MXPA99001329A - Fib coating agents - Google Patents

Abstract

The invention relates to coating agents for fibers and to a process for obtaining them. The invention relates in particular to elastane preparation agents based on a dispersion of metal salts of fatty acids and of an agglomerate inhibitor in polyorganosiloxanes and mineral oils. The preparations are obtained by a precipitate process, in which finely grained and stable sediment dispersions with a narrow grain size distribution are obtained, which are free of agglomerates.

Description

FIBER COATING AGENTS. Field of the invention. The invention relates to coating agents for fibers and to a process for their obtaining. The invention relates in particular to elastane preparation agents based on a dispersion of metal salts of fatty acids and agglomeration inhibitors in polyorganosiloxanes and in mineral oils. The preparations are obtained by a precipitation process, from which finely grained and stable dispersions result in sedimentation with a narrow grain size distribution and which are free of agglomerates. The coating agents reduce the electrical resistance of the elastanes, so that deposits of the coating agents do not occur on the parts of the machines neither during the application nor during the processing of the elastanes even during a prolonged period of time. The elastanes treated with the coating agents also do not stick to a prolonged storage time and remain processable. The expression, used in the scope of the present invention, of discontinuous fibers and / or continuous filaments. Fibers, for example elastanes, can be manufactured by spinning processes known in principle such as the dry spinning process, the wet spinning process or the melt spinning process. Description of the prior art. Such spinning processes have been described for example in Polyurethan-Elastomerfasern, H. Gal] and M. Kausch in Kunststoff-Handbuch 7, Polyurethane, Editor: G. Oertel, Carl Hanser Verlag München ien, 1993, pages 679 to 694. elastanes, that is to say elastic polyurethane fibers consisting of long-chain synthetic polymers, which are formed at least by 85% by segmented polyurethanes based on, for example, polyethers, polyesters and / or polycarbonates, are perfectly known. The yarns constituted by such fibers are used for the manufacture of plain articles or fabrics or fabrics, which, for their part, are suitable, inter alia, for the manufacture of support hosiery, bedding, socks, sportswear and clothing. tapes The polyurethane fibers have, in combination with other textile fibers, non-elastic, considerable tack. Adhesives of elastans are especially present when the elastanes are wound on a coil or on a partial warp beam. Especially observed is a sticking of the elastanes or an in-creased adhesion of the fibers to each other when the fibers have been stored for a prolonged time before further processing. This effect is reinforced when the storage of the material has been verified at elevated temperature. The stickiness or adhesion of the elastanes on the coils or on the partial warp beams can lead to too strong stresses of the fibers during the unwinding when the polyurethane fibers are made, for example with polyamide fibers or with cotton by a process of warp knitting or circular knitting or looms for hosiery, which can lead to breakage of the fibers and, in the extreme case, can make it impossible to work with coils or bending machines. Partial warp of such fibers. In practice, the aim is to achieve a reduction in the stickiness or adhesion of the elastanes after storage, even at high temperature, by treating the fibers directly after fiber manufacture, by applying special preparation oils on the fibers. For the reduction of adhesion or tackiness of elastanes, it is recommended in the specification of US Pat. No. 3 039 895 for the use of mineral oils and metal soaps dispersed therein, preferably magnesium stearate. In the patent application EP-704 571 and in the specification of the US patent US-4 296 174 it is recommended, for the reduction of the tackiness of the elastanes, the use of linear and branched polysiloxanes, of low viscosity, with metallic soaps dispersed therein, with magnesium stearate being equally preferred. The disadvantage of the described preparations, however, is that the metal soaps more dispersed in oil can lead to deposits in the preparation system, or to obstructions during the coating of the polyurethane fibers, for example by means of the roller, thread guide or roller technique. of spraying, one of its consequences consists, for example, in a shorter running time of the spinning machines and a higher cost for cleaning the spinning machines and the preparation system. Therefore, a safe, homogeneous preparation of the polyurethane fibers for a prolonged period of time with the use of the aforementioned preparation agents is not possible. It is described in the specification of the US Pat. No. 5,135,575 the obtaining of dispersions, stabilized, centers the sedimentation, constituted by magnesium stearate in polyorganosiloxanes or in mineral oils. In the process described therein, magnesium stearate is prepared with organic solvents, such as for example isopropanol, chloroform, acetone or heptane, to give a paste, mixed with polyorganosiloxane or with mineral oil and milled in a mill. The disadvantage of this method of obtaining is that magnesium stearate is incorporated in a finely divided form in the silicone oil by means of an expensive grinding process. Furthermore, the use of organic solvents requires the expensive recovery of the solvents, in this case, depending on the type of solvent, the danger of ignition or explosion of the solvent is also presented. In the specification of the patent JP-188 875 a preparation for the reduction of the adhesion of polyurethane fibers is described. This is constituted by a polydimethylsiloxane, a higher alcohol, its ethers or a fatty acid ester, constituted by a fatty acid with at least 12 carbon atoms, a modified silicone and the metal salt of a fatty acid with at least 8 carbon atoms. carbon. The drawback of the mentioned preparation is, however, similar to that of the other known preparation, described above. These dispersed metal jacks lead to deposits in the preparation system during application to polyurethane fibers, which can reach, for example, the obstruction of the feed lines of the preparation. In this regard, the running time of the spinning machines is reduced. The cleaning cost for cleaning the spinning machines and the preparation system increases considerably. A safe or homogeneous preparation of the polyurethane fibers over a prolonged period of time is not achieved with such preparations. In the specification of the patent JP-60-67 442 it is described, in order to reduce the adhesion of the elastanes, the obtaining of finely divided particles of metal salts of fatty acids in polydimethylsiloxane for the preparation. In this case magnesium stearate or calcium oleate is dissolved in a pressure-stable vessel, in hexane or benzene, at 140 to 130 ° C and precipitated by rapid cooling at a rate of 10 ° C / minute. Finally, the introduction of this dispersion in low viscosity polydimethylsiloxane and subsequent removal by distillation of hexane or benzene leads finally to the preparation ready for use. The drawback of this preparation consists in the complicated and costly preparation process according to the distillation of hexane or benzene. Furthermore, through the use of organic solvents there is a danger of contamination of the environment or ignition or explosion of the solvent. Descriptive DD-251 578 describes the use of an aqueous suspension with magnesium stearate and / or finely divided calcium stearate and, optionally, polydimethylsiloxane, by way of preparation, to reduce the adhesion of elastanes, which are manufactured according to the wet spinning process. The drawback of this invention, however, is that special drying of the fibers is required for the removal of water from the dispersion after application on the polyurethane fibers. Related to this is an additional elaboration step that leads to an increase in the cost of the product. Detailed description of the invention. The object of the invention is to provide a preparation for fibers, especially elastanes, which is produced without difficulty during application, for example by means of the roller, thread guide or spray technique and which does not drive during application and, especially, during the preparation of elastanes for example with cotton or with polyamide fibers, to give smooth articles, to deposits in the preparation system or on the processing machines. The tackiness of the elastanes must be reduced by the preparation and must be guaranteed even for a prolonged time of the processing capacity with the elastanes coated with the preparation. Other requirements to be met by elastane preparations, which are in the form of dispersions, when they contain solid products, is to ensure a homogeneous application of the preparation and, in this respect, a homogeneous application of the solid product by means of a stabilized the preparation against sedimentation. For this reason a special requirement that is required to a preparation containing adequate solid product consists in that the solid product does not sediment in a proportion greater than 20% in the preparation even after a prolonged period of rest of for example 10 days and that the oil of the preparation can be transformed again into a homogeneous dispersion also from this state by means of simple measures. The stability of the dispersions depends on many factors such as, for example, the size and shape of the particles, the polarity, the charge and the density. Among all these factors, however, the most important influencing variable for the stabilization of sedimentation is the size of the particles.

Therefore, in the manufacture of suitable dispersions, it should be a primary objective to adjust as small as possible the grain size of the solid product in the preparation, the primary particles should not agglomerate to give lumps. In order to obtain the known preparations, expensive wet or dry grinding is practically carried out. Another task of the invention is to provide an improved method for obtaining fiber preparations, which makes milling unnecessary. Surprisingly it has been found that fiber preparation oils, especially for polyurethane fibers, which have to fulfill the aforementioned requirements, can be obtained by a suitable choice of the composition of the preparation, in combination with a special precipitation process. The object of the invention is a re-covering agent for fibers, especially for elastane fibers, based on a dispersion of metal salt of fatty acid and of agglomeration inhibitor in a mixture constituted by polyorganosiloxane and mineral oil, containing at least A) from 30 to 98.97% by weight, preferably from 5Q 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 by weight, of metal salt of a fatty acid with 6 to 30 carbon atoms saturated or unsaturated, mono or bifunctional, the metal being one of the first, second or third main group of the Periodic System of the Elements 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 Pas (25 ° C) , a density of 800 to 900 kg / m3 (15 ° C) and a viscosity-density constant (VDK) of 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 the agglomeration inhibitor selected from the series consisting of active cation compounds, active or non-ionogenic anions, especially active or non-ionogenic antistatic anion compounds. Depending on the incompatibility of the metal salts of the fatty acids with the polyorganosiloxanes, the preparation oils according to the invention for fibers, especially for polyurethane fibers, are in the form of dispersions. The mineral oil will be understood here as a liquid product of distillation (for example 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, more preferably, linear polydimethylsiloxanes with a viscosity of 2 to 150 mPas (25 ° C), preferably with a viscosity of 2.5 to 25. 50 mPas (25 ° C) and more preferably with a viscosity of 2.5 to 20 mPas (25 ° C). The content of linear or branched polyorganosiloxane, preferably linear polyorganosiloxane and more preferably linear polydimethylsiloxane is from 30 to 98.97% by weight, preferably from 50 to 96.9% by weight, and particularly preferably from 70 to 70% by weight. up to 94.8% by weight, based on the weight of the preparation according to the invention. The metal salts of the fatty acids, used in the preparation of the preparations according to the invention, are constituted by those whose metal is a metal of the first to third major groups of the Periodic Table of the Elements or zinc. The fatty acids are saturated or unsaturated, consisting of at least 6 and at most 30 carbon atoms and are mono or bifunctional. The metal salts of the fatty acids consist in particular of lithium saltsof magnesium, calcium, aluminum and zinc of the oleic, palmitic or stearic acids, especially preferably consisting of magnesium stearate, calcium stearate or aluminum stearate. The content of metal salts of 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, very preferably from 0.1 to 2% by weight, based on the weight of the preparation. The mineral oils of the coating agent according to the invention have a viscosity of 2 to 500 mPa.s (25 ° C), preferably 3 to 300 mPa.s (25 ° C), and particularly preferably 3 to 200 mPas (25 ° C). . Mineral oils are also characterized by a density of 800 to 900 kg / m3 (15 ° C) and a viscosity-density constant (VDK, determined according to DIN 51378) of 0.770 to 0.825. The content of mineral oils 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 active cation, active anion or non-ionogenic compounds, if appropriate also in a mixture. A compilation on possible anti-static compounds is given in the book "Kunststoffadditive" by R. Gachter and H. Müller, Cari Hanser-Verlag München, Vol. 3, 1990, pages 779 to 805. Examples of inhibitors of cation agglomeration active are ammonium compounds, for active anion agglomeration inhibitors, salts of sulfonic or phosphoric acids and for non-ionogenic agglomeration inhibitors, fatty acid or phosphoric acid esters, alkoxylated fatty alcohols, polyalminylsiloxanes or alkoxylated polyorganosiloxanes. Suitable active anion agglomeration inhibitors are: fatty alcohols such as sodium lauryl sulfate or ammonium lauryl sulfate, fatty alcohol ether sulfates of the formula R- (0-CH2-CH2) n-OS03Na, where R means hydrogen or an alkyl group with 1 to 30 carbon atoms and n means a number from 1 to 20, sodium ifoacetates alkyls of the formula R-0-CO-CH2-S03Na, where R means an alkyl group with 1 to 30 carbon atoms, alkylolamido sulphates of the formula R-CONH- (CH2) n-0S03Na, where R represents an alkyl group with 1 to 30 carbon atoms and n means a number of 1 to 6 fatty alcohol ether phosphates of the formula RO- (CH2-CH2-0) n -PO (ONa) 2 wherein R means hydrogen or an alkyl group with 1 to 30 carbon atoms and n means a number from 1 to 20. Suitable active cation agglomeration inhibitors are: quaternary ammonium salts of the formula R1R2R3R4N + C1 ~ where R-j_, R2, R3 and R4, independently of each other, are i different or different and they mean hydrogen or an alkyl group with 1 to 30 carbon atoms. Suitable non-ionogenic agglomeration inhibitors are: fatty polyoxyethylene alcohols, polyoxyethylene fatty acids, polyoxyethylene glycol esters of fatty acids, diethylene glycol mono esters of fatty acids, fatty acid alkolamides of the formula R-CO-NH- (CH2-CH2) n- OH, where R represents an alkyl group with 1 to 30 carbon atoms and n means a number of 1 to 20, sucrose esters, for example sucrose palmitate, partial esters of pentaerythritol, for example pentaerythritol monostearate, partial esters of pentaerythritol ethoxylated , for example pentaerythritol monostearate polyglycol ether, sorbitan fatty acid esters or ethoxylated sorbitan fatty acid esters. Preferably, active and / or non-ionogenic anion agglomeration inhibitors will be added to the preparation according to the invention, with the agglomeration inhibitors of the group of sulfonic acids and esters of fatty acids and phosphoric acid being particularly preferred. The agglomeration inhibitors of the group consisting of dialkyl sul-phosuccinates are very particularly preferred., non-ionogenic phosphoric acid esters and sugars esterified with fatty acids. The dialkyl sulfosuccinates correspond to the general formula (1)R1OOC-CH-S03"M (1) R2OOC CH2 wherein R1 and R2 'independently of one another are the same or different and denote hydrogen or an alkyl group having 1 to 30 carbon atoms, and preferably means an alkyl group having 4 to 18 carbon atoms and M + means H +, Li + , Na +, K + or NH4 +. The preparation of the dialkyl sulfosuccinates can be carried out, for example, as described in the journal C.R. Carly, Ind. Eng. Chem., Vol. 31, page 45, 1939. Preferred examples of dialkyl sulfosuccinates are sodium bistridecyl sulfosuccinate, sodium dioc-tyl sulfosuccinate, sodium dihexylsulfosuccinate, sodium diamyl sulfosuccinate, sodium diisobutyl sulfosuccinate and sodium dicyclohexylsulfosuccinate. . Particularly preferred dialkyl sulfosuccinates are sodium bistridecylsulfosuccinate, sodium d-octylsulfosuccinate and sodium dihexylsulfosuccinate. Phosphoric acid esters, as suitable non-ionic agglomeration inhibitors, preferably correspond to the general formula (2) (R-, 0) v-P- [(CH-CH-O) 2H "] Jy OR R ^ wherein R, and R2, independently of one another, mean hydrogen or an alkyl group with 1 to 30 carbon atoms and, preferably, mean an alkyl group with 4 to 22 carbon atoms, x and y, independently of each other, mean numbers of 0 to 3 and in their sum they take the value 3 and z means a number from 1 to 25. Especially preferred examples of esters of phosphoric acid are those in which R-_ means an alkyl group with 14 to 20 carbon atoms, R2 means hydrogen or a methyl group and x and y signify a number 1 or 2 and z means the number from 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 from 0.05 to 5% by weight and more preferably 0.1 to 3% by weight, based on the weight of the preparation. The object of the invention is also a process for obtaining fiber coating agents based on a dispersion of metal salts of fatty acids and an agglomeration inhibitor in a mixture consisting of polyorganosiloxane and mineral oil, characterized in that it dissolves 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 of metal salt B) of a fatty acid with 6 to 30 carbon atoms saturated or unsaturated, mono- or bifunctional, 1 to 69% by weight, preferably 3 to 50% by weight, particularly preferably 5 to 30% by weight of a mineral oil C) ba or heating at 70 to 170 ° C, preferably at 100 to 140 ° C, because the hot solution is mixed, in a mixing device, intensively and rapidly with 30 to 98 , 97% by weight, preferably with 50 to 96.9% by weight, particularly preferably with 70 to 94.8% by weight of polyalkylsiloxane A), because the dispersion formed is subsequently homogenized directly and subsequently added to the mineral oil C) or to polyalkylsiloxane A) before mixing or to the dispersion formed 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 up to 3% in pesos of agglomeration inhibitor D). The homogenization is preferably carried out by applying shear energy with an energy density, relative to the volume of the preparation, of at least 10 J / rr, particularly preferably at least 3 x 10, J / m, very special preferably at least 4x10 ° J / m3. In this way the fine division and the stability to the sedimentation are favored. The preparation of the preparations according to the invention, which take the form of dispersions, is carried out by means of a precipitation process by dissolving the metal salts of fatty acids in hot hydrocarbons and the combination of this phase with the phase containing the polyorganosiloxane. The precipitation can be carried out in a precipitation device, consisting of one, two or more dispersion devices with connected homogenization stage, if applicable, downstream. The preparation of the preparations according to the invention can also be carried out by introducing the phase containing the metal salt into the phase containing the polyorganosiloxane in a tank with subsequent homogenization by means of a homogenizing device. The addition of the agglomeration inhibitor can be carried out in all cases during the preparation of the preparation at an arbitrary point. A suitable dispersing device with several stages and a homogenizing nozzle are described in the specification of US Pat. No. 5,302,660. The described installation is used to alloy a rapid mixture of the two streams of products, which must be carried to a chemical reaction with each other. However, the implementation of a precipitation process in the aforementioned installation with subsequent homogenisation, where appropriate, which leads to fine grain dispersions and stable to sedimentation with a narrow distribution of grain size, which are free of agglomerates. In the patent application EP-399 266 the obtaining of dispersions by crystallization of emulsions has been described. The process is based on the fact that a melt is mixed with a cooler liquid phase at a temperature below the crystallization point and is emulsified therein, the solidification being only solidified after the emulsification in the form of the dispersed particles. For this purpose, melting is introduced into the liquid phase by means of nozzles for the formation of a pre-emulsion and the pre-emulsion is finally dispersed in a homogenized nozzle, connected downstream, to form an emulsion, which is then solidified to give the crystal suspension finished. However, it has not been described in EP-399 266 the realization of a precipitation process in which, immediately after the combination of one phase, constituted by a solid material and by a solvent, with another phase, essentially a non-solvent, in nozzle mixers with, if necessary homogenized in the following, in which finely grained and stable dispersions are formed to the sedimentation with a narrow grain size distribution, which are free of agglomerates. The known dispersion devices make it possible to mix two streams of products very quickly with one another. It has been found that, depending on the incorporation of high shear energy, when such devices are used for the preparation of fiber preparation oils according to the preparation process according to the invention, the metal salts of fatty acids can incorporated in the absence of agglomerates and stable to sedimentation with polyorganosiloxanes with formation of a good and narrow grain size distribution. The process for obtaining the preparations according to the invention by means of a two-stage or multistage dispersion device with subsequent homogenization, if appropriate, is preferred over a process of tank precipitation with subsequent homogenization since this process can be work continuously. The subject of the invention are also fibers, especially 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, are in particular made up of segmented polyurethane polymers, for example those based on polyethers, polyesters, polyetheresters and / or polycarbonates. Such fibers can be manufactured according to basically known processes, such as, for example, which have been described in the publications 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. In addition, the polyurethane fibers can be constituted by thermoplastic polyurethanes , the preparation of which has been described, for example, in US 5 565 270. The polyurethane is based in particular on organic diisocyanates and on a chain extender with several active hydrogen atoms, such as, for example, di- and polyols, and polyamines, hydroxylamines, hydrazines, semicarbazides, water or a mixture of these components. The preferred diols are glycol, butanediol and hexanediol. Preferred diamines are ethylene diamine, 1,2-propanediamine, 2-methyl-1,5-diaminopentane, 1,3-diaminocyclohexane and 1-methyl-2,4-diaminocyclohexane. The fibers may contain a plurality of other various additives for various purposes, such as for example antioxidants, heat stabilizers, anti-light and anti-UV, pigments and matting agents, colorants, lubricants and glidants, examples of antioxidants, stabilizers against heat, against light and against UV rays are stabilizers of the group of sterically hindered phenols, of HALS stabilizers (hindered amine light stabilizer), of triazines, of benzophenones and of benzotriazoles. Examples of pigments and matting agents are titanium dioxide, zinc oxide and barium sulfate. Examples of dyes are acidic dispersion dyes and optical pigments and brighteners. Examples of lubricants and glidants are metal salts of fatty acids and silicone oils and mineral oils. The mentioned additives are dosed in such a way that they do not have opposite effects to the preparation oil applied externally on the fibers or manufactured by a precipitation process. The coating compositions according to the invention for fibers, which are in the form of dispersions and which can be manufactured by means of a simple and economical precipitation process, compared to a conventional milling process, in a mixing nozzle or in a tank with Subsequent homogenization, have, as demonstrated in Example 1, the surprising advantage that they are very finely divided, with an average grain size of D50 < 3 μm having in this case a very narrow grain size distribution, presenting with a D90 of < 10 μm a very small proportion in coarse-sized particles. The coating agents are free of agglomerates and are perfectly stable against sedimentation with a sedimentation ratio of < 20% for 10 days Also in the case of a composition of the coating agent according to the invention, having only 2% by weight and a proportion below this value of the metal salt of fatty acid, the excellent properties of the coating agent are maintained. covering. In the case of the known preparation agent, which contains metal salt of fatty acid, the proportion of sedimentation of the salt is significantly higher. Metallic salt accumulates for example at the point of preparation. A homogeneous application of the metal salt on the fibers is prevented. Another drawback of the known preparation agent is that during the further processing of the fibers coated therewith to give smooth articles, metal salt of fatty acid is deposited on the parts of the machine for example on the triceate needles and cause obstructions of the oil with long beak or breakage of the fibers. With a content of less than 4% by weight of the fatty acid metal salt, a failure of the coating on the fibers has also been observed in the case of the known preparations. The consequence is that the fibers stick together. Furthermore, in the application of the coating agent according to the invention on polyurethane fibers, as shown in Example 2, a surprising reduction in the electrical resistance of the fibers is already found by means of small amounts of agglomeration inhibitor in the preparation. In this way an electrostatic finishing of the fibers is achieved which reduces or prevents, for example, electrostatic charges during the further processing of the fibers. In the application of the coating agent according to the invention to polyurethane fibers, it has surprisingly been found, as shown in Example 3, that the reinforcing of the adhesion is already strongly reduced by small amounts of a fatty acid salt in the coating agent. during a prolonged storage time of the fibers even at high temperature and, in this connection, the stickiness of the polyurethane fibers and the fiber processing, for example in a circular knitting machine runs perfectly and without deposits on the needles of knitted It was found especially surprising, as shown in example 3, that the coating compositions according to the invention have no deposits or obstructions in the coating agent pipes or in the preparation tanks even in long-term tests during the Application on polyurethane fibers mediance a preparation roller. In this way, an application of the coating agent is possible for a prolonged period of time. In addition, the homogeneity of the application is improved and an interruption of the production process is made unnecessary due to necessary cleaning tasks. The test procedures, described below, are used to measure the parameters mentioned above in the examples. The measurements to determine the grain size distributions are carried out with Master-sizer M20, Malvern Instruments Firm by means of laser light diffraction and laser light diffusion. Dispersing agent is polydimethylsiloxane with a viscosity of 10 mPas (25 ° C). The grain size of the particles in microns (μm) is indicated as a function of the volume distribution of the particles at 10, 50 and 90 before and after an ultrasonic treatment for 180 seconds. The difference between grain size distributions before and after treatment with ultrasounds is a measure of the presence of agglomerates. If the difference is small, no agglomerates are present. To determine the behavior of the sedimentation, 100 ml of the oil of the preparation are placed in the form of a dispersion in a graduated beak and determined in percentage, after 3 or 10 days, the proportion of Disintegrated phase. A stabilization against sedimentation is reached when the clear phase is, even after 10 days, <;twenty % . The determination of the viscosity of the preparation oils is carried out with a Haake viscometer, Model CV 100 at a temperature of 20 ° C and with a shear rate of 300 s ~. The determination of the electrical conductivity of the polyurethane fibers, which have been fanned with various preparations, is carried out with the aid of the measurement described in DIN 54 345 for the determination of the flow resistance. The determination of the adhesion of the fibers on a coil is carried out by first cutting the fibers of a coil with a speed of 500 g up to 3 mm above the housing of the coil. Then a weight of the fibers is recorded and the speed with which the coils of the coil are unwound is determined. The adhesion determined in this way is a measure of the ability to process the coils. If the adhesion is too high, the processability can be made difficult to give smooth articles due to the breakage of the fibers. The determination of the adhesion after a storage time of 8 weeks at an elevated temperature of 40 ° C, describes an aging process and is a measure of the development of the adhesion after a prolonged storage time at room temperature. The storage of the coils is carried out at 40 ° C in a heating cabinet with a relative humidity of 60%. After storage, the adhesion is measured as described above. The verification of the processability of the polyurethane fibers was carried out in a circular knitting machine of the firm Terrot. Plain articles were manufactured with 20% by weight of polyurethane fibers and 80% by weight of cotton. The test was carried out in a complete circular knitting equipment for a period of 5 hours.

The determination of the deposits in the preparation system was carried out by applying the preparation oil in a long-term test for 14 days without interruption by means of the roller technique on a polyurethane fiber. At the end of the test the amount of solid product, coming from the dispersion, that has been deposited on the preparation system is evaluated. The more deposits that are present, the less the preparation will be adequate, since the preparation system with tanks, pipes and buckets and preparation rollers or thread guides or spray nozzles, has to be cleaned more frequently and, therefore, has than to interrupt more frequently a production process. In the following, the precipitation process for obtaining the coating agents according to the invention is illustrated in an exemplary manner by means of the figures. Figure 1 shows a schematic of the whole of the process for obtaining the coating agent according to the invention by means of a two-stage dispersion device with subsequent homogenization, if appropriate. Figure 2 shows a diagram of another set of the procedure for obtaining the recovery people according to the invention with a homogenate after precipitation in a capsule, previously performed. FIG. 1 shows, by way of example, the flow diagram of the process for the precipitation of the metal salt of the fatty acid into polyorganosiloxane. In the momentary mixing device 1 and in a homogenising device 2, connected downstream, the two product streams are metered, for example metal salts of fatty acids dissolved in mineral oil and polyorganosiloxanes by means of the dosing pumps 8 and 9 to from the tanks 6 and 7 and the oil of the finished preparation is discharged into the product tank 12. The agglomeration inhibitor can be added in the tank 6 or 7, or in the product tank 12 in a suitable manner. The pre-pressure in front of the mixing device is controlled by the pressure gauges 10 and 11. Figure 2 shows the flow diagram of a variant of the method according to the invention. The fate is constituted by the metal salt of fatty acid and mineral oil from the tank 6 is introduced into the polyorganosiloxane in the mixing vessel 7 and mixed. The mixture is transported by means of the dosing pump 9 through the homogenizer 15 and the oil of the finished preparation is discharged into the reservoir for the product 12. The agglomeration inhibitor D can be added in the depots 6 or 7 or in the tank for the product 12 in a suitable way. The invention will be explained in more detail by means of the following examples. However, the examples do not represent any limitation of the preparations according to the invention or of their preparation processes. The following examples document the advantageous composition and the improved production processes of the coating agents for fibers according to the invention by means of a precipitation process. Examples The preparation of the polyurethane fibers for the test of the processing properties of the fibers with the new preparations is carried out by reaction of polytetrahydrofuran (PTHF) with an average molecular weight of 2,000 g / mol with methylene-bie (4 - phenyldiisocyanate) (MDI) in a molar ratio of 1 to 1.8. The polymer, prepared in this way, was diluted with dimethyl acetamide and then subjected to a chain extension in dimethylacetamide with a mixture consisting of ethylenediamine (EDA) and diethylamine (DEA) (proportion 97: 3). The molar ratio between the chain lengtheners and the chain switches with respect to the unreacted isocyanate in the prepolymer was 1.075. The solids content of the segmented polyurethane, manufactured in this way, was 30% by weight. The polyurethane-urea solution had a viscosity of 120 Pas (50 ° C) and the polymer had an intrinsic viscosity of 0, 98 g / dl (measured at 25 ° C in dimethylacetamide with a concentration of 0.5 g of polymer in 100 ml of dimethylacetamide). Prior to the dry spinning process, the following additives were added to the polyurethane-urea spinning solution (indications in% with respect to the weight of the finished fibers): (a) 1.0% of 1,3,5-tris (4-tert -butyl-3-hydroxy-2, 5-dimethylbenzyl) -l, 3, 5-triazin-2, 4, 5, 6- (1H, 3H, 5H) -frione (Cyanox 1790, Fa. Cytec), (b) 0.05% titanium dioxide (Typ RKB 2, Fa. Bayer AG), (c) 0.15% magnesium stearate, (d) 0.001% macrolex violet (Fa. Bayer AG ) and 0.15% of polyalkoxy-modified polydi-methylsiloxane (Silwet L 7607, Fa OSI Specialties). The finished spinning solution was spun through spinning nozzles in a typical spinning facility for a dry spinning process to give filaments with a 11 dtex titer, four individual filaments respectively being assembled to give coalescing filament yarns. The preparations in the form of dispersions were applied to the fibers with 4% by weight, based on the weight of the fibers, by means of a preparation roller. The fibers were then wound with a speed of 900 m / minute. Example 1. In this example, grain size distribution, viscosity and sedimentation behavior were compared with each other as properties of the preparations as a function of the composition and the procedure for obtaining the preparations. The results have been gathered in table 1.

Table 1. Comparison between the preparations according to the obtaining procedure L? a) US = Treatment by ultrasound in the ultrasound bath. b) Polydimethylsiloxane (10 mPas / 20 ° C); c) Crosslinked polyamylethyloxane (15 Pas / 20 ° C) d) Polydimethylsiloxane (3 mPas / 20 ° C) e) The hexane is further removed by distillation; f) Medicinal white oil (15 mPas / 20 ° C); g) Ester distearylpentaethylene oxide of phosphoric acid; h) Pentaethylene oxide with 12/14 carbon atoms; j) After precipitation in the tank; k) Bring the homogenate. Preparations 1-1 to 1-3 contain, in addition to low viscosity silicone oil, and polyamylsiloxane, magnesium stearate, which was introduced by a milling process with a bead mill (type MS 12, Firma Fryma). The grain size distribution shows that the particles do not present themselves in the form of agglomerates, however the proportion of grossly divided particles is large, even after carrying out five milling processes with a D90 value of > 10 μm. The stabilized against sedimentation is improved as the grain size decreases (tests 1-1 and 1-2), on the contrary they worsen, as shown in test 1-3, as the content of stearate decreases of magnesium in the preparation. The reason for this may be an over-weak interaction of the individual particles with each other. In any case, however, the stabilization of the preparations obtained by a grinding process, with a sedimentation of > 20% / 10 days is too strong to be able to guarantee a homogenous application of the pre-paration on the fibers. Furthermore, the grinding process is not suitable for the incorporation of finely divided magnesium stearate in silicone oils due to the effectiveness too bad and, related to it, due to bad economy. The preparation of preparations 1-4 to 1-8 was carried out by means of the precipitation process described in the scheme of figure 1 in a mixing nozzle 1. In this case a stream, heated to 130 ° C, was combined. constituted by hydrocarbons and magnesium stearate (in experiments 1-7 and 1-8 additionally esters of phosphoric acid as an agglomeration inhibitor) with a stream consisting 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 J /.

The proportions between product streams corresponded to the composition of the finished preparation. In experiment 1-4 hexane was removed in an additional step by distillation and in experiment 1-8 ee was incorporated in the preparation dioctylsulfo-sodium succinate as an agglomeration inhibitor after precipitation. In all cases, preparations having a narrow grain size distribution and very fine particles with a D50 value of < 3 μm, which did not contain agglomerates and, with D90 values of < 10 μm, a fraction of rough grain particles in the preparation clearly lower than in relation to the grinding process. The distributions of the grain size are therefore narrow, the size of the particles are therefore arbitrary. In addition all the preparation oils obtained were stable against sedimentation, especially also those with a small amount of 1% in magnesium stearate, with a proportion of sedimentation of < 20% / 10 days. The preparation of preparations 1-9 and 1-10 was carried out by means of the precipitation process described schematically in Figure 2 in a tank with subsequent homogenization. In this case a current was added, heated to 120 ° C, constituted by mineral oil, magnesium stearate and adduct of fatty alcohol-EO or esters of phosphoric acid, under stirring, in a vat with silicone oil at 20 ° C and then homogenized by means of a homogenizer 15 (see Figure 2) with an energy density of 5x10 J / m3. Directly after the precipitation process, the preparations contained agglomerates and showed a high gross proportion but however the experiment 1-9 had a good stabilized against sedimentation. By means of the homogenate, the agglomerates were broken in the preparation and the stabilization was improved against sedimentation. The preparations obtained by precipitation in the tank with subsequent homogenisation were exempt, in the same way as the preparations obtained by precipitation in a mixing nozzle, from agglomerates, a very small coarse ratio with D90 values of <10 μm, present an etched grain size distribution and, with a sedimentation ratio of < 20% / 10 days, a good stabilized against sedimentation. Experiment 1-11 shows the result of the characterization of a preparation, which was prepared according to the specification of the patent JP-60-67 442 by means of a process of precipitating, of magnesium stearate in hexane in a tank with subsequent addition of oil of silicon and polyamylsiloxane and elimination of hexane by distillation. The preparation shows a good stabilization against sedimentation, however it is not suitable as preparation oil for obtaining fibers, especially polyurethane fibers due to the strong tendency to agglomeration and greater visibility, probably due to the strong interactions of the particles of the solid product in the preparation with each other. Example 2. In this example it is shown that the electrical conductivity of the polyurethane fibers can be modified depending on the composition of the preparation. All the preparations, which are in the form of a die scattering, were obtained by means of a precipitation in a mixing nozzle 1 and subsequent homogenization (according to example 1-4). The results have been indicated in table 2. Table 2. Electrical conductivity of polyurethane fibers with various preparations. a) Polydimethylsiloxane (3 mPas / 20 ° C); b) Polydimethylsiloxane (10 mPas / 20 ° C) • c) Crosslinked polyamylsiloxane (15 Pas / 20 ° C), -d) Medicinal white oil (15 mPas / 2 ° C); e) Distearyl-pentylethylenedioxide ester of phosphoric acid. Experiment 2-2 demonstrates that the poly-amylsiloxane, as a component of the preparation, reduces the electrical pass-through resistance of the polyurethane fibers, therefore this branched siloxane increases the electrical conductivity. This result corresponds to the observation made in the specification of the US patent US-3296 063. By incorporating ethereal phosphoric acid and / or sodium dioctylsulfo-succinate, however, the resistance of the fibers was further reduced of polyurethane, that is to say that the electrical conductivity was further increased. In this case the dioctyl sulfosuccinate of eodium ee, in front of the ester of the foephoric acid, and this in turn ahead of the polyamylsiloxane, the most active agent for the reduction of the step resistance. Example 3. In this example, it is demonstrated, depending on the preparation procedure and the composition of the preparations, which of the preparations reduces the stickiness of the polyurethane fibers and, therefore, guarantees their suitability for processing. after a prolonged standing time at elevated temperature.

Furthermore, it is shown which of the preparations, which is presented in the form of a dispersion, can be applied for a prolonged period of time without formation of deposits. The results have been gathered in table 3.

Table 3 Polyurethane fiber preparation tests with various preparations ui a) Polydimethylsiloxane (3 mPas / 20 ° C); b) Polydimethylsiloxane (10 mPas / 20 ° C); c) Crosslinked polyamylsiloxane (15 Pas / 20 ° C); d) Medicinal white oil (15 mPas / 20 ° C); e) Distearyl ester-pentaethylene oxide of phosphoric acid; f) Pentaethylene oxide with 12/14 carbon atoms; g) Magnasoft Fluid product of the Fa. Witco. Experiments 3-1 and 3-2 show that in the application of silicone oil-based preparations or in silicone oil with polyamylsiloxane the increase in the adhesion of polyurethane fibers with a storage time of 8 weeks and at a temperature of 40 ° C, such as that which occurs frequently during transport, in warehouses or in subtropical countries, is very strong and that the ability to process the coils is often not possible. The values obtained in these experiments for the adhesion are located above 1 cN, which constitutes a limit value for a suitability to the successful processing of the polyurethane fibers, for example in a circular knitting machine. In this way, adhesions with a value greater than 1 cN can lead to the breakage of the fibers during the processing of the coils, with the consequence of stopping the machines. In the extreme case, no fiber of the coil can no longer be unwound. The preparations employed 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 through 3-12 show that the generation of adhesion of the polyurethane fibers on the coils is reduced when the preparation contains, with magnesium stearate, a metal eal of the fatty acid and, therefore, is present in the form of a dispersion. In all cases they are on the polyurethane coils, after storage for more than 8 weeks at a temperature of 40 ° C, adhesion values of < 1 cN. Based on this, it is perfectly possible to process even coils stored in a circular knitting machine. The activity of magnesium stearate in the preparations to reduce the stickiness of polyurethane fibers however is in thoseof. , which have been prepared by a grinding process, less than in the case of those that have been prepared by means of precise mixing in the mixing nozzle or by means of precipitate in the tank with subsequent homogenization. Thus, in the case of the preparations, which have been obtained by the described precipitate process, 1% by weight of magnesium stearate is sufficient to reduce the poly-urethane fiber peginess to the desired level. In the case of the preparations obtained by a precipitate process, a magnesium stearate content of 4% by weight is required for the establishment of the same behavior with regard to adhesion. One drawback of the preparations, which are obtained by a grinding process, is that strong deposits are formed on the needles of the circular knitting machine during the processing of the polyurethane fibers, whose Deposits can lead to breakage of the fibers. To avoid breaking the fibers, therefore, a higher cost of cleaning the circular knitting machine is required, which results in shorter machine run times. However, in the case of the preparations obtained by the processes of precipitate described, no deposits are formed on the needles, with good processability in circular knitting machines due to the lower content of magnesium stearate. Long-term tests for the evaluation of the deposits and of the blockages in the pipes and in the buckets of the preparation due to the preparations of the experiments 3-3 to 3-12, which are presented in the form of dispersions, led to the result that, regardless of the manufacturing process by grinding, precipitate in the mixing nozzle 1 or by precipitate in the tank with subsequent homogenization, many deposits and obstructions occurred. These deposits and obstructions are undesirable in the application of the preparations on the polyurethane fibers since in this way frequent cleaning is required. There were no deposits or obstructions in the pipes or in the buckets of the preparation, as shown in experiments 3-8 to 3-12, when the preparations obtained are applied by means of a precipitate in the mixing nozzle or by means of a precipitate in the tank. with subsequent homogenization, in which agglomeration inhibitors have been additionally incorporated, such as, for example, sulfonic acid salts, esterified sugars or functionalized silicone oils. It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the one that is clear from the present description of the invention.

Claims (16)

CLAIMS Having described the invention as above, the content of the following is claimed as property:
1. l.- Coating agents for fibers, especially elastane fibers, based on a dispersion of metal salt of fatty acid and of agglomeration inhibitor in a mixture consisting of polyorganosiloxane and prinecal oil, cfr-rJwzadb cmügB al rrepcs 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) ), 3) 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 4% by weight, 2% by weight, of metal salt of a fatty acid with 6 to 30 carbon atoms saturated or unsaturated, mono or bifunctional, the metal being one of the first, second or third main group of the Periodic System of the Elements or Zn,
2. 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), density of 800 to 900 kg / m3 (15 ° C) and a viscosity-density constant (VDK) of 0.770 to 0.825. D) from 0.02 to 15% by weight, preferably from 0.0 to 5% by weight, particularly preferably from 0.1 to 3% by weight, of the agglomeration inhibitor selected from the series consisting of active cation compounds, anion active or non-ionogenic, especially active or non-ionogenic antiaesthetic compounds. 2 . Coating agents according to claim 1, characterized in that the polyalkylsiloxanes A) are linear polyalkylsiloxanes, preferably linear polydimethylsiloxanes with a viscosity of 2.5 to 50 mPas (25 ° C), particularly preferably with a viscosity of 2, 5 to 20 mPas (25 ° C).
3. 3. Coating agents according to claims 1 or 2, characterized in that the metal salt of fatty acid B) is a salt of lithium, magnesium, calcium, aluminum or zinc of oleic acid, palmitic acid and acid stearic, especially preferred is magnesium stearate, calcium stearate or aluminum stearate and is present alone or in any mixture.
4. 4. Coating agents according to one of claims 1 to 3, characterized in that the mineral oil C) has a viscosity of 3 to 300 mPas (25 ° C), preferably 3 to 200 mPas (25 ° C).
5. 5. Coating agents according to one of claims 1 to 4, characterized in that an ammonium compound is selected as the active cation agglomeration inhibitor D), the salt of a sulphonic acid is selected as the active anion agglomeration inhibitor D). or a dialkyl phosphoric acid or a dialkyl sulfosuccinate, as an inhibitor of the nonionic agglomeration D), a fatty acid ester or an ester of phosphoric acid, alkoxylated fatty alcohol, amino-functionalized or alkoxylated polyorganosiloxane is chosen.
6. 6. Coating agents according to claim 5, characterized in that the agglomeration inhibitor D) is selected from the group consisting of dialkyl sulfosuccinates, esters of phosphoric acid, polyamino-functionalized polyorganosiloxanes and sugars esterified with fatty acids.
7. 7. Coating agents according to claim 5, characterized in that the agglomeration inhibitor D) is a dialkyl eulfosuccinate corresponding to the general formula (1) R ^ OOC-CH- -SO, ~ MJ (i: R200C-CH2 wherein R, and R2, independently of one another, are the same or different and mean hydrogen or an alkyl group with 1 to 30 carbon atoms, and preferably mean an alkyl group with 4 to 18 carbon atoms and M + means H +, Li + , Na +, K + or NH4 +.
8. 8. Coating agents according to claim 5, characterized in that the agglomeration inhibitor D) is a dialkyl sulfosuccinate chosen from the series consisting of sodium bistridecyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium dihexylsulfosuccinate, sodium diamyl sulfosuccinate, sodium diisobutylsulfosuccinate and sodium dicyclohexylsulfosuccinate, especially sodium bistridecyl sulfosuccinate, sodium dioctyl sulfosuccinate and sodium dihexylsulfosuccinate.
9. 9. Coating agents according to claim 5, characterized in that the agglomeration inhibitor D) is an ester of phosphoric acid corresponding to the general formula (2), lR O)? -P- [(CH2-CH-0) 2Hj 0 R. wherein R, and R2, independently of one another, mean hydrogen or an alkyl group with 1 to 30 carbon atoms and, preferably, mean an alkyl group with 4 to 22 carbon atoms, x and y, independently of each other, mean numbers of 0 to 3 and in their sum they take the value 3 and z means a number from 1 to 25. 10. Coating agents according to claim 9, characterized in that the agglomeration inhibitor D) is an ester of the phosphoric acid of the formula , wherein R ^ means an alkyl group with 14 to 20 carbon atoms, R2 means hydrogen or a methyl group and x and y signify a number 1 or 2 and z means a number from 3 to
10. 10.
11. 11.- Coating agents according to one of claims 1 to 10, characterized in that they occur in the form of finely divided dispersions, have an average grain size of the dispersed solid matter particles of D50 < 3 μm, and have a very narrow grain size distribution, with a D90 value of < 10 μm.
12. 12. - Coating agents according to one of claims 1 to 10, characterized in that they have a sedimentation ratio of < 20% in 10 days.
13. 13. - Process for obtaining a coating agent for fibers according to one of claims 1 to 12, based on a dispersion of metal salts of fatty acids and an agglomeration inhibitor in a mixture consisting of polyorganosiloxane and mineral oil, characterized because it is dissolved 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 by weight of metal salt B) of a fatty acid with 6 to 30 carbon atoms saturated or unsaturated, mono or bifunctional, by 1 to 69% by weight, preferably by 3 to 50% by weight, in particular preferably from 5 to 30% by weight of a mineral oil C) ba or heating at 70 to 170 ° C, preferably at 100 to 140 ° C, because the hot solution is mixed, in a mixing device, intensively and rapidly with 30 to 98.97% by weight, preferent with 50 to 96.9% by weight, particularly preferably with 70 to 94.8% by weight of polyalkylsi-loxane A), because the dispersion formed is subsequently directly homogenized and added to the mineral oil C) or polyalkylsiloxane A) before mixing or to the dispersion formed before or preferably after the homogenate, from 0.02 to 15% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0 to 5% by weight. , 1 to 3% by weight of agglomeration inhibitor D).
14. 14. Process according to claim 13, characterized in that the agglomeration inhibitor D) is added to the dispersion of the coating agent directly after homogenization.
15. 15. Method according to claims 13 or 14, characterized in that the homogenization is carried out by incorporating shear energy with an energy density referred to the volume of the preparation of at least 10 J / m, particularly preferably of less 3x10 ° J / m3, very preferably at least 4x10 J / m3.
16. 16. Fibers, especially polyurethane fibers, coated with a coating agent according to one of claims 1 to 12.