WO2016195112A1

WO2016195112A1 - Tire

Info

Publication number: WO2016195112A1
Application number: PCT/JP2016/066808
Authority: WO
Inventors: 博雅山下; 秀章竹之内; 正洋本間
Original assignee: 株式会社ブリヂストン
Priority date: 2015-06-05
Filing date: 2016-06-06
Publication date: 2016-12-08

Abstract

A tire (10) is formed from a resin material and has a circular tire frame (17). The resin material comprises a polyamide thermoplastic elastomer and carbon black, and the carbon black content is less than 1 mass% relative to the resin material.

Description

tire

The present invention relates to a tire mounted on a rim, and particularly relates to a tire in which at least a part of a tire frame (tire case) is formed of a resin material.

Conventionally, pneumatic tires made of rubber, organic fiber materials, steel members, and the like are used for vehicles such as passenger cars. Conventional rubber materials conventionally used for pneumatic tires have no problem in heat resistance. However, in the tire manufacturing process, a plurality of processes such as kneading, sheeting, molding, and vulcanization are usually performed, and improvement in productivity has been demanded.

On the other hand, in recent years, from the viewpoint of weight reduction, ease of molding, and ease of recycling, the use of resin materials, particularly thermoplastic resins and thermoplastic elastomers, as tire materials has been studied. These thermoplastic polymer materials (thermoplastic resins) have many advantages from the viewpoint of improving productivity, such as being capable of injection molding.

Japanese Patent Application Laid-Open No. 2011-246626 discloses a thermoplastic elastomer containing, as a tire using a resin material, an air permeation prevention layer (inner liner) containing 1 to 15 parts by mass of furnace carbon black with respect to 100 parts by mass of an elastomer component. Tires using the composition have been proposed.

A tire using a thermoplastic polymer material (thermoplastic resin) is easier to manufacture and less expensive than a conventional rubber tire.
However, the surface of the thermoplastic resin may be deteriorated by exposure to light. For example, the surface of the thermoplastic resin may be deteriorated by UV (wavelength 300 nm to 400 nm) irradiation. In order to suppress a decrease in strength (breaking stress, breaking elongation, etc.), a tire using a thermoplastic resin has been required to have excellent light resistance.

In light of the above circumstances, an object of the present invention is to provide a tire that is formed using a resin material and has excellent light resistance.

[1] It is formed of a resin material and has an annular tire skeleton, the resin material includes a polyamide-based thermoplastic elastomer and carbon black, and the content of the carbon black is 1% by mass with respect to the resin material. Tires that are less than.

According to the present invention, a tire formed using a resin material and having excellent light resistance can be provided.

1 is a perspective view showing a partial cross section of a tire according to an embodiment of the present invention. It is sectional drawing of the bead part with which the rim | limb was mounted | worn in the tire which concerns on one Embodiment of this invention. It is sectional drawing along the tire rotating shaft which shows the state by which the reinforcement cord was embed | buried under the crown part of the tire case of the tire of 1st Embodiment. It is explanatory drawing for demonstrating the operation | movement which embeds a reinforcement cord in the crown part of a tire case using a cord heating apparatus and rollers.

The tire of the present invention is formed of a resin material (that is, formed of at least a resin material) and has an annular tire skeleton. The resin material includes a polyamide-based thermoplastic elastomer and carbon black, and the carbon black content is less than 1% by mass with respect to the resin material.

The resin material according to the present invention contains carbon black in an amount of less than 1% by mass with respect to the resin material in addition to the polyamide-based thermoplastic elastomer, thereby obtaining excellent light resistance.
The reason why this effect is achieved is not necessarily clear, but carbon black contained in the resin material functions as a UV absorber, and absorbs UV and converts it into thermal energy. Therefore, it is considered that the molecular chain breakage by UV of the polyamide-based thermoplastic elastomer is suppressed, and the decrease in molecular weight is suppressed. As a result, it is presumed that surface degradation, generation of cracks, and the like can be suppressed.
In addition, by using a polyamide-based thermoplastic elastomer (TPA) as a thermoplastic resin, carbon black can absorb UV and absorb energy efficiently, so that, for example, polyurethane (TPU) or polyolefin can be used as a thermoplastic resin. Compared to the case of containing only (TPO), it is considered that thermal deterioration due to heat from carbon black is also suppressed.
From the above points, according to the present invention, excellent light resistance can be obtained.

-Carbon black content-
Moreover, in the resin material in the present invention, the carbon black content is less than 1% by mass, and if it exceeds this range, minute cracks may occur, resulting in poor tire durability. The reason why this effect is achieved is not necessarily clear, but if a large amount of carbon rack is included in the resin material, a minute crack may be caused by this carbon black as a nucleus when a strong impact is applied. It is considered that the durability of the tire is inferior with the occurrence of this crack. On the other hand, in the present invention, it is considered that the carbon black content is less than 1% by mass, whereby the number of the nuclei described above is suppressed, generation of minute cracks is suppressed, and excellent durability is obtained.

The upper limit of the content of carbon black in the resin material is less than 1% by mass, preferably 0.5% by mass or less, and more preferably 0.2% by mass or less.
On the other hand, the lower limit is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and particularly preferably 0.05% by mass or more. When the lower limit value of the carbon black content is within the above range, more excellent light resistance can be obtained.
The range of the carbon black content in the resin material is preferably 0.01% by mass or more and less than 1% by mass, more preferably 0.05% by mass or more and 0.5% by mass or less, and more preferably 0.05% by mass or more and 0.0. 2 mass% or less is more preferable.

<Resin material>
The tire according to the present invention has a tire skeleton using a resin material. The resin material includes at least a polyamide-based thermoplastic elastomer and carbon black at the above-described content.
The resin material may contain a thermoplastic elastomer other than the polyamide-based thermoplastic elastomer or an arbitrary component. However, the content of the polyamide-based thermoplastic elastomer with respect to the total amount of the resin material is preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 70% by mass or more.
In the present specification, “resin” is a concept including a thermoplastic resin and a thermosetting resin, but does not include natural rubber.

(Polyamide thermoplastic elastomer)
In the present invention, “polyamide thermoplastic elastomer” means a part or all of a soft segment having a low crystalline and low glass transition temperature and a polymer constituting part or all of a crystalline hard segment having a high melting point. It is a thermoplastic resin material of a copolymer having a polymer that has an amide bond (—CONH—) in the main chain of the polymer constituting a part or all of the hard segment.
The polyamide-based thermoplastic elastomer may be simply referred to as “TPA” (Thermoplastic Amid elastomer).

As the polyamide-based thermoplastic elastomer, at least part of the polyamide is crystalline and has a high melting point, and other polymers (for example, polyester or polyether) are amorphous and have a glass transition temperature. Materials that constitute part or all of the low soft segment. Further, the polyamide-based thermoplastic elastomer may use a chain extender such as dicarboxylic acid as a bonding part between the hard segment and the soft segment.

-Hard segment-
Examples of the polyamide forming part or all of the hard segment include polyamides synthesized using monomers represented by the following general formula (1) or general formula (2).

In the general formula (1), R ¹ represents a hydrocarbon molecular chain having 2 to 20 carbon atoms (for example, an alkylene group having 2 to 20 carbon atoms).

In the general formula (2), R ² represents a molecular chain of a hydrocarbon having 3 to 20 carbon atoms (for example, an alkylene group having 3 to 20 carbon atoms).

In general formula (1), R ¹ is preferably a hydrocarbon molecular chain having 3 to 18 carbon atoms (for example, an alkylene group having 3 to 18 carbon atoms), and a hydrocarbon molecular chain having 4 to 15 carbon atoms (for example, (Alkylene group having 4 to 15 carbon atoms) is more preferable, and a molecular chain of a hydrocarbon having 10 to 15 carbon atoms (for example, an alkylene group having 10 to 15 carbon atoms) is particularly preferable. In the general formula (2), R ² is preferably a hydrocarbon molecular chain having 3 to 18 carbon atoms (eg, an alkylene group having 3 to 18 carbon atoms), and a hydrocarbon molecular chain having 4 to 15 carbon atoms. (For example, an alkylene group having 4 to 15 carbon atoms) is more preferable, and a molecular chain of a hydrocarbon having 10 to 15 carbon atoms (for example, an alkylene group having 10 to 15 carbon atoms) is particularly preferable.
Examples of the monomer represented by the general formula (1) or the general formula (2) include ω-aminocarboxylic acid and lactam. Examples of the polyamide that forms part or all of the hard segment include polycondensates of these ω-aminocarboxylic acids and lactams, and co-condensation polymers of diamines and dicarboxylic acids.

Examples of the ω-aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, or 12-aminododecanoic acid. 20 aliphatic ω-aminocarboxylic acids and the like. Examples of the lactam include lauryl lactam, ε-caprolactam, undecane lactam, ω-enantolactam, and aliphatic lactam having 5 to 20 carbon atoms such as 2-pyrrolidone.
Examples of the diamine include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2, Examples thereof include diamine compounds such as aliphatic diamines having 2 to 20 carbon atoms such as 4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 3-methylpentamethylenediamine, or metaxylenediamine. The dicarboxylic acid can be represented by HOOC- (R ³ ) _m —COOH (R ³ : a hydrocarbon molecular chain having 3 to 20 carbon atoms, m: 0 or 1). For example, oxalic acid, succinic acid And aliphatic dicarboxylic acids having 2 to 22 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, or dodecanedioic acid.

Polyamides that form part or all of the hard segments include polyamides obtained by ring-opening polycondensation of ε-caprolactam (polyamide 6), polyamides obtained by ring-opening polycondensation of undecane lactam (polyamide 11), and lauryl lactam Condensed polyamide (polyamide 12), polyamide polycondensed with 12-aminododecanoic acid (polyamide 12), polycondensed polyamide of diamine and dibasic acid (polyamide 66) or polyamide having meta-xylenediamine as a structural unit (amide MX) And the like.

The polyamide 6 can be represented by, for example, {CO— (CH ₂ ) ₅ —NH} _n (n represents an arbitrary number of repeating units). For example, n is preferably 2 to 100, and 3 to 50 Is more preferable.
The polyamide 11 can be represented by, for example, {CO— (CH ₂ ) ₁₀ —NH} _n (n represents an arbitrary number of repeating units). For example, n is preferably 2 to 100, and 3 to 50 Is more preferable.
The polyamide 12 can be represented by, for example, {CO— (CH ₂ ) ₁₁ —NH} _n (n represents an arbitrary number of repeating units). For example, n is preferably 2 to 100, and 3 to 50 Is more preferable.
The polyamide 66 can be represented by, for example, {CO (CH ₂ ) ₄ CONH (CH ₂ ) ₆ NH} _n (n represents an arbitrary number of repeating units). For example, n is preferably 2 to 100 3 to 50 are more preferable.

The amide MX having meta-xylenediamine as a structural unit can be represented, for example, by the following structural unit (A-1) [in (A-1), n represents an arbitrary number of repeating units], for example, n is preferably 2 to 100, and more preferably 3 to 50.

The polyamide-based thermoplastic elastomer has, as a hard segment, polyamide (polyamide 6) having a unit structure represented by — [CO— (CH ₂ ) ₅ —NH] —, or — [CO— (CH ₂ ) ₁₁ —. It preferably has a polyamide (polyamide 12) having a unit structure represented by NH] —, and has a polyamide (polyamide 12) having a unit structure represented by — [CO— (CH ₂ ) ₁₁ —NH] —. It is more preferable.
As described above, the polyamide 12 can be obtained by ring-opening polycondensation of lauryl lactam or polycondensation of 12-aminododecanoic acid.

-Soft segment-
Examples of the polymer that forms part or all of the soft segment include polyester and polyether. Examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (PTMG), and ABA type triblock polyether. These can be used alone or in combination of two or more. Moreover, polyether diamine etc. which are obtained by making ammonia etc. react with the terminal of polyether can be used, for example, ABA type | mold triblock polyether diamine can be used.

Here, examples of the “ABA type triblock polyether” include polyethers represented by the following general formula (3).

In general formula (3), x and z each independently represents an integer of 1 to 20. y represents an integer of 4 to 50.

In the general formula (3), each of x and z is preferably an integer of 1 to 18, more preferably an integer of 1 to 16, particularly preferably an integer of 1 to 14, and most preferably an integer of 1 to 12. . In the general formula (3), y is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, particularly preferably an integer of 7 to 35, and most preferably an integer of 8 to 30.

In addition, examples of the “ABA type triblock polyether diamine” include polyether diamines represented by the following general formula (N).

In general formula (N), X _N and Z _N each independently represents an integer of 1 to 20. Y _N represents an integer of 4 to 50.

In the general formula (N), X _N and Z _N are each preferably an integer of 1 to 18, more preferably an integer of 1 to 16, particularly preferably an integer of 1 to 14, and an integer of 1 to 12 Most preferred. In the general formula (N), Y _N is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, particularly preferably an integer of 7 to 35, and most preferably an integer of 8 to 30.

Examples of the combination of the hard segment and the soft segment include the combinations of the hard segment and the soft segment mentioned above. Among these, the following combinations are preferable.
-Lauryl lactam ring-opening polycondensate / polyethylene glycol combination-Lauryl lactam ring-opening polycondensate / polypropylene glycol combination-Lauryl lactam ring-opening polycondensate / polytetramethylene ether glycol combination-Lauryl lactam opening Ring polycondensate / ABA type triblock polyether combination, Lauryl lactam ring-opening polycondensate / ABA type triblock polyether diamine combination, aminododecanoic acid polycondensate / polyethylene glycol combination, aminododecanoic acid combination Polycondensate / polypropylene glycol combination ・ Aminododecanoic acid polycondensate / polytetramethylene ether glycol combination ・ Aminododecanoic acid polycondensate / ABA type triblock polyether combination ・ Aminododecanoic acid polycondensate / ABA Combination of triblock polyether diamine, ring-opening polycondensate of ε-caprolactam / polyethylene glycol, ring-opening polycondensate of ε-caprolactam / polypropylene glycol, ring-opening polycondensate of ε-caprolactam / polytetra Combination of methylene ether glycol, ring-opening polycondensate of ε-caprolactam / ABA type triblock polyether, combination of ε-caprolactam ring-opening polycondensate / ABA type triblock polyether diamine, and the following combinations Is particularly preferred.
・ Combination of lauryl lactam ring-opening polycondensate / ABA type triblock polyether ・ Combination of lauryl lactam ring-opening polycondensate / ABA type triblock polyether diamine ・ Aminododecanoic acid polycondensate / ABA type triblock Combination of polyether / Aminododecanoic acid polycondensate / ABA type triblock polyether diamine combination

The polymer that forms part or all of the soft segment contains a branched saturated diamine having 6 to 22 carbon atoms, a branched alicyclic diamine having 6 to 16 carbon atoms, or a diamine such as norbornane diamine as a monomer unit. May be. These branched saturated diamines having 6 to 22 carbon atoms, branched alicyclic diamines having 6 to 16 carbon atoms, or norbornane diamines may be used alone or in combination. . However, you may use in combination with the above-mentioned ABA type | mold triblock polyether and the said ABA type | mold triblock polyether diamine.

Examples of the branched saturated diamine having 6 to 22 carbon atoms include 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, and 1,2- Examples include diaminopropane, 1,3-diaminopentane, 2-methyl-1,5-diaminopentane, and 2-methyl-1,8-diaminooctane.

Examples of the branched alicyclic diamine having 6 to 16 carbon atoms include 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine and 5-amino-1,3,3-trimethylcyclohexanemethyl. An amine etc. can be mentioned. These diamines may be either cis isomers or trans isomers, or may be a mixture of these isomers.

Examples of the norbornane diamine include 2,5-norbonane dimethylamine, 2,6-norbonane dimethylamine, and mixtures thereof.

Furthermore, the polymer constituting part or all of the soft segment may contain a diamine compound other than those described above as a monomer unit. Examples of other diamine compounds include ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2, Aliphatic diamines such as 2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, or 3-methylpentanemethylenediamine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane and other alicyclic diamines, metaxylylenediamine, or paraxylylenediamine And aromatic diamines such as.
The above diamines may be used alone or in combination of two or more.

-Chain extender-
The polyamide-based thermoplastic elastomer may use a chain extender such as dicarboxylic acid in addition to the hard segment and the soft segment. As the dicarboxylic acid, for example, at least one selected from aliphatic, alicyclic and aromatic dicarboxylic acids or derivatives thereof can be used.

Specific examples of the dicarboxylic acid include adipic acid, decanedicarboxylic acid, oxalic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Chain aliphatic dicarboxylic acids; dimerized aliphatic dicarboxylic acids having 14 to 48 carbon atoms obtained by dimerization of unsaturated fatty acids obtained by fractionation of triglycerides, and aliphatic dicarboxylic acids such as hydrogenated products thereof, 1,4-cyclohexane Mention may be made of alicyclic dicarboxylic acids such as dicarboxylic acids and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid.

-Molecular weight-
In the present invention, the weight average molecular weight of the polyamide-based thermoplastic elastomer contained in the resin material is not particularly limited, but is preferably 10,000 to 400,000. From the viewpoint of improving the rim assembly property and the pressure resistance against the internal pressure of the tire, the weight average molecular weight of the polyamide-based thermoplastic elastomer is preferably 15,700 to 300,000, and more preferably 22,000 to 200,000. .
Moreover, in this invention, since carbon black is contained in the range of the said content rate in the resin material, even if it is a case where it exposes to light, the fall of the molecular weight of a polyamide-type thermoplastic elastomer is suppressed.

The weight average molecular weight of the polyamide-based thermoplastic elastomer can be measured by gel permeation chromatography (GPC). For example, GPC (gel permeation chromatography) such as “HLC-8320GPC EcoSEC” manufactured by Tosoh Corporation may be used.

Also, the number average molecular weight of the polymer (polyamide) constituting part or all of the hard segment is preferably 300 to 15000 from the viewpoint of melt moldability. The number average molecular weight of the polymer constituting part or all of the soft segment is preferably 200 to 6000 from the viewpoint of toughness and low temperature flexibility.

-Ratio of hard segment to soft segment-
In the polyamide-based thermoplastic elastomer, the mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 50:50 to 90:10, and preferably 50:50 to 80:20 is more preferable.
The content of the hard segment in the polyamide thermoplastic elastomer is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and particularly preferably 15 to 90% by mass with respect to the total amount of the polyamide thermoplastic elastomer. .
The content of the soft segment in the polyamide thermoplastic elastomer is preferably 10 to 95% by mass, more preferably 10 to 90% by mass, based on the total amount of the polyamide thermoplastic elastomer.
When the chain extender is used, its content is preferably set so that the hydroxyl group or amino group of the monomer that is the raw material of the soft segment and the carboxyl group of the chain extender are approximately equimolar. .

-Synthesis of polyamide thermoplastic elastomer-
The polyamide-based thermoplastic elastomer can be synthesized by copolymerizing a polymer forming part or all of the hard segment and a polymer forming part or all of the soft segment by a known method. For example, the polyamide-based thermoplastic elastomer is composed of a monomer (eg, ω-aminocarboxylic acid such as 12-aminododecanoic acid, lactam such as lauryl lactam, or ε-caprolactam) that is a raw material of the hard segment, It is obtained by polymerizing a monomer as a raw material (for example, the ABA type triblock polyether or the ABA type triblock polyether diamine) and a chain extender (for example, adipic acid or decanedicarboxylic acid) in a container. be able to. In particular, when ω-aminocarboxylic acid is used as a monomer that is a raw material for the hard segment, it can be synthesized by performing atmospheric pressure melt polymerization or atmospheric pressure melt polymerization, followed by reduced pressure melt polymerization. When lactam is used as a monomer as a raw material for the hard segment, an appropriate amount of water can coexist, and melt polymerization under a pressure of 0.1 to 5 MPa, followed by normal pressure melt polymerization and / or reduced pressure melt polymerization. It can manufacture by the method which has this. These synthesis reactions can be carried out either batchwise or continuously. In the above synthesis reaction, a batch type reaction vessel, a single tank type or multi-tank type continuous reaction apparatus, a tubular continuous reaction apparatus or the like may be used alone or in appropriate combination.

In the production of the polyamide-based thermoplastic elastomer, the polymerization temperature is preferably 150 to 300 ° C, more preferably 160 to 280 ° C. The polymerization time can be appropriately determined depending on the relationship between the polymerization average molecular weight of the polyamide-based thermoplastic elastomer to be synthesized and the polymerization temperature. For example, it is preferably 0.5 to 30 hours, and more preferably 0.5 to 20 hours.

In the production of the polyamide-based thermoplastic elastomer, monoamines such as laurylamine, stearylamine, hexamethylenediamine, and metaxylylenediamine or the like for the purpose of adjusting the molecular weight and stabilizing the melt viscosity at the time of molding as necessary. Additives such as monocarboxylic acids such as diamine, acetic acid, benzoic acid, stearic acid, adipic acid, sebacic acid, and dodecanedioic acid, or dicarboxylic acids may be added. These additives can be appropriately selected in relation to the molecular weight and viscosity of the resulting polyamide-based thermoplastic elastomer within a range that does not adversely affect the effects of the present invention.

In the production of the polyamide-based thermoplastic elastomer, a catalyst can be used as necessary. The catalyst includes at least one selected from the group consisting of P, Ti, Ge, Zn, Fe, Sn, Mn, Co, Zr, V, Ir, La, Ce, Li, Ca, and Hf. Compounds.
Examples thereof include inorganic phosphorus compounds, organic titanium compounds, organic zirconium compounds, and organic tin compounds.
Specifically, examples of the inorganic phosphorus compound include phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphorous acid, and hypophosphorous acid, phosphorus-containing acids, phosphorus-containing acid alkali metal salts, or phosphorus-containing acid alkalis. Examples include earth metal salts.
Examples of the organic titanium compound include titanium alkoxide [titanium tetrabutoxide, titanium tetraisopropoxide, and the like].
Examples of the organic zirconium compound include zirconium alkoxide (zirconium tetrabutoxide (also referred to as “Zr (OBu) ₄ ” or “Zr (OC ₄ H ₈ ) ₄ )”).
Examples of organotin compounds include distannoxane compounds [1-hydroxy-3-isothiocyanate-1,1,3,3-tetrabutyldistanoxane, etc.], tin acetate, dibutyltin dilaurate, or butyltin hydroxide oxide hydrate, etc. Is mentioned.
The catalyst addition amount and the catalyst addition timing are not particularly limited as long as the target product can be obtained quickly.

As the polyamide-based thermoplastic elastomer, for example, the following combinations are preferable.
-Ring-opening polycondensate of lauryl lactam / polyethylene glycol / adipic acid combination- Ring-opening polycondensate of lauryl lactam / polypropylene glycol / adipic acid combination- Ring-opening polycondensate of lauryl lactam / polytetramethylene ether glycol / Combination of adipic acid, ring-opening polycondensate of lauryl lactam / ABA type triblock polyether / adipic acid combination, ring opening polycondensate of lauryl lactam / ABA type triblock polyetherdiamine / adipic acid combination, lauryl lactam Ring-opening polycondensate / polyethylene glycol / decane dicarboxylic acid combination, lauryl lactam ring-opening polycondensate / polypropylene glycol / decane dicarboxylic acid combination, lauryl lactam ring-opening polycondensate / polytetramethylene ether glycol / Combination of candicarboxylic acid ・ Ringyl lactam ring-opening polycondensate / ABA type triblock polyether / decane dicarboxylic acid combination ・ Lauryl lactam ring opening polycondensate / ABA type triblock polyetherdiamine / decane dicarboxylic acid combination・ Aminododecanoic acid polycondensate / polyethylene glycol / adipic acid combination ・ Aminododecanoic acid polycondensate / polypropylene glycol / adipic acid combination ・ Aminododecanoic acid polycondensate / polytetramethylene ether glycol / adipic acid Combinations ・ Aminododecanoic acid polycondensate / ABA type triblock polyether / adipic acid combination ・ Aminododecanoic acid polycondensate / ABA type triblock polyetherdiamine / adipic acid combination ・ Aminododecanoic acid polycondensate / Polyet A combination of lenglycol / decanedicarboxylic acid, a polycondensate of aminododecanoic acid, a combination of polypropylene glycol / decanedicarboxylic acid, a polycondensate of aminododecanoic acid, a combination of polytetramethylene ether glycol / decanedicarboxylic acid, and a combination of aminododecanoic acid Polycondensate / ABA type triblock polyether / decane dicarboxylic acid combination / Aminododecanoic acid polycondensate / ABA type triblock polyether diamine / decane dicarboxylic acid combination / ε-caprolactam ring-opening polycondensate / polyethylene Glycol / adipic acid combination • ε-caprolactam ring-opening polycondensate / polypropylene glycol / adipic acid combination • ε-caprolactam ring-opening polycondensate / polytetramethylene ether glycol / adipic acid combination • ε-capro Ring-opening polycondensate of cumam / ABA type triblock polyether / adipic acid combination. Ring-opening polycondensate of ε-caprolactam / ABA type triblock polyetherdiamine / adipic acid combination. Ring-opening weight of ε-caprolactam. Combination of condensate / polyethylene glycol / decane dicarboxylic acid. Ring-opening polycondensate of ε-caprolactam / polypropylene glycol / decane dicarboxylic acid combination. Ring-opening polycondensate of ε-caprolactam / polytetramethylene ether glycol / decane dicarboxylic acid. Ε-caprolactam ring-opening polycondensate / ABA triblock polyether / decane dicarboxylic acid combination ε-caprolactam ring-opening polycondensate / ABA triblock polyether diamine / decane dicarboxylic acid combination Is a combination of Particularly preferred.
-Ring opening polycondensate of lauryl lactam / ABA type triblock polyether / adipic acid combination- Aminododecanoic acid polycondensate / ABA type triblock polyether / adipic acid combination- Aminododecanoic acid polycondensate / Combination of ABA type triblock polyether diamine / decane dicarboxylic acid ・ Aminododecanoic acid polycondensate / polytetramethylene ether glycol / adipic acid combination ・ Aminododecanoic acid polycondensate / polytetramethylene ether glycol / decane dicarboxylic acid As the polyamide-based thermoplastic elastomer, a combination of the preferred embodiments described above with respect to the combination of structural units, the structural ratio, the molecular weight, and the like can be used.

Various additives such as rubber, various fillers (for example, silica, calcium carbonate, clay), anti-aging agents, oils, plasticizers, colorants, weathering agents, and reinforcing materials are added to the resin material as desired. May be included. The content of the additive in the resin material (tire frame) is not particularly limited, and can be appropriately used as long as the effects of the present invention are not impaired. When a component other than a resin such as an additive is added to the resin material, the content of the resin component in the resin material is preferably 50% by mass or more, and more preferably 90% by mass or more based on the total amount of the resin material. The content of the resin component in the resin material is the balance obtained by subtracting the total content of various additives from the total amount of the resin component.

(Carbon black)
As carbon black contained in the resin material in the present invention, conventionally known carbon black can be used.

Examples of carbon black include furnace black, channel black, acetylene black, and thermal black. Carbon black may be used individually by 1 type, may use 2 or more types together, and may use a commercial item.

· The BET specific surface area of the carbon black BET specific surface area of _{(N 2),} preferably at least ^{10 m} 2 / g, more preferably at least ^{20 m} 2 / g, particularly preferably at least ^{30 m} 2 / g.
When the BET specific surface area is equal to or greater than the lower limit, it is possible to suppress the occurrence of minute cracks with the carbon black serving as a nucleus when a strong impact is applied.

The BET specific surface area is a value measured according to ASTM D3037-88, and is measured by an N ₂ gas adsorption method using a specific surface area measuring device.

Oil absorption amount The oil (dibutyl phthalate) absorption amount (DBP oil absorption amount) of the carbon black is preferably 400 ml / 100 g or less, more preferably 300 ml / 100 g or less, further preferably 200 ml / 100 g or less, and 150 ml / 100 g or less. Is particularly preferred.
When the DBP oil absorption is less than or equal to the above upper limit value, it is possible to suppress the occurrence of minute cracks with the carbon black serving as a nucleus when a strong impact is applied.

The DBP oil absorption is JIS K6221 (1982) 6.1.2. This is a value measured according to the method A and means the amount (ml) of dibutyl phthalate absorbed per 100 g of carbon black.

-Particle size The particle size of the carbon black is preferably 500 nm or less, more preferably 200 nm or less, and particularly preferably 100 nm or less.
When the particle size is not more than the above upper limit, it is possible to suppress the occurrence of minute cracks with the carbon black serving as a nucleus when a strong impact is applied.

The particle size is a value measured using a laser diffraction type particle size distribution meter (MICROTRAC FRA type) with a water refractive index of 1.33 and a rubber chemical refractive index of 1.57.

(Physical properties of resin materials)
Next, preferred physical properties of the resin material constituting part or all of the tire frame body will be described. The tire frame in the present invention uses the above-mentioned resin material.

The melting point (or softening point) of the resin material (tire frame) itself is usually about 100 ° C. to 350 ° C., preferably about 100 ° C. to 250 ° C., but from the viewpoint of tire productivity, 120 ° C. to 250 ° C. The degree is preferable, and 120 ° C. to 200 ° C. is more preferable.
In this way, by using a resin material having a melting point of 120 ° C. to 250 ° C., for example, when a tire skeleton is formed by fusing the divided bodies (frame pieces), the periphery of 120 ° C. to 250 ° C. Even if the frame body is fused in the temperature range, the bonding strength between the tire frame pieces is sufficient. For this reason, the tire of this invention is excellent in durability at the time of driving | running | working, such as puncture resistance and abrasion resistance. The heating temperature is preferably 10 ° C. to 150 ° C. higher than the melting point (or softening point) of the resin material forming part or all of the tire frame piece, more preferably 10 ° C. to 100 ° C.

The resin material can be obtained by adding various additives as necessary and mixing them appropriately by a known method (for example, melt mixing).
The resin material obtained by melt mixing can be used in the form of pellets if necessary.

The tensile yield strength defined in JIS K7113: 1995 of the resin material (tire frame) itself is preferably 5 MPa or more, preferably 5 MPa to 20 MPa, and more preferably 5 MPa to 17 MPa. When the tensile yield strength of the resin material is 5 MPa or more, the resin material can withstand deformation against a load applied to the tire during traveling.

The tensile yield elongation defined by JIS K7113: 1995 of the resin material (tire frame) itself is preferably 10% or more, preferably 10% to 70%, and more preferably 15% to 60%. When the tensile yield elongation of the resin material is 10% or more, the elastic region is large and the air sealability can be improved.

The tensile elongation at break specified in JIS K7113: 1995 of the resin material (tire frame) itself is preferably 50% or more, preferably 100% or more, more preferably 150% or more, and particularly preferably 200% or more. When the tensile elongation at break of the resin material is 50% or more, the rim assembly property is good and it is possible to make it difficult to break against a collision.

The deflection temperature under load (when loaded with 0.45 MPa) of the resin material (tire frame) itself as defined in ISO 75-2 or ASTM D648 is preferably 50 ° C. or more, preferably 50 ° C. to 150 ° C., and preferably 50 ° C. to 50 ° C. 130 ° C. is more preferable. When the deflection temperature under load of the resin material is 50 ° C. or higher, deformation of the tire skeleton can be suppressed even when vulcanization is performed in the manufacture of the tire.

[First Embodiment]
A tire according to a first embodiment of the tire of the present invention will be described below with reference to the drawings.
The tire 10 of this embodiment will be described. FIG. 1A is a perspective view showing a partial cross section of a tire according to an embodiment of the present invention. FIG. 1B is a cross-sectional view of a bead portion attached to a rim. As shown in FIG. 1, the tire 10 of the present embodiment has a cross-sectional shape substantially similar to that of a conventional general rubber pneumatic tire.

As shown in FIG. 1A, the tire 10 includes a pair of bead portions 12 that contact the bead seat 21 and the rim flange 22 of the rim 20 shown in FIG. 1B, and side portions 14 that extend outward from the bead portion 12 in the tire radial direction. A tire case (tire frame body) 17 having a crown portion 16 (outer peripheral portion) for connecting a tire radial direction outer end of one side portion 14 and a tire radial direction outer end of the other side portion 14 is provided. Yes.

Here, the tire case 17 of the present embodiment includes, for example, a polyamide thermoplastic elastomer and carbon black as a resin material, and the carbon black content is less than 1% by mass with respect to the resin material. Can be used.

In the present embodiment, the tire case 17 is formed of only a single resin material, but the present invention is not limited to this configuration, and each tire case 17 is similar to a conventional general rubber pneumatic tire. You may use the thermoplastic resin material which has a different characteristic for every site | part (the side part 14, the crown part 16, and the bead part 12 etc.). Further, a reinforcing material (polymer material, metal fiber, cord, nonwoven fabric, woven fabric, etc.) is embedded in the tire case 17 (for example, the bead portion 12, the side portion 14, and the crown portion 16). The tire case 17 may be reinforced with a reinforcing material.

The tire case 17 of the present embodiment is obtained by joining a pair of tire case halves (tire frame pieces) 17A formed only of a resin material. The tire case half 17A is formed by injection molding or the like so that one bead portion 12, one side portion 14, and a half-width crown portion 16 are integrated with each other so as to face each other. It is formed by joining at the tire equator part. The tire case 17 is not limited to the one formed by joining two members, and may be formed by joining three or more members.

The tire case half 17A formed using at least the resin material can be formed by, for example, vacuum forming, pressure forming, injection forming, melt casting, or the like. For this reason, it is not necessary to perform vulcanization compared to the case where the tire case is molded with rubber as in the prior art, the manufacturing process can be greatly simplified, and the molding time can be omitted.
In the present embodiment, the tire case half body 17A has a symmetrical shape, that is, the one tire case half body 17A and the other tire case half body 17A have the same shape. There is also an advantage that only one type of mold is required.

In this embodiment, as shown in FIG. 1B, an annular bead core 18 made of only a steel cord is embedded in the bead portion 12 as in a conventional general pneumatic tire. However, the present invention is not limited to this configuration, and the bead core 18 can be omitted if the rigidity of the bead portion 12 is ensured and there is no problem in fitting with the rim 20. In addition to the steel cord, an organic fiber cord, a resin-coated organic fiber cord, or a hard resin may be used.

In this embodiment, the portion that contacts the rim 20 of the bead portion 12 and at least the portion that contacts the rim flange 22 of the rim 20 are more excellent in sealing performance than the resin material constituting part or all of the tire case 17. An annular sealing layer 24 made of only a material such as rubber is formed. The seal layer 24 may also be formed at a portion where the tire case 17 (bead portion 12) and the bead sheet 21 are in contact with each other. As a material having a better sealing property than a resin material constituting part or all of the tire case 17, a softer material can be used than a resin material constituting part or all of the tire case 17. As the rubber that can be used for the seal layer 24, it is preferable to use the same type of rubber as that used on the outer surface of the bead portion of a conventional general rubber pneumatic tire. Moreover, you may use the other thermoplastic resin (thermoplastic elastomer) which is more excellent in the sealing performance than the said resin material. Examples of such other thermoplastic resins include polyurethane resins, polyolefin resins, polystyrene thermoplastic resins, resins such as polyester resins, blends of these resins with rubbers or elastomers, and the like. Thermoplastic elastomers can also be used, for example, polyester-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polystyrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers, combinations of these elastomers, and blends with rubber. Thing etc. are mentioned.

As shown in FIG. 1, a reinforcing cord 26 having higher rigidity than a resin material constituting part or all of the tire case 17 is wound around the crown portion 16 in the circumferential direction of the tire case 17. The reinforcing cord 26 is wound spirally in a state in which at least a part thereof is embedded in the crown portion 16 in a cross-sectional view along the axial direction of the tire case 17, thereby forming a reinforcing cord layer 28. On the outer circumferential side of the reinforcing cord layer 28 in the tire radial direction, a crown 30 made of only a material superior in wear resistance than a resin material constituting part or all of the tire case 17, for example, rubber, is disposed.

The reinforcing cord layer 28 formed by the reinforcing cord 26 will be described with reference to FIG. FIG. 2 is a cross-sectional view along the tire rotation axis showing a state where a reinforcing cord is embedded in the crown portion of the tire case of the tire of the first embodiment. As shown in FIG. 2, the reinforcing cord 26 is spirally wound in a state in which at least a part is embedded in the crown portion 16 in a sectional view along the axial direction of the tire case 17. A reinforcing cord layer 28 indicated by a broken line portion in FIG. 2 is formed together with a part of the outer peripheral portion 17. A portion embedded in the crown portion 16 of the reinforcing cord 26 is in a state of being in close contact with a resin material that constitutes a part or all of the crown portion 16 (tire case 17). As the reinforcing cord 26, a monofilament (single wire) such as a metal fiber or an organic fiber, or a multifilament (twisted wire) obtained by twisting these fibers such as a steel cord twisted with a steel fiber can be used. In the present embodiment, a steel cord is used as the reinforcing cord 26.

Further, in FIG. 2, the burying amount L indicates the burying amount of the reinforcing cord 26 in the tire rotation axis direction with respect to the tire case 17 (crown portion 16). The embedding amount L of the reinforcing cord 26 in the crown portion 16 is preferably 1/5 or more of the diameter D of the reinforcing cord 26, and more preferably more than 1/2. Most preferably, the entire reinforcing cord 26 is embedded in the crown portion 16. When the embedment amount L of the reinforcing cord 26 exceeds 1/2 of the diameter D of the reinforcing cord 26, it is difficult to jump out of the embedded portion due to the size of the reinforcing cord 26. Further, when the entire reinforcing cord 26 is embedded in the crown portion 16, the surface (outer peripheral surface) becomes flat, and even if a member is placed on the crown portion 16 where the reinforcing cord 26 is embedded, Air can be prevented from entering. The reinforcing cord layer 28 corresponds to a belt disposed on the outer peripheral surface of the carcass of a conventional rubber pneumatic tire.

As described above, the crown 30 is disposed on the outer peripheral side of the reinforcing cord layer 28 in the tire radial direction. The rubber used for the crown 30 is preferably the same type of rubber used in conventional rubber pneumatic tires. Instead of the crown 30, a crown formed of another type of resin material that is more excellent in wear resistance than a resin material that constitutes part or all of the tire case 17 may be used. Moreover, the crown 30 is formed with a crown pattern including a plurality of grooves on the ground contact surface with the road surface in the same manner as a conventional rubber pneumatic tire.
Hereinafter, the manufacturing method of the tire of this embodiment is explained.

(Tire case molding process)
First, as described above, a tire case half is formed using a resin material containing the polyamide-based thermoplastic elastomer. These tire cases are preferably formed by injection molding. Next, the tire case halves supported by the thin metal support ring face each other. Next, a joining mold (not shown) is installed so as to be in contact with the outer peripheral surface of the abutting portion of the tire case half. Here, the said joining metal mold | die is comprised so that the periphery of the junction part (butting part) of the tire case half body 17A may be pressed with a predetermined pressure. Next, the periphery of the joint portion of the tire case half is pressed at a temperature equal to or higher than the melting point (or softening point) of the resin material constituting part or all of the tire case. When the joint portion of the tire case half is heated and pressed by the joining mold, the joint portion is melted and the tire case halves are fused together, and the tire case 17 is formed by integrating these members. In the present embodiment, the joining portion of the tire case half is heated using a joining mold, but the present invention is not limited to this. For example, the joining portion is heated by a separately provided high-frequency heater or the like. Alternatively, the tire case halves may be joined by being softened or melted in advance by hot air, infrared irradiation, or the like, and pressurized by a joining mold.

(Reinforcement cord member winding process)
Next, the reinforcing cord winding process will be described with reference to FIG. FIG. 3 is an explanatory diagram for explaining an operation of embedding a reinforcing cord in a crown portion of a tire case using a cord heating device and rollers. In FIG. 3, the cord supply device 56 is disposed on the reel 58 around which the reinforcing cord 26 is wound, the cord heating device 59 disposed on the downstream side of the reel 58 in the cord transport direction, and the downstream side of the reinforcing cord 26 in the transport direction. The first roller 60, the first cylinder device 62 that moves the first roller 60 in the direction of contacting and separating from the outer peripheral surface of the tire, and the downstream side in the conveying direction of the reinforcing cord 26 of the first roller 60 A second roller 64, and a second cylinder device 66 that moves the second roller 64 in a direction in which the second roller 64 comes into contact with and separates from the tire outer peripheral surface. The second roller 64 can be used as a metal cooling roller. Further, in the present embodiment, the surfaces of the first roller 60 and the second roller 64 are made of fluororesin (in this embodiment, Teflon (registered trademark)) in order to suppress adhesion of a molten or softened resin material. It is coated. In the present embodiment, the cord supply device 56 has two rollers, the first roller 60 and the second roller 64, but the present invention is not limited to this configuration, and either one of the rollers. It is also possible to have only one (that is, one roller).

The cord heating device 59 includes a heater 70 and a fan 72 that generate hot air. Further, the cord heating device 59 includes a heating box 74 through which the reinforcing cord 26 passes through an internal space in which hot air is supplied, and a discharge port 76 for discharging the heated reinforcing cord 26.

In this step, first, the temperature of the heater 70 of the cord heating device 59 is raised, and the ambient air heated by the heater 70 is sent to the heating box 74 by the wind generated by the rotation of the fan 72. Next, the reinforcing cord 26 unwound from the reel 58 is fed into a heating box 74 in which the internal space is heated with hot air (for example, the temperature of the reinforcing cord 26 is heated to about 100 to 200 ° C.). The heated reinforcing cord 26 passes through the discharge port 76 and is wound spirally around the outer peripheral surface of the crown portion 16 of the tire case 17 rotating in the direction of arrow R in FIG. Here, when the heated reinforcing cord 26 comes into contact with the outer peripheral surface of the crown portion 16, the resin material at the contact portion is melted or softened, and at least a part of the heated reinforcing cord 26 is embedded in the outer peripheral surface of the crown portion 16. Is done. At this time, since the heated reinforcing cord 26 is embedded in the molten or softened resin material, there is no gap between the resin material and the reinforcing cord 26, that is, a tight contact state. Thereby, the air entering to the portion where the reinforcing cord 26 is embedded is suppressed. In addition, by heating the reinforcing cord 26 to a temperature higher than the melting point (or softening point) of the resin material of the tire case 17, melting or softening of the resin material in a portion in contact with the reinforcing cord 26 is promoted. By doing in this way, it becomes easy to embed the reinforcement cord 26 in the outer peripheral surface of the crown part 16, and air entry can be effectively suppressed.

Further, the burying amount L of the reinforcing cord 26 can be adjusted by the heating temperature of the reinforcing cord 26, the tension applied to the reinforcing cord 26, the pressing force by the first roller 60, and the like. In the present embodiment, the embedding amount L of the reinforcing cord 26 is set to be 1/5 or more of the diameter D of the reinforcing cord 26. The burying amount L of the reinforcing cord 26 is more preferably more than 1/2 of the diameter D, and most preferably the entire reinforcing cord 26 is embedded.

Thus, the reinforcing cord layer 28 is formed on the outer peripheral side of the crown portion 16 of the tire case 17 by winding the heated reinforcing cord 26 while being embedded in the outer peripheral surface of the crown portion 16.

Next, the vulcanized belt-shaped crown 30 is wound around the outer peripheral surface of the tire case 17 by one turn, and the crown 30 is bonded to the outer peripheral surface of the tire case 17 using an adhesive or the like. The crown 30 may be, for example, a precure crown that is used in conventionally known retreaded tires. This step is the same step as the step of bonding the precure crown to the outer peripheral surface of the base tire of the retreaded tire.

Then, if the seal layer 24 made of only vulcanized rubber is bonded to the bead portion 12 of the tire case 17 using an adhesive or the like, the tire 10 is completed.

(Function)
In the tire 10 of the present embodiment, the tire case 17 includes a polyamide-based thermoplastic elastomer and carbon black, and part or all of the tire case 17 is formed of a resin material having a carbon black content of less than 1% by mass. Therefore, excellent light resistance can be obtained.
The tire 10 is light in weight because it has a simple structure as compared with a conventional rubber tire. For this reason, the tire 10 of this embodiment has high friction resistance and durability. Further, since the tire case 17 can be injection-molded, the productivity is very excellent.

Further, in the tire 10 of the present embodiment, the reinforcing cord 26 having a rigidity higher than that of the resin material is spirally formed in the circumferential direction on the outer peripheral surface of the crown portion 16 of the tire case 17 partially or entirely formed of the resin material. It is wound. Therefore, puncture resistance, cut resistance, and circumferential rigidity of the tire 10 are improved. In addition, creep of the tire case 17 partially or wholly formed of a resin material is prevented by improving the circumferential rigidity of the tire 10.

In addition, at least the reinforcing cord 26 is provided on the outer peripheral surface of the crown portion 16 of the tire case 17 partially or entirely formed of a resin material in a cross-sectional view along the axial direction of the tire case 17 (the cross section shown in FIG. 1). A part is embedded and is in close contact with the resin material. Therefore, air entry during manufacture is suppressed, and movement of the reinforcing cord 26 due to input during travel is suppressed. Thereby, it is suppressed that peeling etc. arise in the reinforcement cord 26, the tire case 17, and the crown 30, and durability of the tire 10 improves.

When the reinforcing cord layer 28 is configured to include a resin material in this way, the difference in hardness between the tire case 17 and the reinforcing cord layer 28 is reduced as compared with the case where the reinforcing cord 26 is fixed with cushion rubber. it can. Therefore, the reinforcing cord 26 can be further adhered and fixed to the tire case 17. Thereby, the above-mentioned air entering can be prevented effectively, and it can control effectively that a reinforcement cord member moves at the time of driving.
Further, when the reinforcing cord 26 is a steel cord, the reinforcing cord 26 can be easily separated from the resin material by heating and recovered at the time of disposal of the tire, which is advantageous in terms of recyclability of the tire 10. In addition, since the resin material has a lower loss coefficient (tan δ) than vulcanized rubber, if the reinforcing cord layer 28 contains a large amount of the resin material, the rolling property of the tire can be improved. Furthermore, the resin material has an advantage that the in-plane shear rigidity is larger than that of the vulcanized rubber, and the handling property and wear resistance during running of the tire are excellent.

And since the embedding amount L of the reinforcement cord 26 is 1/5 or more of the diameter D as shown in FIG. 2, the air entry at the time of manufacture is suppressed effectively, the input at the time of driving, etc. This further suppresses the movement of the reinforcing cord 26.

In addition, since the crown 30 in contact with the road surface is made of a rubber material that is more resistant to wear than the resin material that forms part or all of the tire case 17, the wear resistance of the tire 10 is improved.
Further, since an annular bead core 18 made of only a metal material is embedded in the bead portion 12, the tire case 17, that is, the tire 10 is mounted on the rim 20 in the same manner as a conventional rubber pneumatic tire. Firmly held.

By providing a seal layer 24 made of only a rubber material having a sealing property rather than a resin material constituting part or all of the tire case 17 at a portion of the bead portion 12 that contacts the rim 20, the tire 10 and the rim 20 The rim assembly property between the two can be further improved.

In the above-described embodiment, the reinforcing cord 26 is heated, and the surface of the tire case 17 where the heated reinforcing cord 26 contacts is melted or softened. However, the present invention is not limited to this configuration. For example, the reinforcing cord 26 may be embedded in the crown portion 16 after the outer peripheral surface of the crown portion 16 in which the reinforcing cord 26 is embedded is heated using a hot air generator without heating the reinforcing cord 26.

In the first embodiment, the heat source of the cord heating device 59 is a heater and a fan. However, the present invention is not limited to this configuration, and the reinforcement cord 26 may be directly heated by radiant heat (for example, infrared rays). Good.

Further, in the first embodiment, the portion in which the resin material in which the reinforcing cord 26 is embedded is melted or softened is forcibly cooled by the metal second roller 64, but the present invention is not limited to this configuration. . For example, a configuration may be adopted in which cold air is directly blown onto a portion where the resin material is melted or softened to forcibly cool and solidify the melted or softened portion of the resin material.

In the first embodiment, the reinforcing cord 26 is heated. However, for example, the outer periphery of the reinforcing cord 26 may be covered with the same resin material as the tire case 17. In this case, when the covering reinforcing cord is wound around the crown portion 16 of the tire case 17, the resin material covered together with the reinforcing cord 26 is also heated, thereby effectively suppressing air entry when embedded in the crown portion 16. can do.

In addition, it is easy to manufacture the reinforcing cord 26 in a spiral manner, but a method of making the reinforcing cord 26 discontinuous in the width direction is also conceivable.

The tire 10 of the first embodiment is a so-called tubeless tire in which an air chamber is formed between the tire 10 and the rim 20 by attaching the bead portion 12 to the rim 20, but the present invention is limited to this configuration. It may be a complete tube shape. Further, the tire of the present invention is an embodiment using a reinforcing cord member in which the cord member is coated with a resin material as shown in the second embodiment (FIGS. 4 and 5) of JP 2012-46030 A. May be.

The embodiments of the present invention have been described above with reference to the embodiments. However, these embodiments are merely examples, and various modifications can be made without departing from the scope of the invention. It goes without saying that the scope of rights of the present invention is not limited to these embodiments.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to this.

[Examples 1 to 8, Comparative Examples 1 and 2]
The thermoplastic elastomer shown in Table 1 and carbon black were mixed in the composition shown in Table 1 to obtain a resin material. In addition, the quantity of the carbon black described in Table 1 represents a mass ratio (% by mass) with respect to the resin material.
The obtained resin material was pelletized and injection molded at 220 ° C. to obtain a sample piece (length 150 mm × width 270 mm × thickness 2.0 mm). Various measurements were carried out using this sample piece itself or a test piece punched from the sample piece.

-Evaluation-
[Light resistance]
The test was conducted using a xenon arc type light resistance tester (Atlas, Ci-4000) under the following conditions.
Irradiation intensity: 60 W / m ² (irradiation intensity at a wavelength of 300 to 400 nm)
・ Black panel temperature: 65 ℃
・ Humidity: 50% RH
The samples after the 800-hour and 1200-hour irradiation tests were evaluated by the following evaluation tests.
The light resistance was evaluated by visual inspection and judged by the presence or absence of cracks on the sample surface. If there were no cracks, the test was accepted (A), and if there were cracks, the test was rejected (B).

[Molecular weight]
The weight average molecular weight (Mw) of the sample piece before irradiation, after irradiation for 800 hours, and after irradiation for 1200 hours in the test using the xenon arc light resistance tester was measured by gel permeation chromatography (GPC, manufactured by Tosoh Corporation). "HLC-8320GPC EcoSEC" (gel permeation chromatography).
The measurement results are shown in Table 1 with the molecular weight before irradiation as a reference (100%) and the molecular weight after irradiation (800 hours and 1200 hours) in%. In addition, as an evaluation standard of molecular weight, it was judged that there was no problem in performance if it was within ± 20% of the pre-irradiation (initial) after 800 hours irradiation and 1200 hours irradiation.

[Durability (crack resistance)]
Durability (crack resistance) was evaluated by the following evaluation test. The sample was punched into a JIS-3 dumbbell shape, and a test sample was prepared in which a crack starting point was previously placed in the center of the sample. The test sample was repeatedly pulled using a Shimadzu Corporation servo pulsar device (17 Hz constant strain 11%), and the number of times until the crack progressed and the sample broke was recorded. If the number of breaks was 5 million times or more, it was considered acceptable.

The components shown in Table 1 are as follows.
-TPA: The polyamide-type thermoplastic elastomer used was produced as follows.
In a reaction vessel having a volume of 2 liters equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet, 43.7 g of 12-aminododecanoic acid (manufactured by Aldrich), 601 g of aminododecanolactam (lauryl lactam) (manufactured by Aldrich), And 15.5 g of adipic acid (manufactured by Aldrich). After the inside of the vessel was sufficiently purged with nitrogen, the temperature was raised to 280 ° C. and reacted for 4 hours under a pressure of 0.6 MPa. After releasing the pressure, the mixture was further reacted under a nitrogen stream for 1 hour to obtain a white solid which was a nylon 12 polymer having a weight average molecular weight of 6000 (hard segment “PA12” having a chain extender bonded to the end) (polymerization). Reaction A).
To 250 g of the obtained nylon 12 polymer, polyoxypropylene-polytetramethylene glycol-polyoxypropylene diamine (PPG-PTMG-PPG, manufactured by HUNTSMAN Co., Ltd., product name: Jeffamine, model number: XTJ-548, weight average) 70.9 g of molecular weight 1700) and 71 mg of tetra-tert-butoxyzirconium were added and stirred at 230 ° C. for 6 hours (polymerization reaction B). Further, 1 g of Irganox 1010 (BASF) was added to obtain a white polyamide-based thermoplastic elastomer (TPA, weight average molecular weight: 75,000).

Carbon black a: manufactured by Asahi Carbon Co., Ltd., trade name “Asahi # 70” (BET specific surface area 77 m ² / g, oil absorption (DBP oil absorption) 101 ml / 100 g, average particle diameter 28 nm)
Carbon black b: manufactured by Asahi Carbon Co., Ltd., trade name “Asahi # 15HS” (BET specific surface area 14 m ² / g, oil absorption (DBP oil absorption) 90 ml / 100 g, average particle diameter 120 nm)
Carbon black c: manufactured by Asahi Carbon Co., Ltd., trade name “SB605” (BET specific surface area 85 m ² / g, oil absorption (DBP oil absorption) 77 ml / 100 g, average particle diameter 25 nm)
Carbon black d: manufactured by Asahi Carbon Co., Ltd., trade name “Asahi F-200” (BET specific surface area 51 m ² / g, oil absorption (DBP oil absorption) 180 ml / 100 g, average particle diameter 38 nm)
Carbon black e: manufactured by Asahi Carbon Co., Ltd., trade name “HS-500” (BET specific surface area 39 m ² / g, oil absorption (DBP oil absorption) 380 ml / 100 g)
Carbon black f: manufactured by Asahi Carbon Co., Ltd. (BET specific surface area 962 m ² / g, oil absorption (DBP oil absorption) 226 ml / 100 g)

As can be seen from Table 1, the example in which the resin material contained in the tire case contains a polyamide-based thermoplastic elastomer and contains carbon black in a range of less than 1% by mass is superior to Comparative Example 1 that does not contain carbon black. It can be seen that it has high light resistance. Moreover, it turns out that it is excellent in durability (crack resistance) compared with the comparative example 2 which contains carbon black in the quantity of 1 mass% or more.

The disclosures of Japanese application 2015-114960 and Japanese application 2015-238530 are incorporated herein by reference in their entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.

Claims

Formed of a resin material and having an annular tire frame,
A tire in which the resin material includes a polyamide-based thermoplastic elastomer and carbon black, and the content of the carbon black is less than 1% by mass with respect to the resin material.
The tire according to claim 1, wherein the resin material has a carbon black content of 0.01% by mass or more.