WO2024043136A1 - Câble de fibres polyamide, composite de caoutchouc et fibres, et pneumatique - Google Patents

Câble de fibres polyamide, composite de caoutchouc et fibres, et pneumatique Download PDF

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Publication number
WO2024043136A1
WO2024043136A1 PCT/JP2023/029459 JP2023029459W WO2024043136A1 WO 2024043136 A1 WO2024043136 A1 WO 2024043136A1 JP 2023029459 W JP2023029459 W JP 2023029459W WO 2024043136 A1 WO2024043136 A1 WO 2024043136A1
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Prior art keywords
polyamide
fiber
fibers
cord
fiber cord
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PCT/JP2023/029459
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English (en)
Japanese (ja)
Inventor
将大 藤江
倩 呉
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株式会社ブリヂストン
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Publication of WO2024043136A1 publication Critical patent/WO2024043136A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • D—TEXTILES; PAPER
    • 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
    • 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

Definitions

  • the present invention relates to a polyamide fiber cord, a rubber-fiber composite, and a tire.
  • a carcass including a reinforcing cord is placed inside a tire in order to reinforce the strength and rigidity of the tire, and a belt including a reinforcing cord is placed outside the carcass in the tire radial direction.
  • a belt reinforcing layer also called a "cap layer” including reinforcing cords may be disposed on the outside of the belt in the tire radial direction in order to reinforce the belt.
  • organic fiber cords such as polyamide (nylon) fiber cords and polyester fiber cords are usually used as reinforcing cords for carcass and belt reinforcing layers.
  • Patent Document 1 discloses a pneumatic tire that includes a reinforcing member (rubber-fiber composite) in which a cord having polyester fibers using biomass-derived components as at least part of the raw material is coated with rubber. It is taught that, according to the tire, deterioration of tire characteristics can be suppressed while reducing environmental load.
  • a reinforcing member rubber-fiber composite
  • Patent Document 1 is a technology related to replacing polyester fiber cords among organic fiber cords used in tires, but in addition to polyester fiber cords, various organic fiber cords can be applied to tires depending on the purpose. has been done.
  • polyamide fiber cords particularly polyamide 6,6 (PA66) fiber cords
  • PA66 polyamide 6,6
  • PA66 raw material polyamide 6,6
  • the present inventors have investigated polyamide fiber cords using polyamide at least partially derived from biomass as an alternative to polyamide 6,6, but the physical properties at high temperatures (particularly the modulus of elasticity and ) is low, and if such a polyamide fiber cord is applied to a tire, the tire properties will deteriorate.
  • organic fiber cords are also used in rubber products such as conveyor belts and hoses, and these rubber products are also required to reduce their environmental impact.
  • an object of the present invention is to provide an organic fiber cord that can reduce environmental impact while maintaining physical properties at high temperatures, and a rubber-fiber composite using such an organic fiber cord.
  • a further object of the present invention is to provide a tire that includes such an organic fiber cord and can reduce environmental load while maintaining tire characteristics.
  • the main structure of the organic fiber cord (polyamide fiber cord), rubber-fiber composite, and tire of the present invention that solves the above problems is as follows.
  • the biomass-derived carbon content (bio conversion rate) of the entire cord is 15% or more, A polyamide fiber cord, characterized in that the cord has a heat shrinkage rate of 9.0% or less.
  • the polyamide fiber cord according to [1] which includes fibers having a biomass-derived carbon content (bio conversion rate) of 40% or more.
  • the fibers with a bio conversion rate of 40% or more include polyamide 4 fiber, polyamide 4,4 fiber, polyamide 4,6 fiber, polyamide 5,4 fiber, polyamide 5,6 fiber, polyamide 6 fiber, polyamide 6,
  • the polyamide according to [5], wherein the fiber with a bioconversion rate of 100% is at least one selected from the group consisting of polyamide 11 fiber, polyamide 4,10 fiber, and polyamide 10,10 fiber. fiber cord.
  • the polyamide fiber cord according to [7] which is a cord made by twisting two aramid fibers and one polyamide 4,10 fiber.
  • the polyamide fiber cord according to [1] comprising only polyamide fibers with a biomass-derived carbon content (bio conversion rate) of 15% or more.
  • polyamide fiber cord according to [9] or [10], wherein the polyamide fiber is at least one selected from the group consisting of polyamide 4,6 fibers and polyamide 5,6 fibers.
  • a rubber-fiber composite comprising the polyamide fiber cord according to any one of [1] to [11].
  • a tire comprising the polyamide fiber cord according to any one of [1] to [11].
  • the present invention it is possible to provide a polyamide fiber cord and a rubber-fiber composite that can reduce environmental impact while maintaining physical properties at high temperatures. Further, according to the present invention, it is possible to provide a tire that can reduce environmental load while maintaining tire characteristics.
  • 1 is a sectional view of one embodiment of a tire of the present invention.
  • polyamide fiber cord refers to a cord containing at least polyamide fibers, and also includes cords consisting only of polyamide fibers.
  • the fibers included in the cord are also called a “fiber bundle” or a “filament bundle.”
  • the heat shrinkage rate of the cord is measured according to ASTM D885 and ASTM D4974, and is a value measured by heating at 177° C. for 2 minutes.
  • the "number of amide groups in polyamide” and the “number of atoms in the main chain of polyamide” are calculated from the “number of amide groups” in one repeating unit of polyamide and the "number of atoms in the main chain”.
  • the amide density of polyamide 4 and polyamide 4,4 is 20.0
  • the amide density of polyamide 5,4 is 18.2
  • the amide density of polyamide 4,6 is 16.7
  • the amide density of polyamide 5,6 is 15.4
  • the amide density of polyamide 6 and polyamide 6,6 is 14.3
  • the amide density of polyamide 4,10 is 12.5
  • , 10 is 11.1,
  • the amide density of polyamide 9,T is 10.5, the amide density of polyamide 10,10 is 9.1
  • the amide density of polyamide 11 is: It is 8.3.
  • Average amide density [(Fineness of fiber A (dtex) x number of fibers A x amide density of fiber A) + (fineness of fiber B (dtex) x number of fibers B x amide density of fiber B) +... ]/(Fineness of fiber A (dtex) x number of fibers A + fineness of fiber B (dtex) x number of fibers B +%) (4) Calculated from.
  • fiber A is the first type of fiber
  • fiber B is the second type of fiber.
  • the "fineness (dtex) of the fiber concerned x the number of fibers concerned x the amide density of the fiber concerned” is added to the "" part of the molecule.
  • the fineness (dtex) of the fiber concerned x the number of fibers concerned is added to the "" part of the denominator.
  • biomass-derived refers to origin from biological resources such as plant resources, animal resources, microbial resources, etc., and is synonymous with “bio-derived”.
  • the polyamide fiber cord of the present embodiment is characterized in that the content ratio (bioconversion rate) of biomass-derived carbon in the entire cord is 15% or more; In addition to the components, it may also contain components that are not derived from biomass.
  • the compounds described in this specification may be partially or entirely derived from fossil resources, and may be derived from biological resources such as plant resources (biomass-derived). It may be derived from recycled resources such as used tires. Moreover, it may be derived from a mixture of any two or more of fossil resources, biological resources, and recycled resources.
  • the polyamide fiber cord of this embodiment is characterized in that the content ratio of biomass-derived carbon (bioconversion rate) in the entire cord is 15% or more, and the heat shrinkage rate of the cord is 9.0% or less.
  • the polyamide fiber cord of this embodiment has a biomass-derived carbon content (bio conversion rate) of 15% or more in the entire cord, the environmental load can be reduced. Further, since the polyamide fiber cord of this embodiment has a heat shrinkage rate of 9.0% or less, sufficient strength can be ensured, and physical properties such as elastic modulus and strength can be maintained even at high temperatures. Further, the polyamide fiber cord of this embodiment can achieve physical properties equivalent to cords using petroleum-derived polyamide 6,6 (PA66) fibers because the cord has a heat shrinkage rate of 9.0% or less. Therefore, according to the polyamide fiber cord of this embodiment, the environmental load can be reduced while maintaining the physical properties at high temperatures (particularly the elastic modulus and strength).
  • PA66 petroleum-derived polyamide 6,6
  • the polyamide fiber cord of this embodiment has a biomass-derived carbon content (bioconversion rate) of 15% or more in the entire cord. If the bio conversion rate of the entire cord is less than 15%, the effect of reducing environmental load will be small. From the viewpoint of further reducing the environmental load, the polyamide fiber cord of this embodiment preferably has a bio conversion rate of 20% or more, and may be 100%.
  • the polyamide fiber cord of this embodiment has a heat shrinkage rate of 9.0% or less. If the heat shrinkage rate of the cord exceeds 9.0%, the physical properties (especially elastic modulus and strength) at high temperatures cannot be maintained sufficiently.
  • the polyamide fiber cord of this embodiment preferably has a heat shrinkage rate of 4.0% or less. When the heat shrinkage rate of the polyamide fiber cord is 4.0% or less, uniformity particularly during high-speed running is excellent.
  • the polyamide fiber cord of this embodiment has an amide density (in the case of including a plurality of fibers having different amide densities, an average amide density) of 10.5 or more.
  • the (average) amide density of the polyamide fiber cord is 10.5 or more, hydrogen bonds between amide bonds are formed densely, ensuring sufficient strength and improving thermal properties. It is also possible to maintain physical properties such as elastic modulus and strength.
  • the (average) amide density of the polyamide fiber cord increases, hydrogen bonds between amide bonds are formed densely, so that the heat shrinkage rate tends to decrease.
  • the higher the (average) amide density of a polyamide fiber cord the denser the formation of hydrogen bonds between amide bonds. E') tends to be high. Therefore, polyamide fiber cords with high (average) amide density tend to have excellent physical properties (thermal properties) at high temperatures.
  • the polyamide fiber cord of the first embodiment of the present invention includes fibers with a biomass-derived carbon content (bio conversion rate) of 40% or more.
  • the polyamide fiber cord of the first embodiment includes fibers with a bio conversion rate of 40% or more, thereby increasing the effect of reducing environmental load.
  • the polyamide fiber cord of the first embodiment includes fibers with a bioconversion rate of 40% or more, but may further include other fibers (fiber bundles).
  • the fibers (polyamide fibers) having a bio conversion rate of 40% or more include polyamide 4 (PA4) fibers, polyamide 11 (PA11) fibers, polyamide 4,4 (PA44) fibers, polyamide 5,4 (PA54) fibers, and polyamide fibers.
  • PA4 polyamide 4
  • PA46 polyamide 5,6 (PA56) fiber
  • PA410 polyamide 410
  • PA6 polyamide 6
  • PA66 polyamide 6,6
  • PA610 polyamide 6,10
  • PA10101010101010101010101010101010101010 polyamide 10,10
  • Fibers are preferred.
  • Fibers with a bio conversion rate of 40% or more include polyamide 4 fiber, polyamide 4,4 fiber, polyamide 4,6 fiber, polyamide 5,4 fiber, polyamide 5,6 fiber, polyamide 6 fiber, polyamide 6,6 fiber, polyamide 11 fiber, polyamide 4,10 fiber, polyamide 6,10 fiber, and polyamide 10,10 fiber, a cord using petroleum-derived polyamide 6,6 (PA66) fiber It is possible to achieve the same physical properties as the previous one, while further reducing the environmental impact.
  • the fibers with a bio conversion rate of 40% or more include polyamide 4,6 fibers, polyamide 5,6 fibers, polyamide 11 fibers, polyamide 4,10 fibers, polyamide 6,10 fibers, and polyamide 10,10 fibers.
  • the environmental load can be further reduced while achieving physical properties equivalent to cords using petroleum-derived polyamide 6,6 (PA66) fibers.
  • Polyamide which is a raw material for these polyamide fibers, can be synthesized from biomass-derived components.
  • the biomass-derived components are components derived from biological resources such as plant resources, animal resources, and microbial resources.
  • Polyamide 4 is obtained by ring-opening polymerization of ⁇ -butyrolactam, and ⁇ -butyrolactam is obtained from glucose, glutamic acid, and the like.
  • Polyamide 11 (PA11) is obtained by polymerizing aminoundecanoic acid, and aminoundecanoic acid is obtained from plant resources such as castor beans.
  • Polyamide 4,4 (PA44) is obtained by a condensation polymerization reaction of tetramethylene diamine (4 carbon atoms) and succinic acid (4 carbon atoms), and tetramethylene diamine is obtained from plant resources such as sugar cane. Acid is obtained from plant sources such as sugar cane and corn.
  • Polyamide 5,4 (PA54) is obtained by a condensation polymerization reaction of pentamethylene diamine (5 carbon atoms) and succinic acid (4 carbon atoms), and pentamethylene diamine is obtained from plant resources such as corn. Acid is obtained from plant sources such as sugar cane and corn.
  • Polyamide 4,6 (PA46) is obtained by a condensation polymerization reaction of tetramethylene diamine (4 carbon atoms) and adipic acid (6 carbon atoms), and tetramethylene diamine is obtained from plant resources such as sugar cane.
  • Polyamide 5,6 is obtained by a condensation polymerization reaction of pentamethylene diamine (5 carbon atoms) and adipic acid (6 carbon atoms), and pentamethylene diamine is obtained from plant resources such as corn.
  • Polyamide 4,10 (PA410) is obtained by a condensation polymerization reaction of tetramethylene diamine (4 carbon atoms) and sebacic acid (10 carbon atoms). Tetramethylene diamine is obtained from plant resources such as sugar cane, and sebacic acid Acid is obtained from plant sources such as castor beans.
  • Polyamide 6 (PA6) is obtained by ring-opening polymerization of ⁇ -caprolactam (6 carbon atoms), and ⁇ -caprolactam is obtained from plant resources.
  • Polyamide 6,6 is obtained by a condensation polymerization reaction of hexamethylene diamine (with 6 carbon atoms) and adipic acid (with 6 carbon atoms), and hexamethylene diamine and adipic acid are obtained from plant resources.
  • Polyamide 6,10 (PA610) is obtained by a condensation polymerization reaction of hexamethylene diamine (6 carbon atoms) and sebacic acid (10 carbon atoms), and sebacic acid is obtained from plant resources such as castor beans.
  • Polyamide 10,10 is obtained by a condensation polymerization reaction of decamethylene diamine (10 carbon atoms) and sebacic acid (10 carbon atoms), and decamethylene diamine and sebacic acid are obtained from plant resources such as castor beans.
  • tetramethylene diamine also called “putrescine”
  • Sebacic acid can also be obtained by mechanically pressing castor beans to obtain castor oil, methanolysis of the castor oil to obtain methyl ricinoleate, and saponifying the methyl ricinoleate.
  • the polyamide fiber cord of the first embodiment is preferably a cord in which the fibers with a bio conversion rate of 40% or more and aramid fibers are twisted together.
  • Such polyamide fiber cords are rigid and have excellent thermal properties due to the aramid fibers, and are highly effective in reducing environmental load due to the fibers having a bio conversion rate of 40% or more.
  • the polyamide fiber cord of the first embodiment preferably includes fibers with a bio conversion rate of 100% (that is, completely derived from biomass). By including fibers with a bio conversion rate of 100%, the effect of reducing environmental load will be even greater.
  • the fibers with a bio conversion rate of 100% include polyamide 4 (PA4) fiber, polyamide 11 (PA11) fiber, polyamide 4,4 (PA44) fiber, polyamide 5,4 (PA54) fiber, and polyamide 4,10 (PA410) fiber. ) fibers, polyamide 10,10 (PA1010) fibers, etc. Among these, polyamide 11 fibers, polyamide 4,10 fibers, and polyamide 10,10 fibers are preferred.
  • the fiber with a bio conversion rate of 100% is at least one selected from the group consisting of polyamide 11 fiber, polyamide 4,10 fiber, and polyamide 10,10 fiber, petroleum-derived polyamide 6,6 (PA66) While achieving the same physical properties as cords using fibers, the environmental impact can be further reduced.
  • the polyamide fiber cord of the first embodiment is preferably a cord made by twisting polyamide 4,10 fibers and aramid fibers.
  • Such polyamide fiber cords are rigid and have excellent thermal properties due to the aramid fibers, while reducing environmental impact due to the polyamide 4,10 fibers that can be used with a bio conversion rate of 100%. The reduction effect is large.
  • the polyamide fiber cord of the first embodiment is preferably a cord made of three fibers twisted together.
  • a cord made of three fibers twisted together can ensure sufficient rigidity as a tire reinforcing material compared to a cord made of two fibers twisted together, and a cord made of four fibers twisted together can ensure sufficient rigidity as a tire reinforcement material. It can be lighter compared to.
  • the polyamide fiber cord of the first embodiment is preferably a cord made by twisting two aramid fibers and one polyamide 4,10 fiber.
  • This polyamide fiber cord is rigid due to the two aramid fibers and has excellent thermal properties, and due to the polyamide 4,10 fiber that can be used with a bio conversion rate of 100%, It is highly effective in reducing environmental impact.
  • the polyamide fiber cord of the second embodiment of the present invention consists only of polyamide fibers with a biomass-derived carbon content (bio conversion rate) of 15% or more.
  • the polyamide fiber cord of the second embodiment is made only of polyamide fibers with a bio conversion rate of 15% or more, thereby increasing the effect of reducing environmental load.
  • the polyamide fiber preferably has an amide density of 14.0 or more.
  • Polyamide fibers have higher melting point (Tm), glass transition temperature (Tg), moisture content, and elastic modulus (E') because the higher the amide density, the denser the hydrogen bonds between amide bonds are formed.
  • Tm melting point
  • Tg glass transition temperature
  • E' elastic modulus
  • polyamide fibers with an amide density of 14.0 or higher have sufficient strength due to the close formation of hydrogen bonds between amide bonds, and can maintain sufficient physical properties such as elastic modulus and strength even at high temperatures. Can be maintained.
  • Examples of the polyamide fibers having an amide density of 14.0 or more include polyamide 4 fibers, polyamide 4,4 fibers, polyamide 5,4 fibers, polyamide 4,6 fibers, polyamide 5,6 fibers, and the like.
  • the polyamide fiber is preferably at least one selected from the group consisting of polyamide 4,6 fibers and polyamide 5,6 fibers.
  • the polyamide fiber is at least one selected from the group consisting of polyamide 4,6 fibers and polyamide 5,6 fibers, it has physical properties equivalent to cords using petroleum-derived polyamide 6,6 (PA66) fibers. While achieving this goal, the environmental impact can be further reduced.
  • PA66 petroleum-derived polyamide 6,6
  • the polyamide fiber cord of this embodiment contains at least one type of polyamide fiber, may further contain other fibers, and may have a single-twist structure or a twisted structure (such as a double-twist structure).
  • a twisted yarn cord can be obtained by aligning the raw yarns and twisting them in one direction.
  • the number of twists is preferably in the range of 4 to 20 twists/10 cm. If the number of twists in a single-stranded structure exceeds 20 twists/10cm, the strength of the twisted cord may decrease, and if it is less than 4 twists/10cm, the twisted cord may not have sufficient fatigue resistance. There is.
  • a twisted yarn cord in the case of a double-twisted structure, for example, can be obtained by first twisting the raw yarn, then combining a plurality of them and applying final twist in the opposite direction.
  • the number of first twists is preferably in the range of 10 to 60 times/10 cm, and the number of first twists is preferably in the range of 10 to 60 times/10 cm. If the number of first twists exceeds 60 times/10 cm, the strength of the twisted cord may decrease, and if it is less than 10 times/10 cm, the twisted cord may not have sufficient fatigue resistance. Furthermore, if the number of twists exceeds 60 turns/10cm, the strength of the twisted cord may decrease, and if it is less than 10 twists/10cm, the twisted cord may not have sufficient fatigue resistance. be.
  • the number of first twists of the aramid fibers is 10 to 60 times/10 cm.
  • the number of ply twists of fibers with a bio conversion rate of 40% or more is also preferably in a range of 10 to 60 times/10 cm. If the number of first twists of the aramid fiber exceeds 60 times/10cm, the strength of the twisted cord may decrease, and if it is less than 10 times/10cm, the twisted cord may not have sufficient fatigue resistance. There is.
  • the strength of the twisted cord may decrease, and if it is less than 10 times/10cm, the twisted cord may not have sufficient durability. There is a possibility that fatigue properties may not be obtained.
  • the total fineness of the polyamide fiber cord of this embodiment is preferably in the range of 1000 to 6000 dtex. If the total fineness of the polyamide fiber cord is less than 1000 dtex, sufficient strength as a fiber for tires may not be obtained, and if it exceeds 6000 dtex, the treat will become thick and the weight of the tire will increase.
  • the fineness of the aramid fibers is preferably in the range of 1000 to 4000 dtex, and the bio conversion rate is preferably 1000 to 4000 dtex.
  • the fineness of the fibers with a conversion rate of 40% or more is preferably in the range of 400 to 3000 dtex. If the fineness of the aramid fiber is less than 1000 dtex, sufficient strength as a fiber for tires may not be obtained, and if it exceeds 4000 dtex, the treat will become thick and the weight of the tire will increase.
  • the fineness of the fiber with a bio conversion rate of 40% or more is less than 400 dtex, sufficient strength as a tire fiber may not be obtained, and if it exceeds 3000 dtex, the treat will become thick and the weight of the tire will increase. becomes larger.
  • the breaking strength of the polyamide fiber cord of this embodiment is preferably 6.0 cN/dtex or more. Moreover, the breaking strength of the polyamide fiber cord is preferably 200N or more. Here, the breaking strength is measured at room temperature (23° C.) according to ASTM D855M. This is because a sufficient reinforcing effect can be obtained when the breaking strength of the polyamide fiber cord is 6.0 cN/dtex or more, or 200 N or more.
  • the breaking elongation (elongation at break) of the polyamide fiber cord of this embodiment is preferably 8.0% or more.
  • the cutting elongation is measured at room temperature (23° C.) according to ASTM D855M. If the breaking elongation of the polyamide fiber cord is less than 8.0%, a sufficient reinforcing effect cannot be obtained.
  • the moisture content of the polyamide fiber cord of this embodiment is preferably 3.0% or less.
  • the moisture content is measured according to JIS L1013.
  • the moisture content of the polyamide fiber cord exceeds 3.0%, the physical properties deteriorate and a sufficient reinforcing effect cannot be obtained.
  • the polyamide fiber cord of this embodiment can reduce environmental impact while maintaining physical properties at high temperatures, so it can be used as a tire cord that requires excellent physical properties (especially elastic modulus and strength) at high temperatures. Particularly preferred as Moreover, since the polyamide fiber cord of this embodiment has sufficient physical properties (thermal properties) at high temperatures, it is suitable not only for tires but also for conveyor belts, hoses, etc.
  • the polyamide fiber cord (organic fiber cord) is preferably treated with an adhesive using an adhesive composition.
  • the adhesive composition may be, for example, a thermoplastic polymer having at least one functional group having crosslinking properties as a pendant group and containing substantially no addition-reactive carbon-carbon double bonds in the main chain structure.
  • examples include adhesive compositions containing a combination (A), a heat-reactive water-based urethane resin (B), and an epoxy compound (C), and optionally further containing a rubber latex (D).
  • the adhesive treatment for organic fiber cords involves applying epoxy or isocyanate to the cord surface, and then treating the cord with a resin made of a mixture of resorcinol, formaldehyde, and latex (hereinafter referred to as RFL resin).
  • RFL resin a resin made of a mixture of resorcinol, formaldehyde, and latex
  • Two-bath treatment is being performed.
  • the resin used in the first bath becomes very hard, which increases the strain input to the organic fiber cord and may reduce the cord fatigue resistance.
  • RFL resins can exhibit sufficient adhesion between the cord and the elastomer at room temperature, but the adhesion may be extremely reduced at high temperatures of 130° C. or higher.
  • thermoplastic polymer (A) which has at least one functional group having crosslinking properties as a pendant group and which does not substantially contain addition-reactive carbon-carbon double bonds in its main chain structure;
  • a one-bath mixed solution adheresive composition
  • a heat-reactive water-based urethane resin (B) and an epoxy compound (C) are mixed
  • the polyamide fiber cord organic fiber cord
  • Adhesion to the elastomer (covering rubber) can be sufficiently ensured even at high temperatures of 180° C. or higher.
  • the main chain of the thermoplastic polymer (A) mainly has a linear structure, and examples of the main chain include ethylene polymers such as acrylic polymers, vinyl acetate polymers, and vinyl acetate/ethylene polymers. Polymers such as addition polymers; urethane-based polymers; and the like are preferred. However, the thermoplastic polymer (A) only needs to have the function of suppressing the resin fluidity at high temperatures and ensuring the breaking strength of the resin by crosslinking the functional groups of the pendant groups. It is not limited to the ethylenic addition polymer and urethane-based polymer described above.
  • an oxozaline group a bismaleimide group, a (blocked) isocyanate group, an aziridine group, a carbodiimide group, a hydrazino group, an epoxy group, an epithio group, etc. are preferable. .
  • thermoplastic polymer (A), heat-reactive aqueous urethane resin (B), epoxy compound (C), and rubber latex (D) are those described in Japanese Patent Application No. 2023-040157, respectively.
  • the one described in Japanese Patent Application No. 2023-030762 can be used.
  • a mixed solution of three types (adhesive)
  • a mixed solution (adhesive composition) of the thermoplastic polymer (A), heat-reactive water-based urethane resin (B), epoxy compound (C), and rubber latex (D) is used. It is also possible to process using only one bath.
  • the proportion of the thermoplastic polymer (A) (dry mass ratio) is preferably 2 to 75%, and the proportion of the heat-reactive aqueous urethane resin (B) (dry mass ratio) is preferably 2 to 75%. ) is preferably 15 to 87%, the proportion of the epoxy compound (C) (dry mass ratio) is preferably 11 to 70%, and the proportion of the rubber latex (D) (dry mass ratio) is preferably , preferably 20% or less.
  • a dip treatment liquid that does not contain resorcin and formalin as the adhesive composition for the polyamide fiber cord (organic fiber cord).
  • a dipping liquid include rubber latex (a) having an unsaturated diene, a compound having a skeleton structure consisting of polyether and an amine functional group, a compound having an acrylamide structure, polypeptide, polylysine, and Examples include compositions containing one or more compounds (b) selected from carbodiimides.
  • an aqueous compound (c) having a (thermally dissociable blocked) isocyanate group may be used.
  • polyphenols (d) polyphenols (d)
  • polyvalent metal salts (e) polyvalent metal salts
  • a composition may further contain at least one of an isocyanate compound (III) and a rubber latex (IV) in addition to the polyphenols (I) and the aldehydes (II).
  • the adhesive composition for treating (coating) the polyamide fiber cord (organic fiber cord) with an adhesive contains polyphenols (I) and aldehydes (II), so that resorcinol can be used in consideration of the burden on the environment. Good adhesiveness can be achieved even when not using.
  • polyphenols (I) When the adhesive composition contains polyphenols (I) as a resin component, the adhesiveness with the polyamide fiber cord (organic fiber cord) can be improved.
  • polyphenols (I) are typically water-soluble polyphenols, and are not particularly limited as long as they are polyphenols other than resorcinol.
  • polyphenols (I) the number of aromatic rings or the number of hydroxyl groups can be selected as appropriate.
  • the polyphenols (I) preferably have two or more hydroxyl groups, more preferably three or more hydroxyl groups, from the viewpoint of achieving better adhesiveness.
  • the polyphenols or polyphenol condensates are water-soluble in the adhesive composition (dip treatment liquid) containing water. This allows the polyphenols to be uniformly distributed within the adhesive composition, thereby achieving better adhesiveness.
  • the polyphenol (I) is a polyphenol containing a plurality of (two or more) aromatic rings, two or three hydroxyl groups are located at the ortho, meta, or para positions, respectively, in those aromatic rings. exists in
  • polyphenols (I) for example, those described as polyphenol compounds in WO2022/130879 can be used. These polyphenols (I) may be used alone or in combination of two or more.
  • aldehydes (II) When the adhesive composition contains aldehydes (II) as a resin component in addition to the polyphenols (I) described above, high adhesiveness can be achieved together with the polyphenols (I) described above.
  • the aldehyde (II) is not particularly limited and can be appropriately selected depending on the required performance.
  • aldehydes (II) also include derivatives of aldehydes whose source is aldehydes.
  • aldehydes (II) examples include monoaldehydes such as formaldehyde, acetaldehyde, butyraldehyde, acrolein, propionaldehyde, chloral, butyraldehyde, caproaldehyde, and allylaldehyde, or glyoxal, malonaldehyde, succinaldehyde, and glutaric acid.
  • Examples include aliphatic dialdehydes such as aldehydes and adipaldehyde, aldehydes having an aromatic ring, and dialdehyde starch. These aldehydes (II) may be used alone or in combination of two or more.
  • the aldehyde (II) is an aldehyde having an aromatic ring or contains an aldehyde having an aromatic ring. This is because better adhesion can be obtained. Moreover, it is preferable that the aldehyde (II) does not contain formaldehyde.
  • formaldehyde-free means, for example, that the content of formaldehyde in the total mass of aldehydes is less than 0.5% by mass.
  • polyphenols (I) and aldehydes (II) are in a condensed state, and the mass ratio of polyphenols to aldehydes having an aromatic ring (content of aldehydes having an aromatic ring/ The content of polyphenols) is preferably 0.1 or more and 3 or less.
  • the hardness and adhesiveness of the resin which is a product of the condensation reaction that occurs between polyphenols and aldehydes having an aromatic ring, become more suitable.
  • the mass ratio of polyphenols to aldehydes having an aromatic ring (content of aldehydes having an aromatic ring/content of polyphenols) in the adhesive composition is 0.25 or more. More preferably, it is 2.5 or less.
  • the said mass ratio is the mass (solid content ratio) of a dry material.
  • the total content of polyphenols (I) and aldehydes (II) in the adhesive composition is preferably 3 to 30% by mass. This is because in this case, better adhesion can be ensured without deteriorating workability or the like. From the same viewpoint, the total content of polyphenols (I) and aldehydes (II) in the adhesive composition is more preferably 5% by mass or more, and preferably 25% by mass or less. More preferred. In addition, the said total content is the mass (solid content ratio) of a dry material.
  • the adhesive composition further contains an isocyanate compound (III) in addition to the above-mentioned polyphenols (I) and aldehydes (II).
  • the adhesive properties of the adhesive composition can be further improved due to the synergistic effect with polyphenols (I) and aldehydes (II).
  • the isocyanate compound (III) promotes adhesion of the adhesive composition to the adherend resin material (for example, a phenol/aldehyde resin obtained by condensing polyphenols (I) and aldehydes (II)). It is a compound that has an isocyanate group as a polar functional group.
  • adherend resin material for example, a phenol/aldehyde resin obtained by condensing polyphenols (I) and aldehydes (II)
  • It is a compound that has an isocyanate group as a polar functional group.
  • These isocyanate compounds (III) may be used alone or in combination of two or more.
  • the isocyanate compound (III) is not particularly limited, but preferably contains a (blocked) isocyanate group-containing aromatic compound from the viewpoint of further improving adhesiveness. Since the adhesive composition contains the (blocked) isocyanate group-containing aromatic compound, the (blocked) isocyanate group-containing aromatic compound is present in the vicinity of the interface between the polyamide fiber cord (organic fiber cord) and the adhesive composition. As a result of the distribution of the group compound, a further adhesion promoting effect is obtained, and this effect can further improve the adhesion of the adhesive composition to the polyamide fiber cord (organic fiber cord).
  • the content of the isocyanate compound (III) in the adhesive composition is not particularly limited, but is preferably from 5 to 65% by mass from the viewpoint of more reliably ensuring excellent adhesiveness. From the same viewpoint, the content of the isocyanate compound (III) in the adhesive composition is more preferably 10% by mass or more, and more preferably 45% by mass or less. In addition, the said content is the mass (solid content ratio) of a dry material.
  • the adhesive composition can substantially further contain rubber latex (IV). Thereby, the adhesive composition can further improve adhesiveness with the rubber member.
  • the rubber latex (IV) is not particularly limited, and in addition to natural rubber (NR), polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), ethylene Examples include synthetic rubbers such as -propylene-diene rubber (EPDM), chloroprene rubber (CR), halogenated butyl rubber, acrylonitriole-butadiene rubber (NBR), and vinylpyridine-styrene-butadiene copolymer rubber (Vp). These rubber latexes (IV) may be used alone or in combination of two or more.
  • NR natural rubber
  • IR polyisoprene rubber
  • SBR styrene-butadiene copolymer rubber
  • BR polybutadiene rubber
  • ethylene Examples include synthetic rubbers such as -propylene-diene rubber (EPDM), chloroprene rubber (CR), halogenated butyl rubber, acrylonit
  • the rubber latex (IV) is mixed with phenols (I) and aldehydes (II) before blending the isocyanate compound (III). It is preferable.
  • the content of rubber latex (IV) in the adhesive composition is preferably 20% by mass or more, more preferably 25% by mass or more, and preferably 70% by mass or less, More preferably, it is 60% by mass or less.
  • the method for producing the adhesive composition is not particularly limited, but includes, for example, a method of mixing and aging raw materials such as polyphenols (I), aldehydes (II), and rubber latex (IV); , a method in which polyphenols (I) and aldehydes (II) are mixed and aged, and then rubber latex (IV) is further added and aged.
  • the method for producing the adhesive composition may be a method of adding rubber latex (IV), aging, and then adding isocyanate compound (III).
  • the rubber-fiber composite of this embodiment is characterized by comprising the polyamide fiber cord of this embodiment described above. Since the rubber-fiber composite of this embodiment includes the polyamide fiber cord of this embodiment described above, it is possible to reduce the environmental load. Note that the fiber portion of the rubber-fiber composite corresponds to the above-mentioned polyamide fiber cord.
  • the rubber-fiber composite includes a polyamide fiber cord and a coating rubber covering the polyamide fiber cord.
  • the coating rubber a rubber composition is used in which a rubber component such as natural rubber or synthetic rubber is blended with a filler such as carbon black, an anti-aging agent, a vulcanizing agent such as sulfur, a vulcanization accelerator, etc. can do.
  • the tire of this embodiment is characterized by comprising the polyamide fiber cord of this embodiment described above. Since the tire of this embodiment includes the above-mentioned polyamide fiber cord, it is possible to reduce environmental load while maintaining tire characteristics.
  • the polyamide fiber cord is preferably applied to the carcass or the belt reinforcing layer (also referred to as a "cap layer"), with the carcass being particularly preferred.
  • FIG. 1 is a cross-sectional view of one embodiment of the tire of the present invention.
  • the tire 100 shown in FIG. 1 includes a pair of bead portions 10, a pair of sidewall portions 20, a tread portion 30, and a carcass 50 extending in a toroidal shape between bead cores 40 embedded in the bead portions 10.
  • a belt 60 consisting of two belt layers 60A and 60B disposed on the tread portion 30 (more specifically, disposed on the outside in the tire radial direction of the crown portion of the carcass 50), and a belt 60 on the outside of the belt 60 in the tire radial direction.
  • the carcass 50 is composed of one carcass ply, and includes a main body portion extending in a toroidal shape between a pair of bead cores 40 respectively embedded in the bead portion 10, and It consists of a folded part that is wound radially outward from the inside to the outside in the tire width direction around the bead core 40, but in the tire of the present invention, the number of plies and structure of the carcass 50 are not limited to this. do not have.
  • the carcass ply constituting the carcass 50 may be formed by covering a plurality of reinforcing cords with coating rubber, which extend in a direction substantially perpendicular to the tire circumferential direction (for example, extend at an angle of 70 to 90 degrees).
  • the carcass 50 is preferably a radial carcass.
  • the above-mentioned polyamide fiber cord is preferable, but when the above-mentioned polyamide fiber cord is applied to other tire members, other organic fiber cords or steel cords may be used.
  • other organic fiber cords include polyethylene terephthalate cords, rayon cords, and the like.
  • a rubber composition is used in which a rubber component such as natural rubber or synthetic rubber is blended with a filler such as carbon black, an anti-aging agent, a vulcanizing agent such as sulfur, a vulcanization accelerator, etc. be able to.
  • the belt layer 60A is formed by coating a reinforcing cord extending at an angle of 50° with a coating rubber, preferably a steel cord coated with a coating rubber.
  • 60B are laminated to intersect with each other across the tire equator plane to form the belt 60.
  • the belt 60 in the figure consists of two belt layers 60A and 60B, in the tire of the present invention, the number of belt layers constituting the belt may be three or more.
  • the belt reinforcing layers 70A and 70B include reinforcing cords arranged substantially parallel to the tire circumferential direction (for example, at an angle of 0 to 5 degrees with respect to the tire circumferential direction) and coated with rubber. It will be covered.
  • the belt reinforcing layers 70A and 70B are formed by continuously spirally winding a narrow strip prepared by covering a reinforcing cord with a coating rubber in the tire circumferential direction. In this case, since there is no joint in the circumferential direction of the tire, the uniformity of the tire is good, and since there is no joint, concentration of strain on the joint can be prevented.
  • the above-mentioned polyamide fiber cord is preferable, but when the above-mentioned polyamide fiber cord is applied to other tire members, other organic fiber cords may be used.
  • other organic fiber cords include polyethylene terephthalate cords, rayon cords, and the like.
  • a rubber composition is used in which a rubber component such as natural rubber or synthetic rubber is blended with a filler such as carbon black, an anti-aging agent, a vulcanizing agent such as sulfur, a vulcanization accelerator, etc. be able to.
  • each of the belt reinforcing layers 70A and 70B is one layer, but may be two or more layers.
  • the conveyor belt of this embodiment is characterized by comprising the polyamide fiber cord of this embodiment described above. Since the conveyor belt of this embodiment includes the polyamide fiber cord of this embodiment described above, the environmental load can be reduced. In one embodiment, the polyamide fiber cord can be used as reinforcement for a conveyor belt.
  • the hose of this embodiment is characterized by comprising the polyamide fiber cord of this embodiment described above. Since the hose of this embodiment includes the polyamide fiber cord of this embodiment described above, the environmental load can be reduced.
  • the hose includes an inner rubber layer (inner pipe rubber) located on the inside in the radial direction, an outer rubber layer located on the outside in the radial direction, and reinforcement located between the inner rubber layer and the outer rubber layer. and the polyamide fiber cord is used as a reinforcing layer.
  • Example 1 A polyamide fiber cord ( A hybrid code) [cord structure: (1100 ⁇ 2,940)/3] was created.
  • the number of first twists of the aramid fibers is 52.0 times/10cm
  • the number of first twists of PA410 fibers is 46.0 times/10cm
  • the number of final twists of these fibers is 52.0 times/10cm. It is.
  • a polyamide fiber cord containing PA410 fibers and aramid fibers and having a bioconversion rate of 15% or more contains PA66 fibers and aramid fibers and has a bioconversion rate of 15% or more. It can be seen that the cutting strength is equivalent to that of a polyamide fiber cord with a polyamide fiber cord of 0%.
  • the polyamide fiber cord and rubber-fiber composite of the present invention can be used not only for tires but also for conveyor belts, hoses, etc.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

Abstract

L'invention a pour objet de fournir un câble de fibres organiques qui tout en préservant ses propriétés physiques à haute température, permet de réduire son impact environnemental. À cet effet, l'invention concerne un câble de fibres polyamide qui est caractéristique en ce que la proportion de teneur en carbone dérivé de la biomasse de son ensemble (rapport de biomasse) est supérieure ou égale à 15%, et en ce que son retrait thermique est inférieur ou égal à 9,0%.
PCT/JP2023/029459 2022-08-25 2023-08-14 Câble de fibres polyamide, composite de caoutchouc et fibres, et pneumatique WO2024043136A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03287402A (ja) * 1990-04-02 1991-12-18 Ohtsu Tire & Rubber Co Ltd :The ラジアルタイヤ
JP2006321323A (ja) * 2005-05-18 2006-11-30 Bridgestone Corp 空気入りタイヤ
JP2013531107A (ja) * 2010-07-07 2013-08-01 コンティネンタル・ライフェン・ドイチュラント・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 補強のための直線テキスタイル構造を含むエラストマー製品
JP2019511411A (ja) * 2016-03-17 2019-04-25 コンティネンタル・ライフェン・ドイチュラント・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 空気入り車両タイヤ用の、好ましくは空気入り車両タイヤのベルトバンデージプライ用の補強プライ
WO2022071172A1 (fr) * 2020-09-29 2022-04-07 日本精工株式会社 Palier à roulement
JP2022109339A (ja) * 2018-12-27 2022-07-28 シージェイ チェイルジェダン コーポレーション オルニチン脱炭酸酵素変異型及びそれを用いたプトレシンの生産方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03287402A (ja) * 1990-04-02 1991-12-18 Ohtsu Tire & Rubber Co Ltd :The ラジアルタイヤ
JP2006321323A (ja) * 2005-05-18 2006-11-30 Bridgestone Corp 空気入りタイヤ
JP2013531107A (ja) * 2010-07-07 2013-08-01 コンティネンタル・ライフェン・ドイチュラント・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 補強のための直線テキスタイル構造を含むエラストマー製品
JP2019511411A (ja) * 2016-03-17 2019-04-25 コンティネンタル・ライフェン・ドイチュラント・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 空気入り車両タイヤ用の、好ましくは空気入り車両タイヤのベルトバンデージプライ用の補強プライ
JP2022109339A (ja) * 2018-12-27 2022-07-28 シージェイ チェイルジェダン コーポレーション オルニチン脱炭酸酵素変異型及びそれを用いたプトレシンの生産方法
WO2022071172A1 (fr) * 2020-09-29 2022-04-07 日本精工株式会社 Palier à roulement

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