KR20050118335A - Polyketone dip cord - Google Patents

Abstract

The present invention relates to a polyketone deep cord containing 90 mol% or more of a ketone unit represented by -CH ₂ CH ₂ -CO- as a repeating unit, and more specifically, (A) a ketone in an aqueous solution containing zinc bromide. Preparing a polyketone solution by dissolving a polyketone containing 90 mol% or more of the unit as a repeating unit; (B) extruding the polyketone solution through a spinning nozzle, and then passing through an air layer to reach a coagulation bath to solidify it to obtain a multifilament (C) washing, drying and emulsion treatment of the multifilament obtained Drawing by drawing; (D) a method for producing a polyketone deep cord comprising the step of weaving the drawn yarn by a twisting machine to produce a raw cord, and then woven into the dipping liquid.

In addition, the polyketone deep cord manufactured by the above method is excellent in adhesive strength, strength and modulus with rubber, and tires manufactured by applying this to the carcass layer or the belt reinforcing layer as reinforcing fibers have excellent shape stability and steering stability.

Description

Polyketone dip cord

The present invention is to provide a high strength polyketone deep cord and a tire using the same.

More specifically, (A) dissolving a polyketone containing 90 mol% or more of ketone units in a repeating unit in an aqueous solution containing zinc bromide to prepare a polyketone solution; (B) extruding the polyketone solution through a spinning nozzle, and then passing through an air layer to reach a coagulation bath to solidify it to obtain a multifilament; (C) stretching the obtained multifilament by washing, drying and emulsion treatment; (D) a method for producing a polyketone deep cord comprising the step of weaving the drawn yarn by a twisting machine to produce a raw cord, and then woven into the dipping liquid.

It is known that polyketones in which carbon monoxide and olefins are alternately polymerized by polymerizing carbon monoxide with olefins such as ethylene and propylene using a transition metal complex such as palladium or nickel as a catalyst. Since polyketones are difficult to melt and thermal crosslinking reactions occur, wet spinning is preferable when the polyketones are fiberized.

In the case of wet spinning polyketones, hexafluoroisopropanol and m-cresol, phenolic solvents such as resorcinol / water, and organic solvents such as resorcinol / carbonate are known. However, these solvents have a high toxicity or flammability problem.

Further, US Patent No. 5955019 proposes a method of spinning using a polyketone solution prepared by dissolving polyketone in an aqueous solution such as zinc chloride, zinc bromide, lithium bromide, lithium iodide, or lithium thiocyanate. In addition, the above document discloses that a strength of 1.5 GPa is achieved with a monofilament. However, in the spinning of the fiber, it is much harder to control the spinning, stretching, drying, and washing conditions of the fiber during the spinning of the multifilament than the spinning of the monofilament. It is difficult to manufacture an industrial yarn of 2000 filaments. In addition, little research has been made on polyketone fibers for tire cords consisting of 200 to 2000 filaments.

Tire cords that are used as the skeleton that forms the inside of tires are currently using tire cords of various materials, including polyester cords, nylon cords, aramid cords, rayon cords, and steel cords. In terms of performance, (1) the strength and initial modulus are large (2) heat resistant and not brittle in dry and wet heat (3) fatigue resistance (4) form stability (5) excellent adhesion to rubber, etc. Can be mentioned. However, all tire cords currently known do not satisfy all of the various necessary functions, and are used according to their intrinsic properties of each cord material.

For example, in the case of a high-speed radial tire for a passenger car, which requires initial modulus, heat resistance, and shape stability among the above-mentioned performances, a tire made of rayon fiber having a low shrinkage rate and excellent shape stability due to the intrinsic properties of the fiber itself Code is mainly used. Initial modulus is expressed as the slope of the load to produce a level of elongation, which is the slope of the elongation-load curve in the elongation test. In the case of tires with a large modulus tire cord, less tire deformation occurs at a certain level of load, thereby improving tire fatigue performance, heat generation and durability, and in particular, improving steering stability in radial tires. do.

Textiles used in tire cords or industrial materials sectors have different physical properties, such as strength and modulus, in contrast to apparel sectors where color expression and handling are important.

Considering the fact that the tire cord filament is made of several hundred strands of filament to be around 1,500 denier, it is determined that it is difficult to secure the required physical properties of the tire cord after the twisting and dipping. In addition, since the process stability and cooling efficiency for the adhesion of the filaments discharged to the spinning nozzle vary with the increase in the number of filaments, the outer diameter of the spinning nozzle, the orifice diameter, the orifice spacing, the air layer length, the direction of coagulating fluid and the spinning direction A new design is required considering the drying conditions according to the speed, and the design may cause a difference in properties.

Therefore, in order to solve the problems of the prior art, the present inventors can prepare a homogeneous polyketone solution by dissolving a polyketone containing 90 mol% or more of ketone units in a repeating unit in an aqueous solution containing zinc bromide. In addition, it is possible to produce a polyketone fiber of excellent strength by the wet and dry spinning method, found that it is suitable for the tire cord and came to complete the present invention.

The present invention has been made in order to solve the problems and disadvantages described above, to prepare a homogeneous polyketone solution by dissolving a polyketone containing 90 mol% or more of the ketone unit in a repeating unit in an aqueous solution containing zinc bromide And, to provide a polyketone fiber and a deep cord excellent in strength from the polyketone solution.

Accordingly, the present invention,

(A) dissolving a polyketone containing 90 mol% or more of ketone units in a repeating unit in an aqueous metal salt solution containing zinc bromide to prepare a polyketone solution; (B) extruding the polyketone solution through a spinning nozzle, and then passing through an air layer to reach a coagulation bath to solidify it to obtain a multifilament (C) washing, drying and emulsion treatment of the multifilament obtained Drawing by drawing; (D) providing a polyketone deep cord for a tire cord having the following physical properties, which is manufactured by a method comprising the step of twisting the drawn yarn with a twisting machine to produce a raw cord, and then weaving the same. It features. (1) Cutting load 14.0 to 35.0 kg, (2) Fineness 2,000 to 6,000 denier, (3) Resistance to fatigue at least 80%, (4) Adhesion to rubber 10.0 to 20.0 kg

In addition, the concentration of the polyketone in the polyketone solution of step (A) is preferably 2 to 20% by weight.

In addition, calcium bromide or lithium bromide may be further included in the aqueous metal salt solution containing zinc bromide.

Moreover, it is preferable that the density | concentration of the metal salt in aqueous metal salt solution is 30 to 80 weight%.

In the twisting step of the step (D), it is preferable that the upper and lower softening water is 200/200 TPM to 500/500 TPM.

In addition, the present invention relates to a radial pneumatic tire having a flatness of 0.65 or less, comprising: a pair of parallel bead cords and at least one radial carcass ply wound around the bead core and a belt stacked on the outer periphery of the carcass. And a circumferential belt reinforcement layer formed on an outer circumferential side of the belt layer, wherein the carcass ply or belt reinforcement layer comprises the polyketone deep cord.

Hereinafter, with reference to the accompanying drawings, the present invention will be described in detail.

1 is a schematic diagram of a spinning process for producing a polyketone filament as an embodiment of the present invention and a detailed description is as follows.

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

After that, the filament passed through the coagulation bath is passed through the washing tank. At this time, the temperature of the coagulation bath and the water washing tank is maintained at about 0 to 80 ° C. in order to prevent the deterioration of physical properties due to the formation of pores in the fibrous structure due to the rapid desolvent.

The fiber passed through the washing tank is washed with acid in an aqueous solution containing acid, and then passed through a second washing bath to remove the acid, and then passed through a dryer to contain an oil and an additive in an emulsion treatment apparatus. do.

In addition, it passed through an interlace nozzle to improve flatness and improve focusing. At this time, the air pressure was supplied at 0.5 to 4.0 kg / cm ² and the number of entanglements per meter of filament was 2 to 40 times.

Thereafter, the filament yarn passing through the interlace nozzle is dried while passing through the drying apparatus. At this time, the drying temperature and drying method have a great influence on the post process and the physical properties of the filament.

And the filament which passed the drying apparatus is finally wound up by a winding machine via a secondary tanning apparatus.

In addition, the stretching process in the polyketone fibers of the present invention is very important for high strength and hot water resistance improvement. There are hot air heating and roller heating in the drawing process, but hot air heating is more effective in producing high-strength polyketone fibers because the filament is in contact with the roller surface and the fiber surface is easily damaged. Although heating is possible at the temperature of 140-270 degreeC, 160-260 degreeC is preferable. If the heating temperature is below 140 ° C, the molecular chain is not sufficiently behaved, so high magnification thermal stretching is impossible, and above 270 ° C, polyketone is easily decomposed, resulting in deterioration of physical properties.

First, the polyketone which comprises the polyketone fiber of this invention is demonstrated. Such polyketones comprise ketone units represented by —CH ₂ CH ₂ —CO— as the main repeating unit, at least 90 mol%. Moreover, in this invention, repeating units other than the said ethylene, for example, a propylene, butylene, 1-phenylethylene repeating unit can be contained in the quantity less than 10 mol% with respect to all the repeating units.

However, since the strength, elastic modulus, dimensional stability and heat resistance of polyketone fibers decrease when the amount of repeating units such as propylene other than the repeating unit of ethylene increases, the amount of ketone units of the general formula (1) is preferably It is 95 mol% or more, More preferably, it is 98 mol% or more. In the present invention, it is most preferable that the polyketone fibers include only ketone units represented by -CH ₂ CH ₂ -CO-. In addition, such polyketones may optionally further comprise additives such as antioxidants, radical inhibitors, ultraviolet absorbers, flame retardants and the like.

The polyketone fibers of the present invention have an intrinsic viscosity of 1 to 20 dl / g, preferably 3 to 10 dl / g. If the intrinsic viscosity is less than 1 dl / g, the strength or fatigue resistance of the polyketone fiber is not sufficient, and if the intrinsic viscosity is more than 20 dl / g, it is economically time-consuming and expensive, and uniformly dissolving It is difficult.

The polyketone polymers according to the invention are prepared by the specific polymerization process described below. The following production methods are only intended to more clearly understand the present invention and are not intended to limit the scope of the present invention.

The autoclave was filled with methanol, and a catalyst solution prepared by stirring palladium acetate, 1,3-bis (di (2-methoxyphenyl) phosphino) propane and trifluoroacetic acid was added thereto. Thereafter, the autoclave was charged with a mixed gas containing carbon monoxide and ethylene in a molar ratio of 1: 1, and the mixed gas was continuously added at a pressure of 1 to 10 MPa while reacting at 50 to 100 ° C for several hours. After completion of the reaction, the pressure was released and the obtained white polymer was washed repeatedly with heated methanol and 1,3-pentanedione. The obtained polyketone was found to be poly (1-oxotrimethylene) by analysis such as nuclear magnetic resonance spectra. Moreover, molecular weight distribution was 2.8 and intrinsic viscosity was 5.0 dl / g.

The content of the polyketone in the polyketone solution of the present invention is such that the concentration is 2 to 20% by weight, more preferably 5 to 14% by weight, based on the degree of polymerization of the polyketone polymer with respect to an aqueous solution such as zinc bromide. At this time, when the content of the polyketone polymer is less than 2% by weight it does not have physical properties as a fiber, when it exceeds 20% by weight it is difficult to dissolve in an aqueous solution such as zinc bromide to obtain a homogeneous solution.

On the other hand, 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 as a solvent for dissolving the polyketone. Specifically, zinc salts include zinc bromide, zinc chloride, zinc iodide, and the like, and calcium salts include calcium bromide, calcium chloride, calcium iodide, and the like, and lithium salts such as lithium bromide, lithium chloride, and lithium iodide. And the like, and iron salts include iron bromide and iron iodide. Among these metal salts, it is particularly preferable to use at least one member selected from the group consisting of zinc bromide, calcium bromide, lithium bromide and iron bromide in view of solubility of the raw polyketone and homogeneity of the polyketone solution.

Moreover, it is preferable that the density | concentration of metal salt in the metal salt aqueous solution of this invention is 30 to 80 weight%. If the concentration of the metal salt is less than 30% by weight solubility is lowered, if the concentration of the metal salt is 80 or more, the cost of concentrating increases, which is disadvantageous economically. Water, methanol, ethanol and the like may be used as a solvent for dissolving the metal salt, but in particular, water is used in the present invention because it is advantageous in terms of economics and solvent recovery.

In order to obtain a polyketone fiber having high strength and excellent fatigue resistance and dimensional stability as a key technical matter in the present invention, 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 and 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 weight ratio of the sum 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 and lithium bromide at the time is 40/60 to 90/10, preferably 60/40 to 85/15.

Although it does not restrict | limit especially as a manufacturing method of a polyketone solution, The example of a preferable manufacturing method is demonstrated below.

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

In addition, in the present invention, the polyketone polymer may be used by mixing other polymer materials or additives. Polymeric materials include polyvinyl alcohol, carboxymethyl polyketone, polyethylene glycol, and the like, and additives include viscosity enhancing agents, titanium dioxide, silica dioxide, carbon, and ammonium chloride.

Hereinafter, a method for producing polyketone fibers, including the steps of spinning, washing, drying and stretching the prepared 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.

More specifically, the spinning process of the method according to the present invention is an orifice having a diameter of 100 to 500 µm and a length of 100 to 1500 µm, wherein the ratio (L / D) of the diameter to the length is 1 to 3 to 8 times, The spacing between the orifices is extruded and spun through the spinning solution through a spinning nozzle including a plurality of orifices of 1.0 to 5.0 mm, so that the fibrous spinning solution passes through the air layer to reach a coagulation bath, and then coagulates to obtain a multifilament. do.

 The spinning nozzle used is usually circular in shape and has a nozzle diameter of 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 adhesion may occur before the discharged solution is solidified. If the nozzle diameter is too large, peripheral devices such as a spinning pack and a nozzle are enlarged, which is disadvantageous to the installation surface. In addition, when the diameter of the nozzle orifice is less than 100 μm, a large number of trimmings occur during spinning, which adversely affects radioactivity. When the nozzle orifice exceeds 500 μm, the solidification rate of the solution in the coagulation bath after spinning is slow, Desolvent and flushing will be difficult.

In view of the application, especially for tire cords, and considering the orifice spacing for uniform cooling of the solution, the number of orifices is 100 to 2,200, more preferably 300 to 1,400.

If the number of orifices is less than 100, the fineness of each filament becomes thick, so that the solvent cannot be sufficiently released within a short time, so that solidification and washing with water are not completed. If the number of orifices is more than 2,200, the filaments and affixes close to the filament are likely to occur in the air layer section, and the stability of each filament decreases after spinning, rather than the deterioration of physical properties. Can cause.

When the fibrous spinning stock solution passed through the spinning nozzle is solidified in the upper coagulating solution, the larger the diameter of the fluid, the greater the difference in the coagulation rate between the surface and the inside, thus making it difficult to obtain a dense and uniform fiber. Therefore, when spinning the polyketone solution, even the same discharge amount can be obtained into the coagulating liquid with a smaller diameter while maintaining the appropriate air layer. The air layer is preferably 5 to 50 mm, more preferably 10 to 20 mm. Too short air gap distances increase the rate of micropores generated during rapid surface layer solidification and desolvation, which hinders the increase in elongation ratio, while too long air gap distances are associated with filament adhesion, atmospheric temperature, and humidity. It is difficult to maintain process stability by receiving a lot.

The composition of the coagulation bath used in the present invention is such that the concentration of the aqueous metal salt solution is 1 to 20% by weight. The coagulation bath temperature is kept at -10 to 60 ° C, more preferably at -5 to 20 ° C. In the coagulation bath, when the filament passes through the coagulation bath, if the spinning speed increases more than 500m / min, the coagulation fluid shakes due to friction between the filament and the coagulation solution. In order to improve productivity by extending the excellent physical properties and spinning speed through the stretching orientation, such a phenomenon is a factor that impairs process stability, it is necessary to minimize it.

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

In the present invention, the dryer temperature is 100 ℃ or more, preferably 200 ℃ or more to impart an emulsion, heat-resistant agent, antioxidant or stabilizer to the fiber passed through the dryer.

 In addition, the stretching process in the polyketone fibers of the present invention is very important for high strength and hot water resistance improvement. There are hot air heating and roller heating in the drawing process, but hot air heating is more effective in producing high-strength polyketone fibers because the filament is in contact with the roller surface and the fiber surface is easily damaged. Although heating is possible at the temperature of 140-270 degreeC, 160-260 degreeC is preferable. If the heating temperature is below 140 ℃, the molecular chain does not behave sufficiently, high magnification thermal stretching is impossible, and above 260 ℃ polyketone is easy to decompose, leading to the deterioration of physical properties.

The stretching is carried out in one or two or more stages of multistage for stretching the polyketone fibers. In addition, when performing multistage stretching, it is preferable that the temperature-stretching at which the stretching temperature gradually increases as the draw ratio is increased. As conditions for specific temperature-stretching, it is 180-200 degreeC in the 1st stage, 200-220 degreeC in the 2nd stage, and 230-260 degreeC in the 3rd stage. The draw ratio of the present invention has a total draw ratio of 5 to 40 times, preferably 10 to 30 times.

The multifilaments produced by the process according to the invention are polyketone multifilaments with a total denier range of 500 to 3,500 and a cutting load of 6.0 to 40.0 kg. The multifilament is composed of 100 to 2200 individual filaments having a fineness of 0.5 to 8.0 denier. At this time, the strength of the multifilament is 5.0 to 30 g / d, elongation is 3 to 10%, shrinkage rate of 0.5 to 3%, it can be advantageously used as a tire cord for a passenger car.

In the present invention, the wound yarn is twisted with a twister to produce a raw cord, and then weaved it to be immersed in the dipping liquid to provide a tire cord and a tire.

When explaining the twisting process of the present invention in more detail, the polyketone multi-filament produced by the above method is a 'raw cord (Raw Cord) for the tire cord by twisting two wound yarns with a direct twisting machine that the twisting and joining proceeds simultaneously Manufacture. Raw cords are manufactured by adding Ply Twist to a polyketone yarn for tire cords and then adding them together with Cable Twist. In general, the upper and lower ends are applied with the same or different years as needed.

An important result of the present invention is that the physical properties of the cord, elongation, mesophilic, fatigue resistance, etc. are changed depending on the level (year) of twist applied to the polyketone multifilament. In general, when the twist is high, the strength decreases, and the trunk and the body tend to increase. The fatigue fatigue tends to improve with the increase of twist. The soft water of the polyketone tire cord manufactured in the present invention was produced at 200/200 TPM to 500/500 TPM at the same time as the upper and lower edges, and giving the same value as the upper and lower edges does not indicate the rotation or twist of the manufactured tire cords. It is to maximize physical expression by making it easy to maintain a straight line without. At this time, if less than 200/200 TPM, the extension of the raw cord is reduced, fatigue fatigue is easy to fall, and if it exceeds 500/500 TPM, the strong degradation is large, it is not suitable for the tire cord.

'Raw Cord' is manufactured by using a weaving machine (weaving machine), weaving the obtained fabric in the dipping liquid, and then cured for the tire cord with a resin layer attached to the 'Raw Cord' surface Make a 'Dip Cord'.

In more detail, the dipping process of the present invention, dipping is achieved by impregnating a surface of the fiber with a resin layer called RFL (Resorcinol-Formaline-Latex), which is a disadvantage of the fibers for tire cords that are inherently poor in adhesion to rubber. Is carried out to improve. In general, rayon fiber or nylon is subjected to one bath dipping, and in the case of using PET fiber, since the reactor on the surface of PET fiber is less than that of rayon fiber or nylon fiber, the surface of the PET is activated first and then the adhesive treatment is performed. (2 bath dipping). The polyketone multifilament according to the present invention uses one bath dipping. The dipping bath uses a known dipping bath for the tire cord.

The deep cord manufactured according to the above-described method has a total denier of 1000 to 6000 days and a cutting load of 14.0 to 35.0 kg, which can be advantageously used as a tire cord for a passenger car.

In addition, the polyketone deep cord produced according to the present invention is used as a material of carcass ply or cap ply of pneumatic radial tires.

Specifically, a code as shown in FIG. 3 is produced. More specifically, the carcass cord 13 using the polyketone deep cord manufactured according to the present invention has a total denier of 2,000 to 8,000. The carcass ply 12 comprises at least one layer of carcass ply reinforcement tire cords 13. In the carcass ply, the deep cord reinforcement density of 15 to 35 EPI is preferable, since the mechanical properties of the carcass ply are drastically reduced when the reinforcement density is less than 15 EPI, and it is economically disadvantageous when it exceeds 35 EPI.

The carcass ply 12 having the radially outer fly turnup 14 preferably comprises one to two carcass cords. The reinforcement carcass cord 13 is oriented at an angle of 85 ° to 90 ° with respect to the circumferential intermediate surface of the tire 11. In the particular embodiment shown, the reinforcing carcass cord 13 is arranged at 90 ° with respect to the circumferential intermediate plane. In the case of the fly turn up 14, it is preferred to have a height of about 40 to 80% with respect to the tire maximum cross-sectional height. If the fly turn-up is less than 40%, the stiffness complementary effect of the tire sidewall is too low, and if it is 80% or more, the tire sidewall stiffness is too high, which adversely affects the riding comfort.

The bead regions 15 of the tire 11 each have an annular bead core 16 that is inextensible. The bead core is preferably made of a single or single filament steel wire wound continuously. In a preferred embodiment, high strength steel wires of 0.95 mm to 1.00 mm diameter form a 4x4 structure, and it is also possible to form a 4x5 structure.

In certain embodiments of the present invention, the bead region also has a bead filler 17, in the case of the bead filler, it is necessary to have a hardness of at least a certain level, preferably Shore A hardness of 40 or more is preferred.

In the present invention, the tire 11 is reinforced by the crown portion by the belt 18 and the cap ply 19 structure. The belt structure 18 comprises two cutting belt plies 20 and the cords 21 of the belt plies are oriented at an angle of about 20 degrees with respect to the circumferential central face of the tire. The cord ply 21 of the belt ply is arranged opposite to the direction of the cord 22 of the other belt ply in a direction opposite to the circumferential center surface. However, the belt 18 may comprise any number of plies and may preferably be arranged in the range of 16 to 24 °. The belt 18 serves to provide lateral rigidity to minimize the rise of the tread 23 from the road surface during operation of the tire 11. The cords 21 and 22 of the belt 18 are made of steel cords and have a 2 + 2 structure, but can be produced in any structure. The cap ply 21 and the edge ply 24 are reinforced on the upper portion of the belt 18. The cap ply cord 25 in the cap ply 19 is reinforced in parallel to the circumferential direction of the tire, thereby increasing the speed of the tire. It serves to suppress the change in the size of the circumferential direction, and a cap fly cord 25 having a large heat shrinkage stress at high temperature is used. One layer of cap ply 19 and one layer of edge ply 21 may be used, but preferably 1-2 layers of cap ply and also one or two layers of edge plies are reinforced. The cap fly cord may use a polyketone deep cord manufactured according to the method of the present invention.

Hereinafter, the configuration and effects of the present invention will be described in more detail with specific examples and comparative examples, but these examples are only intended to more clearly understand the present invention and are not intended to limit the scope of the present invention. In Examples and Comparative Examples, properties of the tire cord and the like were evaluated in the following manner.

(a) intrinsic viscosity

Intrinsic viscosity [IV] of the dissolved polyketone was measured at 25 ± 0.01 ° C. and a concentration range of 0.1 to 0.6 g / dl using a Uberod viscometer with 0.5M hexafluoroisopropanol solution prepared according to ASTM D539-51T. . Intrinsic viscosity is obtained by extrapolating specific viscosity according to concentration.

(b) Dry heat shrinkage (%, Shrinkage)

After drying for 24 hours at 25 ° C and 65% RH, dry heat shrinkage was determined using the ratio of the length (L ₀ ) measured during 20g stop and the length (L ₁ ) after treatment at 20g static load for 30 minutes at 150 ° C. Indicates.

S (%) = (L ₀ -L ₁ ) / L ₀ × 100

(c) strength (kgf) and elongation (%)

After drying at 107 ° C. for 2 hours, Instron's low-strength tensile tester was used. After twisting at 80 Tpm (80 twist / m), the sample was measured at 250 mm and a tensile speed of 300 m / min. The elongation at specific load imposed here represents the elongation at the point of 4.5g / d load.

(d) even with fatigue

The fatigue strength of the tire cord was measured using the Goodrich Disc Fatigue Tester, which is commonly used for fatigue testing of tire cords. Fatigue test conditions were 120 ℃, 2500RPM, compression 10% and 18% conditions, and after the fatigue test was swelled in a tetra chloroethylene solution for 24 hours to swell the rubber and the rubber and the cord was separated to measure the residual strength. The residual strength was measured after drying at 107 degrees for 2 hours using a conventional tensile strength tester according to the method (c) above.

(e) adhesion

Adhesion was measured by the H-test method based on ASTM D4776-98 method.

Example 1

A 60% by weight zinc bromide solution was injected into the extruder maintained at an injection temperature of 55 ° C and 78 ° C at a speed of 6900 g / hour with a gear pump. Inject the extruder at 784g / hour to set the residence time in the extruder swelling zone to 0.8 minutes and to raise the temperature to 60-80 ° C. So that the polyketone powder is sufficiently dissolved in the metal salt solution. The polyketone fibers were produced by wet and dry spinning by maintaining the screw at 200 ° C. and operating the screw at 200 rpm. At this time, the number of nozzle odds and hole diameters were 500 and 0.5 mm, respectively, and a circular nozzle having an L / D of 5 was used and the air gap was 10 mm.

The concentration of polyketone in the discharged solution was 6.8% by weight and homogeneous without undissolved polyketone particles. After the obtained fiber was stretched in three steps while gradually increasing the temperature at 180 ° C, 210 ° C, and 235 ° C, the final filament fineness was adjusted to 1,000 deniers.

 The filament stretched yarn was twisted in two joints with the same soft water of 300TPM each using a direct twister, and then immersed in a conventional RFL solution and heat-treated to prepare a 'Dip Cord' to evaluate physical properties.

EXAMPLE 2, 3, 4

A stretched yarn and a treatment cord were prepared by performing experiments in the same manner as in Example 1 while changing the type and composition ratio of zinc bromide or metal bromide containing zinc bromide as shown in Table 1 below. The physical properties of the drawn yarn and the treatment cord thus prepared are shown in Table 1 below.

[Comparative Examples 1 and 2]

A stretched yarn and a treatment cord were manufactured by performing experiments in the same manner as in Example 1 while changing the type and composition ratio of zinc chloride or metal chloride including zinc chloride as shown in Table 1 below. The physical properties of the drawn yarn and the treatment cord thus prepared are shown in Table 1 below.

TABLE 1

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 menstruum ZnBr ₂ ZnBr _{2 /} CaBr ₂ ZnBr ₂ / LiBr ZnBr ₂ / LiBr / CaBr ₂ ZnCl ₂ ZnCl _{2 /} CaCl ₂ Composition ratio of metal salt 100 80/20 60/40 50/30/20 100 35/65 Polyketone Intrinsic Viscosity (㎗ / g) 5.0 5.0 5.0 5.0 5.0 5.0 Extrusion Temperature (℃) 80 90 80 80 80 60 Drawing material Fineness (denier) 1000 1000 1000 1000 1000 1000 Strength (g / d) 18.0 20.0 19.1 20.5 17.5 17.6 Elongation (%) 3.9 3.6 3.8 4.2 4.6 4.7 Dry Heat Shrinkage (%) 1.0 1.6 1.6 1.7 1.9 2.0 Deep Code Properties    Soft water (TPM) up / down 300/300 300/300 300/300 300/300 300/300 300/200    Construction (Ply) 2 2 2 2 2 2    Strong (kgf) 30.5 29.1 29.5 29.1 22.8 23.8    Intermediate Elongation (%) 1.7 1.8 2.0 2.2 2.2 2.3    Dry heat shrinkage (%) 0.2 0.2 0.3 0.3 0.4 0.4    Adhesion 16.0 16.8 16.9 16.3 15.5 14.9    Fatigue resistance (%) 85 85 86 87 77 78

Example 5

The radial tire manufactured from the polyketone deep cord manufactured according to Example 1 of the present invention has a carcass layer having a radially outer fly turn-up, and the carcass layer is installed such that one layer of the deep cord is included. At this time, the specification of the carcass cord was as shown in Table 2 below, and was oriented at a 90 degree angle with respect to the circumferential intermediate surface of the tire. The fly turn-up 14 was to have a height of 40 to 80% with respect to the tire maximum cross-sectional height. The bead portion 15 had a bead core 16 having a high strength steel wire having a diameter of 0.95 to 1.00 mm and a bead filler 17 having a shore A hardness of 40 or more. The belt 18 is reinforced by a belt reinforcement layer with a top layer of cap ply 19 and a first layer of edge ply 24 so that the cap fly cord in the cap ply 19 is parallel to the circumferential direction of the tire. Placed.

Example 6

A tire was manufactured in the same manner as in Example 4 except that the polyketone deep cord manufactured according to Example 1 of the present invention was used as the cap fly cord in the cap ply 19.

Comparative Example 3

A tire was manufactured in the same manner as in Example 5, except that the polyketone deep cord prepared according to Comparative Example 1 of the present invention was used.

[Comparative Example 4]

A tire was manufactured in the same manner as in Example 4, except that the polyketone deep cord prepared according to Comparative Example 1 of the present invention was used.

The 215/60 R15 V tires manufactured according to Example 5 6 and Comparative Examples 3 and 4 were mounted on a 2000cc class passenger car, and the noise generated in the vehicle was measured while driving at a speed of 60 km / h. The noise was expressed in dB, and the steering stability and the riding comfort were evaluated by experienced drivers by driving the test course in units of 5 out of 100 points, and the results are shown in Table 2 below. Durability is based on FMVSS 109's P-metric tire endurance test method, measuring 38 degrees Celsius (± 3 degrees) and 85, 90, 100% of the tire's nominal load. A total of 34 hours was used to determine the pass (OK) when no trace of bead separation, cord cutting, belt separation, etc. was found in any part of the tread, sidewall, carcass cord, inner liner, or bead. .

[Table 2]

Example 5 Example 6 Comparative Example 3 Comparative Example 4 Carcass Material Polyketone Polyketone Polyketone Polyketone Specification (d / ply twisted yarn) 1000d / 2 1000d / 2 1000d / 2 1000d / 2 Strong (Kg) 25.6 25.6 22.8 22.8 Cap fly Material nylon Polyketone nylon nylon Specification (d / ply twisted yarn) 1260d / 2 1000d / 2 1260d / 2 1260d / 2 Strong (Kg) 24 30.5 24 24 tire Flat ratio 0.60 0.60 0.60 0.60 Carcass floors One One One One Cap fly floor One One One One Tire weight (kg) 9.73 9.76 9.94 10.01 Ride 100 100 91 94 Steering stability 100 100 94 94 durability OK OK OK OK Uniformity 100 100 94 96 Noise (dB) 60.4 59.8 64.5 63.2

According to the test results in Table 2, the tire using polyketone fibers prepared from a solution dissolved in a metal salt containing zinc bromide according to the present invention (Example 5) was prepared from a solution dissolved in a metal salt containing zinc chloride. It can be seen that the weight of the tire is reduced compared to the tires using the manufactured polyketone fibers (Comparative Examples 3 and 4), and thus it is possible to reduce the rolling resistance. In addition, the tire (Example 6) in which the polyketone fibers are applied to the carcass layer and the cap ply at the same time significantly reduces the noise of the tire.

In addition, it can be seen that in the case of the present invention using the polyketone cord prepared by the present invention for the carcass or cap ply, the effect is excellent in terms of riding comfort, steering stability, and uniformity.

The present invention provides a homogeneous polyketone solution by dissolving a polyketone containing 90 mol% or more of ketone units in a repeating unit in an aqueous solution containing zinc bromide, and polyketone fibers and dip having excellent strength from the polyketone solution. To provide the code. Polyketone fibers and deep cords prepared according to the present invention are excellent in strength and modulus, and tires manufactured by applying them to the carcass layer or the belt reinforcing layer as reinforcing fibers are excellent in form stability and steering stability.

1 is a schematic diagram of a spinning process for producing a polyketone filament of the present invention.

Figure 2 is a schematic diagram showing the structure of a tire for a passenger car manufactured using the polyketone deep cord according to the present invention.

Claims (6)

(A) dissolving a polyketone containing 90 mol% or more of ketone units in a repeating unit in an aqueous metal salt solution containing zinc bromide to prepare a polyketone solution; (B) extruding the polyketone solution through a spinning nozzle, and then passing through an air layer to reach a coagulation bath to solidify it to obtain a multifilament. (C) stretching the obtained multifilament by washing, drying and emulsion treatment; (D) a polyketone deep cord for a tire cord having the following physical properties, which is manufactured by a method comprising the step of twisting the drawn yarn with a twisting machine to produce a raw cord, and then weaving the same. (1) cutting load 14.0 to 35.0 kg, (2) fineness 2,000 to 6,000 denier, (3) resistance to fatigue of 80% or more, (4) adhesion to rubber 10.0 to 15.0 kg, The method of claim 1, Polyketone deep cord for a tire cord, characterized in that the concentration of polyketone in the polyketone solution of step (A) is 2 to 20% by weight. The method of claim 1, The polyketone deep cord for a tire cord, further comprising calcium bromide or lithium bromide in the aqueous metal salt solution containing zinc bromide. The method of claim 1, Polyketone deep cord for a tire cord having a concentration of metal salt in the polyketone solution of 30 to 80% by weight. The method of claim 1, Polyketone deep cord for a tire cord, characterized in that the number of upper and lower stations in the twisting step of step (D) is 200/200 TPM to 500/500 TPM. A radial pneumatic tire having a flatness of 0.65 or less, comprising: a pair of parallel bead cords and at least one radial carcass ply wound around the bead core and a belt layer laminated on the outer periphery of the carcass; A radial pneumatic tire comprising a circumferential belt reinforcement layer formed on the outer circumferential side of the layer, wherein the carcass ply or belt reinforcement layer comprises the polyketone deep cord of claim 1.