EP0187136B1 - Method for dyeing and lubricating sewing threads in a single bath - Google Patents

Description

It is known to treat sewing thread with agents which contain diorganopolysiloxanes as heat protection agents and paraffin waxes as lubricants, for example from DE-OS 21 61 813 and 25 35 768. The techniques used for this treatment are varied. The godet process (DE-OS 21 62 417 and 27 08 650), the immersion process (DE-OS 27 53 200) and the exhaust process (DE-OS 28 16 196 and 31 15 679) are known to this day. Disadvantages of the individual processes are mentioned: in the godet process, the complex finishing process on the individual thread, in the immersion process, the limited reusability of the immersion baths and in the exhaust process, the need for heating and an exact adjustment of the pH.

All of the finishing processes for sewing threads that have been used up to now have a common disadvantage: they require an additional process step after the dyeing phase has ended.

DE-A-21 01 227 also discloses a process for dyeing textured fibers, in which a lubricant based on an essentially linear organopolysiloxane is incorporated into the dye bath.

JP-A-76 12 000 describes the dyeing of nylon sewing threads by padding with mixtures of a dye solution in an alcohol and from a paraffin, followed by a heat treatment.

The present invention relates to a process for the finishing (finishing) of yarns from synthetic yarns, native yarns or from core yarns (for example, covered twisted yarns made from PES and Bw) by means of a finishing agent based on polymeric organosilicon compounds, in which the finishing agent is used in the dye bath and simultaneous dyeing and finishing are carried out in one process step, which is characterized in that the finishing agent defined below, dispersed or dissolved in water, is used to finish sewing thread. The disadvantages of the previously known sewing thread finishing methods mentioned do not occur with this method.

The process according to the invention is made possible by a special composition of the finishing agent used, as will be explained below.

The applicant has determined that when the following finishing agents are used in the dyebath (containing dyes) there is no disruption in the course of the dyeing, the dye extraction and the fastness of the dyed yarns. This is all the more surprising since anionic and cationic components are present in the bath. The yarns dyed and finished in the same bathroom surprisingly meet all the requirements of the quality standard that was previously obtained in two or more operations. The invention thus enables an extremely economical operation, saving time and one or more treatment baths.

The invention is explained in detail below.

Examples of synthetic yarns are polyester yarns (PES) and polyamide yarns (PA), such as PA 6.6. Cotton yarns (BW) are examples of native yarns. Examples of core yarns are core threads made from polyester (PES) and cotton (Bw).

• a) 1 bis 80 Gew.-% Siliconöl einer Viskosität von 500 bis 100 000 mPa.s bei 25 C;
• b) 1 bis 50 Gew.-% Pflanzenwachs, tierisches Wachs, Montanwachs, Wachs aus Erdöl (insbesondere Paraffinwachs) und/oder Polyolefin-Wachs, wobei diese Wachse einen Schmelzpunkt von jeweils ? 35 C haben;
• c) 0 bis 20 Gew.-% einer quartären Ammonium-Verbindung der Formel
  
• Ri = Alkyl G 2-C22
• R_{2 =} Alkyl C₁-C₂₂
• R₃ = Alkyl C₁-C₂₂
• R4 = Alkyl C_l-C₄
• A = salzbildendes Anion und/oder einer diquartären Ammonium-Verbindung der Formel
  
  worin R_i, R₂, R₃ und A wie oben definiert sind, und x 2 oder 3 bedeutet, und/oder eines Alkylimidazolinsalzes mit Alkylresten von 12 bis 22 C-Atomen;
• d) 1 bis 10 Gew.-% eines Fettsäure-Kondensationsproduktes, aufgebaut aus C₁₂-C₂₂-Fettsäuren und Alkanolaminen bzw. Polyaminen, in Form eines Salzes;
• e) 0 bis 5 Gew.-% Aminoxid der Formel
  
  wobei R C₈-₁₂-Alkyl oder -Alkenyl, R₁ C_1-4-Alkyl, R₂ H oder C_1-4-Alkyl und n Zahlen von 0 bis 6 bedeuten;
• f) 1 bis 10 Gew.-% nichtionogene Emulgatoren, Basis C₁₂-C₂₂-Fettalkohol oder -Fettsäure oder lso- tridecylfettsäureester,mit jeweils 2 bis 50 Mol angelagertem Ethylenoxid (EO);
• g) 0 bis 10 Gew.-% nichtionogene Emulgatoren auf Basis ethoxylierter Triglyzeride;
• h) 0 bis 10 Gew.-% kationaktive Emulgatoren, Basis C₁₂-C₂₂ Fettamin mit 2 bis 30 Mol angelagertem

The special finishing agents suitable for the process according to the invention are characterized in that they contain the following constituents, dispersed or dissolved in water:

• a) 1 to 80 wt .-% silicone oil with a viscosity of 500 to 100,000 mPa.s at 25 C;
• b) 1 to 50% by weight of vegetable wax, animal wax, montan wax, wax from petroleum (in particular paraffin wax) and / or polyolefin wax, these waxes each having a melting point of? Have 35 C;
• c) 0 to 20 wt .-% of a quaternary ammonium compound of the formula
  
• Ri = alkyl G 2 -C22
• R _{2 =} alkyl C ₁ -C ₂₂
• R ₃ = alkyl C ₁ -C ₂₂
• R4 = alkyl C _l -C ₄
• A = salt-forming anion and / or a diquartary ammonium compound of the formula
  
  wherein R _i , R ₂ , R ₃ and A are as defined above, and x is 2 or 3, and / or an alkylimidazoline salt with alkyl radicals of 12 to 22 carbon atoms;
• d) 1 to 10% by weight of a fatty acid condensation product, built up from C ₁₂ -C ₂₂ fatty acids and alkanolamines or polyamines, in the form of a salt;
• e) 0 to 5 wt .-% amine oxide of the formula
  
  wherein RC _8-12 alkyl or alkenyl, R _{1 is} C _1-4 alkyl, R ₂ is H or C _1-4 -alkyl and n are numbers from 0 to 6;
• f) 1 to 10% by weight of nonionic emulsifiers, based on C ₁₂ -C ₂₂ fatty alcohol or fatty acid or isotidecyl fatty acid ester, each with 2 to 50 mol of ethylene oxide (EO) added;
• g) 0 to 10% by weight of nonionic emulsifiers based on ethoxylated triglycerides;
• h) 0 to 10 wt .-% cationic emulsifiers, based on C ₁₂ -C ₂₂ fatty amine with 2 to 30 mol of added

Ethylene oxide (EO).

The weight percentages given above are each based on the finishing agent in the form of the aqueous dispersion. The following explanations apply to the individual components a) to h). Component a): Its amount is generally 1 to 80% by weight, preferably 5 to 50% by weight, and in particular 20 to 40% by weight. The silicone oil is, for example, a methyl silicone oil (in particular dimethylpolysiloxane) with a viscosity of 500 to 100,000 mPa.s, preferably 2000 to 30,000 mPa.s, in each case at 25 ^. C to name. However, longer-chain alkyl groups (such as ethyl or propyl groups) and / or phenyl groups can also be present as substituents in the silicone oil. The chain ends are formed from trimethylsilyl groups and, to a limited extent, also from dimethylhydroxysilyl groups. The amount of silicone oil in the agents according to the invention depends on the type of sewing thread to be treated. In the case of synthetic yarns, preparations with a high proportion of silicone oil (for example 20 to 50% by weight) can be used. If the sewing thread consists essentially or at least on its surface of native fiber material, then finishing agents can be used whose silicone content is reduced in favor of the wax component; the agent can then contain, for example, 1 to 20% by weight, preferably 1 to 5% by weight, of silicone oil.

Component b): Its amount is generally 1 to 50% by weight, preferably 1 to 20% by weight, and in particular 2 to 10% by weight. The claimed waxes each have a melting point of ≥ 35 ° C. Carnauba wax and jojoba oil are particularly worthy of an example for plant waxes. Beeswax and wool wax in particular are examples of animal waxes. Montan Waxes are, for example, ester and acid waxes produced by refining montan wax. Paraffin waxes are particularly worth mentioning among the waxes from petroleum. For polyolefin waxes, for example, high-pressure polyethylene wax oxidates and low-pressure polyolefin wax oxidates should be mentioned.

Fully refined paraffins (oil content: for example 0.5% by weight, color: pure white, odor: none) and / or semi-refined paraffins (oil content: for example 1.0 to 2.5% by weight, color: pure white) are preferred , Smell: slight), as described in "Ullmann's Encyclopedia of Technical Chemistry", volume 24, Verlag Chemie GmbH, D-6940 Weinheim, 1980.

Preferred lubricants are also macrocrystalline paraffins (paraffin waxes) with a melting point between 40 and 65 ° C. Higher-melting microcrystalline paraffins (microwaxes) are also suitable. These are then preferred (for the purpose of easier emulsification) blended with lower melting paraffins; Mixtures of 10 to 30 parts by weight of low-melting paraffin and 90 to 70 parts by weight of higher-melting paraffin should be mentioned in particular. Mixtures of different waxes can also be used.

Constituent c): The amount of this component which may be present is generally 0 to 20% by weight, preferably 0 to 10% by weight. Within the claimed alkyl chain length of R ₁ , alkyl radicals with C ₁₂ -C ₁₄ , with C ₁₆ -C ₁₈ and with C _{22 are} preferred. The alkyl chain lengths of R ₂ and R ₃ are in particular alkyl radicals with C ₁ , with C ₂ , with C ₁₂ -C ₁ and with C ₁₆ -C ₁ . Methyl and ethyl are particularly preferred as alkyl chain lengths in R4. Examples of salt-forming anions A are, above all, chlorides and methosulfates and ethosulfates. Within the claimed C ₁₂ -C ₂₂ alkyl radicals in the alkylimidazoline salts, alkyl radicals with C ₁₂ -C ₁₄ , with C ₁₆ -C ₁₈ and with C ₂₂ can be mentioned, for example.

Component d): Its amount is generally 1 to 10% by weight, in particular 1 to 6% by weight.

Examples of C ₁₂ -C ₂₂ fatty acid components (of the fatty acid condensation products) are those with C ₁₂ -C ₁₄ , with C ₁₆ -C ₁₈ and with C ₂₂ , in particular stearic acid or behenic acid. Triethanolamine may be mentioned as alkanolamine, for example, dimethylaminopropylamine as polyamine. The salts can be formed with inorganic acids or with lower organic carboxylic acids or hydroxycarboxylic acids. Preferred salts of inorganic acids are chlorides, sulfates, formates and acetates.

Constituent e): In this component which may be present, examples of the alkyl radicals in R ₁ and R ₂ include, above all, methyl and ethyl. Preferred meanings of n are 0.1 and 2.

Component f): Its amount is generally 1 to 10% by weight, preferably 1 to 5% by weight. The chain length of the fatty alcohol, fatty acid or fatty acid ester component mentioned is, for example, C ₁₂ -C14 or C ₁₆ -C ₁₈ . Among the ethylene oxide addition products, those with 15 to 25 moles of EO are preferred. Particular mention should be made of stearyl alcohol x 50 EO and isotridecyl stearate x 2 EO as constituent f).

Constituent g): The amount of this component which may be present is generally 0 to 10% by weight, preferably 0 to 5% by weight. Castor oil x 8 EO should only be mentioned as an example for the demanding group.

Constituent h): The amount of this component which may be present is generally 0 to 10% by weight, preferably 0 to 5% by weight. Within the fatty amines, examples include those with C ₁₂ -C ₄ or with C ₁₆ -C ₁₈ alkyl radicals. Among the ethylene oxide addition products mentioned, those with 2 to 10 mol EO are preferred. Oleylamine x 2 EO and stearylamine x 5 EO are only examples of representatives of component h).

The components c), d) and e) fulfill several functions, depending on whether the yarn consists of synthetic, native or soul yarn. In the agents according to the invention they act on the one hand as anti-electrostatics, as softening agents and in a synergism with the waxes also as lubricants, on the other hand they have a stabilizing effect, act as co-emulsifiers in the preparation of the preparations (finishing agents) and promote the uniform pull-out behavior of the agents during the dyeing process.

The constituents f), g) and h) act as emulsifiers in the preparation of the dyebath finishing agents, promote the anti-electrostatic activity of the auxiliaries described and stabilize the use of the agents in the individual dyeing liquors.

The finishing agents can be manufactured in various ways. They are preferably prepared in such a way that components a) and b) are emulsified separately, it being possible for emulsifier f) to be used alone or together with emulsifiers g) and / or h). The components c), d) and e) are preferably emulsified together with component b).

The resulting dispersions of a) and b) can be mixed with one another after completion, or the emulsion of component b) can be used to emulsify a pre-emulsion of component a). In the agents described, water is the outer phase, ie it is an oil-in-water emulsion (O / W emulsion). The emulsions can either be produced without pressure (water-in-wax process or wax-in-water process) or in a low-pressure autoclave. For optimum stability in the dyeing liquors, it is advantageous to homogenize the agents, for example by pumping the mixtures through a colloid mill and / or a high-pressure homogenizing machine.

The finishing agent can be used in different amounts in the dye bath. The amount of the finishing agent is advantageously 5 to 25% by weight, in particular 10 to 20% by weight, of the weight of the goods to be dyed.

With regard to the details which are common in practice for dyeing sewing thread twists from synthetic threads, native threads and from core threads, reference is made to the relevant specialist literature and to the color cards of the color manufacturers. The usual dye classes for sewing thread are therefore only summarized. These are: the usual disperse dyes at PES; for PA 6.6 the usual acid dyes, but also usual 1: 2 metal complex dyes and occasionally also usual dispersion dyes for light colors; in the case of PES / Bw mixtures of customary disperse and customary reactive or custom vat dyes; and at Bw the class of the usual reactive and vat dyes. The dyeing liquor can (apart from the dyes) contain the usual dyeing aids, e.g. Dispersing, leveling and adjusting agents as well as coloring accelerators.

The finishing agent dispersions are applied in the customary manner in customary dyeing apparatuses such as are used for dyeing textile yarns. Is preferably carried out in liquor ratios of 1: 4 to 1:50, in particular 1: 4 to 1:15 and at temperatures of 40 to 140 ° C, preferably 100 to 140 ° C.

The invention will be explained in more detail with the aid of the following examples, but its application should not be restricted in any way.

The indication ( ^* ) for the disperse dye in Example 1, number 2 and for the disperse / vat dye in Example 2, number 2 means that the amount of dye to be used depends on the desired shade; the dye specialist is familiar with the setting of this amount of dye and can be found at any time on the color cards of the color manufacturers.

example 1

• a) 35,0 Gew.-% Dimethylpolysiloxan (20 000 mPa.s)
• b) 8,0 Gew.-% Paraffinwachs, Fp. 58 bis 60 C
• c) 3,0 Gew.-% eines 1:1-Kondensates aus Behensäure und Dimethylaminopropylamin, in Form des Chlorids
• d) 1,5 Gew.-% Stearylalkohol x 50 EO (Ethylenoxid)
• e) 1,5 Gew.-% Rizinusöl x 8 EO
• f) 1,0 Gew.-% Oleylamin x 2 EO
• g) 50,0 Gew.-% demineralisiertes Wasser

1. Composition of the preparation (finishing agent)

• a) 35.0% by weight of dimethylpolysiloxane (20,000 mPa.s)
• b) 8.0 wt .-% paraffin wax, mp. 58 to 60 C.
• c) 3.0% by weight of a 1: 1 condensate of behenic acid and dimethylaminopropylamine, in the form of the chloride
• d) 1.5% by weight of stearyl alcohol x 50 EO (ethylene oxide)
• e) 1.5% by weight castor oil x 8 EO
• f) 1.0% by weight oleylamine x 2 EO
• g) 50.0% by weight of demineralized water

2. Application of the preparation according to the invention

• 1 bis 2 g/I nichtionogenes Waschmittel
• 0,5 bis 1 g/I calcinierte Soda
• 20 min 50 bis 60 °C
• 10 min 40°C spülen
• 10 min 20° C spülen

PES sewing thread made of filament yarn, spun fiber yarn (cotton or cardboard spun) or texture yarn is first pre-cleaned in the usual way according to the following recipe, for example:

• 1 to 2 g / l non-ionic detergent
• 0.5 to 1 g / l calcined soda
• 20 min 50 to 60 ° C
• Rinse at 40 ° C for 10 min
• Rinse at 20 ° C for 10 min

• x Dispersionsfarbstoff (^*)
• 1 bis 2 g/I anionaktives Egalisier- und Durchfärbemittel
• 0,5 bis 1 g/I Färbebeschleuniger
• 0,5 g/I anionaktives Dispergiermittel
• 10 bis 15 % erfindungsgemäße Zubereitung ph 4,5 bis 5,5 mit Essigsäure

Then the dyeing and finishing liquor is made up as a single bath as follows:

• x disperse dye ( ^* )
• 1 to 2 g / l of anionic leveling and coloring agent
• 0.5 to 1 g / l dyeing accelerator
• 0.5 g / l anionic dispersant
• 10 to 15% preparation according to the invention pH 4.5 to 5.5 with acetic acid

In the case of cross-winding, the liquor is preferably pumped alternately through the winding former and / or coils, e.g. 4 minutes from outside to inside and 2 minutes from inside to outside.

Treat for 5 minutes at approx. 40 ° C, heat at 1.5 to 2 ° / min to 130 to 135 ° C (HT conditions, ie high temperature conditions), dye for 30 to 60 minutes at 130 to 135 ° C, HT drain or cool, rinse twice for 3 minutes at 80 ° C

• 1 bis 2 g/l nichtionogenes Egalisier- und Dispergiermittel
• 3 bis 6 ml/l Natronlauge, 38° Be
• 3 bis 6 g/l Hydrosulfit
• 20 Minuten 90° C, zweimal heiß spülen, zweimal warm spülen, eventuell neutralisieren auf pH 5,5.

If necessary, reductively clean with dark colors

• 1 to 2 g / l non-ionic leveling and dispersing agent
• 3 to 6 ml / l sodium hydroxide solution, 38 ° Be
• 3 to 6 g / l hydrosulfite
• 20 minutes at 90 ° C, rinse twice hot, rinse twice warm, if necessary neutralize to pH 5.5.

The dye liquor is perfectly stable. There are no precipitates between the weakly cationic preparation according to the invention and the anionic dispersing, leveling and adjusting agents. The color and rub fastness correspond to the high demands usual in the sewing thread sector. The sewing thread is fully equipped, has the required sliding and sewing properties and, after drying, does not require any further finishing before winding into the sales presentation.

Example 2

• 1. Composition of the preparation
• (Finishing agent)

as in example 1.1 2. Application of the preparation according to the invention

PES / Bw sewing thread made of soul thread, consisting of a PES filament core and a Bw sheath, is pre-cleaned in the usual way (e.g. according to example 1.2), optionally with the addition of 1 g / l of an anionic complexing agent and then, as described below, in dyed and finished at the same time in one process step: a mixture of disperse and vat dyes is selected - only as an example.

In the usual way, 0.5 to 1 g / l of an anionic leveling and coloring agent is allowed to run for 5 minutes at about 40 ° C. at pH 4.5 to 5.5 (acetic acid). This is followed by the addition of x / y% dispersion / vat dye ( ^* ) and 10 to 15% of the preparation according to the invention

The liquor circulation is set to 4 minutes outside-inside, 2 minutes inside-outside (see example 1.2), heated to 1.5 to 2 ° / min to 130 to 135 ° C (HT conditions), dyes 30 to 45 Minutes at 130 to 135 ° C, cools, veils and then oxidizes as prescribed for vat dyes.

The dye liquor is perfectly stable. The sewing thread complies with the usual quality requirements and does not require any further finishing before winding into the sales presentation.

Example 3

1. Composition of the preparation

(Finishing agent)

• a) 35.0% by weight of dimethylpolysiloxane (12,500 mPa.s)
• b) 5.0% by weight paraffin wax, mp. 54 to 56 ° C
• c) 1.5 wt .-% paraffin wax, mp 44 to 46 ° C.
• d) 4.5% by weight of a 2: 1 condensate of stearic acid and triethanolamine, in the form of the sulfate
• e) 2.5% by weight isotridecyl stearate x 2 EO
• f) 1.5% by weight stearylamine x 5 EO
• g) 50.0% by weight of demineralized water

2. Application of the preparation according to the invention

The preparation is again described as a finishing agent in the dyebath as described in Examples 1 and 2 of sewing thread made of synthetic thread, native thread and soul thread and enables simultaneous dyeing and finishing in one process step.

Claims (1)

1. Process for finishing (avivage) yarns of synthetic yarns, natural yarns or core yarns with a lubricating agent on the basis of polymeric organosilicon compounds, the lubricating agent being applied in the dyebath and a simultaneous dyeing and lubricating being carried out in a single processing step, characterized in that for the finishing of sewing threads a lubricating agent is employed which contains the following components dispersed or dissolved in water:

a) 1 to 80 weight percent silicone oil of a viscosity of 500 to 100 000 mPa.s at 25° C;

b) 1 to 50 weight percent vegetable wax, animal wax, montan wax, mineral wax (especially paraffin wax) and/or polyolefin wax, these waxes having each a melting point of ≧ 35°C;

c) 0 to 20 weight percent of a quaternary ammonium compound of the formula

R, = alkyl C₁₂-C₂₂

R₂ = alkyl C₁-C₂₂

R₃ = alkyl C_l-C₂₂

R₄ = alkyl C₁-C₄.

A = salt forming anion and/or a diquaternary ammonium compound of the formula

wherein R₁ , R₂, R₃ and A are as defined above and x is 2 or 3, and/or an alkylimidazolinium salt with alkyl radicals of 12 to 22 carbon atoms:

d) 1 to 10 weight percent of a fatty acid condensation product formed by C₁₂-C₂₂ fatty acids and alkanolamines or polyamines, respectively, in the form of a salt;

e) 0 to 5 weight percent amine oxide of the formula

wherein R is C₈-C₁₂ alkyl or C₈-C_{1 2} alkenyl, Ri is C_1-4 alkyl, R₂ is H or C_1-4 alkyl, and n is a figure from 0 to 6;

f) 1 to 10 weight percent of non-ionogenic emulsifiers, based on C₁₂-C₂₂ fatty alcohol or -fatty acid or isotridecyl fatty acid ester, each with 2 to 50 moles of added ethylene oxide;

g) 0 to 10 weight percent non-ionogenic emulsifiers based on ethoxylated triglycerides;

h) 0 to 10 weight percent cation-active emulsifiers, based on C₁₂-C₂₂ fatty amines with 2 to 30 moles of added ethylene oxide.