Patent GB-1075501-A (GB)
Title: Improvements relating to dyestuffs of the dioxazine series, and their use
IPC: C08K5/35
Filed: 1965-02-05
Abstract: The invention comprises dioxazine pigments free from SO3H groups having the general formula <FORM:1075501/C4-C5/1> wherein Ar1 is a benzene radical which may be substituted and Ar21, together with the two carbon atoms to which it is attached, constitutes an arylene radical which can contain non-ionic substituents.  Preferably Ar1 is a phenyl radical which may be substituted by halogen, C1-C4 alkyl group, C1-C4 alkoxy groups or a phenyl or phenoxy group which may be further substituted by halogen, alkyl or alkoxy groups.  The above mentioned arylene radical may be substituted by non-ionic substituents or may contain a fused ring e.g. a furan or a 1 : 4-dioxine ring.  The pigments are prepared by condensing a compound of the formula <FORM:1075501/C4-C5/2> wherein X is hydrogen or halogen with an amine H2N-Ar2 wherein Ar2 is an aromatic radical containing ortho to the NH2 group hydrogen or a replaceable substituent e.g. a hydroxy, ether or a thioether group; preferably Ar2 is a benzene or naphthalene radical; in presence of an inert organic solvent and if necessary buffering agents or acid condensing agents. Specified solvents used are xylenes, chlorobenzenes, nitrobenzene naphthalene and chloronaphthalenes, alcohols, glycols and esters derived therefrom.  The reaction takes place at 40 DEG  to 300 DEG  C.  When X in Formula I above is halogen and H2N-Ar2 is not further substituted and also when X is hydrogen the presence of an oxidizing agent e.g. atmospheric oxygen, nitrobenzene or nitrobenzene sulphonic acid is advantageous.  Acid buffering agents used are alkali metal hydroxides, carbonates and salts of low fatty acids, alkaline earth metal oxides, hydroxides and pyridine.  Acid condensing agents used are acid halides of carboxylic or sulphonic acids, thionyl chloride, phosphorus pentachloride, and inorganic chlorides. The pigments may also be prepared by a Friedel-Crafts reaction using compounds of the formula <FORM:1075501/C4-C5/3> wherein Y is Cl or Br with a benzene compound corresponding to Ar1 as defined above.  The pigments may be subsequently finely dispersed by dissolving in acid and precipitating with water or dry milling with inorganic and organic salts which can be removed by solvents. Example 105 describes a paste for printing inks containing hydrate of alumina, linseed oil varnish and cobalt linoleate in admixture with a dioxazine pigment of the formula <FORM:1075501/C4-C5/4>ALSO:Example 106 describes the colouring of a composition containing polyvinyl chloride, dioctyl phthalate, dibutyl tin dilaurate and titanium dioxide with a dioxazine pigment of the formula <FORM:1075501/C3/1> wherein the benzoylamino groups are replaced by acetyl amino groups. Example 107 describes compositions containing titanium dioxide, a modified alkyd resin, xylene, butanol, turpentine oil and either of the following pigments <FORM:1075501/C3/2> and <FORM:1075501/C3/3> in which the benzoyl amino groups contain a p-chlorine atom.ALSO:Compounds of general formula <FORM:1075501/C2/1> wherein X is H or halogen and Ar1 is a benzene radical which may be substituted are prepared by halogenating the 1,4-dihydroxy compounds which are subsequently oxidized to the 1,4-benzoquinones.