DE3830468A1 - POLYURETHANE SPIDER PREPARATIONS - Google Patents

Description

The invention relates to polyurethane-containing spin finishes Process for improving thread closure during melt spinning synthetic fiber materials and the use of Polyurethanes as thread closure agents in spin finishes.

When melt spinning synthetic fiber materials and their Further processing to textile or technical yarns are the multifilament threads wound onto the spool without twisting. The Single capillaries are present as parallel bundles of threads, the Cohesion of the individual capillaries only through the more or less pronounced adhesive effect of the spin finishes is effected. These are obtained in the subsequent stretching process Yarns normally have a protective twist of a few turns per Meter. This protective twist is, however, for many subsequent processing processes unsatisfactory. In many cases, therefore the threads are twisted in a separate process step. The However, twisting is an expensive, additional process step. To the Reducing the cost of twisting has already been suggested that Swirl bundles of threads with the help of an air stream and if necessary to twist afterwards. The process of swirling is however also expensive and difficult to control. Of further, the degree of intermingling is reduced when the yarn is under Tension is passed through thread guide. The result is that it is too  There are knots that negatively affect the appearance of the tissues (US 46 32 874).

Another way to solve the cost problem is to use it of thread closure agents in spin finishes. For example in DE-OS 34 02 155 epoxyalkyl compounds as thread-closing agents described. After applying such spin finishes however, heat treatment is required on the bundles of threads. Furthermore, epoxyalkyl compounds cause permanent thread closure, which affects the properties of the finished textile. In most cases, however, spin finishes are said to have no effect leave on the fiber and easily washed out again can be removed (chemical fibers / textile industry 1977, 328).

Preparations are known from US 35 05 220, the mineral oils, Polybutenes with average molecular weights between 150 and 750, Alkyl or alkenyl acid phosphates with 13 to 19 carbon atoms in the Contain alkyl or alkenyl residues and oxidized vegetable oils. However, the high viscosity of these agents leads to difficulties in use.

The object of the invention was to develop spin finishes, which has a very good adhesion of the individual threads of a bundle of threads effect and the swirling and / or twisting of Make thread bundles unnecessary. Furthermore, the spin finishes should be applicable in a simple manner and none Require thermal treatment.

Surprisingly, it was found that these high requirements of polyurethane-containing spin finishes.  

Accordingly, the subject of the invention are spin finishes Basis of smoothing agents, emulsifiers, wetting agents, thread closing agents and / or antistatic agents, which are characterized in that based on total active substance content, 1 to 40% by weight Polyurethanes included.

Another object of the invention is a method for improvement the thread closure when melt spinning synthetic fiber materials, which is characterized in that following the Melt spinning, based on the weight of the thread bundle, 0.3 to 2.0 wt .-% polyurethane-containing spin finish active substance the bundles of threads are applied.

Furthermore, the use of polyurethanes as thread closure agents in amounts of 1 to 40% by weight, based on the total active substance content, Subject of the invention in spin finishes.

The polyurethanes to be used according to the invention are in themselves manufactured in a known manner (see for example in Ullmanns Encyclopedia of Technical Chemistry, Volume 19, pages 302 ff., Publisher Chemie (1980)) by combining polyisocyanates with polyols and Hydroxycarboxylic acids in the presence of solvents and optionally Catalysts in 1 to 6 hours at temperatures between 60 and 120 ° C to be converted into prepolymers. Related to the Polyol component, the OH / NCO equivalent ratio is between 0.4 and 1.1, preferably between 0.5 and 0.7. After the mixture 1 was heated to reflux for up to 3 hours, if necessary Cooled 18 to 30 ° C and dissolved in organic solvents neutralized tertiary alkyl amines. The polyurethane mass is then dispersed in water and then, based on a original NCO equivalent, with 0 to 0.7 equivalents of mono- and / or diamines, dissolved in water. After removing the  Solvents by distillation become anionic Obtain polyurethane dispersions that have no free NCO functions own more. The polyurethane content is in the dispersions between 10 and 60% by weight, preferably between 25 and 40% by weight.

Suitable polyisocyanates are those known from polyurethane chemistry aliphatic and / or aromatic, cyclic and / or noncyclic polyisocyanates, for example 4 ′, 4 ′ ′, 4 ′ ′ ′ - triisocyanato-triphenylmethane, 2,4,4′-triisocyanato-diphenyl ether, Tris (4-isocyanatophenyl) thiophosphate, toluene-2,4- and / or toluene ol-2,6-diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalenedi isocyanate, 1,4-phenylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,6-hexane diisocyanate and / or 3- Isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (Isophorone diisocyanate). Preferably aliphatic Diisocyanates, particularly preferably dicyclohexyl methane-4,4'-diisocyanate and / or isophorone diisocyanate used.

As a polyol component with at least 2 alcoholic hydroxyl groups for the preparation of the prepolymers, for example, glycerol, Trimethylolpropane, polyethers and polyester polyols are used. Polyether polyols, preferably by addition of alkylene oxides Ethylene oxide and / or propylene oxide on polyfunctional starter molecules are most important as polyethers. Examples of starter molecules are ethylene glycol, 1,2-propylene glycol, trimethylolpropane, trimethylolethane, glycerin, Pentaerytrite, sorbitol, sugar or ethylenediamine are used. Polyester polyols are di- and trifunctional polyols with dicarboxylic acids or their anhydrides or by ring-shaped polymerization of caprolactan or Pivalone lactone on low molecular weight starter diols. As di- and trifunctional polyols are suitable for ethylene glycol, 1,2-  Propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, Diethylene glycol, glycerin, trimethylolpropane and / or hexanetriol. Examples of suitable dicarboxylic acids or acid anhydrides are succinic acid, Adipic acid, phthalic anhydride, Hexahydrophthalic acid, maleic acid or isophthalic acid. As Polyol components are preferably polyester polyols with medium Molecular weights between 500 and 5000, particularly preferred Polycaprolactones with average molecular weights between 500 and 3000, produced by ring opening polymerization of Caprolactone on low molecular weight diols as starter molecules, for example Ethylene glycol or 1,4-butanediol used. Polycaprolactans are commercially available products, for example by Interox Chemicals Ltd. offered under the name "CAPA" will.

Suitable polyhydroxycarboxylic acids are, for example, dihydroxypropionic acid, Dimethylolpropionic acid, dihydroxysuccinic acid and / or dihydroxybenzoic acid. 2,2-Dimethylolpropionic acid is preferred for use.

Particularly suitable solvents are methyl ethyl ketone, Ethyl glycol acetate, N-methylpyrollidone, triacetin and / or Diethylene glycol diacetate.

The reactions of polyisocyanates with polyols and polyhydroxycarboxylic acids are optionally in the presence of catalysts, for example 1,4-diaza- (2.2.2) bicyclooctane and / or dibutyl-di- lauryl stannate carried out, the amount of catalyst between 0.001 and 0.1% by weight, based on the total active substance content of the obtained polyurethanes.  

The prepolymers are neutralized with tertiary alkylamines, dissolved in the above-mentioned solvents, for example with triethylamine, Dimethylethanolamine, triethanolamine, dimethylisopropanolamine, Dimethylamino-3-propanol, diethylethanolamine, Triiso propanolamine and / or methyldiisopropanolamine performed. As Chain extenders are suitable for diamines, especially in the form of aqueous ones Solutions, for example ethylenediamine, hexamethylenediamine and / or piperazine, as chain terminators monoamines, especially in Form of aqueous solutions, for example monoethanolamine and / or Morpholine.

The polyurethane dispersions are in aqueous emulsified spin finishes, the smoothing agents, emulsifiers, wetting agents, antistatic agents and / or optionally contain further additives at temperatures incorporated between 18 and 25 ° C by mixing. The received Polyurethane-containing spin finish emulsions have one Total active substance content between 3 and 40 percent by weight. The polyurethane content in the emulsions is based on total Active substance content between 1 and 40 weight percent (wt .-%). Based on total active substance content, the emulsions contain

35 to 95 wt .-% smoothing agent
0 to 50% by weight of emulsifiers, antistatic agents and / or wetting agents
1 to 40% by weight of polyurethane
0 to 10% by weight of additives, for example pH regulators, bactericides and / or anti-corrosion agents

preferably

35 to 95 wt .-% smoothing agent
0 to 50% by weight of emulsifiers, antistatic agents and / or wetting agents
5 to 20% by weight of polyurethane
0 to 10% by weight additives.

The spin finish emulsions according to the invention contain, for example, mineral oils, fatty acid esters with 8 to 22 carbon atoms in the fat residue and 1 to 22 carbon atoms in the alcohol residue, for example methyl palmitic acid ester, isobutyl stearate and / or 2-ethylhexyl tallow fatty acid, silicones, for example dimethylpolysiloxane and / or or polyalkylene glycols, for example ethylene oxide / propylene oxide mixed polymers with average molecular weights between 600 and 6000. Suitable emulsifiers, wetting agents and / or antistatic agents are anionic, cationic and / or nonionic surfactants (see, for example, in chemical fibers / textile industry, 1977, 335) , such as mono- and / or diglycerides, for example glycerol mono- and / or glycerol dioleate, alkoxylated, preferably ethoxylated and / or propoxylated fats, oils, fatty alcohols having 8 to 24 carbon atoms and / or C _8-18 alkylphenols, for example castor oil 25 moles of ethylene oxide and / or C _16-18 fatty alcohol with 8 moles of propylene oxide + 6 moles of ethylene oxide, if desired alkoxylated C _8-24 fatty acid mono- and / or diethanolamides, for example oleic acid mono- and / or diethanolamide, tallow fatty acid mono- and / or diethanolamide and / or coconut fatty acid monoethanolamide with 4 moles of ethylene oxide, alkali and / or ammonium salts of alkoxylated, preferably ethoxylated and / or propoxylated, optionally end-capped C _8-22 -Alkylalkoholsulfonate, for example, oleyl alcohol · 20 moles of ethylene oxide-butanol-sodium sulfonate, reaction products of optionally alkoxylated C _8-22 alkyl alcohols with phosphorus pentoxide or phosphorus oxychloride, for example ethylhexanol · 2 Mol ethylene oxide P₂O₅ ester, potassium salt, alkali and / or ammonium salts of C _8-22 alkyl sulfosuccinates, for example sodium dioctyl sulfosuccinate, and / or amine oxide, for example dimethyl dodecylamine oxide. As optional ingredients include spin finishes pH adjusters, for example, C _1-4 carboxylic acids and / or C _1-4 hydroxycarboxylic acids, such as acetic acid and / or glycolic acid, alkali hydroxides such as potassium hydroxide and / or amines such as triethanolamine, bactericides and / or anti-corrosion agents.

The application of polyurethane-containing spin finish emulsions takes place in a known manner after the capillaries have emerged from the Spinneret. The preparations that have a temperature between 18 and 30 ° C, with the help of application rollers or by means of metering pumps applied over suitable applicators. The Aktivsub Stamping order quantity of the spin finish emulsions, if necessary with water to an active substance content between 3 and 20% by weight diluted is about 0.3 to 2.0 wt .-%, based on the weight of the thread bundle. After treatment with the preparations the bundles of threads are wound on spinning bobbins. It is surprising that with the spin finishes of the invention treated thread bundle in addition to an improved thread closure have reduced dynamic thread / solid friction coefficients. The thread bundles can be made of polyamides, polyesters or Polyolefins exist.

Examples Preparation of the polyurethane dispersion I

0.015 mole CAPA 210 (Interox Chemicals Ltd., average molecular weight = 1000, OH number = 112) and 0.01 mol of dimethylolpropionic acid were dissolved in 10.06 g of methyl ethyl ketone in a stirred reactor and heated to 60 ° C with stirring. After homogenization 0.0321 mole of isophorone diisocyanate was added and the mixture for 2 hours heated to 85 to 90 ° C. Having a constant NCO value has been set, heating was continued for a further 30 minutes. after the Mixture has been cooled to 25 to 30 ° C, 0.019 mol Trimethylamine in 6.567 g of methyl ethyl ketone was added for neutralization. After about a quarter of an hour, the polyurethane mass was in 50 g Dispersed water and then 0.07 mol of ethylenediamine in 8.3 g Water added. Methyl ethyl ketone was under reduced pressure distilled off at 35 to 40 ° C, and it became an aqueous Polyurethane dispersion with an active substance content of 30% by weight receive.

Examples of use

Spin finishes of the following compositions were used:

Spin preparation A:
61% by weight of 2-ethylhexyl tallow fatty acid
6% by weight rapeseed oil / triolein sulfate
6% by weight sodium dioctyl sulfosuccinate
10 wt.% Oleyl alcohol. 20 moles of ethylene oxide butanol sodium sulfonate
4% by weight oleic acid diethanolamide
7% by weight oleic acid mono / diglyceride
5% by weight olein
1% by weight KOH, 45% by weight

Spin preparation B:
70% by weight of 2-ethylhexyl tallow fatty acid
3% by weight sodium dioctyl sulfosuccinate
2 wt .-% ethylhexanol · 2 moles of ethylene oxide P₂O₅ ester, potassium salt
18% by weight dimethyl-dodecylamine oxide
4 wt% C _16-18 fatty alcohol x 8 moles propylene oxide x 6 moles ethylene oxide
2% by weight olein
1% by weight of triethanolamine

Spin preparation C:
20% by weight mineral oil, viscosity (25 ° C) = 6 m² / sec
30 wt .-% poly- α- olefin, viscosity (40 ° C) = 5.1 m² / sec
20 wt .-% poly- α- olefin, viscosity (40 ° C) = 16.9 m² / sec
3% by weight sodium dioctyl sulfosuccinate
2 wt .-% ethylhexanol · 2 moles of ethylene oxide P₂O₅ ester, potassium salt
18% by weight dimethyl-dodecylamine oxide
4 wt% C _16-18 fatty alcohol x 8 moles propylene oxide x 6 moles ethylene oxide
2% by weight olein
1% by weight of triethanolamine

9 parts by weight (parts by weight) of spin finish emulsified in water A was with 3.3 parts by weight (preparation A1) or with 6.6 parts by weight (Preparation A2) of polyurethane dispersion I, 9 parts by weight in water emulsified spin preparation B with 3.3 parts by weight (preparation B1) and 6.6 parts by weight (preparation B2) of polyurethane dispersion I and 9 parts by weight spinning preparation C emulsified in water with 6.6 parts by weight (Preparation C1) Polyurethane dispersion I mixed at 20 ° C. The total active substance content of the spin finish emulsions was 7.5% by weight.  

Nylon 6 115 F 34 POY (P artially O riented Y arn) was treated with a spinning speed of 4500 m / min spun. The polyurethane-containing spinning preparation emulsions, which had a temperature of 20 ° C., were applied via a metering pump (oil coating: 0.8% by weight, emulsion concentration: 7.5% by weight of active substance).

The following parameters were used in the evaluation of the spinning test certainly:

Friction coefficient against steel at a speed of 300 meters per minute measured on the F-meter from Rothschild (climate: 20 ° C, 65% relative air humidity)
Electrostatic charging on steel at a speed of 300 meters per minute measured on the F-meter from Rothschild (climate: 20 ° C, 65% relative air humidity)
Half-life (static voltmeter from Rothschild; climate: 20 ° C, 65% relative air humidity)
Thread closure (measuring device of the Textile and Fiber Institute, Denkendorf; climate: 20 ° C, 65% relative air humidity)

The results are summarized in Table 1.  

Table 1

Claims (6)

1. Spin finishes based on smoothing agents, emulsifiers, thread-closing agents, wetting agents and / or antistatic agents, characterized in that they contain 1 to 40% by weight of polyurethane, based on the total active substance content. 2. spin finishes according to claim 1, characterized in that these, based on the total active substance content, 5 to 20% by weight Polyurethanes included. 3. spin finishes according to one or both of claims 1 to 2, characterized in that the polyurethanes as polyisocyanates aliphatic diisocyanates, preferably Dicyclohexylmethane-4,4'-diisocyanate and / or isophorone diisocyanate contain. 4. spin finishes according to one or more of claims 1 to 3, characterized in that the polyurethanes as Polyol component Polyester polyols with average molecular weights between 500 and 5000, preferably polycaprolactones with average molecular weights between 500 and 3000 included. 5. Process for improving thread closure in melt spinning synthetic fiber materials, characterized in that after the capillaries emerge from the spinneret, based on the Weight of the thread bundle, 0.3 to 2.0% by weight of spin finish active substance according to one or more of claims 1 to 4 the bundles of threads are applied.   6. Use of polyurethanes as thread closure agents in spin finishes in amounts of 1 to 40% by weight, based on the total active substance content.