KR20180064592A - An Excellent Fatigue Resistance Tire Cord using Nylon 6,6 or Nylon 6 and Polyketone, and Radial Tires Produced by the Same - Google Patents

Abstract

The present invention relates to a method to manufacture a hybrid dip cord using a nylon 6.6 yarn and a polyketone yarn, pre-twisting each of the nylon 6.6 yarn and the polyketone yarn by using one or more methods selected from a group including a method to adjust tension applied to a raw cord, a method to adjust a heat treatment temperature, and a method to adjust a heat treatment time, heat-treating a raw cord made by double-twisting the same while dipping the raw cord in adhesives, so as to manufacture a dip cord with the more shrunk nylon 6.6 yarn. Another objective of the present invention is to provide a hybrid dip cord for a carcass ply or a cap ply layer of a pneumatic radial tire with fatigue resistance of a predetermined value, which is manufactured by dipping a raw cord using a nylon 6.6 yarn and a polyketone yarn in a dipping solution and then performing heat treatment to more shrink the nylon 6.6 yarn. According to the present invention, a raw cord is manufactured while equally maintaining the numbers of twisting of the nylon 6.6 yarn and the polyketone yarn during twisting and passes a heat treatment process, thus the nylon yarn is shrunk and the length of the polyketone yarn per unit length is longer than that of the nylon yarn when untwisting the dip cord, so as to increase fatigue resistance thereby. Accordingly, a disadvantage difficult in modification inside a mold due to high modulus when polyketone is solely used in a conventional method is able to be overcame, lower fatigue resistance and adhesion force caused when the polyketone is solely used is able to be improved, and low modulus caused when nylon 6.6 is solely used is able to be improved, thereby being able to manufacture high performance tire.

Description

[0001] The present invention relates to a tire cord having excellent fatigue resistance using nylon 6,6 or nylon 6 and polyketone yarns, and radial pneumatic tires using the same. the Same}

The present invention relates to a high-strength tire cord using nylon 6,6 or nylon 6 and polyketone yarn, and a radial pneumatic tire using the same.

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.

Polyethylene terephthalate is widely used as an air inlet radial tire, and more particularly, as a carcass ply material of air inlet radial tires having a flatness ratio of 0.65 to 0.82. In addition, a flat flat tire having a low flatness ratio, more specifically, a flatness ratio of less than 0.70 Rayon is used as a carcass ply reinforcement of high-speed air inlet radial tires.

In recent years, some of polyethylene naphthalate has been used for radial tires having a low flatness ratio at high speed. However, polyethylene naphthalate is superior to polyethylene terephthalate in terms of high temperature property and shape stability, but its price is high and its application is restricted. U.S. Patent No. 6,601,378 proposes a hybrid cord made by twisting a wound yarn of polyethylene terephthalate and polyethylene naphthalate, respectively. Polyethylene naphthalate fibers have a significantly higher modulus than polyethylene terephthalate fibers. Due to such differences in physical properties, when one of each of the wound yarns of polyethylene terephthalate and polyethylene naphthalate is twisted, it causes unevenness of tension in the raw cord. Due to such a problem, the strength utilization ratio at the time of twisting and dipping is rapidly deteriorated.

Generally, yarn twisting conditions are the same when twisted yarns are produced by twisting yarns of the same kind, but in the case of hybrid yarns, the twist condition of each yarn can be set differently to control the properties of the raw cord. In the conventional technology, the properties of raw cord are changed by imparting softener to the yarn differently in the production of hybrid cord. In this case, when the former is applied to a yarn having a high modulus and a short yarn, the yarn is given less twist of the yarn, When the yarn having the same modulus as that of the yarn is given to the lower yarn, the yarn having a high modulus after twisting is given a twist in the twisting direction of the yarn, while the yarn having a low modulus is not twisted, It has the effect of increasing fatigue. However, this is applicable only to the spinning machine (DRT, RT) to which the post-spinning is given, and there is a problem that it can not be used in the Direct Cabler spinning machine in which the up and down spinning occurs simultaneously.

U.S. Patent No. 6601378

Disclosure of Invention Technical Problem [8] The present invention has been made to solve the problems of the prior art described above, and an object of the present invention is to provide a method of manufacturing a hybrid cord using nylon 6,6 yarn and polyketone yarn, A nylon 6,6 yarn or a nylon 6 yarn, and a polyketone yarn are kneaded by using one or more methods selected from the group consisting of a method of controlling the temperature and a method of adjusting the heat treatment time, And then heat-treating the nylon 6,6 or nylon 6 yarn to further shrink the nylon 6,6 or nylon 6 yarn. Therefore, when the deep cords are melted, a hybrid dipped cord is produced which is characterized in that the polyketone yarn is longer than that of nylon 6,6.

Another object of the present invention is to provide a method for producing a nylon 6,6 or nylon 6 yarn by dipping a raw cord using the nylon 6,6 or nylon 6 yarn and a polyketone yarn in a dipping solution, To provide a hybrid dip code for a carcass ply or cap ply layer of an air inlet radial tire with fatigue.

According to a preferred embodiment of the present invention, the hybrid dipped cord comprises a raw cord each of which is formed by joining and nipping one nylon 6,6 or nylon 6 yarn and one polyketone yarn; And the raw cord is dipped in a dipping solution and then heat-treated to heat-shrink the nylon 6,6 or nylon 6 yarn so that the length of the nylon 6,6 or the nylon 6 yarn becomes shorter than that of the polyketone yarn.

According to another preferred embodiment of the present invention, the hybrid dipped cord is heat-treated to heat-shrink the nylon 6,6 or nylon 6 yarn so that the length of the nylon 6,6 or nylon 6 yarn becomes shorter than that of the polyketone yarn. The method of controlling the tension applied to the raw cord, And a method of adjusting a heat treatment time, are used.

According to another preferred embodiment of the present invention, the hybrid dipped cord is characterized in that the polyketone yarn is 5 to 100 mm / m longer than the nylon 6,6 or nylon 6 yarn when the dipped cord is finished.

According to another preferred embodiment of the present invention, the hybrid dipped cord is characterized in that the polyketone yarn is 10 to 30 mm / m longer than the nylon 6,6 or the nylon 6 yarn when the dipped cord is kneaded.

According to another preferred embodiment of the present invention, the hybrid dipped cord is characterized by having an internal fatigue of 85% or more.

According to a preferred embodiment of the present invention, a method of manufacturing hybrid dipped cords for radial pneumatic tires is to provide a single nylon 6,6 or nylon 6 yarn and a single polyketone yarn with twist of 200-500 TPM yarns Thereby producing a lowered 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 and then heat-treating the nylon 6,6 or nylon 6 yarn so that the length of the nylon 6,6 or nylon 6 yarn is shorter than that of the polyketone yarn.

According to another preferred embodiment of the present invention, a method of manufacturing a hybrid dipped cord for a radial pneumatic tire is characterized in that the further shrinking of the nylon 6,6 or the nylon 6 yarn in the heat treatment step is performed by a method of controlling the tension applied to the raw cord, A method of controlling a heat treatment temperature, and a method of controlling a heat treatment time.

According to another preferred embodiment of the present invention, a method of manufacturing a hybrid dipped cord for a radial pneumatic tire is characterized in that the tension is controlled through the speed of the feed roller and the winding roller, the heat treatment temperature is 130 to 240 占 폚, Seconds.

According to another preferred embodiment of the present invention, a method of manufacturing a hybrid dipped cord for a radial pneumatic tire is characterized in that the polyketone yarn is 5 to 100 mm / m longer than the nylon 6,6 or nylon 6 yarn when the dipped cord is formed .

According to another preferred embodiment of the present invention, a method of manufacturing a hybrid dipped cord for a radial pneumatic tire is characterized in that a polyketone yarn is 10 to 30 mm / m longer than a nylon 6,6 or a nylon 6 yarn when a dipped cord is formed .

According to still another preferred embodiment of the present invention, a method for producing a hybrid dipped cord for radial pneumatic tires is characterized in that the fineness of nylon 6,6 or nylon 6 yarn and polyketone yarn is 500 to 3000 denier, respectively.

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, the twist number of polyketone yarn and nylon yarn is kept the same during twist yarn, so that the nylon yarn is shrunk by subjecting the nylon yarn to heat treatment after the production of the raw cord. When the dipped cord is loosened, So that the fatigue can be increased. In the tensile test, the initial deformation induces low modulus by the nylon, and the high modulus can be developed from the section where the polyketone begins to receive the force, and the green tires are inflated into the bladder inside the mold during vulcanization. So that it can be easily deformed during the operation and the tire can be easily manufactured. 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 , It is possible to manufacture high-performance tires by improving low modulus and heat resistance which are problematic when using nylon alone.

Fig. 1 schematically shows spinning and drawing processes of nylon 6,6 yarn or nylon 6 yarn according to the present invention.
Fig. 2 schematically shows a manufacturing process of a polyketone yarn according to the present invention.
Fig. 3 schematically shows 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.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to the accompanying drawings.

The polyketone yarn and the nylon 6,6 or nylon 6 yarn for the production of the hybrid dipped cord according to the present invention are produced through the following process.

First, a manufacturing method of nylon yarn used in the present invention will be described in detail with reference to the accompanying drawings.

The nylon used in the production of the hybrid tire cord of the present invention contains an amide group having a strong polarity in the main chain and has a stereoregularity and a symmetry and is crystalline. Generally, a polyamide refers to a generic term of a polymer linked by an amide bond (-CONH-), which can be obtained by condensation polymerization of a diamine and a dicarboxylic acid. Polyamides are characterized by amide bonds in the molecular structure, and their physical properties vary depending on the ratio of amide groups. For example, when the ratio of amide groups in the molecule is increased, specific gravity, melting point, absorbency, rigidity and the like are increased.

In addition, polyamide is a material used in a wide range of fields such as clothing, tire cord, carpet, rope, computer ribbon, parachute, plastic and adhesive due to its excellent resistance to corrosion, abrasion resistance, chemical resistance and insulation.

Generally, polyamides are classified into aromatic polyamides and aliphatic polyamides. Representative aliphatic polyamides include nylon. Nylon is originally a trademark of DuPont, Inc., but is now used as a generic name.

Nylon is a hygroscopic polymer and is sensitive to temperature. Representative nylons include nylon 6, nylon 6,6, and nylon 46.

First, nylon 6 is characterized by excellent heat resistance, moldability and chemical resistance, and is produced by ring-opening polymerization of ε-caprolactam in order to produce it. Nylon 6 means that caprolactam has 6 carbon atoms.

(Scheme 1) Nylon 6 polymerization of caprolactam

On the other hand, nylon 6,6 is generally similar in properties to nylon 6, but is superior in heat resistance to nylon 6, and has excellent self-extinguishing and abrasion resistance. Nylon 6,6 is prepared by dehydration condensation polymerization of hexamethylenediamine and adipic acid.

(Scheme 2) Dehydration condensation of hexamethylenediamine with adipic acid Nylon 6,6 polymerization

The polyhexamethylene adipamide polymer contains at least 85 mole percent hexamethylene adipamide repeat units, preferably only hexamethylene adipamide units.

Alternatively, optional polyamide homopolymers and copolymers may be used in place of polyhexamethylene adipamide. Such polyamides can be predominantly aliphatic. Poly (hexamethylene adipamide) (nylon 6,6); Poly (epsilon -caproamide) (nylon 6); And nylon 6,6 are most preferred, although widely used nylon polymers such as their copolymers can be used.

In order to improve the thermal stability during the production of the polyhexamethylene adipamide chip, the residual amount of the copper metal in the final polymer may be 20 to 50 ppm. If this amount is less than 20 ppm, the thermal stability is lowered during the spinning and pyrolysis occurs. If it exceeds 50 ppm, more than necessary copper metal acts as a foreign substance, which may be a problem in spinning. The polyhexamethylene adipamide chips prepared are made of fibers by the apparatus shown in Fig.

1, a polyhexamethylene adipamide chip is packaged through a pack 1 and a nozzle 2, preferably at a spinning temperature of 270 to 310 DEG C, preferably a radiation draft ratio of 20 to 200 The linear velocity on the roller / the linear velocity on the nozzle). This process is intended to prevent a decrease in the viscosity of the polymer due to thermal decomposition. If the spinning draft ratio is less than 20, the uniformity of the filament cross section may be deteriorated to deteriorate the drawability. If it exceeds 200, filament breakage may occur during spinning, thereby making it difficult to produce normal yarns.

The filtration residence time in the pack of chips in the melt spinning process should be adjusted to 3 to 30 seconds. If the filtration retention time in the pack is less than 3 seconds, the filtering effect of the foreign substance is insufficient, and if it exceeds 30 seconds, the excessive packing pressure may increase the pyrolysis. It is also preferred that the L / D (length / diameter) of the extruder screw in the melt spinning process is from 10 to 40. If the L / D of the screw is less than 10, uniform melting is difficult. If the screw has an L / D of more than 40, the molecular weight may be lowered due to excessive shear stress.

The produced melt discharge yarn 4 is quenched and solidified by passing through the cooling zone 3. The quenching and solidifying process is classified into an open quenching method, a circular closed quenching method and a radial outflow quenching method according to a method of blowing cooling air in the cooling zone 3, Of these methods, an open quenching method is preferred. Thereafter, the discharged yarn 4 which has passed through the cooling zone 3 and solidified is oiled to 0.5 to 1.0% by the emulsion applying device 5 and becomes unstretched.

The preferred spinning speed of the prepared non-drawn yarn is 200 to 1,000 m / min. The yarn passed through the first stretching roller 6 is stretched by a spin draw method while passing through a series of stretching rollers 7, 8, 9 and 10 so that the total yarn ratio is 4.0 times or more, preferably 4.5 to 6.5 To obtain the final drawn yarn 11.

It is advantageous that the value of the dry heat shrinkage (160 DEG C, 30 minutes) of the produced fiber is 3 to 6%. The low shrinkage ratio of such fibers can be obtained by stabilizing the crystal structure of the drawn yarn in the heat treatment step after the two-stage stretching process. The multi-stage drawing process in the fiber manufacturing process includes a primary drawing process which proceeds at a high drawing magnification at a low drawing temperature and a secondary drawing process which proceeds at a relatively low drawing magnification at a high temperature. In the primary drawing step, crystallization mainly proceeds by orientation. Crystallization by this orientation is a factor that determines the heat shrinkage of the cord. The preferred stretching temperature in the primary stretching step is 20 to 50 DEG C and the stretching ratio is 3.0 times or more. If an additional cooling device is not provided in the drawing roller in the process, it is difficult to control the drawing temperature to be less than 20 캜, which is economically disadvantageous. On the other hand, if the drawing temperature exceeds 50 캜, crystallization by heat may proceed. Further, if the draw ratio is less than 3.0 times, sufficient orientation crystallization hardly occurs.

Through the second elongation process, crystallization proceeds by heat at a high temperature. At these high temperatures, heat-induced crystals affect the heat shrinkage of the cord. In the secondary drawing step of the present invention, the drawing temperature is preferably 200 to 250 ° C and the drawing magnification is 2.0 times or less. When the drawing temperature is less than 200 ° C, sufficient crystallization does not proceed by heat. When the drawing temperature exceeds 250 ° C Causing damage to the product. Also, when the draw ratio exceeds 2.0 times, the elongation of the yarn decreases sharply. The relaxation temperature is adjusted to 200 to 250 ° C and the relaxation rate is adjusted to 3 to 7% in order to stabilize the crystal structure of the drawn yarn. The low shrinkage characteristics of such fibers can be prevented from rapidly shrinking in the treatment process for a tire cord, and thus they are represented by a high strength utilization ratio.

(2) a strength of 9.0 g / d or more; (3) an elongation of 10% or more; (4) a shrinkage of 10% or more; ) 500 to 3000 denier.

Hereinafter, a method for producing polyketone yarn used in the present invention will be described in detail with reference to the accompanying drawings.

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 as shown in FIG. 2 was used at a temperature of 180 ° C. for a retention time of about 3 minutes and 30 seconds. This has the effect of achieving uniform drying and improving the affixation, but it is difficult to generate fusion, loops, static electricity, and fusion structure, so that the structure is not as dense (see FIG. 4). The present invention uses a hot-roll drying method as shown in Fig. 3 for a retention time of about 1 minute and 30 seconds at a temperature of 220 to 230 ° C. 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 (see FIG. 5).

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 with a fineness of 0.5 to 8.0 denier.

At this time, the strength of the multifilament is 5.0 to 30 g / d, and the elongation is 3 to 10%, which can be advantageously used as a tire cord for a passenger car.

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.

The hybrid dipped cord according to the present invention is obtained by dipping one raw nylon 6,6 or nylon 6 yarn and one polyketone yarn into a dipping solution and then heat-treating the raw cord to obtain nylon 6,6 or Characterized in that the nylon 6 yarn is heat shrunk so that the length of the nylon 6 yarn is shorter than that of the polyketone yarn. When the thus prepared dip cord is melted, the polyketone yarn is 5 to 100 mm / m longer than the nylon 6,6 or nylon 6 yarn .

In the production of hybrid cords using the manufactured nylon 6,6 or nylon 6 and polyketone yarns. And a step of giving a cord to the cord as a pre-stage of dip code production (a twisting process).

The nylon 6,6 yarn and the nylon 6 yarn and the polyketone yarn manufactured by the above method are respectively wound by a direct twisted yarn in which twisted yarns and twisted yarns are simultaneously wound, And produces a "raw code" for the code. The raw cord is manufactured by applying ply twist to nylon 6,6 or nylon 6 and polyketone for tire cords followed by joining by cable twist. Generally, do.

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 the nylon 6,6 or nylon 6 yarn and the polyketone yarn used in the twist yarn 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 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, the surface of the polyethylene terephthalate is first exposed to the surface of the fiber because the reactor on the surface of the fiber is smaller than that of the rayon fiber or the nylon fiber After activation, the adhesive treatment is performed (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.

In order to further shrink the nylon 6,6 or nylon 6 yarn in the heat treatment step, one or more methods selected from the group consisting of a method of controlling the tension applied to the raw cord, a method of adjusting the heat treatment temperature, and a method of controlling the heat treatment time Was used.

The tension was controlled through the speed of the feed roller and the winding roller, the heat treatment temperature was 130 to 240 占 폚, and the heat treatment time was 50 to 90 seconds.

Regarding this heat treatment process, when the twist number of the polyketone yarn and the nylon 6,6 or the nylon 6 yarn is kept the same in the twisting step, the nylon 6,6 or the nylon 6 yarn is shrunk when subjected to the heat treatment after the production of the cord, When the cord is loosened, the length of polyketone is longer than that of nylon 6 or nylon 6 per unit length. As nylon 6,6 or nylon 6 shrinks sharply and polyketone yarn becomes longer, the initial strain is generated by nylon 6,6 or nylon 6 yarn during tensile test, and then the deformation is generated by polyketone yarn.

The length difference due to shrinkage of the nylon 6,6 or nylon 6 yarn is effective when the length difference of each yarn is about 5 to 100 mm / m when the dipped cord is loosened, and preferably polyketone yarn is effective. If the difference is less than 5mm, the fatigue is reduced and it is not suitable. If the difference exceeds 100mm, the strength is decreased and it is not appropriate. According to one embodiment of the present invention, it is most preferable that the difference is 10 to 30 mm / m.

In the manufacturing method according to the present invention, the strength of the polyketone is lower than that of the nylon 6,6 or nylon 6, and the tendency to increase in the middle / turn is expected to be increased. In contrast, the shorter the length of the polyketone (Longer than nylon 6,6 or nylon 6, but shorter as the length of the polyketone yarn is increased), the strength is increased, and the mid / turn and fatigue tends to be lowered. In particular, in this case, the initial strain in the tensile test causes low modulus by nylon 6,6 or nylon 6, and high modulus is expressed from the point where polyketone begins to receive the force.

The hybrid dipped cord produced according to the above-described method is characterized by having an internal fatigue of 85% or more. If the fatigue strength is less than 85%, the durability of the tire is reduced.

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 produced through such a process is applied to tires for passenger cars. It is mainly applied to cap ply and carcass ply to improve low fatigue resistance and adhesion, which is a problem when polyketone is used alone, and nylon 6 , 6 or nylon 6 is used alone to improve the low modulus and heat resistance which is a problem and is used to manufacture a high performance tire having excellent fatigue resistance.

Fig. 3 shows the structure of a tire for a passenger car in which the hybrid dipped cord according to the present invention is applied as a carcass ply or a cap ply.

Referring to Fig. 3, the bead region 35 of the tire 31 becomes an annular bead core 36 that 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. 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.

3, reference numerals 32 and 34 denote a carcass layer 32 and a fly turn 34. And reference numeral 33 denotes a carcass layer reinforcing cord 33. [

Embodiments and comparative examples which do not limit the scope of the present invention are described below. 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]

Nylon 6,6 and polyketone fibers were obtained in the same manner as described above to produce tire reinforcing fibers. A twist of 400 TPM was given to one nylon 6,6 yarn (1260D) and one polyketone yarn (1000D), respectively, and they were folded together to give a twist of 400 TPM to produce a raw cord. And then passed through an adhesive liquid prepared by the following method to give an adhesive liquid.

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% ammonia water, 23.8 parts by weight After the components were added, they were aged at 25 캜 for 20 hours to maintain a solid content concentration of 19.05%.

After the adhesive liquid was applied and dried at 150 ° C for 2 minutes, heat treatment was performed while stretching at 240 ° C for 60 seconds to shrink the nylon 6,6 yarn, and the polyketone yarn was lengthened by 10 mm / m to finish the adhesive treatment Respectively. The physical properties of the thus-prepared hybrid dip cords were evaluated and are shown in Table 1.

[Example 2]

A raw cord and a deep cord were prepared in the same manner as in Example 1, except that the polyketone yarn was longer by 20 mm / m when it was heat-treated for 90 seconds and then melted. The properties of the thus-prepared dip cords were evaluated and are shown in Table 1.

[Example 3]

The raw cord and the dip cord were prepared in the same manner as in Example 1 except that nylon 6,6 yarn (840D) and polyketone yarn (1000D) were used. The properties of the thus-prepared dip cords were evaluated and are shown in Table 1.

[Example 4]

Except that nylon 6,6 yarn (840D) and polyketone yarn (1000D) were used and the polyketone yarn was longer by 20 mm / m when the yarn was heat-treated for 90 seconds. A dip cord was prepared. The properties of the thus-prepared dip cords were evaluated and are shown in Table 1.

[Comparative Example 1]

The raw cord and the dip cord were prepared in the same manner as in Example 1, except that nylon 6,6 yarn was added 10 mm / m longer at the time of yarn winding. The properties of the thus-prepared dip cords were evaluated and are shown in Table 1.

[Comparative Example 2]

The raw cord and the dip cord were prepared in the same manner as in Example 1, except that the polyketone yarn was fed at a rate of 15 mm / m. The properties of the thus-prepared dip cords were evaluated and are shown in Table 1.

[Comparative Example 3]

The raw cord and the dip cord were prepared in the same manner as in Example 1, except that the polyketone yarn was inserted 20 mm / m longer at the time of yarn folding. The properties of the thus-prepared dip cords were evaluated and are shown in Table 1.

[Comparative Example 4]

The raw cord and dip cord were prepared in the same manner as in Example 1, except that the polyketone yarn was inserted 25 mm / m longer at the time of yarn winding. The properties of the thus-prepared dip cords were evaluated and are shown in Table 1.

[Comparative Example 5]

The raw cord and the dip cord were prepared in the same manner as in Example 1, except that the polyketone yarn was inserted 30 mm / m longer when the yarn was wound. The properties of the thus-prepared dip cords were evaluated and are shown in Table 1.

division Processing Code Properties Remarks strong
(kg) Intermediate stretch
6.8kg (%) Shrinkage rate
(%) ES value
(%) My Fatigue
(%) Adhesion
(kg) Example 1 29.7 3.6 3.1 6.7 86.3 18.6 Example 2 29.5 3.7 3.0 6.7 86.2 19.2 Example 3 28.6 4.8 2.9 7.7 85.8 19.9 Example 4 28.4 4.8 2.9 7.7 85.9 18.8 Comparative Example 1 29.6 3.7 3.1 6.8 83.4 18.3 High ES value, low fatigue Comparative Example 2 29.6 3.7 3.1 6.8 83.2 18.2 High ES value, low fatigue Comparative Example 3 29.4 3.8 3.2 7.0 83.8 17.9 High ES value, low fatigue Comparative Example 4 29.8 3.9 3.2 7.1 82.9 18.0 High ES value, low fatigue Comparative Example 5 29.7 4.0 3.3 7.3 83.0 18.5 High ES value, low fatigue

In the case of the hybrid dipped cord according to the present invention (Examples 1, 2, 3 and 4), when the nylon 6,6 yarn was cast for a longer period of time, the nylon 6,6 yarn and the poly It can be seen that the fatigue resistance is improved as compared with the hybrid dip cord (Comparative Example 1) in which the length difference of the ketone yarn is not generated.

In addition, hybrid dipped cords (Comparative Examples 2, 3, 4, and 5) into which polyketone yarns were added for a longer time were found to be stronger than those of the hybrid dip cords according to the present invention, but the fatigue thereof was low.

[Example 5]

A radial tire manufactured using the hybrid dipped cord produced 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 are as shown in Table 3 below 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 hardness of 40 or more and a shore A 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 6]

Tires were prepared in the same manner as in Example 5, except that the cord material for tire fabrication was a hybrid dip cord manufactured by Comparative Example 1.

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

[Example 9]

A radial tire manufactured using the hybrid dip code manufactured by Example 1 of the present invention has a carcass layer having a radially outer side fly-turn, and the carcass layer is provided so as to include one layer. The specifications of the cap ply and carcass cord were as shown in the following Table 3, and tires were produced in the same manner as in Example 5.

[Example 10]

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 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 7]

Tires were prepared in the same manner as in Example 5, except that the cord material for tire fabrication was a hybrid dip cord manufactured by Comparative Example 1.

Example 9 Example 10 Example 11 Example 12 Comparative Example 7 Kakas Material The hybrid dip code of Example 1 The hybrid dip code of Example 2 The hybrid dip code of Example 3 The hybrid dip code of Example 4 The hybrid dip code of Comparative Example 1 Cap fly Material Nylon 6,6 Nylon 6,6 Nylon 6,6 Nylon 6,6 Nylon 6,6 Specification (d / summing speaker) 1260D / 2P 1260D / 2P 1260D / 2P 1260D / 2P 1260D / 2P Power (kg) 22.4 22.4 22.4 22.4 22.4 tire Flat rate 0.60 0.60 0.60 0.60 0.60 Number of carcass layers 2 2 2 2 2 Cap fly layer number 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 6 and 7 was mounted on a 2000cc class passenger car, (DB) in the audible frequency range by measuring the noise generated in the vehicle. The steered driver rides the test course and evaluates the driving stability and riding comfort in five points on the scale of 100 points. The results are shown in Table 4 below. The durability was measured in accordance with the P-metric tire endurance test of FMVSS 109 at a temperature of 38 ° C (Celsius), 85, 90 and 100% of the rated tire load, at a running speed of 80 km / h And it was judged as OK (OK) when no traces such as bead separation, cord cutting, belt separation were found in any part such as tread, sidewall, carcass cord, inner liner and bead.

division Tire weight
(kg) Ride comfort Steering stability durability Uniformity Noise (dB) Example 5 9.54 100 100 OK 100 61.2 Example 6 9.70 100 100 OK 100 61.4 Example 7 9.55 100 100 OK 100 61.4 Example 8 9.69 100 100 OK 100 61.3 Comparative Example 6 9.60 96 95 OK 96 63.5 Example 9 9.64 100 100 OK 100 60.4 Example 10 9.70 100 100 OK 100 61.0 Example 11 9.63 100 100 OK 100 60.3 Example 12 9.71 100 100 OK 100 61.1 Comparative Example 7 9.60 93 94 OK 92 64.3

As a result of the test of Table 4, when using the hybrid cord according to the present invention (Examples 5, 6, 7 and 8), nylon 6, It was found that the effect of noise reduction and steering stability was superior to that of Comparative Example 6 using hybrid dipped cord having no difference in length between 6 and polyketone, and the unity of tire was 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 (13)

In hybrid dipped cords for radial pneumatic tires,
One raw nylon 6,6 yarn or nylon 6 yarn and one polyketone yarn, each of which is made up of a raw cord; And
Wherein the raw cord is immersed in a dipping solution and then heat-treated to heat-shrink the nylon 6,6 yarn or the nylon 6 yarn so that the length of the yarn is shorter than that of the polyketone yarn. The method according to claim 1,
The heat shrinkage of the nylon 6,6 or nylon 6 yarn to shorten the length of the polyketone yarn is controlled by controlling the tension applied to the raw cord, adjusting the heat treatment temperature, and controlling the heat treatment time Characterized in that at least one selected method is used. The method according to claim 1,
Characterized in that the polyketone yarn is 5 to 100 mm / m longer than the nylon 6,6 or nylon 6 yarn when the dipped cord is finished. The method according to claim 1,
When the dip cord is melted, the polyketone yarn is 10 to 30 mm / m longer than the nylon 6,6 yarn or the nylon 6 yarn. The method according to claim 1,
Hybrid dip cords with a fatigue of 85% or more A method of manufacturing a hybrid dipped cord for a radial pneumatic tire,
Preparing a warp yarn by imparting a twist of each of 200 to 500 TPM yarns to one nylon 6,6 yarn or nylon 6 yarn and one polyketone 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
And dipping the raw cord in a dipping solution followed by heat treatment to heat-shrink the nylon 6,6 yarn or the nylon 6 yarn so that the length of the nylon 6,6 yarn or the nylon 6 yarn becomes shorter than that of the polyketone yarn The method according to claim 6,
In order to further shrink the nylon 6,6 or nylon 6 yarn in the heat treatment step, one or more methods selected from the group consisting of a method of controlling the tension applied to the raw cord, a method of adjusting the heat treatment temperature, and a method of controlling the heat treatment time A method of manufacturing a hybrid dip cord 8. The method of claim 7,
Wherein the tensile force is adjusted through the speed of the feed roller and the take-up roller, the heat treatment temperature is 130 to 240 ° C, and the heat treatment time is 50 to 90 seconds. The method according to claim 6,
Characterized in that the polyketone yarn is 5 to 100 mm / m longer than the nylon 6,6 or nylon 6 yarn when the dipped cord is melted. The method according to claim 6,
And the polyketone yarn is 10 to 30 mm / m longer than the nylon 6,6 yarn or the nylon 6 yarn when the dip cord is formed. The method according to claim 6,
And the fineness of the nylon 6,6 yarn or the nylon 6 yarn and the polyketone yarn are respectively 500 to 3,000 denier 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, 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,
Characterized in that the carcass layer comprises the hybrid dipped cord according to any one of claims 1 to 11 and the carcass layer is used as one or two layers. 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, 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 any one of claims 1 to 11 and the cap ply is used as one or two layers.

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