DE1248835B - Writing pastes and duplicating compounds - Google Patents

Description

GERMAN

PATENT OFFICE

EDITORIAL

German class: 22 g -1

Number: 1248 835.

File number: B 63140IV c / 22 g

Filing date: July 5, 1961

Opened on August 31, 1967

For the production of high-quality, indelible stamp inks, ballpoint pen pastes and duplicating materials The dyes required should have good fastness properties and high color intensity have a high solubility in only one specific solvent. How to use to manufacture such paints and pastes N-substituted sulfonic acid amides of copper phthalocyanines or also N-substituted aminomethylphthalocyanines in benzyl alcohol and possibly also in glycol ethers soluble in other solvents, ζ. B. in aliphatic alcohols, esters and ketones, however, practical are insoluble (see German Auslegeschrift 1 097 596).

Such ballpoint pen pastes are obtained in accordance with the characteristic shades of the phthalocyanines but only in strong greenish blue tones. To adjust other nuances, it is necessary to in addition, other alcohol-soluble dyes or fatty acid salts of color bases to use. However, all previously known shading dyes have the disadvantage that they are from the Scriptures produced with such pastes bleed out very heavily when treated with solvents.

It has now been found that ballpoint pen pastes and duplicating compositions have excellent fastness properties and excellent selective solubility in benzyl alcohol when they have salt-like reaction products from acidic dyes as dyes and optionally acidic resins and from basic substituted phthalocyanines of the general formula

Pc - CHo-N

in which Pc is the radical of a metal-containing or metal-free phthalocyanine _{molecule, optionally substituted one or more times by chlorine or by phenyl groups, in which R 1} and R _{2 are} hydrogen or Rj and R ₂ together contain no more than 6 carbon atoms or Rj and R _{2 are} common constituents of one can be heterocyclic ring and in which η can have the values 2 to 8, preferably 2 to 5, contain.

_{Salts of those basic substituted phthalocyanines in which R 1} and R ₂ together contain no more than 6 carbon atoms are suitable for the mixtures of substances according to the invention, e.g. B. those where the grouping

Writing pastes and duplicating compounds

Applicant:

Aniline & Soda Factory in Baden
Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Wolfgang Gerstner, Heidelberg;

Dr. Hans Otterbach, Frankenthal;

Helmut Finkenauer,

Dr. Walter Seibert, Ludwigshafen / Rhine;

Dr. Arnold Tartter, Lambsheim (Palatinate)

the rest of the Propylamine, Dipropylamine, Isopropylamms, Diisopropylamine, of N-methylethanol

amines, N-ethylethanolamine, cyclohexylamine, des pyrrolidine, piperidine, hexamethyleneimine or morpholine.

The basic substituted phthalocyanines can be metal-free or metal complexes, in particular those that do not release their metal when treated with sulfuric acid, such as nickel complexes, Cobalt, iron, aluminum, chromium, zinc and preferably copper. In addition, the basic substituted phthalocyanines still singly or multiply by chlorine or by phenyl groups be substituted.

As acidic dyes, i.e. H. as acidic components - they can also be used as laking components denote - many acidic dyes come into consideration, z. B. carboxyl groups or sulfonic acid groups bearing azo and triaryl methane dyes. May be mentioned e.g. B. the following in the Color Index registered dyes: 45 190, 13 045, 44 075, 43 525, 42 745, 73 015, 45 380, 45 435, 15 580 and 18 690. The dyes used according to the invention can be used in a conventional manner, for. B. by mutual Precipitation of the basic and acidic dye components or their water-soluble salts aqueous solution. If both components are already soluble in benzyl alcohol, is it is advantageous to start from benzyl alcoholic solutions of the dyes.

709 639/536

3 4

It is often also useful to prepare the basic substituted (Color Index No. 45 190) from aqueous solution with phthalocyanine together with the acidic dye 80 ⁰ C and then washed and finely ground and then dried in benzyl alcohol, with 50 parts of Benzylzu to solve. In general, such hydrochloric alcohol is used on a water bath for about 30 minutes with similar reaction products as dyes, in which stirring is heated to 90 ° C until the dyestuff residue, the acidic and basic components have dissolved as freely as possible. Then 25 parts are used in equimolar amounts. Such colored varnishes of a solvent-free, brittle urea form are further processed as usual with benzyl alcohol and binder aldehyde resin (softening point about 5S ^ C ^ acids; the proportion of binder is practically zero) and warmed up, birdie is usually 20 with ballpoint pen pastes until io mass is homogeneous. After cooling down! ErTÜsÜffi r $ at 35 percent by weight. Pastes and colors of various a ballpoint pen paste that have a reiri &. Reddish-tinged compositions can of course also result in blue writing, which can be mixed with handling to achieve further nuances. Water and alcohol does not bleed.

The dye solutions have to be used for some purposes, e.g. B. for the production of ball 15 Example2
Pen pastes are mixed with a binding agent
will. This is achieved by adding neutral, ', 20 parts of tri- (N-pyrrolidino-aminomethyl) copper

Resins soluble in benzyl alcohol and bearing acidic groups. When talking about phthalocyanine components goes out, which carry more basic groups than are claimed by the dye anions, also forms

phthalocyanine are dissolved along with 5 parts of the chromium complex of the azomethine dye from Nitraminsäure and salicylaldehyde in 50 parts of benzyl alcohol at 90 ⁰ C. Dissolves in the warm solution

the binder - e.g. B. acidic polyester resins or then 25 parts of a phthalic acid hexanetriol ester

acidic phenolic resins - one unit with the dye. the acid number 80 to 90. The paste produced in this way gives

Fonts made with such pastes are opposed to a bright green font that is in water and alcohol

particularly resistant to chemical influences. 25 does not bleed to death.

With a suitable combination of the acidic and basic example 3
Dye components are obtained in benzyl alcohol

soluble dyes in all nuances from the yellowish 50 parts tri - (N - methyl - N - hydroxyethyl - amino-

to bluish green, from greenish to red methyl) copper phthalocyanine with 50 parts

cast blue and purple as well as black dyes. 30 finely grind oxalic acid. The aqueous solution of this

Containing pastes such dyes must therefore mixture is at 6O ⁰ C with an aqueous solution

no shading dyes are added. of a sulfated triarylmethane dye (Color Index

It is surprising that No. 44 075) according to the invention is added until what is used is filtered off salt-like dyes on the one hand, a colorless filtrate is obtained. 25 parts have excellent fastness properties and other 35 of the washed and dried precipitate on the other hand are selectively soluble in benzyl alcohol. Together with 25 parts of the example 1 Writings and stamps with dye solutions, said resin dissolved in 50 parts of benzyl alcohol, which contain the dyes according to the invention in A paste is obtained with the brilliant deep blue to an unexpected extent resistant to all stamps or writings that are in water, common solvents are, for. B. water, 40 ethanol and acetone do not bleed, on paper or Alcohols, acetone or esters, will be applied by the pre- other materials The present invention meets the need for a greater variety of di- (N-diethyl-aminomethyl) copper uses document-proof ballpoint pen and star phthalocyanine as the basic dye component, see above fur-colored account. a paste with similar properties is obtained.

The subject of the earlier patent 1132 275 is dye 45 '.

pastes for ballpoint pens, which were obtained by implementing an example 4

basic substituents containing phthalocyanines 15TeüeTri- (N-diethyl-aminomethyl) -kupferphthalo-

with an acidic triphenylmethane dye in a cyanine are mixed with 10 parts of the in Example 2

Amount from 0.4 to about 60%, based on the azomethine dye mentioned and with 5 parts

Phthalocyanine derivative, in the presence of one and 50 tetrabromofluorescein (free acid) in a ball mill

or or polyhydric alcohols and / or finely ground.

Ketones are obtained. 30. Parts of this mixture are then with

Deviating from these general recommendations 50 parts of benzyl alcohol and 25 parts of the in Example 2 one receives the writing pastes and duplication-called phthalic acid ester resin on the water masses of the present invention heated by reaction 55 bath until the mass is homogeneous. After the sour of organic dyes with basic substi- cools you get a ballpoint pen paste, whose Phthalocyanines of a certain constitution have neutral black writing in the usual solvents and optionally acidic resins. This implementation does not bleed out.

products differ from those of the If you combine 15 parts of the phthalocyanine dye

older proposal due to particularly good properties. 60 substance with 10 parts of the sulfoic acid of the azo dye

The parts mentioned in the examples are by weight from 2-amino-naphthalene-l-sulfonic acid and 2-hydroxy

share. naphthalene, a paste of blue-gray is obtained

Example 1 paint with similar properties.

25 parts of a violet dye, which by 65 B e 1 s ρ 1 e 1 5
Precipitation of the hydrochloride of tri- (N-hexamethylene-20 parts of penta- (N-pyrrolidino-aminomethyl) -nickelimino-methyl) -copper phthalocyanine with equivalent phthalocyanine, together with 5 parts of tetrates, amounts of a sulfated triarylmethane dye bromofluorescein (free acid) analogous to example 4 to a

Processed paste. This paste produces a purple font with very good solvent resistance.

Claims (1)

Claim: Writing pastes and duplicating masses with a content of salt-like reaction products of acidic substances or acidic dyes and basic substituted phthalocyanine as Dyes, characterized in that they are salt-like reaction products of acidic organic dyes with basic substituted phthalocyanines of the general formula Pc-CH in which Pc is the radical of a metal-containing or metal-free phthalocyanine _{molecule, optionally substituted one or more times by chlorine or by phenyl groups, in which R 1} and R _{2 are} hydrogen or R ₁ and R ₂ together contain no more than 6 carbon atoms, or R ₁ and R ₂ can be common constituents of a heterocyclic ring and in which η can assume the values 2 to 8, and optionally contain acidic resins. Considered publications:
British Patent Nos. 803 525, 828 394;
Belgian Patent No. 540187;
U.S. Patent No. 2,950,285. When the registration was announced, 2 staining tables were laid out. 709 639/535 3.67 © Bundesdruckerei Berlin