EP0935019A1 - Coating agent for fibers - Google Patents

Abstract

A fiber-coating material, especially for elastan fibers, comprises a dispersion of fatty acid metal salt and an agglomeration inhibitor, especially an anionic or nonionic antistatic additive, in a mixture of polyorganosiloxane and mineral oil. A coating material for fibres, especially elastan fibres, comprises a dispersion in silicone/oil containing at least (A) 30-98.97 (preferably 70-94.8) wt% polyalkylsiloxane with a viscosity of 2-150 mPa.s (25 degrees C), (B) 0.01-20 (preferably 0.1-2) wt% of the salt of a 6-30C fatty acid (saturated or unsaturated, mono- or bifunctional) and a Main Group I, II or III metal, (C) 1-69 (preferably 3-50, most preferably 5-30) wt% mineral oil with a viscosity of 2-500 mPa.s (25 degrees C), a density of 800-900 kg/m<3> (15 degrees C) and a viscosity-density constant of 0.770-0.825 and (D) 0.02-15 (preferably 0.05-5, most preferably 0.1-3) wt% cationic, anionic or nonionic antistatic compounds, especially anionic or non-ionic antistatic compounds, as agglomeration inhibitor. Independent claims are also included for (a) a process for the production of this fiber-coating material by dissolving the metal salt (B) in the mineral oil (C) at 70-170 degrees C and rapidly mixing/homogenising the hot solution with the silicone (A) in an intensive mixer, the agglomeration inhibitor (D) being added either to component (C) or (A) before mixing or to the resulting dispersion, preferably after homogenising; (b) fibers, especially polyurethane fibers, coated with this material.

Description

The invention relates to coating compositions for fibers and a method for their Manufacturing. The invention relates in particular to preparation agents for elastanes Basis of a dispersion of fatty acid metal salts and agglomeration inhibitors in Polyorganosiloxanes and mineral oils. The preparations are made through a precipitation process made from fine-grained and sedimentation-stable dispersions result in a narrow grain size distribution and are free of agglomerates. The Coating agents reduce the electrical resistance of elastanes, whereby neither in the application nor in the processing of the elastane, even with one deposits of coating agents on machine parts for a long period of time. Elastanes treated with the coating agents stick even after a long time Storage time not and remain processable.

The term fiber used in the present invention includes fiber Staple fibers and / or continuous filaments. The fibers e.g. Elastane can by spinning processes known in principle, such as the dry spinning process, the wet spinning process or the melt spinning process.

Such spinning processes are described, for example, in polyurethane elastomer fibers, H. Gall and M. Kausch in Kunststoff-Handbuch 7, Polyurethane, publisher: G. Oertel, Carl Hanser Verlag Munich Vienna, 1993. Pages 679 to 694.

Elastane, i.e. elastic polyurethane fibers made from long-chain synthetic polymers, which are at least 85% segmented polyurethanes based on e.g. Polyethers, polyesters and / or polycarbonates are well known. Yarns made from such fibers are used to manufacture fabrics or fabrics or fabrics that are used for the manufacture of corsetry, Linen, stockings, sportswear and ribbons are suitable. Polyurethane fibers have considerable compared to other, non-elastic textile fibers Stickiness. Bonding of the elastanes occurs particularly when elastanes be wound on a spool or a partial warp beam. A sticking of the Spandex or the increased adhesion of the fibers to one another is particularly then observed when the fibers are stored for a long time before further processing were. This effect is exacerbated if the storage of the material is elevated Temperature.

The stickiness or the adhesion of elastanes to spools or partial warp beams can be used when processing the polyurethane fibers with, for example, polyamide fibers or cotton by a warp or circular knitting process or automatic hosiery lead to strong tension in the fiber during unwinding, which can lead to thread breakage can lead and in extreme cases bobbins or partial warp beams made of such fibers no longer processable.

In practice, the reduction in stickiness or adhesion of elastanes is followed by Storage, even at elevated temperatures, through fiber treatment immediately after The aim is to manufacture the fiber by applying special preparation oils to the fiber become.

To reduce the adhesion or stickiness of elastanes, the patent step US 3,039,895 the use of mineral oils and dispersed therein Metal soaps, preferably from magnesium stearate, are recommended. In the patent application EP-704 571 and the patent US-4 296 174 are used to reduce the Stickiness of elastanes the use of low viscosity linear and branched Polysiloxanes with metal soaps dispersed therein are recommended, too Magnesium stearate is preferred. Disadvantage of the preparations described is, however, that the metal soaps dispersed in the oil when coating polyurethane fibers through, for example, roller, thread guide or spray technology for deposits in the preparation system, or can lead to constipation. A The consequence of this is, for example, the shortened running time of the spinning machines and increased effort for cleaning the spinning machines and the preparation system.

A safe, even preparation of the polyurethane fiber over a long time The time period is therefore not possible using the preparation agents mentioned.

The production of dispersions stabilized against sedimentation, consisting of Magnesium stearate in polyorganosiloxanes or mineral oils is described in the patent US 5 135 575. In the process described there, magnesium stearate with organic solvents such as Isopropanol, chloroform, Acetone or heptane made into a paste with polyorganosiloxane or mineral oil mixed and ground in a mill. The disadvantage of this manufacturing process is that magnesium stearate is finely divided into the silicone oil by a complex grinding process is incorporated. Furthermore, the use of organic solvents the time-consuming recovery of the solvents is necessary depending on the type of solvent, there is still a risk of ignition or explosion of the solvent.

JP-188 875 is used to reduce the adhesion of polyurethane fibers described a preparation. This consists of a polydimethylsiloxane, a higher alcohol, its ether or a fatty acid ester consisting of a Fatty acid with at least 12 carbon atoms, a modified silicone and the, metal salt of a fatty acid with at least eight carbon atoms. The disadvantage however, the preparation mentioned is similar to that of the others described above known preparation. The dispersed metal soaps list during application Polyurethane fibers to build up deposits in the preparation system, for example can lead to the blockage of preparation lines. Associated with it the running time of the spinning machines is shortened. The cleaning effort for cleaning the spinning machines and the preparation system is increased considerably. A safe and even preparation of the polyurethane fiber over a long period of time is not achieved with such preparations.

JP-60-67 442 describes the preparation of finely divided particles of fatty acid metal salts in polydimethylsiloxane for the preparation to reduce the adhesion of elastanes. Magnesium stearate or calcium oleate is dissolved in a pressure-stable vessel in hexane or benzene at 140 or 130 ° C and precipitated by rapid cooling at 10 ⁰ C / min. Entering this dispersion in low-viscosity polydimethylsiloxane and then distilling off hexane or benzene finally leads to the ready-to-use preparation. The disadvantage of this preparation is the complex and costly preparation process for the preparation caused by the distillation of hexane or benzene. In addition, there is a risk of contamination of the environment or ignition or explosion of the solvent through the use of organic solvents.

In the patent specification DD-251 578 is used to reduce the adhesion of elastanes be prepared by the wet spinning process, the use of an aqueous Suspension with finely divided magnesium and / or calcium stearate and optionally Polydimethylsiloxane described as a preparation. The disadvantage of this invention is however. that to remove the water from the dispersion after application the polyurethane fiber requires special drying of the fiber. So that's a additional processing step connected, which increases the cost of the product leads.

The invention has for its object a preparation for fibers, in particular for elastanes, to be made available, for example, during application Roll, thread guide or spray technology is easy to process and those in the application and especially in the processing of elastanes with, for example Cotton or polyamide fibers for surface goods not for deposits in the preparation system or on processing machines. The stickiness Elastane is said to be reduced by the preparation and the processability of using the preparation coated elastane guaranteed even after a long storage period be. Further requirement for preparations for elastane, if they are solids contained, in the form of dispersions, is to ensure a uniform Preparation order and coupled with it an even application of solids by stabilizing the preparation against sedimentation. For this The reason is a special requirement for a suitable solid-containing preparation. that the solid remains in the preparation even after a long standing time of e.g. 10 days off by no more than 20% and also see the preparation oil this state by simple measures back into a homogeneous dispersion can be transferred.

The stability of dispersions depends on many factors such as the particle size and shape, polarity, charge and density. However, among all these factors is the Particle size is the most important factor influencing sedimentation stability. Therefore it must be a primary goal in the production of suitable dispersions, set the grain size of the solid in the preparation as low as possible. the primary particles must not agglomerate into clusters.

To produce the known preparations, complex wet or Dry grinding carried out. Another object of the invention is an improved Processes for making preparations for fibers are available too make grinding unnecessary.

It has surprisingly been found that preparation oils for fibers. especially for Polyurethane fibers, which should meet the above requirements, through a certain selection of the composition of the preparation, in connection can be produced with a special precipitation process.

A) von 30 bis 98,97 Gew.-%, bevorzugt von 50 bis 96.9 Gew.-%, besonders bevorzugt von 70 bis 94,8 Gew.-% Polyalkylsiloxan mit einer Viskosität von 2 bis 150 mPas (25°C),

B) von 0,01 bis 20 Gew.-%, bevorzugt von 0,05 bis 8 Gew.-%, besonders bevorzugt von 0,1 bis 4 Gew.-%, ganz besonders bevorzugt von 0,1 bis 2 Gew.-%, Metallsalz einer gesättigten oder ungesättigten, mono- oder bifunktionellen C-₆-C₃₀-Fettsäure, wobei das Metall eines aus der ersten, zweiten oder dritten Hauptgruppe des Periodensystems oder Zn ist,

C) von 1 bis 69 Gew.-%, bevorzugt von 3 bis 50 Gew.-%, besonders bevorzugt von 5 bis 30 Gew.-%, eines Mineralöls mit einer Viskosität von 2 bis 500 mPas (25°C), einer Dichte von 800 bis 900 kg/m³ (15°C) und einer Viskositäts-Dichte-Konstante (VDK) von 0,770 bis 0,825,

D) von 0,02 bis 15 Gew.-%, bevorzugt von 0,05 bis 5 Gew.-%, besonders bevorzugt von 0,1 bis 3 Gew.-% Agglomerationsinhibitor ausgewählt aus der Reihe der kationenaktiven, anionenaktiven oder nichtionogenen, insbesondere der anionenaktiven oder nichtionogenen antistatischen Verbindungen.

The invention relates to a coating agent for fibers, in particular for elastane fibers, based on a dispersion of fatty acid metal salt and agglomeration inhibitor in a mixture of polyorganosiloxane and mineral oil containing at least

A) from 30 to 98.97% by weight, preferably from 50 to 96.9% by weight, particularly preferably from 70 to 94.8% by weight, of polyalkylsiloxane with a viscosity of 2 to 150 mPas (25 ° C.),

B) from 0.01 to 20% by weight, preferably from 0.05 to 8% by weight, particularly preferably from 0.1 to 4% by weight, very particularly preferably from 0.1 to 2% by weight %, Metal salt of a saturated or unsaturated, mono- or bifunctional C ₆ -C ₃₀ fatty acid, the metal being one of the first, second or third main group of the periodic table or Zn,

C) from 1 to 69% by weight, preferably from 3 to 50% by weight, particularly preferably from 5 to 30% by weight, of a mineral oil with a viscosity of 2 to 500 mPas (25 ° C.), a density from 800 to 900 kg / m ³ (15 ° C) and a viscosity-density constant (VDK) from 0.770 to 0.825,

D) from 0.02 to 15% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 3% by weight, of agglomeration inhibitor selected from the series of cationic, anionic or nonionic, in particular of anionic or nonionic antistatic compounds.

Due to the incompatibility of the metal salts of fatty acids with polyorganosiloxanes are the preparation oils according to the invention for fibers, in particular Polyurethane fibers. in the form of dispersions.

Mineral oil is understood here as a liquid distillation product (e.g. from petroleum), which consists essentially of a mixture of saturated hydrocarbons.

The coating compositions according to the invention contain linear and / or branched Polyorganosiloxanes, preferably linear polyorganosiloxanes and particularly preferred linear polydimethylsiloxanes with a viscosity of 2 to 150 mPas (25 ° C) ` preferably with a viscosity of 2.5 to 50 mPas (25 ° C) and particularly preferred with a viscosity of 2.5 to 20 mPas (25 ° C). The content of linear, or branched Polyorganosiloxane, preferably linear polyorganosiloxane and especially preferably linear polydimethylsiloxane is from 30 to 98.97% by weight, preferably 50 to 96.9% by weight and particularly preferably 70 to 94.8% by weight, based on the Weight of the preparation according to the invention.

In the metal salts used to produce the preparations according to the invention of fatty acids are those whose metal is a metal of the first to the third main group of the periodic table or zinc. The fatty acids are saturated or unsaturated, from at least six and at most 30 carbon atoms constructed and are mono- or bifunctional. For the metal salts of fatty acids it is particularly lithium, magnesium, calcium, aluminum and Zinc salts of oleic, palmitic or stearic acid, particularly preferably around magnesium stearate, Calcium stearate or aluminum stearate. The content of metal salts from Fatty acids in the preparation according to the invention is from 0.01 to 20% by weight preferably from 0.05 to 8% by weight, particularly preferably from 0.1 to 4% by weight, entirely particularly preferably from 0.1 to 2% by weight, based on the weight of the preparation.

The mineral oils of the coating composition according to the invention have a viscosity of 2 to 500 mPas (25 ° C), preferably 3 to 300 mPas (25 ° C) and particularly preferably 3 to 200 mPas (25 ° C). The mineral oils are further characterized by a density of 800 to 900 kg / m ³ (15 ° C) and a viscosity-density constant (VDK, determination according to DIN 51378) of 0.770 to 0.825. The mineral oil content in the preparation according to the invention is from 1 to 69% by weight, preferably from 3 to 50% by weight and particularly preferably from 5 to 30% by weight. based on the weight of the preparation.

As an agglomeration inhibitor, the preparations according to the invention contain cation-active, anion-active or nonionic antistatic compounds, if appropriate also in a mixture. An overview of possible antistatic compounds is given in the book "Kunststoffadditive" by R. Gächter and H. Müller, Carl Hanser-Verlag Munich, Vol. 3, 1990, pages 779 to 805. Examples of cationic agglomeration inhibitors are ammonium compounds, for anionic agglomeration inhibitors salts of sulfonic or phosphoric acids and for nonionic agglomeration inhibitors fatty or phosphoric acid esters, alkoxylated fatty alcohols, polyaminosiloxanes or alkoxylated polyorganosiloxanes. Suitable anionic agglomeration inhibitors are: fatty alcohols such as sodium lauryl sulfate or ammonium lauryl sulfate, fatty alcohol ether sulfates of the formula
R- (O-CH ₂ -CH ₂ ) n-OSO ₃ Na, where R is hydrogen or an alkyl group having 1 to 30 hydrocarbon atoms and n is a number from 1 to 20,
Sodium alkylsulfoacetate of the formula RO-CO-CH ₂ -SO ₃ Na, where R represents an alkyl group with 1 to 30 hydrocarbon atoms,
Alkylolamide sulfates of the formula
R-CONH- (CH ₂ ) _n -OSO ₃ Na, where R is an alkyl group with 1 to 30 hydrocarbon atoms and n is a number from 1 to 6 or
Fatty alcohol ether phosphates of the formula RO- (CH ₂ -CH ₂ -O) _n -PO (ONa) ₂ , where R is hydrogen or an alkyl group having 1 to 30 hydrocarbon atoms and n is a number from 1 to 20.

Suitable cationic agglomeration inhibitors are:
quaternary ammonium salts of the formula R ₁ R ₂ R ₃ R ₄ N ⁺ Cl ^- , where R ₁ R ₂ , R ₃ and R ₄ independently of one another are identical or different and represent hydrogen or an alkyl group having 1 to 30 carbon atoms.

Suitable nonionic agglomeration inhibitors are:
Polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty acid esters, polyoxyethylene glycol fatty acid esters, diethylene glycol monofatty acid esters, fatty acid alkanolamides of the formula R-CO-NH- (CH ₂ -CH ₂ ) _n -OH, where R is an alkyl group with 1 to 30 hydrocarbon atoms and n is a number from 1 to 20, sucrose esters , for example sucrose palmiat, pentaerythritol partial esters, for example pentaerythritol monostearate, ethoxylated pentaerythritol partial esters, for example pentaerythritol monostearate polyglycol ether, sorbitan fatty acid esters or ethoxylated sorbitan fatty acid esters. Anion-active and / or non-ionic agglomeration inhibitors are preferably added to the preparation according to the invention; agglomeration inhibitors from the groups of the sulfonic acids and the fatty and phosphoric acid esters are particularly preferred. Agglomeration inhibitors from the groups of the dialkyl sulfosuccinates, the nonionic phosphoric acid esters and the sugars esterified with fatty acids are very particularly preferred.

wobei

R₁ und R₂

unabhängig voneinander gleich oder verschieden für Wasserstoff oder eine Alkylgruppe mit 1 bis 30 Kohlenstoffatomen, und bevorzugt für eine Alkylgruppe mit 4 bis 18 Kohlenstoffatomen stehen und

M⁺

H⁺, Li⁺, Na⁺, K⁺ oder NH₄ ⁺ ist.

The dialkyl sulfosuccinates correspond to the general formula (1)

in which

R ₁ and R ₂

independently of one another, identically or differently, represent hydrogen or an alkyl group having 1 to 30 carbon atoms, and preferably an alkyl group having 4 to 18 carbon atoms, and

M ⁺

Is H ⁺ , Li ⁺ , Na ⁺ , K ⁺ or NH ₄ ⁺ .

The dialkyl sulfosuccinates can be prepared, for example, as in the magazine C.R. Carly, Ind. Eng. Chem., Vol. 31, page 45, 1939.

Preferred examples of the dialkyl sulfosuccinates are sodium bistridecyl sulfosuccinate, Sodium dioctyl sulfosuccinate, sodium dihexyl sulfosuccinate. Sodium diamyl sulfosuccinate, Sodium diisobutyl sulfosuccinate and sodium dicyclohexyl sulfosuccinate.

Particularly preferred dialkyl sulfosuccinates are sodium bistridecyl sulfosuccinate, Sodium dioctyl sulfosuccinate and sodium dihexyl sulfosuccinate.

wobei

R₁ und R₂

unabhängig voneinander für Wasserstoff oder eine Alkylgruppe mit 1 bis 30 Kohlenstoffatomen und bevorzugt für eine Alkylgruppe mit 4 bis 22 Kohlenstoffatomen steht,

x und y

unabhängig voneinander eine Zahl von 0 bis 3 und in ihrer Summe 3 sind und

z

eine Zahl von 1 bis 25 ist.

Phosphoric acid esters as suitable nonionic agglomeration inhibitors preferably correspond to the general formula (2)

in which

R ₁ and R ₂

independently of one another represents hydrogen or an alkyl group having 1 to 30 carbon atoms and preferably an alkyl group having 4 to 22 carbon atoms,

x and y

are independently a number from 0 to 3 and in total 3 and

e.g.

is a number from 1 to 25.

Particularly preferred examples of the phosphoric acid esters are those in which R _{1 represents} an alkyl group having 14 to 20 carbon atoms, R _{2 represents} hydrogen or a methyl group and x and y correspond to 1 or 2 and z corresponds to 3 to 10.

The content of agglomeration inhibitor D) in the preparation according to the invention is from 0.02 to 15% by weight, preferably 0.05 to 5% by weight and particularly preferred 0.1 to 3 wt .-%, based on the weight of the preparation.

The invention also relates to a process for producing coating compositions for fibers based on a dispersion of fatty acid metal salts and an agglomeration inhibitor in a mixture of polyorganosiloxane and mineral oil, which is characterized in that from 0.01 to 20% by weight, preferably from 0.05 to 8% by weight, particularly preferably from 0.1 to 4% by weight, very particularly preferably from 0.1 to 2% by weight, metal salt B) of a saturated or unsaturated, mono- or bifunctional C ₆ -C ₃₀ fatty acid in from 1 to 69% by weight, preferably from 3 to 50% by weight, particularly preferably from 5 to 30% by weight, of a mineral oil C) with heating to from 70 to 170 ° C. , preferably from 100 to 140 ° C, that the warm solution in a mixing device intensively and quickly with from 30 to 98.97 wt .-%, preferably from 50 to 96.9 wt .-%, particularly preferably from 70 to 94.8% by weight, polyalkylsiloxane A) is mixed in such a way that the resulting dispersion may be directly connected nd is homogenized, and that the mineral oil C) or the polyalkylsiloxane A) before mixing or the resulting dispersion before or preferably after the homogenization from 0.02 to 15% by weight, preferably from 0.05 to 5% by weight , particularly preferably from 0.1 to 3% by weight of agglomeration inhibitor D) are added.

The homogenization is preferably carried out by entering shear energy with an energy density of at least 10 ⁶ J / m ³ based on the volume of the preparation. particularly preferably at least 3x10 ⁶ J / m ³ , very particularly preferably of at least 4x10 ⁶ J / m ³ .
This promotes fine particle size and sedimentation stability.

The preparation of the preparations according to the invention in the form of dispersions are present, is carried out by a precipitation process by dissolving fatty acid metal salts in hydrocarbons in the heat and combining this phase with the polyorganosiloxane-containing phase. The precipitation can consist of a precipitation device from a two- or multi-stage dispersing device with an optional subsequent one Honiogenization stage are carried out. The preparation of the invention Preparations can also be made by entering the metal salt Phase in the polyorganosiloxane-containing phase in a boiler with subsequent Monogenization done by a homogenizer. The addition of Agglomeration inhibitor can in all cases in the preparation of the preparation anywhere.

A suitable multi-stage dispersing device and a homogenizing nozzle will in U.S. Patent No. 5,302,660. The apparatus described is used to achieve a rapid mixing of two material flows, the to be brought together to a chemical reaction. The implementation a precipitation process in the above-mentioned apparatus with, if necessary, a subsequent one Homogenization leading to fine-grained and sedimentation-stable dispersions leads with narrow grain size distribution, which are free of agglomerates, however not described.

In the patent application EP-399 266 the preparation of dispersions is by Crystallization of emulsions described. The method is based on the fact that a Melt with a colder liquid phase at a temperature below the crystallization point is mixed and emulsified therein, the melt first solidified after emulsification in the form of the dispersed particles. To this end the melt is injected into the liquid phase to form a pre-emulsion and the pre-emulsion in a downstream homogenizing nozzle to form an emulsion finely dispersed, which then solidifies to the finished crystal suspension. The implementation a precipitation process in which there is a phase immediately after merging from one, solid and a solvent, with another phase, in essentially a non-solvent, in nozzle mixers with optionally subsequent Homogenization in which fine-grain and sedimentation-stable dispersions with a narrow grain size distribution that are free of agglomerates are, however, not described in EP 399 266.

The known dispersion devices enable two material flows very much to mix quickly with each other. It was found that due to the entry high shear energy when using such devices for manufacturing of preparation oils for fibers according to the precipitation process according to the invention the fatty acids Metal salts to form a good and narrow grain size distribution incorporated into polyorganosiloxanes free of agglomerates and stable to sedimentation can be.

The method for producing the preparations according to the invention by means of a two- or multi-stage dispersing device with optionally subsequent Homogenization is compared to a precipitation process in the boiler with subsequent Homogenization preferred because this process is operated continuously can.

The invention further relates to fibers, in particular polyurethane fibers, which are coated with the coating agent according to the invention.

The polyurethane fibers coated with the coating agent according to the invention order especially from segmented polyurethane polymers, for example those based on polyethers, polyesters, polyether esters and / or polycarbonates. Fibers of this type can be produced by processes which are known in principle such as those described in US 2,929,804, 3 097 192, 3 428 711, 3 553 290 and 3 555 115 and in the publication WO-9 309 174 to be discribed. Furthermore, the polyurethane fibers made of thermoplastic Order polyurethanes, their production, for example, in writing US 5,565,270. The polyurethane is based in particular on organic Diisocyanates and a chain extender with several active hydrogens, such as. Di- and polyols, di- and polyamines, hydroxylamines, hydrazines, Semicarbazides, water or a mixture of these components. Preferred Diols are glycol, butanediol and hexanediol. Preferred diamines are ethylenediamine, 1,2-propanediamine, 2-methyl-1,5-diaminopentane, 1,3-diaminocyclohexane and 1-methyl-2,4-diaminocyclohexane.

The fibers can contain a variety of different other additives for different purposes, such as antioxidants. Stabilizers against heat, light and UV radiation, pigments and matting agents. Dyes, lubricants and lubricants. Examples of antioxidants, stabilizers against heat, light and UV radiation are stabilizers from the group of sterically hindered phenols, HALS stabilizers (h indered a mine l ight s tabilizer), the triazines, the benzophenones and the benzotriazoles. Examples of pigments and matting agents are titanium dioxide, zinc oxide and barium sulfate. Examples of dyes are acidic disperse and pigment dyes and optical brighteners. Examples of lubricants and lubricants are metal salts of fatty acids and silicone and mineral oils. The additives mentioned are dosed in such a way that they show no effects contrary to the preparation oil applied to the outside of the fiber and produced by a precipitation process.

The coating compositions according to the invention for fibers in the form of dispersions available and by a compared to a conventional grinding process simple and economical precipitation process in a mixing nozzle or in a boiler with subsequent homogenization can have, as in Example 1 is shown, the surprising advantage that it has a medium Grain size of D50 <3 µm are very fine, with a very narrow grain size distribution have a very low proportion of coarse-grained with a D90 of <10 µm Have particles. The coating agents are free from agglomerates and are good against sedimentation with a sedimentation rate of <20% per 10 days stable.

Even with a composition of the coating composition according to the invention, the has only 2 wt .-% and less fatty acid metal salt, remain the excellent Preserve properties of the coating agent.

In the case of known preparation agents that contain fatty acid metal salt, the Sedimentation rate of the salt significantly higher. Metal salt is stored e.g. at the Preparation site. An even application of the metal salt to the fiber will prevented. Another disadvantage of the known preparation agent is that in the Further processing of the fibers coated with it into flat goods becomes fatty acid Metal salt on machine parts e.g. Knitting needles and blockages of the Needles or thread breaks caused.

With a content of less than 4 wt .-% fatty acid metal salt is also known in Preparations to observe a coating failure on the fiber. This results in the fibers sticking together.

Furthermore, when applying the coating compositions of the invention Polyurethane fibers, as shown in Example 2, by small amounts of Agglomeration inhibitor in the preparation a surprising reduction in electrical resistance of the fiber found. This will make an electrostatic Equipment of the fiber is reached, which contributes, for example, to electrostatic discharges the processing of the fiber is reduced or prevented.

When applying the coating compositions of the invention to polyurethane fibers is also surprisingly found, as shown in Example 3, that already by the small amount of a fatty acid salt in the coating agent the strengthening of the adhesion over a longer storage period of the fibers even with increased Temperature, and with it the stickiness of the polyurethane fiber is greatly reduced and the processing of the fibers e.g. good on a circular knitting machine and runs without deposits on knitting needles.

As was also shown in Example 3, it was found to be particularly surprising. that the coating compositions of the invention also in long-term tests during application no deposits or on polyurethane fibers via a preparation roll Blockages in the pipes of the coating material or in preparation trays showed. As a result, application of the coating agent is carried out via a enables a long period of time. The uniformity of the application is also improved and an interruption of a production process due to necessary Cleaning work unnecessary.

The test procedures described below are used to measure those discussed above Parameters used in the examples.

The measurements to determine the grain size distributions are carried out with Mastersizer M20, company Malvern Instruments about laser light diffraction and laser light scattering. Polydimethylsiloxane with a viscosity of 10 mPas (25 ° C) are used. The grain size of the particles is given in micrometers (µm) depending on the volume distribution of the particles at 10, 50 and 90% before and after treatment with ultrasound for 180 s. The difference between the grain size distributions before and after the ultrasound treatment a measure of the presence of agglomerates. If the difference is small, there are none Agglomerates present.

To determine the sedimentation behavior, 100 ml of preparation oil, which is in the form of a dispersion, placed in a measuring cylinder and after three or ten days, the percentage of unmixed phase determined. A stabilization Against sedimentation is achieved when the clear phase continues even after ten days Is <20%.

The viscosity of the preparation oils is determined using a Haake viscometer, model CV 100 at a temperature of 20 ° C. and a viewing speed of 300 s ^-1 .

Determination of the electrical conductivity of polyurethane fibers using different preparations have been made, is carried out in DIN 54 345 Measurement described to determine the volume resistance.

The adhesion of the thread to a bobbin is determined by first of all Thread from a bobbin weighing 500 g up to 3 mm above the bobbin tube is cut off. Then a weight is hung on the thread and determines the weight with which the load rolls off the spool. The so certain liability is a measure of the processability of the coils. Is liability too high, can be difficult to process into flat goods due to thread breaks become. The determination of liability after a storage period of 8 weeks at an elevated temperature of 40 ° C describes an aging process and is a measure for the development of liability after a long storage period at RT. Warehousing the coils take place at 40 ° C in a heating cabinet with a rel. humidity of 60%. After storage, liability becomes as described above measured.

The processability of polyurethane fibers was checked on a circular knitting machine carried out by Terrot. Flat goods with 20 wt .-% Polyurethane fiber and 80 wt .-% cotton manufactured. The exam was on performed a full circular knitting attachment over a period of 5 hours.

Deposits in the preparation system are determined by using the preparation oil in a long-term test over 14 days without interruption due to roller technology is applied to a polyurethane fiber. At the end of the experiment it is assessed how much solid is deposited from the dispersion in the preparation system Has. The more deposits there are, the less suitable the preparation is, because the preparation system with storage container, piping and preparation tubs and rolls or thread guides or spray nozzles cleaned more often, and thus a production process has to be interrupted more often.

Fig. 1

zeigt ein Schema des Gesamtverfahrens zur Herstellung des erfindungsgemäßen Beschichtungsmittels durch eine zweistufige Dispergiervorrichtung mit gegebenenfalls anschließeiider Homogenisierung.

Fig. 2

zeigt ein Schema eines weiteren Gesamtverfahrens zur Herstellung des erfindungsgemäßen Beschichtungsmittels mit einer Homogenisierung nach zuvor erfolgter Fällung in einem Kessel.

The precipitation process for the production of the coating compositions according to the invention is explained below using examples.

Fig. 1

shows a diagram of the overall process for the preparation of the coating composition according to the invention by a two-stage dispersing device with optionally subsequent homogenization.

Fig. 2

shows a schematic of a further overall process for the production of the coating agent according to the invention with a homogenization after a previous precipitation in a boiler.

Fig. 1 shows an example of the flow diagram of the process for the precipitation of fatty acid Metal salt in polyorganosiloxane. In the short-term mixing device 1 and one downstream homogenizing device 2, the two material flows, e.g. in Mineral oil dissolved fatty acid metal salts and polyorganosiloxanes using the metering pumps 8 and 9 dosed from the batch containers 6 and 7 and the finished preparation oil drained into the product container 12. The agglomeration inhibitor can in the batch containers 6 or 7, or in the product container 12 in a suitable form be added. The pre-pressure in front of the mixing device is via pressure gauge 10 and 11 checked.

2 shows the flow diagram of a variant of the method according to the invention. The Phase of fatty acid metal salt and mineral oil from the batch container 6 is in the Polyorganosiloxane entered in the mixing container 7 and mixed. The mixture is conveyed through the homogenizer 15 by means of the metering pump 9 and the finished Preparation oil drained into the product container 12.

The agglomeration inhibitor D can be in the batch containers 6 or 7 or in the Product container 12 can be added in a suitable form.

The invention is explained in more detail in the following examples. The examples do not place any restriction on the preparations or represent their manufacturing process.

The following examples demonstrate the advantageous composition and the improved ones Manufacturing method of coating agents for fibers according to the invention through a precipitation process.

Examples

The production of polyurethane fibers to check the processing properties of fibers with the new preparations was made by implementing Polytetrahydrofuran (PTHF) with an average molecular weight of 2000 g / mol with methylene bis (4-phenyl diisocyanate) (MDI) in a molar ratio from 1 to 1.8. The prepolymer thus produced was treated with dimethylacetamide diluted and then with a mixture of ethylenediamine (EDA) and diethylamine (DEA) (97: 3 ratio) chain extended in dimethylacetamide. The molar ratio from chain extender and chain terminator to unreacted isocyanate in the prepolymer was 1.075. The solids content of the segmented so produced Polyurethane was 30% by weight. The polyurethane urea solution has one Viscosity of 120 Pas (50 ° C) and the polymer has an intrinsic viscosity of 0.98 g / dl (measurement at 25 ° C in dimethylacetamide with a concentration of 0.5 g Polymer in 100 ml of dimethylacetamide). Before the dry spinning process, the The following additives were added to the polyurethane-urea spinning solution (percentages in relation on the weight of the finished fiber): (a) 1.0% 1, `3,5-tris (4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl) - 1,3,5-triazine 2,4,6- (1H, 3H, 5H) -trione (Cyanox 1790, Cytec), (b) 0.05% titanium dioxide (type RKB 2, Bayer AG), (c) 0.15% magnesium stearate. (d) 0.001% Makrolex violet (Bayer AG) and 0.15% polyalkyloxy-modified Polydimethylsiloxane (Silwet L 7607, from OSI Specialties). The finished spinning solution was through spinnerets in a spinning apparatus typical for a dry spinning process spun into filaments with a titer of 11 dtex, four each Individual filaments were combined into coalescing filament yarns. The Preparations in the form of dispersions were 4% by weight. based on the Weight of the fiber, applied to the fiber via a preparation roller. The fiber was then wound up at a speed of 900 m / min.

example 1

In this example, the grain size distribution, the viscosity and the sedimentation behavior as properties of preparations are compared with one another depending on the composition and the method for producing the preparations. The results are summarized in Table 1.

Preparations 1-1 to 1-3 contain low-viscosity silicone oil and polyamylsiloxane Mg stearate, which is obtained by a milling process with a pearl mill (type MS 12, Fryma) was registered. The grain size distribution shows that the particles not in the form of agglomerates, the proportion of coarse particles Particles, however, even after 5 grinding cycles with a D90 value of> 10 µm. Stabilization against sedimentation improves with decreasing Grain size (tests 1-1 and 1-2), however, deteriorates, as in experiment 1-3, with decreasing content of Mg stearate in the preparation. The reason for this can be a weak interaction of the individual particles be with each other. In any case, however, is the stabilization by a grinding process prepared preparations with a sedimentation of> 20% / 10 d too strong, in order to be able to guarantee an even preparation application on fibers. Furthermore, the grinding process is due to poor effectiveness and associated poor economy not for incorporating finely divided Mg stearate suitable in silicone oils.

Preparations 1-4 to 1-8 were produced by the precipitation process described schematically in FIG. 1 in a mixing nozzle 1. A 130 ° C. hot stream of hydrocarbon and Mg stearate (in experiments 1-7 and 1- 8 additionally phosphoric acid ester as agglomeration inhibitor) with a stream of low-viscosity silicone oil (in experiment 1-6 additionally polyamylsiloxane) at 20 ° C with a pressure of 50 bar in the mixing nozzle 1 and then homogenized with an energy density of 5x10 ⁶ J / m ³ . The ratios of the material flows corresponded to those of the composition of the finished preparation. In experiment 1-4, hexane was removed by distillation in an additional step and in experiment 1-8 Na-dioctylsulfosuccinate was added to the preparation as an agglomeration inhibitor after the precipitation. In all cases, preparations were obtained which had a narrow particle size distribution and with a D50 value of <3 µm very fine particles, which had no agglomerates and a D90 value of <10 µm which had a significantly lower proportion of coarse-grained particles in the Preparation included. The grain size distributions are therefore narrower, so the particle size is more uniform. Furthermore, all the preparation oils obtained, in particular also those with small amounts of 1% Mg stearate, were stabilized against sedimentation with a sedimentation rate of <20% / 10 d.

Preparations 1-9 and 1-10 were produced by the precipitation process described schematically in FIG. 2 in a kettle with subsequent homogenization. A 120 ° C hot stream of mineral oil, Mg stearate and fatty alcohol EO adduct or phosphoric acid ester was added with stirring to a kettle with silicone oil at 20 ° C and then through a homogenizer 15 (see Fig. 2) at an energy density homogenized of 5x10 ⁶ J / m ³ . Immediately after the precipitation process, the preparations contain agglomerates and show an increased coarse fraction but with good stabilization against sedimentation in experiment 1-9. Homogenization breaks the agglomerates in the preparation and improves stabilization against sedimentation. Like the preparations made by precipitation in a mixing nozzle, the preparations made by precipitation in the kettle with subsequent honing contain no agglomerates, with a very small coarse fraction with D90 values of <10 µm, have a narrow grain size distribution and a sedimentation rate of <20% / 10 d a good stabilization against sedimentation.

Experiment 1-11 shows the result of the characterization of a preparation, which according to the patent specification JP-60-67 442 by a precipitation process of Mg stearate in Hexane in a kettle followed by the addition of silicone oil and polyamylsiloxane and removal of hexane by distillation. The preparation shows good stabilization against sedimentation, but is due to the strong Tendency to agglomeration and the increased viscosity, probably due to strong interactions between the solid particles in the preparation, not as a preparation oil for the production of fibers, especially polyurethane fibers, suitable.

Example 2

This example shows that the electrical conductivity of polyurethane fibers can be changed depending on the composition of the preparation. All preparations, which are in the form of a dispersion, were obtained by precipitation in a mixing nozzle 1 and subsequent; Homogenization (corresponding to Ex. 1-4). The results are shown in Table 2. Electrical conductivity of polyurethane fibers with various preparations experiment Composition of the preparation /% by weight (preparation of the dispersions by precipitation in the mixing nozzle 1) Contact resistance / 10 ¹¹ ohms (DC measurement voltage: 100 v) 2-1 (comparison) 100% silicone oil 2nd 2-2 90% silicone oil 1.2 10% polyamylsiloxane 2-3 88.5% silicone oil 1.4 10% mineral oil 0.5% phosphoric acid ester 1% Mg stearate 2-4 88% silicone oil 0.8 10% mineral oil 1% phosphoric acid ester 1% Mg stearate 2-5 87.5% silicone oil 0.07 10% mineral oil 1% phosphoric acid ester 0.5% Na dioctyl sulfosuccinate 1% Mg stearate 2-6 88.5% silicone oil 0.07 10% mineral oil 0.5% Na dioctyl sulfosuccinate 1% Mg stearate

Experiment 2-2 shows that polyamylsiloxane is part of the preparation Electrical volume resistance of polyurethane fibers reduced, this branched So siloxane increases electrical conductivity. This result corresponds the observation made in U.S. Patent 3,296,063. By incorporation The volume resistance of phosphoric acid ester and / or Na dioctyl sulfosuccinate was increased however, the polyurethane fibers are further lowered, i.e. the electrical Conductivity increased further. Na dioctyl sulfosuccinate is in front of the phosphoric acid ester and this in turn is the most effective before polyamylsiloxane Means for reducing volume resistance.

Example 3

In this example, depending on the manufacturing process and the composition of the preparations, it is shown which preparations reduce the stickiness of polyurethane fibers and thus ensure their workability even after a long period at high temperature. It also shows which preparations, which are in the form of a dispersion, can be applied over a long period of time without the formation of deposits. The results are summarized in Table 3.

Experiments 3-1 and 3-2 show that when applying preparations based on silicone oil or silicone oil with polyamylsiloxane the increase in Adhesion of polyurethane fibers with a storage time of 8 weeks and a temperature of 40 ° C, as is often the case during transport, in warehouses or subtropical Countries occurs, is very strong and the processability of the coils is often not possible is. The adhesion values obtained in these experiments are above 1 cN, which is a limit for successful processability of polyurethane fibers on a circular knitting machine, for example. Liability of more than 1 cN when processing the bobbins into thread breaks, with the consequence of Machine downtime. In extreme cases, even a thread of the Be pulled out. The preparations used in experiments 3-1 and 3-2 based on silicone oil or silicone oil with polyamylsiloxane are therefore not suitable for the preparation of polyurethane fibers.

Experiments 3-3 to 3-12 show that the adhesion build-up of polyurethane fibers is reduced to coils when the preparation is made with Mg stearate contains fatty acid metal salt and is therefore in the form of a dispersion. In all Cases are added to the polyurethane coils, even after storage for 8 weeks a temperature of 40 ° C, adhesion values of <1 cN found. Due to this the processing of stored bobbins on a circular knitting machine is good possible. The effectiveness of Mg stearate in the preparations for reducing the Tackiness of polyurethane fibers is, however, among those who go through a milling process were produced, less than those produced by precipitation in the Mixing nozzle or precipitation in the boiler with subsequent homogenization were. This is enough for preparations caused by the case processes described were produced, 1 wt .-% Mg stearate from the stickiness of polyurethane fibers to reduce to the desired level. The one produced by a precipitation process Preparation is to set the same behavior regarding liability behavior a Mg stearate content of 4% by weight is necessary. An associated Disadvantage of preparations which are produced by a milling process, is that when processing the polyurethane fibers on the needles of the circular knitting machine form strong deposits that lead to thread breaks can. To avoid thread breaks there is therefore an increased cleaning effort the circular knitting machine required, which shortened in its consequence Machine run times. In the case of the precipitation processes described Preparations prepared, however, form with good processability on the Circular knitting machine no deposits due to the lower content of Mg stearate on needles.

Long-term tests to assess deposits and blockages in pipes and preparation trays through those in the form of dispersions Preparations of experiments 3-3 to 3-12 resulted in the result being independent of the manufacturing process by grinding. Precipitation in the mixing nozzle 1 or Precipitation in the boiler with subsequent; Many deposits and homogenization Constipation occurred. These deposits and blockages are in the application the preparation on the polyurethane fiber undesirable, as this makes frequent Cleanings become necessary. No deposits and blockages in pipes and preparation trays, as shown in experiments 3-8 to 3-12, when applying by precipitation in the mixing nozzle or precipitation in the boiler with subsequent; Preparations made on homogenization, in addition Agglomeration inhibitors such as salts of sulfonic acids, esterified Sugar or functionalized silicone oils were incorporated.

Claims (16)

Coating agent for fibers, in particular for elastane fibers, based on a dispersion of fatty acid metal salt and agglomeration inhibitor in a mixture of polyorganosiloxane and mineral oil containing at least A) from 30 to 98.97% by weight, preferably from 50 to 96.9% by weight, particularly preferably from 70 to 94.8% by weight, of polyalkylsiloxane with a viscosity of 2 to 150 mPas (25 ° C.), B) from 0.01 to 20% by weight, preferably from 0.05 to 8% by weight, particularly preferably from 0.1 to 4% by weight, very particularly preferably from 0.1 to 2% by weight %, Metal salt of a saturated or unsaturated, mono- or bifunctional C ₆ -C ₃₀ fatty acid, the metal being one of the first, second or third main group of the periodic table or Zn, C) from 1 to 69% by weight, preferably from 3 to 50% by weight, particularly preferably from 5 to 30% by weight, of a mineral oil with a viscosity of 2 to 500 mPas (25 ° C.), a density from 800 to 900 kg / m ³ (15 ° C) and a viscosity-density constant (VDK) from 0.770 to 0.825, D) from 0.02 to 15% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 3% by weight, of agglomeration inhibitor selected from the series of cationic, anionic or nonionic, in particular the anion-active or non-ionic antistatic compounds. Coating composition according to claim 1, characterized in that the polyalkylsiloxanes A) linear polyalkylsiloxanes, preferably linear polydimethylsiloxanes with a viscosity of 2.5 to 50 mPas (25 ° C), particularly preferred with a viscosity of 2.5 to 20 mPas (25 ° C). Coating composition according to claim 1 or 2, characterized in that the fatty acid metal salt B) a lithium, magnesium, calcium, aluminum and Zinc salt of oleic, palmitic and stearic acid, particularly preferably magnesium stearate, Calcium stearate or aluminum stearate is and alone or in any mixture is present. Coating agent according to one of claims 1 to 3, characterized in that mineral oil C) has a viscosity of 3 to 300 mPas (25 ° C), preferably from 3 to 200 mPas (25 ° C). Coating agent according to one of claims 1 to 4, characterized in that as a cationic agglomeration inhibitor D) an ammonium compound, the salt as anion-active agglomeration inhibitor D) a sulfonic or phosphoric acid or a dialkyl sulfosuccinate, as a nonionic Agglomeration inhibitor D) a fatty acid ester or phosphoric acid ester, alkoxylated fatty alcohol, amino functionalized or alkoxylated Polyorganosiloxane is selected. Coating composition according to claim 5, characterized in that the Agglomeration inhibitor D) from the group of the dialkyl sulfosuccinates, the Phosphoric acid esters, polyaminofunctionalized polyorganosiloxanes and the sugar esterified with fatty acids is selected. Coating composition according to claim 5, characterized in that the agglomeration inhibitor D) is a dialkyl sulfosuccinate corresponding to the general formula (1)

is where

R ₁ and R ₂

independently of one another, identically or differently, represent hydrogen or an alkyl group having 1 to 30 carbon atoms, and preferably an alkyl group having 4 to 18 carbon atoms, and

M ⁺

is a cation from the group H ⁺ , Li ⁺ , Na ⁺ , K ⁺ or NH ₄ ⁺ .

Coating composition according to claim 5, characterized in that the Agglomeration inhibitor D) a dialkyl sulfosuccinate selected from the series Sodium bistridecyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium dihexyl sulfosuccinate, Sodium diamyl sulfosuccinate, sodium diisobutyl sulfosuccinate, and sodium dicyclohexyl sulfosuccinate, especially a sodium bistridecyl sulfosuccinate, Sodium dioctyl sulfosuccinate and sodium dihexyl sulfosuccinate is. Coating agent according to Claim 5, characterized in that the agglomeration inhibitor D) is a phosphoric acid ester corresponding to the general formula (2),

in which

R ₁ and R ₂

independently of one another represents hydrogen or an alkyl group having 1 to 30 carbon atoms and preferably an alkyl group having 4 to 22 carbon atoms,

x and y

are independently a number from 0 to 3 and in total 3 and

e.g.

is a number from 1 to 25.

Coating composition according to Claim 9, characterized in that the agglomeration inhibitor D) is a phosphoric acid ester of the formula 2 in which R _{1 represents} an alkyl group having 14 to 20 carbon atoms, R _{2 represents} hydrogen or a methyl group and x and y represent a number 1 or 2 and z is a number from 3 to 10. Coating agent according to one of claims 1 to 10, characterized in that that they are in the form of finely divided dispersions, an average Grain size of the dispersed solid particles of D50 <3 microns, and have a very narrow grain size distribution, with a value of D90 of <10 µm. Coating agent according to one of claims 1 to 10, characterized in that that they have a sedimentation rate of <20% in ten days. Process for the production of a coating agent for fibers according to one of Claims 1 to 12, based on a dispersion of fatty acid metal salts and an agglomeration inhibitor in a mixture of polyorganosiloxane and mineral oil, characterized in that from 0.01 to 20% by weight, preferably from 0.05 to 8% by weight, particularly preferably from 0.1 to 4% by weight, metal salt B) of a saturated or unsaturated, mono- or bifunctional C ₆ -C ₃₀ fatty acid in from 1 to 69% by weight , preferably from 3 to 50% by weight, particularly preferably from 5 to 30% by weight, of a mineral oil C) with heating to from 70 to 170 ° C., that the warm solution is mixed intensively and quickly in a mixing device 30 to 98.97% by weight, preferably from 50 to 96.9% by weight, particularly preferably from 70 to 94.8% by weight, of polyalkylsiloxane A) is mixed in such a way that the resulting dispersion is then immediately homogenized is, and that the mineral oil C) or the polyalkylsiloxane A) before de m mixing or the resulting dispersion before or preferably after homogenizing from 0.02 to 15% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 3% by weight of agglomeration inhibitor D) be added. A method according to claim 13, characterized in that the agglomeration inhibitor D) the dispersion of the coating agent directly after the Homogenization is added. A method according to claim 13 or 14, characterized in that the homogenization by input of shear energy of an energy density based on the volume of the preparation of at least 10 ⁶ J / m ³ , particularly preferably at least 3 x 10 ⁶ J / m ³ , very particularly preferably of at least 4 x 10 ⁶ J / m ³ . Fibers, especially polyurethane fibers, coated with a coating agent according to one of claims 1 to 12.

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