DE1202920B - Process for the production of dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Ct:

number
File number:
Registration date:
Display day:

C09b

German KI .: 22a-l

1 202 920
Z9924IVc / 22a
February 18, 1963
October 14, 1965

The invention relates to a method for the production of novel, in particular as a raw material for Ballpoint pen color pastes of suitable dyes.

A number of very color-intensive and brilliant color bases are known, but only a small one Have resistance to light. By reacting these basic dyes with acidic dyes one obtains products that are practically insoluble in water. In British patent specification 828 394 is the production of such dyes for the spirit ro carbon process, that is, for duplication purposes described. These products should have a particularly high solubility in ethyl alcohol. In contrast for this purpose, ballpoint pen color pastes, which are standardized in Germany, have to have particularly high fastness properties to chemicals and organic solvents, for reasons of Protection against counterfeiting the resistance to alcohol, i.e. the insolubility in ethyl alcohol, is one of the most important Properties represents.

As a solvent for the production of ballpoint pen color pastes Usually, in addition to some glycols, mainly benzyl alcohol is used.

This has posed a difficult problem that those used in the manufacture of ballpoint pen color pastes The dyes used in benzyl alcohol, i.e. in an alcohol, have a very high solubility but should be insoluble in another alcohol, namely spirit. This The problem could originally only be caused by the use of the extremely weakly colored copper phthalocyanine bases or their esters are dissolved, but they all have the disadvantage that it is they are not about uniform, pure products and that they are only used for the production of blue ballpoint pen color pastes suitable. In order to overcome this disadvantage, there is a phthalocyanine dye provided with sulfonic acid groups and these acidic, non-substantive dyes with certain Color bases combined to form salts that meet the diverse requirements for colorants for ballpoint pen color pastes should suffice. Such dyes are disclosed in British Patent 902,110 and US Pat U.S. Patents 2,950,285 and 2,950,286. In these patents there are also those listed various requirements to which a dye intended for ballpoint pen color pastes meet got to. It is then quite understandable that so far only a few dye compounds have been found proved to be suitable for ballpoint pen color pastes. The need for dyes of the Process for the production of dyes

Applicant:

Dr.-Ing. Bruno v. Zychlinski,

Mittenwald (Obb.), Innsbrucker Str. 35

Named as inventor:
Dr.-Ing. Bruno v. Zychlinski,
Horst Erb, Mittenwald (Obb.)

different color nuances is therefore by no means sufficiently covered.

The invention is therefore the production of dyes particularly high solubility in the for Ballpoint pen color pastes suitable for organic solvents, but with extremely low solubility in water and lower alcohols, which cover the largest possible range of color tones and combine high lightfastness with high resistance to chemicals. In particular The invention aims to produce the very color-intensive and brilliant, but not light-fast Color bases by chemical addition reactions into uniform, easily reproducible, new types of color to convert, in addition to a high solubility in those suitable for ballpoint pen color pastes Solvents have a high lightfastness and a particularly high degree of purity. Further The invention aims to provide a chemical manufacturing process specifically for this purpose is suitable, the modified by reaction with a suitable addition product basic To obtain dyes in a particularly pure form.

It has been found that these goals can be achieved 'if you use the basic dyes converts such acidic dyes that have substantive properties, as they are in the textile industry are used in a very large selection for dyeing textiles.

The invention accordingly relates to a process for the production of dyes which are used as raw materials suitable for ballpoint pen color pastes by reacting color bases with dye acids

509 717/390

water-soluble color salts, which are characterized is that substantive dyes are used as dye acids, which at least one Contain sulfonic acid and / or carboxyl group.

A preferred method is this. Dye bases with several basic groups and / or color acids with several - SOgH groups to be used. Particularly favorable results are shown when using dye acids that are at least contain a - COOH group.

It is of particular technical interest to implement either a polybasic dye base selected as the central molecule with several different dye bases or a polyhydric dye base selected as the central molecule with several different coloring acids in succession.

This makes it possible to produce different color nuances in a targeted manner.

The method according to the invention opens up the possibility, by far the most important To make the dye class, namely that of the azo dyes, usable for the ballpoint pen color pastes. These noun dye acids dissolve in the solvents suitable for ballpoint pen color pastes little or practically none at all. In addition, they are commercially available as textile dyes available preparations are set to a certain standard type, as they are with appropriate salts, z. B. table salt, Glauber's salt, etc. can be put to a certain color strength. So contain many marketable ones Azo dyes even in the form of the maximum accessible concentration only about 50 to 70 per cent. Dye, the rest is thickening agent. However, since even the slightest contamination of the dyes for use in ballpoint pen color pastes The free coloring acids of these nouns would have to be rendered useless, acidic dyes bring to use. However, these too have little or virtually no solubility in the solvents suitable for ballpoint pen color pastes, and they also have the The major disadvantage is that the pH of the paste is increased by the presence of free, i.e. not saturated SO3H or COOH groups moved in the strongly acidic range. The acidic action causes the mine tubes to become inevitably corroded, so that the resistance of the paste is greatly reduced.

The conversion of basic dyes with the nouns, acidic textile dyes leads to modification products, which meet the requirements discussed above in an excellent manner. They have an unusually high solubility in solvents suitable for ballpoint pen color pastes, are largely insoluble in alcohol and show excellent light and chemical 5s authenticity.

In addition to the advantages described, which result from the large selection of nouns dye acids as an implementation partner for the production of the modification products of color bases is also extremely useful in the field of technical production of these modification products favorable conditions shown. For the already known implementation of color bases with non-nouns Color acids is the use of the reactants either directly or in each case Form of their water-soluble salts has already been described. It has been stated that the products precipitate in resinous form after removing the supernatant solvent and cooling solidify and have to be scraped out of the reaction vessels. Partly is hereafter a Weddings and sifting described. It is now of particular advantage that when implementing with Substantive dye acids, in which the reactants each in the form of their water-soluble salts get used in aqueous solution, the reaction products in powdery crystalline form fail and therefore do not require any mechanical processing. In this way it is avoided that the Metal particles or the like originating from the milling process get into the dye products. Even the smallest firm Impurities on the order of less than 5 microns make ballpoint pen color pastes unusable because of these the clearances between the ball and the ball bed elements, especially the beaded edge.

The reactants remaining dissolved in the aqueous reaction medium include, on the one hand, the salt-binding ions, which are used for the production of the color base salts and the salts of nouns • dye acids were used, but it also includes those starting salts that are in excess were used. However, it is undesirable that such excesses remain because they reduce the yield do not increase and get lost unused, make cleaning difficult and pollute the wastewater. In addition, they harbor the risk of later crystallization and rendering useless Ballpoint pen color pastes if traces of them remain in the reaction product. The hiring of a exactly equivalent ratio is made much easier by the fact that both output partners Represent dyes. Reaching the neutralization point can therefore easily be monitored and adhered to by making sure that the aqueous solution is colorless after precipitation.

In the process according to the invention, the nouns listed below have dye acid classes proved to be very suitable:

I. Indulin and nigrosine dyes with reactive SOsH groups. such as B .:

CI Acid Black (Color Index No. 50 420)
CI Acid Blue 20 (Color Index No. 50 405)

II. Monoazo, disazo and trisazo dyes with 1 to 4 reactive SO ₃ H and / or COOH groups, such as. B .:

C. I. Direct Blue I (Color Index No. 24 410) C. I. Direct Blue 84 (Color Index No. 23 160) C. I. Direct Blue 3 (Color Index No. 23 705)

C. I. Direct Orange 29

(Color Index No. 29 155) C. I. Direct Orange 26

(Color Index No. 29,150) C. I. Direct Orange 34, 39

(Color Index No. 40,215) C. I. Direct Brown 101

(Color Index No. 31 740)

III. Chromating and staining dyes (cf.W i η η acker - Weingärtner: Chem. Technologie. P. 221 and 222) with 1 to 4 reactive SOeH groups that are both metal-free and can be used as a metal complex:

a) Dyes of the most varied classes of dyes, the following groupings in ortho- or in peri-position contain:

1. 2 hydroxyl groups.

2. 1 hydroxyl group and 1 COOH group.

3. 2 COOH groups.

b) Azo dyes which are in ortho or peri position to the azo group in or in two aromatic nuclei a hydroxyl ίο or carboxyl group or in one nucleus a hydroxyl or carboxyl group and in the other nucleus of the azo dye contain an amino group, e.g. B. o.o'-dioxy-, o-oxy-o'-carboxy-. o-amino-o'-oxy-, o-amino-o'-carboxy and o.o'-dicarboxy azo dyes.

According to their constitution, the chromizing and staining dyes belong to the following Dye classes on:

1. Azo dyes.

2. Triarylmethane dyes.

3. Anthraquinone dyes.

4. Oxazine dyes.

5. quinone dyes.

IV. Acid triphenylmethane dyes with 1 to reactive SOsH groups, such as:

C. I. Acid Blue 110 (Color Index No. 42 750) C. I. Acid Blue 48 (Color Index No. 42 770) C. I. Acid Blue 22 (Color Index No. 42 755) The acidic nouns falling under I to IV Dyes are the preferred usable partners for the implementation with the color bases.

The following are listed as representatives of the usable color bases:

A. triphenylmethane dye bases, e.g. B .:

C. I. Solvent Blue 2

(Color Index No. 42 563 B) C. I. Solvent Blue 4

(Color Index No. 44 045 B) C. I. Solvent Blue 5

(Color Index No. 42 595 B) C. I. Solvent Red 49

(Color Index No. 45 170 B) C. I. Solvent Violet 9

(Color Index No. 42 555 B) C. I. Solvent Violet 8

(Color Index No. 42 535 B) C. I. Solvent Brown 12

(Color Index No. 21 010 B) C. I. Solvent Green 1

(Color Index No. 42 000 B)

B. Basic dyes, such as ζ. Β .:

C. I. Basic Blue 1 (Color Index No. 42 025)

C. I. Basic Blue 5 (Color Index No. 42 140)

C. I. Basic Violet 4 (Color Index No. 42 600)

C. I. Basic Blue 18 (Color Index No. 42 705)

C. I. Basic Blue 11 (Color Index No. 44 040)

20th

C. Copper phthalocyanine bases. such as the following structural formula: CH ₃

N-CH ₂ -CH2-CH2-NH-O ₂ S
CH ₃

The implementation is expediently carried out as follows:

Preparation of the solution I.

7.5 parts of a color base are obtained by adding the corresponding equivalent amount of an acid, mostly acetic acid or hydrochloric acid, dissolved in 100 parts of hot water and filtered.

Preparation of the solution II

Parts of a noun dye acid are obtained by adding the corresponding equivalents Amount of a base, mostly sodium hydroxide solution, dissolved in 100 parts of hot water and filtered.

The filtered solution II is slowly introduced into solution I with stirring until a colorless mother liquor just arises. The CH _{3 SO 2} —NH — CH 2 —CH ₂ —CH ₂ —N

CH ₃

Water-insoluble precipitation product located aqueous solution can depending on the type of substantive used Dye and the color base warmed or heated to the boil and after about 10 minutes be separated from the precipitate by filtration or centrifugation. Because the two solutions I and II are filtered before the precipitation, no water-insoluble impurities can be in it be included. Depending on the type of acid and base used, readily water-soluble substances are formed during the reaction Salts, usually table salt or sodium acetate, which can be extracted easily and without difficulty Let the precipitate wash out so that an absolutely pure dye is obtained. After this Filtering, the dye can be dried at temperatures of up to 100 ° C. For a more detailed explanation are some examples of the manufacture of individual

Dyes listed that are modified in the context of the general description and by others Representatives can be added.

example 1
Solution I.

9 g of the basic dye »C. I. Basic Red 1 «are dissolved in 100 ml of hot water to the boil heated and filtered.

Solution II

6.5 g dye »C. I. Direct Orange 26 "are dissolved in 200 ml of hot water and heated to the boil and filtered.

Both solutions are combined at a temperature of 60 ° C. in such a way that solution II is allowed to slowly run into solution I until the mother liquor just becomes colorless. It is then ^{heated to 95 °} C., then the water-insoluble precipitate is separated from the mother liquor, washed out with water and dried.

A dye which is suitable for red ballpoint pen color paste and has excellent lightfastness is obtained, which, after being applied to paper, cannot be washed out by either alcohol or acetone.

Example 2
Solution I.

7.5 g of the basic dye »C. I. Basic Violet 3 «are dissolved in 80 ml of hot water, heated to boiling and filtered.

Solution II

11.5g sodium salt of the acidic nigrosine dye »C. I. Acid Black 2 «are hot in 150 ml Dissolved water, heated to boiling and filtered.

Both solutions are combined at 80 ^° C. in such a way that solution II is allowed to slowly run into solution I. The procedure of Example 1 is then followed.

An excellent dye which is suitable for bluish-black ballpoint pen color paste is obtained Lightfastness that cannot be washed off the paper by either alcohol or acetone leaves.

Example 3
Solution I.

10.5 g of the basic dye »C. I. Basic Blue 7 " are dissolved in 180 ml of hot water, heated to boiling and filtered.

Solution II

8 g of the disazo dye "Mordant Dye (Color Index No. 23 100)" are dissolved in 200 ml of hot water dissolved, heated to boiling and then filtered.

Both solutions are combined at 70 "C so that that solution II slowly runs into solution I. Then proceed as in example 1.

A dye of excellent quality which is suitable for dark navy blue ballpoint pen color paste is obtained Lightfastness that cannot be washed off the paper by either alcohol or acetone leaves.

Example 4
Solution I.

9 g of the copper phthalocyanine base under IV; C given structural formula are in 200 ml Dissolved 1/10 normal hydrochloric acid, heated to boiling and filtered.

Solution II

ίο 6.7 g of triphenylmethane dye acid "CI Acid Blue 48" are dissolved in 200 ml of 1/10 normal sodium hydroxide solution, heated to the boil and then filtered.
Both solutions are combined at 95 ^° C. in such a way that solution II slowly runs into solution I. Then proceed as in example 1.

A dye suitable for blue ballpoint pen color paste and having excellent lightfastness is obtained, which cannot be washed off the paper by either alcohol or acetone.

Example 5
Solution I.

10.0 g of the basic triphenylmethane dye »C. I. Basic Blue 8 «are in 250 ml hot Dissolved water, heated to boiling and filtered.

Solution II

8.7 g sodium salt of trisazo dye acid »C. I. Direct Brown 110 "are in 200 ml of hot water dissolved, heated to boiling and filtered.

Both solutions are combined at 40 ^° C. in such a way that solution II slowly runs into solution I. Then proceed as in example 1.

A dye of excellent quality which is suitable for brownish-black ballpoint pen color paste is obtained Lightfastness that cannot be washed off the paper by either alcohol or acetone leaves.

Claims (8)

Patent claims: 1. Process for the production of dyes, which are used as a base for ballpoint pen color pastes suitable, by reacting color bases with dye acids, to water-sparingly soluble Salts, characterized in that substantive dyes are used as dye acids can be used which contain at least one sulfonic acid and / or carboxyl group. 2. The method according to claim 1, characterized in that the reaction in aqueous Solution carried out and the color base in the form of a water-soluble salt with a suitable acid residue and the dye acid in the form of a water-soluble salt with a suitable base residue is used, the base residue and acid residue being selected so that that these two residues in turn form salts which are readily soluble in water with one another. 3. The method according to claim 2, characterized in that the color bases and the dye acids be used in exactly the same amount, whereby the neutralization point is reached is determined by the absence of excess reactive Dyes is determined by checking the colorlessness of the mother liquor. 4. The method according to claim 1 to 3, characterized in that color bases with several basic groups can be used. 5. The method according to claim 1 to 4, characterized in that dye acids with several SOaH groups are used. 6. The method according to claim 1 to 5, characterized in that dye acids with at least a COOH group can be used. 7. The method according to claim 1 to 6, characterized in that two or more different Dye bases with a polybasic dye acid compound selected as the central molecule 10 can be implemented one after the other. 8. The method according to claim 1 to 6, characterized in that two or more different Color acids successively with a polyacid color base selected as the central molecule implemented. Considered publications:
British Patent No. 902,110;
U.S. Patent Nos. 2,950,285, 2,950,286, 966,418.