US3619109A

US3619109A - Cobalt-phthalocyanine-polyamine complexes for the dyeing and printing of textiles

Info

Publication number: US3619109A
Application number: US754709A
Authority: US
Inventors: Heinrich Vollman; Peter Mertens; Johannes Eibl; Ulrich Altmann
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1967-08-31
Filing date: 1968-08-22
Publication date: 1971-11-09
Anticipated expiration: 1988-11-09
Also published as: ES357756A1; CH533202A; IL30530A; DK133344B; FR1580613A; FI46086C; IL30530A0; FI46086B; AT284776B; NL161828B; NO127358B; CH1168368A4; OA02882A; DK133344C; NL6812409A; GB1242449A; BE719863A; NL161828C; DE1619546A1; SE336772B

Abstract

A process for dyeing and printing textile materials made of natural or regenerated cellulose wherein an insoluble cobaltphthalocyanine is solubilized by oxidizing to a hexavalent state and complexing with two molecules of an amine which complex contains an anion, is dissolved in a solvent and is applied to the textile materials which materials are subsequently treated to a heating treatment above 100* C. or to a treatment with reducing agents to convert the salts of cobalt-phthalocyanine to the original insoluble state.

Description

United States Patent nu 3,619,109

[72] Inventors Heinrich Vollman ISI 1 Int. Cl 006p 3/60 Leverkusen; [50] Field of Search I. 8/l .3 54.2; Peter Mertens. Cologne-Marlenburg; 260/3 14 5 Johannes Eibl. Burscheid-Kaltenherberg; Ulrich Altmann. Cologne-Duennwald. all 0! I RQIEI'QIIWS Ciled Germany UNITED STATES PATENTS I 1 PP Ne 754309 2.772.284 ll/l956 Barnhart et al. 260/3145 [22] Filed Aug. 22, I968 [45] Pmemed No 9 1971 Primary Examiner-George F. Lesmes Farbenl'abriken Bayer Aktiengesellschal'l Leverkusen. Germany [73] Assignee [32] Priority Aug. 31. I967 [331 Germany [3| 1 F 53376 [54] COBALT-PHTHALOCYANINE-POLYAMINE COMPLEXES FOR THE DYEING AND PRINTING 0F TEXTILES l0 Claims. No Drawings 521 vs. Cl 8/541. 8/l.3 260/3145 Amman! E.llllllillt'f Patricia C. Ives Allurm' Plumley. Tyner & Sandt ABSTRACT: A process for dyeing and printing textile materials made of natural or regenerated cellulose wherein an insoluble cobalt-phthalocyanine is solubilized by oxidizing to a hexavalent state and complexing with two molecules of an amine which complex contains an anion. is dissolved in a solvent and is applied to the textile materials which materials are subsequently treated to a heating treatment above l()0 C. or to a treatment with reducing agents to convert the salts of cobalt-phthalocyanine to the original insoluble state.

COBALT-PHTHALOCYANTNE-POLYAMINE COMPLEXES FOR THE DYEING AND PRINTING OF TEXTILES The present invention relates to a process for dyeing and printing textile materials made of natural or regenerated cellulose. More particularly it concerns a process wherein the dyeing and printing is carried out by applying coordinatively hexavalent complex salts of trivalent cobalt. in which four of the six coordination points are occupied by the phthalocyanine ring which has a double negative charge. and each of the remaining two points is occupied by a primary. secondary or tertiary polyamine. and which contain an ion from the series Cl. Br. 1'. HCO;,'. N and CH;,COO as anion. dissolved in solvents to the textile materials and subsequently developing said complex salts into cobalt-phthalocyanines on the textile material by an aftertreatment.

The dyeing process is based on the property of the cobaltphthalocyanine-polyamine complex salts to be used according to the invention to separate quantitatively and in a pure form the cobalt-phthalocyanine from which they are derived within a few minutes when they are heated to 60-l00 C. in solvents. especially in weakly acidic aqueous solutions.

Dyeing according to the process of the invention therefore only requires padding of the textile materials with a solution of the cobalt-phthalocyanine-polyamine complex salts. for example with an approximately 0.5-3 percent acetic acid containing 3 percent ofthe complex salt. at about -30 C.. squeezing off and developing after drying by steaming or hot calendering at temperatures above 100 C. The dyeings can subsequently be finished in the usual manner. for example. by rinsing. soaping at the boil. rinsing again and drying. Obviously. it is also possible to work in the presence of reducing agents. such as sodium bisulfite or sodium dithionite. whereby the short time of 1-5 minutes required for developing the dyestuff by steaming or dry heating. can be reduced to less than one minute. The cobalt-phthalocyanine-polyamine complex salts can also be developed to cobalt-phthalocyanines on the fiber by the action oflight. for example. by hanging in sunlight or by illumination with ultraviolet rays.

For printing the weakly acidic complex salt solution is adjusted to the desired viscosity by the addition of a suitable thickening agent. and the prints are aftertreated as stated above for pad dyeing.

lnstead of dilute acetic acid there may be used for dissolving the cobalt-phthalocyanine-polyamine complex salts also dilute aqueous solutions of other organic acids. for example. formic acid. lactic acid. oxalic acid and citric acid or inorganic acids. such as phosphoric acid. sulfuric acid or hydrochloric acid. furthermore also solvents. such as lower alcohols. e.g. methanol. ethanol. propanol. acetonitrile. formamide or dimethylformamide. advantageously in mixture with water. The acid concentration in the dilute aqueous solutions of the acids generally amounts to 0.5-3 percent by weight.

The cobalt-phthalocyanine-polyamine complexes used in the present dyeing and printing process are prepared according to one of the processes described below. starting from cobalt-phthalocyanine or from its easily obtainable substitution products. for example. cobalt-phthalocyanine compounds which are substituted in their benzene nuclei by halogen. C,-C.,,'""- ",-C.-alkoxy or phenyl radicals. but which are free from water-solubilizing radicals:

a. The cobalt-phthalocyanine (l) is first converted with a halogenating agent. such as chlorine. into a dihalo-cobaltphthalocyanine of the structure (II) and this is subsequently converted with a primary. secondary or tertiary polyamine. preferably l-amino-3-dimethylamino-propane. into the complex (III) which is soluble in acetic acid.

b. The cobalt-phthalocyanine is first stirred with the polyamine whereupon a loose amine--cobalt-phthalocyanine complex (IV) is primarily formed. and this is subsequently converted into the dyestuff (III) in the presence of halide. acetate. carbonate or nitrate ions by means of an oxidizing agent. preferably atmospheric oxygen.

polyamines. Examples of aliphatic polyamines are ethylenediamine. bis- 1 .Z-dimethylamino-ethane. l.3-diaminopropane. bis-lJ-amino-propyll-methylamine and especially the diamines of the formula lii lI:Y\.'\-N

wherein denote A a straight or branched C C -.-alkylene radical. R, hydrogen or a C,-C.-alkyl radical and R a C,C -alkyl or a cyclohexyl radical.

As examples for the diamines of the above formula are mentioned: l-amino-2-dimethylamino-ethane. l-amino-3- methylamino-propane and especially -l-amino-3- dimethylamino-propane and l-amino-3-diethylaminopropane.

The cobalt-phthalocyanine-polyamine complex salts to be used according to the invention possess an excellent texturing power on natural or regenerated cellulose fibers. that means. the depth of color of the dyeings produced increases corresponding to the increasing concentration of the complex salts in the dyeing liquor.

Furthermore. the cobalt-phthaloeyanine-polyamine complex salts are well applicable together with other types of dyestuffs. since for developing the complex salts to cobaltphthalocyanines no reducing agents or other auxiliaries are necessary and. therefore. no turbidity of the accompanying dyestuffs which often results from the use of reducing agents. occurs.

Moreover. the cobalt-phthalocyanine-polyamine complex salts can excellently be used together with acid-soluble basic dyestuffs for dyeing or printing mixed fiber materials of natural and regenerated cellulose and polyacrylonitrile in a single bath or together with dispersion dyestuffs for dyeing and printing mixed fiber materials of natural and regenerated cellulose and polyesters in a single bath. When the cobalt-phthalocyanine-polyamine complex salts are used in stronger acidic printing pastes. excellent clear resist prints are obtained with these pastes under dyestuffs. which are fixed under alkaline conditions, especially reactive dyestuffs.

The parts given in the following examples are parts of weight if not otherwise stated.

EXAMPLE 1 A cotton fabric is padded with a liquor which is prepared from 1-60 parts of the cobalt-phthalocyaninecomplex salt described below 10-15 parts of 50 percent acetic acid 989-925 parts of water of l5-25 C. After squeezing to a weight increase of about -90 percent and drying the dyestuff is fixed by neutral steaming at l00-l02 C. for 1-2 minutes. The fabric is subsequently rinsed. soaped at the boil. rinsed and dried. A clear blue dyeing of excellent fastness properties is obtained if. instead ofsteaming. the padded and dried fabric is heated to l30-l50 C. by means of hot air or by contact action for 3-5 minutes. the development of the dyestuff is equally complete and the same blue clear dyeing is obtained by the usual finishing.

The cobalt-phthalocyanine-polyamine complex salt used above was prepared as follows: 57 parts cobalt-phthalocyanine were stirred in 300 parts by volume l-amino-3- dimethylamino-propane. 6 parts ammonium chloride were added. and the mixture was heated to 60-70 C. Ammonia escaped while the equivalent amount of diamine hydrochloride was formed. Air was then passed over the wellstirred dispersion at 60-70 C. for several hours until the starting material had completely disappeared and the initially blue solution had turned green. After cooling to 2030 C. the crystal slurry was filtered off with suction. washed with 1-2 parts by volume of the diamine and finally with water until neutral. After drying at 40-40 C., there were obtained about 78 parts (=80 percent of theory) of a dark-green crystal powder (empirical formula: C H N Clco; molecular weight 812).

Elementary analysis:

calculated: 62.10% C 5.59% H 20.69 71 N 4.37% CI 7.26 percent Co found: 61.90% C 5.60% H 20.50% N 4.40%

Cl 6.90% Co 10 parts of the product so obtained yield 6.85 parts of pure cobalt-phthalocyanine. when aftertreated with boiling dimethyl-aniline.

EXAMPLE 2 A cotton fabric is printed with a printing paste which is prepared from 1-60 parts of the cobalt-phthalocyanine-polyamine complex salt described below,

10-15 parts of50 percent acetic acid,

459-435 parts of water and 530-490 parts of wheat starch/tragacanth thickening agent. After drying, the dyestuff is developed by acidic steaming for 1-5 minutes. After rinsing. soaping at the boil, rinsing and drying, prints ofa very clear-blue shade and excellent fastness to wet processing and light are obtained.

The cobalt-phthalocyanine-polyamine complex salt used above was prepared as follows: 7.5 parts chlorine were passed into a suspension of 57 parts cobalt-phthalocyanine in 300 parts by volume o-dichlorobenzene. Stirring was continued for minutes, air was then blown through the black-brown suspension of dichloro-cobalt-phthalocyanine in order to remove any excess chlorine which may be present. 35 parts N.N-dimethyl-ethylene-diamine were then added and the mixture was heated to 80 C. After cooling to room temperature the product was filtered off with suction, washed with benzene and dried at 60-70 C., in a vacuum. There were obtained 62.5 parts of a dark-green crystalline powder which was freed from any adhering amine hydrochloride by stirring in a 5 percent sodium chloride solution.

EXAMPLE 3 A cotton fabric is printed with a printing paste which is prepared from -40 parts of the complex salt described in example 1. parts of crystalline tartaric acid, 455-435 parts of water and 500 parts of a mixture of wheat starch/tragacanth and dextrinated starch (2:1 After drying the fabric is padded with a liquor which is prepared from 40 parts of the dyestuff described in example 216 of the British Patent Specification No. 1 120 761, 675 parts of water of -50 C.. 25 parts of calcined sodium carbonate, 10 parts of the sodium salt of m-nitrobenzene-sulphonic acid and 100 parts ofcarrageenatc /100 dissolved in water.

After squeezing to a weight increase of about percent and drying. steaming. rinsing, soaping, rinsing and drying clear-blue resists with sharp outlines are obtained under the reactive dyeing.

EXAMPLE 4 A cotton fabric is padded at room temperature with a liquor which contains per liter l-60 parts of the cobalt-phthalocyanine-polyarnine complex salt described below and 10-15 parts of 50 percent acetic acid.

After squeezing to a weight increase of 80-90 percent and drying the fabric is padded with a second liquor which contains per liter 30-80 parts sodium dithionite.

10-50 parts sodium hydroxide and 20-30 parts ethyl alcohol.

After squeezing to a weight increase of 80-100 percent without intermediate drying. the fabric is steamed wet for 20-30 seconds, rinsed. soaped and finished in the usual manner. The clear-blue dyeing completely corresponds to the dyeing obtained according to example 1. V

The cobalt-phthalocyanine-polyamine complex salt used above was prepared as follows: To a suspension of 32.5 parts dichloro-cobalt-phthalocyanine (prepared from cobaltphthalocyanine and chlorine as mentioned in example 2) in 150 parts by volume dioxan 50 parts of volume ethylenediamine were added in portions at below 15 C. The product was filtered off with suction and washed with dioxan and cyclohexane. The precipitate was dried at 40 C. in a vacuum and then well stirred in 250 parts by volume of 10 percent aqueous acetic acid. From the solution which was freed from undissolved matter by filtration the complex salt was precipitated by the addition of sodium chloride. The precipitate was washed with a sodium chloride solution until neutral and dried in a vacuum at 40 C. The resultant deepgreen crystal powder dissolved in dilute acids without a residue.

EXAMPLE 5 A cotton fabric is padded with a liquor which contains per liter 5-40 parts of the complex salt described in example 2.

10-50 parts ethyl or methyl alcohol.

10-20 parts of50 percent acetic acid,

10-100 parts triethylene glycol and 5-10 parts of an aryl polyglycol ether.

50-70 parts of urea.

After squeezing to a weight increase of 80-90 percent the fabric is aftertreated with a 3-5 percent sodium dithionite solution at 50 C., for 30 seconds. It is then rinsed. acidified with 3-5 percent hydrochloric acid at 70 C. for 30 seconds, rinsed. soaped at the boil, and finished in the usual manner. As in example 1, there is obtained a clear-blue dyeing.

EXAMPLE 6 A cotton fabric which has been bottomed with the dyestuff color index no. 37 610 is printed with a printing paste which is prepared as follows:

30 parts of the complex salt described in example 1 dissolved in 0-50 parts ethyl alcohol and 320-270 parts of water are stirred together with a solution of 50 parts of the dyestuff color index no. 37 in 200 parts of water into 400 parts of a wheat starch/tragacanth thickening agent After drying the dyestuff is developed by steaming for 1-3 minutes. Very brilliant distinct prints in deep-green shades are obtained after the usual finishing.

lnstead of steaming, it is also possible to carry out a weakly reductive development by means of a sodium hydrogen sulfite bath, the same result being achieved.

We claim:

I. Process for dyeing and printing textile materials made of natural or regenerated cellulose which comprises dissolving in a solvent an insoluble cobalt-phthalocyanine which has been solubilized by oxidizing to the hexavalent state and complexing with a polyamine selected from the group consisting of an alkylene polyamine. an N-alkyl-alkylene polyaminc. an N.N- dialkyl-alkylene polyamine. an N-cyclohexyl-alkylene polyamine. an N-alkyl-N-cyclohexyl-alkylene polyamine and an Nlalkyl-polyalkylene-polyamine. and which contains an anion. applying the solution to the textile materials and subsequently converting the said solubilized cobalt-phthalocyanines to insoluble cobalt-phthalocyanine compounds by subjecting said textile material to a heat treatment at a temperature above 60 C. or to a treatment with reducing agents wherein the solvent is a member selected from the group consisting of aqueous solutions of formic acid. acetic acid. lactic acid. oxalic acid. citric acid. phosphoric acid. sulfuric acid. hydrochloric acid; and methanol. ethanol. propanol. acetonitrile. formamide, dimethylformamide. and mixtures of said solvents with water.

2. Process according to claim 1. wherein as solvents for the cobalt-phthalocyanine-polyamine complex are used said dilute aqueous acids.

3 Process according to claim 2. wherein as dilute aqueous acids are used said dilute aqueous organic acids.

4. Process according to claim I. wherein the aftertreatment consists in a neutral steaming without the addition of auxiliaries.

wherein denote A a straight or branched C- c -alkylene radical.

R hydrogen oraC,-C.-alkyl radical and R; a C.C.-alkyl or a cyclohexyl radical.

9. Process according to claim I, wherein cobalt-phthalocyanine-polyamine soluble complexes are used which contain as polyamines l-amino-3-dimethylamino-propane.

l0. Textile materials made of natural or regenerated cellulose dyed or printed according to claim 1.

i i i i

Claims

2. Process according to claim 1, wherein as solvents for the cobalt-phthalocyanine-polyamine complex are used said dilute aqueous acids.
3. Process according to claim 2, wherein as dilute aqueous acids are used said dilute aqueous organic acids.
4. Process according to claim 1, wherein the aftertreatment consists in a neutral steaming without the addition of auxiliaries.
5. Process according to claim 1, wherein the aftertreatment consists in an acidic steaming without the addition of auxiliaries.
6. Process according to claim 1, wherein the aftertreatment consists in a dry heating at 130*-150* C. without the addition of auxiliaries.
7. Process according to claim 1, wherein the aftertreatment consists in a treatment with reducing baths.
8. Process according to claim 1, wherein cobalt-phthalocyanine-polyamine soluble complexes are used which contain as polyamines diamines of the formula wherein denote A a straight or branched C2-C5-alkylene radical, R1 hydrogen or a C1-C4-alkyl radical and R2 a C1-C4-alkyl or a cyclohexyl radical.
9. Process according to claim 1, wherein cobalt-phthalocyanine-polyamine soluble complexes are used which contain as polyamines 1-amino-3-dimethylamino-propane.
10. Textile materials made of natural or regenerated cellulose dyed or printed according to claim 1.