KR100894384B1 - Method of manufacturing a hybird dipped cord and radial tire containg the same - Google Patents

Abstract

A method for manufacturing hybrid dip cord and a radial tire using the same are provided to increase coefficient of utilization by adding appropriate twist on polyethylene terephthalate yarn of 1 and poly phenylene terephthalamide of 2. A method for manufacturing hybrid dip cord for a radial inflated tire comprises the following steps of: manufacturing pre twisted yarn by adding twist of a S direction of 30 - 200 TPM on polyethylene terephthalate yarns of 1; manufacturing a post twisted yarn by adding twist of Z direction of each 300 - 500 TPM on polyethylene terephthalate yarnsof 2; manufacturing raw cord by adding the pre twisted yarn of 300 - 500 TPM; and dipping the raw cord on a dipping solution. A tire(31) is reinforced by a belt body(38) and a cap ply(39). The belt body includes a cut belt ply(40) consisting of two belt cords(41)(42).

Description

Method of Manufacturing A Hybird Dipped Cord and Radial Tire Containg The Same}

The present invention relates to a method for producing a hybrid dip cord made of poly (p-phenylene terephthalamide) and polyethylene terephthalate and a radial tire including the hybrid dip cord in a carcass layer or a belt reinforcement layer.

In recent years, tire performance has been continuously improved according to the improvement of the road environment and the performance of the vehicle, and in particular, the safety is recognized as an important factor to be equipped with the tire as the weight of the vehicle increases and the limit speed increases. In line with the demand for increasing tire safety, tire safety standards are also changing, and the tire industry is actively researching methods for providing tire safety.

The radial tire includes a carcass ply reinforced with rubber with a fiber cord such as polyethylene terephthalate, rayon or aramid, and a belt structure reinforced with rubber with a steel cord. In order to prevent the tire from falling off the rim and to maintain stability, the bead wire is reinforced at the contact portion between the tire and the rim, and the bead wire simultaneously serves to fix the carcass splice.

Recently, some of poly (p-phenylene terephthalamide) is also used in such high speed low flat radial tires, but poly (p-phenylene terephthalamide) has very high mechanical and thermal properties and shape stability compared to polyethylene terephthalate. Excellent but expensive, its application is limited.

Prior art European Patent No. 4893665, which relates to a hybrid cord, discloses a hybrid cord made by twisting one each of a poly (p-phenylene terephthalamide) fiber and a wound yarn of nylon or polyethylene terephthalate. Poly (p-phenylene terephthalamide) fibers have a significantly higher modulus than nylon or polyethylene terephthalate fibers. This difference in physical properties may result in a nonuniformity of tension in the live cord when twisting one each of a poly (p-phenylene terephthalamide) fiber and a wound yarn of nylon or polyethylene terephthalate. Due to this problem, the strong utilization rate during the continuous shooting and dipping is sharply lowered.

The present invention is to solve this problem to solve the following technical problems.

The first object of the present invention is to provide a method for producing a hybrid dip cord for pneumatic radial tires prepared by imparting proper twist to one polyethylene terephthalate company and two poly (p-phenylene terephthalamide) companies. It is.

Another object of the present invention is to provide a pneumatic radial tire comprising a carcass ply and a cap ply (belt reinforcement layer) made of the hybrid dip cord.

According to a preferred embodiment of the present invention, the method for producing a hybrid dip cord of the present invention is to give a twist of 30 to 200 TPM (twist number / m) in the S direction to one polyethylene terephthalate yarn to produce the twisted yarn step; Preparing twisted yarns by imparting twist of 300 to 600 TPM in the Z direction to the one polyethylene terephthalate linear twisted yarn and two non-twisted poly (p-phenylene terephthalamide) yarns; Plying the lower twisted yarn into three and adding an upper edge of 300 to 600 TPM in the S direction to manufacture a raw cord; And treating the raw cord by dipping in a dipping solution.

According to another suitable embodiment of the present invention, the method for producing a hybrid dip cord is compared to poly (p-phenylene terephthalamide) in one polyethylene terephthalate yarn and two poly (p-phenylene terephthalamide) yarns. Giving a soft twist of polyethylene terephthalate yarn to 30 to 200 TPM to prepare a Z-direction low twist yarn of 300 to 600 TPM; Plying the lower twisted yarn into three and adding S-phase upper edge of 300 to 600 TPM to produce a raw cord; And immersing the raw cord in a dipping solution for processing.

In the present invention, the fineness of polyethylene terephthalate and poly (p-phenylene terephthalamide) for the production of a hybrid dip cord are 1000 to 4000 denier, respectively.

Radial pneumatic tire according to the present invention has a flatness ratio of 0.7 or less, a pair of parallel bead cord, at least one radial carcass ply wound around the bead core, the belt layer laminated on the outer periphery of the carcass ply ;, And a circumferential belt reinforcement layer formed on an outer circumferential side of the belt layer, wherein the carcass layer or cap fly (belt reinforcement layer) is made of polyethylene terephthalate and poly (p-phenylene terephthalamide) multifilament. A deep cord, wherein the hybrid deep cord comprises: (1) an intensity of at least 13.0 g / d; (2) elongation at least 2.5% at a load of 6.8 kg; (3) at least 13 kg of adhesion to rubber; (4) at least 85% fatigue resistance; (5) a fineness of 2000 to 8000 deniers; And (6) a contraction force of 4.0 N or more.

The poly (p-phenylene terephthalamide) company and the polyethylene terephthalate company for hybrid dip cord manufacturing according to the present invention are each manufactured using the following process.

The poly (p-phenylene terephthalamide) polymer used in the present invention contains at least 95 mol% of p-phenylene terephthalamide units, preferably composed of only p-phenylene terephthalamide units, and silica compounds It may include. The poly (p-phenylene terephthalamide) polymer according to the present invention preferably has a ratio of 10.0 to 13.0 wt% of p-phenylenediamine and terephthaloyl chloride raw material relative to the sum of all raw materials and the solvent system. The solution was then condensation-polymerized in an N-methyl pyrrolidone (NMP) solution at a temperature of 10 ° C. or less at an equivalence ratio of 0.95 to 1.01, and neutralized, washed with water and dried to obtain pure poly (p-phenylene terephthalate). Amide) polymers. The intrinsic viscosity of the poly (p-phenylene terephthalamide) polymer thus obtained is in the range of 5.5 to 7.0.

The poly (p-phenylene terephthalamide) polymer thus prepared is made of fibers according to the following method.

In the spinning step (step A) of the production method according to the invention, the poly (p-phenyleneterephthalamide) dope of the optically anisotropic stock solution having an intrinsic viscosity in the range of 5.5 to 7.0 is carried out at a temperature of 70 to 85 ° C. through a pack and a nozzle. It is a cold shock spinning, whereby the lowering of the viscosity of the polymer by pyrolysis and hydrolysis of the dope is prevented. A static mixer or the like may be installed in the upper portion of the pack to uniformly mix the spun polymer and to increase the uniformity of the dope viscosity for each part of the polymer.

In the solidification cooling step (step B) of the present invention, an air layer is formed in the intervening region directly under the nozzle to the start point of the solidification zone before solidifying the discharge sand produced in the step A through the solidification zone. The zone becomes an air gap and may have a length of 3 to 15 mm and a temperature of 10 to 40 ° C. In the coagulation zone, the coagulation solution becomes water containing sulfuric acid, and the coagulation solution may have a temperature of 1 to 15 ° C.

The coagulating solution is preferably water containing 3 to 12 wt% sulfuric acid. If the sulfuric acid is less than 3wt%, sulfuric acid on the surface of the fiber quickly escapes to solidify rapidly, but sulfuric acid inside the fiber is difficult to escape easily, resulting in a skin-core structure of the fiber structure, which significantly reduces the strength of the yarn. If the amount exceeds 12 wt%, the solidification of the fiber is slowed down, resulting in fusion between fibers, cutting, and the like, which makes the spinning operation difficult.

The yarn which has been solidified through the step B is wound around the feed roller a certain number of times, and wound with water evaporated from the drying roller through washing and neutralizing.

Poly (p-phenyleneterephthalamide) fibers prepared according to the above method have a fineness of 500 to 2000 denier, and (1) intrinsic viscosity of 5.0 to 6.0; (2) an intensity of 18.0 to 26.0 g / d; (3) elongation between 2.8 and 4.5%; And (4) a shrinkage of 0 to 3%.

Polyethylene terephthalate, which is used to prepare a hybrid deep cord, is manufactured through the following process.

Polyethylene terephthalate polymers for the production of polyethylene terephthalate may contain at least 85 mole% of ethylene terephthalate units but may optionally comprise only ethylene terephthalate units.

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

The terephthalic acid (TPA) and ethylene glycol raw materials are melt mixed in a ratio of 2.0 to 2.3 in the prepared polyethylene terephthalate chip, and the melt mixture is transesterified and axially-polymerized to produce low chips having an intrinsic viscosity of 0.60 to 0.70. raw chips). The low chip is then subjected to solid phase polymerization to have an intrinsic viscosity of 0.90 to 1.20 and a moisture content of 30 ppm or less under a temperature of 240 to 260 ° C and a vacuum.

If the intrinsic viscosity of the low chip is lower than 0.90, the intrinsic viscosity of the final stretched yarn is lowered, so that it is impossible to exhibit high strength as a treatment cord after heat treatment. On the other hand, if the intrinsic viscosity of the chip is higher than 1.20, the radial tension is excessively increased and the cross section of the emitter is uneven. This results in a large number of filament cuts during stretching, resulting in poor stretchability. In addition, if the moisture content of the chip exceeds 30ppm may cause hydrolysis during melt spinning.

Optionally, an antimony compound, preferably antimony trioxide, may be added as a polymerization catalyst in the course of the polycondensation reaction so that the amount of antimony metal remaining in the final polymer is 180 to 300 ppm. If the residual amount is less than 180 ppm, the polymerization reaction rate is lowered, and the polymerization efficiency is lowered. If the amount is more than 300 ppm, more than necessary antimony metal acts as a foreign material, which may lower the radio-stretching workability.

Polyethylene terephthalate chip produced in this way is fiberized through the process shown in FIG.

Referring to FIG. 2, the polyethylene terephthalate chip has a spinning temperature of 290 to 310 ° C. and a spinning draft ratio of 200 to 800 (line speed at the first winding roller / nozzle through the pack 1 and the nozzle 2). Low-temperature melt spinning to prevent a decrease in the viscosity of the polymer by pyrolysis and hydrolysis. If the draft ratio is less than 200, the filament cross-section uniformity is worse, the drawing workability is significantly reduced, whereas if the spinning draft ratio exceeds 800, filament breakage occurs during spinning, making normal yarn production difficult.

The produced melt discharged yarn 4 is quenched and solidified through the cooling zone 3 and, if necessary, the distance to the start point of the cooling zone 3 immediately below the nozzle 2, that is, the length L of the hood. Short heating devices can be installed in the

The length L section of the hood becomes a delay cooling zone or heating zone and has a length of 50 to 250 mm and a temperature of 250 to 400 ° C. (air contact surface temperature).

According to the method of blowing cooling air in the cooling zone 3, open quenching method, circular closed quenching method and radial outflow quenching method may be applied, but the present invention is not limited thereto. It is not. The discharge yarn 4 solidified by passing through the cooling zone 3 is oiled to 0.5 to 1.0% by the oil imparting device 5 to become unburned yarn.

Undrawn yarn is passed through a series of drawing rollers (6), (7), (8), (9) and (10) by a spin draw method, and the total draw ratio is 2.0 times or less, preferably 1.5 to 2.0 times. It extends and is obtained as the final stretched yarn 11 by the winding roller.

In the stretching process, the unstretched yarn is three-stage stretched, each stretching temperature is characterized in that 95 ℃ the glass transition temperature of the unstretched yarn. If the stretching temperature is lower than the glass transition temperature, the stretchability is inferior, and if the stretching temperature is higher than 95 ° C, crystallization during the stretching proceeds rapidly, making three-stage stretching difficult.

Making the distance between the nozzle and the top of the cooling unit as small as possible during spinning makes it advantageous to have high strength in the final stretched yarn. If the distance from the bottom of the heater to the bottom of the heater is 50 mm or less during spinning, the distance from the bottom of the heater to the bottom of the heater is 100 mm), or when the distance between the lower end of the heating device and the upper part of the cooling device is 50 to 150 mm, non-uniformity of undrawn yarn is generated to a considerable level, which makes it difficult to draw normal physical properties.

The stretched polyethylene terephthalate fiber thus prepared has (1) an inherent viscosity of 0.8 to 1.0; (2) a strength of at least 8.0 g / d; (3) at least 10% elongation; And (4) shrinkage of 3 to 5%.

The method for producing a hybrid dip cord according to the present invention using the prepared poly (p-phenylene terephthalamide) and polyethylene terephthalate yarn includes a step of preparing a raw cord by twisting the cord as a previous step (twisting step). Include.

The method for producing a raw cord according to the present invention comprises the steps of producing a twisted yarn by giving a twist in the S direction of 30 to 200 TPM to one polyethylene terephthalate yarn; Preparing low twisted yarn by imparting Z-direction twist of 300 to 600 TPM to each of the one polyethylene terephthalate linear twisted yarn and two non-twisted poly (p-phenylene terephthalamide) yarns; Plying the lower twisted yarn into three and adding the upper edge in the S direction of 300 to 600 TPM to produce a raw cord; And treating the raw cord by dipping in a dipping liquid. In addition, the production method of the raw cord according to the present invention is polyethylene terephthalate compared to poly (p-phenylene terephthalamide) in one polyethylene terephthalate yarn and two poly (p-phenylene terephthalamide) yarns in the lower rolling process Preparing lower twisted yarn to impart twist in the Z direction to lower the soft water of the yarn by 30 to 200 TPM; And it may include a method of producing a raw cord by adding the upper edge yarn in three directions by plying the lower twist yarn in three. The raw cord manufactured according to the manufacturing method of the present invention is immersed and treated in a dipping liquid to form a hybrid deep cord.

The present invention provides one twisted yarn in a S-direction twist of 30 to 200 TPM to one polyethylene terephthalate yarn, or one polyethylene terephthalate yarn and two poly (p-phenylene terephthales) in the lower rolling process. Amide) to give a twist of the polyethylene terephthalate yarn compared to poly (p-phenylene terephthalamide) yarn 30 to 200 TPM low Z direction to prepare a low-twisted yarn, characterized in that the method of twisting in the upper twisting process. This process is designed so that the tensile stress acts preferentially on the polyethylene terephthalate yarn during the initial extension of the raw material by adjusting the final twist number (the twisted number after the lower edge is added to the upper edge) to the polyethylene terephthalate yarn having a relatively high elongation. The break point of the terephthalate yarn and the poly (p-phenylene terephthalamide) yarn is the same, thereby improving the strong utilization and physical properties of the raw code. If giving polyethylene terephthalate less than 30 TPM or less than 30 TPM less than that of poly (p-phenylene terephthalamide), the effect of the margin is less. Too much tensile stress is applied to the (p-phenyleneterephthalamide) yarn. On the other hand, if the polyethylene terephthalate yarn is given a lead of more than 200 TPM, or the lower lead is given to the polyethylene terephthalate yarn over 200 TPM compared to the poly (p-phenylene terephthalamide), the polyethylene terephthalate The tensile stress is excessively concentrated at.

In the production method of the present invention, the properties of the cords such as elongation, stiffness, fatigue resistance, etc., depending on the level of twisting (number of years) imparted to the poly (p-phenylene terephthalamide) and polyethylene terephthalate yarns at lower or upper edges. Is changed. In general, when the twist is high, the strength decreases, and the trunk and the body tend to increase. In addition, fatigue fatigue tends to improve with increasing twist. The hybrid tire cord manufactured according to the present invention was manufactured such that the upper and lower edges together had a service life of 300/300 TPM to 600/600 TPM. The upper and lower edges are set to the same value so that the manufactured tire cords are easily maintained in a straight line without exhibiting rotation or twisting, thereby maximizing physical property expression. If it is less than 300/300 TPM, the elongation of the raw cord is reduced and fatigue resistance is likely to be lowered. On the other hand, if it exceeds 600/600 TPM, the strong drop is large and not suitable for tire cords.

Raw cords are woven using a weaving machine, and the woven fabric is immersed and cured in a dipping solution, and a dip cord for tire cords having a resin layer attached to the surface of the raw cord. Is manufactured).

In the manufacturing process according to the present invention, dipping refers to impregnating a surface of a fiber with a resin layer called RFL (Resorcinol-Formaline-Latex). The dipping process is carried out to ameliorate the disadvantages of the fibers for tire cords that are less adhesive with rubber.

In the present invention, the adhesive solution for the adhesion of the hybrid cord and rubber can be prepared using the following method.

Manufacturing method of adhesive liquid

45.6 parts by weight of 29.4 wt% resorcinol;

55.5 parts by weight of distilled water;

20 parts by weight of 37% formalin; And

10 wt% sodium hydroxide 3.8 parts by weight

      Prepare a solution containing the reaction after stirring for 5 hours at 25 ℃ add the following components.

40wt% VP-latex 300 parts by weight

129 parts by weight of distilled water

23.8 parts by weight of 28% aqueous ammonia.

After the addition of the ingredients it is aged for 20 hours at 25 ℃ to maintain a solid concentration of 19.05%.

After the hybrid cord is dried, the adhesive solution is attached. In order to control the adhesion amount of the adhesive liquid, a stretch of 1 to 5% is required, and preferably 2 to 4% of stretching can be made. If the elongation ratio is too high, the adhesion amount of the adhesive liquid can be controlled but the elongation is reduced and consequently the fatigue resistance is reduced. On the other hand, when the elongation ratio is too low, for example, when the elongation ratio is lowered to less than 1%, the dipping liquid penetrates into the polyethylene terephthalate cord, thereby making it impossible to control a defect per unit (DPU).

The adhesive amount is preferably 4 to 6% by weight of the fiber based on the solid content. After attaching the adhesive solution, the hybrid dip cord is dried at 120 to 150 ° C. The drying time can be from 180 seconds to 220 seconds, and the drying process is performed while the hybrid deep cord is stretched by 1 to 2%. When the elongation ratio is low, the core and the elongation of the cord may increase, indicating physical properties that are difficult to apply to the tire cord. On the other hand, if the elongation rate is more than 2%, the central body level is appropriate, but the body length may be too small, leading to poor fatigue resistance.

After drying, heat treatment is carried out in a temperature range of 130 to 170 ℃. The elongation rate during the heat treatment is maintained between -1 and 0%, and the heat treatment time is appropriate for 50 seconds to 90 seconds. If heat treatment is performed for less than 50 seconds, the reaction time of the adhesive solution is insufficient, resulting in low adhesive strength.In contrast, if the heat treatment is performed for more than 90 seconds, the hardness of the adhesive solution is increased, resulting in the fatigue resistance of the cord. Can be reduced.

The hybrid deep cord manufactured through such a process is applied to a carcass ply and a cap fly and used for manufacturing a passenger car tire.

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

Referring to FIG. 1, the bead regions 35 of the tire 31 become annular bead cores 36 each of which are inextensible. The bead core 36 is preferably made from a single filament steel wire wound continuously. Preferred embodiments are those wherein the high strength steel wire of 0.95 mm to 1.00 mm diameter forms a 4x4 structure, or forms a 4x5 structure.

In the embodiment of the tire cord according to the present invention, the bead region 35 may have a bead filler 37, the bead filler 37 should have a hardness of a predetermined level or more, preferably Shore A hardness ( Shore A hardness) It may have a hardness of 40 or more.

According to the present invention, the tire 31 may be reinforced with the crown portion by the belt structure 38 and the cap fly 39. The belt structure 38 comprises a cutting belt ply 40 consisting of two belt cords 41 and 42 and the belt cord 41 of the belt ply 40 is about 20 with respect to the circumferential center surface of the tire. Can be oriented at an angle of °. One belt cord 41 of the belt ply 40 may be arranged in a direction opposite to the circumferential center surface, opposite to the direction of the belt cord 42 of the other belt ply 40. However, the belt structure 38 may comprise any number of plies and may preferably be arranged in the range of 16 to 24 °. The belt structure 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 belt cords 41 and 42 of the belt structure 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 structure 38. The cap ply cord 45 of the cap ply 39 is reinforced in parallel to the circumferential direction of the tire so that It acts to suppress the size change in the circumferential direction, and a large heat shrinkage stress at high temperature is used. The capply cord 45 of the capply 39 may be manufactured using a hybrid deep cord made of polyhexamethyleneadipamide and polyethylene terephthalate, manufactured according to the method of the present invention. One layer of cap ply 39 and one layer of edge ply 44 may be used, preferably one or two layers of cap plies and one or two layers of edge plies.

Reference numerals 32 and 34 not described in FIG. 1 denote carcass layer 32 and fly turn-up 34. Reference numeral 33 denotes a carcass layer reinforcing cord 33.

The present invention is designed so that the tensile stress acts more on the polyethylene terephthalate yarn during the initial extension of the raw material by adjusting the final twist number (twist applied to the upper edge after applying the lower edge lead) to the high-strength polyethylene terephthalate yarn poly ( The breaking time point of the p-phenylene terephthalamide) company and the polyethylene terephthalate company can be made the same, and it has the advantage that the strong utilization rate of a cord can be improved.

According to the present invention, a car tire ply and cap ply (belt reinforcement layer) of a pneumatic radial tire for a passenger car are applied to a hybrid deep cord made of poly (p-phenylene terephthalamide) and polyethylene terephthalate. Satisfactory results can be obtained for noise reduction and steering stability.

Examples and comparative examples which do not limit the scope of the invention are described below. In the following Examples and Comparative Examples, the physical properties of the hybrid deep cord were measured by the following method.

Property evaluation method

(a) Hybrid Deep Code Strength (kgf) and Elongation (%)

After drying at 107 ° C. for 2 hours, the strength and the median elongation were measured under conditions of 250 mm and a tensile speed of 300 m / min using an Instron low speed tensile tester. Elongation at specific load was measured at a load of 6.8 kg.

(b) Dry heat shrinkage (%, Shrinkage)

After standing at 25 ° C. and 65% RH for 24 hours, the length (L ₀ ) measured at a static load of 0.05 g / d and the length (L ₁ ) after treatment at a static load of 0.05 g / d for 30 minutes at 150 ° C. Dry heat shrinkage was measured using the ratio. Building contraction rate (S) can be expressed as follows.

S (%) = [(L ₀ -L ₁ ) / L ₀ ] × 100

     (c) Shrinkage Force

After 24 hours at 25 ° C and 65% RH, the maximum value of stress (F) generated after treatment for 2 minutes at 177 ° C at 0.05g / d static load (F ') using a Testrite instrument It measured using. Dry heat shrink force (SF) can be expressed as follows.

SF (N) = F′-F.

     (d) Hybrid Deep Code ES Values

Elongation under a constant load is referred to as the median elongation (E) in the present invention, 'S' means the dry heat shrinkage of the above (b), the sum of the median elongation (E) and dry heat shrinkage (S) to 'ES' Indicated.

ES = median elongation (%) + dry heat shrinkage (%)

(e) Even with fatigue

The fatigue strength was measured by comparing the fatigue strength after the fatigue test using a belt fatigue tester (Belt Fatigue Tester) commonly used for fatigue testing of tire cords. The fatigue test conditions were 40 ° C., 70 kg of load, and 34.58% of compression, and after the fatigue test, the rubber was swelled by immersion in tetrachloroethylene solution for 24 hours, and the rubber and cord were separated to measure residual strength. . The residual strength was measured by drying at 107 ° C. for 2 hours using a conventional tensile strength tester according to the method (a) above.

EXAMPLES 1-4

Example 1

Poly (p-phenylene terephthalamide) and polyethylene terephthalate fibers were obtained in accordance with the above-described methods for producing tire reinforcing fibers. After giving one lead of polyethylene terephthalate yarn (1000D) of 40 TPM, one of said polyethylene terephthalate yarns (1000D) and two poly (p-phenylene terephthales) without twisting were given. Amide) yarn (1500D) was each twisted 470TPM to give a low-twist yarn, and the three low-twisted yarn was spliced into three and added to the 470TPM, the raw cord was prepared. The resulting hybrid raw cord was dried at 100 ° C. for 130 seconds, and then passed through an adhesive liquid prepared by the following method to give an adhesive liquid. During drying, 2 to 4% stretch was added to adjust the non-uniformity of the raw cord due to heat shrinkage.

                                      Below

                      45.6 parts by weight of 29.4 wt% resorcinol;

255.5 parts by weight of distilled water;

20 parts by weight of 37% formalin; And

10 wt% sodium hydroxide containing 3.8 parts by weight

The solution was prepared and then reacted with stirring at 25 ° C. for 5 hours and the following ingredients were added:

                      40wt% VP-latex 300 parts by weight

129 parts by weight of distilled water

23.8 parts by weight of 28% aqueous ammonia

After the addition of the ingredients were aged for 20 hours at 25 ℃ to maintain a solid concentration of 19.05%.

The adhesive solution was applied and dried at 150 ° C. for 2 minutes, and then heat treated at 170 ° C. for 1 minute to terminate the adhesive treatment. The physical properties of the hybrid dip cord thus prepared are shown in Table 1 below.

Example 2

A raw cord and a treatment cord were prepared by performing the experiment in the same manner as in Example 1, except that polyethylene terephthalate was bound to 80 TPM. Table 1 shows the physical properties of the dip cord thus prepared.

Example 3

One polyethylene terephthalate yarn and two poly (p-phenylene terephthalamide) yarns were twisted with 410 TPM and 470 TPM, respectively, to prepare a lower twisted yarn, and the lower twisted yarn was spliced into three 470 TPM. A treatment code was prepared by performing experiments in the same manner as in Example 1, except that raw code was added to prepare a raw cord. Table 1 shows the physical properties of the dip cord thus prepared.

Example 4

One twisted yarn was prepared by imparting twist of 350 TPM and 470 TPM to one polyethylene terephthalate yarn and two poly (p-phenylene terephthalamide) yarns, and the lower twisted yarn was spliced into three to 470 TPM. A treatment code was prepared by performing experiments in the same manner as in Example 1, except that raw cord was added to prepare a raw cord. Table 1 shows the physical properties of the dip cord thus prepared.

[Comparative Examples 1-5]

Comparative Example 1

A raw cord and a treatment cord were prepared in the same manner as in Example 1 except that polyethylene terephthalate was bound to 0 TPM. Table 1 shows the physical properties of the dip cord thus prepared.

Comparative Example 2

A raw cord and a treatment cord were prepared in the same manner as in Example 1, except that polyethylene terephthalate was bound at 10 TPM. Table 1 shows the physical properties of the dip cord thus prepared.

Comparative Example 3

A raw cord and a treatment cord were prepared in the same manner as in Example 1 except that polyethylene terephthalate was bound at 210 TPM. Table 1 shows the physical properties of the dip cord thus prepared.

Comparative Example 4

One polyethylene terephthalate yarn and two poly (p-phenylene terephthalamide) yarns were twisted with 460 TPM and 470 TPM, respectively, to prepare a lower twisted yarn, and the lower twisted yarn was spliced into three 470 TPM. A treatment cord was prepared in the same manner as in Example 1, except that raw cord was added to prepare a raw cord. Table 1 shows the physical properties of the dip cord thus prepared.

Comparative Example 5

One twisted yarn was prepared by imparting twist of 260 TPM and 470 TPM to one polyethylene terephthalate yarn and two poly (p-phenylene terephthalamide) yarns respectively. A treatment cord was prepared in the same manner as in Example 1, except that raw cord was added to prepare a raw cord. Table 1 shows the physical properties of the dip cord thus prepared.

Table 1

division Treatment Code Properties  Remarks burglar (g / d) middle Shinto 6.8 kg (%) Shrinkage (%) ES Chi (%) Retraction (N) Even with my fatigue (%) Example 1 13.5 2.5 1.8 4.3 4.0 85.3 Example 2 14.5 2.6 2.0 4.6 4.5 88.1 Example 3 13.9 2.5 1.9 4.4 4.2 88.7 Example 4 14.8 2.7 2.2 4.9 4.7 90.2 Comparative Example 1 12.0 1.9 1.5 3.4 3.5 68.2 Low strength, very low fatigue resistance. Comparative Example 2 12.4 2.2 1.8 4.0 3.9 70.3 Low contraction force, low fatigue resistance Comparative Example 3 11.9 2.7 2.4 5.1 4.8 75.7 Low strength, low fatigue resistance Comparative Example 4 12.3 2.2 1.8 4.0 3.8 70.5 Low contraction force, low fatigue resistance Comparative Example 5 11.8 2.7 2.4 5.1 4.7 76.1 Low strength, low fatigue resistance

Based on the test results of Table 1, the hybrid deep cords according to the present invention (Examples 1, 2, 3, and 4) were compared to the hybrid deep cords (Comparative Example 1) using polyethylene terephthalate, which was not given a rim. It can be seen that the strength, shrinkage and fatigue resistance are greatly improved.

In addition, hybrid deep cords (comparative examples 2 and 3) using polyethylene terephthalate yarn imparted with lead 10 TPM and 210TPM and hybrid dip cords using polyethylene terephthalate yarns imparted with lower lead 460 TPM and 260 TPM (comparative examples 4 and 5). It can be seen that the strength and fatigue resistance are lower compared to the hybrid deep cord according to the present invention.

[Examples 5 to 8 and Comparative Example 6]

Example 5

The radial tire manufactured by using the hybrid deep cord manufactured according to the first embodiment of the present invention as a cap ply may have a single layer of carcass with radial outer fly turnup. The type of carcass cord is shown in Table 2 below, and the carcass cord is oriented at an angle of 90 degrees with respect to the circumferential intermediate surface of the tire. The fly turn-up 34 was to have a height of 40 to 80% with respect to the tire maximum cross-sectional height. The bead region 35 has a bead core 36 having a high strength steel wire having a diameter of 0.95 to 1.00 mm and a bead filler 37 having a shore A hardness of 40 or more. The belt structure 38 is reinforced by a belt reinforcement layer consisting of a top layer cap ply 39 and a first layer edge ply 44, and the cap fly cord 45 in the cap ply 39 It is arranged parallel to the circumferential direction.

Example 6

A tire was manufactured in the same manner as in Example 5, except that a cord material for manufacturing a tire was used as the hybrid deep cord manufactured in Example 2.

Example 7

A tire was manufactured in the same manner as in Example 5, except that a cord material for manufacturing a tire was used as the hybrid deep cord manufactured in Example 3.

Example 8

A tire was manufactured in the same manner as in Example 5, except that a cord material for manufacturing a tire was used as the hybrid deep cord manufactured according to Example 4.

Comparative Example 6

A tire was manufactured in the same manner as in Example 5, except that a cord material for manufacturing a tire was used as the deep cord manufactured according to Comparative Example 1.

TABLE 2

Example 5 Example 6 Example 7 Example 8 Comparative Example 6 Carcass Material Polyethylene Terephthalate Polyethylene Terephthalate Polyethylene Terephthalate Polyethylene Terephthalate Polyethylene Terephthalate standard (d / combined yarn) 1000d / 2 1000d / 2 1000d / 2 1000d / 2 1000d / 2 strong( Kg ) 14 14 14 14 14 Modulus of elasticity (g / d) 60 60 60 60 60 Cap fly         Material Example 1 hybrid Deep code Example 2 hybrid Deep code Example 3 hybrid Deep code Example 4 hybrid Deep code Of Comparative Example 1 hybrid Deep code tire Flat ratio 0.60 0.60 0.60 0.60 0.60 Carcass   Floor One One One One One Cap fly floor One One One One One

[Examples 9 to 12 and Comparative Example 7]

Example 9

The radial tire manufactured by using the hybrid 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 to include one layer. At this time, the type of the cap ply and the carcass cord were as shown in Table 3 below, and tires were manufactured in the same manner as in Example 5.

Example 10

A tire was manufactured in the same manner as in Example 5, except that a cord material for manufacturing a tire was used as the hybrid deep cord manufactured in Example 2.

Example 11

A tire was manufactured in the same manner as in Example 5, except that a cord material for manufacturing a tire was used as the hybrid deep cord manufactured in Example 3.

Example 12

A tire was manufactured in the same manner as in Example 5, except that a cord material for manufacturing a tire was used as the hybrid deep cord manufactured according to Example 4.

Comparative Example 7

A tire was manufactured in the same manner as in Example 5, except that a cord material for manufacturing a tire was used as the deep cord manufactured according to Comparative Example 1.

     TABLE 3

Example 9 Example 10 Example 11 Example 12 Comparative Example 7 Carcass Material Hybrid Deep Code of Example 1 Hybrid Deep Code of Example 2 Hybrid deep code of Example 3 Hybrid Deep Code of Example 4 Hybrid Deep Code of Comparative Example 1 Cap fly Material Nylon 66 Nylon 66 Nylon 66 Nylon 66 Nylon 66 Specification (d / ply twisted yarn) 840D / 2P 840D / 2P 840D / 2P 840D / 2P 840D / 2P strong( Kg ) 15.0 15.0 15.0 15.0 15.0 tire Flat ratio 0.60 0.60 0.60 0.60 0.60 Carcass floors 2 2 2 2 2 Cap fly floor One One One One One

The 205/65 R15 V tires manufactured according to Examples 5, 6, 7, 8, 9, 10, 11, 12 and Comparative Examples 6 and 7 were mounted on a passenger vehicle having an engine displacement of 2000 cc and run at a speed of 60 km / h. While measuring the noise generated in the vehicle, the value of the audible frequency range was expressed as noise (dB) .Manipulation stability and ride comfort were evaluated by an experienced driver on a scale of 5 out of 100 points on the test course. The results are shown in Table 4 below. Durability is based on FMVSS 109's P-metric tire endurance test method, measuring temperatures of 38 ° C (± 3 ° C) and 85, 90, and 100% of the tire's nominal load. / h for a total of 34 hours and if no trace of bead separation, cord cutting, or belt separation is found in any part of the tread, sidewall, carcass cord, innerliner, or bead, Determined.

Table 4

division Example 5 Example 6 Example 7 Example 8 Comparative Example 6 Tire weight kg ) 10.64 10.80 10.65 10.79 10.60 Ride 100 100 100 100 96 Steering stability 100 100 100 100 95 durability OK OK OK OK OK Uniformity 100 100 100 100 96 noise( dB ) 59.2 59.4 59.0 58.8 62.2

Table 5

division Example 9 Example 10 Example 11 Example 12 Comparative Example 7 Tire weight (kg) 10.54 10.60 10.53 10.61 10.55 Ride 100 100 100 100 94 Steering stability 100 100 100 100 93 durability OK OK OK OK OK Uniformity 100 100 100 100 94 Noise (dB) 58.4 59.0 58.3 59.1 63.3

As a result of the test results of Table 4, the tire using the hybrid cord according to the present invention (Examples 5, 6, 7, 8) was made using a hybrid cord prepared by connecting polyethylene terephthalate to 0 TPM on the cap ply. Compared with Comparative Example 6, the effect was excellent in terms of noise reduction and steering stability, and the uniformity of the tire was also improved. In addition, from the test results of Table 5, the tire using the hybrid cord according to the present invention (Examples 9, 10, 11, 12) is a hybrid cord prepared by connecting polyethylene terephthalate to 0 TPM on the carcass layer. Compared with Comparative Example 7, the effect was excellent in terms of noise reduction and steering stability, and the uniformity of the tire was also improved.

1 is a cross-sectional view showing the structure of a tire for a passenger car including a carcass layer or a belt reinforcement layer of a hybrid cord made of poly (p-phenylene terephthalamide) or polyethylene terephthalate according to the present invention.

Figure 2 is a schematic diagram showing the manufacturing process of polyethylene terephthalate fiber used in the present invention.

Claims (5)

A method for producing a hybrid dip cord for a radial pneumatic tire, comprising: providing a twisted yarn in an S direction of 30 to 200 TPM to one polyethylene terephthalate yarn to manufacture a twisted yarn; Preparing low twisted yarn by imparting Z-direction twist of 300 to 500 TPM to each of the one polyethylene terephthalate linear twisted yarn and two non-twisted poly (p-phenylene terephthalamide) yarns; Plying the lower twisted yarn into three and adding a top edge in the S direction of 300 to 500 TPM to manufacture a raw cord; And dipping the raw cord into the dipping liquid to process the hybrid deep cord. In the manufacturing method of a hybrid dip cord for a radial pneumatic tire, polyethylene tere compared to poly (p-phenylene terephthalamide) in one polyethylene terephthalate company and two poly (p-phenylene terephthalamide) company Producing a low-twist yarn by giving a softening direction of phthalate yarn in a Z direction twist of 300 to 500 TPM to a low of 30 to 200 TPM; Plying the lower twisted yarn into three and adding the upper edge in the S direction of 300 to 500 TPM to produce a raw cord; And dipping the raw cord into the dipping liquid to process the hybrid dip cord. The method for producing a hybrid dip cord according to any one of claims 1 to 3, wherein the fineness of poly (p-phenylene terephthalamide) and polyethylene terephthalate is 500 to 3000 denier, respectively. A hybrid dip cord for producing a carcass layer or cap ply of a pneumatic radial tire made of poly (p-phenylene terephthalamide) and polyethylene terephthalate multifilament, comprising: a strength of at least 13.0 g / d; Elongation at least 2.5% at a load of 6.8 kg; Adhesion of at least 13 kg with rubber; At least 85% fatigue resistance; Fineness of 2000 to 8000 deniers; And a contraction force of 4.0 N or more. In a radial pneumatic tire comprising a pair of bead cores, a carcass ply, a belt layer laminated on the outer circumferential side of the carcass ply, and a belt reinforcement layer in the circumferential direction formed on the outer circumferential side of the belt layer, a hybrid dip cord having the following physical properties: Radial pneumatic tire, characterized in that it comprises a carcass layer or belt reinforcement layer made of.                                   next                      Strong: 13.0g / d or more                      Elongation at 6.8kg load: 2.5% or more                      Adhesion with rubber: more than 13kg                     Fatigue resistance; More than 85%                     Fineness: 2000 to 8000 denier                     Retraction: 4.0N or more

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