WO2021124895A1 - タイヤ - Google Patents

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Publication number
WO2021124895A1
WO2021124895A1 PCT/JP2020/044850 JP2020044850W WO2021124895A1 WO 2021124895 A1 WO2021124895 A1 WO 2021124895A1 JP 2020044850 W JP2020044850 W JP 2020044850W WO 2021124895 A1 WO2021124895 A1 WO 2021124895A1
Authority
WO
WIPO (PCT)
Prior art keywords
tire
dicarboxylic acid
aromatic
belt
diamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/044850
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
佐々木　陽祐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bridgestone Corp
Original Assignee
Bridgestone Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bridgestone Corp filed Critical Bridgestone Corp
Priority to US17/785,489 priority Critical patent/US20230030693A1/en
Priority to JP2021565451A priority patent/JP7477531B2/ja
Publication of WO2021124895A1 publication Critical patent/WO2021124895A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B60C9/18—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
    • B60C9/22—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre
    • 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
    • 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
    • B60C9/005—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
    • B60C9/18—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
    • B60C9/2009—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 comprising plies of different materials
    • 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
    • D02G3/045—Blended or other yarns or threads containing components made from different materials all components being made from artificial or synthetic material
    • 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
    • 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
    • B60C9/22—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre
    • B60C2009/2214—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre characterised by the materials of the zero degree ply 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
    • B60C9/18—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
    • B60C9/22—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre
    • B60C2009/2219—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre with a partial zero degree ply at the belt edges - edge band
    • 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
    • B60C9/22—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre
    • B60C2009/2252—Physical properties or dimension of the zero degree ply cords
    • B60C2009/2266—Density of the cords in width direction
    • B60C2009/2271—Density of the cords in width direction with variable density
    • 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
    • B60C9/22—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre
    • B60C2009/2252—Physical properties or dimension of the zero degree ply cords
    • B60C2009/2285—Twist structures
    • 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
    • B60C2200/00—Tyres specially adapted for particular applications
    • B60C2200/04—Tyres specially adapted for particular applications for road vehicles, e.g. passenger cars
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to a tire, and more particularly to a tire having improved low rolling resistance by using a reinforcing cord containing a polyamide multifilament as a reinforcing cord of a tire reinforcing member.
  • tires are required to be lightweight and have low fuel consumption.
  • tires have been actively improved and developed in terms of shape, structure, rubber characteristics such as tread, etc., and the weight has been reduced by reducing the amount of rubber used and the rolling resistance of the tire.
  • Fuel efficiency has been improved. Since the rubber member is greatly involved in rolling resistance, for example, the loss of the rubber member itself such as tread rubber, bead filler rubber, belt coating rubber, and bead filler rubber can be reduced, and the shape and structure of the rubber member can be adjusted. Low distortion has been studied and optimized.
  • Members other than the rubber member include a carcass ply layer, a belt layer, a belt reinforcing layer, etc.
  • the belt reinforcing layer has a large strain fluctuation at the time of rolling contact, so that the loss of the belt reinforcing layer is reduced.
  • Patent Document 1 it can be suitably used as a cap ply layer (belt reinforcing layer) in a tire, has excellent mechanical characteristics such as rigidity, thermal characteristics, etc., and reinforcement with reduced loss only. Cord materials have been proposed.
  • nylon fiber which is a polyamide fiber
  • fuel efficiency is not always sufficient, and the current situation is that rolling resistance is required to be further improved.
  • an object of the present invention is to provide a tire having improved low rolling resistance by using a reinforcing cord containing a polyamide multifilament as a reinforcing cord of a tire reinforcing member.
  • the present inventor uses a reinforcing cord containing a polyamide multifilament having a predetermined molecular structure as a reinforcing cord of the belt reinforcing layer, and configures the belt reinforcing layer. It has been found that the above-mentioned problems can be solved by setting the predetermined values, and the present invention has been completed.
  • the tire of the present invention has a belt composed of at least one belt layer on the outer side in the tire radial direction of the carcass, and at least one belt reinforcing layer covering the entire width of the belt on the outer side in the tire radial direction of the belt.
  • the belt reinforcing layer is a semi-aromatic polyamide composed of a rubber and a polycondensate of a dicarboxylic acid containing an aromatic dicarboxylic acid and a non-aromatic diamine or a polycondensate of a diamine containing a non-aromatic dicarboxylic acid and an aromatic diamine.
  • the belt has a reinforcing cord containing a multifilament and a rubber-cord composite composed of a multifilament as a constituent element, and
  • W width of the maximum width belt layer constituting the belt
  • at least 0.35 W or more from the tire equatorial plane E is a sparse region in the number of the reinforcing cords driven in the belt reinforcing layer, and the sparse region It is characterized in that the outer side in the tire width direction is a dense region.
  • the range of the sparse region is preferably 0.45 W or less from the equatorial plane of the tire.
  • the semi-aromatic polyamide is preferably a polycondensate of a dicarboxylic acid containing an aromatic dicarboxylic acid and a non-aromatic diamine, and the non-aromatic diamine is an aliphatic diamine. And at least one of the alicyclic diamines is preferred.
  • the glass transition temperature of the reinforcing cord taken out from the tire is preferably 80 to 230 ° C.
  • the value of (100 ° C.) / E'(25 ° C.) is preferably 0.7 to 1.0.
  • the moisture content of the reinforcing cord taken out from the tire is preferably 0.1 to 2.0% by mass.
  • the ratio of the aromatic dicarboxylic acid to the dicarboxylic acid of the reinforcing cord is preferably 50 mol% or more.
  • the ratio of the dicarboxylic acid having one aromatic ring to the aromatic dicarboxylic acid is 20 mol% or more, and the dicarboxylic acid having two aromatic rings to the aromatic dicarboxylic acid.
  • the ratio of the dicarboxylic acid having three aromatic rings to the aromatic dicarboxylic acid is 20 mol% or more, and the ratio of the dicarboxylic acid having three aromatic rings is 20 mol% or more.
  • the ratio of the diamine having 7 to 12 carbon atoms to the diamine is preferably 20 mol% or more.
  • the reinforcing cord is the multifilament of the polyamide, polyester fiber, nylon fiber, aramid fiber, polyketone fiber, glass fiber, carbon fiber, polyparaphenylene benzobisoxazole fiber and polyallylate. It is preferably a hybrid cord of at least one fiber selected from the group consisting of fibers.
  • the reinforcing cord taken out from the tire is the following formulas (1) and (2).
  • ⁇ 1 N1 ⁇ ⁇ (0.125 ⁇ D1 / ⁇ ) ⁇ 10 -3
  • ⁇ 2 N2 ⁇ ⁇ (0.125 ⁇ D2 / ⁇ ) ⁇ 10 -3 (2)
  • N1 is the number of lower twists [times / 10 cm]
  • D1 is the fineness of one lower twist yarn [dtex]
  • N2 is the number of upper twists [times / 10 cm]
  • D2 is the total fineness of the cord [dtex]
  • ⁇ is the reinforcing cord.
  • the lower twist coefficient ⁇ 1 represented by the density [g / cm 3 ]) is preferably 0.1 to 0.9, and the upper twist coefficient ⁇ 2 is preferably 0.1 to 1.2. Further, in the tire of the present invention, it is preferable that the ⁇ 1 is 0.1 to 0.5 and the ⁇ 2 is 0.1 to 0.7. Furthermore, in the tire of the present invention, the total fineness of the reinforcing cord is preferably 1000 to 8000 dtex. Further, in the tire of the present invention, the number of lower twists N1 of the reinforcing cord is preferably 10 to 30 times / 10 cm.
  • the tire of the present invention is suitable for a passenger car tire.
  • the tan ⁇ of the reinforcing cord is a leolograph solid, a leovibron, a spectrometer, under the conditions of a predetermined temperature, a measurement frequency of 10 Hz, a static tension of 100 g, and a dynamic repeating strain of 1000 ⁇ m, with the reinforcing cord having a length of 5 cm. It is a value measured using metravib or the like.
  • the glass transition temperature (Tg) is a value measured by differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the dynamic elastic modulus E'of the reinforcing cord can be measured under the same conditions as the measurement of tan ⁇ of the reinforcing cord.
  • the ratio of the dicarboxylic acid having one aromatic ring to the aromatic dicarboxylic acid is 20 mol% or more
  • the ratio of the structural unit derived from the aromatic dicarboxylic acid to the structural unit derived from the raw material monomer component is 10 mol. It means “% or more”.
  • the ratio of a dicarboxylic acid having two aromatic rings to an aromatic dicarboxylic acid is 20 mol% or more
  • the ratio of a dicarboxylic acid having three aromatic rings to an aromatic dicarboxylic acid is 20 mol% or more
  • diamine The ratio of diamine having 7 to 12 carbon atoms to 20 mol% or more is the same.
  • FIG. 1 is a schematic cross-sectional view of a tire according to a preferred embodiment of the present invention in the tire width direction.
  • the tire 10 of the present invention has a belt 2 composed of at least one belt layer on the outer side of the carcass 1 in the tire radial direction, and at least one belt reinforcing layer covering the entire width of the belt 2 on the outer side of the belt 2 in the tire radial direction. It is a tire equipped with 3.
  • the carcass 1 straddling the pair of bead cores 4 is composed of one layer of carcass ply
  • the belt 2 is composed of two layers of belt layers 2a and 2b
  • the bead core 4 is outside in the tire radial direction.
  • a bead filler 5 is arranged in the bead filler 5.
  • the belt reinforcing layer 3 is composed of a cap layer 3a arranged so as to cover the entire belt 2 and a pair of layer layers 3b arranged so as to cover only both ends of the cap layer 3a.
  • the cap layer 3a is arranged so as to intersect and continue with the tire equatorial plane E from one tire half to the other tire half, whereas the layer layer 3b does not intersect with the tire equatorial plane E, respectively.
  • the tire is composed of a pair arranged so as to cover only the end portion of the cap layer 3a in the half portion of the tire.
  • the belt reinforcing layer 3 may include both the cap layer 3a and the layer layer 3b, or may be only the cap layer 3a.
  • the cap layer 3a may be two or more layers, or may be a combination with two or more layer layers 3b.
  • the belt reinforcing layer 3 is usually composed of a rubberized layer of cords arranged substantially parallel to the tire circumferential direction.
  • At least one belt reinforcing layer 3 covering the entire width of the belt 2 is a polycondensate of rubber, a dicarboxylic acid containing an aromatic dicarboxylic acid, and a non-aromatic diamine, or a non-aromatic dicarboxylic acid. It has a reinforcing cord containing a multifilament of a semi-aromatic polyamide composed of a polycondensate of a diamine containing an aromatic diamine and a rubber-cord composite composed of the same.
  • the dicarboxylic acid may contain an aromatic dicarboxylic acid, or the diamine may contain an aromatic diamine, but in particular, the dicarboxylic acid contains an aromatic dicarboxylic acid and the diamine contains a fat.
  • the code contains a multifilament of a semi-aromatic polyamide using at least one of a group diamine and an alicyclic diamine.
  • Nylon 66 is generally used as the reinforcing cord of the belt reinforcing layer 3, but since such a reinforcing cord has a low glass transition temperature Tg (50 ° C.), it has low rigidity at high temperature and excellent steering stability. Absent.
  • Tg 50 ° C.
  • the reinforcing cord using aramid fiber can secure the rigidity at high temperature, but has a problem that the rigidity is too high and the tire manufacturability is remarkably poor.
  • semi-aromatic polyamide has high Tg due to intermolecular interaction and has appropriate rigidity. Therefore, by using it as a reinforcing cord of the belt reinforcing layer 3, high-speed running is performed without impairing tire productivity. Durability and steering stability at times can be improved. In addition, the loss tangent tan ⁇ in the tire use range is small, which is advantageous for reducing the rolling of the tire. Further, the polyamide fiber composed of an alicyclic dicarboxylic acid and an aliphatic diamine has high water absorption and low physical stability. On the other hand, since the semi-aromatic polyamide fiber has low water absorption, it is possible to secure the stability of physical properties.
  • the number of reinforcing cords driven in the belt reinforcing layer 3 is at least 0.35 W sparse from the tire equatorial plane E. (Sparse region), and is dense in the range outside the tire width direction of this sparse region (dense region). In this way, by reducing the number of belt reinforcing layers 3 driven in the vicinity of the tire equatorial plane E of the tire 10, low rolling resistance can be realized. In addition, weight reduction is expected by reducing the number of driving lines.
  • the number of reinforcing cords driven is preferably sparse in the range of at least 0.40 W or more from the tire equatorial plane E.
  • the range of the sparse region is preferably 0.45 W or less from the equatorial plane E of the tire. If the range of the sparse area extends from the equatorial plane of the tire to the outside of 0.45 W, the durability of the tire may decrease. Considering this viewpoint, less than 0.45 W is more preferable.
  • the number of reinforcing cords driven in the sparse region is preferably 25 to 75% of the number of reinforcing cords driven in the dense region.
  • the number of reinforcing cords driven in the sparse region of the belt reinforcing layer 3 is more preferably 40 to 60% of the number of driven cords in the dense region.
  • the belt reinforcing layer 3 can be formed by spirally winding a ribbon-shaped strip formed by rubber-coating a cord containing a multi-filament of the semi-aromatic polyamide according to the present invention in the circumferential direction of the tire. .. At this time, the number of reinforcing cords to be driven can be reduced by widening the winding interval of the ribbon-shaped strip, and the number of reinforcing cords to be driven can be increased by narrowing the winding interval of the ribbon-shaped strip.
  • the Tg of the reinforcing cord taken out from the tire 10 is preferably 80 to 230 ° C.
  • the cord having a high Tg as the reinforcing cord of the belt reinforcing layer 3 the loss tangent tan ⁇ in the tire use area can be reduced, and the rolling resistance of the tire 10 can be improved. Further, since the rigidity can be ensured even at a high temperature, the steering stability at a high speed can be improved.
  • Tg is 100-160 ° C.
  • the ratio of the loss tangent tan ⁇ (25 ° C.) at 25 ° C. and the loss tangent tan ⁇ (100 ° C.) at 100 ° C. of the reinforcing cord taken out from the tire 10 is tan ⁇ (25 ° C.) / tan ⁇ .
  • the value of (100 ° C.) is preferably 0.7 to 1.0.
  • the tangent tan ⁇ (25 ° C.) of the reinforcing cord taken out from the tire at 25 ° C. is 0.01 to 0.06.
  • tan ⁇ 25 ° C.
  • tan ⁇ 100 ° C.
  • the value of tan ⁇ (25 ° C.) / tan ⁇ (100 ° C.) is 0.85 to 1.0.
  • the value of'(100 ° C.) / E'(25 ° C.) is preferably 0.7 to 1.0.
  • the reinforcing cord taken out from the tire preferably has a dynamic elastic modulus E'(25 ° C.) at 25 ° C. of 0.7 to 0.8.
  • the moisture content of the reinforcing cord taken out from the tire 10 is 0.1 to 2.0% by mass.
  • the semi-aromatic polyamide fiber according to the reinforcing cord of the tire 10 of the present invention has low water absorption, so that the stability of the cord physical properties can be ensured.
  • those having a water content of 0.1 to 2.0% by mass can satisfactorily obtain the effects of the present invention.
  • the value of tan ⁇ (25 ° C.) / tan ⁇ (100 ° C.) and the value of E'(100 ° C.) / E'(25 ° C.) of the reinforcing cord are determined by the type of reinforcing cord, the number of twists, and the surface of the reinforcing cord. It can be adjusted by appropriately selecting the immersion conditions when immersing in the adhesive to be applied, the type of adhesive, and the heat treatment conditions after the adhesive treatment.
  • the number of the reinforcing cords to be driven in the belt reinforcing layer 3 can be appropriately set according to the strength of the reinforcing cords, but preferably, the number of the reinforcing cords to be driven is 20 to 20 or more in the dense region. It is 100 lines / 50 mm, more preferably 30 to 80 lines / 50 mm, and further preferably 40 to 60 lines / 50 mm.
  • the reinforcing cords taken out from the tire are represented by the following equations (1) and (2).
  • ⁇ 1 N1 ⁇ ⁇ (0.125 ⁇ D1 / ⁇ ) ⁇ 10 -3
  • ⁇ 2 N2 ⁇ ⁇ (0.125 ⁇ D2 / ⁇ ) ⁇ 10 -3
  • the lower twist coefficient ⁇ 1 represented by is preferably 0.1 to 0.9
  • the upper twist coefficient ⁇ 2 is preferably 0.1 to 1.2.
  • N1 is the number of lower twists [times / 10 cm]
  • D1 is the fineness of one lower twist yarn [dtex]
  • N2 is the number of upper twists [times / 10 cm]
  • D2 is the total fineness of the cord [dtex]
  • ⁇ is reinforcement.
  • ⁇ 1 is 0.1 to 0.5 and ⁇ 2 is 0.1 to 0.7.
  • the rigidity and fatigue of the reinforcing cord can be highly compatible with each other.
  • the lower twist number N1 of the reinforcing cord is preferably 10 to 30 times / 10 cm
  • the upper twist number N2 is preferably 10 to 30 times / 10 cm.
  • the total fineness is preferably 1000 to 8000 dtex. By setting the total fineness to 1000 dtex or more, sufficient strength can be secured. On the other hand, from the viewpoint of spinnability and post-processing, 8000 dtex or less is preferable. More preferably, it is 5000 dtex or less.
  • a cord composed of only a multifilament of semi-aromatic polyamide may be used, or a so-called hybrid cord in which other fibers are used in combination may be used.
  • other fibers include at least one fiber selected from the group consisting of polyester fiber, nylon fiber, aramid fiber, polyketone fiber, glass fiber, carbon fiber, polyparaphenylene benzobisoxazole fiber and polyallylate fiber. be able to.
  • the multifilament of a semi-aromatic polyamide is a polyfilament of a polyamide composed of a polycondensate of a dicarboxylic acid containing an aromatic dicarboxylic acid and a non-aromatic diamine or a polycondensate of a diamine containing a non-aromatic dicarboxylic acid and an aromatic diamine. is there.
  • the dicarboxylic acid may contain an aromatic dicarboxylic acid, and the diamine may contain an aromatic diamine, but in particular, the dicarboxylic acid contains an aromatic dicarboxylic acid, and the diamine is an aliphatic diamine and a fat.
  • a multifilament made of a polyamide containing at least one of the cyclic diamines is preferable.
  • the multifilament of the semi-aromatic polyamide according to the tire 10 of the present invention preferably has a ratio of aromatic dicarboxylic acid to dicarboxylic acid of at least 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more. .. Thereby, a multifilament of semi-aromatic polyamide having high Tg, excellent fiber strength and spinnability can be obtained.
  • the aromatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose.
  • terephthalic acid isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methyl
  • aromatic dicarboxylic acids having 8 to 20 carbon atoms, which are unsubstituted or substituted with various substituents such as isophthalic acid and 5-sodium sulfoisophthalic acid.
  • the semi-aromatic polyamide multifilament according to the tire 10 of the present invention contains, for example, an alicyclic dicarboxylic acid or a carbon atom having an alicyclic structure having 3 to 10 carbon atoms as a dicarboxylic acid other than the aromatic dicarboxylic acid.
  • a linear or branched aliphatic dicarboxylic acid of the number 3 to 20 can be used.
  • the alicyclic dicarboxylic acid having an alicyclic structure having 3 to 10 carbon atoms include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. And so on.
  • the alicyclic dicarboxylic acid may be unsubstituted or have a substituent.
  • substituents examples include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert-butyl group.
  • 1,4-cyclohexanedicarboxylic acid is preferable from the viewpoint of heat resistance, dimensional stability, strength and the like of the reinforcing cord.
  • the alicyclic dicarboxylic acid one type may be used alone, or two or more types may be used in combination.
  • cyclic dicarboxylic acid has geometric isomers of trans form and cis form.
  • 1,4-cyclohexanedicarboxylic acid as a raw material monomer may be used as either a trans form or a cis form, or may be used as a mixture of various ratios of the trans form and the cis form.
  • linear or branched aliphatic dicarboxylic acid having 3 to 20 carbon atoms examples include malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, and 2,2.
  • the aromatic ring contained in the dicarboxylic acid may be adjusted according to the required durability at high speed and steering stability.
  • the ratio of a dicarboxylic acid having one aromatic ring to an aromatic dicarboxylic acid is 20 mol% or more
  • the ratio of a dicarboxylic acid having two aromatic rings to an aromatic dicarboxylic acid is 20 mol% or more.
  • the semi-aromatic polyamide multifilament according to the tire 10 of the present invention has a diamine ratio of 7 to 12 carbon atoms to diamine of 20 mol% or more from the viewpoint of spinning stability, heat resistance, and low water absorption. Is preferable. It is more preferably 30 mol% or more and 80 mol% or less, further preferably 40 mol% or more and 75 mol% or less, and particularly preferably 45 mol% or more and 70 mol% or less.
  • a polymer having a high Tg tends to have a high Tm as well. If the Tm is too high, the polyamide is thermally decomposed at the time of melting, the molecular weight and strength are lowered, coloring and decomposition gas are mixed, and the spinnability is deteriorated.
  • the polyamide containing a diamine having 7 to 12 carbon atoms has high thermal stability at the time of melting, it is possible to obtain a multifilament having excellent spinning stability and good uniformity.
  • amide groups in the polyamide, it is possible to obtain a multifilament having excellent dimensional stability during water absorption.
  • 1,9-nonanediamine and 1,10-decamethylenediamine are preferable from the viewpoint of achieving both spinning stability and strength.
  • the diamine other than 1,9-nonanediamine and 1,10-decamethylenediamine is not particularly limited, and even an unsubstituted linear aliphatic diamine is branched having a substituent such as an alkyl group having 1 to 4 carbon atoms. It may be an aliphatic diamine or an alicyclic diamine.
  • substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and the like.
  • diamines other than 1,9-nonandamine and 1,10-decamethylenediamine include ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and undecamethylenediamine.
  • Dodecamethylenediamine Linear aliphatic diamines such as tridecamethylenediamine, 2-methylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, 2,4-dimethyloctamethylenediamine , 1,4-Cyclohexanediamine, 1,3-cyclohexanediamine, 1,3-cyclopentanediamine and the like.
  • aromatic diamine may be added to the diamine as long as the fluidity of the polyamide is not impaired.
  • the aromatic diamine is a diamine containing an aromatic, and examples thereof include, but are not limited to, metaxylylenediamine, orthoxylylenediamine, and paraxylylenediamine.
  • the diamine other than 1,9-nonanediamine and 1,10-decamethylenediamine it is more preferable that the diamine contains 5 to 6 carbon atoms and the ratio of the diamine having 5 to 6 carbon atoms is 20 mol% or more.
  • diamine having 5 to 6 carbon atoms examples include pentamethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, 2,5-dimethylhexanediamine, 2,2,4-trimethylhexamethylenediamine and the like. ..
  • 2-methylpentamethylenediamine is preferable from the viewpoint of spinnability, fluidity, and strength. If the ratio of 2-methylpentamethylenediamine is too high, 2-methylpentamethylenediamine self-cyclizes and decomposes at the time of melting, causing a decrease in molecular weight, resulting in deterioration of spinnability and strength.
  • the ratio of 2-methylpentamethylenediamine in the diamine needs to be set within a range in which decomposition does not occur at the time of melting while ensuring fluidity, and is preferably 20 mol% or more and 70 mol% or less, more preferably 20 mol%. It is 60 mol% or more, more preferably 20 mol% or more and 55 mol% or less.
  • hexamethylenediamine is preferable from the viewpoint of heat resistance of the reinforcing cord according to the tire 10 of the present invention. If the ratio of hexamethylenediamine is too high, the melting point becomes too high and spinning becomes difficult. Therefore, the ratio of hexamethylenediamine in the diamine is preferably 20 mol% or more and 60 mol% or less, more preferably 20 mol% or more and 50 mol. % Or less, more preferably 20 mol% or more and 45 mol% or less.
  • the amount of dicarboxylic acid added and the amount of diamine added are preferably around the same mol amount in order to increase the molecular weight. Considering the amount of diamine escaping to the outside of the reaction system during the polymerization reaction in terms of mol ratio, the mol amount of the entire diamine is 0.90 to 1.20 with respect to the mol amount of 1.00 of the entire dicarboxylic acid. It is preferably 0.95 to 1.10, and even more preferably 0.98 to 1.05.
  • a known end-capping agent can be further added to adjust the molecular weight.
  • the terminal encapsulant include acid anhydrides such as monocarboxylic acid, monoamine and phthalic anhydride, monoisocyanate, monoacid halides, monoesters and monoalcohols, and from the viewpoint of thermal stability. , Monocarboxylic acid, monoamine are preferable.
  • the end sealant may be used alone or in combination of two or more.
  • the cross ratio is preferably 1.7 or less.
  • the cross ratio is a value obtained by dividing the maximum diameter in the multifilament by the minimum diameter, and is a measure of uniformity between single yarns. Since the strength of the multifilament is pulled by the low physical properties in the strength distribution of the single yarn, the strength does not appear if the variation between the single yarns is large. Therefore, in the semi-aromatic polyamide multifilament according to the tire 10 of the present invention, the cross ratio is preferably 1.7 or less, more preferably 1.6 or less, and further preferably 1.5 or less. When the cross ratio is 1.7 or less, stretching at the single yarn level is uniformly performed, there is little variation in single yarn strength, and excellent strength as a multifilament of semi-aromatic polyamide is exhibited. The lower limit of the cross ratio is 1.0.
  • Examples of the method for producing a semi-aromatic polyamide include (1) a method in which an aqueous solution of a dicarboxylic acid / diamine salt or a mixture thereof or a suspension of water is heated and polymerized while maintaining a molten state (thermal melt polymerization method). , (2) A method of increasing the degree of polymerization of the polyamide obtained by the hot melt polymerization method while maintaining the solid state at a temperature below the melting point (hot melt polymerization / solid phase polymerization method), (3) Diamine dicarboxylate.
  • a method of heating an aqueous solution or a suspension of water of the mixture and further melting the precipitated prepolymer with an extruder such as a kneader to increase the degree of polymerization prepolymer / extrusion polymerization method
  • an extruder such as a kneader
  • Phase polymerization method (5) A method of polymerizing a diamine dicarboxylate or a mixture thereof while maintaining a solid state (solid phase polymerization method), (6) A dicarboxylic acid halide component and a diamine component equivalent to the dicarboxylic acid. Examples thereof include a method of polymerizing using the method (solution method).
  • the polymerization form may be a batch type or a continuous type.
  • the polymerization apparatus is not particularly limited, and examples thereof include known apparatus such as an autoclave type reactor, a tumbler type reactor, and an extruder type reactor such as a kneader.
  • the semi-aromatic polyamide multifilament according to the tire 10 of the present invention is a fibrous version of the above-mentioned semi-aromatic polyamide.
  • Various methods can be used for producing the multi-filament of the semi-aromatic polyamide, but melt spinning is usually used, and it is preferable to use a screw type melt extruder.
  • the spinning temperature (melting temperature) of the polyamide is preferably 300 ° C. or higher and 360 ° C. or lower. If the temperature is 300 ° C. or higher, it is possible to suppress the mixing of undissolved substances due to insufficient heat. When the temperature is 360 ° C. or lower, the thermal decomposition of the polymer and the generation of decomposed gas are significantly reduced, and the spinnability is improved.
  • the semi-aromatic polyamide multifilament cord according to the tire 10 of the present invention it is preferable to use an adhesive for adhering the rubber constituting the tire and the semi-aromatic polyamide multifilament cord, and this adhesive.
  • an adhesive for adhering the rubber constituting the tire and the semi-aromatic polyamide multifilament cord, and this adhesive.
  • a resorcin-formalin-latex solution RTL solution
  • the RFL liquid After adhering the RFL liquid, the RFL liquid is dried, fixed and relaxed.
  • the drying temperature of the RFL liquid is preferably 120 to 250 ° C., more preferably 140 to 200 ° C., and the drying time is preferably 10 seconds or longer, more preferably 20 to 120 seconds.
  • the twisted material is subsequently heat-treated in the heat set zone and the normalizing zone.
  • the temperature and time in the heat set zone and the normalizing zone are preferably 150 to 250 ° C. and 10 to 300 seconds, respectively. At this time, stretching of 2% to 10% is performed, and it is preferable that stretching of 3% to 9% is performed.
  • the tire 10 of the present invention has a belt 2 composed of at least one belt layer on the outer side in the tire radial direction of the carcass 1, and at least one belt reinforcing layer covering the entire width of the belt 2 on the outer side in the tire radial direction of the belt 2.
  • at least one belt reinforcing layer 3 covering the entire width of the belt 2 is a polycondensate of rubber, a dicarboxylic acid containing an aromatic dicarboxylic acid, and a non-aromatic diamine, or a non-aromatic dicarboxylic acid.
  • W width of the belt layer
  • at least 0.35 W or more from the tire equatorial plane E is a sparse region, and the range outside the sparse region in the tire width direction is defined as the sparse region.
  • the tire 10 of the present invention at least one layer of the belt reinforcing layer 3 may be made of the rubber-cord composite, and the other layers may have a conventional structure.
  • the carcass 1 is composed of one layer of carcass ply, but in the tire 10 of the present invention, the number of layers of the carcass ply is not limited to this, and two or more layers are used. There may be.
  • a cord other than the cord containing the multifilament of the semi-aromatic polyamide described above is used as the reinforcing cord of the carcass 1 and the belt reinforcing layer 3
  • a known organic fiber cord can be used, and the angle of the cord of the carcass is , The direction substantially orthogonal to the tire circumferential direction, for example, 70 to 90 °.
  • the organic fiber cord a commonly used known one can be used.
  • nylon or polyethylene terephthalate (PET) cords can also be used.
  • the locking structure of the carcass ply in the bead portion is not limited to the structure in which the carcass ply is wound and locked around the bead core 4 as shown in the figure, and the end portion of the carcass ply may be sandwiched between two layers of bead cores. (Not shown).
  • the belt 2 is composed of two layers of belt layers 2a and 2b, but in the tire 10 of the present invention, the belt layer may be three or more layers.
  • the belt layer can be, for example, a rubberized layer of a cord extending at an inclination of ⁇ 15 to 40 ° with respect to the tire circumferential direction, preferably a rubberized layer of a metal cord such as steel.
  • the two belt layers 2a and 2b shown in the figure may be laminated so that the metal cords constituting the respective belt layers intersect each other with the tire equatorial plane E in between.
  • the metal cord may be a metal cord in which a plurality of metal filaments are twisted together, or may be a metal cord in which a plurality of metal filaments are bundled without being twisted. Further, a plurality of metal filaments may be arranged in parallel without being twisted, and the metal filaments at that time may be straight or molded.
  • the form of the metal cord in which a plurality of metal filaments are arranged in parallel without twisting is preferably 2 or more, more preferably 5 or more, preferably 20 or less, and more preferably. Examples thereof include those in which metal filaments are arranged in parallel as a bundle of 12 or less, more preferably 10 or less, and particularly preferably 9 or less.
  • a rubber-metal cord complex having a metal cord in which a plurality of metal filaments are arranged in parallel without twisting or a bundled metal cord can be produced by a known method.
  • metal cords can be arranged in parallel at predetermined intervals, and the metal cords can be coated from both the upper and lower sides with a sheet made of an elastomer and having a thickness of about 0.5 mm.
  • the metal filament can be molded by a conventional method using a normal molding machine.
  • an inner liner may be arranged in the innermost layer.
  • the gas to be filled in the tire normal or variable oxygen partial pressure air or an inert gas such as nitrogen can be used.
  • the tire of the present invention is suitable for a passenger car tire.
  • the type of tire shown in FIG. 1 was manufactured with a tire size of 205 / 55R16.
  • the carcass is composed of a single layer of carcass ply, which is arranged in a direction substantially orthogonal to the tire circumferential direction.
  • the number of carcass plies driven was 50/50 mm.
  • the belt reinforcing layer one cap layer and one layer layer are arranged so as to be substantially parallel (0 ° to 5 °) in the tire circumferential direction.
  • the structure of the belt reinforcing layer is as shown in Table 1.
  • the semi-aromatic polyamide mainly consists of terephthalic acid and 1,9-diaminenonane.
  • the physical characteristics of the reinforcing cord are as follows.
  • the rolling resistance of the obtained tires was evaluated by the following procedure.
  • the values of Tg, tan ⁇ (25 ° C.) / tan ⁇ (100 ° C.), and E'(100 ° C.) / E'(25 ° C.) of the code composed of multifilaments of semi-aromatic polyamide are relative to the dicarboxylic acid.
  • the ratio of the aromatic dicarboxylic acid, the number of twists, the dipping conditions when immersing in the adhesive, and the heat treatment conditions after the adhesive treatment were adjusted.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Tires In General (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
PCT/JP2020/044850 2019-12-16 2020-12-02 タイヤ Ceased WO2021124895A1 (ja)

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