KR101878784B1 - A Hybrid Dipped Cord Having Excellent Fatigue Resistance and Radial Tire Using the Same - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tire cord and a radial pneumatic tire, and more particularly, to a tire cord and a radial pneumatic tire wherein a polyketone yarn is made of a polyethylene terephthalate yarn and a single polyketone yarn, And more preferably 5 to 100 mm / m longer than the terephthalate yarn. The hybrid dipped cord according to the present invention has an excellent fatigue resistance of 85% or more. In the tensile test, the initial strain causes a low modulus by the polyethylene terephthalate, and a high modulus is generated from the section where the polyketone begins to receive the force Therefore, there is an advantage that the tire can be easily manufactured because the green tire tends to be deformed when the green tire is inflated into the bladder in the mold.

Description

[0001] The present invention relates to a hybrid dipped cord having excellent fatigue resistance and a radial pneumatic tire using the same,

The present invention relates to a method of producing a hybrid dipped cord having excellent fatigue resistance using polyethylene terephthalate and polyketone yarn, and a radial pneumatic tire to which the method is applied.

In recent years, the performance of tires has been continuously improved according to improvement of the road environment and the performance of the vehicle. Especially, as the weight of the vehicle increases and the limit speed increases, safety is more importantly considered as a quality factor of the tire. The safety standards of tires are also being changed in accordance with the increasing demand for safety of tires. Researches on methods for imparting safety of tires in the tire industry are also being actively conducted.

Generally, a tire cord is formed by twisting a yarn of the same kind to make a raw cord, dipping it in a dipping solution, and then heat-treating the same to form a dip cord. The hybrid cord is made of different kinds of yarns Is a code made by twisting two kinds of yarns in order to express the yarn.

On the other hand, in the step of imparting twist to the yarn, when the number of kinks is increased, the strength is lowered, the middle / consecutive is increased, and the fatigue is increasing. When the number of kinks is lowered, the strength is higher, . ≪ / RTI >

The twist is accomplished by a step (Ply) giving the lead to each yarn, followed by a step of twisting the yarns together. Leading the ply is to prevent double twisting during cabling.

In the case of producing the raw cord by twisting the same kind of yarn, it is common that the conditions of the inter-ply twist are the same, but in the case of the hybrid code, the properties of the raw code and further the dipped cord are adjusted .

In the hybrid cord, conventionally, there has been a method of giving twist numbers of different types of yarns differently to each other in the method of varying the twist conditions for the different types of yarns. That is, a fiber yarn having a high modulus and a low yarn endurance (for example, polyketone yarn) is given less than the number of twisted yarns when the yarn is fed, and a yarn having a low modulus and a high yarn endurance (for example, nylon yarn) If the number of twists is given, twist is given in the twist direction of the upper yarn since the lower twist yarn is less than the upper twist yarn after the upper side of the fiber yarn. However, since the lower twist yarns of the lower- The initial modulus of the polymer is lowered. However, such a technique can be applied only to a spinner (DRT, RT) to which a posterior edge is given, and can not be used in a direct barrel in which a vertical bar is simultaneously generated.

U.S. Patent No. 6601378

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a method of manufacturing a hybrid cord using a polyethylene terephthalate yarn and a polyketone yarn in a direct cabin In the step of stretching the raw cord, the polyketone yarn is inserted longer than the polyethylene terephthalate yarn to produce a twisted yarn, and the twisted yarn is folded to give a twisted yarn, thereby producing a raw cord having improved fatigue resistance Method.

Another object of the present invention is to provide a carcass ply or cap ply layer of an air inlet radial tire having a certain degree of fatigue produced by dipping a raw cord using the polyethylene terephthalate yarn and polyketone yarn in a dipping solution and then heat- To provide a hybrid dip code.

According to a preferred embodiment of the present invention, when the hybrid cord is formed by combining one raw polyethylene terephthalate yarn and one polyketone yarn and combining the raw cord, the polyketone yarn is prepared in the ratio of polyethylene terephthalate yarn 5 to 100 mm / m.

According to another preferred embodiment of the present invention, when the raw cord is melted, the polyketone yarn is inserted into the polyethylene terephthalate yarn by 5 to 50 mm / m longer than that of the polyethylene terephthalate yarn.

According to another preferred embodiment of the present invention, the hybrid dip code is produced by dipping the raw cord into an adhesive liquid.

According to another preferred embodiment of the present invention, the fatigue resistance of the hybrid dip cord is 80% or more.

According to a preferred embodiment of the present invention, a method of manufacturing a hybrid dipped cord for a radial pneumatic tire comprises the steps of: preparing one polyethylene terephthalate yarn and one polyketone yarn; Adding the single polyketone yarn longer than the polyethylene terephthalate yarn to produce twisted yarns of 200 to 500 TPM yarns each to produce a lower yarn; Folding the twisted yarn in two, and twisting the twisted yarn in a number of 200 to 500 TPM to produce a cord; And dipping the raw cord in a dipping solution followed by heat treatment to produce a dipped cord, wherein the polyketone fiber is 5 to 100 mm / m longer than the polyethylene terephthalate fiber in the raw cord step .

According to another preferred embodiment of the present invention, the fineness of the polyethylene terephthalate yarn and the polyketone yarn are respectively 500 to 3000 denier.

According to a preferred embodiment of the present invention, there is provided a belt comprising: a pair of parallel bead cores; at least one radial carcass layer wound around the bead cores; a belt layer laminated on the outer circumferential side of the carcass layer; A radial pneumatic tire comprising a belt reinforcing layer in the direction comprises a hybrid dipped cord as shown above for a carcass ply or belt layer, and may be used as one or two layers.

In the present invention, since the polyketone yarn is inserted into the polyethylene terephthalate yarn for a long time, the strength is lowered and the mid / yarn height is increased, thereby increasing the fatigue resistance. As a result, the initial strain during the tensile test is lowered by the polyethylene terephthalate yarn And the high modulus can be developed from the section where the polyketone begins to receive the force. Therefore, when the green tire is blown into the bladder inside the mold at the time of vulcanization, It is easy to manufacture. According to the present invention, it is possible to overcome the disadvantage that the polyketone is difficult to deform in a mold with high modulus when the polyketone is used alone, and it is possible to improve the low fatigue resistance and the adhesive strength, which are problems in using polyketone alone , Polyethylene terephthalate or nylon 6 alone, it is possible to manufacture a high-performance tire by improving low modulus and heat resistance.

Fig. 1 is an example schematically showing a structure of a tire for a passenger car produced by using the hybrid dipped cord according to the present invention in a carcass layer or a cap ply layer.

Hereinafter, preferred embodiments of the present invention will be described in detail. The present invention is not limited to the scope of the present invention, but is merely an example, and various modifications can be made without departing from the technical spirit of the present invention.

The method for producing a polyethylene terephthalate tire cord according to the present invention will be described in detail as follows.

First, a polyethylene terephthalate chip having an intrinsic viscosity of 1.0 to 1.15 is melted and extruded while passing through a nozzle to produce a discharged yarn. Here, the polyethylene terephthalate polymer may contain at least 85 mol% of ethylene terephthalate units, but may optionally contain only ethylene terephthalate units.

Optionally, the polyethylene terephthalate may comprise small amounts of units derived from ethylene glycol and terephthalenedicarboxylic acid or derivatives thereof and one or more ester-forming components in copolymer units. Examples of other ester forming components copolymerizable with the polyethylene terephthalate unit include glycols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and the like, and glycols such as terephthalic acid, isophthalic acid, hexahydroterephthalic acid, Dicarboxylic acids such as dicarboxylic acid, dicarboxylic acid, dicarboxylic acid, dicarboxylic acid, dicarboxylic acid, dicarboxylic acid,

The terephthalic acid (TPA) and the ethylene glycol raw material are melt-mixed at a ratio of 2.0 to 2.3 to the polyethylene terephthalate chip thus prepared, and the molten mixture is transesterified and condensed to form a raw chip. Then, the low chip is subjected to solid phase polymerization so as to have an intrinsic viscosity of 1.0 to 1.15 at a temperature of 240 to 260 DEG C and a vacuum. If the intrinsic viscosity of the raw chips is less than 1.0, the intrinsic viscosity of the final drawn yarn is lowered and the processed cord after heat treatment can not exhibit high strength. If the intrinsic viscosity of the chips exceeds 1.15, the radiation tension is excessively increased, The cross section becomes nonuniform, and many filament cuts occur during stretching, resulting in poor workability in stretching.

Alternatively, an antimony compound, preferably antimony trioxide, may be added as a polymerization catalyst in the course of the condensation polymerization reaction so that the residual amount of antimony metal in the final polymer is 180 to 300 ppm. If the residual amount is less than 180 ppm, the polymerization reaction rate is slowed to lower the polymerization efficiency. If the residual amount exceeds 300 ppm, unnecessary antimony metal acts as a foreign substance and the radiation-drawing workability may be lowered. The polyethylene terephthalate chip is melted and extruded while passing through a nozzle to produce a discharged yarn. At this time, the diameter of the nozzle is preferably 1.1 to 1.4 mm.

Thereafter, the discharged yarn is quenched and solidified by passing through a cooling zone. At this time, if necessary, a heating device of a certain length is provided in a distance from the nozzle to the starting point of the cooling zone, that is, the length (L) of the hood. This zone is referred to as the delayed cooling zone or heating zone, which has a length of 50 to 250 mm and a temperature of 250 to 400 ° C (air contact surface temperature).

In the cooling zone, an open quenching method, a circular closed quenching method, a radial outflow quenching method, and a radial in flow quenching ) Method, but the present invention is not limited thereto.

At this time, the temperature of the cooling air injected for quenching in the cooling zone is adjusted to 20 to 50 캜. Such quenching using the sudden temperature difference between the hood and the cooling zone is intended to increase the solidification point and the radiation tension of the radiated polymer to increase the orientation of the undrawn yarn and the formation of the connection chain between the crystal and the crystal.

Thereafter, the solidified yarn passing through the cooling zone can be oiled at 0.5 to 1.2% by weight with respect to the discharged yarn by reducing the coefficient of friction between the tweezers and applying an emulsion applying apparatus having excellent stretchability and thermal efficiency.

And the oiled discharged yarn is radiated to form an unstretched yarn. In this case, the spinning draft is preferably 1500 to 1800, and the spinning speed is preferably 3,000 to 3,200 m / min. When spinning at the spinning draft and spinning speed in the above range, excellent strength of the yarn can be secured even at a low stretching ratio.

If the radiation draft is less than 1,500 or the spinning speed is less than 3,000 m / min, the uniformity of the cross section of the yarn is deteriorated to deteriorate the drawing workability and the degree of orientation of the unstretched yarn is decreased to degrade the crystallization degree. , The thermal stability is lowered, the strength of the tire cord is lowered, and the shape stability may be lowered when the high stretching is performed to improve the strength and modulus. When the breaking strength is higher than 3,200 m / min, The strength and elongation workability are deteriorated.

If the degree of orientation of the undrawn yarn is less than 0.06, the crystallinity and the denseness of the crystal can not be increased in the microstructure of the yarn. If the degree of orientation is less than 0.80, the drawability is deteriorated.

Thereafter, the non-drawn yarn is passed through a stretching roller to be multi-step stretched to produce a yarn. The yarn passed through the first stretching roller is stretched while passing through a series of stretching rollers by a spin draw method to form a yarn. In the drawing step, the non-drawn filaments may be multi-filament drawn, and the temperature of each of the drawn filaments is preferably higher than the glass transition temperature of the unstretched filament and lower than 95 캜, but the final filament roller temperature is preferably 200 to 250 캜. If the temperature of the last stretching roller is lower than 200 ° C, the crystallinity and the size of crystals do not increase in the stretching process, and the strength and thermal stability of the yarn are not exhibited, so that the morphological stability is deteriorated at high temperature. There is a problem that the microstructure of the yarn becomes uneven and the strength of the yarn is lowered. At this time, the winding speed of the drawn yarn is preferably 5,800 m / min or more. If the winding speed is less than 5,800 m / min, the productivity may be deteriorated.

Further, it is preferable that the total yarn m of the yarn formed by winding as described above is 2.14 to 2.22. When the stretching ratio is less than 2.14, the productivity is lowered and the strength of the yarn and the cord is lowered. When the stretching ratio exceeds 2.22, crystallization of the oriented non-gelling portion is increased, It is not preferable because the molecular chain of the noncrystalline chain is broken and the uniformity of the molecular chain is lowered and the strength utilization ratio may be lowered.

Hereinafter, the production method of polyketone yarn used in the present invention will be described in detail.

First, the polymerization method of the polyketone used in the present invention is as follows.

One or more olefinically unsaturated compounds (simply referred to as " A "), wherein the monomer units are alternating, and thus the polymer is composed of units of the formula - (CO) -A'- wherein A 'represents the monomer units derived from the applied monomer A ) And a high molecular weight linear polymer of carbon monoxide can be prepared by contacting monomers with a solution of a palladium-containing catalyst composition in a dilute solution in which the polymer does not dissolve or actually dissolve. During the polymerization process, the polymer is obtained in the form of a suspension in a diluent. The polymer preparation is carried out primarily batchwise.

The batchwise preparation of the polymer is typically carried out by introducing the catalyst into a reactor containing the diluent and the monomer and having the desired temperature and pressure. As the polymerization proceeds, the pressure drops, the concentration of the polymer in the diluent increases, and the viscosity of the suspension increases. The polymerization is continued until the viscosity of the suspension reaches a high value, for example, to the point where difficulties associated with heat removal occur. During batch polymer preparation, monomers can be added to the reactor during polymerization, if desired, to maintain the temperature as well as the pressure constant.

In the present invention, not only methanol, dichloromethane or nitromethane, which has been conventionally used for producing polyketones, but also mixed solvents comprising acetic acid and water, ethanol, propanol, and isopropanol can be used as the liquid medium.

When a mixed solvent of acetic acid and water is used as a liquid medium, when the concentration of water is less than 10% by volume, the effect of the catalyst is less affected. When the concentration of water is 10% by volume or more, the catalytic activity increases sharply. On the other hand, when the concentration of water exceeds 30% by volume, the catalytic activity tends to decrease. In the present invention, it is preferable to use a mixed solvent comprising 70 to 90% by volume of acetic acid and 30 to 10% by volume of water as the liquid medium.

In the present invention, the organometallic complex catalyst comprises (a) a Group 9, Group 10 or Group 11 transition metal compound of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition, 1989), (b) And (c) an anion of an acid having a pKa of 4 or less.

Examples of the Group 9 transition metal compound in the ninth, tenth, or eleventh group transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamates, and sulfonates, Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate and ruthenium trifluoromethanesulfonate.

Examples of the Group 10 transition metal compounds include complexes of nickel or palladium, carbonates, phosphates, carbamates, and sulfonates. Specific examples thereof include nickel acetate, nickel acetyl acetate, palladium acetate, palladium trifluoroacetate , Palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium and palladium sulfate.

Examples of the Group 11 transition metal compound include a complex of copper and silver, a carbonate, a phosphate, a carbamate, and a sulfonate, and specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, Examples of the trifluoroacetic acid include silver acetyl acetate, trifluoromethanesulfonic acid and the like.

Of these, transition metal compounds (a), which are inexpensive and economically preferable, are nickel and copper compounds, and preferable transition metal compounds (a) in terms of yield and molecular weight of polyketones are palladium compounds, It is most preferable to use palladium acetate.

Examples of ligands (b) having a Group 15 atom include 2,2-bipyridyl, 4,4-dimethyl-2,2-bipyridyl, 2,2- (Diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,3-bis (diphenylphosphino) Bis [di (2-methylphenyl) phosphino] propane, 1,3-bis [di (2-isopropyl) Bis (diphenylphosphino) cyclohexane, 1,2-bis (diphenylphosphino) phosphine, ) Benzene, 1,2-bis [(diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) Bis (diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxyphenyl) ) Phosphino] propane, 2,2-dimethyl-1,3-bis [di (2-methoxyphenyl) Phosphino] propane, and the like.

Among these ligands, preferred ligands (b) having a Group 15 element are phosphorus ligands having an atom of Group 15, and particularly preferred ligands in terms of yield of polyketone are 1,3-bis [di (2- Methoxyphenyl) phosphino] propane and 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, Di (2-methoxyphenyl) phosphino] propane, and it is safe in that it does not require an organic solvent. Soluble sodium salts such as 1,3-bis [di (2-methoxy-4-sulfonic acid sodium-phenyl) phosphino] propane, 1,2- ] Methyl] benzene, and 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane are preferred for ease of synthesis and availability in large quantities and economically.

The ligand (b) having a group 15 atom preferred in the present invention, which focuses on the intrinsic viscosity and catalytic activity of the polyketone, is 1,3-bis- [di (2-methoxyphenyl) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine), and more preferably 1,3-bis Bis (methylene)) bis (bis (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5- ) Phosphine) is better.

[Chemical Formula 1]

Bis (bis (2-methoxyphenyl) phosphine) bis ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Activity equivalent to that of 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, which is known to exhibit the highest activity among polymerization catalysts The structure is simpler and has a lower molecular weight. As a result, the present invention has been able to provide a novel polyketone polymerization catalyst having the highest activity as a polyketone polymerization catalyst of the present invention, while further reducing its manufacturing cost and cost. A method for producing a ligand for a polyketone polymerization catalyst is as follows. ((2,2-dimethyl) -2,3-dioxolane was obtained by using bis (2-methoxyphenyl) phosphine, 5,5-bis (bromomethyl) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) is obtained by reacting a bis (methylene) . The process for preparing a ligand for a polyketone polymerization catalyst according to the present invention is a process for producing a ligand for a polyketone polymerization catalyst which comprises reacting 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially synthesized in a large amount.

In a preferred embodiment, the process for preparing a ligand for a polyketone polymerization catalyst of the present invention comprises: (a) introducing bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) into a reaction vessel under nitrogen atmosphere, Adding sodium and stirring; (b) adding 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the resulting mixture, followed by stirring and reacting; (c) adding methanol and stirring after completion of the reaction; (d) adding toluene and water, separating the layers, washing the oil layer with water, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And (e) the residue was recrystallized from methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5- diyl) bis (methylene)) bis (bis (2- methoxyphenyl) And a step of acquiring the image data.

The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) varies depending on the kind of the ethylenically unsaturated compound to be selected and other polymerization conditions. But is usually 0.01 to 100 mmol, preferably 0.01 to 10 mmol, per liter of the reaction volume of the reaction zone. The capacity of the reaction zone means the liquid phase capacity of the reactor.

Examples of the anion (c) of the acid having a pKa of 4 or less include an anion of an organic acid having a pKa of 4 or less, such as trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, or m-toluenesulfonic acid; Anions of inorganic acids having a pKa of 4 or less such as perchloric acid, sulfuric acid, nitric acid, phosphoric acid, heteropoly acid, tetrafluoroboric acid, hexafluorophosphoric acid, and fluorosilicic acid; And anions of boron compounds such as trispentafluorophenylborane, trisphenylcarbenium tetrakis (pentafluorophenyl) borate, and N, N-dimethylarinium tetrakis (pentafluorophenyl) borate.

Particularly, the anion (c) of the acid having a pKa of 4 or less, which is preferable in the present invention, is p-toluenesulfonic acid, which has high catalytic activity when used with a mixed solvent of acetic acid and water as a liquid medium, It becomes possible to produce a polyketone having a high intrinsic viscosity suitable for the polyolefin.

The molar ratio of (a) the ninth, tenth or eleventh group transition metal compound and (b) the ligand having an element of Group 15 element is 0.1 to 20 moles of the Group 15 element of the ligand per 1 mole of the palladium element, Is preferably added in a proportion of 0.1 to 10 moles, more preferably 0.1 to 5 moles. When the ligand is added in an amount of less than 0.1 mole based on the palladium element, the binding force between the ligand and the transition metal decreases, accelerating the desorption of the palladium during the reaction, and causing the reaction to terminate quickly. When the ligand exceeds 20 moles When added, the ligand is shielded from the polymerization reaction by the organometallic complex catalyst, so that the reaction rate is remarkably lowered.

The molar ratio of (a) the anion of the ninth, tenth or eleventh group transition metal compound and (c) the anion of the acid having a pKa of 4 or less is 0.1 to 20 mol, preferably 0.1 to 10 mol, Mol, and more preferably 0.1 to 5 mol. When the acid is added in an amount of less than 0.1 mol based on the palladium element, the effect of improving the intrinsic viscosity of the polyketone is unsatisfactory. If the acid is added in an amount exceeding 20 mol based on the palladium element, the catalytic activity for producing the polyketone tends to be rather reduced. not.

In the present invention, the reaction gas to be reacted with the catalyst for producing polyketone is preferably a mixture of carbon monoxide and an ethylenically unsaturated compound.

Examples of the ethylenically unsaturated compound copolymerized with carbon monoxide in the present invention include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, - C2 to C20 alpha-olefins including tetradecene, 1-hexadecene, vinylcyclohexane; Styrene, C2-C20 alkenyl aromatic compounds including? -Methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclo undecene, pentacyclopentadecene, pentacyclohexadecene, C4 to C40 cyclic olefins including cyclododecene; C2 to C10 halogenated vinyls containing vinyl chloride; Ethyl acrylate, methyl acrylate, and mixtures of two or more selected from among C3 to C30 acrylic esters. These ethylenically unsaturated compounds are used singly or as a mixture of plural kinds. Of these, preferred ethylenically unsaturated compounds are? -Olefins, more preferably? -Olefins having 2 to 4 carbon atoms, and most preferably ethylene.

In the production of polyketones, the charging ratio of the carbon monoxide and the ethylenic unsaturated compound is generally 1: 1. In the present invention, the charging ratio of the carbon monoxide and the ethylenic unsaturated compound is adjusted to a molar ratio of 1:10 to 10: 1 . As in the present invention, when an ethylenically unsaturated compound and carbon monoxide are mixed in an appropriate ratio, they are effective also in terms of catalytic activity, and the intrinsic viscosity improvement effect of the produced polyketone can be simultaneously achieved. When carbon monoxide or ethylene is added in an amount of less than 5 mol% or more than 95 mol%, the reactivity is poor and the physical properties of the produced polyketone may be deteriorated.

On the other hand, the polyketone copolymer used as the fiber may be composed of ethylene, propylene and carbon monoxide. The larger the molar ratio of propylene is, the more unsuitable as a tire cord, and the molar ratio of ethylene to propylene is preferably 100: 0 to 90:10 .

On the other hand, it is preferable that the molecular weight distribution of the polyketone is 3.0 to 3.5. When the molecular weight distribution is less than 3.0, the polymerization yield is lowered. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst is increased or when the polymerization temperature is 100 ° C or higher, the molecular weight distribution becomes larger.

Particularly preferred are polyketone polymers having a number average molecular weight of from 100 to 200,000, especially from 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer are determined according to the molecular weight, depending on whether the polymer is a copolymer or a terpolymer and, in the case of a terpolymer, the properties of the second hydrocarbon part. The melting point of the total of the polymers used in the present invention is 175 ° C to 300 ° C, and generally 210 ° C to 270 ° C. The intrinsic viscosity (LVN) of the polymer measured by HFIP (Hexafluoroisopropylalcohol) at 60 DEG C using a standard tubular viscosity measuring apparatus is 0.5 dl / g to 10 dl / g, and preferably 5.0 dl / g to 7.0 dl / g . At this time, when the intrinsic viscosity of the polyketone polymer is less than 5.0, the mechanical strength is lowered in production of the fiber, and when it exceeds 7.0, the workability is lowered.

The polyketone tire cord made of the polyketone preferably has a tensile strength lowering rate of 20% or less after being treated at 150 ° C for 30 minutes in order to test a high temperature occurring during traveling, 20 g / d is preferable.

The production method of the polyketone fiber of the present invention will be described.

First, the solution extruded from the spinning nozzle passes through an air gap in a vertical direction and solidifies in a coagulating bath. At this time, in order to obtain a dense and uniform fiber, the air gap is radiated within a range of about 1 to 300 mm in order to give a smooth cooling effect.

Thereafter, the filament passing through the coagulation bath passes through the water bath. At this time, the temperature of the coagulation bath and the water bath is maintained at about 0 to 80 ° C to prevent deterioration of physical properties due to the formation of pores in the fiber structure due to rapid desolvation

The fibers having passed through the water-washing tank were subjected to acid washing in an aqueous solution containing the acid, passed through a second water-washing bath to remove the acid, passed through a dryer, and then emulsified in an emulsion- do.

In addition, in order to improve the flatness and improve the property of the housing, it passed the interlace nozzle. At this time, the air pressure was supplied at 0.5 to 4.0 kg / cm 2, and the number of entanglement per filament was 2 to 40.

Thereafter, the filament yarn passed through the interlace nozzle is dried while passing through the drying apparatus. In this case, the drying temperature and the drying method have a great influence on the post-processing and physical properties of the filament.

Then, the filament passing through the drying device is finally wound in the winder through the secondary emulsion treatment device.

Further, the stretching process in the polyketone fibers of the present invention is very important for improvement of high strength and water resistance. In the drawing method, hot air heating method and roller heating method are used, but since the filament is in contact with the roller surface in the roller heating method, the fiber surface is likely to be damaged, so that hot air heating method is more effective in manufacturing high strength polyketone fiber. However, the inventors of the present invention have found that by applying a heat-resistant stabilizer while applying a roller heating method, particularly a hot-roll drying method, and performing a stretching process in the course of washing the fibers in the range of 1.1 to 2.0 times, preferably 1.2 to 1.6 times, more preferably 1.4 times High strength multifilament could be obtained. At this time, the strength of the fiber at drawing of less than 1.0 times is lowered, and the workability at the time of drawing of more than 2.0 times is lowered.

On the other hand, as the solvent for dissolving the polyketone, it is preferable to use an aqueous solution containing at least one metal salt selected from the group consisting of zinc salts, calcium salts, lithium salts, thiocyanates and iron salts. Specific examples of the zinc salt include zinc bromide, zinc chloride and zinc iodide. Examples of the calcium salt include calcium bromide, calcium chloride and calcium iodide. Examples of the lithium salt include lithium bromide, lithium chloride, lithium iodide . Examples of the iron salts include iron bromide and iron iodide. Among these metal salts, it is particularly preferable to use at least one selected from the group consisting of zinc bromide, calcium bromide, lithium bromide and iron bromide in terms of the solubility of the raw material polyketone and the homogeneity of the polyketone solution.

The concentration of the metal salt in the metal salt aqueous solution of the present invention is preferably 30 to 80% by weight. If the concentration of the metal salt is less than 30% by weight, the solubility is lowered. If the concentration of the metal salt is 80 or more, the cost for concentration increases, which is disadvantageous in terms of economy. As the solvent for dissolving the metal salt, water, methanol, ethanol and the like can be used. In particular, water is used in the present invention because it is economical and advantageous in solvent recovery.

In order to obtain polyketone fibers having high strength and excellent fatigue resistance and dimensional stability, an aqueous solution containing zinc bromide is preferable, and the composition ratio of zinc bromide in the metal salt is an important factor. For example, in an aqueous solution containing only zinc bromide and calcium bromide, the weight ratio of zinc bromide to calcium bromide is 80/20 to 50/50, more preferably 80/20 to 60/40. Further, in the aqueous solution containing zinc bromide, calcium bromide and lithium bromide, the total weight ratio of zinc bromide, calcium bromide and lithium bromide is 80/20 to 50/50, more preferably 80/20 to 60/40, , The weight ratio of calcium bromide to lithium bromide is 40/60 to 90/10, preferably 60/40 to 85/15.

The production method of the polyketone solution is not particularly limited, but an example of a preferable production method will be described below.

The metal salt aqueous solution maintained at 20 to 40 캜 is defoamed at a pressure of 200 torr or less, the polyketone polymer is heated to 60 to 100 캜 under a vacuum of 200 torr or less, and stirred for 0.5 to 10 hours to prepare a sufficiently dissolved homogeneous dope .

In the present invention, the polyketone polymer may be mixed with other polymer materials or additives. Examples of the polymer material include polyvinyl alcohol, carboxymethyl polyketone, and polyethylene glycol. Examples of additives include viscosity improvers, titanium dioxide, silica dioxide, carbon, and ammonium chloride.

Hereinafter, a method of producing a polyketone fiber including spinning, washing, drying and stretching the homogeneous polyketone solution of the present invention will be described in more detail. However, the polyketone fibers claimed in the present invention are not limited by the following process.

The spinning process of the method according to the present invention will be described in more detail. An orifice having a diameter of 100 to 500 μm and a length of 100 to 1500 μm, wherein the ratio of the diameter to the length (L / D) is 1 to 3 to 8 times, The spinning stock solution is extruded and spun through a spinning nozzle containing a plurality of orifices having a distance between orifices of 1.0 to 5.0 mm so that the fiber spinning solution passes through the air layer to reach the coagulation bath and then coagulated to obtain a multifilament do.

The shape of the spinning nozzle used is usually circular, and the nozzle diameter is 50 to 200 mm, more preferably 80 to 130 mm. When the nozzle diameter is less than 50 mm, the distance between the orifices is too short, so that the adhesion may occur before the discharged solution solidifies. If the nozzle diameter is too large, peripheral devices such as spinning packs and nozzles become large, If the diameter of the nozzle orifice is less than 100 탆, a large number of yarn breaks occur at the time of spinning, which adversely affects the spinnability. If the diameter exceeds 500 탆, the coagulation speed of the solution in the spinning coagulating bath is slow, Solvent removal and washing become difficult.

The number of orifices is set to 100 to 2,200, more preferably 300 to 1,400, in consideration of the orifice interval for uniform cooling of the solution, taking into account the fact that it is for industrial use, particularly for tire cords.

If the number of orifices is less than 100, the fineness of each filament becomes thick and the solvent can not sufficiently escape within a short time, so that the coagulation and flushing can not be completely performed. If the number of orifices is more than 2,200, adjacent filaments are likely to be formed in close contact with each other in the air layer section, and the stability of each filament after spinning is deteriorated. In addition to the deterioration of physical properties, .

When the fiber stock solution passing through the spinning nozzle coagulates in the upper coagulating solution, the larger the diameter of the fluid becomes, the larger the difference in the coagulation speed between the surface and the inside becomes, and it becomes difficult to obtain a dense and uniform tissue fiber. Therefore, when the polyketone solution is spun, even if the same discharge amount is maintained, the spun fibers having a smaller diameter can be obtained in the coagulating solution while maintaining an appropriate air layer.

The air layer is preferably 5 to 50 mm, more preferably 10 to 20 mm. It is difficult to increase the spinning speed because the too short air layer distance increases the micropore generation rate due to the rapid surface layer coagulation and desolvation process, and it is difficult to increase the spinning speed. On the other hand, the too long air layer distance is affected by the adhesion of the filament, It is difficult to maintain process stability.

The composition of the coagulating bath used in the present invention is such that the concentration of the metal salt aqueous solution is 1 to 20% by weight. The coagulating bath temperature is maintained at -10 to 60 캜, more preferably -5 to 20 캜. In the coagulation bath, when the filament passes through the coagulation bath of the multifilament, when the spinning speed is increased by 500 m / min or more, the coagulation of the coagulating solution becomes severe due to the friction between the filament and coagulating liquid. In order to improve the productivity by increasing the excellent physical properties and the spinning speed through the stretching orientation, such a phenomenon is a factor that hinders the process stability, so that it is necessary to minimize such a phenomenon.

In the present invention, the coagulating bath is characterized by a temperature of -10 to 40 ° C and a metal salt concentration of 1 to 30% by weight, and the water bath is preferably at a temperature of 0 to 40 ° C and a metal salt concentration of 1 to 30% The acid washing bath preferably has a temperature of 0 to 40 캜 and an acid concentration of 0.5 to 2% by weight, and the secondary washing bath for acid removal is maintained at a temperature of 30 to 70 캜.

Also, in the present invention, the temperature of the dryer is 100 ° C or higher, preferably 200 ° C or higher, and the emulsion, heat-resistant agent, antioxidant or stabilizer is added to the fiber passed through the dryer.

Further, the stretching process in the polyketone fibers of the present invention is very important for improvement of high strength and water resistance.

The drawing process and the drying method will be described.

The present invention provides a high-strength fiber by securing the heat stability of the polyketone during wet spinning and by directly drying the fiber. In the conventional spinning process, the maximum strength is 13 g / d even at the time of germination drying and optimization of the stretching temperature. However, the present invention optimizes the heating method and the temperature profile of the drying method to form a dense structure by fusion- As a result, the draw ratio and the strength are improved. Further, in order to prevent thermal deterioration of the polyketone at the time of heating, the stretching magnification and strength are improved by a process including a heat stabilizer during drying and stretching.

Polyketone fibers have oxidation or degradation mechanisms at high temperatures. As a radical oxidation mechanism, polyketone releases carbon dioxide and oxidative degradation occurs when exposed to oxygen at temperatures above 90 ° C. In addition, due to the radical deterioration mechanism, when the polyketone is exposed to a high temperature of 200 ° C or more, carbon monoxide and ethylene are released and thermal degradation occurs. A heat-resistant stabilizer is used to prevent oxidation and deterioration of the polyketone at such a high temperature. As the heat-resistant stabilizer, both of antioxidants capable of preventing radical oxidation and deterioration can be used.

Preferably, phenolic heat stabilizers are used, and one or more heat stabilizers may be used alone or in combination. Oxidation and deterioration prevention mechanisms prevent radicals by radicals by capturing radicals with heat stabilizers (alkyl radicals) generated by heat or ultraviolet rays (see FIG. 1). The heat stabilizer may be used before drying or before stretching, and the immersion or application method may be used alone or in combination. Specifically, in an embodiment of the present invention, 0.1% of a solution of a phenolic heat stabilizer obtained by mixing a phenolic heat stabilizer with a methanol solvent in a pre-drying step and a stretching step is applied in a pre-drying step and a drawing step, Of the heat stabilizer was 250 ppm, but after the drying and the stretching step, 25 ppm remained. The heat stabilizer should be used in an appropriate amount depending on the process. If the heat stabilizer is large, the workability is poor. If the heat stabilizer is small, the heat stabilization effect is not sufficient. The heat stabilizer may be used in one-pot or two-pot or more.

Meanwhile, in order to increase the strength of the fiber, the present invention uses a direct drying method of a hot roller drying method, rather than an indirect drying method of a hot air drying method. In the conventional hot air drying method, a hot air drying method was used at a temperature of 180 ° C. for a residence time of about 3 minutes and 30 seconds. This has the effect of achieving uniform drying and improving the adhesion, but it is difficult to generate fusion, loops, and static electricity, and it is difficult to generate a fusion structure. The present invention uses a hot roll drying method at a temperature of 220 to 230 DEG C for a residence time of about 1 minute and 30 seconds. When such a drying method is used, there is no entanglement, less static electricity is generated, and a fine structure is formed due to the formation of a fusion structure, which is easy to apply for commercialization.

In addition, the present invention is subjected to a stretching process in which the fibers are stretched 15 to 18 times. For stretching the polyketone fibers, stretching is carried out in one or more stages. In the case of multi-stage stretching, it is preferable to perform the temperature-raising stretching in which the stretching temperature gradually increases with an increase in the stretching magnification. Specifically, the stretching process is performed at a temperature of 240 to 270 ° C, and the residence time is within about 1 minute and 30 seconds, and the first and second stages are performed. Stretching is carried out from step 1 to step 7, second step to step 2.5, and step 2 is stepwise stretching in a 3 step form. After the first stage, the elongation of the polyketone fibers is 10% and the strength is 8 g / d. After the second stage, the elongation is about 5.2%, and the strength of the polyketone fibers is 20 g / d.

In addition, since the polyketone is thermally deteriorated at a high temperature due to the drying and stretching process as described above, a heat stabilizer is added. It is applied before drying or before stretching. In the present invention, both raw or dip can be used. In general, when the two-dip or more is performed, the elongation of the fiber is decreased independently of the increase in the strength, but in the case of the hot-roll drying method according to the present invention, there is little decrease in elongation.

The multifilament produced by the method according to the present invention is a polyketone multifilament with a total denier range of 500 to 3,500 and a breaking load of 6.0 to 40.0 kg. The multifilament is composed of 100 to 2,200 individual filaments having a fineness of 0.5 to 8.0 denier, wherein the multifilament has a strength of 5.0 to 30 g / d and an elongation of 3 to 10% Can be advantageously used as a code.

The fiber density of the monofilament is 1.295 to 1.310 g / cm < 3 > by the hot-roll drying method of the present invention and the process of adding the heat stabilizer. As a result, the initial modulus value of the polyketone monofilament prepared by the above process is 200 g / , Elongation at 10.0 g / d is 2.5 to 3.5%, and elongation of at least 0.5% at 19.0 g / d or more.

In the present invention, in the production of a hybrid cord using the polyethylene terephthalate yarn and the polyketone yarn, a step of imparting a kite to the cord as a pre-stage of dip cord production (twisting process) is performed.

The polyethylene terephthalate yarn and the polyketone yarn manufactured by the above method will be described in detail with reference to the drawing process of the present invention in which one yarn of each wound yarn is twisted by a direct twisted yarn in which both the twisted yarn and the twin yarn are simultaneously wound, '. The raw cord is made by adding Ply Twist to polyethylene terephthalate and polyketone yarns for tire cords followed by joining by applying cable twist. Generally, both the upper and lower margins apply the same softener. In the twisting process, which is important in the present invention, the polyketone yarn is injected at a rate of 5 to 100 mm / m longer than that of the polyethylene terephthalate yarn at the time of applying the bottom yarn for producing the raw cord.

A method of producing a hybrid dipped cord excellent in fatigue resistance according to the present invention comprises the steps of: preparing one polyethylene terephthalate yarn and one polyketone yarn; Adding the single polyketone yarn to the polyethylene terephthalate yarn at a rate of 5 to 100 mm / m and applying a twist to each of the 200 to 500 TPM yarns to produce a twisted yarn; Folding the twisted yarn in two, and twisting the twisted yarn in a number of 200 to 500 TPM to produce a cord; And dipping the raw cord in a dipping solution followed by heat treatment to produce a dipped cord; .

Generally, when the twist is high, the strength decreases, and the midline and the twist tend to increase. My fatigue also shows a tendency to improve with increasing kinks. The hybrid tire cord manufactured according to the present invention was manufactured at 200 to 500 TPM (twist per meter) at the same time. At this time, when the temperature is less than 200/200 TPM, the loss of the cord is reduced and the fatigue resistance tends to be lowered. When the pressure is higher than 500 TPM, the strength drop is large and is not suitable for tire cords.

The fineness of polyethylene terephthalate yarn and polyketone yarn used for twisting yarns is preferably 500 to 3000 denier. Below 500 denier, the strength drop is very large at 500 TPM and above 3000 denier is not preferred because the fatigue is reduced at 200 TPM.

The hybrid cord according to the present invention is characterized in that the polyketone yarn is inserted into the polyethylene terephthalate yarn by 5 to 100 mm / m longer than that of the polyethylene terephthalate yarn. When the load is less than 5 mm, the fatigue is reduced and it is not appropriate. When the load exceeds 100 mm, the strength is decreased, which is not suitable. When the raw cord is melted, the polyketone is more preferably inserted into the polyethylene terephthalate film by 5 to 50 mm / m, and when the raw cord is melted, the polyketone is 10 to 30 mm / m longer than the polyethylene terephthalate It is most preferable to be charged.

It is possible to produce a raw cord in which polyketone yarn is inserted longer than polyethylene terephthalate yarn when the input amount of polyketone yarn having a high initial elongation and low yarn end is high and the input amount of polyethylene terephthalate yarn is shortened.

In the manufacturing method according to the present invention, as the length of the polyketone yarn is increased compared to that of the polyethylene terephthalate yarn, the strength is lowered, and the middle / folding tendency is increased, thereby increasing the fatigue resistance. Especially, in this case, the initial strain in the tensile test causes low modulus by polyethylene terephthalate, and high modulus is expressed from the section where polyketone begins to receive the force.

 On the contrary, as the input amount of polyketone is shorter (longer than that of polyethylene terephthalate), the strength becomes higher and the tendency of mid / turn and fatigue becomes lower as the length of polyketone becomes shorter.

The manufactured 'Raw Cord' is woven using a weaving machine, and the obtained fabric is immersed and cured in the dipping solution to form a 'cord' Dip cord ".

The dipping process of the present invention will be described in more detail. Dipping is accomplished by impregnating the surface of the fiber with a resin layer called RFL (Resorcinol Formalin-Latex). The disadvantage of the fiber for tire cords, .

In the case of using polyethylene terephthalate or polyethylene naphthalate fiber, since the reactor on the surface of the fiber is smaller than that of rayon fiber or nylon fiber, polyethylene terephthalate or polyethylene naphthalate The surface of the phthalate is activated first, followed by an adhesion treatment (2 bath dipping).

In the present invention, an adhesive liquid for bonding a hybrid cord and rubber can be manufactured by the following method. It is to be understood that the following examples are intended only for a better understanding of the present invention and are not intended to limit the scope of the present invention.

29.4 wt% resorcinol 45.6 parts by weight; 255.5 parts by weight of distilled water; 37% formalin 20 parts by weight; And 3.8 parts by weight of 10 wt% sodium hydroxide were prepared and reacted at 25 DEG C for 5 hours with stirring.

 Next, 300 parts by weight of 40% by weight of VP-latex, 129 parts by weight of distilled water and 23.8 parts by weight of 28% ammonia water were added and aged at 25 DEG C for 20 hours to maintain a solid concentration of 19.05%.

A stretch of 0 to 3% is required to adjust the adhesion amount of the adhesive liquid, and preferably 1 to 2% of the elongation can be achieved. If the elongation percentage is too high, the adhesion amount of the adhesive liquid can be adjusted but the yield is reduced and the fatigue resistance is reduced as a result. On the other hand, if the elongation percentage is too low, for example, if it is lowered to less than 0%, there is a problem that it is impossible to control the DPU by penetrating the dipping solution into the polyhexamethylene adipamide cord.

The adhesion amount of the adhesive is preferably 2 to 7% based on the weight of the fibers on a solid basis. After passing through the adhesive solution, the hybrid dip cords are dried at 120-180 占 폚. Dried for 180 seconds to 220 seconds, and dried in a state where the hybrid dipped cord is stretched to about 1 to 2% in the drying process. If the elongation ratio is low, the cords and the cord of the cord increase, which may result in a property that is difficult to apply to the tire cord. On the other hand, if the elongation ratio is more than 3%, the level of the medium is adequate but the turnover may be too small to reduce the fatigue resistance.

After drying, heat treatment is performed at a temperature range of 130 to 260 ° C. The elongation ratio during the heat treatment is maintained between -2 and 3%, and the heat treatment time is suitably between 50 and 90 seconds. If the heat treatment is performed for less than 50 seconds, the reaction time of the adhesive solution is insufficient and the adhesive force is lowered. If the heat treatment is performed for more than 90 seconds, the hardness of the adhesive solution becomes high and the fatigue resistance of the cord may be decreased have.

The hybrid dipped cord produced according to the above-described method is characterized in that its fatigue resistance is 80% or more. When the fatigue strength is less than 80%, the durability of the tire is reduced, which is not preferable.

The hybrid dipped cord manufactured through such a process is used for the manufacture of tires for passenger cars. In the process of inflating a green tire into a bladder in a mold during vulcanization, the polyketone is used alone The deformation is easy to perform as compared with the case where there is difficulty in deformation, so that it is used to facilitate the manufacture of the tire. The hybrid dipped cord manufactured through such a process is applied to tires for passenger cars. It is mainly applied to cap ply and carcass ply and improves low fatigue resistance and adhesion which is a problem when using polyketone alone, It is used to produce high performance tires with excellent fatigue resistance by improving low modulus and heat resistance which are problematic when phthalate is used alone.

1 shows a structure of a tire for a passenger car in which a hybrid dipped cord according to the present invention is applied as a carcass ply or a cap ply.

1, the bead region 35 of the tire 31 becomes an annular bead core 36 which is non-stretchable. The bead core 36 is preferably made of a single or single filament wire wound continuously. In a preferred embodiment, a high strength steel wire having a diameter of 0.95 mm to 1.00 mm forms a 4x4 structure and a 4x5 structure.

In an embodiment of the tire cord according to the present invention the bead region 35 may have a bead filler 37 and the bead filler 37 should have a hardness above a certain level and preferably a Shore A hardness 40 Or more.

According to the present invention, the tire 31 can be reinforced by the belt 38 and the cap ply 39. The belt 38 comprises a cut belt ply 40 consisting of two cords 41 and 42 and the cord 41 of the belt ply 40 is oriented at an angle of about 20 degrees with respect to the circumferential center plane of the tire . One cord 41 of the belt ply 40 may be disposed opposite the direction of the cord 42 of the other belt ply 40 in a direction opposite the circumferential center plane. However, the belt 38 may comprise any number of plys, and may preferably be located in the range of 16 to 24 degrees. The belt 38 serves to provide lateral stiffness to minimize the rise of the tread 33 from the road surface during operation of the tire 31. The cords 41 and 42 of the belt 38 may be made of steel cords and have a 2 + 2 structure, but may be made of any structure. The cap ply 39 and the edge ply 44 are reinforced on the upper portion of the belt 38 so that the cord 45 of the cap ply 39 is reinforced in parallel with the circumferential direction of the tire, And the cord 45 of the cap ply 39 having a large heat-shrinking stress at a high temperature is used. The cord 45 of the cap ply 39 may be manufactured using a hybrid dipped cord made of polyethylene terephthalate yarn produced according to the method of the present invention and polyketone yarn. One layer of cap ply 39 and one layer of edge ply 44 may be used, and preferably one or two layers of cap ply and one or two layers of edge ply may be reinforced.

Reference numerals 32 and 34, which are not described in FIG. 2, denote the carcass layer 32 and the fly-turn 34. And reference numeral 33 denotes a carcass layer reinforcing cord 33. [

Hereinafter, the present invention will be described in more detail with reference to specific examples and comparative examples. However, the present invention is not intended to limit the scope of the present invention. In the following Examples and Comparative Examples, the properties of the hybrid dip cords were evaluated by the following methods.

(a) Hybrid dip cord strength (kgf) and moderate elongation (%)

Dried at 107 DEG C for 2 hours, and then measured at a sample length of 250 mm and a tensile speed of 300 m / min using a low-speed stretching type tester manufactured by Instron. The elongation at specific load was measured at a load of 4.5 kg.

(b) Dry Heat Shrinkage (%, Shrinkage)

The ratio of the length (L0) measured at a constant load of 0.05 g / d and the length (L1) after treatment at a constant load of 0.05 g / d for 30 minutes at 150 ° C To show dry heat shrinkage ratio.

S (%) = (L0 - L1) / L0 100

(c) hybrid dip code E-S value

The term "elongation under a constant load" is referred to as "elongation (E)" in the present invention. "S" means the dry heat shrinkage rate in the above (b), and the sum of the elongation at break (E) Respectively.

E-S = moderate elongation (%) + dry heat shrinkage (%)

(d) My fatigue

The residual fatigue strength was measured by using a Belt Fatigue Tester, which is commonly used for fatigue test of tire cords, and fatigue resistance was compared. The fatigue test conditions were normal temperature, load of 80 kg, and repeated 37,500 times. After the fatigue test, the rubber and cord were separated and the residual strength was measured. The residual strength was measured according to the above method (a) using a normal tensile strength tester.

Example 1

Polyethylene terephthalate and polyketone fibers were obtained according to the above-described method for producing tire reinforcing fibers. One thousand polyethylene terephthalate yarns (1000D) and one polyketone yarn (1000D) were each twisted with 400 TPM, and were wound together to give a twist of 400 TPM. At this time, polyketone was inserted 10 mm / m longer than polyethylene terephthalate. And passed through an adhesive liquid prepared by the following method to give an adhesive liquid. A 2% stretch was applied during drying to prevent unevenness of raw cord due to heat shrinkage.

29.4 wt% resorcinol 45.6 parts by weight; 255.5 parts by weight of distilled water; 37% formalin 20 parts by weight; And 3.8 parts by weight of 10 wt% sodium hydroxide were prepared and reacted with stirring at 25 DEG C for 5 hours, and the following components were added: 300 parts by weight of 40 wt% VP-latex, 129 parts by weight of distilled water, 28% 23.8 parts by weight After the components were added, the mixture was aged at 25 DEG C for 20 hours to maintain the solid content concentration at 19.05%. The adhesive solution was applied and dried at 150 캜 for 2 minutes and then subjected to heat treatment at 170 캜 for 60 seconds to evaluate the physical properties of the prepared hybrid dip cords,

Example 2

A hybrid dipped cord was prepared in the same manner as in Example 1, except that the length of the polyketone yarn was 20 mm / m longer than that of the polyethylene terephthalate yarn at the time of providing the bottom yarn at the twisting stage in the production of the raw cord. The properties of the cord were evaluated and are shown in Table 1.

Example 3

A hybrid dipped cord was prepared in the same manner as in Example 1, except that the length of the polyketone yarn was 30 mm / m longer than that of the polyethylene terephthalate yarn at the time of providing the lower yarn at the twisting stage in the production of the raw cord. The properties of the cord were evaluated and are shown in Table 1.

Example 4

Experiments were carried out in the same manner as in Example 1 except that the length of the polyketone yarn was longer than that of the polyethylene terephthalate yarn at the time of providing the lower yarn at the twisting stage in the production of raw cord, Respectively. The properties of the thus-prepared dip cords were evaluated and are shown in Table 1.

Comparative Example 1

In the twisting process for producing a raw cord, one polyketone yarn (1000D) was subjected to a lead of 40 TPM, and then one polyketone yarn (1000D) provided with the leading edge and one untwisted Polyethylene terephthalate yarn (1000D) was subjected to twisting of 400 TPM to prepare a hybrid yarn, and a hybrid dipped cord was produced in the same manner as in Example 1, except that polyketone yarn and polyethylene terephthalate yarn were charged in the same length while being combined . The properties of the thus-prepared dip cords were evaluated and are shown in Table 1.

Comparative Example 2

In the twisting process for the production of raw cord, a polyethylene terephthalate yarn (1000D) and a polyketone yarn (1000D) were each twisted with a twist of 400 TPM to produce a twisted yarn, and a polyketone yarn and a polyethylene terephthalate yarn A hybrid dipped cord was prepared in the same manner as in Example 1, except that it was added in the same length. The properties of the dipped cords prepared as described above were evaluated and are shown in Table 1.

Processing Code Properties
Remarks Power (kg) Intermediate stretch
4.5kg (%) Shrinkage (%) ES value (%) My fatigue (%) Example 1 22.5 2.0 2.5 4.5 85.4 Example 2 22.1 2.2 2.6 4.8 85.8 Example 3 22.0 2.4 2.7 5.1 87.8 Example 4 22.0 2.6 2.8 5.4 89.7 Comparative Example 1 22.5 2.2 2.3 4.5 72.1 High ES value Comparative Example 2 21.3 1.9 2.2 4.1 71.2 My fatigue is low

From the results of the tests in Table 1, it can be seen that the fatigue resistance of the hybrid dipped cord according to the present invention is improved as compared with the comparative example.

Example 5

A radial tire manufactured using the hybrid dipped cord manufactured by Example 1 of the present invention as a cap ply has a carcass layer having a radially outer side fly-turn, and the carcass layer is provided so as to include one layer. At this time, the specifications of the carcass cords were as shown in the following Table 2 and aligned at an angle of 90 degrees with respect to the circumferential intermediate surface of the tire. The fly-turn 34 has a height of 40 to 80% with respect to the maximum cross-sectional height of the tire. The bead portion 35 has a bead core 36 having a high strength steel wire 4 having a diameter of 0.95 to 1.00 mm and a bead filler 37 having a shore hardness of 40 or more. The belt 38 is reinforced by a belt reinforcing layer consisting of one layer of cap ply 39 and one layer of edge ply 44 at the top so that the cap ply cords in the cap ply 39 are parallel to the circumferential direction of the tire Respectively.

Example 6

A tire was prepared in the same manner as in Example 5, except that the cord material for tire fabrication was the hybrid dipped cord prepared in Example 2. [

Example 7

A tire was produced in the same manner as in Example 5, except that the cord material for tire fabrication was the hybrid dipped cord prepared in Example 3.

Example 8

A tire was produced in the same manner as in Example 5, except that the cord material for tire fabrication was the hybrid dipped cord prepared in Example 4.

Comparative Example 3

A tire was produced in the same manner as in Example 5, except that the cord material for tire fabrication was a dip cord manufactured by Comparative Example 1.

Comparative Example 4

A tire was produced in the same manner as in Example 5, except that the cord material for tire production was a dip cord manufactured by Comparative Example 2.

Example 5 Example 6 Example 7 Example 8 Comparative Example 3 Comparative Example 4 Kakas Material Polyethylene
Terephthalate Polyethylene
Terephthalate Polyethylene
Terephthalate Polyethylene
Terephthalate Polyethylene
Terephthalate Polyethylene
Terephthalate Specification (d / summing speaker) 1500d / 2 1500d / 2 1500d / 2 1500d / 2 1500d / 2 1500d / 2 Strong (Kg) 24 24 24 24 24 24 Modulus of elasticity (g / d) 60 60 60 60 60 60 Cap fly Material The hybrid dip code of Example 1 Example 2
Hybrid dip code Example 3
Hybrid dip code Example 4
Hybrid dip code The hybrid dip code of Comparative Example 1 Comparative Example 2
Hybrid dip code tire Flat rate 0.60 0.60 0.60 0.60 0.60 0.60 Number of carcass layers One One One One One One Cap fly layer number One One One One One One

Example 9

A radial tire produced by using the hybrid dipped cord manufactured by Example 1 of the present invention in a carcass layer has a carcass layer having a radially outer fly-up, and the carcass layer is installed so as to include one layer Respectively. At this time, specifications of the cap fly and carcass cord were as shown in Table 3 below, and tires were produced in the same manner as in Example 5.

Example 10

Tires were produced in the same manner as in Example 5, except that the cord material for making tires was a hybrid dipped cord prepared in accordance with Example 2.

Example 11

A tire was produced in the same manner as in Example 5, except that the cord material for tire fabrication was the hybrid dipped cord prepared in Example 3.

Example 12

A tire was produced in the same manner as in Example 5, except that the cord material for tire fabrication was the hybrid dipped cord prepared in Example 4.

Comparative Example 5

A tire was produced in the same manner as in Example 5, except that the cord material for tire fabrication was a dip cord manufactured by Comparative Example 1.

Comparative Example 6

A tire was produced in the same manner as in Example 5, except that the cord material for tire production was a dip cord manufactured by Comparative Example 2.

Example 9 Example 10 Example 11 Example 12 Comparative Example 5 Comparative Example 6 Kakas Material The hybrid dip code of Example 1 Example 2
Hybrid dip code Example 3
Hybrid dip code Example 4
Hybrid dip code The hybrid dip code of Comparative Example 1 Comparative Example 2
Hybrid dip code Cap fly Material Nylon 6,6 Nylon 6,6 Nylon 6,6 Nylon 6,6 Nylon 6,6 Nylon 6,6 Specification (d / summing speaker) 1260d / 2 1260d / 2 1260d / 2 1260d / 2 1260d / 2 1260d / 2 Power (kg) 24 24 24 24 24 24 Modulus of elasticity
(g / d) 50 50 50 50 50 50 tire Flat rate 0.60 0.60 0.60 0.60 0.60 0.60 Number of carcass layers One One One One One One Cap fly layer number One One One One One One

The 205/65 R15 V tire manufactured according to Examples 5, 6, 7, 8, 9, 10, 11, 12 and Comparative Examples 3, 4, 5 and 6 was mounted on a 2000cc class passenger car, (DB) in the audible frequency range, and the stability and ride quality of the vehicle are measured by a skilled driver on a test course and evaluated in units of 5 points on a scale of 100 And the results are shown in Table 4 below. The durability was measured in accordance with FMVSS 109 P-metric tire endurance test method at a measurement temperature of 38 ° C (° C), 85, 90, 100% (OK) when no traces of bead separation, cord cutting, belt separation, etc. were found in any part of the tread, sidewall, carcass cord, inner liner, bead or the like.

division Tire weight
(kg) Ride comfort Steering stability durability Uniformity Noise (dB) Example 5 9.98 100 100 OK 100 60.4 Example 6 9.98 100 100 OK 100 60.4 Example 7 9.99 100 100 OK 100 60.5 Example 8 10.02 100 100 OK 100 61.2 Comparative Example 3 10.01 97 96 OK 92 62 Comparative Example 4 10.08 94 95 OK 93 62.1 Example 9 10.2 100 100 OK 100 60.4 Example 10 10.2 100 100 OK 100 60.3 Example 11 10.12 100 100 OK 100 60.4 Example 12 10.0 100 100 OK 100 60.6 Comparative Example 5 10.5 95 97 OK 94 61.5 Comparative Example 6 10.6 95 94 OK 93 63

As a result of the tests of Table 4, the tires (Examples 6 to 15) using the hybrid cord according to the present invention were more effective in noise reduction and steering stability than Comparative Examples 3 to 6, Te is also improved.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art in light of the above teachings. will be.

31: Tire 32: Carcass layer
33: Carcass layer reinforcement cord 34: Fly turn-up
35: bead region 36: bead core
37: bead filler 38: belt structure
39: cap fly 40: belt fly
41, 42: belt cord 43: tread
44: edge fly 45: cap fly cord

Claims (9)

In hybrid dipped cords for radial pneumatic tires,
One polyethyleneterephthalate yarn and one polyketone yarn were each laid one on top of the other, and the raw cord made by joining the raw cord was melted, the polyketone yarn was inserted into the polyethylene terephthalate yarn by 30 to 40 mm / m,
The hybrid dipped cord prepared by dipping the raw cord into an adhesive solution had an internal fatigue of 87.8 to 89.7%, an intermediate elongation of 2.4 to 2.6%, a shrinkage of 2.7 to 2.8%, an ES (modulus of elongation + dry heat shrinkage) 5.4%. ≪ / RTI > delete delete delete delete A pair of parallel bead cores and at least one radial carcass layer wound around the bead cores, a belt layer laminated on the outer circumferential side of the carcass layer, and a radial air layer including a circumferential belt reinforcing layer formed on the outer circumferential side of the belt layer In the mouth tires,
Wherein the carcass layer comprises the hybrid dipped cord according to claim 1, wherein the carcass layer is used as one or two layers. A pair of parallel bead cores and at least one radial carcass layer wound around the bead cores, a belt layer laminated on the outer circumferential side of the carcass layer, and a radial air layer including a circumferential belt reinforcing layer formed on the outer circumferential side of the belt layer In the mouth tires,
Wherein the cap ply as the belt reinforcing layer comprises the hybrid dipped cord according to claim 1, wherein the cap ply is used as one or two layers. A method of manufacturing a hybrid dipped cord for a radial pneumatic tire,
Preparing one polyethylene terephthalate yarn and one polyketone yarn;
Adding the single polyketone yarn longer than the polyethylene terephthalate yarn to produce twisted yarns of 200 to 500 TPM yarns each to produce a lower yarn;
Folding the twisted yarn in two, and twisting the twisted yarn in a number of 200 to 500 TPM to produce a cord; And
Immersing the raw cord in a dipping solution, and then heat-treating the raw cord to produce a dipped cord; Wherein the polyketone yarn is 30 to 40 mm / m longer than the polyethylene terephthalate yarn when the raw cord is melted,
Wherein the dip cord has an internal fatigue of 87.8 to 89.7%, an intermediate elongation of 2.4 to 2.6%, a shrinkage of 2.7 to 2.8% and an ES (modulus of elongation + dry heat shrinkage) of 5.1 to 5.4% Gt; 9. The method of claim 8,
Wherein the fineness of the polyethylene terephthalate yarn and the polyketone yarn is 500 to 3000 denier, respectively.

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