JP7100479B2 - Adhesive compositions for organic fibers, organic fiber treatment methods, organic fibers, and tires - Google Patents

Description

The present invention relates to an adhesive composition for organic fibers, a method for treating organic fibers, organic fibers, and a tire.

Various fibers such as polyester fiber and nylon fiber have been widely used as reinforcing materials for tires, and are properly used to meet the required performance and various members. For example, polyester fibers have excellent mechanical properties (eg, high elastic modulus) and excellent dimensional stability. However, on the other hand, it has the disadvantage that the adhesiveness to rubber, which is the material of the tire, is significantly reduced compared to nylon fiber, especially when the tire is embedded in a rubber compound and exposed to high temperature for a long time. ..

In Patent Document 1, the heat-resistant adhesiveness is improved by treating the polyester fiber with a treatment liquid containing a carrier, a blocked isocyanate aqueous solution, an epoxy resin dispersion liquid, and a resorcin formalin latex (RFL) adhesive. It is proposed that.

Further, in Patent Document 2, the polyester fiber is treated with an adhesive treatment agent containing a polyepoxide compound, a blocked polyisocyanate compound, a silicate compound, and an ethylene-based unsaturated acid-modified styrene-butadiene rubber latex. It has been proposed that adhesion deterioration at high temperatures is reduced.

Japanese Unexamined Patent Publication No. 2000-21285 Japanese Unexamined Patent Publication No. 2008-169504

However, none of them can be said to have sufficient heat-resistant adhesiveness as compared with nylon fibers. Under such circumstances, the present invention provides an adhesive composition for organic fibers having excellent heat-resistant adhesiveness, which can maintain a high adhesive strength between the organic fiber and the rubber composition even when exposed to a high temperature. The challenge is to provide.

The first aspect of the present invention relates to an adhesive composition for organic fibers containing (a) an epoxy compound which is a sorbitol polyglycidyl ether and has a chlorine content of 9.6% by mass or less, and (b) a blocked isocyanate. ..

In the adhesive composition for organic fibers, the organic fibers may be at least one selected from the group consisting of polyester fibers, nylon fibers, and aramid fibers.

The second aspect of the present invention relates to a method for treating organic fibers, which comprises the following steps (1) and (2).
(1) The step of treating the organic fiber with the adhesive composition for organic fiber according to claim 1 as the first treatment agent; and (2) the organic fiber treated with the first treatment agent is resorcin, formalin, rubber latex ( Step of treating with a second treatment agent containing RFL)

In the method for treating organic fibers, the organic fibers may be at least one selected from the group consisting of polyester fibers, nylon fibers, and aramid fibers.

The third aspect of the present invention relates to organic fibers treated with the above-mentioned adhesive composition for organic fibers.

A fourth aspect of the present invention relates to a tire having at least one member selected from the group consisting of a jointless band containing organic fibers, a carcass ply, a chafer, and a filler.

According to the present invention, it is possible to obtain an adhesive composition for organic fibers having excellent heat-resistant adhesiveness, in which the organic fibers and the rubber composition can maintain a high adhesive force even when exposed to a high temperature.

It is a figure which shows an example of the embodiment of a tire. It is a figure which shows an example of embodiment of a jointless band.

Hereinafter, an example of a preferred embodiment of the present invention will be specifically described. The adhesive composition for organic fibers of the present invention contains (a) an epoxy compound which is a sorbitol polyglycidyl ether and has a chlorine content of 9.6% by mass or less, and (b) a blocked isocyanate.

(Epoxy compound)
The epoxy compound is a compound having an epoxy group in the molecule. Sorbitol polyglycidyl ether is used as the epoxy compound. As the sorbitol polyglycidyl ether, sorbitol diglycidyl ether, sorbitol triglycidyl ether, sorbitol tetraglycidyl ether, sorbitol pentaglycidyl ether, sorbitol hexaglycidyl ether, or a mixture thereof can be used, and sorbitol monoglycidyl ether is included. May be. Since the sorbitol polyglycidyl ether has a large number of epoxy groups in one molecule and can form a high crosslinked structure, the adhesive composition for organic fibers of the present disclosure is excellent in adhesiveness.

The epoxy compound has a chlorine content of 9.6% by mass or less, preferably 9.5% by mass or less, more preferably 9.4% by mass or less, and further preferably 9.3% by mass or less. The lower limit value is not particularly limited, but may be, for example, 1% by mass or more.

The lower chlorine content in the epoxy compound increases the purity of the epoxy groups in the epoxy compound and enhances the reactivity of the epoxy compound with isocyanates. Therefore, more excellent heat-resistant adhesiveness can be obtained.

Further, by increasing the purity of the epoxy group in the epoxy compound, the viscosity of the adhesive composition for organic fibers is lowered, so that the permeability to the organic fibers is enhanced. Therefore, when the organic fiber is to be adhered to the rubber composition, the contact between the amine compound contained in the rubber composition and the organic fiber, which is one of the causes of the decrease in the adhesive strength at high temperature, can be reduced. Deterioration of organic fibers can be suppressed. As a result, more excellent heat-resistant adhesiveness can be obtained.

The chlorine content in the epoxy compound can be determined by the method described in JIS K 7243-3 or the like.

The chlorine content of the epoxy compound can be reduced by reducing the amount of epichlorohydrin used when synthesizing the epoxy compound.

(Blocked isocyanate)
Blocked isocyanate is a compound that is produced by the reaction of an isocyanate compound and a blocking agent and is temporarily inactivated by a group derived from the blocking agent. When heated at a predetermined temperature, the group derived from the blocking agent dissociates. , Produces an isocyanate group.

As the isocyanate compound, a compound having two or more isocyanate groups in the molecule can be used. Examples of the diisocyanates having two isocyanate groups include hexamethylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, phenylenedi isocyanate, tolylene diisocyanate, trimethylhexamethylene diisocyanate, metaphenylenedi isocyanate, naphthalenedi isocyanate, and diphenyl ether diisocyanate. Diphenylpropane diisocyanate, biphenyldiisocyanate, isomers thereof, alkyl substituents, halides, hydrogenated additives to the benzene ring and the like can be used. Further, triisocyanates having three isocyanate groups, tetraisocyanates having four isocyanate groups, polymethylene polyphenyl polyisocyanate and the like can also be used. These isocyanate compounds can be used alone or in combination of two or more.

Among these, tolylene diisocyanate, metaphenylenedi isocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate are particularly easy to obtain industrially and have good heat-resistant adhesiveness of the obtained adhesive composition for organic fibers after treatment. , Polymethylene polyphenyl polyisocyanate is preferred.

Examples of the blocking agent include lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-propiolactam; phenol-based agents such as phenol, cresol, resorcinol and xylenol; methanol, ethanol, n-propyl alcohol and isopropyl. Alcohols such as alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and benzyl alcohol; Oxime-based substances such as acetoxime, methylethylketoxim, diacetylmonooxime, benzophenone oxime, and cyclohexanone oxime; active methylene-based substances such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, and acetylacetone can be mentioned. Of these, lactam-based, phenol-based, and oxime-based blocking agents are preferable because they rapidly dissociate from the isocyanate compound at a relatively low temperature.

The content of blocked isocyanate in the adhesive composition for organic fibers of the present disclosure is preferably 50 parts by mass or more and 500 parts by mass or less, and more preferably 200 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the epoxy compound. .. Within this range, better heat-resistant adhesiveness between the organic fiber and the rubber composition can be obtained. If it is less than 50 parts by mass, cross-linking may be insufficient, which may cause deterioration of adhesive strength and heat resistance, and if it exceeds 500 parts by mass, the fiber may become too hard or the fatigue resistance may be lowered. Therefore, it is not preferable. The content of the blocked isocyanate can be appropriately adjusted depending on the type of the rubber composition to which the organic fiber is to be adhered.

(Optional ingredient)
The adhesive composition for organic fibers of the present disclosure may contain the following optional components, if necessary, within a range that does not interfere with the object and effect of the present invention. For example, epoxy compounds other than sorbitol polyglycidyl ether, resins copolymerizable with sorbitol polyglycidyl ether, curing agents other than blocked isocyanate, organic thickeners, antioxidants, light stabilizers, adhesive enhancers, reinforcing agents. , Softeners, colorants, leveling agents, flame retardants, antistatic agents and the like.

Examples of epoxy compounds other than sorbitol polyglycidyl ether include ethylene glycol glycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, novolak glycidyl ether, and the like. And glycidyl ethers such as brominated bisphenol A diglycidyl ether; glycidyl esters such as hexahydrophthalic acid glycidyl ester and dimer acid glycidyl ester; triglycidyl isocyanurate, glycidyl hindantin, tetraglycidyl diaminodiphenylmethane, triglycidyl paraaminophenol, Glycidyl amines such as triglycidyl metaaminophenol, diglycidyl aniline, diglycidyl toluidin, tetraglycidyl metaxylene diamine, diglycidyl tribromaniline, and tetraglycidyl bisaminomethylcyclohexane; and 3,4-epoxycyclohexylmethylcarboxylate, epoxy. Examples thereof include alicyclic groups such as polybutadiene and epoxidized soybean oil, or aliphatic epoxisides.

[Organic fiber]
The adhesive composition for organic fibers of the present disclosure can be used for treating various organic fibers. The organic fiber treated with the adhesive composition for organic fiber of the present disclosure can maintain high adhesive strength with the rubber composition even when exposed to high temperature, and is excellent in heat-resistant adhesiveness.

Examples of various organic fibers include tires; various hoses; and fibers usually used as reinforcing materials for belts and the like for transmitting rotation of timing belts, conveyor belts, V-belts and the like. Examples of the fiber type include polyester fibers such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); nylon fibers; rayon fibers; vinylon fibers; aramid fibers; and polyurethane fibers.

Among these organic fibers, polyester fiber and nylon fiber are excellent in resistance to load and impact during use even when used for a material obtained by adhering the organic fiber and the rubber composition, for example, a tire. , And at least one selected from the group consisting of aramid fibers.

The form of these organic fibers is not particularly limited, and examples thereof include filament yarns, cords, woven fabrics, and woven fabrics. The cord may be formed by twisting one or more filament yarns together.

As the cord made of polyester fiber (polyester cord), for example, i) 2 or 3 multifilaments of 1100 decitex are combined (in other words, 1100/2 decitex or 1100/3 decitex), 10 to 60 times. After twisting / 10 cm, the two lower twist cords are combined and the same number of upper twists are applied in the opposite direction to the lower twist (intermediate elongation 4.30% when a constant load of 44 N is applied). , Ii) Two 1670 decitex multifilaments are combined (in other words, 1670/2 decitex), twisted 20 to 50 times / 10 cm, and then the two lower twist cords are combined to oppose the lower twist. The same number of upper twists in the direction (intermediate elongation 4.30% when a constant load of 66 N is applied) can be used. The intermediate elongation can be determined in accordance with the test method of "elongation rate under constant load" of JIS L1017.

As the cord made of nylon fiber (nylon cord), for example, i) two 940 decitex multifilaments are combined (in other words, 940/2 decitex), twisted 31 to 48 times / 10 cm, and then twisted. These two lower twist cords are combined and the same number of upper twists are applied in the opposite direction to the lower twist (intermediate elongation 8.80% when a constant load of 44 N is applied), or ii) 1400 decitex multifilament. Two of each are combined (in other words, 1400/2 decitex), twisted 30 to 51 times / 10 cm, and then the two lower twist cords are combined and the same number of upper twists are applied in the opposite direction to the lower twist. (Intermediate elongation 8.80% when a constant load of 66 N is applied) can be used.

As a cord made of rayon fiber (rayon cord), for example, two 1840 decitex multifilaments are combined (in other words, 1840/2 decitex), twisted 20 to 50 times / 10 cm, and then twisted. A combination of two lower twist cords and the same number of upper twists in the opposite direction to the lower twist (intermediate elongation 4.80% when a constant load of 44 N is applied) can be used.

As the cord made of aramid fiber (aramid cord), for example, two or three aromatic polyamide multifilaments (Kevlar manufactured by DuPont) of 1670 decitex are combined (in other words, 1670/2 decitex or 1670 /). (3 decitex), after twisting 30 to 78 times / 10 cm, the two lower twist cords are combined and the same number of upper twists are applied in the opposite direction to the lower twist (intermediate when a constant load of 44 N is applied). Elongation 0.7-1.5%) can be used.

As the cord composed of polyester fiber and nylon fiber (polyester-nylon hybrid cord), for example, two 1440 decitex polyester multifilaments and 1440 decitex nylon multifilaments are combined (in other words, 1440-P / 1400-N decitex). ), After twisting 30 to 38 times / 10 cm, the two lower twist cords are combined and the same number of upper twists are applied in the opposite direction to the lower twist (intermediate elongation when a constant load of 44 N is applied). 4.40%, intermediate elongation 6.30% when a constant load of 66N is applied) can be used.

As the cord composed of aramid fiber and nylon fiber (aramid-nylon hybrid cord), for example, two 1100 decitex aramid multifilaments and 940 decitex nylon multifilaments are combined (in other words, 1100-K / 940-N decitex). ), After twisting 42 times / 10 cm, the two lower twist cords are combined and the same number of upper twists are applied in the direction opposite to the lower twist (intermediate elongation when a constant load of 44 N is applied). 60%) can be used.

[Processing method]
The method for treating an organic fiber of the present invention includes the following steps (1) and (2).
(1) A step of treating the organic fiber with the adhesive composition for organic fiber as the first treatment agent; and (2) the organic fiber treated with the first treatment agent containing resorcin, formalin, and rubber latex (RFL). (2) The process of treating with a treatment agent.

(1) The step of treating the organic fiber with the adhesive composition for organic fiber as the first treatment agent will be described in detail.

The first treatment agent is the adhesive composition for organic fibers, and treating organic fibers with the adhesive composition for organic fibers means that various components contained in the adhesive composition for organic fibers are attached to the organic fibers. It includes the treatment performed for the purpose and the subsequent heat treatment.

As the adhesion method, for example, any method such as coating using a roller, spraying from a nozzle, or immersing in a bath liquid (adhesive composition for organic fibers) can be used. Adhesion by immersion is preferable from the viewpoint of evenly adhering and removing excess adhesive.

Further, in order to adjust the amount of adhesion to the organic fiber, means such as squeezing with a pressure welding roller, scraping with a scraper, blowing off with air blowing, suction, and beating with a beater may be further adopted. In particular, it is preferable to further perform a drawing step using a pressure welding roller after the immersion.

As a heating method, for example, the organic fiber to which the adhesive composition for organic fibers is attached is dried at 100 ° C. or higher and 250 ° C. or lower for 1 minute or longer and 5 minutes or shorter, and then further dried at 150 ° C. or higher and 250 ° C. or lower for 1 minute or longer. A method of performing heat treatment in 5 minutes or less can be mentioned. The conditions for the heat treatment after the drying treatment are preferably 180 ° C. or higher and 240 ° C. or lower for 1 minute or longer and 2 minutes or shorter. In particular, in the heat treatment after the drying treatment, if the temperature is too low, the adhesive force to the rubber composition may be insufficient, and if it is too high, the organic fibers may be deteriorated, which may cause a decrease in strength. be.

The amount of the adhesive composition for organic fibers attached to the organic fibers is preferably 0.2% by mass or more and 1.8% by mass or less, and more preferably 0.5% by mass or more and 1.5% by mass or less. If it is less than 0.2% by mass, the amount of adhesion may be insufficient and sufficient adhesive strength may not be obtained. If it exceeds 1.8% by mass, the fibers become hard and the bending fatigue strength and the like become low. Because there is. Here, the unit [mass%] of the adhered amount is the mass of the solid content in the composition obtained with the mass of the organic fiber as 100.

The total solid content concentration of the adhesive composition for organic fibers is preferably 0.9% by mass or more and 8.1% by mass or less in order to prevent the obtained fibers from becoming too hard while obtaining sufficient adhesive strength. More preferably, it is 2.3% by mass or more and 6.5% by mass or less.

(2) The step of treating the organic fiber treated with the first treatment agent with the second treatment agent containing resorcin, formalin, and rubber latex (RFL) will be described in detail.

The second treatment agent is a composition containing resorcin, formalin, and rubber latex (RFL).

Resorcin formalin rubber latex (RFL) can be prepared by mixing and aging an initial condensate of resorcin and formalin and rubber latex.

The initial condensate of resorcin and formarin is to react the resorcin monomer and formaldehyde monomer in water in the presence of an acidic catalyst such as hydrochloric acid or sulfuric acid, an alkali metal hydroxide such as sodium hydroxide, or ammonia to condense them. Obtained by

As the initial condensate, the molar ratio of resorcin monomer to formaldehyde monomer is preferably 1: 0.1 to 1: 8, more preferably 1: 0.5 to 1: 5, and even more preferably 1: 1 to 1: 4. ..

As the rubber latex, natural rubber latex, styrene / butadiene copolymer latex, styrene / butadiene / vinylpyridine copolymer latex and the like can be used. In resorcin / formalin / rubber latex (RFL), the ratio of the initial condensate of resorcin and formalin to the rubber latex is preferably 1: 1 to 1:15, more preferably 1: 3 to 1:12 in terms of solid content ratio. preferable.

These can be used alone or as a mixture of two or more. In particular, styrene-butadiene-vinylpyridine copolymer latex is preferable because high adhesive strength can be obtained for natural rubber and SBR (styrene-butadiene rubber).

The initial condensate of resorcin and formalin can contain a resorcin monomer, a formaldehyde monomer, a trace amount of a molecular weight modifier (for example, calcium chloride, etc.), a solvent (for example, MEK: methyl ethyl ketone, etc.) and the like.

Treatment of organic fibers treated with the first treatment agent with a second treatment agent containing resorcin, formalin, and rubber latex (RFL) is to attach the second treatment agent to the organic fibers treated with the first treatment agent. This treatment can be performed by the same means and conditions as when treating organic fibers with the first treatment agent. Even in the case of treatment with the second treatment agent, as an adhesion method, adhesion by immersion is preferable from the viewpoint of uniformly adhering and removing excess adhesive.

Further, in order to adjust the amount of adhesion to the organic fiber, means such as squeezing with a pressure welding roller, scraping with a scraper, blowing off with air blowing, suction, and beating with a beater may be further adopted. In particular, it is preferable to further perform a drawing step using a pressure welding roller after the immersion.

The amount of the second treatment agent attached to the organic fiber is preferably 1.0% by mass or more and 3.0% by mass or less, and more preferably 1.5% by mass or more and 2.5% by mass or less. If it is less than 1.0% by mass, the amount of adhesion is small and the adhesive strength may be insufficient, and if it exceeds 3.0% by mass, the fibers may become hard and the bending fatigue strength may decrease. be. The amount [mass%] of the second treatment agent attached to the organic fiber indicates the mass of the solid content in the second treatment agent obtained with the mass of the organic fiber as 100.

The total solid content concentration of the second treatment agent is preferably 0.9% by mass or more and 29% by mass or less, preferably 14% by mass or more, in order to prevent the obtained fibers from becoming too hard while obtaining sufficient adhesive strength. More preferably, it is 23% by mass or less.

In addition to the initial condensate of resorcin and formalin and rubber latex, a vulcanization adjuster, zinc oxide, an antioxidant, an antifoaming agent and the like may be added to the second treatment agent.

[Use]
The organic fibers treated with the organic fiber adhesive composition of the present disclosure can be used for tires, various hoses, belts for transmitting rotation, and the like. Specifically, for example, it is provided inside a tire, various hoses, or belts for transmitting rotation, and more specifically, for example, a plurality of organic fibers twisted together (one). (It may be a twisted filament yarn) can be used as a reinforcing material for these by arranging them inside them, making them into short fibers and dispersing them inside.

The organic fiber treated with the adhesive composition for organic fibers of the present disclosure can maintain high adhesive strength with the rubber composition even when exposed to high temperature, and has excellent heat-resistant adhesiveness, so that it is exposed to high temperature for a long time. It can be preferably used for tires used in the environment where it is used. In particular, it can be preferably used for at least one member selected from the group consisting of a jointless band of a tire, a carcass ply, a chafer, and a filler.

As will be described later, the jointless band is a member provided on the outer side of the breaker in the radial direction of the tire in order to prevent the breaker (also referred to as a belt) from floating from the carcass due to the centrifugal force caused by the rotation of the tire when the vehicle is running. .. The breaker is a member arranged inside the tread of the tire and outside the radial direction of the carcass.

The carcass ply or carcass is a member arranged inside the tread of a tire and outside in the radial direction of the inner liner. Here, in particular, a carcass composed of one or more carcass plies is referred to as a carcass. The inner liner is a member formed so as to form a tire lumen surface, and this member can reduce the amount of air permeation and maintain the tire internal pressure.

The chafer is a member that is located at the bead portion of the tire and abuts on the rim of the wheel to protect the carcass ply or carcass inside the tire from friction with the rim.

The filler is a member arranged on the bead portion of the tire to increase the rigidity of the bead portion.

An example of the embodiment of the tire using the organic fiber of the present disclosure will be described in detail with reference to the drawings. FIG. 1 shows a pneumatic tire 2. In FIG. 1, the vertical direction is the radial direction of the tire 2, the left-right direction is the rotation axis direction of the tire 2, and the direction perpendicular to the paper surface is the circumferential direction of the tire 2. In FIG. 1, the alternate long and short dash line CL represents the equatorial plane of the tire 2. The shape of the tire 2 is symmetrical with respect to the equatorial plane except for the tread pattern.

The tire 2 includes a tread 4, a pair of sidewalls 6, a pair of chafers 7, a pair of beads 8, an inner liner 9, a carcass 10, a belt 12, a pair of fillers 13, and a jointless band 14. This tire 2 is a tubeless type. The tire 2 is mounted on a passenger car.

The tread 4 has a shape that is convex outward in the radial direction. The tread 4 forms a tread surface 16 that is in contact with the road surface. A groove 18 is carved in the tread 4. The tread pattern is formed by the groove 18. The tread 4 is made of crosslinked rubber having excellent wear resistance and grip.

Each sidewall 6 extends substantially inward in the radial direction from the end of the tread 4. The radial outer edge of the sidewall 6 is joined to the tread 4. The sidewall 6 is made of crosslinked rubber having excellent cut resistance and weather resistance.

Each chafer 7 is located in the vicinity of the bead 8. When the tire 2 is incorporated into the rim (which is part of the wheel and where the tires are combined, not shown), the chafer 7 comes into contact with the rim. This contact protects the vicinity of the bead 8.

The form of the organic fiber used in the chafer 7 is a cord. The chafer 7 is configured by treating the cord with an organic fiber adhesive composition and adhering it to the rubber composition. Preferred organic fibers include polyester fibers such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); nylon fibers; rayon fibers; and aramid fibers.

Each bead 8 is located axially inside the sidewall 6. The bead 8 has a core 20 and an apex 22 extending radially outward from the core 20. The core 20 is ring-shaped and contains a wound non-stretchable wire. A typical material for wire is steel. Apex 22 is tapered outward in the radial direction. Apex 22 is made of high hardness crosslinked rubber.

The inner liner 9 is formed so as to form a tire lumen surface. The inner liner 9 is formed of a crosslinked rubber that suppresses air permeability.

The carcass 10 is composed of two plies, a carcass ply 10a and a carcass ply 10b. The carcass ply 10a and the carcass ply 10b are bridged between the beads 8 on both sides and run along the tread 4 and the sidewall 6. The carcass ply 10a and the carcass ply 10b are folded back from the inside to the outside in the axial direction around the core 20. The carcass ply 10a and the carcass ply 10b are each composed of a large number of cords and topping rubbers arranged in parallel in the circumferential direction. The absolute value of the angle each code makes with respect to the equatorial plane is 75 ° to 90 °. In other words, the carcass ply 10a and the carcass ply 10b have a radial structure. Further, the carcass 10 may be formed of one or three or more carcass plies in addition to the two.

The form of the organic fiber used in the carcass ply 10a and the carcass ply 10b is a cord. The carcass ply 10a and the carcass ply 10b are each composed by treating the cord with an adhesive composition for organic fibers and adhering the cord to the rubber composition. Preferred organic fibers include polyester fibers such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); nylon fibers; rayon fibers; and aramid fibers.

The belt 12 is located inside the tread 4 in the radial direction. The belt 12 is laminated with the carcass 10. The belt 12 reinforces the carcass 10. The belt 12 is composed of an inner layer 24 and an outer layer 26. As is clear from FIG. 1, the width of the inner layer 24 is slightly larger than the width of the outer layer 26 in the axial direction. Although not shown, each of the inner layer 24 and the outer layer 26 consists of a large number of parallel cords and topping rubbers. Each code is tilted with respect to the equatorial plane. The general absolute value of the tilt angle is 10 ° or more and 35 ° or less. The direction of inclination of the cord of the inner layer 24 with respect to the equatorial plane is opposite to the direction of inclination of the cord of the outer layer 26 with respect to the equatorial plane. As the cord, in addition to the steel cord, the organic fiber of the present disclosure may be used.

Each filler 13 is arranged on the bead portion of the tire. Each filler consists of a number of parallel cords and topping rubber.

The form of the organic fiber used in the filler 13 is a cord. The filler 13 is configured by treating the cord with an organic fiber adhesive composition and adhering it to the rubber composition. Preferred organic fibers include polyester fibers such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); nylon fibers; rayon fibers; and aramid fibers.

The jointless band 14 is located on the outer side in the radial direction of the belt 12. In the axial direction, the width of the jointless band 14 is larger than the width of the belt 12. The jointless band 14 reinforces the belt 12.

FIG. 2 shows the ribbon 28 constituting the jointless band 14. The ribbon 28 has two cords 30 and a topping rubber 32. The ribbon 28 is configured by treating the cord 30 with an organic fiber adhesive composition and adhering it to the topping rubber 32. The ribbon 28 is spirally wound in the circumferential direction to form a jointless band 14. The jointless band 14 has a so-called jointless structure. Each cord 30 extends substantially in the circumferential direction. The angle of the cord 30 with respect to the circumferential direction is preferably 5 ° or less, and particularly preferably 2 ° or less. Since the belt 12 is restrained by this code 30, the lifting of the belt 12 is suppressed. The number of cords 30 in the ribbon 28 may be one or three or more.

Each cord 30 is formed by twisting a plurality of organic fibers. The tire including the code 30 is excellent in heat resistance and durability. Preferred organic fibers forming the cord 30 include polyester fibers such as polyethylene naphthalate (PET) and polyethylene naphthalate (PEN); nylon fibers; rayon fibers; and aramid fibers.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The adhesiveness in the examples and comparative examples was evaluated by the following method.
<Initial adhesive strength>
The treated organic fiber is embedded in uncrosslinked rubber containing natural rubber as the main component, press-crosslinked at 150 ° C. for 30 minutes, and then the organic fiber is pulled out from the rubber block at a speed of 100 mm / min, and the force required for pulling out is applied. It was displayed at N / cm and the adhesiveness was evaluated.

The composition of the uncrosslinked rubber containing natural rubber as a main component is as follows.
TSR20 as natural rubber (TSR is an abbreviation for Technically Specitied Rubber): 60 parts by mass SBR 1502: 40 parts by mass as styrene-butadiene rubber "Cist 300" as a reinforcing agent (manufactured by Tokai Carbon Co., Ltd.): 50 parts by mass Mineral oil as a softener : 2 parts by mass "ROBO RD" (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.): 1 part by mass Stealic acid: 3 parts by mass Zinc oxide: 6 parts by mass Powdered sulfur (manufactured by Tsurumi Chemical Industry Co., Ltd.): 4 Parts by mass "Noxeller NS" (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd .: N-tert-butyl-2-benzothiazolyl sulphenamide): 1.0 part by mass

<Heat-resistant adhesive strength>
The treated organic fiber is embedded in uncrosslinked rubber containing natural rubber as the main component, press-crosslinked at 170 ° C for 90 minutes, and then the organic fiber is pulled out from the rubber block at a speed of 100 mm / min to apply the force required for pulling out. It was displayed at N / cm and the adhesiveness was evaluated. The composition of the uncrosslinked rubber containing natural rubber as a main component is the same as the evaluation of the initial adhesive strength.

(Example 1)
As an epoxy compound, add 11.8 g of ETC-N615 (sorbitol polyglycidyl ether, chlorine content: 9.3% by mass, epoxy equivalent: 163, manufactured by Nagase ChemteX Corporation) to 920 g of water with stirring, and block there. As a diisocyanate, 72.1 g of an aqueous dispersion of ε-caprolactam block diphenylmethane diisocyanate (54% concentration) was added to prepare an adhesive composition for organic fibers as a first treatment agent.

As rubber latex, 172 g of Nipponol 2518FS (Nippon Zeon Co., Ltd., vinyl pyridine, styrene, butadiene terpolymer hydroemulsified solution, total solid content concentration 40.5%) and Nippon Zeon LX-112 (Nippon Zeon Co., Ltd., styrene, butadiene) 73 g of copolymer 41% hydroemulsified solution, total solid content concentration 40.5%) was diluted with 76 g of water, and 270 g of resorcin formalin initial condensation dispersion (molar ratio of resorcin and formaldehyde) was used as resorcin formalin in this diluted solution. 1: 1.5, total solid content concentration 6.5%) was added while slowly stirring to prepare an RFL solution. The obtained RFL solution was diluted with 591 g of water to obtain a second treatment agent (total solid content concentration: 10%).

Polyester (polyethylene terephthalate (PET)) cord as organic fiber (cord composition: 1100/2 (decitex), number of twists of cord: 26 (times / 10 cm), wire diameter: 0.54 mm, ends: 49 lines / 5 cm) Was dipped in the first treatment agent, dried at 150 ° C. for 130 seconds, and subsequently heat-treated at 240 ° C. for 130 seconds. Then, after immersing in the second treatment agent, it was dried at 150 ° C. for 130 seconds, and then heat-treated at 240 ° C. for 70 seconds. The initial adhesive strength and heat-resistant adhesive strength of the treated polyester cord (organic fiber) were measured. The results are shown in Table 1. In addition, the end means the number of cords (number of drives) arranged in the arrangement direction when the cords are arranged in parallel within a certain width, and the unit [book / 5 cm] is the fixed number. It is a unit indicating the number of cords when the width is 5 cm.

(Example 2)
Polyester-nylon hybrid cord as organic fiber (cord composition: 1440-P / 1400-N (decitex), number of twists of cord: 34 (times / 10 cm), wire diameter: 0.67 mm, ends: 49/5 cm) The organic fiber was treated in the same manner as in Example 1 except that the above was used. The initial adhesive strength and heat-resistant adhesive strength of the treated polyester-nylon hybrid cord (organic fiber) were measured. The results are shown in Table 1.

(Example 3)
Implemented except that aramid cord (cord composition: 1670/3 (decitex), cord twist number: 40 (times / 10 cm), wire diameter: 0.85 mm, ends: 35 fibers / 5 cm) was used as the organic fiber. Organic fibers were treated in the same manner as in Example 1. The initial adhesive strength and heat-resistant adhesive strength of the treated aramid cord (organic fiber) were measured. The results are shown in Table 1.

(Example 4)
Aramid-nylon hybrid cord as organic fiber (cord composition: 1100-K / 940-N (decitex), number of twists of cord: 42 (times / 10 cm), wire diameter: 0.55 mm, ends: 49/5 cm) The organic fiber was treated in the same manner as in Example 1 except that the above was used. The initial adhesive strength and heat-resistant adhesive strength of the treated aramid-nylon hybrid cord (organic fiber) were measured. The results are shown in Table 1.

(Example 5)
Polyester (polyethylene naphthalate (PEN)) cord as organic fiber (cord composition: 1100/3 (decitex), number of twists of cord: 40 (times / 10 cm), wire diameter: 0.72 mm, ends: 49 lines / 5 cm ) Was used, and the organic fibers were treated in the same manner as in Example 1. The initial adhesive strength and heat-resistant adhesive strength of the treated polyethylene naphthalate (PEN) cord (organic fiber) were measured. The results are shown in Table 1.

(Comparative Examples 1 to 5)
Except for the fact that EX-614B (sorbitol polyglycidyl ether, chlorine content: 10.1% by mass, epoxy equivalent: 173, manufactured by Nagase ChemteX Corporation) was used as the epoxy compound, the same as in Examples 1 to 5, respectively. And treated the organic fiber. The initial adhesive strength and heat-resistant adhesive strength of the treated organic fibers were measured. The results are shown in Table 1.

(Comparative Example 6)
Nylon cord (cord composition: 940/2 (decitex), cord twist number: 48 (times / 10 cm), wire diameter: 0.55 mm, ends: 49 lines / 5 cm) is immersed in the second treatment agent as organic fibers. After that, it was dried at 150 ° C. for 130 seconds and heat-treated at 240 ° C. for 70 seconds. The initial adhesive strength and heat-resistant adhesive strength of the treated nylon cord (organic fiber) were measured. The results are shown in Table 1.

As shown in Comparative Example 1, the polyester cord treated with the conventional adhesive composition for organic fibers has a lower heat-resistant adhesive strength than the nylon cord treated with only the second treatment agent of Comparative Example 6 (comparative). Example 1: 108 N / cm, Comparative Example 6: 116 N / cm).

However, as shown in Example 1, the polyester cord treated with the organic fiber adhesive composition of the present disclosure has higher heat-resistant adhesive strength than the nylon cord treated with only the second treatment agent of Comparative Example 6 ( Example 1: 121 N / cm, Comparative Example 6: 116 N / cm). Further, as is clear from Comparative Examples 2 to 5 and Examples 2 to 5, the heat-resistant adhesive force is similarly large in any of the various organic fibers treated with the adhesive composition for organic fibers of the present disclosure. Improved.

Claims (7)

It contains (a) an epoxy compound which is a sorbitol polyglycidyl ether and has a chlorine content of 9.6% by mass or less, and (b) a blocked isocyanate.
An organic fiber adhesive composition in which the content of the blocked isocyanate is 200 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the epoxy compound. An adhesive composition for an organic fiber for treating the treated organic fiber with a second treatment agent containing a isocyanate, a formalin, and a rubber latex (RFL) . The adhesive composition for organic fibers according to claim 1, wherein the organic fibers are at least one selected from the group consisting of polyester fibers, nylon fibers, and aramid fibers. The adhesive composition for organic fibers according to claim 1 or 2, wherein the total solid content concentration is 0.9% by mass or more and 8.1% by mass or less. A method for treating organic fibers, which comprises the following steps (1) and (2).
(1) The step of treating the organic fiber with the adhesive composition for organic fiber according to claim 1 as the first treatment agent; and (2) the organic fiber treated with the first treatment agent is resorcin, formalin, rubber latex ( A step of treating with a second treatment agent containing RFL). The method for treating an organic fiber according to claim 4, wherein the organic fiber is at least one selected from the group consisting of polyester fiber, nylon fiber, and aramid fiber. An organic fiber treated with the adhesive composition for organic fibers according to claim 1. A tire having at least one member selected from the group consisting of a jointless band containing organic fibers according to claim 6, a carcass ply, a chafer, and a filler.

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