DE2435624A1 - Aq. emulsions used as sizes for monofilaments - based on hydroxy-pivalyl hydroxy-pivalate diesters - Google Patents

Abstract

Aq. emulsions for applicn. (as sizing agents) to synthetic linear org. polymer fibres, e.g., polyamide or polyester, contain a hydroxypivalvyl hydroxypivalate diester of formula: (where R1 and R2 are 2-24C alkyl(ene) monocarboxylic acids), a surface active emulsifier compatible with the diester, and H2O. The emulsions contain 1-25 wt. % solids comprising 50-80 wt.% diester and 50-20 wt.% surface-active emulsifier. They reduce abrasion between fibres and metal surfaces during the drawing process and achieve a uniform adhesion between adjacent fibres at the same time, remaining stable at elevated temps. and producing no odour. they are resistant to oxidn. and discolouration. Used as lubricants in hot drawing of polymer monofilaments to achieve orientation in e.g., prepn. of tyre cords from nylon and polyesters having uniform tensile strength, making possible continuous mfr.

Description

Aqueous emulsions for treating monofilament polymer threads The invention relates to treatment or finishing agents for synthetic threads linear organic polymers and processes for applying the same to them Threads.

Synthetic linear organic polymers, e.g. B. polyamides such as Nylon, like polyester, are usually made into threads by melt spinning processed, and the threads produced in this way are drawn or drawn in the solid state.

stretched to develop a high degree of toughness, so that they become suitable for use for textile purposes.

About pulling the strings and doing other work To facilitate to which the threads are subjected, it is necessary on that Material just produced by the melt spinning process, a size or the like. to apply so that the friction is reduced while the threads over metal surfaces certain textile machines are running.

Such a reduction in the coefficient of friction between the fibers and the metal surfaces prevent the threads from grinding off. The size must be suitable be the strings too lubricate so that they do not during pulling tear. In the case of multi-thread yarns, it is also necessary that the slits have a creates a certain balanced cohesion between the individual threads of the yarn. One such cohesion is of particular importance in flat warp knitting machines. Furthermore, it is very desirable that the size is resistant to oxidation to a high degree, that it does not discolour and that it does not contain any insoluble resin or polymer compounds forms.

It is also desirable for the size to have high temperature stability and at the temperatures they use when processing synthetic exposed to linear organic polymer filaments does not generate smoke. These The latter properties are particularly important for the "hot stretch" process, carried out in the manufacture of synthetic linear organic polymers will.

The invention is based on the object of meeting the requirements mentioned corresponding sizing compounds for threads made from synthetic linear organic polymers to create that are capable of reducing the coefficient of friction between fibers of the aforementioned Kind and degrade metal surfaces that have a balanced adhesion between adjacent ones Produce fiber surfaces that remain stable at elevated temperatures and none Generate smoke, especially during hot stretching to orient the polymer such that z. B. in the manufacture of nylon and polyester tire cords a tensile strength that is as uniform as possible is achieved, furthermore a method for application of size to threads made of synthetic linear organic polymers to create the production of stores and synthetic linear organic yarn To facilitate polymerizates that the threads or yarns with a sizing mass that have lubricity and at elevated temperatures are resistant to oxidation and discoloration, and finally a lubricant for tire cords that allow processing at high temperatures, when used, the production can be carried out continuously, and when using it, tire cords made of polyester are obtained which are excellent adhere to rubber and have a high resistance to fatigue due to flexing exhibit.

The invention and advantageous details of the invention are set forth in the following explained in more detail using exemplary embodiments.

Generally speaking, the object of the invention is achieved through the use of hydroxypivalyl hydroxypivalate esters, hereinafter referred to as "HPHP ester" for short whose molecules contain stable neopentyl groups. With this one chemical structure, substances are available that are only slightly volatile are and remain stable even at elevated temperatures; the latter property leads to a reduction in the loss of strength of the fibers during processing at high temperature, and it enables working at high temperature.

HPKP is formed by reacting hydroxypivalyl alcohol with hydroxypivalic acid and is also referred to in the literature as neopentylene glycol monohydroxypivalate. HPHP is commercially available from Eastman Chemical Products, Inc. One method for Production of HI) HP is indicated in U.S. Patent 3,057,911.

More precisely, the invention has created sizing compositions for threads made of synthetic linear organic polymers, which are HPHP esters, the chemical structure of which corresponds to the following general formula: Herein R1 and R2 are alkyl or alkylene monocarboxylic acids which contain 2 to 24 carbon atoms and are preferably taken from the fatty acids. The invention takes into account both simple HPHP esters, ie those in which R1 and R2 denote the same radical, and mixed HPHP esters. While it is preferred to derive the radicals R1 and R2 from saturated and unsaturated straight chain acids, groups derived from branched chain acids are also suitable, e.g. B. the neo acids such as neonanonic acid etc. or iso acids, e.g. B.

Isostearic acid. Essential information about some of these compounds are listed in Table I below.

A high molecular weight glycol KPKP offers stability because of its stability the neoconfiguration (C2 or c2 in the above formula) has high temperature stability with low volatility. This suggests that other neoglycol esters provide thermally stable sizing compositions for fibers.

The processes for making KPHP esters are known as they are is an esterification process. Usually 2 moles of the acid or a mixture of acids are used generally under reflux in the presence of toluene or another diluent reacted with one mole of HPHP. The one that takes place without a catalyst Reaction runs at temperatures between 1500 C and 2650 C and for a time from 4 to 12 hours until the theoretically required amount of water of reaction released and collected. The reaction can also be carried out by a catalyst be promoted, e.g. B. by an aromatic sulfonic acid such as paratoluene sulfonic acid, the response time is significantly reduced. Then the essentially fully esterified HPHP esters obtained, e.g. B. by stripping in a vacuum, so that an ester product with a low free fatty acid value is obtained.

As examples of esters in question according to the invention be the following named: HPKP onoacetate monooleate, HPHP dioleate, HPHP distearate, HPHP dilaurate, HPHP diheptanoate, HPHP dicaparat, HPHP monolaurate, HPHP monopalmitate, RPHP monoisonoanoate monostearate etc. It is also possible to use mixtures of acids to produce HPHP esters.

Table 1 Typical HPHP Esters HPHP Esters of Free Fatty Acid Saponification Hydroxyl number number oleic acid 0.03 235 9.5 stearic acid 0.02 232 7.5 palmitic acid 0.02 244 3.0 30% palmitic and 70% lauric acid 0.02 273 2.0 lauric acid 0.01 292 4.0 nonanoic acid 0.01 347 10.0 isononanoic acid 0.01 343 15.0 heptanoic acid 0.01 336 6.0 The sizes can be applied to the threads of synthetic linear organic Polymers directly or dissolved in a solvent or as an aqueous emulsion be applied. Usually the method used is based on the percentage Amount of lubricant, the type of polymer, the procedure and the available facilities. More precisely, the choice of procedure depends according to the type of facility that is best for processing the polymer suitable is. The amount of sizing material applied to the organic polymer is generally 0.5 to 15% by weight. It is also possible to change the finishing to the Organic polymer to be added before the enamel spinning, so that they can be attached later the surface penetrates.

To produce an aqueous emulsion containing the size, Any single surfactant or combination can be used use surfactants compatible with the size and have the ability to form a stable emulsion. Example one can an aqueous emulsion having the following composition using known techniques produce: j e i s p i e 1 A: (60 parts by weight of HPHP ester (10 parts by weight of glycerol monooleate 15 parts by weight (parts by weight of ethoxylated (about 25 mol) (castor oil (15 parts by weight of polyethylene glycol (400) Dilaurate 85 parts by weight water Other suitable surface-active agents are sulfated glycerol trioleate, ethoxylated tridecyl alcohol, polyglycerol ester, such as decaglycerin tetraoleate, triethanolamine oleate, decaglycerin dilaurate, decaglycerin dicaprylate, ethoxylated (8 to 15 moles) nonylphenol, etc., which alone or in combination can be used as in the example above. Usually contains the aqueous Emulsion 1 to 25% by weight non-aqueous solids, which in turn consist of 50 to 80 parts by weight of the size and 50 to 20 parts by weight of the emulsifier.

About the appropriate solvents to use in applying it Sizes include the low molecular weight alkanols such as ethanol or propanol, ketones such as acetone and hydrocarbons such as petroleum ether or Toluene.

The solvent must match the polymer to which it is applied will be compatible.

Furthermore, certain additives, e.g. B. those to prevent static charges, emulsifying acids, lubricants and the like to increase cohesion serve in conjunction with sizing agents can be used according to the invention, provided that they are the sizes do not significantly damage or change their properties.

The invention also deals with the application of the sizes on thread of the type mentioned and with threads treated in this way. The expression 11 threads "here refers to monofilament threads and consisting of several such threads Yarns regardless of whether they are twisted or not.

The synthetic linear organic polymers include polyamides such as polyhexamethylene sebacamide, poly-kappaaminoundecanoic acid, polynepsilon-caprolactam etc., acrylic polymers, which essentially consist of acrylonitrile, polyolefins, such as polymethylene, polyethylene, polypropylene, etc., polyesters such as polyethylene terephthalate and other polyesters which are produced when a dihydric alcohol reacts with a dibasic acid, etc. as well as polyureas, such as polyhexamethylene urea etc.

The invention is further illustrated by the following examples.

Example 1 Compared to a commercially available butyl stearate size different HPHP esters have been used for textile fibers corresponding to those in the preceding designated formulation with regard to their thermal stability and resistance tested against smoke formation and discoloration. The esters according to the invention and the Comparative sizes were exposed to strongly oxidizing conditions; For this each material was placed in an aluminum dish in the form of a very thin film, which has been exposed to high temperature under atmospheric conditions.

The results of these are summarized in Table II below Investigations illustrate in comparison to the commercially available butyl stearate size the high thermal stability, the greater resistance to discoloration and the low level of smoke generated by the HPHP esters.

Table II HPHP-Di-HPHP-Di-HPHP-Di-HPHP-Di-HPHP-Di-butyl stearate oleate palmitate laurate heptanoate stearate 20 min at 160 ° C weight loss,% 0 0 0 0 0.6 1.3 Smoke none none none none easy easy formation discoloration none none none none no exercise 20 min at 260 ° C Weight -0.5 0.75 0.7 1.0 13.0 25.5 loss,% smoke none none none none slight medium formation discoloration none no no no easy exercise Example 2 The friction between the Fibers were determined in 840/192 denier polyester yarn by using of a solvent, an HPRP ester is applied to a yarn in an amount of 1% by weight and this yarn has been compared to another yarn obtained by washing his Plain had been freed. The experiments were carried out at a temperature of 220 C. and a relative humidity of 25%. The test conditions (attenuation) were as follows: Yarn twist 1.5 times (5400) Attached weight 20 g speed of the 2.5 mm / sec registration strip running speed of the yarn G, 2 mm / sec friction mm between the coefficient of jerks, comparison yarn 90 35 (washed) HPHP dioleate 65 50 HPHP diheptanoate 60 60 These results illustrate the significant reduction the coefficient of friction between the polyester threads of yarns made with sizes were treated according to the invention.

The recorded intervals between the jerky ones Movements indicate relative cohesion. The larger the measured interval, the greater the degree of lubricity, and vice versa. So it is can be seen that the relative cohesion between the successive fibers or the lubricating effect is considerably improved if you apply HPHP ester to the threads brings up.

Example 3 The friction between the fibers and a metal surface was made on 840/192 denier polyester yarn onto which a solvent was used an RPHF ester had been applied in an amount of 1 96, it was determined and the yarn was compared to a washed yarn (no size). Here the experimental conditions were as follows: temperature, ° C 22 relative humidity, 96 25 Running speed 100 of the yarn, m / min total weight of the 100 roll, g radian 5 The differential friction, the increase of which indicates an increase in the friction, becomes expressed in grams.

Plain differential friction none (washed 190 reference yarn) HPHP Dioleate 110 HPHP Heptanoate 115 The above results suggest the superior one Recognize lubricity of HPHP esters between fibers and metal.

EXAMPLE 4 The smoke formation, burning and ignition temperatures the HPHP esters were prepared using the A.O.C.S. Procedure Cc-9a-48 with the appropriate Values for a commercially available butyl stearate size for threads compared. The following Results show that the HPHP esters have a significantly lower tendency to smoke recognize.

Smoke, ignition, burning temperature, ° C temperature, ° C temperature, ° C butyl stearate 118 193 204 HPHP diester of stearic acid 191 310 329 oleic acid 210 307 338 Palmitic acid 191 291 318 Example 5 Cord cords made from triple polyester yarn of 1300 denier with a commercially available size (comparison yarn) or with a self-emulsifiable mass according to the invention had been treated molded into test pieces using rubber for tire carcasses.

For this you can use e.g. natural rubber or SBR or natural SBR rubber use. After removing it from the mold, one can determine the adhesion as a force, which is required to separate the cord material from the rubber. The measurement can take place at room temperature or at an elevated temperature, and the separation required force can be given in units of force.

In order to evaluate the adhesion in U-shape, the treated ones were Cords molded into the rubber for 20 minutes at 1440 C in a shape that made it possible to Create U-shaped cord loops, which are embedded 6.35 mm deep into the rubber was. These cord and rubber specimens were heated to 121 C in a special Ancillary equipment for a tensile tester heated, and the force required was to pull one end of the U-shaped thread out of the rubber, was at one Separation speed of 30 cm / min measured.

The fatigue strength of the cords can be determined with the help of the ASUM procedure Determine D-885. In this test, the specimen is alternately subjected to compression and tension stressed, and the fatigue strength results as the number of load cycles, which is reached until the break.

Stripe adhesion / relative peel force adhesion permanent room temperature High temperature at U-i'orm strength Commercially available size (comparison) 100 100 10 32000 trucks

RPRP di stearate 104 130 16 39000 trucks.

Note: The higher the numerical values, the better the results.

Example 6 A with the size according to the invention (HPI2 distearate) treated tire cord and a similar tire cord made with a commercially available size were treated in a sealed tube in oxygen for 48 hours held at 1490 ° C. with a pressure of 0.069 bar. The percentage of retention the breaking strength compared to the breaking strength before aging was taken as Measure for the thermal stability applied. Higher values indicate a more extensive one Retention of strength and less damage to the cord material of the size in question at the elevated temperature.

The breaking strength was measured according to ASTM method D-2256.

Relative thermal stability Commercially available size 100 HPHP distearate 106 Example 7 An aqueous emulsion was prepared according to the formula of Example A. The I2HP esters of the following acids were used: acetic acid, propenoic acid, lutyric acid, Crotonic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, Myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, Lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid, Ricinoleic acid, linoleic acid, linolenic acid, eleostearic acid, licanic acid, arachidonic acid and clupanodoic acid.

EXAMPLE 8 Example 7 was repeated using 99 parts by weight of water and 1 part by weight of the remaining material.

Example 9 Example 7 was repeated using 75 parts by weight Water and 25 parts by weight of the remaining material.

Example 10 Example 8 was repeated using 50 parts by weight of the size (HPHP ester) and 50 parts by weight of the surface-active Emulsifier.

B e i 5 p i e 11 Example 8 was repeated using 80 parts by weight of the size and 20 parts by weight of the emulsifier.

Example 12 Example 9 was repeated using 50 parts by weight of the size (HPHP ester) and 50 parts by weight of the emulsifier.

Example 9 was repeated using 80 parts by weight of the size and 20 parts by weight of the emulsifier.

In all examples (7 to 13), good properties, as in described above.

The above statements apply, as mentioned, to thread-like Materials for use in a continuous process in which the filaments do not remain in an emulsion bath during treatment. According to a second Embodiment of the invention, it may be appropriate to use staple fibers with a length of about 38 mm by means of a discontinuous process with that described Coating emulsion in which the staple fibers are kept in a vat for a long time Or the like. Introduced and then removed again.

In this process, the amount of size (diester) plus the surface-active emulsifier about 0.4 to about 2 wt.96, the Rest is water. In this case, too, the ratio between the size is and the surfactant 50 to 80% by weight of the size to 50 to 20% by weight of the surfactant.

Patent claims:

Claims (16)

Claims 1. Aqueous emulsion for application to synthetic linear organic polymer threads in a continuous working step, characterized by a hydroxypivalyl-hydroxypivalate diester according to the formula wherein K1 and R2 are taken from the group comprising alkyl and alkylene monocarboxylic acids having 2 to 24 carbon atoms, a surface-active emulsifier compatible with the diester, and water, the emulsion containing from about 1 to about 25% by weight non-aqueous solids, and wherein the non-aqueous solids contain about 50 to about 80 weight percent of the diester and about 50 to about 20 weight percent of the surfactant emulsifier. 2. Aqueous emulsion according to claim 1, characterized in that the acids belong to the class of fatty acids. 3. Aqueous emulsion according to claim 1, characterized in that the diesters are taken from the class which hydroxypivalylhydroxypivalate diesterate, Hydroxypivalylhydroxypival atdiol eat, Hydroxypivalylhydroxypivalatdipalmitat, Hydroxyp ivalylhydroxyp ival at dil aureate and hydroxypivalyl-hydroxypivalate diheptanoate includes. 4. Aqueous emulsion according to claim 2, characterized in that the diesters are taken from the class which hydroxypivalylhydroxypivalate distearate, dioleate, dipalmitate, dilaurate and diheptanoate. 5. Aqueous emulsion according to claim 1, characterized in that the surface-active emulsifier is taken from the classes which glycerol monooleate, ethoxylated (about 25 mol) castor oil, polyethylene glycol 400 dilaurate, sulfated Glycerin trioleate, ethoxylated tridecyl alcohol and the polyglycerin esters decaglycerin tetraoleate, Triethanolamine oleate, decaglycerol dilaurate, decaglycerol dicaprylate and ethoxylated Comprises (8 to 11 moles) nonylphenol. 6. Aqueous emulsion according to claim 2, characterized in that the emulsifier is taken from the class containing glycerol monooleate, ethoxylated (about 25 mol) castor oil, polyethylene glycol 400 dilaurate, sulfated glycerol trioleate, ethoxylated tridecyl alcohol and the polyglycerol ester decaglycerol tetraoleate, Triethanolamine oleate, decaglycerol dilaurate, decaglycerol dicaprylate and ethoxylated Comprises (8 to 11 moles) nonylphenol. 7. Aqueous emulsion according to claim 3, characterized in that the emulsifier is taken from the class containing glycerol monooleate, ethoxylated (about 25 mol) castor oil, polyethylene glycol 400 dilaurate, sulfated glycerol trioleate, ethoxylated tridecyl alcohol and the polyglycerol ester decaglycerol tetraoleate, Triethanolamine oleate, decaglycerol dilaurate, decaglycerol dicaprylate and ethoxylated Comprises (8 to 11 moles) nonylphenol. 8. Aqueous emulsion according to claim 4, characterized in that the emulsifier is taken from the class containing glycerol monooleate, ethoxylated (about 25 mol) castor oil, polyethylene glycol 400 dilaurate, sulfated glycerol trioleate, ethoxylated tridecyl alcohol and the polyglycerol ester decaglycerol tetraoleate, Triethanolamine oleate, decaglycerol dilaurate, decaglycerol dicaprylate and ethoxylated (8 to 11 ol) nonylphenol comprises. 9. Aqueous emulsion. for application to staple fibers in a discontinuous work step, characterized by a hydroxypivalylhydroxypivalate diester according to the formula wherein R1 and R2 are taken from the group comprising alkyl and alkylene monocarboxylic acids having 2 to 24 carbon atoms, a surface active emulsifier compatible with the diester, and water, the emulsion containing from about 0.4 to about 2 wt. 96 non-aqueous solids, and wherein the non-aqueous solids contain from about 50 to about 80 percent by weight of the diester and from about 50 to about 20 percent by weight of the surfactant emulsifier. 10. Aqueous emulsion according to claim 9, characterized in that the acids are taken from the class of fatty acids. 11. Aqueous emulsion according to claim 9, characterized in that d e diesters are taken from the class which hydroxypivalylhydroxypivalate distearate, dioleate, dipalmitate, dilaurate and diheptanoate. 12. Aqueous emulsion according to claim 10, characterized in that the diesters are taken from the class which hydroxypivalylhydroxypivalate distearate, dioleate, dipalmitate, dilaurate and diheptanoate. 13. Aqueous emulsion according to claim 9, characterized in that the emulsifier is taken from the class containing glycerol monooleate, ethoxylated (about 25 mol) castor oil, polyethylene glycol 400 dilaurate, sulfated glycerol trioleate, ethoxylated Tridecyl alcohol and the polyglycerol esters decaglycerol tetraoleate, triethanolamine oleate, Decaglycerol dilaurate, decaglycerol dicaprylate and ethoxylated (8 to 11 moles) nonylphenol includes, 14. Aqueous emulsion according to claim 10, characterized in that the Emulsifier is taken from the class which glycerol monooleate, ethoxylated (approx 25 mol) castor oil, polyethylene glycol 400 dilaurate, sulfated glycerol trioleate, ethoxylated tridecyl alcohol and the polyglycerol ester decaglycerol tetraoleate, Triethanolamine oleate, decaglycerol dilaurate, decaglycerol dicaprylate and ethoxylated (8 to 11 moles) nonylphenyl. 15. Aqueous emulsion according to claim 11, characterized in that the emulsifier is taken from the class containing glycerol monooleate, ethoxylated (about 25 mol) castor oil, polyethylene glycol 400 dilaurate, sulfated glycerol trioleate, ethoxylated tridecyl alcohol and the polyglycerol ester decaglycerol tetraoleate, Triethanolamine oleate, decaglycerol dilaurate, decaglycerol dicaprylate and ethoxylated Comprises (8 to 11 moles) nonylphenol. 16. Aqueous emulsion according to claim 12, characterized in that the emulsifier is taken from the class containing glycerol monooleate, ethoxylated (about 25 mol) castor oil, polyethylene glycol 400 dilaurate, sulfated glycerol trioleate, ethoxylated tridecyl alcohol and the polyglycerol ester decaglycerol tetraoleate, Triethanolamine oleate, decaglycerol dilaurate, decaglycerol dicaprylate and ethoxylated Comprises (8 to 11 moles) nonylphenol.