WO2023043074A1 - 고탄성 나일론 코드 및 이의 제조방법 - Google Patents
고탄성 나일론 코드 및 이의 제조방법 Download PDFInfo
- Publication number
- WO2023043074A1 WO2023043074A1 PCT/KR2022/012552 KR2022012552W WO2023043074A1 WO 2023043074 A1 WO2023043074 A1 WO 2023043074A1 KR 2022012552 W KR2022012552 W KR 2022012552W WO 2023043074 A1 WO2023043074 A1 WO 2023043074A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cord
- nylon
- drying
- raw
- elongation
- Prior art date
Links
- 229920001778 nylon Polymers 0.000 title claims abstract description 76
- 239000004677 Nylon Substances 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 57
- 238000007598 dipping method Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 20
- 239000004952 Polyamide Substances 0.000 claims description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 14
- 229920002647 polyamide Polymers 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000012643 polycondensation polymerization Methods 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 7
- 235000011037 adipic acid Nutrition 0.000 claims description 7
- 238000004804 winding Methods 0.000 claims description 7
- 238000000048 melt cooling Methods 0.000 claims description 4
- 238000002074 melt spinning Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 description 20
- 229920002302 Nylon 6,6 Polymers 0.000 description 19
- 230000000704 physical effect Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000009987 spinning Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229920003231 aliphatic polyamide Polymers 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000004953 Aliphatic polyamide Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229920003189 Nylon 4,6 Polymers 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical group NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- -1 poly(hexamethylene adipamide) Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/098—Melt spinning methods with simultaneous stretching
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/48—Tyre cords
Definitions
- the present invention relates to a nylon cord having a high elastic modulus and a manufacturing method thereof.
- the cap ply in the tire is a material that is reinforced on the outermost side excluding the tread, and is reinforced flatly with the circumferential direction of the tire. At high temperatures, it suppresses the size of the tire and prevents the increase in rolling resistance by generating contractile force.
- the most widely used material for such a cap ply material is nylon 6,6, and it is known that this is because nylon 6,6 has a high shrinkage force.
- Nylon has a large change in physical properties depending on whether or not it absorbs moisture due to its material characteristics, and when the moisture content is high, there is a problem in that the elastic modulus is lowered by causing shrinkage of the manufactured fiber.
- the present invention has been made to solve the above problems, and an object of the present invention is to provide a nylon cord that can secure a high modulus of elasticity even when manufacturing a tire cord using nylon, which is sensitive to moisture absorption, and a manufacturing method thereof.
- the load at 2% elongation (LASE 2%) is 0.6 g / d or more, and the load at 4% elongation (LASE) is 1.0 g / d or more,
- LASE 2%) is 0.6 g / d or more
- LASE 4% elongation (LASE) is 1.0 g / d or more
- the nylon cord may have a load (LASE 2%) of 0.6 to 1.2 g/d at 2% elongation and a load (LASE) at 4% elongation of 1.0 to 2.0 g/d.
- the nylon cord of the present invention is characterized in that the moisture content of the raw cord is 0.5 to 3.5% based on the entire raw cord before dipping in the dipping liquid.
- the present invention comprises the steps of melt-spinning and cooling a polyamide polymer prepared by condensation polymerization of hexamethylenediamine and adipic acid to prepare an undrawn yarn, the undrawn yarn being prepared by n number of 3 or more Manufacturing nylon yarn by passing it through a godet roller, drawing it in multiple stages, and winding it up, twisting the nylon yarn up and down at 100 to 550 TPM to produce a green cord, drying the green cord, and drying the dried raw cord It provides a method for manufacturing a nylon cord including; immersing in a dipping liquid and then drying and heat-treating to prepare a dip cord.
- the step of drying the raw cord is characterized in that the raw cord is heat-treated at a temperature of 150 ° C. or higher for 100 seconds or more, and the drying process may be performed at 150 to 240 ° C. for 100 to 300 seconds. .
- the moisture content of the dried green cord may be 0.5 to 3.5%.
- a nylon cord and a manufacturing method thereof according to an embodiment of the present invention can improve the modulus of elasticity of a tire cord finally manufactured by controlling the moisture content of the raw nylon cord through a process of drying the raw nylon cord.
- the load (LASE 2%) at 2% elongation is 0.6 g / d or more
- the load (LASE) at 4% elongation is 1.0 g / d or more
- the initial load is 0.05 for 2 minutes at 177 ° C.
- the present invention comprises the steps of melt spinning and cooling a polyamide polymer prepared by condensation polymerization of hexamethylenediamine and adipic acid to prepare unstretched yarn; manufacturing a nylon yarn by passing the unstretched yarn through n godet rollers of 3 or more, multi-stage drawing, and winding; Preparing a raw cord by twisting and twisting the nylon yarn at 100 to 550 TPM; drying the raw code; and preparing a dip cord by immersing the dried raw cord in a dipping liquid, followed by drying and heat treatment, wherein the drying of the raw cord comprises drying the raw cord at a temperature of 150° C. or higher for 100 seconds or longer. It provides a method for producing a nylon cord, characterized in that.
- the terms “include” or “have” are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.
- a part such as a layer, film, region, plate, etc. is said to be “on” another part, this includes not only the case where it is “directly on” the other part, but also the case where another part is present in the middle.
- a part such as a layer, film, region, plate, etc.
- being disposed “on” may include the case of being disposed not only on the upper part but also on the lower part.
- the present invention relates to a high elasticity nylon tire cord, wherein the load at 2% elongation (LASE 2%) is 0.6 g/d or more, and the load at 4% elongation (LASE) is 1.0 g/d or more, 177 It is characterized in that the shrinkage rate measured at an initial load of 0.05 g / d for 2 minutes at ° C. is 6% or less.
- a method for manufacturing a nylon cord includes the steps of melt-spinning and cooling a polyamide polymer prepared by condensation polymerization of hexamethylenediamine and adipic acid to prepare undrawn yarn, the undrawn yarn being 3 or more Manufacturing nylon yarn by multi-stage drawing and winding by passing through n godet rollers, manufacturing a raw cord by twisting the nylon yarn up and down at 100 to 550 TPM, drying the raw cord, and the dried raw cord.
- a step of preparing a dip cord by immersing the cord in a dipping liquid and then drying and heat-treating the cord may be included.
- the polyamide polymer is polyamide 66 (nylon 66).
- the present invention is characterized in that the elastic modulus of the finally manufactured cord (deep cord) is improved by adjusting the moisture content of the raw nylon cord to a low level through the step of drying the raw nylon cord.
- polyamide prepared according to the cord of the present invention contains an amide group having strong polarity in the main chain, has stereoregularity and symmetry, and has crystallinity.
- polyamide means a generic term for polymers connected by amide bonds (-CONH-), and is obtained by condensation polymerization of diamine and divalent acid. Characteristics of polyamide are changed by amide bonds in the molecular structure, and physical properties vary according to the ratio of amide groups. For example, when the ratio of the amide group in the molecule increases, specific gravity, melting point, water absorption, and stiffness increase.
- polyamide is a material that is applied in a wide range of fields such as clothing, tire cords, carpets, ropes, computer ribbons, parachutes, plastics, and adhesives due to its excellent corrosion resistance, abrasion resistance, chemical resistance, and insulation properties.
- nylon is a representative aliphatic polyamide.
- Nylon was originally a trade name of DuPont in the United States, but is now used as a generic name.
- Nylon is a hygroscopic polymer and reacts sensitively to temperature. Representative nylons include nylon 6, nylon 66 and nylon 46.
- the present invention is characterized in that nylon 66 (polyamide 66) is used.
- Nylon 66 is produced by dehydration condensation polymerization of hexamethylenediamine and adipic acid, and the polymer, nylon 66, is also called polyhexamethylene adipamide.
- a polyamide polymer prepared by condensation polymerization of hexamethylenediamine and adipic acid is used.
- the polyhexamethyleneadipamide polymer contains at least 85 mol% of hexamethyleneadipamide repeat units, and preferably consists only of hexamethyleneadipamide units.
- any polyamide homopolymer and copolymer may be used in place of the polyhexamethyleneadipamide.
- These polyamides are predominantly aliphatic and include poly(hexamethylene adipamide) (nylon 66); poly(e-caproamide) (nylon 6); and copolymers thereof may be used, but nylon 66 is most preferably used.
- Other nylon polymers that may also be advantageously used include nylon 12, nylon 46, nylon 610 and nylon 612.
- Polyhexamethylene adipamide chips may be added in an amount such that the residual amount of copper metal in the final polymer is 50 to 80 ppm in order to improve thermal stability. If the amount is less than 50 ppm, thermal stability during spinning is poor, Thermal decomposition occurs, and if it is more than 80 ppm, copper metal more than necessary acts as a foreign substance, which becomes a problem during spinning.
- polyhexamethyleneadipamide chips are passed through a pack and a nozzle at a spinning temperature of preferably 270 to 310 ° C., preferably at a spinning draft ratio of 20 to 200 (line speed on the first take-up roller / line at the nozzle). speed), it is possible to prevent a decrease in the viscosity of the polymer due to thermal decomposition. If the spinning draft ratio is less than 20, the cross-sectional uniformity of the filament deteriorates and the drawing workability is remarkably deteriorated, and if it exceeds 200, filament breakage occurs during spinning, making it difficult to produce normal yarn.
- the L/D (length/diameter) value of the extruder screw it is preferable to set the L/D (length/diameter) value of the extruder screw to 2.0 to 6.0. At this time, if the L / D value of the screw is less than 2.0, the monofilament denier cross-sectional variation rate increases, resulting in a decrease in the strength utilization rate of the fiber, and if the L / D value exceeds 6.0, a problem in fairness due to the increase in pressure of the pack occurs.
- the melt discharged yarn is rapidly cooled by passing through a cooling zone.
- a cooling zone depending on the method of blowing cooling air, open quenching, circular closed quenching, and radial outflow quenching can be applied. quenching method is preferred.
- the spinning yarn solidified while passing through the cooling zone may be oiled at 0.5 to 1.0% of the spinning yarn by an emulsion imparting device to which an emulsion excellent in stretchability and thermal efficiency is applied while reducing the friction coefficient between single yarns.
- the unstretched yarn is manufactured through the above method.
- the unstretched yarn is passed through n stretching godet rollers of 3 or more, multi-stage drawing, and winding to produce a nylon yarn. At this time, it is preferable to pass through 5 godet rollers.
- the total draw ratio is 4.0 times or more, preferably 4.5 to 6.2, more preferably 4.8 to 6.0, while passing the yarn passing through the first godet roller through the second to fifth godet rollers in a spin draw method. By stretching, the final drawn yarn can be obtained. If the draw ratio is less than 4.0, the strength of the yarn and cord is lowered, and if the draw ratio exceeds 6.2, the drawing workability and productivity are lowered, and the strength utilization rate of the yarn may be reduced, which is undesirable.
- the temperature of the first godet roller is room temperature
- the temperature of the second godet roller is room temperature to 90 ° C
- the temperature of the third godet roller is 120 to 230 ° C
- the temperature of the fourth godet roller is 180 to 250 ° C
- the temperature of the godet roller is preferably room temperature to 150°C.
- the stretching speed (spinning speed) of the first godet roller may be 550 m/min or more, preferably 550 to 900 m/min.
- the stretching speed (winding speed) of the n-1th godet roller, preferably the fourth godet roller may be 3,000 m/min or more, preferably 3000 to 4000 m/min.
- the total stretching ratio which is the speed of the fourth godet roller/speed of the first godet roller, may be 4.8 to 6.4.
- the relaxation rate may be the stretching speed of the n ⁇ 1 th godet roller/stretching speed of the n th godet roller, preferably the speed of the fourth godet roller/the speed of the fifth godet roller.
- a nylon raw cord is prepared by twisting each of the two nylon yarns prepared and twisting them together.
- the raw cord is prepared by twisting two nylon yarns with a twist of 100 to 550 TPM, respectively, to prepare a lower twisted yarn, plying each of the lower twisted yarns, and twisting 100 to 550 TPM of soft yarn and performing the yarn to prepare a nylon raw cord.
- the number of fibers of the nylon cord prepared in the present invention was prepared at 100 to 550 TPM (twist per meter) at the same time as the upper and lower ends.
- a preferred range of soft water is 200 to 500 TPM, more preferably 300 to 440 TPM.
- the elastic modulus of the finally manufactured nylon cord can be improved by performing the step of drying the raw cord.
- a dip cord was prepared by immersing in a dipping liquid without performing a drying process after manufacturing a raw cord.
- nylon has a large change in physical properties due to moisture absorption due to its material characteristics, when the moisture content is high, fiber shrinkage occurs and the elastic modulus decreases.
- nylon having a high moisture content was used, but the draw ratio was increased during yarn manufacturing in order to increase the modulus of elasticity, but due to this, there was a problem in that fairness and quality deteriorated due to the problem of increasing yarn cutting.
- elongate (stretch) at a temperature higher than 250 ° C. in manufacturing the cord but in this case, the elastic modulus could be increased, but there was a problem that it was not suitable for use as a cord due to the problem of lowering fatigue resistance.
- the inventors of the present invention recognized the problems of the conventional method for increasing the modulus of elasticity of nylon cords, and through in-depth research, when the moisture content in the raw cord was lowered by adding a process of drying the raw nylon cord, while increasing the modulus of elasticity, the conventional It was found that the same level could be maintained even in tensile properties, and the present invention was made.
- the present invention is characterized in that the nylon raw cord is dried before being immersed in the dipping liquid, and the drying is specifically characterized in that heat treatment is performed at a temperature of 150 ° C. or higher for 100 seconds or more.
- the drying conditions are set at a temperature of 150 to 240 ° C, more preferably 170 to 240 ° C, and the drying time is 100 to 300 seconds, more preferably 130 to 200 seconds.
- the drying temperature is less than 150 ° C, the moisture content of the raw cord cannot be sufficiently reduced, resulting in a decrease in the elastic modulus, and if it exceeds 240 ° C, the physical properties of the cord produced by excessive heat treatment, such as strength or elongation, There is a problem of deterioration in marketability due to deterioration of physical properties or change in color.
- the water content in the dried raw cord is 0.5 to 3.5% by drying the raw nylon cord as described above.
- the moisture content in the raw cord is 0.5% or less, the cord is damaged by excessive heat and heat treatment time rather than the effect of high elasticity that can be achieved by lowering the moisture content, and the physical properties of the finally manufactured tire cord rather deteriorate.
- the moisture content exceeds 3.5%, there is a problem in that the effect of improving the elastic modulus is not exhibited because the moisture content is not sufficiently lowered.
- the nylon raw cord (dried raw cord) is immersed in a dipping liquid, dried and heat treated to prepare a dip cord.
- 'raw cord' is woven using a weaving machine, and the obtained fabric is immersed in a dipping liquid and cured, so that a resin layer is attached to the surface of the 'raw cord' for tire cords.
- Made with 'Dip Cord' That is, a dip cord for tire cords in which a resin layer is attached to the surface of the green cord is manufactured.
- the process of immersion (immersion) in dipping liquid is generally referred to as the dipping process. Dipping means impregnating the surface of the fiber with a resin layer called RFL (Resorcinol-Formaline-Latex). Adhesion to rubber can be imparted.
- RFL Resorcinol-Formaline-Latex
- Normal nylon fibers are usually subjected to one-bath dipping, but two-bath dipping may be performed.
- a dipping solution for bonding cords and rubber may be used by reacting a solution containing resorcinol, formalin, sodium hydroxide, and the like, adding latex thereto, and aging it.
- a dipping liquid adheresive liquid
- a stretch of 0 to 3% is required, and preferably, a stretch of 1 to 2% may be achieved. If the elongation ratio is too high, the amount of deposition of the dipping liquid can be adjusted, but the breakage is reduced and consequently the fatigue resistance is reduced. On the other hand, if the elongation ratio is too low, for example, if it is lowered to less than 0%, the dipping liquid may permeate into the cord and the physical properties of the cord may deteriorate.
- the adhesion amount of the dipping liquid is preferably 4 to 6% based on the weight of the fiber based on the solid content.
- the dip code is dried at 120 to 150 ° C. It is advantageous to dry for 180 seconds to 220 seconds, and to dry in a state in which the dip cord is stretched by about 1 to 2% in the drying process. If the elongation ratio is low, the mid-strength and cut-off of the cord increase, resulting in physical properties that are difficult to apply to tire cords. On the other hand, if the elongation ratio exceeds 3%, the midsole level is adequate, but the elongation is too small, and fatigue resistance may be reduced.
- heat treatment is performed in a temperature range of 130 to 240 ° C. During heat treatment, the elongation ratio is maintained between -1 and 0%, and the appropriate heat treatment time is 50 seconds to 90 seconds.
- the load (LASE) at a specific elongation is increased and the shrinkage rate of the cord is lowered, resulting in the elastic modulus of the nylon tire cord.
- the nylon tire cord has a load at 2% elongation (LASE 2%) of 0.6 g / d or more, a load at 4% elongation (LASE 4%) is 1.0 g / d or more, and at 177 ° C.
- Shrinkage measured at an initial load of 0.05 g/d for 2 minutes may be 6% or less.
- the nylon tire cord of the present invention also has a load at 2% elongation (LASE 2%) of 0.6 to 1.2 g / d, and a load at 4% elongation (LASE 4%) of 1.0 to 2.0 g / d, It is preferable that the shrinkage ratio is 2 to 6%.
- the nylon cord manufactured as described above makes it possible to manufacture a nylon tire cord with a high elastic modulus without increasing the draw ratio of the yarn or applying high temperature and stretch conditions during cord manufacturing, as in the prior art, and satisfies the physical properties of the high elastic modulus. However, it exhibits the effect of maintaining the same level as the existing ones without deteriorating tensile properties such as strength and elongation.
- Polyhexamethylene adipamide chips having a relative viscosity (RV) of 3.4 prepared by condensation polymerization of hexamethylenediamine and adipic acid were melt-spun at a temperature of 296° C. using an extruder. Then, the spun yarn was solidified by passing through a cooling zone with a length of 600 mm, and then oiled with a spinning emulsion. Thereafter, the unstretched yarn was drawn in two stages and wound up to prepare a 420 denier nylon yarn. At this time, the draw ratio was 4.8.
- RV relative viscosity
- the manufactured raw cord was subjected to a drying process by heat treatment at 240 ° C. for 100 seconds, and at this time, it was confirmed that the moisture content of the raw cord was 0.5% based on the entire raw cord.
- the raw cord that has undergone the drying process is woven, and the woven raw cord is immersed in a dipping liquid containing RFL. Thereafter, drying was performed at 130° C. for 180 seconds in an elongated state of 1%, and heat treatment was performed at 150° C. for 50 seconds with an elongation ratio of 0% to prepare a nylon cord (dip cord).
- Nylon cords were each manufactured through the same process as in Example 1, except that the drying conditions and moisture content of the green cord were adjusted as shown in Table 1 below.
- a nylon cord was manufactured through the same process as in Example 1, except that the process of drying the raw cord was not performed.
- Nylon cords were each manufactured through the same process as in Example 1, except that the drying conditions and moisture content of the green cord were adjusted as shown in Table 1 below.
- a hot air circulation oven equipped with an automatic temperature device is used. After drying at an oven temperature of 125 ⁇ 3°C for 30 ⁇ 0.5 minutes, put it in a desiccator and measure the weight after cooling for 15 minutes. Moisture content is calculated in the following way.
- Moisture content (%) (weight before drying - weight after drying) / weight after drying x 100
- the sample was left in a constant temperature and humidity room under standard conditions, that is, a temperature of 25 ° C and a relative humidity of 65% RH for 24 hours, the sample was measured through a tensile tester according to the ASTM D-885 method.
- the load at specific elongation (2%, 4%) was taken from the elongation load curve obtained by the JIS L1O17 measurement method.
- the sample before measurement was measured after being allowed to stand for 24 hours in an atmosphere of 20 ° C. and 65% RH.
- LASE g/d, 2%) is calculated by dividing the load value at 2% elongation by the denier
- LAES g/d, 48% is calculated by dividing the load value at 4% elongation by the denier.
- the sample is exposed for 2 minutes under a pre-tension of 177°C and an initial load of 0.05 g/d and then measured.
- the measuring instrument uses a Testrite heat shrink tester. Specifically, the shrinkage rate of the dip cord is automatically measured in Testrite, and the shrinkage rate is automatically displayed through the display window 2 minutes after a cord sample with an initial load of 0.05g/d is placed in a chamber heated to 177°C. Therefore, it is possible to measure
- Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 raw code dry Drying temperature (°C) 240 200 160 X 100 300 Drying time (seconds) 100 150 200 X 200 100 raw code Moisture content (%) 0.5 1.5 3.5 4.0 3.8 0.4 deep code strong (kg) 7.6 7.5 7.5 7.5 7.4 6.6 LASE(g/d,2%) 1.1 0.8 0.6 0.5 0.4 LASE(g/d, 4%) 1.7 1.3 1.1 0.9 0.9 0.7 Confidence (%) 17.1 17.4 17.5 17.7 18.0 15.6 Shrinkage (%) 5.9 5.3 5.1 6.1 6.1 5.0 Twists (TPM) 420 420 420 420 420 420 420 420 420 Heat treatment temperature in dipping process (°C) 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150
- the nylon cords prepared according to the examples set the moisture content of the green cords to the optimum range by performing a drying process through an optimal drying temperature and drying holding time after preparing the raw cords.
- the drying process was performed on the green cord, in the case of Comparative Example 2 in which the drying temperature was set lower than the range of the present invention, the moisture content in the green cord increased, finally the LASE value of the deep cord was higher, and the drying process was performed.
- the nylon cords prepared in the examples have excellent tensile properties and desired elastic modulus at the same time by adjusting the moisture content of the raw cords without changing the process such as increasing the drawing ratio or the heat treatment temperature when manufacturing the cords as in the prior art. It can be seen that this is excellent.
- the present invention is an optimal invention capable of increasing the elastic modulus of a tire cord finally manufactured by controlling the water content of the raw nylon cord through a process of drying the raw nylon cord.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Artificial Filaments (AREA)
Abstract
Description
실시예1 | 실시예2 | 실시예3 | 비교예1 | 비교예2 | 비교예3 | ||
생코드 건조 |
건조온도(℃) | 240 | 200 | 160 | X | 100 | 300 |
건조시간(초) | 100 | 150 | 200 | X | 200 | 100 | |
생코드 | 수분율(%) | 0.5 | 1.5 | 3.5 | 4.0 | 3.8 | 0.4 |
딥코드 | 강력(kg) | 7.6 | 7.5 | 7.5 | 7.5 | 7.4 | 6.6 |
LASE(g/d,2%) | 1.1 | 0.8 | 0.6 | 0.5 | 0.5 | 0.4 | |
LASE(g/d,4%) | 1.7 | 1.3 | 1.1 | 0.9 | 0.9 | 0.7 | |
절신(%) | 17.1 | 17.4 | 17.5 | 17.7 | 18.0 | 15.6 | |
수축율(%) | 5.9 | 5.3 | 5.1 | 6.1 | 6.1 | 5.0 | |
꼬임수(TPM) | 420 | 420 | 420 | 420 | 420 | 420 | |
디핑공정에서의 열처리 온도(℃) | 150 | 150 | 150 | 150 | 150 | 150 |
Claims (6)
- 2%의 신장에서의 하중(LASE 2%)이 0.6 g/d이상이고, 4%의 신장에서의 하중(LASE)이 1.0 g/d이상이며,177℃에서 2분 동안 초하중 0.05g/d에서 측정된 수축율이 6% 이하인 것을 특징으로 하는 나일론 코드.
- 제1항에 있어서,상기 나일론 코드는 2%의 신장에서의 하중(LASE 2%)이 0.6 내지 1.2g/d이고, 4%의 신장에서의 하중(LASE)이 1.0 내지 2.0g/d인 것을 특징으로 하는 나일론 코드.
- 제1항에 있어서,상기 나일론 코드는 디핑액에 침적(dipping)하기 전 생코드 전체를 기준으로 생코드의 수분율이 0.5 내지 3.5%인 것을 특징으로 하는 나일론 코드.
- 헥사메틸렌디아민과 아디프산을 축합중합하여 제조한 폴리아미드 폴리머를 용융방사 및 냉각하여 미연신사를 제조하는 단계;상기 미연신사를 3 이상인 n개의 고뎃 롤러를 통과시켜 다단 연신하고 권취하여 나일론 원사를 제조하는 단계;상기 나일론 원사를 100 내지 550TPM으로 상하연 연사하여 생코드를 제조하는 단계;상기 생코드를 건조하는 단계; 및상기 건조된 생코드를 디핑액에 침적한 다음 건조 및 열처리하여 딥코드를 제조하는 단계;를 포함하고,상기 생코드를 건조하는 단계는 상기 생코드를 150℃ 이상의 온도에서 100초 이상 건조하는 것을 특징으로 하는 나일론 코드의 제조방법.
- 제4항에 있어서,상기 생코드를 건조하는 단계는 150 내지 240℃에서 100 내지 300초 동안 건조하는 것을 특징으로 하는 나일론 코드의 제조방법.
- 제4항에 있어서,상기 건조된 생코드의 수분율은 0.5 내지 3.5%인 나일론 코드의 제조방법.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202280061188.3A CN117980553A (zh) | 2021-09-17 | 2022-08-23 | 高弹性尼龙帘线及其制备方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020210124773A KR102573974B1 (ko) | 2021-09-17 | 2021-09-17 | 고탄성 나일론 코드 및 이의 제조방법 |
KR10-2021-0124773 | 2021-09-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023043074A1 true WO2023043074A1 (ko) | 2023-03-23 |
Family
ID=85603134
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2022/012552 WO2023043074A1 (ko) | 2021-09-17 | 2022-08-23 | 고탄성 나일론 코드 및 이의 제조방법 |
Country Status (3)
Country | Link |
---|---|
KR (1) | KR102573974B1 (ko) |
CN (1) | CN117980553A (ko) |
WO (1) | WO2023043074A1 (ko) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100761518B1 (ko) * | 2006-12-28 | 2007-10-04 | 주식회사 효성 | 하이브리드 딥코드의 제조 방법 및 이를 이용한 래디얼타이어 |
JP2008106405A (ja) * | 2006-10-27 | 2008-05-08 | Teijin Fibers Ltd | 補強用繊維コードの製造方法および補強用繊維コード |
KR101602605B1 (ko) * | 2015-06-29 | 2016-03-21 | 코오롱인더스트리 주식회사 | 하이브리드 타이어 코드 및 그 제조방법 |
KR20190016421A (ko) * | 2016-06-09 | 2019-02-18 | 코드사 테크닉 테크스틸 아노님 시르케티 | 고 모듈러스 나일론 6.6 코드 |
KR20200120225A (ko) * | 2019-04-12 | 2020-10-21 | 효성첨단소재 주식회사 | 고내열 폴리에틸렌테레프탈레이트 코드 및 이의 제조방법 |
KR20210124773A (ko) | 2020-04-07 | 2021-10-15 | 이재업 | 건축용 세트 앵커형 지지구 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20170091968A (ko) * | 2016-02-02 | 2017-08-10 | 주식회사 효성 | 내피로도가 우수한 폴리에틸렌테레프탈레이트 코드의 제조방법 |
KR102111334B1 (ko) * | 2018-11-01 | 2020-05-18 | 효성첨단소재 주식회사 | 나일론 원사 및 이의 제조방법 |
KR20200076999A (ko) * | 2018-12-20 | 2020-06-30 | 효성첨단소재 주식회사 | 아라미드 딥코드 및 이를 포함하는 카카스층 및 트럭-버스용 래디얼 타이어 |
-
2021
- 2021-09-17 KR KR1020210124773A patent/KR102573974B1/ko active IP Right Grant
-
2022
- 2022-08-23 CN CN202280061188.3A patent/CN117980553A/zh active Pending
- 2022-08-23 WO PCT/KR2022/012552 patent/WO2023043074A1/ko active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008106405A (ja) * | 2006-10-27 | 2008-05-08 | Teijin Fibers Ltd | 補強用繊維コードの製造方法および補強用繊維コード |
KR100761518B1 (ko) * | 2006-12-28 | 2007-10-04 | 주식회사 효성 | 하이브리드 딥코드의 제조 방법 및 이를 이용한 래디얼타이어 |
KR101602605B1 (ko) * | 2015-06-29 | 2016-03-21 | 코오롱인더스트리 주식회사 | 하이브리드 타이어 코드 및 그 제조방법 |
KR20190016421A (ko) * | 2016-06-09 | 2019-02-18 | 코드사 테크닉 테크스틸 아노님 시르케티 | 고 모듈러스 나일론 6.6 코드 |
KR20200120225A (ko) * | 2019-04-12 | 2020-10-21 | 효성첨단소재 주식회사 | 고내열 폴리에틸렌테레프탈레이트 코드 및 이의 제조방법 |
KR20210124773A (ko) | 2020-04-07 | 2021-10-15 | 이재업 | 건축용 세트 앵커형 지지구 |
Also Published As
Publication number | Publication date |
---|---|
KR20230041316A (ko) | 2023-03-24 |
CN117980553A (zh) | 2024-05-03 |
KR102573974B1 (ko) | 2023-09-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2017003169A1 (ko) | 하이브리드 타이어 코드 및 그 제조방법 | |
WO2014104680A1 (en) | Hybrid fiber cord and method for manufacturing the same | |
WO2013048097A2 (ko) | 아라미드 섬유 코드 및 그 제조방법 | |
US3650884A (en) | Polyamide monofilament having a microporous surface layer | |
EP0384424A2 (en) | Cyclic tensioning of never-dried yarns | |
EP0574538B1 (en) | Method for spinning poly(p-phenylene terephthalamide) fibres of high tenacity and high elongation at break | |
EP0331156A2 (en) | Poly(p-phenyleneterephthalamide) yarns of improved fatigue resistance and process for preparation thereof | |
WO2023043074A1 (ko) | 고탄성 나일론 코드 및 이의 제조방법 | |
WO2021006561A1 (ko) | 타이어 코드용 원사 및 타이어 코드 | |
KR101338505B1 (ko) | 폴리에틸렌테레프탈레이트 연신사의 제조방법, 연신사, 타이어 코오드의 제조방법, 및 타이어 코오드 | |
WO2023055201A1 (ko) | 재생가능한 타이어 코드용 폴리아미드 멀티필라멘트 섬유 및 그를 포함하는 타이어 코드 | |
KR102111334B1 (ko) | 나일론 원사 및 이의 제조방법 | |
JPS62299513A (ja) | ポリフエニレンサルフアイドモノフイラメントの製造方法 | |
WO2021045418A1 (ko) | 내열성이 우수한 폴리에스터 타이어 코드 및 그를 포함하는 타이어 | |
WO2015108312A1 (ko) | 치수안정성이 우수한 폴리에스테르 타이어 코드 및 이의 제조방법 | |
WO2020138996A2 (ko) | 고무에 대한 강한 접착력 및 우수한 내피로 특성을 갖는 하이브리드 타이어 코드 및 그 제조방법 | |
US3402752A (en) | Reinforcing cord and tire therefrom | |
KR20120112206A (ko) | 폴리에틸렌테레프탈레이트 연신사의 제조방법, 폴리에틸렌테레프탈레이트 연신사 및 타이어 코오드 | |
KR20140134031A (ko) | 공중합 아라미드 섬유의 제조방법 | |
KR20140132556A (ko) | 공중합 아라미드 섬유의 제조방법 및 이로 제조된 공중합 아라미드 섬유 | |
US20210262122A1 (en) | Hydrolysis-resistant thermoplastic polyurethane fiber and method for producing the same | |
KR20000041244A (ko) | 고강력 고탄성 폴리에스테르 섬유 및 제조방법 | |
US20050106389A1 (en) | Process of making a dimensionally stable yarn | |
JPH02210018A (ja) | Vベルト補強用ポリアミド繊維 | |
KR100215641B1 (ko) | 폴리아미드 6 연신사 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22870160 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280061188.3 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2022870160 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2022870160 Country of ref document: EP Effective date: 20240417 |