EP0881324A2 - Process for simultaneously dyeing and removing brightening agents from synthetic fibers - Google Patents

Abstract

A process for the simultaneous removal of brightening agents and dyeing of synthetic fibres or materials containing the fibres, that have been treated with mineral oil and/or silicone oil brightening agents is claimed. The synthetic fibres or textile material is treated with an aqueous composition containing: (A) an anionic or amphoteric surfactant (B) a colouring agent consisting of an acid dye, metal complex dye or dispersion dye and (C) optionally a non-ionic surfactant, terpene hydrocarbon, terpene alcohol, sorbitol ester and/or mannitol ester and the corresponding oxalate, fatty acid ethanolamide, alkylpolyglycoside or solvent, at pH 4.0-7.5, 80-110 degrees C and at a goods to liquor ratio of 1:5 - 1:100.

Description

The present invention relates to a method that it in synthetic fibers or textile materials made from it, with mineral oil additives, silicone oil additives or both are permitted, in one operation at the same time to remove these additives and such synthetic fibers or from them Coloring textile materials. For this purpose, the fibers or textile materials are used treated in an aqueous liquor, the essential ingredients a) one or more Surfactant (s) from the group of anionic and amphoteric surfactants, b) one or several dye (s) and c) optionally one or more further substance (s) the group of nonionic surfactants, terpene hydrocarbons, terpene alcohols and their esters with lower carboxylic acids, the sorbitol ester and their Oxalkylates, fatty acid ethanolamides, alkyl polyglycosides and solvents included. This treatment is in the pH range from 4.0 to 7.5, at final temperatures in the range of 80-110 ° C and at a liquor ratio of 1: 5 to 1: 100.

Synthetic fibers to be treated according to the invention are, for example, polyamide fibers, made of polyamide-6 (Perlon and others) or polyamide-66 (nylon and others), Polyester fibers, polyurethane fibers and other known to those skilled in the art and their Mixtures with each other and their mixtures with other fibers of vegetable and animal Origin. The method according to the invention particularly relates to fibers of polyamides and of polyurethanes and their mixtures with one another and their Mixtures with fibers of vegetable and animal origin, particularly preferred Wise fibers made of polyamide, polyurethane or polyamide / polyurethane mixtures. Textile materials made from it are twisted or other textile-mechanical treated yarns and knitted fabrics, knitted fabrics or woven fabrics made therefrom. For some applications, For example, for the production of stockings, combined yarns are used used, for example, a polyurethane fiber and a crimped or uncrimped Include polyamide fiber.

To increase the machinability of fibers and yarns made from them these are provided with a finish, which is then also in the manufactured from it textile materials. In the field of synthetic fibers, these are often mineral oils or silicone oils. However, these oils as finishing agents interfere with the coloring process of Fibers, yarns and textile materials due to heavy staining. Therefore a Mineral oil or silicone oil softener removed by washing before staining will. Such a pre-wash is known in principle and is known in Apparatus carried out. The disadvantage of this laundry to be carried out separately consists once in the time required (about 80-90 min for a washing process) in which Need to keep separate apparatus for this purpose in personnel expenses for this separate process, in the formation of large additional amounts of waste water, that have to be disposed of, as well as in the energy required for heating and cooling in this separate process. Only then is the dyeing process possible, which are carried out with renewed effort of the resources mentioned got to.

It has now been found that it is possible to use the prewash previously carried out separately and to carry out the dyeing process with a fleet at the same time if one a fleet that uses one or more dye (s) or more surfactant (s) from the group of anionic and amphoteric surfactants and optionally one or more further substances from the group of nonionic surfactants, the terpene hydrocarbons, the terpene alcohols and their Esters with lower carboxylic acids, the sorbitol ester and their oxalkylates, the Fatty acid ethanol amides containing alkyl polyglycosides and solvents.

a) ein oder mehrere Tensid(e) aus der Gruppe der anionischen und amphoteren Tenside,

b) einen oder mehrere Farbstoff(e) aus der Gruppe der Säurefarbstoffe, Metallkomplexfarbstoffe und Dispersionsfarbstoffe und

c) gegebenenfalls einen oder mehrere weitere Stoff(e) aus der Gruppe der nichtionischen Tenside, der Terpenkohlenwasserstoffe, der Terpenalkohole und deren Ester mit niederen Carbonsäuren, der Sorbitester bzw. der Mannitester und deren Oxalkylate, der Fettsäureethanolamide, der Alkylpolyglykoside und der Lösungsmittel

enthält und die Behandlung im pH-Bereich von 4,0 bis 7,5, bei Endtemperaturen im Bereich von 80-110°C und bei einem Flottenverhältnis von 1:5 bis 1:100 durchführt.The invention therefore relates to a process for the simultaneous removal and dyeing of synthetic fibers or textile materials made therefrom, which are charged with mineral oil additives, silicone oil additives or both, which is characterized in that such synthetic fibers or textile materials made therefrom an aqueous liquor treated as the essential ingredients

a) one or more surfactants from the group of anionic and amphoteric surfactants,

b) one or more dye (s) from the group of acid dyes, metal complex dyes and disperse dyes and

c) optionally one or more further substance (s) from the group of the nonionic surfactants, the terpene hydrocarbons, the terpene alcohols and their esters with lower carboxylic acids, the sorbitol esters or the mannitol esters and their oxalkylates, the fatty acid ethanolamides, the alkyl polyglycosides and the solvents

contains and carries out the treatment in the pH range of 4.0 to 7.5, at final temperatures in the range of 80-110 ° C and at a liquor ratio of 1: 5 to 1: 100.

The method according to the invention is accordingly characterized by the coloring of synthetic fibers containing Avivage or textile materials made from them. The removal of mineral oil or silicone oil additives or both and the coloring in only one fleet. The invention The process is carried out under the conditions specified below.

Suitable amphoteric surfactants for the process according to the invention are amine oxides, betaines and sulfobetaines which contain a C ₁₀ -C ₂₂ hydrocarbon radical, or mixtures thereof.

X

eine Einfachbindung oder die Gruppe -CO-NH-(C₂-C₃-Alkyl)- bedeutet und

R¹ und R²

unabhängig voneinander Wasserstoff, Methyl oder Hydroxyethyl darstellt.

Preferred amphoteric surfactants are betaines of the formula (C ₁₀ -C ₂₂ alk (en) yl) ―XN ⊕ (R ¹ , R ² ) - (C ₁ -C ₄ - (hydroxy) alkylene) -COO ^⊖ in the

X

is a single bond or the group -CO-NH- (C ₂ -C ₃ alkyl) - and

R ¹ and R ²

independently represents hydrogen, methyl or hydroxyethyl.

Among these betaines are those of the formula (C ₁₀ -C ₂₂ alkyl) ―― N ⊕ (R ¹ ) ₂ ――CH ₂ COO ^⊖

X, R¹ und R²

die obige Bedeutung haben.

Among the amine oxides are those of the formula (C ₁₀ -C ₂₂ alk (en) yl) ―XN ⊕ (R ¹ , R ² ) → O preferred in the

X, R ¹ and R ²

have the above meaning.

Particularly preferred amine oxides are those of the formula (C ₁₀ -C ₂₂ alkyl) ―N ⊕ (R ¹ ) ₂ → O

Individual examples of suitable betaines (II) are: dodecyldimethylbetaine, cocoalkyldimethylbetaine, Tetradecyldimethylbetaine, octadecyldimethylbetaine, talc fatty alkyldimethylbetaine, Oleyl-dimethyl-betaine, cocoalkyl-bis-hydroxyethyl-betaine, stearyl-bis-hydroxyethyl-betaine, Tallow fatty alkyl bis-hydroxyethyl betaine.

Individual examples of suitable amine oxides (IV) are e.g. Dodecyl dimethyl amine oxide, Cocoalkyldimethylamine oxide, tetradecyldimethylamine oxide, octadecyldimethylamine oxide, Tallow fatty alkyl dimethyl amine oxide, oleyl dimethyl amine oxide, coconut alkyl bis-hydroxyethyl amine oxide, Stearyl-bis-hydroxyethyl-amine oxide, tallow fatty alkyl-bis-hydroxyethyl-amine oxide.

Suitable anionic surfactants are, for example, sulfation products of C ₁₀ -C ₂₂ -alkanols, -alkenols or their reaction products with 1-50 units of ethylene oxide (EO), preferably 1-40 units of EO. These sulfated products can be present as alkali metal, alkaline earth metal, ammonium, amine or ethanolamine salts. Other anionic surfactants are soaps from C ₁₂ -C ₁₈ fatty acids, mersolates and alkylbenzenesulfonic acids, which are in the form of the abovementioned salts. Other suitable anionic surfactants are polyether carboxylates of the formulas C ₈ -C ₂₀ -alk (en) yl- (O-CH ₂ -CH ₂ -) _x -O-CH ₂ -COO-M, where X is preferably from _{2 to} 30 of 3-10, and M represents an equivalent of one of the above salt-forming cations.

Amphoteric and anionic surfactants of the type mentioned above are used in many different ways Used in the field of textile treatment and are known to those skilled in the art.

With the help of the amphoteric and anionic surfactants mentioned and optionally the other substances succeed on the synthetic fibers mentioned above or from them Manufactured textile materials contain additives from mineral oils and silicone oils or to remove their mixtures without the simultaneous coloring the synthetic fibers or the textile materials. Rather, it will be surprisingly achieved colorations of high uniformity. Mineral oil additives widely used for polyamide or polyester fibers, while silicone oil additives are widely used in polyurethane fibers. Mineral oils are for example Paraffin oils in the viscosity range of 10-40 mPa.s; Silicone oils are, for example, M oils in the viscosity range of 3-100 mPa.s. It has been found that anionic Surfactants are preferably able to wash off mineral oil finishers while Amphoteric surfactants are cheaper when removing silicone oil additives. For the Case of blended fabrics, for example polyamide / polyurethane or polyester / polyurethane one is therefore preferred mixtures of anionic and amphoteric Use surfactants.

The treatment liquor also contains dyes, preferably those from the group of Acid dyes, metal complex dyes or disperse dyes. All these Dyes are known to the person skilled in the art and require no further explanation.

The treatment liquor optionally contains one or more further substances from the group of nonionic surfactants, terpene hydrocarbons, terpene alcohols and their esters with lower carboxylic acids, for example C ₁ -C ₄ carboxylic acids, preferably acetic acid, the sorbitol ester or mannitol ester and their oxalkylates, the Fatty acid ethanol amides, alkyl polyglycosides and solvents.

Nonionic surfactants are, for example, alcohols, such as alcohols from fat chemistry or oxo alcohols, or almines or carboxylic acids from fat chemistry 9-13 carbon atoms, with 3-10 units of EO and optionally with 2-5 Units of propylene oxide (PO) have been implemented. Among these implementation products the alcohols of the number of carbon atoms mentioned are preferred. Such non-ionic Surfactants are known to the person skilled in the art and require no further explanation.

As a terpene hydrocarbon, for example limonene, orange terpene, α-terpine, balsam terpin oil B, diterpene DS, diterpene B, diterpene A, limonene DL, piperitone, pine oil 70; as terpene alcohol and esters thereof with lower carboxylic acids, for example pineol terpinylacetate, terpineol may be mentioned. Sorbitol esters or mannitol esters are, for example, those with saturated or unsaturated C ₁₂ -C ₁₈ fatty acids; at the same time, their oxalkylates, for example with 2-40 units of EO and optionally 2-10 units of PO, are suitable.

Fatty acid ethanolamides, for example, have an alkyl radical with 12-18 C atoms. Alkyl polyglycosides, for example, have an alkyl radical with 8-12 C atoms. As Solvents come, for example, isopropanol, methoxypropanol and others solvents known to the person skilled in the art in question.

Preferred polyether carboxylates are, for example, carboxy-methylated emulsifier made from technical lauryl alcohol (C ₁₂ with proportions up to C ₁₈ ) with 4 to 8 mol EO; preferred alkyl polyglycosides have 8-10 C atoms; preferred anionic surfactants are C ₁₂ -C ₁₈ alkyl sulfates with 0-40 units of ethylene oxide. Preferred nonionic surfactants are C ₉ -C ₁₃ alcohols with 3-10 units of ethylene oxide. Preferred fatty acid ethanolamides are mixtures with alkyl radicals with 12-18 C atoms.

a) anionische und/oder amphotere Tenside in einer Menge von 0,05-2 g/l Wasch-/Färbeflotte, bevorzugt 0,1-1 g/l, bei Verwendung von anionischen und amphoteren Tensiden im Gewichtsverhältnis beider von 9:1-1:9;

b) 0,01-1 g/l eines oder mehrerer Farbstoffe für einen großen Bereich unterschiedlicher Farbtiefen, bevorzugt 0,03-0,3 g/l;

c) 0-1 g/l anionisches Tensid und/oder 0-1 g/l Terpenkohlenwasserstoffe/Terpenalkohole/deren Ester und/oder 0-1 g/l Sorbitester/Mannitester/deren Oxalkylate und/oder 0-2 g/l Fettsäureethanolamide und/oder 0-1 g/l Alkylpolyglykoside und/oder 0-2 g/l Lösemittel.

The following amounts of the substances mentioned are used in the treatment baths according to the invention:

a) anionic and / or amphoteric surfactants in an amount of 0.05-2 g / l washing / dyeing liquor, preferably 0.1-1 g / l, when using anionic and amphoteric surfactants in a weight ratio of both of 9: 1- 1: 9;

b) 0.01-1 g / l of one or more dyes for a wide range of different color depths, preferably 0.03-0.3 g / l;

c) 0-1 g / l anionic surfactant and / or 0-1 g / l terpene hydrocarbons / terpene alcohols / their esters and / or 0-1 g / l sorbitol esters / mannite esters / their oxalkylates and / or 0-2 g / l fatty acid ethanolamides and / or 0-1 g / l alkyl polyglycosides and / or 0-2 g / l solvent.

When ready-to-use mixtures / combinations of surfactants a) and other substances c) are kept in stock, such mixtures / combinations are placed next to the Dyes in an amount of 0.5 to 3 g per liter of liquor.

Typical fleet approaches from this are then, for example (without dyes): 0.2 g / l amphoteric surfactant (I) or 0.4 g / l Alkyl polyglucoside 0.2 g / l anionic surfactant (I) 0.4 g / l anionic surfactant (I) 0.06 g / l Lime 0.2 g / l Fatty acid monoethanolamide 0.06 g / l not. Surfactant rest water 0.06 g / l Solvents rest water

The treatment according to the invention of the synthetic fibers or textiles produced therefrom Materials with a surcharge on finishing for simultaneous execution of Coloring is in the pH range from 4.0 to 7.5, at end temperatures in the range from 80-110 ° C and with liquor ratios from 1: 5 to 1: 100, preferably 1: 5 to 1:10, carried out. For this you can use conventional equipment, such as wide washing machines, Use drum dyeing machines, cotton washing machines and cotton dyeing machines. The final temperatures are after heating from room temperature reached. It is used with heating rates of 0.5 to 8 ° C / min. worked.

(i) Betaine oder Aminoxide, anionische Tenside, ein oder mehrere nichtionische Tenside und mit oder ohne einen Gehalt an Terpenkohlenwasserstoffen/-alkoholen sowie mit oder ohne Lösungsmittel oder

(ii) Betaine oder Aminoxide, anionische Tenside, ein oder mehrere nichtionische Tenside und mit oder ohne einen Gehalt an Fettsäureethanolamiden.

Preferred combinations of surfactants a) and other substances c) which are used in the treatment liquor in addition to the dye or dyes:

(i) betaines or amine oxides, anionic surfactants, one or more nonionic surfactants and with or without a content of terpene hydrocarbons / alcohols and with or without solvents or

(ii) betaines or amine oxides, anionic surfactants, one or more nonionic surfactants and with or without a content of fatty acid ethanolamides.

Examples Examples 1-41 and I-IV

Combinations of surfactants a) and other substances c) according to the invention, the one allow simultaneous coloring according to the invention (here preliminary tests without dyes); is specified in the last column of the table according to the invention Liquor treatment still remaining avivage content (as petroleum ether (PE) extract); untreated raw material for comparison. The raw materials are socks made of polyamide / polyurethane mixed fibers As examples I to IV are raw materials with various Original content of avivage used and the remaining one afterwards Avivage content indicated. The compositions given are concentrates with the parts specified as parts by weight or in% by weight. From this concentrate 1 g / l wash liquor are used.

Betain 1 =

Talgfett-bis(hydroxyethyl)-betain der Formel (II)

Tensid A =

Cetylaminomethyl-phenol mit 15 Mol EO

Tensid B =

C₁₂-C₁₈-Alkohol mit 30 Mol EO, sulfatiert, Na-Salz

Tensid C =

Gemisch aus i-Tridecanol mit 3 Mol EO und i-Tridecanol mit 9 Mol EO

Betain 2 =

Dimethyl-Kokosfettamin, mit ClCH₂COONa zum Betain der Formel (II) umgesetzt

Tensid D =

carboxymethylierter Laurylalkohol mit 11 Mol EO

Tensid E =

i-Tridecylalkohol mit 4 Mol EO

Tensid F =

Dodecyl-benzolsulfonsäure-Ca-Salz (67 Tle. in 33 Tle. n-Butanol)

Tensid G =

carboxymethylierter Laurylalkohol mit 6 Mol EO

Tensid H =

Dodecylsulfat-Aminoethanol-Salz in Cyclohexanol/Methoxipropanol

Tensid I =

Polyethersiloxan (Tegopren 5878 von Fa. Th. Goldschmidt)

Tensid J =

Alkylpolyglycosid

(Fortsetzung am Ende der Tabellen)

In the tables mean:

Betaine 1 =

Tallow fat bis (hydroxyethyl) betaine of the formula (II)

Surfactant A =

Cetylaminomethyl phenol with 15 moles of EO

Surfactant B =

C ₁₂ -C ₁₈ alcohol with 30 mol EO, sulfated, Na salt

Surfactant C =

Mixture of i-tridecanol with 3 mol EO and i-tridecanol with 9 mol EO

Betaine 2 =

Dimethyl coconut fatty amine, implemented with ClCH ₂ COONa to the betaine of formula (II)

Surfactant D =

carboxymethylated lauryl alcohol with 11 mol EO

Surfactant E =

i-tridecyl alcohol with 4 moles of EO

Surfactant F =

Dodecyl-benzenesulfonic acid Ca salt (67 parts in 33 parts n-butanol)

Surfactant G =

carboxymethylated lauryl alcohol with 6 mol EO

Surfactant H =

Dodecyl sulfate aminoethanol salt in cyclohexanol / methoxypropanol

Surfactant I =

Polyethersiloxane (Tegopren 5878 from Th. Goldschmidt)

Surfactant J =

Alkyl polyglycoside

(Continued at the end of the tables)

Example 42 Hosiery (previous process)

Material:

Polyamide / polyurethane

Machine:

Drum dyeing machine (Dröll and Lohmann) with liquor injection and 700 liters of fleet content

Fleet ratio:

1:10 resp. 70 kg of material

Prewash:

1 g / l surfactant N 1 g / l soda calcined Starting temperature: 25 ° C Heating rate: 4 ° C / min Maximum temperature: 80 ° C Treatment duration: 15 ' Fleet indulgence 1. Rinse bath at 40 ° C Drain / Spin 2. Rinse bath at 40 ° C Drain / Spin Total duration: 80-90 min.

Coloring:

0,5 g/l

Entschäumermischung mit Mineralöl

1 g/l

Talgsulfonat-Na-Salz mit Oleylalkohol mit 19 EO

4 %

Egalisierungsmittel aus Alkylaminomethylphenol mit 15 EO und Kondensat aus Nonylphenol, Formaldehyd und Hexamethylendiamin mit 60 Mol EO

0.5 g / l

Defoamer mixture with mineral oil

1 g / l

Tallow sulfonate sodium salt with oleyl alcohol with 19 EO

4%

Leveling agent from alkylaminomethylphenol with 15 EO and condensate from nonylphenol, formaldehyde and hexamethylenediamine with 60 mol EO

0.004% Telon yellow 3RL micro or A.Y. 240 or A.Y. 242 = Yellow A3RL 0.002% Telon Red FRL micro A.R. 337 A.R 299 = Ruby ASB 0.0021% Telon Blue BRL micro FROM. 324 FROM. 264 = blue AFN

Starting temperature:

25 ° C

Dyeing time at 98 ° C:

30 min, + 30 min

Gesamtdauer:

103 - 120 min.

Cooling down, draining, rinsing, possibly post-treatment to improve authenticity, finishing.

Total duration:

103-120 min.

Example 43 Stocking dyeing (method according to the invention)

Material:

Polyamide / polyurethane

Machine:

Drum dyeing machine (Dröll and Lohmann) with liquor injection and 700 liters of fleet content

Fleet ratio:

1:10 resp. 70 kg of material

Washing and dyeing (single bath)

1 g / l

Agent according to the invention according to Example 16

0.5 g / l

Defoamer mixture with mineral oil

1 g / l

Tallow sulfonate sodium salt with oleyl alcohol with 19EO

4%

Leveling agent as in Example 42

0.5 g / l

Monosodium phosphate

0.25 ml / l

Acetic acid 80%

0.004%

Telon yellow 3RL micro

0.002%

Telon Red FRL micro

0.0021%

Telon Blue BRL micro

Starting temperature:

25 ° C

Heating rate:

1 ° C / min

Maximum temperature:

98 ° C

Dyeing time at 98 ° C:

30 min, + 30 min

Cooling down, draining, rinsing, possibly post-treatment to improve authenticity, finishing. Total duration: 103 - 120 min .; Saving 80 - 90 min.

Claims (7)

A process for the simultaneous removal and dyeing of synthetic fibers or parts made therefrom, which are loaded with mineral oil additives, silicone oil additives or both, characterized in that such synthetic fibers or textile materials made therefrom are treated with an aqueous liquor which as essential ingredients a) one or more surfactants from the group of anionic and amphoteric surfactants, b) one or more dye (s) from the group of acid dyes, metal complex dyes and disperse dyes and c) optionally one or more further substance (s) from the group of the nonionic surfactants, the terpene hydrocarbons, the terpene alcohols, the sorbitol esters or the mannitol esters and their oxalkylates, the fatty acid ethanolamides, the alkyl polyglycosides and the solvents contains and carries out the treatment in the pH range of 4.0 to 7.5, at final temperatures in the range of 80-110 ° C and at a liquor ratio of 1: 5 to 1: 100. A method according to claim 1, characterized in that at a liquor ratio from 1: 5 to 1:10. Process according to Claims 1 and 2, characterized in that a betaine of the formula is used as the amphoteric surfactant (C ₁₀ -C ₂₂ alk (en) yl) ―XN ⊕ (R ¹ , R ² ) - (C ₁ -C ₄ - (hydroxy) alkylene) -COO ^⊖ in the

X

is a single bond or the group -CO-NH- (C ₂ -C ₃ alkyl) - and

R ¹ and R ²

independently represents hydrogen, methyl or hydroxyethyl,

is used. Process according to Claim 3, characterized in that a betaine of the formula is used as the amphoteric surfactant (C ₁₀ -C ₂₂ alkyl) ―― N ⊕ (R ¹ ) ₂ ――CH ₂ COO ^⊖ is used. Process according to Claims 1 and 2, characterized in that an amine oxide of the formula is used as the amphoteric surfactant (C ₁₀ -C ₂₂ alk (en) yl) ―XN ⊕ (R ¹ , R ² ) → O is used in the

X, R ¹ and R ²

have the meaning given in claim 3.

A method according to claim 5, characterized in that one of the formula as amine oxide (C ₁₀ -C ₂₂ alkyl) ―N ⊕ (R ¹ ) ₂ → O is used. Process according to Claims 1 to 6, characterized in that the aqueous liquor contains, in addition to the dye (s), one of the following combinations of surfactants a) and further substances c): (i) betaines or amine oxides, anionic surfactants, one or more nonionic surfactants and with or without terpene hydrocarbons / alcohols and with or without solvents or (ii) betaines or amine oxides, anionic surfactants, one or more nonionic surfactants and with or without fatty acid ethanolamides, (iii) anionic surfactants, one or more nonionic surfactants and with or without fatty acid ethanolamides.