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
• • 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
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • 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
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
• • 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-coated fiber cord, a rubber-fiber cord composite, and a tire.
• Organic fibers such as polyester fibers and nylon fibers have high initial elasticity and excellent thermal dimensional stability, and therefore, in the form of filaments, cords, cables, cord fabrics, canvas, etc., tires, belts, air It is often used as a reinforcing material in rubber articles such as springs and hoses. 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).
• 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.
• an object of the present invention is to provide an adhesive-coated fiber cord that has a small impact on the environment and can be firmly adhered to rubber. Further, the present invention provides a rubber-fiber cord composite in which a rubber and an organic fiber cord are firmly adhered to each other with a small burden on the environment, and a tire having high reinforcing property using the composite. Is the subject.
• the gist structure of the present invention that solves the above problems is as follows.
• the adhesive-coated fiber cord of the present invention is an adhesive-coated fiber cord in which the surface of the organic fiber cord is coated with an adhesive composition.
• the adhesive composition contains polyphenols and aldehydes, and contains The adhesive composition for coating the organic fiber cord has an average coating thickness of 1 ⁇ m or more and 20 ⁇ m or less.
• Another adhesive-coated fiber cord of the present invention is an adhesive-coated fiber cord in which the surface of the organic fiber cord is coated with an adhesive composition.
• the adhesive composition contains polyphenols and aldehydes, and contains The adhesive composition for coating the organic fiber cord has an adhesion rate of 1% or more and 10% or less.
• the rubber-fiber cord composite of the present invention is characterized by comprising a rubber member and the above-mentioned adhesive-coated fiber cord.
• the tire of the present invention is characterized by using the rubber-organic fiber cord composite described above.
• an adhesive-coated fiber cord that has a small impact on the environment and can be firmly adhered to rubber.
• a rubber-fiber cord composite having a small environmental load and a rubber and an organic fiber cord firmly adhered to each other, and a tire having a high reinforcing property using the composite. can do.
• the surface of the organic fiber cord is coated with an adhesive composition.
• the adhesive-coated fiber cord of the present embodiment is characterized in that the adhesive composition contains polyphenols and aldehydes.
• the adhesive-coated fiber cord of the present embodiment has an average coating thickness of 1 ⁇ m or more and 20 ⁇ m or less of the adhesive composition for coating the organic fiber cord, or the adhesive for coating the organic fiber cord.
• the adhesion rate of the composition is 1% or more and 10% or less.
• the adhesive composition contains at least polyphenols and aldehydes, and can appropriately contain a rubber component, a solvent, other components, and the like, if necessary.
• the rubber and the organic fiber cord can be firmly adhered to each other.
• 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 an adhesive composition.
• 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 does not substantially 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 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% by mass or more. Is more preferable. Further, in the above-mentioned adhesive composition, the content of polyphenols in the total solid content is 10% by mass or less from the viewpoint of reliably dissolving aldehydes and ensuring good workability. It is preferably 9% by mass or less, 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 above-mentioned adhesive composition when used 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 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-mentioned polyphenols and the above-mentioned aldehydes may be present in a condensed state.
• the mass ratio of the aldehydes to the polyphenols is preferably 0.1 or more, and is 3 or less. 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.
• solid content means a dry solid content.
• the adhesive composition preferably further contains a rubber component in addition to the above-mentioned polyphenols and aldehydes.
• the rubber and the organic fiber cord can be adhered more firmly.
• the adhesive composition 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), isoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), ethylene-propylene-diene rubber (EPDM), and the like.
• Synthetic rubbers such as chloroprene rubber (CR), butyl halide rubber, acryloni little-butadiene rubber (NBR), and vinylpyridine-styrene-butadiene copolymer rubber (Vp) 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 content of the rubber component in the total solid content is preferably 40% by mass or more, preferably 70% by mass or more. More preferred. Further, in the above-mentioned adhesive composition, in order to sufficiently secure the cohesive fracture resistance, the content of the rubber component in the total solid content is preferably 99% by mass or less, preferably 95% by mass or less. More preferably.
• the adhesive composition 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 when carrying out the step of coating the surface of the organic fiber cord with the adhesive composition, contains a solvent from the viewpoint of workability and the quality of the obtained adhesive-coated fiber cord. Is preferable. Further, after carrying out the above steps, it is preferable to remove the solvent from the coated adhesive composition. In other words, it is preferable that the adhesive composition in the adhesive-coated fiber cord finally contains no solvent.
• the adhesive composition 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, novolak-type phenols / formaldehyde condensates, and the like.
• the method for producing the adhesive composition is not particularly limited, but for example, various raw materials can be prepared and dissolved in a solvent to obtain a solution-like adhesive composition.
• the adhesive composition polyphenols are dissolved in water as a solvent to obtain a solution, then a basic solvent is added to the solution if necessary, and then aldehydes are dissolved in the solution. , It is preferable to manufacture by. As a result, the solubility and dispersibility can be enhanced while avoiding gelation, and the adhesive composition 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 proportion of components other than the solvent is preferably 11 to 25% by mass. In this case, it is possible to more reliably obtain an adhesive-coated fiber cord in which the average coating thickness or adhesion rate and the degree of penetration of the adhesive composition are optimized.
• 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 material of the organic fiber cord used in the present embodiment may be one kind alone or a combination of two or more kinds.
• the organic fiber cord in the composite of the present embodiment is preferably a polyethylene terephthalate (PET) fiber cord.
• PET polyethylene terephthalate
• the form of the organic fiber cord is not particularly limited, and a single fiber filament (monofilament) cord may be used, or an organic fiber cord obtained by twisting a plurality of single fiber filaments can be used.
• the "cord made by twisting a plurality of single fiber filaments" is generally called a multifilament cord.
• a cord formed by twisting several monofilaments having particularly thick fibers may be referred to as a monomultifilament cord.
• a cord formed by twisting 2 to 9 monofilaments of 100 dtex or more is referred to as a monomultifilament.
• the number of filaments to be twisted can be arbitrarily set by the load input added to the reinforcing cord of the rubber reinforcing article.
• the cord fineness (total number of dtexs) indicating the thickness of the organic fiber cord is determined by the single fiber filament fineness (dtex), the number of twisted single fiber filaments, and the twisted structure (twisted structure). ..
• the thickness of the organic fiber cord (total number of dtexes) is preferably 400 to 6000 dtexes. If it is less than 400 dtex, the tensile strength of the cord becomes too low, and when the cord is unwound and processed, it becomes easy to cut (cord breaks) due to a tensile load such as being caught, and the process workability deteriorates. On the other hand, when it exceeds 6000 dtex, the difference in rigidity between the position of the member in which the cord is embedded and the cord during the production of the rubber-fiber cord composite becomes large, and when tension is applied to the composite, the member There is a possibility that a phenomenon such as an increase in the occurrence of surface irregularities may occur.
• the average fiber thickness (fineness) of the single fiber filaments constituting the organic fiber cord varies depending on the total number of dtexes and the number of filaments to be twisted, but in the case of a monofilament cord, 400 to 6000 dtex is preferable, and the multi-monofilament cord In the case of, 70 dtex to 3000 dtex is preferable, and in the case of a multifilament cord, 0.7 dtex to 5 dtex is preferable, and 1 dtex to 3 dtex is more preferable.
• the reason why it is preferable that the fineness of the single fiber filament constituting the multifilament cord is 5 dtex or less is that when the discharge amount of the polymer to be spun is constant and the filament diameter is reduced by the nozzle hole to be spun, the spinning speed becomes faster. This is because the strength per cross-sectional area of the single fiber filament tends to be high due to the influence of the orientation crystallization behavior in the spinning wire, and thus the plurality of malfilament cords tend to be higher in strength.
• the reason why it is preferable that the fineness of the single fiber filament constituting the multifilament cord is 0.7 dtex or more is "3rd Edition Textile Handbook" (Maruzen Co., Ltd., published on December 15, 2004, p. 53).
• Fibers having a thickness of 1 dtex or less are difficult to spin in an industrial sense, and fibers having a thickness smaller than that are usually referred to as ultrafine fibers (the diameter of a fiber of 1 dtex is approximately 10 ⁇ m). There are). Fibers of 0.1 dtex or less are sometimes called ultrafine fibers, and an order of magnitude thinner is sometimes called ultrafine fibers. By the way, the finest practical fiber among natural fibers is silk, and its thickness is about 1 dtex. This is because the spinning process becomes difficult.
• the tire cord is made of synthetic fibers such as polyolefin, polyamide, polyester, polyacrylamide, and vinylon, and a single fiber filament having a diameter of 8 ⁇ m or more is usually used.
• the diameter of the single fiber filament is a value obtained by calculation from the following formula using the fineness and density (specific gravity) of the single fiber filament.
• Single fiber filament Fineness (dtex) (diameter (mm) / 2) 2 x ⁇ x specific gravity x 10000
• the specific gravity of the synthetic fiber used for the tire cord is approximately 1.10 to 1.50, and the diameter of the fiber having a thickness of 1 dtex is approximately 10 ⁇ m.
• the diameter of the single fiber filament is preferably 7 ⁇ m or more, more preferably 10 ⁇ m or more, and the upper limit is not particularly limited, but is 50 ⁇ m or less. It is preferably 30 ⁇ m or less, and more preferably 30 ⁇ m or less. Further, when an organic fiber cord which is a multifilament cord and is made of a synthetic resin such as polyolefin, polyamide, polyester, polyacrylamide, or vinylon is used for the tire cord, the diameter of the single fiber filament is generally about 8 ⁇ m or more. ..
• the diameter of the monofilament filament is not optimized by the effect of improving the fiber orientation by the nozzle hole for spinning, but rather the work of avoiding the yarn breakage of the spun cord. Since it is necessary to ensure the properties, 40 ⁇ m to 130 ⁇ m is preferable, and the fineness of the single fiber filament is 70 dtex to 600 dtex.
• the adhesive-coated fiber cord has a coating thickness (in an adhered state) of the adhesive composition covering the organic fiber cord within a range of 0.1 ⁇ m or more and 50 ⁇ m or less. Is preferable.
• the coating thickness is within 0.1 ⁇ m, the amount of the adhesive composition present on the surface layer of the organic fiber cord is sufficient, and the rubber (rubber member) and the organic fiber cord can be firmly adhered to each other. Further, if the coating thickness is within 50 ⁇ m, deterioration of durability can be suppressed. From the same viewpoint, the coating thickness is preferably within 0.5 ⁇ m or more.
• valleys may be formed on the surface of the cord, so that the coating thickness tends to vary greatly depending on the location of the surface.
• the adhesive-coated fiber cord has an average coating thickness of 1 ⁇ m or more and 20 ⁇ m or less of the adhesive composition that coats the organic fiber cord. If the average coating thickness is less than 1 ⁇ m, the amount of the adhesive composition present on the surface layer of the organic fiber cord is not sufficient, so that the rubber (rubber member) and the organic fiber cord may not be firmly adhered to each other. .. Further, if the average coating thickness exceeds 20 ⁇ m, the durability may deteriorate.
• the average coating thickness of the adhesive composition (average thickness of the coating layer existing on the surface of the organic fiber cord) in the adhesive-coated fiber cord described above can be measured as follows. That is, first, the adhesive-coated fiber cord is immersed in a liquid that can be solidified, the liquid is solidified, and the liquid is embedded (fixed) with the solid material. Then, it is cut with a slicer to reveal a cross section of the embedded adhesive-coated fiber cord, and the cross section is polished if necessary. Next, using an epifluorescence apparatus as a light source, an image of the above cross section is obtained with a microscope. From the obtained image, the thickness of the coating layer existing on the surface of the organic fiber cord can be measured.
• the solidification of the liquid is not particularly limited, and examples thereof include curing using a thermosetting resin such as an epoxy resin, polymerization using a monomer mixed solution, and use of a commercially available embedding agent kit. And can be appropriately selected from these.
• a conical beam capsule known as an instrument for embedding and fixing a sample for an electron microscope can be used, and the liquid can be solidified by a known method.
• the microscope is not particularly limited, and examples thereof include “BX60” manufactured by Olympus Corporation.
• the image analysis software is not particularly limited, and examples thereof include "Image Pro Plus” manufactured by Nippon Roper Co., Ltd.
• the adhesion rate of the adhesive composition calculated from the following formula is 1% or more and 10% or less. If the adhesion rate is less than 1%, the coating amount of the adhesive composition is not sufficient, so that the rubber (rubber member) and the organic fiber cord may not be firmly adhered to each other. Further, if the adhesion rate exceeds 10%, the ratio of the organic fiber cord becomes small, and there is a possibility that the reinforcing property is lowered.
• the preferred range of the adhesion ratio of the adhesive composition varies depending on the filament structure of the organic fiber cord and the penetration of the adhesive composition into the cord.
• the adhesion rate is preferably 1% or more and 2.5% or less.
• the adhesion rate is preferably 2% or more and 10% or less.
• the reason why the preferable range of the adhesion rate differs depending on the filament structure of the organic fiber cord is as follows. That is, when the organic fiber cord is a multifilament cord, the space between the filaments is narrow and the internal structure is a thin tubular. Therefore, when the adhesive composition liquid is attached, not only the surface of the cord but also the inside due to the capillary phenomenon. Also penetrates in large quantities. Therefore, it is necessary to increase the adhesion amount of the adhesive composition as compared with the case of the monofilament cord or the multi-monofilament cord.
• the adhesion rate is more preferably 2.5% or more and 6% or less.
• the organic fiber cord is coated with an adhesive composition having a sufficient thickness, so that weakening of filament binding, filament cutting (fluffing), etc. are effectively suppressed. Adhesiveness can be maintained well.
• the adhesion amount is 6% or less, the restraint between the filaments due to the permeation of the adhesive composition into the organic fiber cord is effectively suppressed, so that the twisting moment remaining in the filament after the plying process causes the cord. The phenomenon of curling can be reduced, and the need for mechanical unraveling of the adhesive composition that constrains the filaments can be reduced.
• the adhesive composition penetrates from the outside of the organic fiber cord to three or four single fiber filaments and these short fiber filaments. Is preferably restrained. When it has penetrated into 3 or 4 single fiber filaments, the coating layer existing on the surface of the organic fiber cord becomes moderately thin, excessive strengthening of filament binding, and eventually filament cutting (fluffing), etc. Is effectively suppressed, and phenomena such as cord curl can be reduced.
• the adhesion rate of the adhesive composition can be measured according to JIS L1017 (2002), 8.15, a) dissolution method.
• a solvent for dissolving materials such as nylon, polyester, rayon, and vinylon used as the organic fiber cord can be appropriately selected and measured.
• the method for producing the adhesive-coated fiber cord of the present embodiment is not particularly limited, but for example, the surface of the organic fiber cord is made to have a predetermined average coating thickness and / or adhesion rate with the above-mentioned adhesive composition. By coating, the adhesive-coated fiber cord of the present embodiment can be obtained.
• the method of coating the surface of the organic fiber cord with the above-mentioned adhesive composition is not particularly limited, and for example, a method of immersing the organic fiber cord in the adhesive composition or an adhesive composition on the surface of the organic fiber cord. Examples include a method of applying, a method of spraying the adhesive composition onto the organic fiber cord, and the like.
• 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 immersion time is not particularly limited, but it is preferably 10 seconds or more.
• the adhesive composition can be quickly impregnated inside the cord by the capillary phenomenon in 10 seconds or more.
• the organic fiber cord is a monofilament or multi-monofilament cord, the surface can be effectively coated with the adhesive composition in 10 seconds or longer.
• the organic fiber cord with a drawing roll after coating the surface of the organic fiber cord with the above-mentioned adhesive composition.
• a drawing roll After coating the surface of the organic fiber cord with the above-mentioned adhesive composition.
• the specific conditions of the drawing roll are not particularly limited, but when the organic fiber cord is a multifilament cord, the drawing roll at the cord position at the time of drawing when the cord diameter of the organic fiber cord is A. It is preferable to narrow the interval so that it is "95% of A to 20% of A". When it is 95% or less of A, the air remaining inside the organic fiber cord is sufficiently removed, and the amount of permeation into the inside due to the capillary phenomenon can be sufficiently increased. Further, when it is 20% or more of A, it is possible to effectively suppress deterioration of cord strength due to cord crushing and occurrence of cord curl due to excessive impregnation inside the cord.
• the organic fiber cord is a monofilament cord or a multi-monofilament cord
• the organic fiber cord there is no impregnation inside the cord, so it is preferable to squeeze the organic fiber cord to such an extent that the excess adhesive composition liquid adhering to the surface of the cord does not drip.
• suction scraping with a vacuum device, spray removal with an air blow, etc. are performed in order to remove the excessive coating of the adhesive composition on the surface. It is preferable to do so. As a result, it is possible to more reliably obtain an adhesive-coated fiber cord in which the coating thickness of the adhesive composition on the surface of the cord is optimized.
• the rubber-fiber cord composite of one embodiment of the present invention (hereinafter, may be referred to as "composite of the present embodiment") includes a rubber member and the above-mentioned adhesive-coated fiber cord. It is a feature.
• 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-coated fiber cord described above, the load on the environment is small, and the rubber and the organic fiber cord are firmly adhered to each other.
• 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 adhesive composition on the surface of the adhesive-coated fiber cord described above is brought into contact with the unvulcanized rubber member, and then optionally pressurized. By vulcanizing while vulcanizing, the composite of the present embodiment can be obtained.
• 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 rubber-fiber cord composite described above is used.
• the tire of this embodiment includes the rubber-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.
• Phloroglucinol manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 10% by mass aqueous solution
• a polyphenol was dissolved in water at 100 ° C. so as to have a concentration of 10% by mass to obtain a solution.
• 18.2 g of a sodium hydroxide solution manufactured by Kanto Chemical Co., Ltd., 4% by mass aqueous solution
• a solvent was added to 33.5 g of the above solution maintained to be stirred at a high temperature, and then with 206 g of water as a solvent.
• composition (composition of solid content) of the obtained adhesive composition is shown in Table 1.
• a polyethylene terephthalate (PET) fiber cord (twisted structure: 1670 dtex / 2) obtained by twisting a polyethylene terephthalate yarn having a cord fineness of 1670 dtex (288 filaments) with a lower twist number of 39 times / 10 cm and an upper twist number of 39 times / 10 cm. 39x36) is prepared and immersed in the above-mentioned solution-like adhesive composition.
• the immersion time is 15 seconds, and the tension of the PET fiber cord at the time of immersion is 0.20 kgf / piece.
• the drawing pressure is set to 0.8 kgf / cm, and the vacuum suction is adjusted so that the mass of the adhesive composition covering the cord is about 4.5% by mass with respect to the mass of the cord.
• a drying treatment of 160 ° C. ⁇ 80 seconds is performed, and further, in order to effectively develop adhesiveness, a heat treatment of 245 ° C. ⁇ 60 seconds is performed. .. In this way, an adhesive-coated fiber cord is obtained in which the entire surface of the PET fiber cord is coated with the adhesive composition.
• the average coating thickness of the adhesive composition measured by the procedure described above is 5.9 ⁇ m.
• the adhesion rate of the adhesive composition according to the above can be measured. , 4.5%.
• a rubber composition in an unvulcanized state is prepared by blending natural rubber, styrene-butadiene rubber, carbon black, a vulcanizing agent and the like.
• the above-mentioned adhesive-coated 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) is obtained.
• the adhesiveness when digging up a PET fiber cord from the obtained rubber-organic fiber cord composite (vulcanized product) is evaluated. More specifically, the drag force when the PET fiber cord is peeled from the vulcanized product at a rate of 30 cm / min under an atmospheric temperature of 25 ⁇ 1 ° C. is measured. As a result, the drag force is 15.6 N / cord, and it can be confirmed that sufficient adhesiveness is exhibited.
• an adhesive-coated fiber cord that has a small impact on the environment and can be firmly adhered to rubber.
• a rubber-fiber cord composite having a small environmental load and a rubber and an organic fiber cord firmly adhered to each other, and a tire having a high reinforcing property using the composite. can do.

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• 2021
  • 2021-03-10 JP JP2022507263A patent/JPWO2021182540A1/ja active Pending
  • 2021-03-10 WO PCT/JP2021/009650 patent/WO2021182540A1/ja not_active Ceased

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