US2135633A - Dyeing process - Google Patents

Description

Patented Nov. 8, 1938 UNITED STATES 2,135,633 PATENT OFFICE.

DYEING PROCESS I 'Berthold Bienert, Ieverkusen-I. G. Work, and

Karl Holzach,

Lndwigshafen on-the-khine,

Germany, asslgnors to General Aniline Works, Inc., New York, N. Y., a corporation of Dela- No Drawing. Application May 2, 1936, Serial No. 77,628. In-Germany May 9, 1935 7 Claims.

0 copper, nickel, cobalt, iron or zinc in a nonionizable complex link whereasothers are free from metals. Both metal-free and metal-containing compounds are "included by the term phthalocyanines". It is known that these phthalocyanines can be sulfonated by the action of fuming sulfuric acid, the number of the sulfuric acid groups entering the molecule depending on the temperature and the strength of the fuming sulfuric acid. Our present invention is limited to the use of the sulfonic acids of such phthalocyanines as are substantially identical with those obtainable by heating ortho-arylenedinitriles of the benzene or naphthalene series with metals, metal compounds and ammonia or ammonium salts. For convenience, compounds of this type are called in the following phthalocyanines of the benzene and naphthalene series.

We have now discovered that sulfonic acids of phthalocyanines of the character described are capable of directly dyeing cellulosic materials. Brilliant shades of excellent fastness to light are obtained. This is the more surprising as most of the sulfonic acids of other dyestuffs show afllnity towards vegetable fibers only in case diphenyl groups or similar groups are present. term "cellulosic materials we mean vegetable fibers, such as cotton, cuprammonium or viscose silk, furthermore, paper or raw materials for the preparation thereof, such as paper pulp, pasteboard, straw, cellulose, jute, linters, cotton, wool, sponges and so on. For the dyeing of textiles such compounds are preferred, as contain about 1 to 2 sulfonic acid groups in the molecule, whereas in case of paper or raw materials for the preparation thereof higher sulfonated compounds, which contain about 3 sulfonic acid groups in the molecule are preferably employed. The dyeing of such as oleyl-oxy-ethane-sulfonic acid can be added to the dyeing bath.

The sulfonic acids of the copper-containing dyestufis yield sky-blue shades, while the sulfonic acids of the nickel or zinc containing dyestufis and those of the metal free dyestuflfs yield more greenish shades. The dyeings, which are By the (Cl. 8a-1) obtained from the sulfonic acids of the cobaltcontaining dyestuffs, are'of a more reddish-blue tint, while the iron-containing dyestuffs yield steel-blue dyeings.

The fastness to water of the dyeings on textiles may be still further improved by subjecting the same to an aftertreatment with organic basicreacting compounds, which are capable of forming diilicultly soluble salts with'the sulfonic acids and show affinity towards cellulosic materials, As example for these basic-reacting compounds there may be mentioned ethylene diamine, which is partially acylated by means of a higher fatty acid, polyethylene polyamines, which are either peralkylated or likewise partially acylated by means of a higher fatty acid, furthermore ammonium, phosphonium or sulfonium bases with higher alkyl groups such as cetylpyridinium bromide or benzylethyl-dodecylsulfonium chloride.

The following examples illustrate the invention, without, however, restricting it thereto, the parts being by weight.

EXAMPLE 1 g Dyeing of cotton with metal-containing dyestufis 1 part of a sulfonic acid of a metal-containing phthalocyanine is dissolved in 100 parts of water; 1 part of soda dissolved in 10 parts of water and 10 parts of sodium sulfate dissolved in 100 parts of water are added thereto. The solution is then made up with hot water to 1000 parts. In the dyeing bath thus obtained 50 parts of cotton are dyed for 1 hour at Bil- C. Thereupon it is rinsed and dried. Clear shades of excellent fastness to light are thus obtained which in case of applying acopper-containing phthalocyanine sulfonic acid show a sky-blue shade, in case of applying a nickel-containing phthalocyanine sulfonic acid show a more greenish shade and in case of applying a cobalt-containing dyestufi show a more reddish tint. Clear green shades are obtained by applying a dyestufi obtained in the following manner:

'10 parts of the copper-phthalocyanine, which is obtainable from 1.2-dicyanonaphthalene by heating with copper salt, are introduced into parts of a 30% fuming sulfuric acid and stirred for 1 hour at room temperature. The reaction mixture is poured onto ice and the precipitating sulfonic acid filtered off by suction. The sulfonic acid is then neutralized by means of soda and isolated by salting out.

EXAMPLE 2 Dyeing of cotton with metal-free dyetufis A metal-free phthalocyanine, which is obtained by heating a phthalonitrile in the presence of sodium amylate, is sulfonated by a treatment with a 32% fuming sulfuric acid at 70-80 c,

1 part; of 'the'-sodium salt, of-the sulfonic acid thus' obtained is-dissolved in 100 parts of water. After the addition of 1 part of soda and 10 parts of sodium sulfate the mixture is filled up with 'water to 1,000 parts. In this dyeing liquor 50 bluish-green shares of good fastness to water and Y washing are obtained.

EXAMPLE 3 Dyeing of viscose-artificial silk 0.8 part of sulfonic acid of a phthalocyanineare dissolved in 100 parts of water. 20 parts of sodium sulfate dissolved in 200 parts of water are then added and the solution is made up with hot water to 1,000 parts. Into the dyeing bath thus obtained 40 parts of viscose silk are dyed for one hour at 85-90 C. After dyeing the viscose silk is rinsed and dried.

For this dyeing process metal-containing as well as metal-free phthalocyanines may be employed. Clear bluish-green shades are obtained by using the sulfonic acid of a zinc phthalocyanine, which may be prepared in the following manner:

30 parts of zinc phthalocyanine which is obtained by heating phthalonitrile with zinc oxide and formamide are heated for 2 hours with 300 parts of a fuming sulfuric acid of a sulfur trioxide content of 30%. The sulfonic acid is isolated by pouring the reaction solution obtained onto ice. It is converted into its sodium salt by mixing with water, neutralizing with soda and salting out in the usual manner.

EXAMPLE 4 Dyeing of sulfite cellulose pulp Bleached sulfite cellulose pulp is dyed in the usual manner in the'hollander with 1% of the sodium salt of a copper-phthalocyanine sulfonic acid, which is obtained by sulfonating the copperphthalocyanine with a 30% fuming sulfuric acid, and, if necessary, sized with a 3% resin soap and 4% aluminum sulfate. The paper pulp thus obtained is worked up in the usual manner to paper. An evenly dyed paper is thus obtained which is distinguished by an especially brilliant blue shade.

Instead of the sulfite cellulose pulp there may be used with the same result a paper pulp consisting of 50% of mechanical wood pulp and.

-in the usual manner and converted into the sodium salt. This sulfonic acid yields greenish shades.

EXAMPLE 5 Dyeing of paper 30 parts of a copper phthalocyanine sulfonic acid are dissolved in 1,000 parts of water. The solutionis kept at a temperature (for example 40 C.) sufiicient to keep it in solution. Thin paper may be dyed by'a simple dipping into or passage through this solution. Brilliant blue shades are thus obtained. Also in this case the sulfonic acid of the metal-free phthalocyanines or of metal-containing phthalocyanines may be employed. I

Exmru 6 Dyeing of a film of regenerated cellulose A. colorless film of. regenerated cellulose is passed for 2 minutes through an aqueous dye bath consisting of 1% of the sodium salt of the sulfonic acid of a metal-free phthalocyanine and 5% of glycerine. The film is subsequently dried in a suitable drying apparatus. A clear greenish blue shade is thus obtained.

Other phthalocyanine sulfonic acids, such as the copper-containing dyestuif, may be employed with a similar result.

We claim:

1. The process of dyeing cellulosic materials which comprises directly applying to such materials unreduced sulfonic acids of phthalocyanines selected from the group consisting of phthalocyanines of the benzene and naphthalene series.

2. The process of dyeing cellulosic materials which comprises directly applying to such materials unreduced sulfonic acidsv of phthalocyanines selected from the group consisting of phthalocyanines of the benzene andnaphthalene series containing copper in complex combination.

3. The process of dyeing cellulosic materials which comprises directly applying to such materials unreducd sulfonic acids of metal-free phthalocyanines selected from the group consisting of phthalocyanines of the benzene and naphthalene series.

4. The process of dyeing textiles from cellulosic materials which comprises directly applying to such materials unreduced sulfonic acids of phthalocyanines selected from the group consisting of phthalocyanines of the benzene and naphthalene series containing one to two sulfonic acid groups in the molecule.

5. The process of dyeing paper which comprises directly applying to the paper unreduced sulfonic acids of phthalocyanines selected from the group consisting of phthalocyanines of the benzene and naphthalene series containing three sulfonic acid groups in the molecule.

6. The process of dyeing textiles from cellulosic materials which comprises directly applying to such materials unreduced sulfonic acids of phthalocyanines selected from the group consisting of phthalocyanines of the benzene and naphthalene series and subjecting the dyeings thus obtained to an after-treatment with organic basicreacting compounds which are capable of forming insoluble salts with the phthalocyanine sulfonic acids.

'7. The process of dyeing cellulosic materials which comprises directly applying to such materials unreduced sulfonic acids of phthalocyanines selected from the group consisting of phthalocyanines of the benzene and naphthalene series containing nickel in complex combination BERTHOLD BIENERT. KARL HOLZACH.