DE1250404B - Modification- and flocculation-resistant pigment mixtures of copper phthalocyanines of the a modification - Google Patents

Description

HE) JtS KE FUB LIK DEUTSC: H ί, AND Jj

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C09b

€ US ν - e. 7/00

German AI: 8 m -13

Number: I 250 404

File number: B 73997 IV c / 8 m

Filing date: October 25, 1963

Opened on: September 21, 1967

The ^ modification of halogen-free copper phthalocyanine is characterized by a reddish blue, brilliant hue and high color strength. However, it has the disadvantage of not being solvent-resistant. So remains in paints, enamels and paints containing organic solvents do not maintain the brilliant color tone of the product and gradually changes to faint and greenish blue tones. The ^ modification of the polymorphic Copper phthalocyanine is converted into the coloristically less valuable / ^ modification around. The crystals resulting from this modification change form coarsely dispersed aggregates and flake out. A paint or varnish in which such flocculation phenomena occur is practically useless.

Several processes have already been described for the modification of copper phthalocyanine to stabilize against paint solvents. Some of the suggested routes are very cumbersome and expensive, partly by changing the pigment chemically or by adding other phthalocyanines the color strength is reduced or the hue shifted to a greenish blue.

For example, by introducing a chlorine atom or more into the 4-positions of the benzene nuclei reached a modification stability on the phthalocyanine.

Also by adding other phthalocyanines such as tin phthalocyanine, aluminum phthalocyanine or zinc phthalocyanine, the Λ modification stability becomes achieved. However, this is accompanied by a clouding of the hue or a drop the lightfastness of the pigment mixture.

Compared to the US Pat. No. 3057872, from German Pat. No. 1,127,323 and from Swiss patent 352 436 known pigments was a pigment of greater color strength, higher purity and reddish tone desired. An undesirable property of the United States patent 2 116196 and the pigments known from British patent specification 468 043 is the greenish hue.

It has now been found that pigment mixtures of copper phthalocyanines of the \ form are resistant to modification, that are resistant to flocculation and strong 2 to 20 percent by weight, based on the pigment mixture of a 4-monobenzoyl copper phthalocyanine, contain, in which the benzoyl radical still has substituents, such as halogen atoms, alkyl, alkoxy or arylamino groups.

These pigment mixtures are z. B. received when one

Modification and flocculation resistant
Pigment mixtures of copper phthalocyanines
the ^ modification

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Willy Braun, Heidelberg;

Dr. Dietwulf von Pigenot, Ludwigshafen / Rhine;

Dr. Rudolf Polster, Frankenthal;

Dr. Ernst Schefczik,

Dr. Rudolf Schrödel, Ludwigshafen / Rhine

a) in the synthesis of copper phthalocyanine functional derivatives of 4-monobenzoylphthalic acid used in such an amount that the resulting mixture is 2 to 20 percent by weight 4-monobenzoyl copper phthalocyanine contains, or if one

b) mixing copper phthalocyanine with appropriate amounts of 4-monobenzoyl copper phthalocyanine and then in the usual way into the «modification, e.g. B. by pasting with concentrated Sulfuric acid, transferred.

If such mixtures are boiled with benzene or xylene, there is no change in color.
For economic reasons, the percentage of monobenzoyl copper phthalocyanine will be chosen as low as possible; In addition, the desired red cast and the brilliance of the blue pigment are more pronounced, the lower the content of a 4-monobenzoyl copper phthalocyanine.

Thus, a content of 2 to 5 percent by weight of the monobenzoyl copper phthalocyanine is sufficient to produce the end product to make completely benzene-proof, a content of about 8 to 9 percent by weight is sufficient, that the pigment in the a-modification does not change color even after boiling in xylene for several hours shows. However, you can also use much larger amounts, for. B. up to 20 percent by weight, mix without

709 648/327

3 4

that the color strength of the pigment mixture is significantly. After boiling for 2 hours in xylene, a

sinks. The mixtures should preferably be pigmented, which is even stronger and redder than the

against 2 to 15 weight percent of a 4-monobenzoyl gang material.

copper phthalocyanine, especially the one on the benzoyl B e i s d i e 1 3

rest of unsubstituted 4-benzoyl copper phthalocyanine 5

contain. 144 parts of phthalic anhydride and 7.5 parts

While chlorocopper phthalocyanine contains 4-benzoylphthalic anhydride, a mixture of 1 mole of copper 300 parts of urea in 1000 parts of trichlorobenzene phthalocyanine and 1 mole of 4-monochloro-copper phthalocyanine are heated with stirring together with the mixtures. Are added at about 50 ⁰ C is not more cyanin is completely solvent-stable, io 36 parts of copper (II) chloride and 1 part Ammongenügt it here if the mixture to more than 10 moles of molybdate to and heated with stirring to 200 ⁰ C. Copper phthalocyanine 1 mole of monobenzoyl copper- After stirring for 5 hours at this temperature, phthalocyanine is added to an organic in the usual way.
Solvent completely stable mixture of pigments obtained after dissolving from concentrated sulfur. This makes it possible to obtain a green acid, a blue pigment that does not undergo any change in the boiling temperature of the color shade and a reduction in the color xylene,
to avoid starch of the «copper phthalocyanine.

The parts given in the examples are Example 4
Parts by weight and percentages relate to

Weight percent. 20 100 parts of crude copper phthalocyanine of the ß-mode

fication are dissolved in 2000 parts of 90 ° / ₀ sulfuric acid

Example 1 entered. Then 8 parts are carried with stirring

4-monobenzoyl copper phthalocyanine and stir

291 parts of phthalic anhydride and 6.5 parts at room temperature for 15 hours. The sulfuric acid

4-Benzoylphthalic anhydride together with 25 solution is now poured onto ice water, the

600 parts of urea in 2000 parts of nitrobenzene precipitate filtered off with suction and washed neutral,

heated with stirring to 13O ⁰ C, were then added, giving a reddish pigment of the "-Modi-

2 parts ammonium molybdate and 70 parts water fication, which even after several hours of boiling in

Free copper (H) chloride is added and the mi-xylene is still heated according to the radiographic findings

Schung to 180 to 190 ⁰ C. 30 consists of practically 100% «modification.

The mixture temperature is kept for 4 to 5 hours. The 4-monobenzoylkupferphthalocy-

to 180 to 190 ⁰ C, cools down and diluted with anin is produced as follows:

Methanol. Then it is suctioned off and the residue 444 parts of phthalic anhydride are combined

first with 10 ° / _o aqueous sodium hydroxide solution, then with concentric with 251 parts of 4-Benzoylphthalimid and 800 parts of

trated hydrochloric acid is stirred at 8O ⁰ C for 1 hour. 35 heated urea in 5000 parts of trichlorobenzene.

After suctioning off, washing and drying, 10 parts of ammonium molybdate are obtained

one 260 parts of a blue pigment. and 105 parts of copper (II) chloride added and the

Heated after redissolution of the 15 times the weight of approach to 190 ⁰ C.

amount of concentrated sulfuric acid is obtained. After a reaction time of 10 hours, it is cooled,

reddish, brilliant pigment of high color strength. 40 driven off the solvent with steam and

The small amount of Monobenzoylkupferphthalo- the residue boiled out,
cyanine is not noticeable in the analysis of the pigment mixture. Example 5

³ ^ ^1β u * _t / - * r 1 ο λ ο X ₁ m ac / ^ 11 ac 45 148 parts of phthalic anhydride are mixed with 250 parts

£ ΓΪ !? "C SS H \ 7 'NQ 4' o ^U ii 7 ' ^{len urea} <1 ^part ammonium molybdate and 26 dough found ... C 66.9, H 2.7, N 19.4, Cu 10.7. _{Len copper ( I)} . _{Chloride in 1000 part} / _n trichlorobenzene

Heated after several hours of boiling in benzene at 130 ⁰ C. 7 parts of 4-mono are then obtained, a product which has been added to benzoyl copper phthalocyanine with a slightly stronger color and which has become more reddish and tinged. 50 schung heated to 190 to 200 ° C. After east

Stirring at this temperature is cooled, the

Example 2 Sucked off solvent and the press cake with

Acetone washed thoroughly.

145 parts of phthalic anhydride and 5 parts of 4-Ben- 130 parts of a blue pigment mixture are obtained,

zoylphthalimide in 1000 parts of nitrobenzene with 55 by dissolving from concentrated sulfuric acid 500 parts of urea, 1 part of molybdenum oxide and in the coloristically valuable «modification above-26 Parts of copper (I) chloride as in Example 1 is carried out. When treating with organic wrote implemented. Solvents the pigment shows even in the heat

After the reaction has ended, the solution will not change color,
medium removed with steam and the back 60

stood after boiling with caustic soda and example 6

Dried hydrochloric acid. 140 parts of crude product are obtained. 125 parts of phthalonitrile and 6 parts of 4-benzoyl

By redissolving from concentrated sulfuric acid phthalonitrile is obtained with 35 parts of copper (II) you get a product that compared to a 65 chloride in 1000 parts of nitrobenzene about 6 hours stabilized by chlorine content, e.g. B. 0.7 gram heated to the boil. You work on and as usual Atoms of chlorine per mole of copper phthalocyanine contains a product with those specified in Example 1 holding mixture appears significantly redder. Properties.

Claims (1)

Claim: Modification and flocculation resistant pigment mixtures of copper phthalocyanines of the «modification, characterized by a content of 2 to 20 percent by weight of a 4-monobenzoyl copper phthalocyanine, in which the Benzoyl radical can still carry substituents. Considered publications: German Auslegeschrift No. 1 127 323; Swiss Patent No. 352 436; U.S. Patent No. 3,057,872; Moser - Thomas, "Phthalocyanine Compounds", New York, 1963, p. 316. When the application was announced, four color tables with two test reports were displayed.