WO2020138996A2 - 고무에 대한 강한 접착력 및 우수한 내피로 특성을 갖는 하이브리드 타이어 코드 및 그 제조방법 - Google Patents
고무에 대한 강한 접착력 및 우수한 내피로 특성을 갖는 하이브리드 타이어 코드 및 그 제조방법 Download PDFInfo
- Publication number
- WO2020138996A2 WO2020138996A2 PCT/KR2019/018556 KR2019018556W WO2020138996A2 WO 2020138996 A2 WO2020138996 A2 WO 2020138996A2 KR 2019018556 W KR2019018556 W KR 2019018556W WO 2020138996 A2 WO2020138996 A2 WO 2020138996A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- yarn
- tire cord
- hybrid
- aramid
- multifilament
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 229920001971 elastomer Polymers 0.000 title abstract description 26
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 96
- 239000004760 aramid Substances 0.000 claims abstract description 92
- 229920001778 nylon Polymers 0.000 claims description 32
- 239000004677 Nylon Substances 0.000 claims description 31
- 229920000728 polyester Polymers 0.000 claims description 28
- 239000000853 adhesive Substances 0.000 claims description 24
- 230000001070 adhesive effect Effects 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 9
- 230000014759 maintenance of location Effects 0.000 claims description 8
- 241001589086 Bellapiscis medius Species 0.000 claims description 7
- 238000009661 fatigue test Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000004816 latex Substances 0.000 claims description 5
- 229920000126 latex Polymers 0.000 claims description 5
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000011120 plywood Substances 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 14
- -1 poly(p-phenylene terephthalamide) Polymers 0.000 description 14
- 239000000835 fiber Substances 0.000 description 13
- 229920002302 Nylon 6,6 Polymers 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 238000009987 spinning Methods 0.000 description 7
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000010959 steel Substances 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
- B60C9/005—Reinforcements made of different materials, e.g. hybrid or composite cords
-
- 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
- B60C9/0042—Reinforcements made of synthetic materials
-
- 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
- B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
- B60C9/20—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel
- B60C9/2003—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel characterised by the materials of the belt cords
- B60C9/2006—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel characterised by the materials of the belt cords consisting of steel cord plies only
-
- 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
- D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
- D02G1/02—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist
- D02G1/0206—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist by false-twisting
-
- 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
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
- D02G3/04—Blended or other yarns or threads containing components made from different materials
- D02G3/047—Blended or other yarns or threads containing components made from different materials including aramid fibres
-
- 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
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/26—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre with characteristics dependent on the amount or direction of twist
- D02G3/28—Doubled, plied, or cabled threads
-
- 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
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J13/00—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
-
- 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
- B60C2009/0071—Reinforcements or ply arrangement of pneumatic tyres characterised by special physical properties of the reinforcements
-
- 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
- B60C2009/0071—Reinforcements or ply arrangement of pneumatic tyres characterised by special physical properties of the reinforcements
- B60C2009/0092—Twist structure
-
- 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
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/26—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre with characteristics dependent on the amount or direction of twist
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
- D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/02—Reinforcing materials; Prepregs
- D10B2505/022—Reinforcing materials; Prepregs for tyres
Definitions
- the present invention relates to a hybrid tire cord made of different types of yarns having different physical properties and a method for manufacturing the same, more specifically, it has not only high strength and high modulus, but also strong adhesion to rubber and excellent fatigue resistance properties It relates to a hybrid tire cord and a method of manufacturing the same that can realize high performance and light weight of the tire by having.
- fiber cords As a reinforcement material for rubber products such as tires, conveyor belts, V-belts and hoses, fiber cords, in particular adhesive-treated fiber cords (so-called "dip cords"), are widely used.
- Materials of the fiber cord include nylon fiber, polyester fiber, rayon fiber, and the like.
- One of the important ways to improve the performance of the final rubber product is to improve the properties of the fiber cord used as a reinforcement.
- the fiber cord used as a reinforcement material for the tire is referred to as a tire cord.
- a tire cord The fiber cord used as a reinforcement material for the tire.
- the tire which is a composite of fiber/metal/rubber, is located on the outermost side and treads in contact with the road surface, a cap ply under the tread, a belt under the cap ply, and under the belt Carcass.
- a hybrid tire cord made of nylon multifilament yarn and aramid multifilament yarn has been developed as a tire cord for a cap ply to prevent deformation of a belt (for example, a steel belt) when driving at high speed.
- the nylon-aramid hybrid tire cord is advantageous in preventing the deformation of the belt during high-speed driving due to the high shrinkage stress of nylon, and is advantageous in preventing tire deformation (so-called'flat spot') due to long parking due to the high modulus of aramid. .
- nylon-aramid hybrid tire cord is a tire cord for carcass that acts as the overall skeleton of the tire and greatly affects the shape stability of the tire, since nylon properties are initially expressed on the SS curve pattern to show low modulus. Is not suitable.
- polyester-aramid hybrid tire cord which replaced nylon multifilament yarn with a polyester (eg, PET) multifilament yarn having a higher modulus than nylon multifilament yarn, was developed as a tire cord for carcass.
- the present invention is to provide a hybrid tire cord and a method for manufacturing the same, which can prevent problems caused by limitations and disadvantages of the related art.
- one aspect of the present invention is to provide a hybrid tire cord capable of realizing high performance and light weight of a tire by having not only high strength and high modulus, but also strong adhesion to rubber and excellent fatigue resistance.
- Another aspect of the present invention high strength and high modulus, as well as having a strong adhesion to the rubber and excellent fatigue properties to produce a hybrid tire cord capable of realizing high performance and light weight of the tire at high productivity and low cost Is to provide a way to do it.
- the first multi-filament yarn and the first spun yarn formed by lowering the first spun yarn together; And a second lower twisted yarn formed by lowering the second multifilament yarn; and a plied yarn staged together, wherein the first multifilament yarn is an aramid multifilament yarn, the first spun yarn is an aramid spun yarn, and the second multifilament yarn is A hybrid tire cord is provided, which is a nylon multifilament yarn or a polyester multifilament yarn.
- the length of the first lower twisted yarn may be 1.005 to 1.050 times the length of the second lower twisted yarn.
- the first multifilament yarn may have a fineness of 500 to 3000 denier, and the first spun yarn may have a fineness of 30 to 8'S.
- the second multifilament yarn may have a fineness of 500 to 3000 denier.
- the first lower twisted yarn and the second lower twisted yarn may each have a first twist number.
- the first lower twisted yarn and the second lower twisted yarn may be staged together as a second twist number, and the second twist number may be the same as the first twist number.
- the weight ratio of the second lower twisted yarn to the first lower twisted yarn may be 20:80 to 80:20.
- the hybrid tire cord may further include an adhesive coated on the first lower twisted yarn and the second lower twisted yarn.
- the tear tenacity of the hybrid tire cord measured by ASTM D885/D885M-10a (2014) may be 8.0 to 15.0 g/d, and the hybrid measured by ASTM D885/D885M-10a (2014)
- the elongation at break of the tire cord may be 5 to 15%, and the strength retention rate of the hybrid tire cord after a disk fatigue test conducted according to JIS-L 1017 (2002) may be 95% or more.
- the second, third, and fourth steps may be performed by a single twister.
- the tension applied to the hybrid yarn is such that when the upper edge of the hybrid tire cord of a predetermined length is untwisted, the length of the first lower yarn is the second lower yarn. It may be less than the tension applied to the second multi-filament yarn to the extent that it is 1.005 to 1.050 times the length.
- the lower edge of the second step and the lower edge of the third step may be performed with a first twist number, respectively.
- the stage of the fourth step may be performed with a second twist number, and the second twist number may be the same as the first twist number.
- the first multifilament yarn may have a fineness of 500 to 3000 denier
- the first spun yarn may have a fineness of 30 to 8'S
- the second multifilament yarn may have a fineness of 500 to 3000 denier.
- the method includes immersing the plied yarn in an adhesive solution containing an RFL (Resorcinol Formaldehyde Latex) adhesive or an epoxy adhesive; Drying the plied yarn impregnated with the adhesive solution at 70 to 200° C. for 30 to 120 seconds; And heat-treating the dried plied yarn at 200 to 250° C. for 30 to 120 seconds.
- RFL Resorcinol Formaldehyde Latex
- a high-performance hybrid tire cord including a plied yarn in which aramid multifilament yarns and aramid hybrid yarns of aramid spinning yarn are staged together with nylon or polyester yarns
- aramid spun yarn due to the use of the aramid spun yarn can have a strong adhesion to the rubber and excellent fatigue properties, it is possible to implement a high performance and light weight of the tire.
- the aramid multifilament yarn is used together with the aramid spun yarn, it is possible to prevent a low cutting elongation problem, and at the same time, due to the use of the aramid multifilament, it can have high strength and high modulus.
- the process of forming the aramid hybrid twisted yarn and the nylon or polyester lower twisted yarn i.e., the lowered twisting step
- the step of forming the plied yarn with the aramid hybrid lower twisted yarn and the nylon or polyester lower twisted yarn i.e., the upper edge
- first and second terms are used to describe various components, and the terms are used only to distinguish one component from another component.
- multifilament yarn refers to a yarn made of a number of continuous filaments.
- spun yarn refers to a yarn made by twisting a number of staple fibers in the longitudinal direction.
- Z-twist means twisting the thread in a counterclockwise direction
- S-twist means twisting the thread in a clockwise direction.
- the term "cabled yarn” means a yarn made by reproducing two or more strands of Z-twisted yarns, and is also referred to as "raw cord.”
- tire cord is a concept that includes not only the “low cord” but also a “dip cord” which means a plywood coated with an adhesive so that it can be applied directly to a rubber product.
- twist number (twist number) means the number of twists per 1m, the unit is TPM (Twist Per Meter).
- "'S" as used herein refers to the number of yarns representing the length of the fiber of the same weight (weight type) means the number of British cotton yarns ( ⁇ , count). Since it is a method for indicating the length with respect to the weight, the larger the value, the thinner the thread, and the smaller the thicker the thread.
- the symbol of the number of cotton yarns in England is Ne, and the notation for this is OO (number)'s.
- the calculation of the number of cotton yarns in the United Kingdom counts how many times the length of 1 lb weight is 840 yd, and is calculated using Equation 1 below.
- the number of cotton means the number of 840 yards (768 m) length included when the weight of cotton yarn is 1 pound (453 g), as is well known, and this case is referred to as number 1. As described above, the number means a larger thread as the number increases.
- the first multi-filament yarn and the first lower yarn formed by lowering the first spun yarn together; And a second lower twisted yarn formed by lowering the second multifilament yarn; and a plied yarn staged together, wherein the first multifilament yarn is an aramid multifilament yarn, the first spun yarn is an aramid spun yarn, and the second multifilament yarn is A hybrid tire cord that is a nylon multifilament yarn or a polyester multifilament yarn may be provided.
- the hybrid tire cord of the present invention includes a first lower yarn formed by lowering the first multifilament yarn and the first spun yarn together and a second lower yarn formed by lowering the second multifilament yarn.
- the first lower speaker and the second lower speaker are staged together.
- the present invention by using aramid multifilament yarns and aramid hybrid yarns of aramid spinning yarns, problems such as low modulus problems and low cutting elongation due to the use of aramid multifilaments can be solved. That is, the aramid spun yarn included in the hybrid lower twist yarn can have strong adhesion to rubber and excellent fatigue resistance, thereby realizing high performance and light weight of the tire. In addition, since the aramid multifilament used together for the production of the hybrid lower yarn is used together with the aramid spinning yarn, it is possible to prevent deterioration in physical properties. Therefore, high strength and high modulus can be realized thanks to the aramid multifilament.
- the first multifilament yarn is an aramid multifilament yarn
- the first spun yarn is an aramid spinning yarn
- the second multifilament yarn is a nylon multifilament yarn or a polyester multifilament yarn.
- the aramid spun yarn formed by aramid short fibers are linearly twisted, can compensate for the low adhesion to the rubber of the aramid multifilament yarn by enabling physical bonding of the hybrid tire cord and rubber of the present invention, and consequently the hybrid tire cord Adhesion to rubber can be improved. Therefore, the hybrid tire cord of the present invention has a similar fineness, but has an adhesive strength to rubber of 10% compared to a hybrid tire cord (i.e., a hybrid tire cord formed of only aramid multifilament yarns and nylon/polyester multifilament yarns). Is higher than
- the aramid spun yarn present in the hybrid tire cord performs a buffer function to absorb shock from the outside, thereby improving the fatigue properties of the hybrid tire cord.
- the aramid multifilament yarn of the present invention may be formed of para-aramid or meta-aramid, preferably poly(p-phenylene terephthalamide).
- the aramid multifilament yarn may have a fineness of 500 to 3000 denier, a tensile strength of 20 g/d or more, and a cutting elongation of 3% or more.
- the aramid short fibers used in the production of the aramid spinning yarn of the present invention may also be formed of para-aramid or meta-aramid, and preferably poly(p-phenylene terephthalamide).
- the aramid spun yarn may have a fineness including a number of 30 to 8'S (corresponding to about 170 to about 660 denier). If the number of the aramid spun yarns is 30'S or more, the aramid spun yarn is too thin to help improve physical adhesion with rubber, and if it is 8'S or less, the ratio of aramid spun yarn for heat is relatively high, resulting in low strength and elastic modulus. There is a problem.
- the nylon multifilament yarn constituting the second multifilament may be formed of nylon 6 or nylon 66.
- the polyester multifilament yarn may be formed of polyethylene terephthalate (PET).
- PET polyethylene terephthalate
- the second multifilament yarn may have a fineness of 500 to 3000 denier.
- the weight ratio of the second lower twisted yarn to the first lower twisted yarn may be determined in consideration of both properties of the tire cord and manufacturing cost. According to an embodiment of the present invention, the weight ratio of the second lower twisted yarn to the first lower twisted yarn may be 20:80 to 80:20.
- the first and second lower twisted yarns have the same twist direction (first twist direction), and may have the same number of twists, for example, a first twist number of 200 to 500 TPM.
- the first lower twisted yarn and the second lower twisted yarn are staged together as a second twist number, and the second twist number may be the same as the first twist number.
- the phase direction is opposite to the first twist direction.
- the hybrid tire cord according to an embodiment of the present invention when the upper edge of the hybrid tire cord of a predetermined length is untwisted, the length of the first lower twisted yarn is 1.005 to 1.050 times the length of the second lower twisted yarn. That is, the hybrid tire cord according to an embodiment of the present invention has a merging structure in which a covering structure (the first lower twisting yarn covers the second lower twisting yarn) is slightly added.
- the hybrid tire cord according to an embodiment of the present invention the stress applied to the hybrid tire cord when the tire tension/compression is repeated is the first lower twisted yarn (ie, Aramid lower twisted yarn) as well as second lower twisted yarn (ie, nylon/polyester lower twisted yarn).
- the hybrid tire cord of the present invention has excellent fatigue resistance properties.
- the hybrid tire cord according to an embodiment of the present invention further includes an adhesive coated on the first lower twisted yarn and the second lower twisted yarn to improve adhesion with other components of the tire (eg, rubber). It may be a dip cord.
- the adhesive may be an RFL (Resorcinol Formaldehyde Latex) adhesive or an epoxy-based adhesive.
- the dip cord has a cutting strength of 8.0 to 15.0 g/d measured by ASTM D885/D885M-10a (2014), and a cutting elongation of 5 to 15% measured by ASTM D885/D885M-10a (2014).
- the strength retention rate after the disk fatigue test conducted according to JIS-L 1017 may be 95% or more.
- the dip cord may have a dry heat shrinkage rate of 0.3 to 2.5% (temperature: 180°C, superload: 0.01 g/d, time: 2 minutes).
- the dry heat shrinkage rate is measured at a superload of 0.01 g/denier for 2 minutes at 180° C. using a Testrite instrument after the sample is left for 24 hours at a temperature of 25° C. and a relative humidity of 65%.
- the multi-filament yarn may be a nylon multi-filament yarn or a polyester multi-filament yarn, a hybrid tire cord manufacturing method may be provided.
- the first multifilament yarn is an aramid multifilament yarn
- the first spun yarn is an aramid spun yarn
- the second multifilament yarn is a nylon multifilament yarn or a polyester multifilament yarn.
- the aramid multifilament yarn may be formed of para-aramid or meta-aramid, and preferably may be formed of poly(p-phenylene terephthalamide).
- the aramid short fibers used in the production of the aramid spinning yarn may also be formed of para-aramid or meta-aramid, and preferably poly(p-phenylene terephthalamide).
- the nylon multifilament yarn may be formed of nylon 6 or nylon 66, and the polyester multifilament yarn may be formed of polyethylene terephthalate (PET).
- PET polyethylene terephthalate
- the second multifilament yarn may have a fineness of 500 to 3000 denier.
- aramid hybrid yarns are combined by combining aramid multifilament yarns having a fineness of 500 to 3000 denier and aramid spun yarns having a fineness (corresponding to about 170 to about 660 denier) containing a number of 30 to 8'S. Form a yarn.
- the aramid hybrid yarn is introduced together with a nylon or polyester multifilament yarn having a fineness of 500 to 3000 denier with a cable cord twister (for example, a cable corder manufactured by Allma) that performs both lower edge and upper edge.
- a cable cord twister for example, a cable corder manufactured by Allma
- the step of lowering the aramid hybrid yarn and the step of lowering the nylon/polyester multifilament yarn to form the nylon/polyester multifilament yarn are simultaneously performed to form the aramid twisted yarn, and forming the plied yarn.
- the step of staged together with the aramid twisted yarn and the nylon/polyester lower twisted yarn is continuously performed following the lowering steps.
- the same number of twists may be applied within a range of 200 to 500 TPM.
- the plied yarn is manufactured by the continuous method in which the lower edge and the upper edge are performed in one twisting machine, the aramid multi-filament yarn and the nylon/polyester multi-filament yarn are respectively lowered with a twisting machine and then staged together with another twisting yarn.
- the productivity of the hybrid tire cord may be improved.
- the tension applied to the hybrid yarn is the second multifilament yarn (ie, nylon/polyester multi) Less than the tension applied to the filament yarn). Therefore, even though the lower edge and the upper edge are performed by one twisting machine, when the upper edge of the hybrid tire cord of a predetermined length is unwrapped, the length of the aramid lower yarn may be slightly longer than that of the nylon/polyester lower yarn. .
- the stress applied to the hybrid tire cord when the tire tension/compression is repeated can be dispersed in the aramid lower yarn and the nylon/polyester lower yarn, and the hybrid tire cord has excellent fatigue properties, thereby driving at high speed for a long time. Even the stability of the tire can be maintained.
- the difference between the tension applied to the hybrid yarn (ie, the aramid hybrid yarn) and the tension applied to the second multifilament yarn (ie, nylon/polyester multifilament yarn) is predetermined. If the length of the hybrid tire cord is untwisted, the length of the first lower twisted yarn (ie, aramid lower twisted yarn) is 1.005 to 1.050 times the length of the second lower twisted yarn (ie, nylon/polyester lower twisted yarn). It can be a difference as much as possible.
- the tension applied to the hybrid yarn (ie, aramid hybrid yarn) and the second multifilament yarn (ie, nylon/polyester multifilament yarn) respectively when the lower edge and the upper edge are performed by the twister is the twister (Allma It can be adjusted by setting'Creel Yarn Tension' and'Inner Yarn Tension' of Cable Corder).
- the plied yarn is RFL (Resorcinol Formaldehyde Latex) adhesive to improve adhesiveness with other components (for example, rubber) of the tire.
- RFL Resorcinol Formaldehyde Latex
- a step of immersing in an adhesive solution containing an epoxy-based adhesive, drying the plied yarn impregnated with the adhesive solution, and heat treating the dried plied yarn may be additionally performed.
- the temperature and time of the drying process may vary depending on the composition of the adhesive solution, but the drying process is usually performed at 70 to 200° C. for 30 to 120 seconds.
- the heat treatment process may be performed at 200 to 250° C. for 30 to 120 seconds.
- the immersion step, the drying step, and the heat treatment step may be continuously performed through a roll-to-roll process.
- Aramid hybrid yarn was prepared by combining 1000 denier aramid [poly(p-phenylene terephthalamide)] multifilament yarn and 20'S aramid [poly(p-phenylene terephthalamide)] spinning yarn.
- the aramid hybrid yarn and the 840 denier nylon 66 multifilament yarn were introduced into a cable cord twister (Allma Co., Ltd. Cable Corder), and a twisted yarn was produced by twisting each of 360 TPM to produce a plywood yarn.
- the tension applied to the aramid hybrid yarn and the nylon 66 multifilament yarn when performing the lower edge and the upper edge the length of the aramid lower yarn with respect to the length (L N ) of the nylon 66 lower yarn in the plied yarn (L A ) Ratio (that is, L A /L N ) was set to 1.03.
- the plied yarn was immersed in a solution of resolsinol-formaldehyde-latex (RFL) adhesive.
- RFL resolsinol-formaldehyde-latex
- a hybrid tire cord was completed in the same manner as in Example 1, except that the fineness of the nylon 66 multifilament yarn was 1260 denier.
- the hybrid tire cord was completed in the same manner as in Example 2, except that the fineness of the aramid multifilament yarn was 1500 denier, and the lower edge and the upper edge were each performed with a twist number of 300 TPM.
- a hybrid tire cord was completed in the same manner as in Example 3, except that the fineness of the aramid yarn was 16'S.
- Example 1 1000 denier PET multifilament yarn was used instead of nylon 66 multifilament yarn, and the hybrid tire cord was completed in the same manner as in Example 1, except that the lower edge and the upper edge were each performed with a twist number of 460 TPM.
- a hybrid tire cord was completed in the same manner as in Example 4, except that 1500 denier PET multifilament yarn was used instead of nylon 66 multifilament yarn.
- a hybrid tire cord was prepared in the same manner as in Example 1, except that the aramid multifilament yarn was inserted into the cable cord twister together with the nylon 66 multifilament yarn without performing affixation with the aramid spun yarn to perform lower and upper edges respectively. was completed.
- a hybrid tire cord was completed in the same manner as in Comparative Example 1, except that the fineness of the nylon 66 multifilament yarn was 1260 denier.
- the hybrid tire cord was completed in the same manner as in Comparative Example 2, except that the fineness of the aramid multifilament yarn was 1500 denier, and the lower edge and the upper edge were each performed with a twist number of 300 TPM.
- a hybrid tire cord was completed in the same manner as in Comparative Example 3, except that 1500 denier PET multifilament yarn was used instead of nylon 66 multifilament yarn.
- Hybrid tire cords obtained by the above examples and comparative examples are (i) strong, (ii) cut strength, (iii) cut elongation, (iv) adhesion to rubber, and (v) strength retention after disk fatigue test Were measured by the following methods, and the results are shown in Table 1.
- the adhesion of the hybrid tire cord to rubber was measured using the H-Test method defined in ASTM D885/D885M-10a (2014).
- Examples 1 to 6 by using the lower twisted yarn using aramid spun yarn together with aramid multifilament, compared to Comparative Examples 1 to 5, the strength, cutting strength, and cutting elongation were all excellent. Particularly, Examples 1 to 6 of the present invention show significantly superior adhesion to rubber and a strong retention rate compared to comparative examples, and improved fatigue resistance, which can result in tire performance and weight reduction.
- Comparative Examples 1 to 5 due to the low cutting elongation of the aramid multifilament yarn, although it may exhibit a certain level of strength and strength, the adhesion to rubber is poor as well as the strength retention is poor, resulting in fatigue resistance characteristics. The results were falling.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Tires In General (AREA)
- Woven Fabrics (AREA)
Abstract
Description
Claims (15)
- 제1 멀티필라멘트사와 제1 방적사가 함께 하연되어 형성된 제1 하연사; 및제2 멀티필라멘트사가 하연되어 형성된 제2 하연사;가 함께 상연된 합연사를 포함하며,상기 제1 멀티필라멘트사는 아라미드 멀티필라멘트사이고,상기 제1 방적사는 아라미드 방적사이고,상기 제2 멀티필라멘트사는 나일론 멀티필라멘트사 또는 폴리에스테르 멀티필라멘트사인,하이브리드 타이어 코드.
- 제1항에 있어서,소정 길이의 상기 하이브리드 타이어 코드의 상연을 언트위스트할 경우 상기 제1 하연사의 길이는 상기 제2 하연사의 길이의 1.005 내지 1.050 배인,하이브리드 타이어 코드.
- 제1항에 있어서,상기 제1 하연사와 상기 제2 하연사는 제1 꼬임수를 각각 갖는,하이브리드 타이어 코드.
- 제1항에 있어서,상기 제1 하연사와 상기 제2 하연사는 함께 제2 꼬임수로 상연되어 있고,상기 제2 꼬임수는 상기 제1 꼬임수와 동일한,하이브리드 타이어 코드.
- 제1항에 있어서,상기 제1 멀티필라멘트사는 500 내지 3000 denier의 섬도(thickness)를 갖고,상기 제1 방적사는 30 내지 8 'S의 섬도를 가지며,상기 제2 멀티필라멘트사는 500 내지 3000 denier의 섬도를 갖는,하이브리드 타이어 코드.
- 제1항에 있어서,상기 제1 하연사에 대한 상기 제2 하연사의 중량비는 20:80 내지 80:20인,하이브리드 타이어 코드.
- 제1항에 있어서,상기 제1 하연사와 상기 제2 하연사 상에 코팅된 접착제를 더 포함하는,하이브리드 타이어 코드.
- 제7항에 있어서,ASTM D885/D885M-10a(2014)에 의해 측정되는 절단강도(tear tenacity)가 8.0 내지 15.0 g/d이고,ASTM D885/D885M-10a(2014)에 의해 측정되는 절단신도(elongation at break)가 5 내지 15%이며,JIS-L 1017(2002)에 따라 실시되는 디스크 피로 테스트 후의 강력 유지율(strength retention rate)이 95% 이상인,하이브리드 타이어 코드.
- 제1 멀티필라멘트사와 제1 방적사를 합사(doubling)하여 하이브리드사(hybrid yarn)를 제조하는 제1 단계;상기 하이브리드사를 하연하여 제1하연사를 제조하는 제2 단계;제2 멀티필라멘트사를 하연하여 제2하연사를 제조하는 제3 단계; 및상기 제1 하연사와 상기 제2 하연사를 함께 상연하여 합연사를 제조하는 제4 단계;를 포함하며,상기 제1 멀티필라멘트사는 아라미드 멀티필라멘트사이고,상기 제1 방적사는 아라미드 방적사이며,상기 제2 멀티필라멘트사는 나일론 멀티필라멘트사 또는 폴리에스테르 멀티필라멘트사인,하이브리드 타이어 코드 제조방법.
- 제9항에 있어서,상기 제2, 제3, 및 제4 단계들은 하나의 연사기에 의해 수행되는,하이브리드 타이어 코드 제조방법.
- 제9항에 있어서,상기 제2, 제3, 및 제4 단계들이 수행될 때 상기 하이브리드사에 가해지는 장력은, 소정 길이의 상기 하이브리드 타이어 코드의 상연을 언트위스트할 경우 상기 제1 하연사의 길이가 상기 제2 하연사의 길이의 1.005 내지 1.050 배가 될 정도로 상기 제2 멀티필라멘트사에 가해지는 장력보다 작은,하이브리드 타이어 코드 제조방법.
- 제9항에 있어서,상기 제2 단계의 하연과 상기 제3 단계의 하연은 제1 꼬임수로 각각 수행되는,하이브리드 타이어 코드 제조방법.
- 제12항에 있어서,상기 제4 단계의 상연은 제2 꼬임수로 수행되고,상기 제2 꼬임수는 상기 제1 꼬임수와 동일한,하이브리드 타이어 코드 제조방법.
- 제9항에 있어서,상기 제1 멀티필라멘트사는 500 내지 3000 denier의 섬도를 갖고,상기 제1 방적사는 30 내지 8 'S의 섬도를 가지며,상기 제2 멀티필라멘트사는 500 내지 3000 denier의 섬도를 갖는,하이브리드 타이어 코드 제조방법.
- 제9항에 있어서,상기 합연사를 RFL(Resorcinol Formaldehyde Latex) 접착제 또는 에폭시계 접착제를 포함하는 접착제 용액에 침지시키는 단계;상기 접착제 용액이 함침된 상기 합연사를 70 내지 200℃에서 30 내지 120초 동안 건조시키는 단계; 및건조된 상기 합연사를 200 내지 250℃에서 30 내지 120초 동안 열처리하는 단계;를 더 포함하는,하이브리드 타이어 코드 제조방법.
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RS20231004A RS64749B1 (sr) | 2018-12-27 | 2019-12-27 | Hibridni kord za pneumatike sa jakom adhezijom na gumu i odličnim karakteristikama otpornosti na zamor, i postupak njegove proizvodnje |
US17/285,909 US11938765B2 (en) | 2018-12-27 | 2019-12-27 | Hybrid tire cord with strong adhesion to rubber and excellent fatigue resistance, and method for manufacturing the same |
PL19905207.7T PL3854918T3 (pl) | 2018-12-27 | 2019-12-27 | Hybrydowy kord oponowy z silną przyczepnością do gumy i doskonałą odpornością na zmęczenie oraz sposób jego wytwarzania |
ES19905207T ES2966409T3 (es) | 2018-12-27 | 2019-12-27 | Cable para neumáticos híbrido que tiene fuerte adherencia al caucho y excelentes propiedades de resistencia a la fatiga, y procedimiento de fabricación del mismo |
CN201980086004.7A CN113260747B (zh) | 2018-12-27 | 2019-12-27 | 对橡胶的粘附力强且抗疲劳性优异的混合轮胎帘线及其制造方法 |
EP19905207.7A EP3854918B1 (en) | 2018-12-27 | 2019-12-27 | Hybrid tire cord having strong adhesion to rubber and excellent fatigue resistance characteristics, and manufacturing method therefor |
JP2021525067A JP7091559B2 (ja) | 2018-12-27 | 2019-12-27 | ゴムに対する強い接着力および優れた耐疲労特性を有するハイブリッドタイヤコードおよびその製造方法 |
FIEP19905207.7T FI3854918T3 (fi) | 2018-12-27 | 2019-12-27 | Ulkorenkaan hybridikudosrunko, jolla on vahva adheesio kumiin ja erinomaiset väsymislujuusominaisuudet, sekä valmistusmenetelmä |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020180170216A KR102285436B1 (ko) | 2018-12-27 | 2018-12-27 | 고무에 대한 강한 접착력 및 우수한 내피로 특성을 갖는 하이브리드 타이어 코드 및 그 제조방법 |
KR10-2018-0170216 | 2018-12-27 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2020138996A2 true WO2020138996A2 (ko) | 2020-07-02 |
WO2020138996A3 WO2020138996A3 (ko) | 2020-08-20 |
Family
ID=71129255
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2019/018556 WO2020138996A2 (ko) | 2018-12-27 | 2019-12-27 | 고무에 대한 강한 접착력 및 우수한 내피로 특성을 갖는 하이브리드 타이어 코드 및 그 제조방법 |
Country Status (11)
Country | Link |
---|---|
US (1) | US11938765B2 (ko) |
EP (1) | EP3854918B1 (ko) |
JP (1) | JP7091559B2 (ko) |
KR (1) | KR102285436B1 (ko) |
CN (1) | CN113260747B (ko) |
ES (1) | ES2966409T3 (ko) |
FI (1) | FI3854918T3 (ko) |
HU (1) | HUE064093T2 (ko) |
PL (1) | PL3854918T3 (ko) |
RS (1) | RS64749B1 (ko) |
WO (1) | WO2020138996A2 (ko) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022231286A1 (ko) * | 2021-04-30 | 2022-11-03 | 코오롱인더스트리 주식회사 | 바이오 유래 성분을 포함하는 코드 및 그 제조방법 |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2199428A (en) * | 1936-09-29 | 1940-05-07 | Celanese Corp | Textile product |
US2134022A (en) * | 1936-11-26 | 1938-10-25 | Celanese Corp | Production of composite yarns |
US2575753A (en) * | 1948-12-29 | 1951-11-20 | Us Rubber Co | Method of producing chenillelike yarn |
JPH01122304U (ko) * | 1988-02-17 | 1989-08-18 | ||
KR930010804B1 (ko) * | 1991-12-17 | 1993-11-11 | 주식회사 코오롱 | 타이어 코드 |
FR2834724A1 (fr) | 2002-01-17 | 2003-07-18 | Michelin Soc Tech | Cables hybrides guipes, leur procede d'obtention et tissus composites pour pneumatiques les incorporant |
US7594381B1 (en) * | 2004-01-15 | 2009-09-29 | American & Efird, Inc. | Sewing thread |
US7484545B2 (en) * | 2005-12-20 | 2009-02-03 | The Goodyear Tire & Rubber Co. | Radial tire for aircraft with specified merged cords |
CN101126190B (zh) * | 2007-09-25 | 2011-02-16 | 山东滨州亚光毛巾有限公司 | 一种无捻毛巾的生产方法 |
US20090090447A1 (en) * | 2007-10-05 | 2009-04-09 | Baldwin Jr Donald William | Tire cord reinforcement |
JP4751454B2 (ja) | 2007-11-13 | 2011-08-17 | 住友ゴム工業株式会社 | 空気入りタイヤ |
KR101277158B1 (ko) * | 2008-04-30 | 2013-06-20 | 코오롱인더스트리 주식회사 | 아라미드 타이어 코오드 및 그의 제조방법 |
KR101233894B1 (ko) | 2008-05-29 | 2013-02-15 | 밀리켄 앤드 캄파니 | 공기 타이어용 렌드 위브 구조의 밴드 플라이 |
US8083877B2 (en) | 2008-05-29 | 2011-12-27 | Milliken & Company | Process for forming pneumatic tire with leno cap ply |
KR100934271B1 (ko) * | 2009-08-17 | 2009-12-28 | (주)황성 | 고강력 복합가공사 |
CN103249881B (zh) | 2011-02-04 | 2014-07-23 | 横滨橡胶株式会社 | 轮胎用帘线织物和充气轮胎 |
KR101406163B1 (ko) * | 2012-08-20 | 2014-06-12 | 주식회사 효성 | 아라미드 하이브리드 섬유 및 그에 의해 보강된 호스 |
US20140120791A1 (en) | 2012-10-26 | 2014-05-01 | E I Du Pont De Nemours And Company | Composite layer for reinforcement of objects such as tires or belts |
US20140360648A1 (en) * | 2013-06-07 | 2014-12-11 | E. I. Dupont De Nemours And Company | Hybrid cord for a pneumatic tire |
KR20160033851A (ko) * | 2014-09-18 | 2016-03-29 | 금호타이어 주식회사 | 공기입 타이어 및 섬유직물 벨트 |
KR101740769B1 (ko) | 2014-10-21 | 2017-05-29 | 한국타이어 주식회사 | 하이브리드 코드 및 그를 포함하는 고성능 래디얼 타이어 |
KR102498390B1 (ko) | 2015-04-22 | 2023-02-13 | 데이진 아라미드 비.브이. | 비원형 필라멘트를 포함하는 멀티필라멘트 파라-아라미드 얀을 포함하는 코드 |
KR101602605B1 (ko) * | 2015-06-29 | 2016-03-21 | 코오롱인더스트리 주식회사 | 하이브리드 타이어 코드 및 그 제조방법 |
US20170175301A1 (en) | 2015-12-17 | 2017-06-22 | E I Du Pont De Nemours And Company | Hybrid Cord and Use Thereof |
US11639565B2 (en) | 2016-09-29 | 2023-05-02 | Kolon Industries, Inc. | Hybrid tire cord and method for manufacturing the same |
JP7088701B2 (ja) | 2018-03-19 | 2022-06-21 | 帝人株式会社 | ゴム補強用の複合繊維コード及びその製造方法 |
JP7119879B2 (ja) * | 2018-10-12 | 2022-08-17 | 住友ゴム工業株式会社 | 複合コード及びそれを用いたタイヤ |
-
2018
- 2018-12-27 KR KR1020180170216A patent/KR102285436B1/ko active IP Right Grant
-
2019
- 2019-12-27 EP EP19905207.7A patent/EP3854918B1/en active Active
- 2019-12-27 JP JP2021525067A patent/JP7091559B2/ja active Active
- 2019-12-27 HU HUE19905207A patent/HUE064093T2/hu unknown
- 2019-12-27 FI FIEP19905207.7T patent/FI3854918T3/fi active
- 2019-12-27 RS RS20231004A patent/RS64749B1/sr unknown
- 2019-12-27 CN CN201980086004.7A patent/CN113260747B/zh active Active
- 2019-12-27 WO PCT/KR2019/018556 patent/WO2020138996A2/ko active Application Filing
- 2019-12-27 ES ES19905207T patent/ES2966409T3/es active Active
- 2019-12-27 PL PL19905207.7T patent/PL3854918T3/pl unknown
- 2019-12-27 US US17/285,909 patent/US11938765B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
EP3854918A4 (en) | 2022-07-06 |
EP3854918A2 (en) | 2021-07-28 |
JP7091559B2 (ja) | 2022-06-27 |
WO2020138996A3 (ko) | 2020-08-20 |
US20210370720A1 (en) | 2021-12-02 |
ES2966409T3 (es) | 2024-04-22 |
JP2022509044A (ja) | 2022-01-20 |
EP3854918B1 (en) | 2023-10-25 |
CN113260747A (zh) | 2021-08-13 |
HUE064093T2 (hu) | 2024-02-28 |
FI3854918T3 (fi) | 2023-11-07 |
KR20200080602A (ko) | 2020-07-07 |
US11938765B2 (en) | 2024-03-26 |
CN113260747B (zh) | 2022-12-20 |
RS64749B1 (sr) | 2023-11-30 |
KR102285436B1 (ko) | 2021-08-02 |
PL3854918T3 (pl) | 2024-03-18 |
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 | |
US6601378B1 (en) | Hybrid cabled cord and a method to make it | |
WO2013048097A2 (ko) | 아라미드 섬유 코드 및 그 제조방법 | |
CN109843604B (zh) | 混合轮胎帘线及其制造方法 | |
WO2012036427A2 (ko) | 혼합 섬유 및 그 제조방법 | |
KR20060126101A (ko) | 하이브리드 타이어 코오드 및 이의 제조방법 | |
WO2020138996A2 (ko) | 고무에 대한 강한 접착력 및 우수한 내피로 특성을 갖는 하이브리드 타이어 코드 및 그 제조방법 | |
CN107438680B (zh) | 包含含有非圆形丝的复丝对-芳族聚酰胺纱线的帘线 | |
JP2981254B2 (ja) | キャッププライコード | |
KR20220092849A (ko) | 하이브리드 타이어 코드 및 그 제조방법 | |
WO2021066385A1 (ko) | 하이브리드 타이어 코드 및 그 제조 방법 | |
KR102376147B1 (ko) | 카카스용 하이브리드 타이어 코드 및 그 제조방법 |
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: 19905207 Country of ref document: EP Kind code of ref document: A2 |
|
ENP | Entry into the national phase |
Ref document number: 2019905207 Country of ref document: EP Effective date: 20210421 |
|
ENP | Entry into the national phase |
Ref document number: 2021525067 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2101003092 Country of ref document: TH |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: P-2023/1004 Country of ref document: RS |