CH424046A - Process for the preparation of dyes of the phthalocyanine series - Google Patents

Description

  

  Process for the preparation of dyes of the phthaloeyanine series The invention relates to a process for the preparation of dyes of the phthalocyanine series of the .Formel
EMI0001.0007
    where P'c is the remainder of a dye of the phthalocyanine series, y is an optionally. substituted alkylene group or a bridge member bonded to the neighboring basic nitrogen atom via such a group,

            R1 is an optionally substituted alkyl, cycloalkyl or aralkyl radical, or, together with R2 and the adjacent N atom, a heterocyclic ring system, or, together with the bridge member y and the adjacent N atom heterocyclic ring system, R2 optionally,

  substituted alkyl, cycloalkyl or aralkyl radical, or, together with R1 and the adjacent N atom, a heterocyclic ring system, R3 and R4 are hydrogen or the same or different from one another;

  optionally substituted alkyl, cycloalkyl or aralkyl radicals, n is a lower integer and each is one equivalent to the dye cation. Mean anion.

      The dyes of the formula (I) can be obtained by using a compound of the formula Pc - (- y - E) n (II) wherein E is the acid residue of an ester and Pc, y and n have the meanings given above a compound of the formula
EMI0001.0061
    implements.

    Metal-free and metal-containing dyes are suitable as dyes of the phthalocyanine series. The metal-containing phthalocyanine dyes contain coordinatively bound heavy metal atoms, such as copper, nickel, iron, cobalt, zinc, aluminum, cadmium, lead, mercury, tin, Manigan, chromium, etc. Among the.

       The term pthalocyanine dyes includes all metal-free and metal-containing dyes mentioned above, which can be further substituted as desired.



  As substituents are z. B. Mentioned: -SO, H, COOH, halogen (chlorine, bromine, fluorine), nitro, cyano, mercaptan, optionally substituted alkyl, such as haloalkyl, optionally substituted alkoxy, optionally substituted amino, such as alkyl- or phenylamino, optionally substituted Aryl,

          preferably optionally substituted phenyl, optionally substituted alkyl sulfone, optionally substituted sulfonic acid amide, such as alkyl or phenyl sulfonic acid amide, acetyl, etc.



       Preferably, those metal-free or metal-containing phthalocyanine dyes are to be understood which can contain the abovementioned substituents, with the exception of substituents which make them water-soluble. As examples, are; called:

          Phthalocyanine, copper phthalocyanine, nickel, iron, cobalt and aluminum phthalocyanine, chloromethylated copper phthalocyanine, copper octa-3,6-chlorophthalocyanine, copper tetra-4-benzoyl phthalocyanine, TH-3-phenyl tetra 5-cyano-copper phthalocyanine, Copper tetra-4-para-tolyl mercaptophthalocyanine.,

          Tetraphenyl copper phthalocyanine, copper tetra-4benzyl thiophthalocyanine, etc.



  The bridge member y can stand for a divalent radical, preferably an optionally substituted alkylene group or alkenyl group, or a bridge member bonded to the adjacent basic nitrogen atom via such a radical;

       the optionally substituted alkylene group or alkenyl group can also be interrupted by heteroatoms, such as nitrogen, oxygen or sulfur atoms, etc.

   Examples are:
EMI0002.0089
         - (CH2) m- where m is preferably the number 1 to 6, -S02-NH-hydrocarbon residue, -CO- hydrocarbon residue, -NH-CO-hydrocarbon residue, -NH-SO2-hydrocarbon residue, -O hydrocarbon residue,
EMI0002.0098
         -CO-O hydrocarbon radical, oxazolyl, thiazolyl, imidazolyl radical,

      etc., the hydrocarbon radical preferably being an alkylene group with, for example, il to. 6. Means carbon.

   The hydrocarbon radical can, however, also represent an optionally substituted alkylene group or an optionally substituted aromatic radical, preferably an optionally substituted phenyl or naphthyl radical, the aromatic radical preferably being bonded to the adjacent basic N atom via an alkylene radical.



  But y can also form a heterocyclic ring system together with R1 and the adjacent N atom, so that ring groupings such as
EMI0002.0127
    can arise.

   Such compounds are obtained, for example, by reacting dihalogen compounds with hydrazines, such as. B.
EMI0002.0134
         R1 and R2 can, however, also without y together n n ät the neighboring, N-,

  Atom form a heterocyclic ring system, ialso z. B .. a pyrrolidine, piperazine, morpholine or mperidine ring, or an ethyleneimino group.



  Anion X is understood to mean both organic and organic ions, such as. B. methyl sulfate, ethyl sulfate, sulfate, disulfate, perchlorate, chloride, bromide, iodide, phosphorus molybdate, Phosphorwolf rammolybdate, benzenesulfionate. Or 4 chlorobenzene sulfonate ions.



  Examples of acid residues E are those of sulfuric acid (where E stands for SO4H); a sulfonic acid (where E is SOgR; where R is an optionally substituted hydrocarbon radical), of hydrogen sulfide (where E is SH); but preferably those of halo was.serstoffäure, where E stands for chlorine, bromine, etc., into consideration.



       As hydrazines of the formula (III) come into consideration, for example, those which carry 2 hydrocarbon radicals bonded to the same nitrogen atom, u. a. the optionally further substituted N, N-dialkylhydrazines such.

       B. N, N dirnethyl, N, N diethyl, N, NDn-propyl, N, N di-isapropyl, N, N-di-n-butyl, N-methyl-N-ethyl, N -Methyl-Nn-propyl-, N-methyl-Nn butyl-, N-ethyl Nn pro @ pyl-, N ethyl-N "isopropyl-,

            N-methyl N-ss-hydroxy-äthyl-, N Äthyl-N ss-hydroxyäthyl-, N-methyl-N ss-hydroxypropyl-, N-Methyl-Ny-hydroxypropyl-, N, N Di- (ss hydroxyätyhl) - , N, N-di-o-hydroxypropyl) hydrazine; the optionally further substituted N-alkyl-N-cycloalkylhydrazines such. B.

         N-methyl-N-cyclohexyl-, N-ethyl-N-cyclohexyl-, N-methyl-N-4'-methylcyclohexyl-, N, ss hydroxyethyl-N-cyclohexylhydrazine; and N, N-dicyclohexylhydrazine as an example of an N, N-dicycloalkylhydrazine; the optionally further substituted N-alkyl-N-aralkylhydrazines such. B.



       N-methyl-N-benzyl-, N-ethyl-N-benzyl-, Nss-hydroxyethyl-N-benzyl-, N-methyl-N-phenylether-, N-ethyl-N-phenylethyl-, N, ss-hydroxyethyl N phenylethylhydrazine , as well as the N, N-dibenzyl and N, N di (phenylethyl) hydrazines as examples of N, N-di-aralkyl hydrazines;

      but also the, optionally further substituted tri- or tetraalkylhydrazines, such as. B, N, N, N'-trimethyl-, N, N, N 'triethyl-, N, N-dimethyl-N'-ethyl-, N, N diethyl-N'-methyl-, N-methyl-N, N'-diethyl-, N-ethyl-N, N'-dimethyl-, N, N Dmethyl N'-n-, propyl-, N, N-dimethyl-N'-n-butyl-,

            N, N dimethyl-N'ss-hydroxyethyl-, N, N diethyl-N'-ss-hydroxyethyl-, N, N, N ', N' tetramethyl-, N, N, N ', N' tetraethyl-, N , N dsmethyl N ', N'-diethyl-, N, N4-dimethyl N', N'-di-o-hydroxyethyl) -, N, N dimethylN ', N'-di-n propyl hydrazine;

       also N, N dimethyl-N'-benzyl-, N, N-dimethyl-N'-phenylethyl-, N, N dimethyl, N'-cyclohexyl-, N, N, N'-trimethyl N '- # b-enzyl- hydrazine and N, aminopiperidine, N-methylaminopiperidine, N dimethylaminopiperidine, N-aminomorpholine, N methylaminomorpholine, N dimethylaminomorpholine.



       N, N-dimethylhydrazine (asymmetrical dimethylhydrazine) of the formula is preferably used
EMI0003.0113
         The reaction of a compound of the formula (II) with a hydrazine of the formula (11I): is preferably carried out in an organic solvent and at temperatures from -50 to 250 C.

   However, the reaction can also be carried out in an aqueous medium, if appropriate with the addition of an organic solvent at the abovementioned temperatures, if appropriate under pressure, or without a solvent or an excess of a hydrazine.



  The quantitative implementation z. B. a compound of the formula (11I) with a phthalocyanine of the formula (H) mentioned, for example with a chloromethylated phthalocyanine, or with a chloromethylated phthalocyanine mixture, depends on the number of - (- y - E)

  -Groups in the individual phthalocyanine molecules.



  The mixtures can contain, for example, phthalocyanine molecules which each individually have 1, 2, 3 to 8 - (- y - E) groups, so that, for example, a chloromethylated phthalocyanine mixture can be present with a - (- y - E) group content of 3.5.

   This phthalocyanine mixture is now advantageously reacted with at least 3.5 mol of a compound of the formula (11I).



  It can be seen from this that an abovementioned phthalocyanine or a phthalocyanine mixture which has n groups - (- yE), where n is a number from 1 to 8, preferably 1 to 4, advantageously with at least n mol of a compound the formula (11I) is implemented, whereby, as explained above, fractions of whole numbers of moles can also be used.

   The individual phthalocyanine compound of the formulas (1I) is thus n times, i.e. H. reacted with a low integer of a compound of formula (III). In other words, at least one group of a compound of formula (III) should advantageously be reacted with one another per group of formula - (- y - E).



  The dyes formed are separated off after one of the following: the customary basic operations such as filtration, evaporation and filtration, precipitation in a suitable medium and filtration.



       The new dyes are preferably used for printing; Formed from polymers with more than 80% acrylonitrile, for example polyacrylonitrile, z.

   B. Orlon (registered trademark), and copolymers of 80 to 95% acrylonitrile and 20 to 5% vinyl acetate, methyl acrylate or methyl methacrylate. Such products are among the following z. T.

         registered trademarks: Acrilan (the copolymer of 85% acrylonitrile and 15% vinyl acetate or vinylpyridine), Orlon, Dralon, Cour telle, Crylor, Dynel, etc.



  The dyeings have good general fastness properties on these materials, such as light, washing, fulling, perspiration, sublimation, pleating, decatur, ironing, water, seawater, perchlorethylene, bleaching, dry cleaning, over-dyeing - and solvent fastness.



       Some of them are also suitable for dyeing polyacrylonitrile in bulk in lightfast and wetfast shades. In part, those derivatives that have good solubility in organic solvents are also used for coloring oils, varnishes, plastic;

      Masses, plastics, and also suitable for spinning plastic masses dissolved in organic solvents.



  Furthermore, some of the new dyes can be used for many other purposes, for example for dyeing and printing cotton, tannin cotton, rayon, wool, silk, cellulose, regenerated cellulose, synthetic polyamide fibers and paper in, each, .production stage.

   The dyes can also be used for printing polyester fibers. It has been shown that mixtures of two or more dyes of the formula (I) can also advantageously be used.

   Here, too, the following are important general fastness properties:; good light and wet fastness properties, in particular good fastness to washing, perspiration, sublimation, pleating, decatur, ironing, water, seawater, solvents and over-dyeing.



  In the following examples, the parts are parts by weight, the percentages are percentages by weight and the temperatures are given in degrees Celsius.



  <I> Example 1 </I> 18.4 parts (1/4 mol) of a chloromethylated copper phthalocyanine: of the formula
EMI0004.0090
    are mixed in powdered form in 100 parts of dimethylformamide.

   At 20, 6.1 parts (3.35 / 4o mol + <I> 20 </I> / o excess) of asymmetric dimethylhydrazine of the formula are added
EMI0004.0101
    and stir at the same temperature for 24 hours. The precipitated color salt is filtered, washed with 50 parts of ethanol and dried. A blue powder is obtained which colors Orion (registered trademark) in brilliant blue tones.



  <I> Example 1 a </I> 18.4 parts of the chloromethylated copper phthalocyanine dye, of the formula
EMI0004.0111
         stirred in 150 parts of dimethylformamide, and in place of the 6,, 1 part of asymmetric dimethylhydrazine of Example 1, reacted with 1.65 parts of asymmetric dimethylhydrazine,

   this gives a color salt of the formula
EMI0004.0121
    Coloring example A 20 parts of the color staff obtained according to Example 1 are intimately ground with 40 parts of dextrin and 15 parts of Glauber's salt for 24 hours in a ball mill, and a suspension is prepared with 25 parts of butyl carbitol and 50 parts of water and then mixed with 500 parts of crystal rubber 1: 2, 30 parts of glycerine and 3210 parts of water.

   The printing paste obtained in this way is set to a p11 value of 8. Cotton satin, which has been made absorbent by means of an alkaline pretreatment, is wetted with this printing paste and the material to be dyed is then subjected to intermediate drying for 10 minutes at 9.0. The fixation takes place at 140 for <B> 30 </B> minutes.



  A genuine level, brilliant blue print of excellent lightfastness and washfastness and very good general fastness properties is obtained.



  <I> Dyeing example B </I> 70 parts of chemically bleached sulfite cellulose and 310 parts of chemically bleached birch cellulose are whipped into a pulper.



  0.2 part of the dye of Example 1 dissolved in water is added to this mass. After 10 minutes, sheets of paper are used with this mass.



       The absorbent paper produced in this way has a turquoise blue shade of medium intensity. Although the paper is not sized and does not contain any fixing agent, the dye is so well fixed that the wastewater is colorless when the sheets are formed and: the coloring does not bleed onto the white filter paper during a 2-hour sandwich test.

 

Claims (1)

PATENT CLAIMS I. Process for the preparation of dyes of the phthalocyanine series of the formula EMI0005.0003 in which Pe is the remainder of a dye, of the phthalocyanine series, y is an optionally substituted alkylene group or a bridge member bonded to the adjacent basic N atom via such a group, R1 is an optionally; substituted alkyl, cycloalkyl, moderately aralkyl radical or, together with R2 and the adjacent N atom, a heterocyclic ring system or, together with the bridge member y and the adjacent N atom, a heterocyclic ring system, R2 a ; optionally substituted alkyl, cycloalkyl or aralkyl radical or, together with R and the adjacent N atom, a heterocyclic ring system, R3 and R, hydrogen or identical or different, optionally substituted alkyl , Cycloalkyl or aralkyl radicals, n; is a low integer and X is an anion equivalent to the dye cation, be, d: euten, characterized in that a compound of the formula PC - + - y - E) n (I I) in which E is the acid radical of an ester and Pc, y and n have the meanings given above, with a compound of the formula EMI0005.0065 implements. II. Use of the dyes obtained by the process claimed in claim (1) for dyeing or printing paper.