled. After cooling to 180 ° C, a solution of 20.9 g of phthalic acid-N- (4-aminophenylimide) is added. in 150 ecm nitrobenzene and heated to boiling for 15 hours with stirring and reflux. After working up as indicated in Example 1, a red-brown pigment dye is obtained excellent migration fastness.

Claims (13)

Patent claims: 1. Pigment dyes of the general formula / CO CO \ N —R —N R ₁ where R is a phenylene radical, a diphenylene radical or a 3,3-dimethyldiphenylene _{radical and R 1 is} the radical of phthalic acid, naphthalic acid or 3-nitronaphthalic acid. 2. pigment of the formula / OC ^x oc 3. Pigment dye of the formula
O ₂ N ^ CO _x / OC ^x oc - 1 OO & 4. pigment of the formula CH ₃ CH ₃ . CO _x N
_co /. \ = v_y ν / OC ^x oc 5. pigment of the formula C0 \ C0 \ co ^x / OC si ^x oc CH ₃ . / OC ^x oc 6. Process for the production of pigment dyes, consisting of condensation products of perylene-3,4,9,10-tetracarboxylic acid, characterized in that that perylene ^ AQ.lO-tetracarbon- H ₇ NRN acid either in free form or in the form of its anhydride or mixtures of the compounds mentioned with amines of the general formula / OC _x in which R is a phenylene _{radical, a diphenylene radical or a 3,3'-dimethyldiphenylene radical and R 1 is} the radical of phthalic acid, naphthalic acid or 3-nitronaphthalic acid, is condensed in a manner known per se in a liquid reaction medium, optionally in the presence of a condensing agent , where pigment dyes of the general formula ^OC are obtained in which R and R _{1 have} the meaning given above. 7. The method according to claim 1, characterized in that the amine is N, N-naphthalbenzidine is used. 8. The method according to claim 1, characterized in that the amine is 3-nitronaphthalic acid-N- (4-aminophenylimide) is used. 9. The method according to claim 1, characterized that as amine N, N-naphthalene- (3,3 '- <iimethylbenzidine) is used. 10. The method according to claim!, Characterized in that that phthalic acid N- (4-aminophenylimide) is used as the amine. 11. The method according to any one of the preceding claims, characterized in that the amine component is used in an equivalent amount. 12. Method according to one of the preceding Claims, characterized in that the liquid reaction medium is a high-boiling organic Connection is used. 13. The method according to claim 7, characterized in that the reaction medium is nitrobenzene or o-dichlorobenzene is used.