WO2021182539A1 - Composition adhésive, composite caoutchouc/câblé à fibres organiques, et pneumatique - Google Patents

Composition adhésive, composite caoutchouc/câblé à fibres organiques, et pneumatique Download PDF

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Publication number
WO2021182539A1
WO2021182539A1 PCT/JP2021/009649 JP2021009649W WO2021182539A1 WO 2021182539 A1 WO2021182539 A1 WO 2021182539A1 JP 2021009649 W JP2021009649 W JP 2021009649W WO 2021182539 A1 WO2021182539 A1 WO 2021182539A1
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Prior art keywords
rubber
adhesive composition
fiber cord
organic fiber
aldehydes
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PCT/JP2021/009649
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English (en)
Japanese (ja)
Inventor
真悟 尾上
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株式会社ブリヂストン
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Publication of WO2021182539A1 publication Critical patent/WO2021182539A1/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
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J107/00—Adhesives based on natural rubber
    • C09J107/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C09J161/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41—Phenol-aldehyde or phenol-ketone resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof

Definitions

  • the present invention relates to an adhesive composition, a rubber-organic fiber cord composite, and a tire.
  • organic fibers such as polyester fibers have a high initial elastic modulus and excellent thermal dimensional stability, they are in the form of filaments, cords, cables, cord fabrics, canvas, etc., and therefore tires, belts, air springs, hoses, etc. It is often used as a reinforcing material in rubber articles such as. Then, various adhesive compositions have been proposed for adhering these organic fibers and rubber (rubber member).
  • Examples of such an adhesive composition include RFL (resorcin formalin latex) adhesives containing resorcin, formalin, rubber latex and the like, and it is known that adhesiveness can be exhibited by thermally curing the RFL adhesive. (For example, Patent Documents 1 to 3).
  • formalin an aqueous solution of formaldehyde
  • formalin an aqueous solution of formaldehyde
  • a reduction in the amount used has been required in consideration of the working environment.
  • the amount of resorcin used is also required to be reduced from the viewpoint of the environment. Therefore, some adhesive compositions and bonding methods that are environmentally friendly without using resorcin and formalin have been proposed (for example, Patent Document 6).
  • the conventional composition containing no resorcin and formalin requires a long time to cure, so that there is a problem of improving productivity, and further improvement in adhesiveness is required.
  • the composition containing no resorcin and formalin tended to have insufficient adhesive performance between polyethylene terephthalate (PET) fiber and rubber.
  • PET polyethylene terephthalate
  • the polyester fiber material which is a linear polymer having an ester bond in the main chain such as PET, is structurally dense, and the polyester fiber material having few functional groups is water-soluble with latex.
  • the adhesive composition (RFL or the like) obtained by mixing the raw material for cross-linking the sex phenol hardly exhibits adhesiveness.
  • Examples of such a one-bath treatment technique include a method of promoting adhesion by further adding an isocyanate compound to a composition containing rubber latex (for example, Patent Document 7).
  • Patent Document 7 a technique that further considers the environment, such as not using resorcin and formalin, and obtains adhesiveness between rubber and an organic fiber material has not yet been proposed.
  • the present invention provides an adhesive composition which has a small burden on the environment and can firmly bond rubber and organic fibers. Further, the present invention provides a rubber-organic fiber cord composite having a small environmental load and a rubber and an organic fiber cord firmly adhered to each other, and a tire using the composite and having high reinforcing properties. That is the issue.
  • the gist structure of the present invention that solves the above problems is as follows.
  • the adhesive composition of the present invention contains polyphenols and aldehydes, and contains The proportion of raw materials derived from renewable resources in the total solid content is 35% by mass or more.
  • the rubber-organic fiber cord composite of the present invention is a rubber-organic fiber cord composite comprising a rubber member and an organic fiber cord. The surface of at least a part of the organic fiber cord is coated with the above-mentioned adhesive composition.
  • the tire of the present invention is characterized by using the rubber-organic fiber cord composite described above.
  • an adhesive composition that has a small impact on the environment and can firmly bond rubber and organic fibers.
  • a rubber-organic fiber cord composite having a small environmental load and a rubber and an organic fiber cord firmly adhered to each other, and a tire using the composite and having high reinforcing properties are provided. Can be provided.
  • the adhesive composition of one embodiment of the present invention (hereinafter, may be referred to as "adhesive composition of the present embodiment") is characterized by containing at least polyphenols and aldehydes. ..
  • the adhesive composition of the present embodiment may appropriately contain a rubber component, a solvent, other components and the like, if necessary.
  • the rubber and the organic fiber can be firmly adhered to each other.
  • the adhesive composition of the present embodiment is also characterized in that the ratio of the raw material derived from the renewable resource to the total solid content is 35% by mass or more.
  • solid content means a dry solid content.
  • Polyphenols refer to a group of compounds having a structure in which a plurality of hydroxyl groups (phenolic hydroxyl groups) are bonded to an aromatic ring, and are resin components capable of enhancing adhesiveness in the adhesive composition of the present embodiment.
  • the number of aromatic rings and the number of hydroxyl groups in polyphenols are not particularly limited and can be appropriately selected depending on the intended purpose.
  • the polyphenols used in this embodiment may be one kind alone or a combination of two or more kinds.
  • the polyphenols used in the present embodiment are preferably water-soluble from the viewpoint of being dissolved in a solvent such as water to obtain a uniformly dispersed adhesive composition.
  • the polyphenols used in the present embodiment are preferably polyphenols other than resorcin (resorcinol) from the viewpoint of giving sufficient consideration to reducing the environmental load.
  • the adhesive composition of the present embodiment substantially does not contain resorcin (resorcinol).
  • “substantially not contained” means that the ratio in the adhesive composition is less than 0.5% by mass.
  • water-soluble does not necessarily mean only completely water-soluble, but also includes being partially water-soluble or not phase-separated in a solvent containing water. And.
  • the bonding positions of a plurality of hydroxyl groups in the aromatic ring are not particularly limited, and for example, the hydroxyl groups of each other may have a positional relationship of the ortho position, the meta position, or the para position.
  • the above polyphenols may have a plurality of aromatic rings. In this case, it is preferable that a plurality of hydroxyl groups are bonded to all the aromatic rings.
  • the polyphenols preferably have three or more hydroxyl groups. This is because such polyphenols are generally water-soluble, so that they can be uniformly distributed in the adhesive composition and can exhibit better adhesiveness.
  • polyphenols having three or more hydroxyl groups examples include phloroglucinol represented by the following formula (I) and morin represented by the following formula (II) (also known as: 2', 4', 3, 5, 7-Pentahydroxyflavone), phloroglucinol represented by the following formula (III) (also known as 2,4,6,3', 5'-biphenylpentol), and any mixture of two or more of these, etc. Can be mentioned.
  • the adhesive composition of the present embodiment preferably contains at least phloroglucinol as polyphenols from the viewpoint of further improving the adhesiveness.
  • the content of polyphenols in the total solid content is preferably 1.0% by mass or more, preferably 2.5. It is more preferably mass% or more. Further, in the adhesive composition of the present embodiment, from the viewpoint of reliably dissolving aldehydes and ensuring good workability, the content of polyphenols in the total solid content is 10% by mass or less. It is preferably present, and more preferably 9% by mass or less.
  • Aldehydes refer to a group of compounds having an aldehyde group, and are components that can enhance adhesiveness in the adhesive composition of the present embodiment in combination with the above-mentioned polyphenols.
  • the number of aldehyde groups in the aldehydes is not particularly limited and can be appropriately selected depending on the intended purpose. Further, the aldehydes used in the present embodiment may be one kind alone or a combination of two or more kinds.
  • the aldehydes used in this embodiment are preferably aldehydes other than formaldehyde from the viewpoint of sufficiently considering the reduction of environmental load.
  • the adhesive composition of the present embodiment preferably contains substantially no formaldehyde.
  • the aldehydes preferably contain aldehydes having an aromatic ring. This is because aldehydes having an aromatic ring have a smaller environmental load than formaldehyde, and can contribute to improving performance such as adhesiveness, mechanical strength, electrical insulation, acid resistance, water resistance, and heat resistance.
  • the aldehydes having the aromatic ring preferably have two or more aldehyde groups.
  • the degree of cross-linking at the time of cross-linking and condensation is increased, and as a result, the adhesiveness can be further enhanced.
  • the aldehydes having the aromatic ring have two or more aldehyde groups on one aromatic ring.
  • the bonding positions of the two or more aldehyde groups in the aromatic ring are not particularly limited, and for example, the aldehyde groups of each other are in the positional relationship of the ortho-position, the meta-position, or the para-position. You may.
  • the adhesive composition of the present embodiment preferably contains at least 1,4-benzenedicarbaldehyde as aldehydes from the viewpoint of further improving the adhesiveness.
  • aldehydes having an aromatic ring include not only those having a benzene ring but also heteroaromatic compounds.
  • aldehydes that are heteroaromatic compounds include the following general formula (IV): Examples include aldehydes having a furan ring represented by [where X is O; R is -H, -CHO or methylol]. More specifically, the above-mentioned aldehydes having a furan ring include five compounds represented by the following formulas.
  • the above polyphenols and the above aldehydes may be present in a condensed state.
  • the mass ratio of the aldehydes to the polyphenols is preferably 0.1 or more, and 3 The following is preferable. In this case, the hardness and adhesiveness of the product of the condensation reaction of polyphenols and aldehydes become more suitable. From the same viewpoint, the mass ratio of the aldehydes to the polyphenols (aldehyde content / polyphenol content) is more preferably 0.25 or more, and more preferably 2.5 or less. Is more preferable, and 2 or less is further preferable.
  • the total content of polyphenols and aldehydes in the total solid content is preferably 3% by mass or more and 30% by mass or less. In this case, better adhesiveness can be ensured without deteriorating workability. From the same viewpoint, the total content of polyphenols and aldehydes in the total solid content is more preferably 5% by mass or more, and more preferably 25% by mass or less.
  • the adhesive composition of the present embodiment preferably further contains a rubber component in addition to the above-mentioned polyphenols and aldehydes. In this case, the rubber and the organic fiber cord can be adhered more firmly. Further, since the adhesive composition of the present embodiment contains a rubber component, it can take advantage of being relatively flexible and flexible, and can satisfactorily follow the deformation of the organic fiber cord.
  • the rubber component is not particularly limited, and for example, in addition to natural rubber (NR), modified natural rubber (epoxidized natural rubber, hydride natural rubber, etc.), isoprene rubber (IR), styrene-butadiene rubber (SBR). ), Butadiene rubber (BR), ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), butyl halide rubber, acryloni little-butadiene rubber (NBR), vinylpyridine-styrene-butadiene copolymer rubber (Vp) Synthetic rubber such as, etc. can be used. These rubber components may be used alone or in combination of two or more.
  • the rubber component can usually be contained in the adhesive composition by blending a rubber latex.
  • the adhesive composition of the present embodiment contains natural rubber (NR) and the ratio of the natural rubber (NR) to the total solid content is 30% by mass or more.
  • the load on the environment can be further reduced while maintaining good adhesiveness between the rubber and the organic fiber.
  • the ratio of the natural rubber (NR) to the total solid content of the adhesive composition of the present embodiment is more preferably 35% by mass or more, and further preferably 40% by mass or more. preferable.
  • the content of the rubber component in the total solid content is preferably 40% by mass or more, preferably 70% by mass or more. More preferably. Further, in the adhesive composition of the present embodiment, in order to sufficiently secure the coagulation-resistant fracture resistance, the content of the rubber component in the total solid content is preferably 99% by mass or less, preferably 95% by mass. More preferably, it is less than%.
  • the adhesive composition of the present embodiment may further contain a solvent.
  • a basic solvent such as water or a sodium hydroxide solution is preferable from the viewpoint of reliably dissolving the above polyphenols and uniformly dispersing them.
  • a basic solvent such as aqueous ammonia is preferable from the viewpoint of sufficiently dissolving the above aldehydes. From the same viewpoint, it is preferable to use water and sodium hydroxide solution in combination as the solvent, and it is more preferable to use water, sodium hydroxide solution and ammonia water in combination.
  • the adhesive composition of the present embodiment may contain other components other than those described above as long as it does not deviate from the object of the present invention.
  • other components include isocyanate compounds, epoxy compounds, carbodiimide compounds, and oxazoline compounds.
  • the proportion of raw materials derived from renewable resources in the total solid content is 35% by mass or more. In this way, by using a certain percentage or more of the raw materials of the adhesive composition as raw materials derived from renewable resources, it is possible to reduce the burden on the environment and prepare for the future decrease in oil supply. can. From the same viewpoint, in the adhesive composition of the present embodiment, the proportion of the raw material derived from the renewable resource in the total solid content is preferably 40% by mass or more, preferably 50% by mass or more. More preferred.
  • the "raw material derived from renewable resources” refers to a raw material derived from resources other than petroleum. Then, in the adhesive composition of the present embodiment, at least a part of the above-mentioned materials, that is, essential polyphenols and aldehydes, and optional rubber components, solvents and other components are used as renewable resources. It is a raw material from which it is derived, and the solid content as a whole is 35% by mass or more.
  • the adhesive composition of the present embodiment is in the form of a solution at 25 ° C., and the proportion of raw materials derived from renewable resources in the entire solution is preferably 65% by mass or more. In this case, the burden on the environment can be further reduced, and it is possible to prepare for a future decrease in oil supply.
  • the proportion of the raw material derived from the renewable resource in the whole solution is preferably 70% by mass or more, and more preferably 75% by mass or more. preferable.
  • “solution form” also includes colloidal form.
  • phloroglucinol described above as polyphenols can be obtained by biosynthesis by plants, bacteria, or the like.
  • Such phloroglucinol can be used as a raw material derived from renewable resources (see, for example, WO2019 / 002798A1, WO2019 / 00299A1, etc.).
  • aldehydes having a furan ring described above as aldehydes can be obtained from resources other than petroleum such as wood and corn. Aldehydes having such a furan ring can be used as a raw material derived from renewable resources.
  • natural rubber (NR) and modified natural rubber are raw materials derived from renewable resources.
  • styrene-based monomers and butadiene monomers which are the raw materials for styrene-butadiene rubber (SBR)
  • SBR styrene-butadiene rubber
  • water as a solvent and water for diluting various components are not included in the solid content, but are raw materials derived from renewable resources.
  • the sodium hydroxide in the sodium hydroxide solution described above as a solvent can be obtained from a resource other than petroleum, and is immobilized in the dry solid content.
  • Such sodium hydroxide can be used as a raw material derived from renewable resources.
  • ammonia in the ammonia water described above as a solvent can be obtained from a resource other than petroleum, and is immobilized in the dry solid content.
  • ammonia can be used as a raw material derived from renewable resources.
  • the method for producing the adhesive composition of the present embodiment is not particularly limited, but for example, by preparing the raw materials so that the ratio of the raw materials derived from the renewable resources becomes a predetermined value or more and dissolving them in a solvent, the adhesive composition is produced.
  • the adhesive composition of the present embodiment in the form of a solution can be obtained.
  • polyphenols are dissolved in water as a solvent to obtain a solution, then a basic solvent is added to the above solution if necessary, and then aldehydes are added to the above solution. It is preferable to produce by dissolving. As a result, the solubility and dispersibility can be enhanced while avoiding gelation, and the adhesive composition of the present embodiment can be stably and efficiently produced.
  • the temperature of water as the solvent is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of more reliably dissolving polyphenols and aldehydes.
  • Examples of the basic solvent include sodium hydroxide solution, aqueous ammonia and the like.
  • the aldehydes are gradually added to the solution containing the polyphenols and dissolved.
  • the temperature during stirring and aging is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, and suppresses the increase in viscosity due to evaporation of the solvent, from the viewpoint of further enhancing the adhesiveness. Therefore, it is preferably 80 ° C. or lower, and more preferably 60 ° C. or lower.
  • the stirring and aging time is preferably 30 minutes or more, more preferably 1 hour or more, and 6 hours or less from the viewpoint of suppressing a decrease in productivity, from the viewpoint of further enhancing the adhesiveness. It is preferably 4 hours or less.
  • the adhesive composition contains a rubber component
  • the latex can be more reliably solidified, the ease of handling of the adhesive composition can be improved, and the adhesiveness can be improved.
  • aging after adding latex refers to an operation in which a certain period of time elapses for the purpose of improving the characteristics of latex.
  • the aging conditions are not particularly limited, and for example, aging can be carried out at about 25 ° C. for 1 hour to 1 week.
  • the latex can be added as described above, and after aging, the isocyanate compound can be added.
  • the rubber-organic fiber cord composite of one embodiment of the present invention (hereinafter, may be referred to as “composite of the present embodiment”) is a rubber-organic fiber cord composite comprising a rubber member and an organic fiber cord. It is a body, characterized in that at least a part of the surface of the organic fiber cord is coated with the above-mentioned adhesive composition.
  • the composite of the present embodiment has a structure in which the rubber member and the organic fiber cord are bonded by the adhesive composition described above. Since the composite of the present embodiment uses the adhesive composition of the present embodiment described above, the load on the environment is small, and the rubber and the organic fiber cord are firmly adhered to each other.
  • the entire surface of the organic fiber cord is coated with the adhesive composition of the present embodiment.
  • the material of the organic fiber cord is not particularly limited, and for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), aliphatic polyamide such as nylon, aromatic polyamide such as polyketone and aramid, and polyparaphenylene benzobisoxazole. , Rayon, lyocell, etc.
  • the organic fiber cord in the composite of the present embodiment is preferably a polyethylene terephthalate (PET) fiber cord.
  • PET polyethylene terephthalate
  • the organic fiber cord is not particularly limited, and an organic fiber cord made by twisting a plurality of single fiber filaments can be used.
  • the average diameter of the single fiber filament is preferably 2 ⁇ m or more, more preferably 15 ⁇ m or more, and preferably 50 ⁇ m or less from the viewpoint of providing sufficiently high reinforcing property to the rubber article. ..
  • the rubber component constituting the rubber member is not particularly limited, and the rubber member can be produced using the rubber component usually used in the rubber industry.
  • the rubber member contains various compounding agents such as carbon black, silica, a filler such as aluminum hydroxide, a vulcanizing agent such as sulfur, a vulcanization accelerator, an antiaging agent, and a softening agent, which are usually used in the rubber industry. It can be contained as appropriate. Further, the rubber member can be a vulcanized product in the composite of the present embodiment.
  • the method for producing the composite of the present embodiment is not particularly limited, but for example, the surface of the organic fiber cord is coated with the above-mentioned adhesive composition, and then the coated adhesive composition and the unvulcanized rubber member are used.
  • the composite of the present embodiment can be obtained by contacting with and then vulcanizing while arbitrarily pressurizing.
  • the method of coating the surface of the organic fiber cord with the above-mentioned adhesive composition is not particularly limited, and examples thereof include dipping, coating, and spraying.
  • the above-mentioned adhesive composition contains a solvent
  • the solvent may be removed by a drying treatment after coating. Further, after drying, heat treatment may be performed in order to develop adhesiveness more effectively.
  • the surface of the organic fiber cord Before coating the surface of the organic fiber cord with the adhesive composition described above, the surface of the organic fiber cord may be coated with a predetermined pretreatment composition.
  • a pretreatment composition include a composition containing an epoxy compound and an isocyanate compound.
  • the coating amount of the adhesive composition in the organic fiber cord is preferably 0.2 parts by mass or more and 6.0 parts by mass or less with respect to 100 parts by mass of the uncoated organic fiber cord.
  • the use of the complex of this embodiment is not particularly limited.
  • the composite of the present embodiment can be used for rubber articles such as tires, belts, air springs, and hoses.
  • the tire of one embodiment of the present invention (hereinafter, may be referred to as “tire of the present embodiment”) is characterized in that the above-mentioned rubber-organic fiber cord composite is used.
  • the tire of this embodiment includes the rubber-organic fiber cord composite described above. Since the tire of the present embodiment uses the composite of the present embodiment described above, it has a low impact on the environment and has high reinforcing properties.
  • the above-mentioned composite can be used as, for example, a carcass ply, a belt layer, a belt reinforcing layer, a belt peripheral reinforcing layer such as a flipper, and the like.
  • the tire of the present embodiment is not particularly limited except that the above-mentioned composite is used, and can be manufactured according to a conventional method. Further, as the gas to be filled in the tire of the present embodiment, an inert gas such as nitrogen, argon or helium can be used in addition to normal or adjusted oxygen partial pressure.
  • an inert gas such as nitrogen, argon or helium can be used in addition to normal or adjusted oxygen partial pressure.
  • Epoxy compound manufactured by Nagase Chemtech Co., Ltd., "Denacol EX614B" is 1% by mass
  • isocyanate compound manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "Elastron BN77”
  • Isovan manufactured by Clare Co., Ltd.
  • the composition for pretreatment was prepared by diluting with water so as to be 6% by mass.
  • Phloroglucinol manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 10% by mass aqueous solution
  • a polyphenol was dissolved in water at 40 ° C. or higher so as to have a concentration of 10% by mass to obtain a solution.
  • a sodium hydroxide solution manufactured by Kanto Chemical Co., Inc., 4% by mass aqueous solution
  • water, and aqueous ammonia were added in this order.
  • 1,4-benzenedicarbaldehyde manufactured by Tokyo Chemical Industry Co., Ltd., 98% by mass purity
  • aldehydes was gradually added to the above solution.
  • the above addition was carried out while keeping the solution at 40 to 60 ° C. and constantly stirring the solution.
  • stirring was continued, and the mixture was aged at an atmospheric temperature of 25 ⁇ 1 ° C. and for 2 hours.
  • composition of the obtained adhesive composition (composition of solid content and composition of solution) is shown in Table 1.
  • the above-mentioned adhesive composition has a high proportion of raw materials derived from renewable resources in the total solid content of 35% by mass or more, and the raw materials derived from renewable resources in the entire solution. Since the ratio is as high as 65% by mass or more, it can be seen that the burden on the environment is reduced.
  • a polyethylene terephthalate (PET) fiber cord having a cord fineness of 1670 dtex / 2, a lower twist number of 39 times / 10 cm, and an upper twist number of 39 times / 10 cm was first immersed in the above-mentioned pretreatment composition under stirring.
  • a drying treatment at 160 ° C. for 80 seconds was performed, and a heat treatment at 205 ° C. for 60 seconds was further performed. In this way, the entire surface of the PET fiber cord was coated with the pretreatment composition.
  • the PET fiber cord was immersed in the above-mentioned solution-like adhesive composition.
  • a drying treatment of 160 ° C. ⁇ 80 seconds was performed, and further, in order to effectively develop the adhesiveness, a heat treatment of 245 ° C. ⁇ 60 seconds was performed. In this way, the entire surface of the PET fiber cord was further coated with the adhesive composition.
  • a rubber composition (precursor of a rubber member) in an unvulcanized state was prepared by blending natural rubber, styrene-butadiene rubber, carbon black, a vulcanizing agent and the like.
  • the above-mentioned coated PET fiber cord is embedded in this rubber composition, vulcanized at 160 ° C. for 20 minutes under a pressure of 20 kgf / cm 2 , and then cooled to 23 ° C. to obtain a rubber-organic fiber cord composite ( Vulcanized product) was obtained.
  • the adhesiveness when digging up the PET fiber cord from the obtained rubber-organic fiber cord composite (vulcanized product) was evaluated. More specifically, the drag force when the PET fiber cord was peeled from the vulcanized product at a rate of 30 cm / min under an atmospheric temperature of 23 ⁇ 1 ° C. was measured. As a result, the drag force was 21.4 N / cord, and it was confirmed that sufficient adhesiveness was exhibited.
  • an adhesive composition that has a small impact on the environment and can firmly bond rubber and organic fibers.
  • a rubber-organic fiber cord composite having a small environmental load and a rubber and an organic fiber cord firmly adhered to each other, and a tire using the composite and having high reinforcing properties are provided. Can be provided.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Tires In General (AREA)

Abstract

L'invention concerne une composition adhésive qui présente un faible impact environnemental et permet de faire adhérer fermement du caoutchouc et des fibres organiques. La composition adhésive est caractérisée en ce qu'elle contient un polyphénol et un aldéhyde. La composition adhésive est également caractérisée en ce qu'au moins 35 % en masse de la teneur totale en solides de celle-ci sont des matières premières issues de sources renouvelables.
PCT/JP2021/009649 2020-03-11 2021-03-10 Composition adhésive, composite caoutchouc/câblé à fibres organiques, et pneumatique WO2021182539A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06299134A (ja) * 1993-04-20 1994-10-25 Bridgestone Corp ポリエステル繊維用接着剤組成物
JPH10140123A (ja) * 1996-11-08 1998-05-26 Bridgestone Corp タイヤ補強有機繊維用接着剤組成物
JP2014528970A (ja) * 2011-08-04 2014-10-30 コンパニー ゼネラール デ エタブリッスマン ミシュラン ポリアルデヒドとフロログルシノールをベースとする水性接着剤組成物
JP2016528337A (ja) * 2013-07-16 2016-09-15 カンパニー ジェネラレ デ エスタブリシュメンツ ミシュラン バイオ系由来のアルデヒドとポリフェノールの主成分を含む水性接着剤組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06299134A (ja) * 1993-04-20 1994-10-25 Bridgestone Corp ポリエステル繊維用接着剤組成物
JPH10140123A (ja) * 1996-11-08 1998-05-26 Bridgestone Corp タイヤ補強有機繊維用接着剤組成物
JP2014528970A (ja) * 2011-08-04 2014-10-30 コンパニー ゼネラール デ エタブリッスマン ミシュラン ポリアルデヒドとフロログルシノールをベースとする水性接着剤組成物
JP2016528337A (ja) * 2013-07-16 2016-09-15 カンパニー ジェネラレ デ エスタブリシュメンツ ミシュラン バイオ系由来のアルデヒドとポリフェノールの主成分を含む水性接着剤組成物

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