GB1561830A

GB1561830A - Sals of monoazo dyestuffs

Info

Publication number: GB1561830A
Application number: GB53039/76A
Authority: GB
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1975-12-20
Filing date: 1976-12-20
Publication date: 1980-03-05
Also published as: DE2557561A1; JPS5277127A; BE849389A; FR2335493A1; CH606320A5

Description

(54) SALTS OF MONOAZO DYESTUFFS (71) We, BASF AKTIENGESELLSCHAFT, a German Joint Stock Company of 6700 Ludwigshafen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The invention relates to salts of the general formula (I):-

in which X is hydrogen, chloro, bromo, methyl, ethyl, methoxy, ethoxy or trifluoromethyl; Y is hydrogen, chloro or methyl; R is hydrogen or methyl; and A is alkylaryl.

Examples of radicals A are: Ca to Cia alkylphenyl, C4 to C8 monoalkylnaphthyl and C4 to C8 dialkylnaphthyl. As a rule the compounds of the formula (I) do not have uniform anions but mixtures of anions.

Examples of specific radicals A are:n-octylphenyl, n-nonylphenyl, n-dodecylphenyl, n-tetradecylphenyl, n-hexadecylphenyl, n-octadecylphenyl, 2-ethylhexylphenyl, 2-butyloctylphenyl, 2-amylnonylphenyl, 2-propylheptylphenyl, dibutylnaphthyl and butylnaphthyl.

Preferred radicals are:hydrogen or methyl for X; hydrogen for Y; hydrogen or methyl for R; and dodecylphenyl for A, dodecylphenyl being the main component in the mixture of radicals A.

Compounds of the formula (I) may be prepared by reacting a compound of the formula (II):--

with an acid of the formula ASO3H or a salt of a compound of the formula (II) with an acid of the formula ASO3H or an alkali metal salt of the same.

Examples of salts of compounds of the formula (II) having the formula:

are: the chloride, bromide, sulfate, nitrate, hydrogen sulfate, methyl sulfate, phosphate, formate and acetate.

Particularly suitable alkali metal salts of the acids ASO3H are the sodium and potassium salts. It is advantageous to use mixtures of acids of the formula ASO3H.

Special importance attaches to compounds of the formula (Ia):-

in which A' is dodecylphenyl or dibutylnaphthyl or a mixture of the same; and R is as defined above for formula (I) but is preferably hydrogen.

Salts of the formula (I) are particularly suitable as dyes for the production, for example, of printing inks, writing inks or transparent surface coating compositions because they have very high solubility in the solvents generally used in these products, such as Cs to C4 alkanols, C2 to Cos glycols and polyglycols, C3 to C,0 glycol ethers, C3 to C , ketones and mixtures of one or more such solvents with toluene.

Examples of individual important solvents are:-- methanol, ethanol, propanol, methyl glycol, ethyl glycol, propyl glycol, diacetone alcohol, acetone and methyl ethyl ketone.

Salts of the formula (I) have high fastness to sublimation, fastness to water and lack of corrosive action. They are suitable for the production of highly concentrated stock solutions which are stable in storage.

The following Examples illustrate the invention. In the Examples, parts and percentages given are by weight unless otherwise stated and parts by weight bear the same relationship to parts by volume as the litre to the kilogram.

EXAMPLE 1.

249 parts of Basic Orange 2 (C.I. 11270) is dissolved in 2500 parts of water at 80" to 90"C. 326 parts of a mixture of dodecylbenzenesulfonic acids (prepared by alkylation of benzene with n-dodecenes followed by sulfonation with sulfuric acid) dissolved in 1000 parts of water is dripped in over half an hour. The reaction mixture is then cooled to ambient temperature and the precipitated dye is suction filtered and washed with 5000 parts of water. After drying at from 600 to 700C 520 parts of the dodecylbenzene sulfonate salt are obtained.

When the Basic Orange 2 in Example 1 is replaced by a equimolar amount of a dye set out in the following Table, the corresponding dodecylbenzene sulfonate salt is obtained: Example Dye

C.I. 11320 Cl. 11285 CI. 11325 EXAMPLE 13.

261 parts of Basic Orange 1 (C.I. 11320) is dissolved in 3000 parts of water at 90"C. 320 parts of a mixture of dibutylnaphthalene -sulfonic acids (prepared from butanol, sulfuric acid and naphthalene by heating) in 1000 parts of water is added to the dye solution over half an hour. The reaction mixture is stirred for another hour at 80"C and after cooling the dye is suction filtered and washed with 5000 parts of water and dried at 60"C to 700C. 517 parts of the dibutylnaphthalene sulfonate salt are obtained.

The dodecylbenzenesulfonic acids or the dibutylnaphthalenesulfonic acids in Examples 1 to 13 may be replaced by an equimolar amount of an alkylarylsulfonic acid, or a mixture of such acids selected from the following: octylbenzenesulfonic acid, nonylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, 2-ethylhexylbenzenesulfonic acid, 2-butyloctylbenzenesulfonic acid, 2-amylnonylbenzenesulfonic acid, and 2-propylheptylbenzenesulfonic acid.

EXAMPLE 14.

249 parts of Basic Orange 2 (C.I. 11270) is dissolved in 3000 parts of water at 90"C. A mixture of 296 parts of dodecylbenzenesulfonic acids, 30 parts of dibutylnaphthalenesulfonic acids and 1000 parts of water is dripped into this dye solution over half an hour to two hours. The reaction mixture is stirred for another hour at 800C and then cooled to room temperature. The precipitated dye is suction filtered and washed with 5000 parts of water. After drying at 60 to 700C 523 parts of the dye sulfonate are obtained.

EXAMPLE 15.

30 parts of the dye are prepared according to Example 1 is dissolved in 70 parts of a mixture of 1 part by volume of methanol and 1 part by volume of ethyl glycol at 80" to 900C. After the dye concentrate has been stored for two weeks at 200 C, it is unchanged and shows no formation of crystals. It is suitable for the production of orange flexographic inks. For this purpose, 15 parts of the concentrate and 15 parts of an ethanol-soluble resin based on a copolymer of styrene and maleic acid is dissolved in 70 parts of ethanol.

An orange flexographic ink is obtained which, even after storage for long periods, forms no sediment and causes no corrosion of metals such as sheet iron or tin plate. Flexographic prints prepared therewith on paper exhibit not sublimation after they have been kept for several hours at 1000 C.

Only 1 part of the dye hydrochloride, namely Basic Orange 2, dissolves in the said resin solution and moreover the flexographic ink has a corrosive effect on metals and on paper gives prints which sublime appreciably.

EXAMPLE 16.

5 parts of the dye obtained according to Example 1 together with 10 parts of a copolymer of styrene and maleic acid is dissolved in 100 parts of a mixture of 50 parts by volume of toluene and 50 parts by volume of methanol while heating. This solution is suitable as an orange ink for felt-tip pens which writes not only on paper but also on glass, plastics and wood.

EXAMPLE 17.

4 parts of the dye obtained according to Example 1 is dissolved in 100 parts of a solution of 20 parts of shellac in 80 parts of a mixture of ethanol and ethyl glycol in the ratio of 9:1 by volume. The orange flexographic ink obtained is tinctorially similar in a wet film application of 24 microns to a flexographic ink from 9.75 parts of C.I. Basic Yellow 2 (C.I. 4100) and 0.25 parts of C.I. Basic Violet 10 (C.I. 45170) but has clearly better fastness to water.

WHAT WE CLAIM IS: 1. A salt of the general formula (I):-

in which X is hydrogen, chloro, bromo, methyl, ethyl, methoxy, ethoxy or trifluoromethyl; Y is hydrogen, chloro or methyl; R is hydrogen or methyl; and A is alkaryl.

2. A salt as claimed in claim 1 and having the formula (Ia):

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

octadecylbenzenesulfonic acid, 2-ethylhexylbenzenesulfonic acid, 2-butyloctylbenzenesulfonic acid, 2-amylnonylbenzenesulfonic acid, and 2-propylheptylbenzenesulfonic acid.

EXAMPLE 14.

249 parts of Basic Orange 2 (C.I. 11270) is dissolved in 3000 parts of water at 90"C. A mixture of 296 parts of dodecylbenzenesulfonic acids, 30 parts of dibutylnaphthalenesulfonic acids and 1000 parts of water is dripped into this dye solution over half an hour to two hours. The reaction mixture is stirred for another hour at 800C and then cooled to room temperature. The precipitated dye is suction filtered and washed with 5000 parts of water. After drying at 60 to 700C 523 parts of the dye sulfonate are obtained.

EXAMPLE 15.

30 parts of the dye are prepared according to Example 1 is dissolved in 70 parts of a mixture of 1 part by volume of methanol and 1 part by volume of ethyl glycol at 80" to 900C. After the dye concentrate has been stored for two weeks at 200 C, it is unchanged and shows no formation of crystals. It is suitable for the production of orange flexographic inks. For this purpose, 15 parts of the concentrate and 15 parts of an ethanol-soluble resin based on a copolymer of styrene and maleic acid is dissolved in 70 parts of ethanol.

An orange flexographic ink is obtained which, even after storage for long periods, forms no sediment and causes no corrosion of metals such as sheet iron or tin plate. Flexographic prints prepared therewith on paper exhibit not sublimation after they have been kept for several hours at 1000 C.

Only 1 part of the dye hydrochloride, namely Basic Orange 2, dissolves in the said resin solution and moreover the flexographic ink has a corrosive effect on metals and on paper gives prints which sublime appreciably.

EXAMPLE 16.

5 parts of the dye obtained according to Example 1 together with 10 parts of a copolymer of styrene and maleic acid is dissolved in 100 parts of a mixture of 50 parts by volume of toluene and 50 parts by volume of methanol while heating. This solution is suitable as an orange ink for felt-tip pens which writes not only on paper but also on glass, plastics and wood.

EXAMPLE 17.

4 parts of the dye obtained according to Example 1 is dissolved in 100 parts of a solution of 20 parts of shellac in 80 parts of a mixture of ethanol and ethyl glycol in the ratio of 9:1 by volume. The orange flexographic ink obtained is tinctorially similar in a wet film application of 24 microns to a flexographic ink from 9.75 parts of C.I. Basic Yellow 2 (C.I. 4100) and 0.25 parts of C.I. Basic Violet 10 (C.I. 45170) but has clearly better fastness to water.

WHAT WE CLAIM IS: 1. A salt of the general formula (I):-

in which X is hydrogen, chloro, bromo, methyl, ethyl, methoxy, ethoxy or trifluoromethyl; Y is hydrogen, chloro or methyl; R is hydrogen or methyl; and A is alkaryl.
2. A salt as claimed in claim 1 and having the formula (Ia):

in which Al is dodecylphenyl or dibutylnaphthyl and R is hydrogen or methyl.
3. A salt as claimed in claim 1 or 2 and identified in any one of the foregoing Examples.
4. A process for the production of a salt as claimed in claim 1 wherein a compound of the formula (II):--

is reacted with an acid of the formula ASO3H, or a salt of a compound of the formula (II) is reacted with an acid of the formula ASO3H or with an alkali metal salt of the same, A, X, Y and R having the meanings given in claim 1.
5. A process as claimed in claim 4 and substantially as described in any one of the foregoing Examples.
6. A salt as claimed in claim I when obtained by a process as claimed in claim 4 or 5.
7. A printing ink, writing ink or transparent surface coating composition wherein there is present as colorant a salt as claimed in any one of claims 1 to 3 or claim 6.
8. A process for the production of a printing ink, writing ink or surface coating composition in which process a salt as claimed in any one of claims 1 to 3 or claim 6 is used as colorant.
9. A printing ink, writing ink or surface coating composition when obtained by a process as claimed in claim 8.