DE1569773C - Pigment of the bis (tetrachlor isoindo Im 1 on 3 yhdenimino) aryl series and process for its production - Google Patents

Description

The invention relates to a new pigment of the bis (tetrachloroisoindolin-1-one-3-ylidenimino) -aryl series and a method for its production.

Greenish yellow pigments that meet today's requirements in terms of purity, color strength and Fastness properties are sufficient and are relatively rare. Their great importance is based, among other things, on the fact that in combination with well-known real blue pigments they result in very beautiful, pure green tones.

In the series of strongly colored bis (tetrachloroisoindolinl-one-3-ylidenimino) -aryl compounds, which have the properties required for pigments today, are red, orange and reddish yellow Shades before. For example, the pigment containing the 4,4'-diphenyl radical as a bridge member is used orange. However, strong, greenish yellow pigments are very much in demand.

It has now been found that a greenish yellow and strongly colored pigment of the bis (tetrachloroisoindolin-1-one-3-ylidenimino) aryl series is obtained obtained when 1 mole of 2,2'-diaminodiphenyl with 2 moles of a 4,5,6,7-tetrachloro-isoindolin-1-one, which is in the 3-position Contains easily interchangeable substituents which claim two bonds in terms of type and number and are more reactive than double-bonded oxygen to form a compound of the formula

Cl

Cl

Cl

35

40

condensed.

. The 4,5,6,7-tetrachloro-isoindolin-1-ones which can be used as starting materials contain mobile substituents in the 3-position for example two halogen, especially chlorine atoms, two secondary amino groups, especially piperidino or morpholino groups, or two alkoxy, ζ. B. methoxy or Ethoxy groups, an imino or a thio group. They preferably contain two methoxy groups in the 3-position.

These starting materials are known; two halogen atoms Compounds in the 3-position are obtained, for example, by the action of Halogenating agents such as phosphorus pentachloride on tetrachlorophthalic acid imide. The so produced 3,3 - dihalo - 4,5,6,7 - tetrachloro - isoindolin -1 - one can be converted into the 3-imino- or with secondary amines or with ammonia Alkanols into the 3,3-bis-tert-amino- or 3,3-dialkoxy-4,5,6,7-tetrachloro-isoindoline-1 -one convict. 4,5,6,7-tetrachloro-isoindolin-l-ones with two alkoxy groups in the 3-position can also be achieved by reacting a 3,4,5,6-tetrachloro-2-cyano-benzoic acid ester, / .. B. the methyl ester, with the desired alkanol in the presence of alkali or alkaline earth metals, Alkali or alkaline earth oxyden or hydroxides produce which in the reaction with the Alcohols form the corresponding alcoholates.

For technical reasons, preference is given to solutions of the alkaline earth metals, in particular those of Alkali metals, in excess, anhydrous alcohol.

Examples of starting materials which can be used according to the invention are: 3-imino-, 3-thio-, 3,3-bis-piperidino-, 3,3-bis-morpholino-, 3,3-dichloro-, 3,3-dibromo-, 3,3-dimethoxy-, 3,3-diethoxy- or 3,3-dibutoxy-4,5,6,7 -tetrachloroisoindolin-l-one. 3,3-Dimethoxy-4,5,6,7-tetrachloro-isoindolin-1-one is preferred.

The condensation of the 2,2'-diamino-diphenyl with the 4,5,6,7-tetrachloroisoindolin-1-one which is reactive in the 3-position takes place in the cold, if necessary while warming the intimately mixed Components, particularly advantageous in the presence of inert, d. H. not participating in the reaction organic solvent.

If one goes from alkali salts (especially from sodium salt) from S ^ -dialkoxy ^ S ^ J-tetrachloro-isoindolin-1-ones or of 3-imino-, 3-thio- or 3,3-bistert.amino ^ S ^ J-tetrachloro-isoindolin-1-ones off, it is advantageous to use water-miscible organic solvents such. B. low molecular weight aliphatic Alcohols, such as low molecular weight alkanols, for example methanol or ethanol, low molecular weight ones cyclic ethers such as dioxane, low molecular weight aliphatic ketones such as acetones, or low molecular weight Fatty acids, e.g. B. acetic acid. The condensation takes place here even at relatively low temperatures. It is advantageous to work in the presence of base-binding agents; as such are for example low molecular weight fatty acids, which then also serve as solvents, especially acetic acid, to mention.

When using 3,3-dihalo-4,5,6,7-tetrachloroisoindolin-1-ones preference is given to organic solvents free of hydroxyl groups, such as hydrocarbons, z. B. aromatic, such as benzene, toluene, xylenes, tetrahydronaphthalene or diphenyl, or cycloaliphatic, ζ. B. cyclohexane, then also halogenated hydrocarbons, such as aliphatic, z. B. Carbon tetrachloride or tetrachlorethylene, or aromatic ones, such as chlorobenzene or di- and trichlorobenzene ^ also aromatic nitro hydrocarbons, such as nitrobenzene, ethers, namely aliphatic ones, such as dibutyl ether, aromatic, such as diphenyl ether, or low molecular weight cyclic ethers, such as dioxane, also ketones, such as acetone, or esters, namely esters of low molecular weight fatty acids with low molecular weight alkanols.

The new pigment precipitates from the reaction medium immediately after its formation. It is for certain purposes can be used directly as a raw pigment; but it can also be done by methods known per se, for example by crystallization or extraction with organic solvents or by grinding with subsequently removable grinding aids, e.g. B. salts, in their properties, especially with regard to Clarity, shape and opacity are still to be improved.

The new pigment in the bis-letrachloro-isoindolin-1-one series is for pigmenting polymers! organic material suitable, e.g. B. in printing inks for the graphic industry, in paints on an oily basis, such as in linseed oil paints, or on water-based, such as in emulsion paints, or in varnishes of various types, such as in Nilro or Stoving enamels, in the latter case / .. B. such

Alkyd resin base. It can also be used for spin dyeing of viscose or cellulose acetate, for pigmenting plastics such as polyethylene, Polystyrene, polyvinyl chloride, which the latter can also contain plasticizers, of cellulose esters, of curable resins, or for pigmenting rubber and for coloring paper pulp or for coating webs, e.g. B. in the production of laminate paper, use.

The new pigment results in pure, bulging greenish-yellow pigmentations in these materials. The pigment according to the invention is distinguished from known pigments of a similar constitution characterized in that it has the much sought-after, greenish yellow hue with an unexpectedly high color strength remarkably good fastness properties, in particular high light fastness, very good migration fastness in structures Made of plasticized polyvinyl chloride, excellent overcoating, rubbing and dry cleaning fastness and good heat resistance combined.

Compared to known compounds of this class of substances which are comparable in color and which are unsubstituted Having m-phenylene radical as a bridge link, the new pigment stands out, despite the higher Molecular weight, characterized by greater color strength.

The following examples illustrate the invention. The temperatures are in degrees Celsius indicated and the percentages in percentages by weight.

B e i s ρ i e 1 1

16.5 g .V ^ -

1-one and 4.6 g of 2,2'-diaminodiphenyl are in 200 ecm of glacial acetic acid heated to reflux temperature for 2 hours. The pigment formed becomes hot filtered off and washed with ethanol. After drying, 17 g of pigment of the above formula are obtained without any further post-treatment directly as a greenish yellow pigment with excellent fastness properties can be used.

Is used instead of 16.5 g of 3,3-dimethoxy-4,5,6,7-tetrachloro-isoindoIin-l-one 14.2 g 3-imino-4,5,6,7-tetrachloro-isoindolin-1-one or 22.1 g 3,3-dimorphoIino-4,5,6,7-tetrachloro-isoindoline-1 -on and if the rest of the procedure is as indicated in the example, the same pigment is obtained in a similarly good yield.

0.6 g of the pigment prepared according to paragraph I of this example are mixed with 67 g of polyvinyl chloride, 33 g of dioctyl phthalate, 2 g of dibulyltin dilaurate and 2 g of titanium dioxide mixed together and for 10 to 15 minutes Rolled at 140 ". Greenish-tinged yellow polyvinyl chloride films produced with them are migration, heat and dyed lightfast.

10 g of titanium dioxide (rutile) and 2 g of the pigment prepared in accordance with paragraph 1 of this example are mixed with 88 g of a mixture of 26.4 g coconut alkyd resin, 24.0 g melamine-formaldehyde resin (50% solids content), 8.8 g of ethylene glycol rhonomethyl ether and 28.8 g of xylene for 48 hours in a ball mill ground.

If this lacquer is sprayed onto an aluminum foil and after 30 minutes pre-drying at Baked at room temperature for 30 minutes at 120 °, the result is a coating that is characterized by a pure, greenish yellow hue. The paintwork is very well painted over and lightfast.

Example 2

To a solution of 17 g of 3,3,4,5,6,7-hexachloroisoindolin-1-one in 200 ml of 1,2-dichlorobenzene, a solution of 4.6 g of 2,2'-diaminodiphenyl in 100 ecm 1,2-DichförbenzoI added. It forms immediately a yellow precipitate. The suspension is heated to 160 to 170 ° and while stirring Maintained at this temperature for 1 hour. The insoluble pigment is filtered off hot and washed with ethanol and washed water. After drying, 13.9 g of the pigment described in Example 1 are obtained.

^: B is ρ ie 1 3

31.4 g are added to a sodium methylate solution (obtained from 2.7 g of sodium and 120 ecm of methanol) 3,4,5,6-tetrachloro-2-cyanobenzoic acid methyl ester. This produces the sodium salt of 3,3-dimethoxy - 4,5,6,7 - tetrachloro - isoindolin - 1 - one. After 30 minutes, 9.2 g of 2,2'-diamino-diphenyl are added to the solution formed entered and then the mixture was stirred for 10 hours at room temperature, whereby the yellow sodium salt of the dye separates. The reaction mixture is acidified with 40 ecm of glacial acetic acid and heated to reflux temperature for 2 hours. The insoluble pigment is filtered off while hot and washed with ethanol and acetone. After drying, 36 g of that described in Example 1 are obtained Pigments, which in this form can be used directly as a pigment with excellent fastness properties can.

To further improve its color strength, 15 g of crude pigment and 30 g of anhydrous calcium chloride are used in a 1-1 vibratory mill containing 3.5 kg of steel balls with a diameter of 1.5 cm. After 1 hour of vibration, the grist will turn off the vibration mill removed and the calcium chloride dissolved out with water. The dried pigment is now characterized by high color strength and transparency.

55. In order to obtain a pigment with constant color strength and good hiding power, 10 g Salt-ground pigment heated to reflux temperature with 100 ecm of chlorobenzene for 2 hours. Then the pigment is filtered off while hot and dried.

For the production of a color paste for graphic purposes, 2 g of the according to paragraph 2 of this example produced pigments with 36 g of alumina hydrate, 60 g of linseed oil varnish of medium viscosity and 0.2 g of cobalt linoleate mixed and rubbed on the three-roller mill. The greenish yellow ones produced with this coloring paste Prints are strong, pure and extremely lightfast.

Claims (3)

Patent claims: 1. Pigment of the bis (tetrachloroisoindolin-1-one-3-ylidenimino) -aryl series the formula Cl N
II Ci _x Ä / ^C Κλ \ Cl ⁷ γ ^x c Cl O «5 Cl 2. Process for the production of a pigment the bis-itetrachloro-isoindolin-l-one-S-ylidenimino) -aryl series according to claim 1, characterized in that 1 mol of 2,2'-diaminodiphenyl with 2 moles of a 4,5,6,7-tetrachloroisoindolin-l-one, which in the 3-position easily exchangeable substituents contains, which claim two bonds in terms of type and number and are more feasible are as the doubly bonded oxygen, to a compound of the formula Cl Cl Cl condensed. 3. The method according to claim 2, characterized in that 1 mole of 2,2'-diaminodiphenyl with 2 moles of S ^ -dimethoxy ^ SjoJ-tetrachlor-isoindo- f Hn-I-on condensed. ^