DE1619485A1 - Process for dyeing materials made from synthetic fibers or from mixtures containing synthetic fibers - Google Patents

Description

Process for dyeing materials made from synthetic fibers or from mixtures containing synthetic fibers The present invention relates to a process for dyeing materials made from synthetic fibers or from mixtures containing synthetic fibers with dyes suitable for this purpose after the impregnation process with subsequent thermal treatment; The process is characterized in that the aqueous liquor used for impregnation, in addition to the dyes, also contains phosphorus compounds of the formula mean aubstituierten alkyl, aryl, g # aralkyl, alkoxy, aroxy, and / or aralkoxy, wherein two of the three symbols - independently in the X "-Y and Z represent an optionally -., for example, by halogen, cyano or amino groups, X, Y and Z with the phosphorus atom augh can form a heterocyclic five- or six-membered ring containing as Phoophorverbindungen the mentioned formula may be mentioned are:. Phosphinoxideg as tributylphosphine or Diäthylphenylphoaphinoxid, further Phoopholineg such as 1-oxo-l-ethyl-3-methyl -phoopholin-3, 1-Oxo-l-methoxy-phoopholin-3 1-Oxo-l-ethoxy-phoopholin-3, 1-Ozo-l-butoxy-phoopholin-3, #J 1-Ozo-l-stearoxy- phoapholin-3, 1-oxo-1- (ß-ohlorpropoxy) -phoapholin-3 or 1-oxo-l-methoxy-3-ohlor-pli: aopholin-3, further phosphonic acid ster, such as Methanphoophonsäuredimethylester, -Benzolphoaphonsäuredimethylenter or ß- Cyanoäthanphoaphonsäuredimethylester or dibutylester and finally phosphoric acid esters, such as triethylphoaphate, tributylphoaphate od er Diphenylootylpho.aphat. f The phosphorus compounds to be used according to the invention are known; refer to z. B. on Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume XII, 1st and 2nd part (1963). The synthetic fibers, of which the materials to be dyed according to the invention, in whole or in part, can be based on various products, for example cellulose triacetate or polyacrylonitrile and the copolymers of polyacrylonitrile with other vinyl compounds, such as vinyl chloride, vinylidene chloride, vinyl pyridine and acrylic esters or amides, and also polyamides, such as Polycaprolaetam, polyadipic acid-hexamethylene diamide and poly - ur-amino-undecanoic acid, also polyester, z. B. those made from terephthalic acid and ethylene glycol or from terephthalic acid and 1,4-dimethyloloyclohexane, or polyurethanes, e.g. B. those made from polyesters or polyethers containing terminal hydroxyl groups and aliphatic or aromatic diisocyanates. The fibers that may be present in a mixture with the synthetic fibers in the materials to be dyed or printed are wool, cotton and regenerated cellulose fibers. The materials to be dyed can be in the form of tow, threads, flocks, slivers, yarns, woven or knitted fabrics. B. Diapersion dyes, vat dyes, acidic wool dyes, metal complex dyes and basic dyes.

Materials made from different types of fiber can be used in several stages be colored or in a single stage, depending on the dyes to be selected.

Appropriate proportions between the dyes and the phosphorus compounds to be used according to the invention can easily be determined by preliminary experiments; In general, the Phoaphorverbindungen in an amount of about 20 to 200,569, "based on the weight of the dyes, use employed. It is advisable to add a thickener to the impregnation liquor, e.g. B. etherified locust bean gum or British gum.

The impregnation can be carried out by padding, spraying, coating or printing, and the thermal treatment can be carried out continuously or discontinuously in such a way that the materials are thermosolated - i. H. Heated to 170 to 2200 C for 20 to 90 seconds - or in such a way that the materials are exposed to neutral saturated steam for 2 to 30 minutes at 100 to 1300 C; One can also proceed in such a way that the impregnated materials are heated to 100 ° C for several hours in a closed container while they are still moist.

With the help of the method according to the invention it is possible to produce materials from synthetic fibers or from mixtures containing synthetic fibers evenly and to dye in deep tones.

A particular embodiment of the process of the present invention consists in the fact that the cotton wool used for impregnation also contains carboxamides and / or surface-active polyglycol ethers in addition to the phosphorus compounds. Examples of carboxamides are the amides of lower and higher aliphatic carboxylic acids, such as formic acid, acetic acid, lauric acid, stearic acid and oleic acid, also the mono- or dialkylamides and the mono- or dialkanolamides of these acids, furthermore laotams, such as C-caprolaetam, pyrrolidone or polyvinylpyrrolidone, and urea or its alkyl derivatives, and as a surface active polyglycol ether exposure products are for example 6 to 20 moles of ethylene oxide to 1 mol of a fatty alcohol, a fatty amine, a fatty acid, a fatty acid amide or an aliphatic hydrocarbon radical having 9 to 18 carbon atoms possessing Alkylpheno1B into consideration. The weight ratio between the carboxamides and / or the surface-active polyglycol ethers on the one hand and the phosphoric compounds on the other hand is expediently 1: 1 to 1.5 1. By using the carboxamides or the surface-active polyglycol ethers, the depth and the levelness of the colorations can be further improved. There are well-known processes for dyeing synthetic fibers after the impregnation process with subsequent thermal treatment, in which organic compounds containing cyano groups or thiourea are used as auxiliaries. Compared to these processes, the process of the present invention is distinguished by the fact that, under the same conditions with regard to the amount of auxiliary and the duration of the thermal treatment, it leads to deeper colorations.

The parts given in the following examples are parts by weight.

Example 1 A sliver of polyacrylonitrile is impregnated with an aqueous liquor which was prepared by adding a mixture of 30 parts of the Color Index dyes, 2nd edition, No. 48040, 30 parts of 1-oxo-1-butoxy-phoapholine- 3 of the formula and 120 parts of a commercially available thickener based on locust bean gum with a solids content of 5% was brought to 1000 parts by adding water. Subsequently, the sliver is squeezed off to a weight gain of 90%, treated 25 minutes neutral 0 saturated steam at 103 C, hereinafter sser rinsed with Wa and then dried. The top is now colored bright orange. The phosphorus compound used was prepared in the following manner: 117.7 parts of 1-oxo-1-chloro-phoapholine-3, obtained by the action of phosphorus pentachloride on 1-oxo-1- (cC-methyl-β-chloroethoxy) -phoopholin-3 according to Information in Journal of the General Chemistry of the USSR in Englieh Translation, Volume 33, page 775 (1963), was gradually added to 400 parts of n-butanol, the temperature of the reaction mixture being kept at 0 to -5 ° C. by cooling. After the reaction had ended, a suspension of 76 parts of sodium hydrogen carbonate in 200 parts of water was added to the reaction mixture at 0 ° C. and the mixture was then extracted with methylene chloride -butoxy-phospholine-3 was purified by fractional distillation (bp: 84 0 0). Example 2 The procedure described in Example 1 is followed, but using a liquor which instead of the dyestuff specified there contains 30 parts of the color index no. 42040 dyestuff and instead of 30 parts only 15 parts of the phosphorus compound used there and also a mixture which consists of 5 parts of oleic acid ethanolamide, 5 parts of the product of action of 20 moles of ethylene oxide to 1 mole of oleyl alcohol, 2.5 parts of the product of action of 7 moles of ethylene oxide to 1 mole of nonylphenol and 5 parts of urea. A deep green color is obtained. EXAMPLE 3 A fabric made of polyacrylonitrile is impregnated on a padder with an aqueous liquor composed of 30 parts of the dyestuff Golour Index No. 48013, 15 parts of dimethyl methanophonic acid of the formula 17.5 parts of the mixture given in Example 2, 120 parts of a commercially available thickener based on locust bean gum with a solids content of 5% and 817.5 parts of water was prepared. After squeezing to a weight increase of 80% , the fabric is treated with neutral saturated steam for 30 minutes, then rinsed with water and then dried. The fabric is now colored bright red-violet.

The phosphorus compound used was prepared in the following way: 320 parts of trimethyl phosphite were stirred with 7 parts of methyl iodide according to the information in Houben-Weylg Methods of Organic Chemistry, Volume XII, 11, page 434. After the exothermic reaction had ended, the dimethyl methanophonic acid formed was fractionally distilled (boiling point 12 : 660 ° C.). Example 4 A fabric made of polyacrylonitrile is impregnated with a liquor which consists of 15 parts of the dye Color Index No. 48015, 10 parts of triethyl phosphate, 10 parts of the mixture given in Example 2, 120 parts of a commercially available14 thickener based on locust bean gum a solid content of 5% and 845 parts of water was prepared. The fabric is then squeezed off to a weight increase of 100% , then dried and finally heated to 190 ° C. for 30 seconds. A bright red color is obtained.

Example 5 The procedure described in Example 1 is followed, except that 20 parts of the color index No. 51005 dye are used instead of the dye indicated there and 20 parts of 1-oxo-1-methoxy-3-chloro-phoapholin-3 are used instead of the phosphorus compound indicated there the formula a. A uniform blue color is obtained.

The Phoophorverbindung used was prepared as follows: 85, 4 parts of 1-oxo-1,3-dichloro-phoapholin-3 obtained by the action of Phoaphorpentachlorid 1-ozo-3-chloro-l- (CC-methyl-.beta. chloroethoxy) -phoopholin-3 according to the information in Journal of the General Chemistry of the USSR in Englieh Tranalation, Volume 33, page 775 (1963), were gradually added to 800 parts of methanol, the temperature being reduced by cooling to 0 to - 5 0 C was held. The reaction mixture was then worked up in accordance with the instructions given in Example 1 (KP12 of the 1-oxo-1-methoxy-3-chloro-phoapholine-3 formed: 132.0 ). Example 6 A fabric made of polyacrylonitrile is impregnated with an aqueous liquor composed of 20 parts of the dye Color Index No. 42025, 30 parts of ß-cyanoethane phosphonic acid dimethyl ester of the formula 120 parts of a commercially available thickener based on locust bean gum with a solid content of 5% and 830 parts of water was prepared. The fabric is then squeezed off to an increase in weight of 100 Ya, then heated to about -800 C in a continuous run through an infrared heating zone according to the pad-roll dyeing process (Rydboholm-Artos system), then rolled up tension-free in a dyeing chamber and there Heated to 1000 ° C. for 6 hours. The fabric is then rinsed and dried. A blue dyeing with good fastness properties is obtained.

The phosphor compound used was prepared in the following manner: A mixture of 1245 parts of dimethyl phosphite and 600 parts of freshly distilled acrylonitrile was gradually admixed with stirring with a solution of sodium methylate in methanol, which was prepared from 8.6 parts of sodium and 100 parts of methanol. Then the reaction mixture was heated for about 30 minutes to 60 -30o C. The ß-Cyanäthanphoophonsäuredimethylester formed was then purified by fractional distillation (Kplo: 160 0 C).

BeisPiel 7 - A fabric made of cellulose triacetate is printed with a paste that consists of 100 parts of the dye 100 parts of a commercially available thickener based on British Gum with a solids content of 5%, 50 parts of ß-Cyanoäthanphoophonsäuredibutylester of the formula and 750 parts of water was prepared. The fabric is then steamed for 20 minutes in a star steamer at 100 ° C., then washed and dried. A brilliant red-violet print is obtained.

The phosphorus compound used was prepared as follows: A mixture of 1647 parts of di-ii-butylphoaphite and 448 parts of freshly distilled acrylonitrile was gradually admixed with a solution of sodium butoxide, which was prepared from 3.5 parts of sodium and 100 parts of butanol, while stirring.

Ans chließend the Reaktionsg6misch was approximately 50 minutes at 60 - 700 C is heated. The ß-cyanethane phosphonic acid dibutyl ester formed was then purified by fractional distillation (bp 2: 1940 C). Example 8 A fabric made of polyeaprolaetam is impregnated with a liquor which consists of 50 parts of the chromium complex of the compound 15 parts of 1-oxo-1-ethyl-3-methy # 1-ph «ospholin-3 of the formula 15 parts of the adduct of 20 moles of ethylene oxide with 1 mole of oleyl alcohol, 15 parts of urea and 905 parts of water was prepared. After squeezing to a weight increase of 80% , the fabric is dried at 100 ° C., then heated to a temperature of 190 ° C. for 60 seconds and then rinsed and dried. A uniform gray coloration with good fastness properties is obtained. The Phoophorverbindung used was prepared as follows: * A mixture of 137.7 parts of phenyl dichloro-phoaphin and 75 parts of isoprene was prepared according to the instructions of Examples 23 of US patent specification 2 '663 737 in the presence of 1 part copper stearate 11 days Heated to 600 C ; the reaction mixture was then left to stand for a further 6 days at room temperature and then petroleum ether was added. The supernatant solution was then poured off, the remaining reaction product was washed with petroleum ether and then added to an ice-water mixture. The resulting solution was partially neutralized with 30 % sodium hydroxide solution, adjusted to pH 8 with sodium hydrogen carbonate, saturated with sodium chloride and extracted with chloroform. The extract was then worked up in the usual way (KP095 of the 1-oxo-1-ethyl-3-methyl-phoapholine-3 formed: 116-117 ° C.). Example 9 A fabric made of polyester fibers is impregnated with a liquor composed of 100 parts of a commercially available 50 % strength aqueous paste of the dye 50 parts of urea, 50 parts of benzolphoaphonic acid dimethyl ester of the formula 100 parts of a commercially available thickener based on locust bean gum with a solids content of 5% and 700 parts of water was prepared. After squeezing to a weight increase of 80% , the fabric is steamed in a pressure damper for 15 minutes at t27-130 ° C. with neutral saturated steam, then washed and dried. The coloration obtained in this way is deep blue.

The phosphorus compound used was prepared in the following way: 108.7 parts of benzene phosphonic acid dichloride, obtained by chlorinating phenyl dichlorophosphine and then reacting the phenyl phosphorus tetrachloride formed with sulfur trioxide according to the information in Houben-Weyl, 1.c. Volume XII, 1, page 392, was gradually added to 530 parts of methanol, the temperature being maintained at 0 to -50 ° C. by cooling. The reaction mixture was then neutralized with an aqueous solution of 100 parts of sodium hydrogen carbonate and worked up in accordance with the information given in Example 1 (boiling point of the dimethyl benzene phosphonate formed: 97 ° C.).

Claims (2)

Claims 1) Process for dyeing materials made of synthetic fibers or mixtures containing synthetic fibers with dyes suitable for this purpose by the impregnation process with subsequent thermal treatment, characterized in that the aqueous liquor used for impregnation, in addition to the dyes, also contains phosphorus compounds of the formula in which X, Y and Z independently of one another denote an optionally substituted alkyl, aryl, aralkyl, alkoxy, aroxy and / or aralkoxy radical, two of the three symbols X, Y and Z with the phosphorus atom also having a heteroeyelic five- or can form six-membered ring contains. 2) embodiment of the method according to claim 1, characterized in that the liquor used for impregnation contains, in addition to the phosphorus compounds, carboxamides and / or surface-active polyglycol ethers.