DE2009749A1 - Daytime luminous pigments - Google Patents

Description

Daylight luminous pigments The invention relates to daylight luminous pigments, the dyes of the general formulas Ia or Ib in fully condensed melamine-formaldehyde resins which are optionally cocoked with aryl or benzylsulfonamides, where R -a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, one optionally with alkoxy, chlorine, bromine, carboxyl, carbalkoxy, carbonamide or acetoxy substituted alkyl group with 1 to 4 carbon atoms, a cyclohexyl, benzyl or phenylethyl group, R1 is a hydrogen atom, an alkyl group with 1 to 4 Eohlenstoffatoaen or an optionally substituted by alkoxy, chlorine, bromine, carboxyl, carbalkoxy, carbonamide or acetoxy alkyl group with 1 to 4 carbon atoms, R and R1 together with the nitrogen the remainder of a 5- or 6-membered heterocyclic ring, a hydrogen atom or a methyl or ethyl group, R3 a hydrogen, chlorine or bromine atom or a methyl, ethyl, methoxy or ethoxy group, R4 is an optionally substituted lower alkyl radical or benzyl radical, n is the number 0 or 1, be Anion or an —SO3 group and X a radical of the formulas Y, OH, Z, OZ, OR5 or denote, where R5 is an alkyl, aralkyl or aryl radical, R6 is a hydrogen atom, an optionally substituted alkyl radical, a cycloalkyl, aralkyl or aryl radical, a hydrogen atom, an optionally substituted alkyl radical, a cycloalkyl, aralkyl or aryl radical, R6 and R7 together with the nitrogen denote a heterocyclic ring, Y denote an alkyl or substituted alkyl radical and Z denote a cation.

In addition to the radicals already mentioned, examples of substituents are named: for R and R1: methyl, ethyl, n- or i-propyl, n- or i-butyl, ß-methoxyethyl, ß-ethoxyethyl, ß-acetoxyethyl, ß-chloroethyl, ß-carbomethoxyethyl, ß-carboethoxyethyl, ß-carbobutoxyethyl, ß-methoxypropyl, ß-ethoxypropyl, ß-methoxy-γ-chloropropyl or B-acetoxypropyl.

Together with the nitrogen, R and R1 mean z. B. the rest of the pyrrolidine, Piperidine or morpholine.

for R4: methyl, ethyl, β-hydroxyethyl or β-cyanoethyl.

for R5: methyl, ethyl, benzyl or phenyl.

for R6 and R7: methyl, ethyl, butyl, hexyl, ß-aminoethyl, ß-hydroxyethyl, cyclohexyl, benzyl, phenylethyl, phenyl, acetylaminophenyl for R6 and R7 together with the nitrogen: morpholide, piperidide or pyrrolidide.

for Y: methyl, ethyl, ß-cyanoethyl, # -carbonamidoethyl, ß-hydroxyethyl or hydroxypropyl.

for Z: sodium °, potassium °, barium 1/2 °, calcium 1/2 °, ammonium ° or substituted ammonium *.

for Aq: chloride, sulfate, methosulfate, formate, acetate or etrachlorozincate.

Substituted ammonium cations are, for example, those in which one or more hydrogen atoms are substituted by alkyl, cycloalkyl, aralkyl or aryl. In detail z. B. the ammonium cations of the formulas called.

Nelamine formaldehyde resins are made by condensing 1 mole of melamine with 1.5 to 6, preferably 2.5 to 3.5 mol, formula aldehyde or formaldehyde donating Funds received. The cocondensed resins also contain aryl or Benzylealphonamides and an additional amount necessary for their condensation Formaldehyde, expediently 0.5 to 3 mol.

The sulfonamides can, based on melamine, in up to 20 times Amount by weight to be contained in the resins.

The use of toluenesulfonamide is preferred.

The resins are thermoplastic or duroplastic, depending on their composition.

Resins which can be used according to the invention are, for. B. from US patents 2 809 954 or 2 851 424 known.

Technically preferred daylight luminous pigments contain compounds of the general formulas IIa or IIb as dyes whether ei R8 is a methyl or ethyl group, B is a methyl or ethyl group and A ° is an anion and X has the meaning given.

Of the compounds of the formula IIa, preference is again given to those in which X is an amine radical, an O-alkyl or O-phenyl radical, optionally one substituted alkyl or phenyl radical or the radical ° Z1, where Z1 is a substituted one Is ammonium cation.

The new daylight luminous pigments are obtained by the Dyes of the general formula I before or during the condensation reaction to the melamine resins described above. The colored hares can after the complete condensation according to the usual methods in the for the respective Intended use of the most favorable pigment form can be transferred.

The new pigments are characterized by excellent brilliance, good Wet fastness and solvent fastness. They are very suitable for mass coloring of plastics and paper and for use in printing inks, paints and Lacquers.

Parts and percentages in the following examples relate to unless otherwise noted, based on weight.

Example 1 34.2 parts of o, p-toluenesulfonamide, 10.4 parts of melamine, 19.4 parts of paraformaldehyde and 2 parts of the dye of the formula are mixed and melted and homogenized at 10000, then hardened for 1.5 hours at 160 ° C, cooled and ground. About 55 parts of a brilliant yellow pigment are obtained. 1 part of the pigment produced in this way results in a brilliant, yellow plastic incorporated into 100 parts of a soft polyvinyl chloride mixture.

Example 2 171 parts of o, p-toluenesulfonamide, 25.6 parts of melamine and 47.5 parts of formaldehyde are melted at 80 ° C. and then cooled. The melt is dissolved in dimethylformamide with 8 parts of the dye of the formula added and freed from dimethylformamide under reduced pressure. The residue is condensed out at 150 ° for 1.5 hours and then ground.

20 parts of the pigment produced in this way are mixed with 100 parts of a Solution of 40 parts of modified rosin resin in 60 parts of toluene to form a Processed gravure ink, which gives very brilliant, yellow prints.

Example 3 104 parts of melamine, 74 parts of paraformaldehyde and 4.6 parts of the dye of the formula dissolved in dimethylformamide are mixed well, melted at 110 ° C and homogenized. After condensing out for one and a half hours at 160 ° C., the product is ground. 5 parts of the pigment are incorporated into a lacquer which consists of 20 parts of nitrocellulose and 80 parts of solvent. A brilliant, yellow varnish for painting purposes is obtained.

EXAMPLE 4 171 parts of o, p-toluenesulfonamide, 52 parts of melamine and 67 parts of paraformaldehyde are mixed well, melted at 90 ° and 10 parts of the dye of the formula offset. After homogenization, the mixture is cured for 1 hour and, after cooling, it is ground to form the pigment.

40 parts of this pigment, 15 parts of a reaction product the end 1 mole of sperm oil alcohol and 24 to 25 moles of ethylene oxide, 8 parts of ethylene glycol and 30 parts of water are rubbed into a paste with the usual equipment processed.

This paste, in a binder and thickener customary for pigment printing incorporated, printed on textile material and hardened, results in a very brilliant, yellow textile print.

Example 5 171 parts of o, p-toluenesulfonamide, 52 parts of melamine and 6 parts of the dye of the formula are melted at 120 ° C., homogenized, mixed with 80 parts of paraformaldehyde, completely condensed out at 160 ° C. and, after cooling, ground. 40 parts of this pigment are processed into a paste as in Example 4.

500 parts of an aqueous paper pulp containing 50 parts of dry paper pulp, are mixed with 1 part of this pigment paste. From this wet one lets in make brilliant yellow paper.

As in Example 1, the following dyes were converted to brilliant, yellow pigments: Example R 6 ONa 7 OH 8 NHSO2C6H5 9 NHCH2CH2OH 10 NH C4H9 Example R 11 N (CH3) 2 12 Well 13 H5C2NC6H5 14 H5C2NC6H13 15 NHCH2 CH2NH2 16 NH (CH2) 6NH2 17 NHC6H4NHCOCH3 (m) 18 NH-NHC0CH3 S03H 19 C6H5N02 20 NH2 21 CH2CH2CN 22 CE20H20 ° NH2 23 O (Ba) 1/2 C2H5 24 ONH3 (CH2) 30CH2CHC4Hg 25 ON (CH3) 2017H35 0112 C6115 26 N (3) 2 6 5 CH2 C6H5 27 0NH 28 0112 -C6H5 and, as Example 29, the dye of the formula CH, YN -; 0-SO, e (2 5) 2 A SoCH3

Claims (2)

Claims 1. Daylight luminous pigments, the dyes of the general formulas Ia or Ib in fully condensed melamine-formaldehyde resins, which are optionally cocondensed with aryl or benzyl sulfonamides, where R is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, one optionally by alkoxy, chlorine, bromine, carboxyl, carbalkoxy, carbonamide or acetoxy substituted alkyl group with 1 to 4 carbon atoms, a cyclohexyl, benzyl or phenylethyl group, R1 a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or an optionally substituted by alkoxy, chlorine, bromine, carboxyl, carbalkoxy, carbonamide or acetoxy alkyl group with 1 to 4 carbon atoms, R and R1 together with nitrogen the remainder of a 5- or 6-membered heterocyclic ring, R2 a hydrogen atom or a methyl or ethyl group, R a hydrogen, chlorine or bromine atom or a methyl, ethyl, methoxy or ethoxy group, pure optionally substituted lower alkyl radical or bensyl radical, n the numbers 0 or 1, Ae an An ion and X is a radical of the formulas Y, OH, Z, OZ, OR5 or where R5 is an alkyl, aralkyl or aryl radical, R6 is a hydrogen atom, an optionally substituted alkyl radical, a cycloalkyl, aralkyl or aryl radical, R7 is a hydrogen atom, an optionally substituted alkyl radical, a cycloalkyl, aralkyl or aryl radical, R6 and R7 together with nitrogen denotes a heterocyclic ring, Y denotes an alkyl or substituted alkyl radical and Z denotes a cation. 2. daylight luminous pigments according to claim 1, the dyes of the general formulas contain, where R8 is a methyl or ethyl group, 3 is a methyl or ethyl group and A e is an anion and X has the meaning given.