JP2017149183A - tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tire capable of suppressing degradation and appearance deterioration thereof.SOLUTION: The tire has an annular tire skeleton body formed of resin materials and an exterior member formed of rubber materials. The tire skeleton body includes at least either of process oil A and an aging-preventing agent A. The exterior member includes process oil B and an aging-preventing agent B. Contents a1 of the process oil A contained in the tire skelton body are 0 parts by mass or 0.5 parts by mass-15 parts by mass to rubber constituents 100 parts by mass in the rubber materials of the exterior member. Contents a2 of the aging-protecting agent A contained in the tire skelton body are 0 parts by mass or 0.5 parts by mass-20 parts by mass to rubber constituents 100 parts by mass in the rubber materials of the exterior member. At least either one relation of a relation between a1 and b1 represented by a forum 1: a1>b1 and a relation between a2 and b2 represented by a forum 2: a2>b2 is satisfied, and a thickness of the tire skelton body is set to be between 1 mm and 2.5 mm.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a tire mounted on a rim.

  Conventionally, a pneumatic tire formed using rubber, an organic fiber material, a steel member, or the like is used for a vehicle such as a passenger car.

  In recent years, the use of resin materials including thermoplastic polymer materials such as thermoplastic resins and thermoplastic elastomers as tire materials has been studied for reasons such as weight reduction, ease of molding, and ease of recycling. Yes. For example, Patent Document 1 discloses a pneumatic tire formed using a thermoplastic polymer material.

JP 2003-104008 A

The tire described in Patent Document 1 has a resin skeleton and a rubber layer. Such a tire tends to have low light resistance of the rubber layer. Since the skeletal body is an environment in which light does not easily hit when the tire is used, the requirement for improving the light resistance is low, and the skeleton body does not contain an anti-aging agent or the like, or a very small amount even if blended. On the other hand, since the rubber layer is the outermost layer of the tire, it is easily exposed to light or the like. Therefore, even if the anti-aging agent and process oil are contained in the rubber layer, these are consumed and reduced. Furthermore, formulations such as anti-aging agents and process oils tend to move to lower concentrations between adjacent members. Therefore, in the case of a tire having a resin skeleton having the above-described characteristics, the anti-aging agent and the process oil are transferred from the rubber layer to the skeleton, and the tire is more in comparison with the tire having the rubber skeleton. Deterioration tends to proceed easily.
The above measures include increasing the contents of the anti-aging agent and the process oil in the rubber layer. However, if the anti-aging agent and the process oil are excessively contained, they migrate to the tire surface and deteriorate the appearance. And may cause adverse effects such as precipitation at the interface between adjacent members and hindering adhesion between adjacent members.
In the present specification, the deterioration of the tire means that the durability is lowered when the tire is exposed to light.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the tire by which deterioration and external appearance deterioration were suppressed.

Specific means for solving the above problems include the following modes.
[1] An annular tire skeleton formed of a resin material and an exterior member formed of a rubber material, the tire skeleton including at least one of process oil A and anti-aging agent A, The exterior member includes process oil B and an anti-aging agent B, and the content a1 of the process oil A in the tire frame body is 0 part by mass with respect to 100 parts by mass of the rubber component in the rubber material of the exterior member. Alternatively, the content a2 of the anti-aging agent A in the tire skeleton is 0 part by mass or 0 part by mass with respect to 100 parts by mass of the rubber component in the rubber material of the exterior member. The relationship between the content a1 of the process oil A of the tire frame body expressed by the following formula 1 and the content b1 of the process oil B of the exterior member, which is 0.5 to 20 parts by mass; Satisfies at least one of the relationship between the content a2 of the anti-aging agent A of the tire frame body represented by the following formula 2 and the content b2 of the anti-aging agent B of the exterior member, A tire having a thickness of 1 mm to 2.5 mm.
a1> b1 Formula 1
a2> b2 Formula 2
[2] Between the tire frame body and the exterior member, there is an adhesive layer formed of a composition containing resin or rubber, or an adhesive layer formed of a composition containing resorcinol-formaldehyde-latex. The tire according to [1].
[3] The tire according to [2], including an adhesive layer formed of a composition including the resin or rubber, wherein the resin includes at least one resin selected from an epoxy resin and a phenol resin.
[4] The tire according to any one of [1] to [3], wherein the resin material includes at least one selected from a polyamide-based elastomer, a polyester-based elastomer, a polyamide resin, and a polyester resin.

  According to the present invention, a tire in which deterioration and deterioration in appearance are suppressed is provided.

(A)-(D) are schematic diagrams which show the layer structure of a tire frame body and the exterior member. (A) is a perspective view showing a section of a part of a tire concerning a 1st embodiment of the present invention, and (B) is a sectional view of a bead part attached to a rim. It is sectional drawing which showed the laminated structure of the crown part of the tire frame of the tire of 1st Embodiment, and the tread which is an exterior member. (A) is a perspective view showing a section of a part of a tire concerning a 2nd embodiment of the present invention, and (B) is a sectional view of a bead part attached to a rim. It is sectional drawing along the tire rotating shaft which shows the laminated structure by which the reinforcement cord member was embed | buried on the crown part of the tire case of the tire of 2nd Embodiment. It is explanatory drawing for demonstrating the operation | movement which embeds a reinforcement cord in the crown part of a tire frame using a cord heating device and a roller.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. be able to.

In this specification, “resin” is a concept including a thermoplastic resin (including a thermoplastic elastomer) and a thermosetting resin, and does not include vulcanized rubber.
“Rubber” is a polymer compound having elasticity, but is distinguished from a thermoplastic elastomer in the present specification.
“Thermoplastic elastomer” is a high molecular compound having elasticity, and is a crystalline polymer having a high melting point or a hard segment having a high cohesive force, and is amorphous and has a low glass transition temperature. It means a copolymer having a polymer constituting a soft segment.
In the following description of the resin, “same species” means those having a skeleton in common with the skeleton constituting the main chain of the resin, such as ester groups.

In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In addition, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.

≪Tire≫
The tire has an annular tire skeleton formed of a resin material and an exterior member formed of a rubber material, and the tire skeleton includes at least one of process oil A and anti-aging agent A, The exterior member includes process oil B and an anti-aging agent B, and the content a1 of the process oil A in the tire frame body is 0 part by mass with respect to 100 parts by mass of the rubber component in the rubber material of the exterior member. Alternatively, the content a2 of the anti-aging agent A in the tire skeleton is 0 part by mass or 0 part by mass with respect to 100 parts by mass of the rubber component in the rubber material of the exterior member. The relationship between the content a1 of the process oil A of the tire frame body represented by the following formula 1 and the content b1 of the process oil B of the exterior member is 0.5 to 20 parts by mass. Or satisfy | fills at least one relationship of content a2 of the anti-aging agent A of the said tire frame body represented by following formula 2, and content b2 of the anti-aging agent B of the said exterior member, The thickness is 1 mm to 2.5 mm.
a1> b1 Formula 1
a2> b2 Formula 2

A rubber material as an exterior member in a tire having a tire skeleton formed of a resin material is likely to deteriorate when the tire is exposed to light or the like. Therefore, such a tire is likely to be deteriorated by light or the like. In order to suppress the deterioration of the tire, process oil and an anti-aging agent are used for the exterior member, but the process oil and the anti-aging agent are consumed over time, and the exterior member to the tire frame body and the like Since transition occurs, the effect of suppressing deterioration tends not to last for a long time.
For the purpose of maintaining the effect of suppressing deterioration of the tire for a long period of time, the content of process oil and anti-aging agent used in the exterior member may be increased. By increasing these contents, the process oil and anti-aging agent may be increased. This can easily cause a transition to the surface of the tire and deteriorate the appearance of the tire, and can cause precipitation at the interface between adjacent members to inhibit adhesion between adjacent members.

In the tire of the present invention, the exterior member includes process oil B and anti-aging agent B, and the tire frame includes at least one of process oil A and anti-aging agent A. And the content of the process oil and the anti-aging agent in the resin material forming the tire skeleton and the rubber material forming the exterior member is as described above, and at least one of the relationships of the above formulas 1 and 2 Satisfy the relationship.
By forming the tire in the above-described configuration, the process oil and the anti-aging agent are directed from the tire skeleton having a higher content of at least one of the process oil and the anti-aging agent to an exterior member having a lower content of these. At least one of the transitions occurs. That is, since at least one of the process oil and the anti-aging agent is supplied from the tire frame to the exterior member, the process oil and the anti-aging agent contained in the exterior member are consumed and the content of the tire is reduced. It is thought that deterioration can be suppressed for a long time.
Moreover, since at least one of the process oil and the anti-aging agent is supplied from the tire frame to the exterior member by configuring the tire as described above, the content of the process oil and the anti-aging agent in the exterior member is set in advance. Without increasing, the light resistance of the exterior member can be improved and deterioration can be suppressed. Further, since the anti-aging agent and process oil supplied from the tire frame to the exterior member are consumed in the exterior member, the amount of the anti-aging agent and process oil is excessive in the exterior member. Hateful. That is, the contents of the process oil and the anti-aging agent in the exterior member do not increase excessively, and the transition of the process oil and the anti-aging agent to the tire surface and the interface with the adjacent member can be suppressed. For this reason, it is considered that the deterioration of the appearance of the tire and the decrease in durability due to the inhibition of adhesion can be suppressed.
Moreover, since the thickness of the tire frame is 1 mm to 2.5 mm, it is easy to maintain the shape as a tire, and the process oil and the anti-aging agent are more smoothly supplied from the tire frame to the exterior member. it is conceivable that.
From the above, it is considered that the tire of the present invention can achieve both suppression of deterioration and suppression of deterioration in appearance.

<Quantitative relationship between process oil and anti-aging agent in tire frame and exterior member>
The tire includes a tire frame body and an exterior member. The tire frame body includes at least one of process oil A and anti-aging agent A, and the exterior member includes process oil B and anti-aging agent B.

The content a1 of the process oil A in the tire frame body is 0 part by mass or 0.5 part by mass to 15 parts by mass with respect to 100 parts by mass of the rubber component in the rubber material of the exterior member.
Deterioration of the tire can be suppressed when the content a1 of the process oil A is 0.5 parts by mass or more. On the other hand, when the content a1 of the process oil A is 15 parts by mass or less, the transition of the process oil to the tire surface can be suppressed, and deterioration of the appearance of the tire can be suppressed. Further, when the content a1 of the process oil A is 0 part by mass, the content a2 of the anti-aging agent A in the tire skeleton described later is 0 with respect to 100 parts by mass of the rubber component in the rubber material of the exterior member. .5 parts by mass to 20 parts by mass.

The content a2 of the anti-aging agent A in the tire skeleton is 0 part by mass or 0.5 part by mass to 20 parts by mass with respect to 100 parts by mass of the rubber component in the rubber material of the exterior member.
The deterioration of the tire can be suppressed when the content a2 of the anti-aging agent A is 0.5 parts by mass or more. On the other hand, when the content a2 of the anti-aging agent A is 20 parts by mass or less, the migration of the anti-aging agent to the tire surface can be suppressed, and deterioration of the appearance of the tire can be suppressed. Further, when the content a2 of the anti-aging agent A is 0 part by mass, the content a1 of the process oil A in the tire skeleton described above is 0 with respect to 100 parts by mass of the rubber component in the rubber material of the exterior member. .5 parts by mass to 15 parts by mass.

And the relationship between the content a1 of the process oil A of the tire frame body represented by the following formula 1 and the content b1 of the process oil B of the exterior member, or the aging of the tire frame body represented by the following formula 2. Satisfies at least one of the relationship between the content a2 of the inhibitor A and the content b2 of the anti-aging agent B of the exterior member.
a1> b1 Formula 1
a2> b2 Formula 2

That is, the quantitative relationship between the process oil and the anti-aging agent in the tire frame body and the exterior member is as follows.
1) When the tire frame includes a process oil and an anti-aging agent, the content a1 of the process oil A in the tire frame is 0.5 to 15 parts by mass, and the content a2 of the anti-aging agent A2 Is 0.5 parts by mass to 20 parts by mass, and at least one of the content b1 of the process oil B and the content b2 of the anti-aging agent B in the exterior member satisfies the relationship of the above formula 1 or the relationship of the above formula 2. Fulfill.
In this case, from the viewpoint of achieving both suppression of deterioration of the tire and suppression of deterioration of the appearance, the content a1 of the process oil A in the tire frame body, the content a2 of the anti-aging agent A, and the content of the process oil B in the exterior member It is preferable that b1 and the content b2 of the antioxidant B satisfy both the relationship of the above formula 1 and the relationship of the above formula 2.
2) When the tire frame contains process oil and no anti-aging agent, the content a1 of the process oil A in the tire frame is 0.5 to 15 parts by mass, and the content a2 of the anti-aging agent A Is 0 part by mass, and the content b1 of the process oil B in the exterior member satisfies the relationship of the above formula 1.
3) When the tire frame contains an anti-aging agent and no process oil, the content a1 of the process oil A in the tire frame is 0 parts by mass, and the content a2 of the anti-aging agent A is 0.5 parts by mass. The content b2 of the process oil B in the exterior member satisfies the relationship of the above formula 2.

  The content a1 of the process oil A in the tire frame body, the content a2 of the anti-aging agent A, the content b1 of the process oil B in the exterior member, and the content b2 of the anti-aging agent B are expressed by the above formula 1. By satisfying at least one of the relationship or the relationship of Formula 2 above, at least one of the process oil or the anti-aging agent is supplied from the tire frame body to the exterior member, so that deterioration of the tire can be suppressed. The suppression effect is maintained for a long time.

<Tire frame>
The tire has an annular tire skeleton formed of a resin material. The tire frame includes at least one of process oil A and anti-aging agent A. The contents of process oil A and anti-aging agent A are as described above.

[Process oil A]
The process oil A that can be included in the tire skeleton is not particularly limited, and a process oil or the like used as a softening agent for conventionally known rubber products can be used. Specific examples include petroleum oils, vegetable oils, and synthetic oils. These may be used alone or in combination of two or more.
The process oil A that can be included in the tire frame body may be the same as or different from the process oil B that is included in the exterior member described later. From the viewpoint of supplying process oil from the tire frame to the exterior member, it is preferable that the process oil A and the process oil B are the same.

  Specific examples of the petroleum oil include paraffin oil, naphthene oil, and aroma oil.

  Among these, from the viewpoint of weather resistance, an aroma oil is preferable, and a paraffin oil is more preferable.

  The content of the process oil in the tire frame is as described above.

[Anti-aging agent]
The anti-aging agent that can be contained in the tire skeleton is not particularly limited, and anti-aging agents used in conventionally known rubber compositions can be used. Specifically, for example, phenol derivatives, aromatic amine derivatives, amine-ketone condensates, benzimidazole derivatives, dithiocarbamic acid derivatives, and thiourea derivatives are preferable. These may be used alone or in combination of two or more.
The anti-aging agent A that can be contained in the tire skeleton may be the same as or different from the anti-aging agent B contained in the exterior member described later. From the viewpoint of supplying the anti-aging agent from the tire frame to the exterior member, the anti-aging agent A and the anti-aging agent B are preferably the same.

  Specific examples of the phenol derivative include styrenated phenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butylcresol, 4,4′-butylidene-bis (3-methyl). -6-tert-butylphenol), 4,4'-methylene-bis (2,6-di-tert-butylphenol), 4,4'-thio-bis (6-tert-butyl-m-cresol) and the like. It is done.

  Specific examples of the aromatic amine derivative include 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, octylated diphenylamine, N, N′-diphenyl-p-phenylenediamine, and N, N. Examples include '-di-2-naphthyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, and the like.

  Specific examples of the amine-ketone condensate include 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethyl. Examples include quinoline, a reaction product of diphenylamine and acetone.

  Specific examples of the benzimidazole derivative include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptobenzimidazole, and the like.

  Specific examples of the dithiocarbamic acid derivative include nickel diethyldithiocarbamate and nickel dibutyldithiocarbamate.

  Specific examples of the thiourea derivative include 1,3-bis (dimethylaminopropyl) -2-thiourea and tributylthiourea.

  Among these, an aromatic amine derivative is preferable from the viewpoint of weather resistance and cost, and N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine is more preferable.

  The content of the anti-aging agent in the tire frame is as described above.

[Resin material]
The tire frame body in the present invention is formed of a resin material.
In the present invention, the “resin material” includes at least a resin (resin component) and may include other components such as an additive.
In the present specification, the “resin material” is a concept including a thermoplastic resin, a thermoplastic elastomer, and a thermosetting resin, but does not include vulcanized rubber.
Examples of the thermosetting resin include phenol-based thermosetting resins, urea-based thermosetting resins, melamine-based thermosetting resins, and epoxy-based thermosetting resins.
Examples of the thermoplastic resin include polyamide-based thermoplastic resins, polyester-based thermoplastic resins, olefin-based thermoplastic resins, polyurethane-based thermoplastic resins, vinyl chloride-based thermoplastic resins, and polystyrene-based thermoplastic resins. it can.
These may be used alone or in combination of two or more.

Examples of the thermoplastic elastomer include a polyamide-based thermoplastic elastomer (TPA), a polystyrene-based thermoplastic elastomer (TPS), a polyurethane-based thermoplastic elastomer (TPU), an olefin-based thermoplastic elastomer (TPO) defined in JIS K6418, Examples thereof include polyester-based thermoplastic elastomer (TPEE), crosslinked thermoplastic rubber (TPV), and other thermoplastic elastomers (TPZ).
These may be used alone or in combination of two or more.

  Among them, the resin component contained in the resin material forming the tire frame body includes polyamide-based thermoplastic elastomer, polyester-based thermoplastic elastomer, olefin-based from the viewpoint of elasticity required during running and moldability during production. Preferred are thermoplastic elastomers, polyamide-based thermoplastic resins, polyester-based thermoplastic resins, and olefin-based thermoplastic resins, and polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic resins, and polyester-based thermoplastic resins. More preferred.

(Polyamide thermoplastic elastomer)
The polyamide-based thermoplastic elastomer is a thermoplastic resin material made of a copolymer having a crystalline polymer having a high melting point and a non-crystalline polymer having a low glass transition temperature. It means that having an amide bond (—CONH—) in the main chain of the polymer forming the hard segment.
As the polyamide-based thermoplastic elastomer, for example, at least a polyamide is a crystalline hard crystalline segment with a high melting point, and other polymers (for example, polyester, polyether, etc.) are amorphous and have a soft glass transition temperature low soft segment. The material which forms is mentioned. The polyamide-based thermoplastic elastomer may be formed using a chain extender such as dicarboxylic acid in addition to the hard segment and the soft segment.
Specific examples of the polyamide-based thermoplastic elastomer include an amide-based thermoplastic elastomer (TPA) defined in JIS K6418: 2007, a polyamide-based elastomer described in JP-A-2004-346273, and the like. it can.

  In the polyamide-based thermoplastic elastomer, examples of the polyamide that forms the hard segment include polyamides produced from monomers represented by the following general formula (1) or general formula (2).

General formula (1)

In General Formula (1), R ¹ represents a molecular chain of a hydrocarbon having 2 to 20 carbon atoms (for example, an alkylene group having 2 to 20 carbon atoms).

General formula (2)

In 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, 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. In general formula (2), R ² is preferably a hydrocarbon chain having 3 to 18 carbon atoms (for example, an alkylene group having 3 to 18 carbon atoms), and a hydrocarbon molecule having 4 to 15 carbon atoms. A chain (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 forming the hard segment include polycondensates of these ω-aminocarboxylic acids and lactams, and co-condensation polymers of diamines and dicarboxylic acids.

The ω-aminocarboxylic acid has 6 to 20 carbon atoms such as 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. Aliphatic omega-aminocarboxylic acid etc. can be mentioned. Moreover, as a lactam, C5-C20 aliphatic lactams, such as lauryl lactam, (epsilon) -caprolactam, udecan lactam, (omega) -enantolactam, 2-pyrrolidone, etc. can be mentioned.
Examples of the diamine include ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2, 2, 4 Examples include diamine compounds such as aliphatic diamines having 2 to 20 carbon atoms such as trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 3-methylpentamethylenediamine, and metaxylenediamine. Further, dicarboxylic _{^{acids, HOOC- (R 3) m -COOH}} (R 3: the molecular chain of a hydrocarbon of 3 to 20 carbon atoms, m: 0 or 1) can be represented by, for example, oxalic acid, succinic acid And aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid.
As the polyamide that forms the hard segment, polyamide obtained by ring-opening polycondensation of lauryl lactam, ε-caprolactam, or udecan lactam can be preferably used.

Moreover, as a polymer which forms a soft segment, polyester, polyether, etc. are mentioned, for example, Polyethylene glycol, propylene glycol, polytetramethylene ether glycol, ABA type | mold triblock polyether etc. are mentioned, for example. 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 also be used.
Here, the “ABA type triblock polyether” means a polyether represented by the following general formula (3).

General formula (3)

  In general formula (3), x and z represent the integer of 1-20. 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 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.

  As a combination of a hard segment and a soft segment, each combination of the hard segment and the soft segment mentioned above can be mentioned. Among these, 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, and A combination of lauryl lactam ring-opening polycondensate / ABA type triblock polyether is preferred, and a combination of lauryl lactam ring opening polycondensate / ABA type triblock polyether is particularly preferred.

  The number average molecular weight of the polymer (polyamide) forming the hard segment is preferably 300 to 15000 from the viewpoint of melt moldability. Moreover, as a number average molecular weight of the polymer which forms a soft segment, 200-6000 are preferable from a viewpoint of toughness and low temperature flexibility. Furthermore, the mass ratio (x: y) to the hard segment (x) and the soft segment (y) is preferably 50:50 to 90:10, and more preferably 50:50 to 80:20, from the viewpoint of moldability. .

  The polyamide-based thermoplastic elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method.

  Examples of commercially available products of polyamide-based thermoplastic elastomer include UBE Kosan's “UBESTA XPA” series (for example, XPA9063X1, XPA9055X1, XPA9048X2, XPA9048X1, XPA9040X1, XPA9040X2XPA9044, etc.) and “Vestamide” of Daicel Eponic Corporation. ”Series (for example, E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, EX9200, E50-R2, etc.) and the like can be used.

  The polyamide-based thermoplastic elastomer is suitable as a resin material because it satisfies the performance required as a tire frame from the viewpoint of elastic modulus (flexibility), strength, and the like.

(Polyester thermoplastic elastomer)
As the polyester-based thermoplastic elastomer, for example, at least a polyester is crystalline and a hard segment having a high melting point is formed, and another polymer (eg, polyester or polyether) is amorphous and has a low glass transition temperature. The material which forms is mentioned.

An aromatic polyester can be used as the polyester forming the hard segment. The aromatic polyester can be formed, for example, from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol. The aromatic polyester is preferably polybutylene terephthalate derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol, and further, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid Dicarboxylic acid components such as naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or ester-forming derivatives thereof, and a molecular weight of 300 or less Diols such as aliphatic diols such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, 1,4-cyclohexanedimethanol, tricyclodecane dimethyloyl Alicyclic diols such as ruthenium, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4 -(2-hydroxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4'-dihydroxy-p-terphenyl, 4,4'-dihydroxy-p-quarter It may be a polyester derived from an aromatic diol such as phenyl, or a copolymer polyester in which two or more of these dicarboxylic acid components and diol components are used in combination. It is also possible to copolymerize a trifunctional or higher polyfunctional carboxylic acid component, polyfunctional oxyacid component, polyfunctional hydroxy component and the like in a range of 5 mol% or less.
Examples of the polyester forming the hard segment include polyethylene terephthalate, polybutylene terephthalate, polymethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like, and polybutylene terephthalate is preferable.

Moreover, as a polymer which forms a soft segment, aliphatic polyester, aliphatic polyether, etc. are mentioned, for example.
Aliphatic polyethers include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, poly (propylene oxide) And ethylene oxide addition polymer of glycol, and a copolymer of ethylene oxide and tetrahydrofuran.
Examples of the aliphatic polyester include poly (ε-caprolactone), polyenantlactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate.
Among these aliphatic polyethers and aliphatic polyesters, from the viewpoint of the elastic properties of the resulting polyester block copolymer, poly (tetramethylene oxide) glycol, poly (propylene oxide) glycol ethylene oxide adduct, poly (ε- Caprolactone), polybutylene adipate, polyethylene adipate and the like are preferred.

  The number average molecular weight of the polymer forming the soft segment is preferably 300 to 6000 from the viewpoint of toughness and low temperature flexibility. Furthermore, the mass ratio (x: y) between the hard segment (x) and the soft segment (y) is preferably 99: 1 to 20:80, more preferably 98: 2 to 30:70, from the viewpoint of moldability. .

  As a combination of the above-mentioned hard segment and a soft segment, each combination of the above-mentioned hard segment and a soft segment can be mentioned, for example. Among these, a combination in which the hard segment is polybutylene terephthalate and the soft segment is an aliphatic polyether is preferable, and a combination in which the hard segment is polybutylene terephthalate and the soft segment is poly (tetramethylene oxide) glycol is further included. preferable.

  Examples of commercially available polyester-based thermoplastic elastomers include “Hytrel” series (for example, 3046, 5557, 6347, 4047, 4767, etc.) manufactured by Toray DuPont Co., Ltd., and “Perprene” series manufactured by Toyobo Co., Ltd. (For example, P30B, P40B, P40H, P55B, P70B, P150B, P280B, P450B, P150M, S1001, S2001, S5001, S6001, S9001, etc.) can be used.

  The polyester-based thermoplastic elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method.

(Polyamide thermoplastic resin)
Examples of the polyamide-based thermoplastic resin include those having a melting point of 160 ° C. or higher among the polyamides forming the hard segment of the above-mentioned polyamide-based thermoplastic elastomer. Specifically, polyamide-based thermoplastic resins include polyamide (amide 6) obtained by ring-opening polycondensation of ε-caprolactam, polyamide (amide 11) obtained by ring-opening polycondensation of undecane lactam, and ring-opening polycondensation of lauryl lactam. Examples thereof include polyamide (amide 12), polyamide (amide 66) obtained by polycondensation of diamine and dibasic acid, and polyamide (amide MX) having metaxylenediamine as a structural unit.

The amide 6 can be represented by, for example, {CO— (CH ₂ ) 5 —NH} _n . The amide 11 can be represented by, for example, {CO— (CH ₂ ) ₁₀ —NH} _n . The amide 12 can be represented by, for example, {CO— (CH ₂ ) ₁₁ —NH} _n . The amide 66 can be represented by {CO (CH ₂ ) ₄ CONH (CH ₂ ) ₆ NH} _n , for example. Amide MX can be represented by the following structural formula (A-1), for example. Here, n represents the number of structural units.
As a commercially available product of amide 6, for example, “UBE nylon” series (for example, 1022B, 1011FB, etc.) manufactured by Ube Industries, Ltd. can be used. As a commercially available product of amide 11, for example, “Rilsan B” series manufactured by Arkema Co., Ltd. can be used. As a commercially available product of amide 12, for example, “UBE nylon” series (for example, 3024U, 3020U, 3014U, etc.) manufactured by Ube Industries, Ltd. can be used. As a commercially available product of amide 66, for example, “UBE nylon” series (for example, 2020B, 2015B, etc.) manufactured by Ube Industries, Ltd. can be used. As a commercially available product of amide MX, for example, “MX nylon” series (for example, S6001, S6021, S6011, etc.) manufactured by Mitsubishi Gas Chemical Co., Ltd. can be used.

  The polyamide-based thermoplastic resin may be a homopolymer formed only from the above structural unit, or may be a copolymer of the above structural unit and another monomer. In the case of a copolymer, it is preferable that the content rate of the said structural unit in each polyamide-type thermoplastic resin is 40 mass% or more.

(Polyester-based thermoplastic resin)
Examples of the polyester-based thermoplastic resin include polyester that forms the hard segment of the above-described polyester-based thermoplastic elastomer.
Specific examples of the polyester-based thermoplastic resin include polylactic acid, polyhydroxy-3-butylbutyric acid, polyhydroxy-3-hexylbutyric acid, poly (ε-caprolactone), polyenantlactone, polycaprylolactone, and polybutylene. Examples include aliphatic polyesters such as adipate and polyethylene adipate, and aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polystyrene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. Among these, from the viewpoint of heat resistance and processability, polybutylene terephthalate is preferable as the polyester-based thermoplastic resin.

  Examples of commercially available polyester-based thermoplastic resins include “Duranex” series (for example, 2000, 2002, etc.) manufactured by Polyplastics Co., Ltd., and “Novaduran” series (for example, 5010R5) manufactured by Mitsubishi Engineering Plastics Co., Ltd. 5010R3-2 etc.), “Toraycon” series (for example, 1401X06, 1401X31 etc.) manufactured by Toray Industries, Inc. can be used.

(Other thermoplastic resins and thermoplastic elastomers)
In addition to the above resin components, polystyrene-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, and olefin-based thermoplastic elastomers described in paragraphs [0069] to [0086] of International Publication No. 2014/175542 are also included in the present invention. Can be applied to.

The melting point of the resin material forming the tire skeleton is usually about 100 ° C. to 350 ° C., but is preferably about 100 ° C. to 250 ° C., more preferably 100 ° C. to 200 ° C. from the viewpoint of tire durability and productivity.
In addition, the resin material contains various additives such as rubber, elastomer, thermoplastic resin, various fillers (for example, silica, calcium carbonate, clay, etc.), plasticizers, color formers, and weathering agents, as desired. (Blend) may be used.

  The tensile modulus of elasticity defined in JIS K7113: 1995 of the resin material itself forming the tire skeleton is preferably 50 MPa to 1000 MPa, more preferably 50 MPa to 800 MPa, and particularly preferably 50 MPa to 700 MPa. When the tensile modulus of the resin material is 100 MPa to 1000 MPa, the rim can be assembled efficiently while maintaining the shape of the tire frame.

  The tensile strength specified in JIS K7113: 1995 of the resin material itself forming the tire skeleton is usually about 15 MPa to 70 MPa, preferably 17 MPa to 60 MPa, and more preferably 20 MPa to 55 MPa.

  The tensile yield strength specified in JIS K7113: 1995 of the resin material itself forming the tire skeleton is preferably 5 MPa or more, preferably 5 MPa to 40 MPa, and more preferably 5 MPa to 30 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 in JIS K7113: 1995 of the resin material itself forming the tire frame body 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 rim assembly property can be improved.

  The tensile elongation at break specified in JIS K7113: 1995 of the resin material itself forming the tire skeleton 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 assemblability is good, and it is difficult to break against a collision.

  The deflection temperature under load (at the time of 0.45 MPa load) defined in ISO 75-2 or ASTM D648 of the resin material itself forming the tire skeleton 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.

The thickness of the tire skeleton is 1 mm to 2.5 mm.
When the thickness of the tire skeleton is 1 mm or more, the shape as a tire is easily maintained and the durability is excellent. On the other hand, when the thickness of the tire skeleton is 2.5 mm or less, the occurrence of cracks when the tire is deformed (for example, bent) can be suppressed. Further, when the thickness is 2.5 mm or less, the process oil and the antioxidant are easily supplied from the tire frame body to the exterior member.
From the above viewpoint, the thickness of the tire frame body is preferably 1.2 mm to 2.5 mm, and more preferably 1.5 mm to 2.0 mm.

In the present specification, the thickness of the tire frame means the thickness of the thinnest part in the tire frame. A specific method for measuring the thickness is as follows.
The thickness of the center of the maximum bent part and the crown part of the side part of the tire frame is measured, and the thinner one is defined as the thickness of the tire frame.

<Exterior material>
The tire has an exterior member formed of a rubber material. The exterior member includes process oil B and anti-aging agent B. The quantitative relationship between the process oil B and the anti-aging agent B in the exterior member and the process oil A and the anti-aging agent A in the above-described tire frame is as described above.

The exterior member is disposed outside the tire frame body.
Examples of the exterior member include, for example, a tread member installed in a crown portion of a tire frame body, a side member installed in a side portion of the tire frame body, a chafer member installed in a bead portion of the tire frame body, and a rubber coating For example, a coating rubber in the case where the organic fiber or metal cord is used as a reinforcing material. The exterior member in the present invention is not necessarily the outermost layer of the tire of the present invention. For example, a decorative layer or a protective layer may be further provided on the outer surface of the exterior member.

[Process oil B]
The process oil B contained in the exterior member is not particularly limited, and a process oil or the like used as a softening agent for conventionally known rubber products can be used. Specifically, the same thing as the process oil A which can be included in the above-mentioned tire frame can be mentioned, and a preferable aspect is also the same.
The process oil B included in the exterior member may be the same as or different from the process oil A that can be included in the tire frame body. From the viewpoint of supplying process oil from the tire frame to the exterior member, it is preferable that the process oil A and the process oil B are the same.

  The content of the process oil B in the exterior member is preferably 0.1 parts by mass or more and 20 parts by mass or less, and 0.15 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of a rubber component in the rubber material described later. More preferred. However, when the tire skeleton includes the process oil A and does not include the anti-aging agent A, the content of the process oil B in the exterior member satisfies the relationship of the above formula 1.

[Anti-aging agent B]
The anti-aging agent B contained in the exterior member is not particularly limited, and an anti-aging agent used in a conventionally known rubber composition can be used. Specifically, the same thing as the anti-aging agent A which can be included in the above-mentioned tire frame body can be mentioned, and a preferable aspect is also the same.
The anti-aging agent B contained in the exterior member may be the same as or different from the anti-aging agent A that can be contained in the tire skeleton. From the viewpoint of supplying the anti-aging agent from the tire frame to the exterior member, the anti-aging agent A and the anti-aging agent B are preferably the same.

  The content of the anti-aging agent in the exterior member is preferably 0.5 parts by mass or more and 10 parts by mass or less, and 1.0 parts by mass or more and 5.0 parts by mass with respect to 100 parts by mass of the rubber component in the rubber material described later. The following is more preferable. However, when the tire frame includes an anti-aging agent and no process oil, the content of the anti-aging agent in the exterior member satisfies the relationship of the above formula 2.

[Rubber material]
The exterior member in the present invention is formed of a rubber material.
In the present invention, the “rubber material” includes at least rubber (rubber component) and may include other components such as additives.
The rubber component is not particularly limited. For example, natural rubber (NR); polyisoprene synthetic rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene rubber (NBR), Conjugated diene synthetic rubbers such as chloroprene rubber (CR) and butyl rubber (IIR); ethylene-propylene copolymer rubber (EPM); ethylene-propylene-diene copolymer rubber (EPDM); and rubbers such as polysiloxane rubber It is done.
These may be used alone or in combination of two or more.

  Of these, natural rubber (NR) and a mixture of natural rubber and styrene-butadiene copolymer rubber (SBR / NR) are preferable from the viewpoint of wear resistance.

  Examples of the additive include a reinforcing material such as carbon black, a filler, a vulcanizing agent, a vulcanization accelerator, a fatty acid or a salt thereof, a metal oxide, and the like, and these can be appropriately blended.

The exterior member is obtained, for example, by providing an unvulcanized rubber material in which the rubber component contained in the rubber material is in an unvulcanized state on the tire frame and vulcanizing the rubber by heating.
That is, for example, at least a part of the unvulcanized rubber contained in the unvulcanized rubber material is heated in a state of being provided on the tire frame body with or without the adhesive layer, and the unvulcanized rubber is vulcanized. By being vulcanized, an exterior member provided on the tire frame can be obtained.

There is no particular limitation on the heating means, a tire having a tire skeleton and an exterior member is placed in a mold and directly heated, placed in a heating zone, and contactless heating such as infrared or hot air Examples thereof include a method of heating by means and a method of heating using ultrasonic waves and microwaves.
Above all, from the viewpoint of controllability of heat quantity, safety, and simplicity of the apparatus, it is allowed to stand in a hot air drying apparatus at a normal pressure and a predetermined heating temperature, and after heating for a predetermined time, the molded product is taken out at room temperature. It is preferable to cool to.
The pressure in this vulcanization treatment is 10 mmHg or less using a normal vacuum pump device for the purpose of promoting the removal of components such as moisture and monomers contained in the molded product in addition to the desired improvement in heat resistance. When heating in a reduced pressure state, or for the purpose of promoting adhesion with a molded product of a different material or the same material, use a normal compressor device to heat at a high pressure of 0.5 MPa or more. The pressure can be appropriately set according to the above.

In the vulcanization process, when the resin material constituting the molded article is placed under a temperature condition equal to or higher than the glass transition temperature (Tg), micro molecular motion occurs and the elastic modulus of the material is significantly reduced, that is, softens. . Therefore, when stress is applied to the molded product during the vulcanization treatment, it may be easily deformed. For this reason, in order to prevent undesired deformation, a jig made of a material such as iron, stainless steel, aluminum, titanium, etc. that retains the shape of the desired molded product and does not deform at the heating temperature is used. It can arrange | position with the shape along a shape, and can also prevent a deformation | transformation.
By passing through this vulcanization treatment, the tire can achieve both heat resistance and rolling friction resistance at a high level.

~ Thickness of exterior member ~
The thickness of the exterior member is preferably 0.5 mm to 10 mm, more preferably 1 mm to 5 mm, and further preferably 1.5 mm to 3 mm. When the outer layer member is formed by laminating a plurality of members, the total thickness of the laminated body serving as the outer layer member may be included in the above range.
When the thickness of the exterior member is 0.5 mm or more, it is advantageous for ride comfort and wear resistance. On the other hand, when the thickness of the exterior member is 10 mm or less, the anti-aging agent and the process oil can be sufficiently diffused, which is advantageous for light resistance.

When the tire has a tread member as an exterior member, the thickness of the tread member can be appropriately selected depending on the shape, but the thickness of the thickest part (thickest part) is preferably 1.5 mm to 15 mm. 2.0 mm to 13 mm is more preferable, and 3.0 mm to 10 mm is further preferable.
When the thickness of the thickest part of the tread member is 15 mm or less, the unvulcanized state and the over-vulcanized state of the tread surface can be suppressed.
The thickest part refers to the thickest part of the thickness from the surface of the tread member toward the center of the tire and the surface where the tread member and the adjacent member contact.

When the tire has a side member as an exterior member, the thickness of the side member can be appropriately selected depending on the shape, but the thickness of the thinnest part (thinnest part) is preferably 0.5 mm to 10 mm. 1.0 mm to 8.0 mm, more preferably 1.5 mm to 5.0 mm.
When the thickness of the thinnest part of the side member is 1.0 mm or more, it is easy to exert a protective effect on the tire frame body by covering the rubber material.
The thinnest part refers to the thinnest part of the thickness from the surface of the side member to the surface in contact with the member adjacent to the side member.

<Adhesive layer>
The tire has an adhesive layer formed of a composition containing resin or rubber, or an adhesive formed of a composition containing resorcinol-formaldehyde-latex (RFL) between the tire frame body and the exterior member. It is preferable to have a layer.
When the tire has an adhesive layer, the adhesion between the tire frame body and the exterior member is further improved.

  The thickness of the adhesive layer is preferably 5 μm to 200 μm, more preferably 20 μm to 150 μm. When the thickness of the adhesive layer is 5 μm or more, the adhesion between the tire frame body and the exterior member is further improved. On the other hand, when the thickness of the adhesive layer is 200 μm or less, the process oil and the antioxidant are easily supplied from the tire frame to the exterior member.

[Composition containing resin or rubber]
The composition containing a resin or rubber is not particularly limited. For example, an epoxy resin, a phenol resin, an olefin resin, a polyurethane resin, a vinyl resin (for example, vinyl acetate resin, polyvinyl alcohol) Resin, etc.), and a composition containing one or more of synthetic rubbers as a main ingredient.
Among these, from the viewpoint of adhesion between the tire skeleton and the exterior member, a composition containing at least one selected from an epoxy resin, a phenol resin, an olefin resin, and a vinyl resin is preferable. More preferred is a composition containing at least one selected from phenolic resins.

(Epoxy resin)
The epoxy resin that can be contained in the resin or rubber-containing composition is not particularly limited, and examples thereof include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, and phenol novolac type epoxy resins. , Novolak type epoxy resin such as cresol novolac type epoxy resin, aliphatic epoxy resin, cycloaliphatic epoxy resin, polyfunctional epoxy resin, biphenyl type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type Examples include epoxy resins, alcohol-type epoxy resins such as hydrogenated bisphenol A-type epoxy resins, rubber-modified epoxy resins, and urethane-modified epoxy resins.
You may use these individually by 1 type or in combination of 2 or more types. Among these, bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin are more preferable in terms of being widely available in grades having different molecular weights and capable of arbitrarily setting adhesiveness and reactivity. .

(Phenolic resin)
The phenolic resin that can be included in the resin or rubber-containing composition is not particularly limited, and examples thereof include various phenols such as phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin, and the like. Condensates with formaldehyde (for example, alkylphenol resins, xylene formaldehyde resins, etc.), resols obtained by addition reaction of the above various phenols and formaldehyde with an alkali catalyst, and condensation reactions between the above various phenols and formaldehyde with an acid catalyst. And novolaks obtained from the above.
You may use these individually by 1 type or in combination of 2 or more types. Among these, formaldehyde is more preferable in terms of physical properties and workability.

(Rubber)
The rubber that can be contained in the resin or rubber-containing composition is not particularly limited, and examples thereof include conjugates such as halogenated rubber (chlorinated rubber), nitrile rubber, NR, IR, BR, SBR, CR, and IIR. Examples include diene synthetic rubber, EPM, and EPDM. You may use these individually by 1 type or in combination of 2 or more types.

-Adjustment of solvent adhesive-
When the adhesive layer is formed of a composition containing a resin or rubber, it can be performed by first adjusting a solvent-based adhesive in which resin or rubber is dissolved or dispersed in a solvent and applying the adhesive.
Solvent adhesives, for example, improve the wettability to the adherend by using the polarity of the solvent used as the solvent, and can penetrate into the irregularities and gaps on the surface of the adherend. Good adhesion to both the tire frame body and the exterior member can be exhibited. Therefore, if an adhesive layer formed by applying a solvent-based adhesive is interposed between the tire frame body and the exterior member, the tire frame body and the exterior member can be firmly fixed, and the adhesiveness is improved. improves.

-Solvent-
Solvent-based adhesives can be adjusted to solid content by arbitrarily diluting the solvent in accordance with the coating method and coating device, but are diluted with a solvent from the viewpoints of ease of forming the adhesive layer and ensuring adhesive performance. The solid content is preferably 5% by mass to 50% by mass.

In the solvent-based adhesive, the solvent used as the solvent is not particularly limited, and may be appropriately selected according to the main component (main agent). Specific examples include alcohol solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol and n-butanol, aromatic hydrocarbon solvents such as toluene and xylene, ether solvents such as dioxane, tetrahydrofuran and ethylene glycol dimethyl ether. Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ester solvents such as ethyl acetate, isopropyl acetate, butyl acetate, glycol solvents such as methyl glycol, ethyl glycol, isopropyl glycol, acetonitrile, N, N -Solvents such as dimethylformamide can be mentioned.
Commercially available products may be used for these adhesives, for example, Metallock series (for example, “Metalock R-46”, “Metalock PH-56”, “Metalock F-112”, etc.) manufactured by Toyo Chemical Research Co., Ltd. A Chemlock series (for example, “Chemlock 6250”, “Chemlock 210”, etc.) manufactured by Road Corporation can be used as appropriate.

  In addition to the resin as the main component, the solvent-based adhesive includes additives such as the process oil, the anti-aging agent, the tackifier resin, and the heat stabilizer, as necessary. It may be.

[Composition containing RFL]
The composition containing RFL is a composition containing RFL as a main component. RFL is a solution of a composition consisting of a resorcinol-formaldehyde condensate obtained by a resolation reaction and a latex.
The resorcinol-formaldehyde condensate is a reaction product obtained by subjecting resorcinol and formaldehyde or a relatively low molecular weight resorcinol-formaldehyde condensate and formaldehyde to a resorcinol-formaldehyde condensation reaction by a so-called resole reaction. Containing a structural unit derived from formaldehyde and a structural unit derived from resorcinol, maintaining a state where the structural unit derived from formaldehyde is stoichiometrically insufficient, and thereby the resin member can be maintained soluble at a low molecular weight. .

  Examples of the latex include acrylic rubber latex, acrylonitrile-butadiene rubber latex, isoprene rubber latex, urethane rubber latex, ethylene-propylene rubber latex, butyl rubber latex, chloroprene rubber latex, silicone rubber latex, styrene-butadiene rubber latex, and natural rubber latex. Vinyl pyridine-styrene-butadiene rubber latex, butadiene rubber latex, butyl rubber latex, carboxylated butadiene / styrene copolymer latex or chlorosulfonated polyethylene latex, nitrile rubber latex and the like.

  Among these, vinylpyridine-styrene-butadiene rubber latex is preferable from the viewpoint of adhesiveness with a rubber member. Furthermore, in this case, a copolymer rubber latex having a double structure composed of two-stage polymerization of vinylpyridine, styrene and butadiene is more preferable. These may be used alone or as a mixture of two or more thereof, or may be allowed to coexist in the reaction system for reacting resorcinol and formaldehyde before the reaction.

  The copolymer rubber latex having a double structure composed of two-stage polymerization of vinylpyridine, styrene and butadiene is a copolymer rubber latex of vinylpyridine, styrene and butadiene, and (i) the styrene content is 10% by mass to 60% by mass. %, A butadiene content of less than 60% by weight and a vinyl pyridine content of 0.5% by weight to 15% by weight, and then (ii) a styrene content of 10% by weight A monomer mixture composed of 40% by mass, a butadiene content of 45% by mass to 75% by mass and a vinylpyridine content of 5% by mass to 20% by mass is lower than the styrene content used in the polymerization in (i). It can be obtained by polymerization with a styrene content.

-Preparation of RFL adhesive-
When forming an adhesive layer with a composition containing RFL, it can be performed by first adjusting an RFL adhesive and applying the adhesive.
The RFL adhesive has a structure in which a polymer obtained by resorcinol-resorcinol-formaldehyde condensate and a latex are sufficiently entangled three-dimensionally. For this reason, in the preparation of the RFL adhesive, it is preferable that the resolation reaction is performed in a solution in which latex is dispersed.
As the solution used in this case, acidic, neutral or alkaline water, or a solvent such as acetone or alcohol can be used. However, latex has low water solubility in the neutral pH range, and resorcinol / formaldehyde in aging. In order to sufficiently perform the condensation reaction (resorification reaction), it is preferable to use alkaline or neutral water. This resolation reaction is usually carried out at pH 8.0 or higher, preferably pH 8.5 to 10.0.

Here, alkaline water is obtained by dissolving sodium hydroxide, lithium hydroxide, potassium hydroxide, animmonium hydroxide, or an organic amine such as monomethylamine or ammonia in water. Further, any anionic surfactant can be used by being dispersed in neutral water by a ball mill or a sand mill. In this case, in order to effectively develop the adhesive force, it is necessary to make the amount of the surfactant small so that the dispersed state does not deteriorate.

  The molar ratio (F / R) between formaldehyde (F) and resorcinol (R) in the RFL solution and the ratio of resorcinol and formaldehyde total mass (RF) to the solid content mass (L) of the total latex (RF / L) Etc. can be appropriately selected according to the purpose.

  Examples of the method of reacting the resorcinol-formaldehyde condensate obtained by the resorification while mixing with latex include, for example, a raw material of resorcinol-formaldehyde condensate (resorcinol, a relatively low molecular weight resorcinol-formaldehyde in an alkaline liquid) Condensate, formaldehyde) and latex are mixed, and at the beginning of the reaction, it is not mixed with latex, and resorcinol-formaldehyde condensate raw material is started under alkaline liquid condition. Examples thereof include a method in which a reaction intermediate having a low condensation degree is mixed with latex at a stage and the reaction is continued.

~ Adhesion method ~
The adhesion between the tire frame body and the exterior member by the RFL adhesive or the solvent adhesive (hereinafter collectively referred to as the RFL adhesive and the solvent adhesive) is, for example, an unvulcanized exterior After the adhesive is applied to the structural member or the tire frame body, these are stuck, and then heat treatment or the like can be performed as necessary to complete the process.
The pretreatment performed on each member before applying the adhesive is preferably selected as appropriate. For example, the adhesive force can be strengthened by pre-treating the adhesive surface between the tire frame body and the exterior member before applying the adhesive. Examples of such pretreatment methods include electron beam, microwave, corona discharge, plasma discharge, and degreasing treatment. It is also possible to pre-process using simply buffing or file.

  The place where the pretreatment is performed is preferably a tire frame from the viewpoint of sufficient adhesion.

  Here, as a pretreatment, an adhesive treatment (undercoating treatment) other than the above-described adhesive may be performed. The undercoating agent used for the undercoating treatment is not particularly limited as long as it is used when the tire frame body is more sufficiently adhered to the exterior member with an adhesive. For example, an undercoat composition having a water-soluble polymer containing an epoxy compound and an isocyanate compound described in JP-A-2009-191395, an alkylated bisphenol and acrylic (methacrylic) acid described in Table 02-094962 Examples thereof include an undercoat composition having a copolymer and an undercoat composition containing a vinyl chloride plastisol-based polymer described in JP-A No. 11-001658. The undercoat treatment agent and the adhesive may be mixed in the application process.

  The thickness of the undercoat layer formed by the undercoat treatment agent is preferably 1 μm to 15 μm.

  Moreover, the adhesive strength after adhesion | attachment can be strengthened more by making the surface roughness of a tire frame body into a certain range. As the surface roughness of the tire skeleton, for example, arithmetic mean roughness (Ra) is preferably 0.1 μm or more. By being 0.1 μm or more, the adhesion area of the tire skeleton in contact with the adhesive is increased, so that the adhesion can be more sufficiently achieved. Further, from the viewpoint of further reducing the dripping of the adhesive, it is preferably 0.5 μm or more, more preferably 1 μm or more. Similarly, Ra is preferably 10 μm or less from the viewpoint of increasing the adhesive strength.

  Examples of the method for applying the adhesive include dipping, bar coating, kneader coating, curtain coating, roller coating, spin coating, brush coating, and spraying.

  When the tire skeleton and the unvulcanized exterior member are bonded with an adhesive, it is preferable to further perform a vulcanization treatment. The vulcanization treatment in this case may be carried out by a known method, and examples thereof include methods described in JP-A Nos. 11-048264, 11-029658, 2003-238744, and the like. For rubber vulcanization, for example, a reinforcing material such as carbon black, a filler, a vulcanizing agent, a vulcanization accelerator, a fatty acid or a salt thereof, a metal oxide, or the like is appropriately blended with the unvulcanized rubber. It can carry out by heating after kneading using a remixer.

<Reinforcement cord member>
The tire may have a reinforcing cord member wound in the circumferential direction on the outer peripheral portion of the tire skeleton. When the reinforcing cord member is wound around the outer periphery of the tire frame body, the durability of the tire (puncture resistance, cut resistance, tire circumferential rigidity, etc.) is improved. When the circumferential rigidity is improved, creep of the tire frame formed of a resin material (a phenomenon in which the plastic deformation of the tire frame increases with time under a certain stress) is suppressed.
The reinforcing cord member may be coated with at least a part of the member with a coating layer containing a coating resin, and the coating resin is preferably the same type of resin material as the resin material forming the tire skeleton, It is preferable that the coating layer contains an anti-aging agent and process oil similar to those of the above-described tire frame. The content of the anti-aging agent and the process oil in the coating layer is the same as the content of the anti-aging agent and the process oil in the tire frame described above.

  As the reinforcing cord member, a metal cord or the like used in a conventional rubber tire can be appropriately used. For example, a monofilament (single wire) of a metal fiber, a multifilament (twisted steel cord or the like) Line). The cross-sectional shape and size (diameter) of the reinforcing cord member are not particularly limited, and those suitable for a desired tire can be selected and used as appropriate.

  One or a plurality of reinforcing cord members may be wound in the circumferential direction of the tire frame body, or may be continuously wound in a spiral shape in the circumferential direction. Further, the reinforcing cord member may be wound in the circumferential direction at a uniform interval in the width direction of the tire frame body, or may be wound in an intersecting manner.

  The tensile elastic modulus of the reinforcing cord member itself (hereinafter, unless otherwise specified, “elastic modulus” means a tensile elastic modulus) is usually about 100,000 MPa to 300000 MPa, and 120,000 MPa to 270000 MPa. It is preferably 150,000 MPa to 250,000 MPa. The tensile elastic modulus of the reinforcing cord member is calculated from the inclination of a stress-strain curve drawn on a tensile tester using a ZWICK type chuck.

  The breaking elongation (tensile breaking elongation) of the reinforcing cord member itself is usually about 0.1% to 15%, preferably 1% to 15%, and more preferably 1% to 10%. The tensile breaking elongation of the reinforcing cord member can be obtained from the strain by drawing a stress-strain curve using a ZWICK chuck in a tensile tester.

In the reinforcing cord member, at least a part of the member may be covered with a coating resin. Specifically, for example, a state in which a part or the whole of the outer periphery of the reinforcing cord member is covered with a covering layer containing a coating resin, a reinforcing cord covering layer formed including the covering resin, In a case where the reinforcing cord member is provided on the outer peripheral portion of the tire frame body with a part interposed therebetween, a part or all of the reinforcing cord member is embedded in the reinforcing cord covering layer.
In the reinforcing cord member, it is preferable that the entire portion serving as the interface between the reinforcing cord member and the tire frame body is covered with a coating layer, and it is more preferable that the entire surface of the reinforcing cord member is covered with a coating layer. .

  The coating resin contained in the coating layer is preferably selected in consideration of adhesiveness with the resin material used for the tire frame body. In particular, when the same kind of resin is used for the resin material forming the tire frame body and the coating resin contained in the coating layer, the adhesion between the tire frame body and the coating layer can be further enhanced. For example, when a polyamide-based thermoplastic resin is used as the coating resin included in the coating layer, it is preferable to use a polyamide-based thermoplastic elastomer as the resin material for forming the tire frame.

The coating layer that covers the reinforcing cord member preferably contains at least one thermoplastic material selected from thermoplastic resins and thermoplastic elastomers.
Examples of the thermoplastic resin and the thermoplastic elastomer contained in the coating layer include the same type as the thermoplastic resin used in the tire frame body described above.

The thermoplastic material contained in the coating layer is preferably at least one selected from polyamide thermoplastic resins, polyester thermoplastic resins, polyamide thermoplastic elastomers, and polyester thermoplastic elastomers, and polyamide thermoplastics More preferably, it is at least one selected from an elastomer and a polyester-based thermoplastic elastomer.
Specific examples of the polyamide-based thermoplastic resin, the polyester-based thermoplastic resin, the polyamide-based thermoplastic elastomer, and the polyester-based thermoplastic elastomer are as described above.

Even if the coating layer includes both a thermoplastic resin and a thermoplastic elastomer, and has a sea phase that is a matrix phase containing the thermoplastic resin and an island phase that is a dispersed phase containing the thermoplastic elastomer. Good.
The covering layer has a sea-island structure in which a thermoplastic elastomer is dispersed in a matrix of a thermoplastic resin, whereby the pulling resistance of the reinforcing cord member to the covering layer can be improved.

  The mass ratio (p / e) between the thermoplastic resin (p) and the thermoplastic elastomer (e) in the coating layer in the case of the above embodiment is the sea phase containing the thermoplastic resin and the island phase containing the thermoplastic elastomer. From the viewpoint of easily forming the sea-island structure to be configured, it is preferably 95/5 to 55/45, more preferably 90/10 to 60/40, and 85/15 to 70/30. Is particularly preferred.

  The fact that the island phase containing the thermoplastic elastomer is finely dispersed in the sea phase containing the thermoplastic resin can be confirmed by photographic observation using an SEM (scanning electron microscope).

  Further, the size of the island phase containing the thermoplastic elastomer (the major axis of the island phase) is preferably about 0.4 μm to 10.0 μm, more preferably about 0.5 μm to 7 μm, and more preferably 0.5 μm to A thickness of about 5 μm is particularly preferable. The size of each phase can be measured using an observation photograph using an SEM (scanning electron microscope).

~ Example of laminated structure ~
The tire includes a tire frame body and an exterior member.
Examples of the exterior member include a tread member, a side member, and a chafer member formed of a rubber material.
The tire frame body is not particularly limited as long as it is formed of a resin material.

The tire may have a laminated structure in which the tire frame body and the exterior member are directly laminated, and the tire has a laminated structure in which a reinforcing cord member is provided on the tire frame body and the exterior member is laminated thereon. You may have, and you may have the laminated structure which provided the contact bonding layer between the tire frame body and the exterior member.
The tire may have a layer other than the adhesive layer between the tire frame body and the exterior member. The layer other than the adhesive layer is not particularly limited as long as it does not inhibit the movement of the process oil and the antioxidant.
As a layer that does not hinder the movement of process oil and anti-aging agent, a layer containing the same resin component as the resin component contained in the resin material forming the tire skeleton described above, or a rubber material forming the aforementioned exterior member And a layer containing the same rubber component as the rubber component contained in. On the other hand, examples of the layer that easily inhibits the movement of the process oil and the antioxidant include a layer containing a highly polar resin (for example, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH)).

FIG. 1 (A) to FIG. 1 (D) show specific examples (layer configuration) of the laminated structure in the tire of the present invention. The layer configuration shown in FIG. 1 indicates that they are laminated and bonded in this order.
Note that the layer configuration of the tire of the present invention is not limited to the layer configuration shown in FIG.

In FIG. 1A, exterior members 30 are laminated in this order on a tire frame (tire case) 17.
For example, as shown in FIG. 1 (B), the tire skeleton 17 and the exterior member 30 may be laminated via an adhesive layer 26C.
In FIG. 1C, a reinforcing cord member 26 is disposed on the tire frame body 17, and an exterior member 30 is laminated on these surfaces.
For example, as shown in FIG. 1D, a reinforcing cord member 26 is disposed on the tire skeleton body 17, and an exterior member 30 is laminated on these surfaces via an adhesive layer 26C. can do.

Hereinafter, tires according to embodiments of the present invention will be described with reference to the drawings. In addition, each figure shown below (FIG.2 and FIG.3) is the figure shown typically, and the magnitude | size and shape of each part are exaggerated suitably for easy understanding.
Moreover, in 1st Embodiment and 2nd Embodiment, a tire frame is called a tire case.

<First Embodiment>
A first embodiment of a tire according to the present invention will be described with reference to the drawings.
As shown in FIG. 2 (A), the tire 10 includes a pair of bead portions 12 contacting the bead seat 21 and the rim flange 22 of the rim 20 shown in FIG. A tire case 17 comprising: a side portion 14 extending in the direction of a tire; and 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. ing. The adhesive layer is located between the crown portion 16 (outer peripheral portion) of FIG. 2A and the tread 30 that is a rubber member, and is formed along the outer periphery of the crown portion 16. Further, when a rubber member is further provided on the outer peripheral portion of the side portion 14, an adhesive layer may be formed between the rubber member and the side portion 14. Furthermore, the adhesive layer may have a different layer thickness depending on the location, for example, it may be thick at the center of the crown portion and thin near the side portion 14.

  In the first embodiment, the tire case 17 is formed of a single resin material (for example, a polyamide-based thermoplastic elastomer). However, the present invention is not limited to this configuration, and the conventional general rubber pneumatic is used. Similarly to the tire, a resin material having different characteristics for each part of the tire case 17 (side portion 14, crown portion 16, bead portion 12, etc.) may be used. 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, the crown portion 16 and the like), and the reinforcing material is provided. The tire case 17 may be reinforced.

  The tire case 17 of the first embodiment is obtained by joining a pair of tire case half bodies (tire case pieces) 17A formed of a resin material. The tire case body half body 17A is formed by joining one bead portion 12, one side portion 14, and a half-width crown portion 16 together with an annular tire case body half body 17A having the same shape formed by injection molding or the like. It is formed by facing each other at the tire equatorial plane. 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 body 17A formed of the resin material can be molded by, for example, vacuum molding, pressure molding, injection molding, melt casting, or the like. For this reason, it is not necessary to perform vulcanization when forming a tire case, compared to the case where a tire case is molded with rubber as in the prior art, and the manufacturing process can be greatly simplified and molding time can be omitted. it can.
In the first embodiment, the tire case half 17A has a left-right symmetric shape, that is, one tire case half 17A and the other tire case half 17A have the same shape. There is also an advantage that only one type of mold for molding the half body 17A is required.

  In this embodiment, as shown in FIG. 2 (B), an annular bead core 18 made of a steel cord is embedded in the bead portion 12, similar to 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 the first embodiment, a material having a better sealing property than a resin material constituting the tire case 17 at a portion that contacts the rim 20 of the bead portion 12 or at least a portion that contacts the rim flange 22 of the rim 20, for example, An annular sealing layer 24 made of 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 better sealing properties than the resin material constituting the tire case 17, a softer material than the resin material constituting the tire case 17 can be used. 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 resin material which is more excellent in the sealing performance than the said resin material. Examples of such other resin materials include polyurethane resins, polyolefin resins, polystyrene thermoplastic resins, polyester resins, and the like, and blends of these resins with rubbers or elastomers. Thermoplastic elastomers can also be used, for example, polyester-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polystyrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers, or combinations of these elastomers or blends with rubber. Thing etc. are mentioned.

  As shown in FIG. 2 (A), a tread 30 is disposed as an exterior member formed of a rubber material on the tire diameter outer peripheral side of the crown portion 16 of the tire case 17.

  The laminated structure of the tire will be described with reference to FIG. FIG. 3 is a cross-sectional view of a laminated structure in which the crown portion 16, the adhesive layer 26C, and the tread 30 of the tire case 17 are laminated, and the crown portion 16 and the tread 30 are bonded via the adhesive layer 26C. .

The rubber used for the tread 30 is preferably a rubber of the same type as that used in conventional rubber pneumatic tires. Further, the tread 30 is formed with a tread 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 forming process)
First, tire case halves supported by a 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 of the resin material forming the tire case. When the joining portion of the tire case half is heated and pressurized by the joining mold, the joining 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 softening or melting in advance by irradiation with hot air, infrared rays, or the like, and pressurizing with a joining mold.

The resin material forming the tire case can be obtained by kneading a resin component (for example, polyamide-based thermoplastic elastomer), process oil A, and anti-aging agent A with a twin screw extruder.
The content a1 of the process oil A in the resin material is 0.5 to 15 parts by mass with respect to 100 parts by mass of the rubber component in the rubber material of the exterior member described later, and the content a2 of the anti-aging agent A is It is 0.5 mass part-20 mass parts with respect to 100 mass parts of rubber components in the rubber material of an external member.

(Exterior member lamination process)
Next, an RFL adhesive is applied to the surface of the crown portion 16 of the tire case 17 that is in contact with the crown portion 16 of the tread 30. In the application, a commonly used application or coating method or apparatus can be used without particular limitation, but a knife coating method, a bar coating method, a gravure coating method, a spray method, and a dipping method can be used. Among them, it is preferable to use a knife coating method, a bar coating method, or a gravure coating method in terms of uniform application and coating of the adhesive.
The adhesive used in the exterior member laminating step is not limited to the RFL adhesive.

A belt-shaped tread 30 that is an unvulcanized rubber material is wound around the outer peripheral surface of the tire case 17 by one turn, and the tread 30 is attached to the outer peripheral surface of the tire case 17 using an RFL adhesive. In addition, the tread 30 can use the rubber material obtained by kneading | mixing a rubber component, the process oil B, and the anti-aging agent B with a Banbury mixer.
The content b1 of the process oil B and the content b2 of the anti-aging agent B in the rubber material are at least one of the relationship between a1 and b1 represented by Formula 1 or the relationship between a2 and b2 represented by Formula 2. It is selected from the amount that satisfies.

(Vulcanization process)
Next, the tire case 17 to which the tread 30 is adhered is accommodated in a vulcanizing can or a mold and vulcanized. By performing vulcanization, a chemical bond is newly formed between the latex rubber and diene rubber of the RFL adhesive, and as a result, the tread 30 formed of the rubber material and the resin material are used. Bonding with the formed tire case becomes stronger.

  And if the sealing layer 24 which consists of a soft material softer than a resin material is adhere | attached on the bead part 12 of the tire case 17 using an adhesive agent etc., the tire 10 will be completed.

  And if the sealing layer 24 which consists of vulcanized rubber is adhere | attached on the bead part 12 of the tire case 17 using an adhesive agent etc., the tire 10 will be completed.

  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 has this configuration. It is not limited and a perfect tube shape may be sufficient.

<Second Embodiment>
Next, a second embodiment of the tire of the present invention will be described with reference to the drawings. Similar to the first embodiment described above, the tire according to the second embodiment has a cross-sectional shape similar to that of a conventional general rubber pneumatic tire. For this reason, in the following figures, the same number is attached | subjected about the structure similar to the said 1st Embodiment.
As shown in FIG. 4A, the tire 200 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. A tire case 17 comprising: a side portion 14 extending in the direction of a tire; and 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. ing. The adhesive layer is located between the crown portion 16 (outer peripheral portion) of FIG. 4A and the tread 30 that is a rubber member. Further, when a rubber member is further provided on the outer peripheral portion of the side portion 14, an adhesive layer may be formed between the rubber member and the side portion 14. Furthermore, the adhesive layer may have a different layer thickness depending on the location, for example, a thick portion where the reinforcing cord member 26 exists and a thin portion near the side portion 14.

  In the second embodiment, the tire case 17 is formed of a single resin material, that is, a polyamide-based thermoplastic elastomer material. However, the present invention is not limited to this configuration, and a conventional general rubber pneumatic tire is used. Similarly, a resin material having different characteristics may be used for each part of the tire case 17 (side portion 14, crown portion 16, bead portion 12 and the like). 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, the crown portion 16 and the like), and the reinforcing material is provided. The tire case 17 may be reinforced.

  Similar to the first embodiment, the tire case 17 of the second embodiment is formed by joining a pair of tire case body halves (tire case pieces) 17A made of a resin material.

  In the second embodiment, as shown in FIG. 4B, an annular bead core 18 made of a steel cord is embedded in the bead portion 12, similar to 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 the second embodiment, a material having a better sealing property than a resin material constituting the tire case 17 at a portion that contacts the rim 20 of the bead portion 12 or at least a portion that contacts the rim flange 22 of the rim 20, for example, An annular seal layer 24 made of rubber is formed. The preferable aspect of the seal layer 24 and the material that can be used are the same as those in the first embodiment.

  As shown in FIG. 4, in the second embodiment, a reinforcing cord member 26 having higher rigidity than the resin material constituting the tire case 17 is wound around the crown portion 16 in the circumferential direction of the tire case 17. . The reinforcing cord member 26 is spirally wound in a state in which at least a part is embedded in the crown portion 16 in a cross-sectional view along the axial direction of the tire case 17, and is provided with a reinforcing cord ( Resin-coated reinforcing cord) 28 is preferable. On the outer peripheral side of the resin-coated reinforcing cord 28 in the tire radial direction, a material having higher wear resistance than the resin material constituting the tire case 17, for example, a tread 30 that is a rubber member is disposed.

  The resin-coated reinforcing cord 28 formed by the reinforcing cord member 26 will be described with reference to FIG. FIG. 5 is a cross-sectional view along the tire rotation axis showing a state in which the reinforcing cord member 26 is embedded in the crown portion 16 of the tire case of the tire according to the present embodiment, and the tread 30 and the crown portion 16 further include the adhesive layer 26C. Is glued through. As shown in FIG. 5, the reinforcing cord member 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 resin-coated reinforcing cord 28 indicated by a broken line portion in FIG. 5 is formed together with a part of the outer peripheral portion of the case 17. The portion embedded in the crown portion 16 of the reinforcing cord member 26 is in close contact with the resin material constituting the crown portion 16 (tire case 17). As the reinforcing cord member 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 second embodiment, a steel cord is used as the reinforcing cord member 26.

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

As described above, the tread 30 is disposed on the outer circumferential side of the reinforcing cord member 26 in the tire radial direction. The rubber used for the tread 30 is preferably the same type of rubber as that used in conventional rubber pneumatic tires. Further, the tread 30 is formed with a tread 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 forming process)
The tire case in the second embodiment can be formed by the same method as the tire case in the first embodiment.

(Reinforcement cord member winding process)
Next, the reinforcing cord winding process will be described with reference to FIG. FIG. 6 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. 6, the cord supply device 56 is disposed on the downstream side of the reel 58 around which the reinforcing cord member 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 member 26 in the transport direction. The first roller 60, the first cylinder device 62 that moves the first roller 60 in the direction of moving toward and away from the tire outer peripheral surface, and the downstream of the reinforcing cord member 26 of the first roller 60 in the conveying direction. A second roller 64 disposed on the side, and a second cylinder device 66 that moves in a direction in which the second roller 64 contacts and separates from the tire outer peripheral surface. The second roller 64 can be used as a metal cooling roller. In the present embodiment, the surface of the first roller 60 or the second roller 64 is made of a fluororesin (in this embodiment, Teflon (registered trademark)) in order to suppress adhesion of a molten or softened thermoplastic resin material. ). In the present embodiment, the cord supply device 56 includes two rollers, the first roller 60 and the second roller 64, but the present invention is not limited to this configuration, and any 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 member 26 passes through an internal space in which hot air is supplied, and a discharge port 76 that discharges the heated reinforcing cord member 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 member 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 member 26 is heated to about 100 to 200 ° C.). The heated reinforcing cord member 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 member 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 member 26 is outer peripheral surface of the crown portion 16. Buried in At this time, since the heated reinforcing cord member 26 is embedded in the molten or softened resin material, the resin material and the reinforcing cord member 26 are in a state where there is no gap, that is, a close contact state. Thereby, air entry to the portion where the reinforcing cord member 26 is embedded is suppressed. In addition, by heating the reinforcing cord member 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 where the reinforcing cord member 26 is in contact is promoted. By doing in this way, it becomes easy to embed the reinforcement cord member 26 in the outer peripheral surface of the crown part 16, and air entry can be effectively suppressed.

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

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

  Next, an RFL adhesive is applied to the surface of the crown portion 16 of the tire case 17 that is in contact with the crown portion 16 of the tread 30. In the application, a commonly used application or coating method or apparatus can be used without particular limitation, but a knife coating method, a bar coating method, a gravure coating method, a spray method, and a dipping method can be used. Among them, it is preferable to use a knife coating method, a bar coating method, or a gravure coating method in terms of uniform application and coating of the adhesive.

  A belt-shaped tread 30 that is an unvulcanized rubber member is wound around the outer peripheral surface of the tire case 17 by one turn, and the tread 30 is attached to the outer peripheral surface of the tire case 17 using an RFL adhesive. In addition, the tread 30 can use the precure crown used for the retread tire conventionally known, for example. 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.

(Vulcanization process)
Next, the tire case 17 to which the tread 30 is adhered is accommodated in a vulcanizing can or a mold and vulcanized. By performing vulcanization, a chemical bond is newly formed between the latex rubber and the diene rubber of the RFL adhesive, and as a result, the tread 30 that is a rubber member and the tire that is a resin member. Bonding with the case becomes stronger.

  And if the sealing layer 24 which consists of a soft material softer than a resin material is adhere | attached on the bead part 12 of the tire case 17 using an adhesive agent etc., the tire 200 will be completed.

  And if the sealing layer 24 which consists of vulcanized rubber is adhere | attached on the bead part 12 of the tire case 17 using an adhesive agent etc., the tire 200 will be completed.

  Further, after the tire 200 is completed, an annealing process for heating the tire 10 may be further performed as in the first embodiment.

  The tire 200 of the second 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 has this configuration. It is not limited and a perfect tube shape may be sufficient.

  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 specifically described according to the present invention, but the present invention is not limited to these descriptions.

Example 1
<Formation of tire frame>
A polyamide-based thermoplastic elastomer (Ube Industries, XPA9055) and process oil (Idemitsu Kosan, Diana Process Oil PW380) were mixed so as to have the blending amounts shown in Table 1 below. A resin material was obtained by kneading with Technobell Co., Ltd., φ32 mm, L / D = 45).
The obtained resin material was molded into a tire skeleton by an injection molding machine to obtain a tire skeleton formed of the resin material.
The thickness of the center of the crown portion of the tire frame was 1.5 mm.

<Formation of exterior member>
Natural rubber (NR, RSS # 3, rubber component), styrene butadiene rubber (SBR, JSR, JSR1502, rubber component), carbon black (C / B, Asahi Carbon, Asahi # 51), stearic acid , Zinc oxide, sulfur, vulcanization accelerator (Ouchi Shinsei Chemical Industry Co., Ltd.), process oil (Idemitsu Kosan Co., Ltd., Diana Process Oil PW380), and anti-aging agent (Ouchi Shinsei Chemical Industry Co., Ltd.) Nocrack 6C) was mixed so as to have the blending amounts shown in Table 1 below, and kneaded with a Banbury mixer (Kobe Steel Corporation, MIXTRON BB MIXER) to obtain a rubber material.
The obtained rubber material was molded into a sheet shape to obtain an exterior member formed of a rubber member.

<RFL adhesive>
Styrene previously mixed with 9 g of resorcinol, 12 g of formaldehyde (37% by mass solution, Nippon Formalin Kogyo Co., Ltd.) and 28 g of 4% by mass NaOH (0.1 mol / l) added to 217 g of soft water. -96 hours of butadiene latex (SBL) [(JSR2108, manufactured by JSR) 40 mass% latex] and 93 g of vinylpyridine (VP) latex [PYRATEX (41 mass% latex), Nippon A & L Co., Ltd.] for 1 hour By stirring, a 20% by mass solution of resorcinol formalin latex (RFL) was obtained. This was used as an RFL adhesive.

<Production of tire>
The tire frame body obtained above is pasted with the exterior member obtained above using the RFL adhesive obtained above, and vulcanized (vulcanization conditions: 145 ° C., 5 MPa, 20 minutes). The tire was produced. The thickness of the adhesive layer was 100 μm.

(Example 2 to Example 9, Example 11, Example 13, Comparative Example 1, Comparative Example 4 to Comparative Example 7)
Tires of Examples and Comparative Examples were produced in the same manner as in Example 1 except that the components of the resin material and the rubber material were changed to the types and blending amounts shown in Tables 1 and 2 below.
In Tables 1 and 2, the polyamide thermoplastic resins, polyolefin thermoplastic elastomers, polyester thermoplastic elastomers, and anti-aging agents shown below were used.
Polyamide thermoplastic resin: Ube Industries, UBE nylon 3020U
Polyolefin thermoplastic elastomer: Mitsui Chemicals, Tuffmer MH7010
Polyester thermoplastic elastomer: Toray DuPont Co., Ltd., Hytrel 5557
Anti-aging agent: Ouchi Shinsei Chemical Co., Ltd., NOCRACK 6C

(Example 10, Example 12, Comparative Example 2)
In Example 1, the components of the resin material and the rubber material were changed to the types and blending amounts shown in Tables 1 and 2 below, and the RFL adhesive was changed to an organic solvent adhesive (Metaloc, Toyo Chemical Laboratory). Except for the change to a two-component adhesive (undercoat: Metallok PH-56 (composition containing epoxy resin), overcoat: Metallok F-112 (composition containing chlorosulfonated rubber))) Tires were produced in the same manner.

(Example 14, Example 15, Comparative Example 3)
In Example 1, the components of the resin material and the rubber material were changed to the types and blending amounts shown in Tables 1 and 2 below, and the RFL adhesive was changed to an organic solvent adhesive (Chemlock 210 (a composition containing a phenolic resin). Tire) was produced in the same manner as described above except that the product was changed to (Products) and Road Corporation).

<Evaluation>
The tires of Examples and Comparative Examples produced above were evaluated as follows, and the evaluation results are shown in Tables 1 and 2 below.
In order to evaluate the deterioration of the initial appearance of each produced tire, first, the bleed, the appearance after vulcanization, and the adhesive strength of the produced tires of Examples and Comparative Examples were evaluated.
Next, in order to evaluate the deterioration of each tire produced and the deterioration of the appearance after the durability test, the ozone drum durability and the scratched CBU (Cord Breaking Up) drum durability were evaluated.

[Bleed]
The surface of the tire skeleton body is sampled from each of the prepared tires, the gelatin film is pressed against the surface of the sampled tire skeleton body, and the surface of the gelatin film is subjected to Fourier transform infrared spectrophotometer (JASCO Corporation, FT / IR- 4000) was subjected to infrared spectroscopic analysis by total reflection absorption measurement (ATR). As a result of the infrared spectroscopic analysis, a case where a peak derived from the antioxidant and the process oil was detected was judged as “bleeded”, and a case where a peak was not detected was judged as “no bleed”.

[Appearance after vulcanization (deformation by vulcanization)]
The appearance of each example and comparative example after vulcanization was visually observed to confirm the presence or absence of tire deformation. The case where deformation was not observed was designated as “OK”, and the case where deformation was observed was designated as “NG”.

[Initial bond strength]
The tire of each example and comparative example was processed into a strip shape of 150 mm × 20 mm, and used as a sample for initial adhesive strength evaluation. Using the sample for initial bond strength evaluation, the tire frame body of the sample and the exterior member are in different directions in accordance with JIS K 6854-3: 1999 (the exterior member is 180 ° with respect to the tire frame body). The tensile strength at the time of peeling (adhesion strength, unit: kN / m) was obtained by pulling in the direction) at 200 mm per minute, and evaluated according to the following criteria.
A: Adhesive strength was 10 kN / m or more.
B: Adhesive strength was 1 kN / m or more and less than 10 kN / m.
C: Adhesive strength was less than 1 kN / m.

[Tire durability]
The tire of each Example and Comparative Example was mounted on a rim, and the following ozone drum durability and scratched CBU drum durability were evaluated as evaluation of tire durability. After each durability test, the appearance of the tire was visually evaluated to check for the appearance deterioration.

−Ozone drum durability−
The tires of the examples and comparative examples were left for 10 days in an ozone environment. Using this tire, a high-speed performance test was conducted in accordance with JIS D 4230: 1999 (high-speed performance test B), and ozone drum durability was evaluated according to the following criteria.
A: Completed.
B: A failure (crack) occurred at the time of test stage 3, and the test was stopped.
C: A failure (crack) occurred at the time of test stage 2 and the test was stopped.

-Durable CBU drum durability-
A cut of 1.0 mm was made in the side part of the tire of each example and comparative example. A CBU drum durability test was performed on this tire by filling it with maximum air pressure and running it at 40 mph (mile / hour) for 10 minutes with a load 1.2 times the maximum load capacity. The scratched CBU drum durability was evaluated.
A: The cut did not spread even when the mileage was more than 3 miles.
B: The depth of cut increased when the mileage was 1 mile or more and less than 3 miles.
C: The depth of cut increased when the mileage was less than 1 mile.

[Amount of migration of anti-aging agent and process oil after endurance test]
Taking Example 1 as an example, an evaluation method for the migration amount of the anti-aging agent and process oil after the durability test will be described.
First, a 3 g test piece was cut out from the tread portion of the tire shown in Example 1 after the ozone drum durability test, and a fine powder was produced by freeze pulverization. Subsequently, after extracting the anti-aging agent and the process oil from the fine powder obtained by Soxhlet extraction, the anti-aging agent and the process oil were quantified by a liquid chromatograph mass spectrometer (Shimadzu Corporation, LC / MS). .
In Example 1, an ozone drum durability test was performed under the same conditions as in Example 1 using the same control tire as in Example 1 except that the skeleton was not blended with an antioxidant and process oil. Then, the amounts of the anti-aging agent and the process oil after the test were quantified by the same method as described above.
Next, by subtracting the amount of anti-aging agent and process oil obtained from the control tire from the amount of anti-aging agent and process oil obtained from the tire of Example 1, the outer layer from the skeleton in Example 1 The amount of anti-aging agent and process oil transferred to the member was determined.

As in Example 1, for each of the Examples and Comparative Examples, the amount of migration of the anti-aging agent and the process oil from the skeleton after the durability test to the outer layer member was determined using the control tire. The results are shown in Table 1.
In addition, it was judged that there was no migration of the anti-aging agent and the process oil from the skeleton body to the outer layer member when the obtained migration amount was 0 or less. In this case, all the results were described as 0.

  From Table 1 and Table 2, it can be seen that the tires of the examples are tires that have good initial appearance, and that are suppressed from deterioration after deterioration and appearance after the durability test.

  10,200 tires, 12 bead parts, 16 crown parts (peripheral parts), 18 bead cores, 20 rims, 21 bead seats, 22 rim flanges, 17 tire cases (tire frame bodies), 24 seal layers, 25 adhesive layers, 26 reinforcements Cord member, 26C adhesive layer, 30 tread, D Diameter of reinforcing cord member, L Embedding depth of reinforcing cord member

Claims (4)

An annular tire skeleton formed of a resin material, and an exterior member formed of a rubber material,
The tire frame includes at least one of process oil A and anti-aging agent A, and the exterior member includes process oil B and anti-aging agent B,
The content a1 of the process oil A in the tire skeleton is 0 part by mass or 0.5 part by mass to 15 parts by mass with respect to 100 parts by mass of the rubber component in the rubber material of the exterior member, and the tire skeleton Content a2 of anti-aging agent A in the body is 0 part by mass or 0.5 part by mass to 20 parts by mass with respect to 100 parts by mass of the rubber component in the rubber material of the exterior member,
Relationship between the content a1 of the process oil A of the tire frame body represented by the following formula 1 and the content b1 of the process oil B of the exterior member, or the antiaging agent for the tire frame body represented by the following formula 2 Satisfying at least one of the relationships between the content a2 of A and the content b2 of the anti-aging agent B of the exterior member,
A tire having a thickness of the tire skeleton of 1 mm to 2.5 mm.
a1> b1 Formula 1
a2> b2 Formula 2   2. An adhesive layer formed of a composition containing resin or rubber or an adhesive layer formed of a composition containing resorcinol-formaldehyde-latex is provided between the tire frame body and the exterior member. Tire described in.   The tire according to claim 2, further comprising an adhesive layer formed of a composition including the resin or rubber, wherein the resin includes at least one resin selected from an epoxy resin and a phenol resin.   The said resin material contains at least 1 chosen from the polyamide-type thermoplastic elastomer, the polyester-type thermoplastic elastomer, the polyamide-type thermoplastic resin, and the polyester-type thermoplastic resin in any one of Claims 1-3. The described tire.