JP2016002709A - Laminate, and tire using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in adhesive force between a rubber layer and a resin layer, and to provide an easily manufacturable tire in which an exterior member is hardly exfoliated from a tire skeleton material.SOLUTION: In a laminate including a rubber layer formed of a rubber composition containing diene rubber, and a resin layer having at least partially contact with the rubber layer and formed of a resin material, a string-like part of the resin material having a length of 30 nm or longer and a width of 5 nm-40 nm is allowed to enter the rubber layer from the resin layer on the interface between the rubber layer and the resin layer.

Description

  The present invention relates to a laminate of a rubber layer formed of a rubber composition and a resin layer formed of a resin material, and a tire using the laminate as a member.

  Conventionally, a tire in which an exterior member such as a tread using rubber is attached to a tire skeleton including a resin has been proposed (see, for example, Patent Document 1). Conventionally, a method using an adhesive has been used as a means for bonding the exterior member to the tire frame.

JP 2012-46032 A

When an adhesive is used to fix an exterior member such as a tread to the tire frame body, the performance required for a tire can be exhibited in consideration of the compatibility between the material used for both members and the adhesive. Adhesive must be selected. However, when a resin is used for the tire frame body, the rubber used for the exterior member and the resin used for the tire frame body have different properties and compatibility, so it is not always easy to select an adhesive between the members.
Furthermore, when both members are fixed with an adhesive, an adhesive application step is required. For this reason, if the application | coating process of an adhesive agent can be abbreviate | omitted, the efficiency of the manufacturing process of a tire can further be improved.

  In view of the above circumstances, an object of the present invention is to provide a laminate excellent in adhesive strength between a rubber layer and a resin layer, and a tire that can be easily manufactured with an exterior member hardly peeled from a tire frame. And

[1] A rubber layer formed of a rubber composition containing a diene rubber, and a resin layer that is at least partially in contact with the rubber layer and formed of a resin material, the rubber layer and the resin layer In this interface, a part of the resin material is a string-like portion having a length of 30 nm or more and a width of 5 nm to 40 nm, and is a laminate that enters the rubber layer from the surface of the resin layer.
[2] The laminate according to [1], wherein the string-like portion has an aspect ratio of 0.75 to 60.
[3] The laminate according to [1] or [2], wherein the resin material includes a polyamide-based thermoplastic resin elastomer.
[4] The laminate according to any one of [1] to [3], wherein the diene rubber includes a styrene-butadiene copolymer rubber.
[5] A tire using the laminate according to any one of [1] to [4] as a member.
[6] An exterior member formed of a rubber composition containing a diene rubber, and an annular tire skeleton body that is at least partially in contact with the exterior member and formed of a resin material. A tire in which a part of the resin material becomes a string-like portion having a length of 30 nm or more and a width of 5 nm to 40 nm at the interface between the member and the tire frame body, and enters the exterior member from the tire frame body. .

  ADVANTAGE OF THE INVENTION According to this invention, the tire excellent in the adhesive force of a rubber layer and a resin layer, and the tire which can peel easily from the member for exterior from a tire frame body can be provided.

(A) shows sectional drawing for demonstrating the structure of the laminated body of this invention, (B) shows the enlarged view of the area | region M. FIG. (A) is a perspective view showing a section of a part of the tire concerning a 1st embodiment, and (B) is a sectional view of a bead part with which a rim was equipped. It is sectional drawing along the tire rotating shaft which shows the state by which the reinforcement cord was embed | buried under the crown part of the tire case of the tire of 1st Embodiment. It is a cross-sectional photograph of the laminated body in an Example and a comparative example.

[Laminate]
The laminate of the present invention includes a rubber layer formed of a rubber composition containing a diene rubber, and a resin layer that is at least partially in contact with the rubber layer and formed of a resin material. At the interface with the resin layer, a part of the resin material becomes a string-like portion having a length of 30 nm or more and a width of 5 nm to 40 nm, and enters the rubber layer from the surface of the resin layer.
In the laminate of the present invention, the resin material protrudes from the surface of the resin layer as a string-like portion at the interface between the resin layer and the rubber layer, and the protruding resin layer enters the rubber layer. As described above, the laminate of the present invention is excellent in adhesive strength at the interface between the rubber layer and the resin layer because a part of the resin layer becomes a string-like portion and enters the rubber layer. This is presumed that the adhesive force between the rubber layer and the resin layer is improved by the anchor effect of the string-like portion entering the rubber layer.

  In the present specification, “resin” is a concept including a thermoplastic resin and a thermosetting resin, but does not include vulcanized rubber such as natural rubber and synthetic rubber. Further, “rubber” is a polymer compound having elasticity, but in this specification, it is distinguished from a thermoplastic resin elastomer. “Thermoplastic resin elastomer” is a polymer compound having elasticity, a crystalline polymer having a high melting point or a hard segment having a high cohesive force, and an amorphous glass transition temperature. It means a thermoplastic resin material comprising a copolymer having a polymer constituting a low soft segment. In the thermoplastic resin elastomer, the hard segment behaves as a pseudo crosslinking point and develops elasticity (so-called physical crosslinking). On the other hand, rubber has a double bond in the molecular chain, and is crosslinked (vulcanized) by adding sulfur or the like to generate a three-dimensional network structure and develop elasticity (chemical crosslinking). . For this reason, the thermoplastic resin elastomer can be reused after recovery because the hard segment is melted by heating and a pseudo crosslinking point is formed again by cooling.

(Rubber layer)
The rubber layer is a layer formed of a rubber composition containing a diene rubber.
The diene rubber is not particularly limited. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber. (NBR), and styrene-butadiene copolymer rubber (SBR) is preferable. As the SBR, a modified or unmodified one can be used, but a tin-modified SBR can be particularly preferably used. The diene rubber contained in the rubber composition may be used alone or in combination of two or more.

  As the diene rubber, commercially available products can be used as appropriate. As a commercially available diene rubber, for example, JSR SL563 (trade name of JSR Corporation: tin-modified SBR) can be used.

In addition to the diene rubber, the rubber composition includes, 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, a process oil, and an antiaging agent. Etc. can be suitably blended.
The content of the diene rubber contained in the rubber composition is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.
Further, the ratio of the modified or unmodified SBR to the total amount of the diene rubber contained in the rubber composition in the present invention is 100% from the viewpoint of the content of impurities that inhibit the adhesion in the rubber composition. When it is set as mass parts, 60 mass parts or more are preferable, 70 mass parts or more are more preferable, and 80 mass parts or more are especially preferable.
Furthermore, the ratio of the natural rubber to the total amount of the diene rubber contained in the rubber composition in the present invention is a diene rubber from the viewpoint of the content of low molecular weight protein derived from natural rubber, which inhibits the adhesion in the rubber composition. When the total amount is 100 parts by mass, it is preferably 50 parts by mass or less, more preferably 35 parts by mass or less, and particularly preferably 25 parts by mass or less.

  The rubber layer is preferably vulcanized. The rubber composition (rubber layer) may be vulcanized by a known method, for example, as described in JP-A Nos. 11-048264, 11-029658, and 2003-238744. It can be done by the method. Specifically, the rubber layer can be vulcanized by kneading the rubber composition using a Banbury mixer or the like to form a resin layer on the surface and then heating.

  The vulcanization temperature of the rubber layer is preferably 180 ° C to 220 ° C, more preferably 190 ° C to 210 ° C, and particularly preferably 195 ° C to 205 ° C. The rubber layer is preferably pressurized during vulcanization, and the pressure is preferably 0.1 MPa to 20 MPa, more preferably 0.5 MPa to 15 MPa, and particularly preferably 1 MPa to 10 MPa. The vulcanization time of the rubber composition is preferably 1 minute to 10 minutes, more preferably 2 minutes to 5 minutes, and particularly preferably 2 minutes to 3 minutes.

  In the laminate, the shape and size of the rubber layer can be appropriately set according to the use of the laminate.

(Resin layer)
The resin layer is a layer formed of a resin material. The resin material is a material containing “resin”, but may have other materials as necessary as described later.
The resin can be appropriately selected according to the use application of the laminate, but from the viewpoint of sufficiently exerting the effects of the present invention, it is preferable to use a thermoplastic resin, and to use a thermoplastic resin elastomer. Is more preferable.

  Examples of the thermoplastic resin elastomer include polyamide-based thermoplastic elastomer (Thermoplastic Amid elastomer (TPA), polyester-based thermoplastic elastomer (TPC), polyolefin-based thermoplastic elastomer (TPC) defined in JIS K6418: 2007. Thermoplastic PolyOlefin (TPO), polystyrene-based thermoplastic elastomers (Styrenic Thermoplastic Elastomer, TPS), polyurethane-based thermoplastic elastomers (Thermoplastic Polyurethane, TPU), crosslinked thermoplastic rubber (ThermoPlastic Vulcanizates, TPV), or other thermoplastic elastomers ( Thermoplastic elastomers other, TPZ) and the like. As the thermoplastic resin elastomer used in the laminate of the present invention, a polyamide-based thermoplastic resin elastomer is preferable from the viewpoint of sufficiently exhibiting the effects of the present invention.

  As the above-mentioned polyamide-based thermoplastic elastomer, at least polyamide is a crystalline hard segment having a high melting point, and other polymers (eg, polyester or polyether) are amorphous and a soft segment having a low glass transition temperature. The material which is doing is mentioned. The polyamide-based thermoplastic elastomer may use a chain extender such as dicarboxylic acid as a bonding part between the hard segment and the soft segment.

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

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

In General Formula (2), R ² represents a molecular chain of a hydrocarbon having 3 to 20 carbon atoms or 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 or an alkylene group having 3 to 18 carbon atoms, and a hydrocarbon molecular chain having 4 to 15 carbon atoms or 4 carbon atoms. To 15 alkylene groups are more preferable, and hydrocarbon chains having 10 to 15 carbon atoms or alkylene groups having 10 to 15 carbon atoms are particularly preferable. In general formula (2), R ² is preferably a hydrocarbon molecular chain having 3 to 18 carbon atoms or an alkylene group having 3 to 18 carbon atoms, and a molecular chain or carbon having 4 to 15 carbon atoms. 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 or 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.

Examples of the ω-aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. And aliphatic ω-aminocarboxylic acid. Moreover, as a lactam, C5-C20 aliphatic lactams, such as lauryl lactam, (epsilon) -caprolactam, undecane lactam, (omega) -enantolactam, 2-pyrrolidone, etc. can be mentioned.
Examples of the diamine include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2, Examples thereof include diamine compounds such as aliphatic diamines having 2 to 20 carbon atoms such as 4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 3-methylpentamethylenediamine, 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 22 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid.

  As the polyamide forming the hard segment, polyamide (polyamide 6) obtained by ring-opening polycondensation of ε-caprolactam, polyamide (polyamide 11) obtained by ring-opening polycondensation of undecane lactam, and polyamide (polyamide) obtained by ring-opening polycondensation of lauryl lactam 12), polyamide obtained by polycondensation of 12-aminododecanoic acid (polyamide 12), polycondensation polyamide (polyamide 66) of diamine and dibasic acid, or polyamide (amide MX) having meta-xylenediamine as a structural unit Can do.

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

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

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

  Examples of the polymer that forms the soft segment include polyester and polyether, and further examples include polyesters such as polyethylene glycol, polypropylene glycol (PPG), polytetramethylene ether glycol (PTMG), polyester polyol, and ABA. Type triblock polyether diol and the like, and these may be used alone or in combination of two or more. Moreover, polyether diamine etc. which are obtained by making ammonia etc. react with the terminal of polyether can be used, for example, ABA type | mold triblock polyether diamine can be used.

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

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

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

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

In the general formula (N), _{X N} and _{Z N} represent each independently an integer of 1-20. Y _N represents an integer of 4-50.

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

  Examples of the combination of the hard segment and the soft segment include the combinations of the hard segment and the soft segment mentioned above. Among these, lauryl lactam ring-opening polycondensate / polyethylene glycol combination, lauryl lactam ring-opening polycondensate / polypropylene glycol combination, lauryl lactam ring-opening polycondensate / polytetramethylene ether glycol combination, lauryl lactam Ring-opening polycondensate / ABA type triblock polyether diol combination, aminododecanoic acid polycondensate / polyethylene glycol combination, aminododecanoic acid polycondensate / polypropylene glycol combination, aminododecanoic acid polycondensate / Polytetramethylene ether glycol combination, aminododecanoic acid polycondensate / ABA type triblock polyether diol combination, preferably lauryl lactam ring-opening polycondensate / ABA type triblock polyether diol combination Polycondensate / ABA type combination of a triblock polyether diols amino dodecanoic acid, are particularly preferred. These combinations are preferably selected so that the polyamide-based thermoplastic elastomer in the present invention has an ester bond in the molecule.

  The polymer forming the soft segment may contain a diamine such as a branched saturated diamine having 6 to 22 carbon atoms, a branched alicyclic diamine having 6 to 16 carbon atoms, or norbornane diamine as a monomer unit. In addition, these branched saturated diamines having 6 to 22 carbon atoms, branched alicyclic diamines having 6 to 16 carbon atoms, or norbornane diamines may be used alone or in combination. The above-mentioned ABA type triblock polyether diol is preferably used in combination.

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

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

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

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

  As described above, the polyamide-based thermoplastic elastomer may use a chain extender such as dicarboxylic acid in addition to the hard segment and the soft segment. As said dicarboxylic acid, at least 1 type chosen from aliphatic, alicyclic, and aromatic dicarboxylic acid, or these derivatives can be used, for example.

  Specific examples of the dicarboxylic acid include straight chain having 2 to 25 carbon atoms such as adipic acid, decanedicarboxylic acid, oxalic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Aliphatic dicarboxylic acid; aliphatic dicarboxylic acid such as dimerized aliphatic dicarboxylic acid having 14 to 48 carbon atoms obtained by dimerization of unsaturated fatty acid obtained by fractionation of triglyceride and hydrogenated products thereof, 1,4-cyclohexanedicarboxylic acid Mention may be made of alicyclic dicarboxylic acids such as acids and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid.

-Ester bond-
The polyamide-based thermoplastic elastomer in the present invention can have an ester bond in the molecule. The laminate of the present invention can suppress an increase in molecular weight by using a polyamide thermoplastic elastomer having an ester bond, and as a result, the viscosity at the time of melting can be lowered. Accordingly, when a polyamide thermoplastic elastomer having an ester bond is used, a resin having high fluidity easily enters the rubber layer, and a string-like portion is easily formed. The ester bond may be in the hard segment or soft segment of the polyamide-based thermoplastic elastomer, but a copolymer containing polyester such as polyester polyol may be used as the soft segment, and polyethylene as the soft segment. Diol compounds having hydroxyl groups at both ends, such as glycol, polypropylene glycol, polytetramethylene ether glycol (PTMG), or the above-mentioned ABA type triblock polyether diol, and a polyvalent carboxylic acid (dicarboxylic acid) as a chain extender. Acid) and may have an ester bond contained in a structural unit derived from these condensation polymers. From the above viewpoints, the polyamide thermoplastic elastomer in the present invention includes a diol compound as a soft segment, and is derived from a bond between a hydroxyl group of the diol compound and a carboxyl group (for example, in a hard segment or a chain extender). It preferably contains an ester bond. Examples of the diol compound include, but are not limited to, the above-described glycols and diols. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (PTMG), and the above-described general formula. Examples thereof include diol compounds having hydroxyl groups at both ends selected from ABA type triblock polyether diols represented by (3). For example, ABA type triblock polyether diols and PTMGs can be used.

  In addition, by selecting the type and amount of the heart segment, soft segment, and chain extender as the raw material for the polyamide-based thermoplastic elastomer, the amount of ester bonds generated in the polymerization reaction between the raw materials can be controlled. Can do. For example, when synthesizing the above-mentioned polyamide thermoplastic elastomer having the polyamide 12 as a hard segment, ring-opening polycondensation or 12-aminododecanoic acid is used as a raw material of the hard segment, and PTG, PTMG or By using a diol compound selected from the ABA type triblock polyether diol represented by the above general formula (3) and performing a synthesis reaction using adipic acid or decanedicarboxylic acid as a chain extender, an ester bond is formed. It is possible to synthesize a polyamide thermoplastic elastomer.

-Molecular weight-
In the present invention, the weight average molecular weight of the polyamide-based thermoplastic elastomer contained in the resin material is not particularly limited, but is preferably about 10,000 to 400,000. From the viewpoint of further improving the rim assembly property and improving the pressure resistance against the internal pressure of the tire, the weight average molecular weight of the polyamide-based thermoplastic elastomer is preferably 15,700 to 300,000, and 22,000 to 200,000. Further preferred. The weight average molecular weight of the polyamide-based thermoplastic elastomer can be measured by gel permeation chromatography (GPC). For example, GPC (gel permeation chromatography) such as “HLC-8320GPC EcoSEC” manufactured by Tosoh Corporation may be used. Can be used.

  Moreover, as a number average molecular weight of the polymer (polyamide) which comprises the said hard segment, 300-15000 are preferable from a viewpoint of melt moldability. Moreover, as a number average molecular weight of the polymer which comprises the said soft segment, 200-6000 are preferable from a viewpoint of toughness and low temperature flexibility.

  The polyamide-based thermoplastic elastomer can be synthesized by copolymerizing the polymer forming the hard segment and the polymer forming the soft segment by a known method. For example, the polyamide thermoplastic elastomer is composed of a monomer constituting a hard segment (for example, an ω-aminocarboxylic acid such as 12-aminododecanoic acid or a lactam such as lauryl lactam) and a monomer constituting a soft segment (for example, the above-mentioned (ABA type triblock polyether diol) and a chain extender (for example, adipic acid or decanedicarboxylic acid) can be obtained by polymerizing in a container. In particular, when ω-aminocarboxylic acid is used as the monomer constituting the hard segment, it can be synthesized by further performing reduced-pressure melt polymerization on normal-pressure melt polymerization or normal-pressure melt polymerization. When lactam is used as a monomer constituting the hard segment, an appropriate amount of water can coexist, and from melt polymerization under a pressure of 0.1 to 5 MPa, followed by normal pressure melt polymerization and / or reduced pressure melt polymerization. Can be manufactured by the following method. These synthesis reactions can be carried out either batchwise or continuously. In the above synthesis reaction, a batch type reaction vessel, a single tank type or multi-tank type continuous reaction apparatus, a tubular continuous reaction apparatus or the like may be used alone or in appropriate combination.

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

In the production of the polyamide-based thermoplastic elastomer, monoamines or diamines such as laurylamine, stearylamine, hexamethylenediamine, and metaxylylenediamine for the purpose of adjusting the molecular weight and stabilizing the melt viscosity at the time of molding as necessary. An additive such as monocarboxylic acid such as acetic acid, benzoic acid, stearic acid, adipic acid, sebacic acid, dodecanedioic acid, or dicarboxylic acid may be added. These additives can be appropriately selected in relation to the molecular weight and viscosity of the resulting polyamide-based thermoplastic elastomer within a range that does not adversely affect the effects of the present invention.
In the production of the polyamide-based thermoplastic elastomer, a catalyst can be used as necessary. The catalyst includes at least one selected from the group consisting of P, Ti, Ge, Zn, Fe, Sn, Mn, Co, Zr, V, Ir, La, Ce, Li, Ca, and Hf. Compounds.
Examples thereof include inorganic phosphorus compounds, organic titanium compounds, organic zirconium compounds, and organic tin compounds.
Specifically, examples of the inorganic phosphorus compound include phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphorous acid, hypophosphorous acid and other phosphorus-containing acids, phosphorus-containing acid alkali metal salts, and phosphorus-containing acid alkaline earths. A metal salt etc. are mentioned.
Examples of the organic titanium compound include titanium alkoxide [titanium tetrabutoxide, titanium tetraisopropoxide, and the like].
Examples of the organic zirconium compound include zirconium alkoxide (zirconium tetrabutoxide (also referred to as “Zr (OBu) ₄ ” or “Zr (OC ₄ H ₈ ) ₄ )”).
Examples of organotin compounds include distannoxane compounds [1-hydroxy-3-isothiocyanate-1,1,3,3-tetrabutyl distanoxane, etc.], tin acetate, dibutyltin dilaurate, butyltin hydroxide oxide hydrate, and the like. Can be mentioned.
The catalyst addition amount and the catalyst addition timing are not particularly limited as long as the target product can be obtained quickly.

  Examples of the polyamide-based thermoplastic elastomer include lauryl lactam ring-opening polycondensate / polyethylene glycol / adipic acid combination, lauryl lactam ring-opening polycondensate / polypropylene glycol / adipic acid combination, and lauryl lactam ring opening. Polycondensate / polytetramethylene ether glycol / adipic acid combination, lauryl lactam ring-opening polycondensate / ABA triblock polyether / adipic acid combination, lauryl lactam ring-opening polycondensate / polyethylene glycol / decane dicarboxylic acid Acid combination, lauryl lactam ring-opening polycondensate / polypropylene glycol / decane dicarboxylic acid combination, lauryl lactam ring-opening polycondensate / polytetramethylene ether glycol / decane dicarboxylic acid combination, lauryl lacta Ring-opening polycondensate / ABA type triblock polyether / decane dicarboxylic acid combination, aminododecanoic acid polycondensate / polyethylene glycol / adipic acid combination, aminododecanoic acid polycondensate / polypropylene glycol / adipic acid Combinations, polycondensates of aminododecanoic acid / polytetramethylene ether glycol / adipic acid, polycondensates of aminododecanoic acid / ABA triblock polyether / adipic acid, polycondensates of aminododecanoic acid / polyethylene Glycol / decane dicarboxylic acid combination, aminododecanoic acid polycondensate / polypropylene glycol / decane dicarboxylic acid combination, aminododecanoic acid polycondensate / polytetramethylene ether glycol / decane dicarboxylic acid combination, aminododecanoic acid A combination of polycondensate / ABA type triblock polyether / decane dicarboxylic acid is preferable, lauryl lactam ring-opening polycondensate / ABA type triblock polyether / adipic acid combination, aminododecanoic acid polycondensate / ABA type Triblock polyether / adipic acid combination, aminododecanoic acid polycondensate / polytetramethylene ether glycol / adipic acid combination, aminododecanoic acid polycondensate / polytetramethylene ether glycol / decane dicarboxylic acid combination preferable. As said polyamide-type thermoplastic elastomer, what combined the preferable aspect mentioned above about the combination of a structural unit, the structural ratio, molecular weight, etc. can be used.

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

  As the amide-based thermoplastic resin elastomer, commercially available products can be used as appropriate. As the commercially available amide-based thermoplastic resin elastomer, for example, Pebax 5533 (trade name of Arkema: copolymer of polyamide and polyether) can be used.

The melting point (or softening point) of the resin material itself is usually 100 ° C. to 350 ° C., preferably about 100 ° C. to 250 ° C., but preferably about 120 ° C. to 250 ° C. from the viewpoint of tire productivity. More preferably, the temperature is from 200 ° C to 200 ° C.
In this way, by using a resin material having a melting point of 120 ° C. to 250 ° C., for example, when a tire skeleton is formed by fusing the divided bodies (frame pieces), the periphery of 120 ° C. to 250 ° C. Even if the frame body is fused in the temperature range, the bonding strength between the tire frame pieces is sufficient. For this reason, the tire of this invention is excellent in durability at the time of driving | running | working, such as puncture resistance and abrasion resistance. The heating temperature is preferably 10 ° C to 150 ° C higher than the melting point (or softening point) of the resin material forming the tire frame piece, and more preferably 10 ° C to 100 ° C higher.
From the viewpoint of effectively forming the string-like portion of the resin layer in the heat treatment step described later, the viscosity of the resin material at 200 ° C. is preferably 100 Pa · s to 300 Pa · s, and 100 Pa · s to 250 Pa · s. More preferred is 100 Pa · s to 200 Pa · s.

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

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

  The tensile yield elongation defined by JIS K7113: 1995 of the resin material itself is preferably 10% or more, preferably 10% to 70%, and more preferably 15% to 60%. When the tensile yield elongation of the resin material is 10% or more, the elastic region is large, and the rim assembly property can be improved.

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

  As a deflection temperature under load (at the time of 0.45 MPa load) specified in ISO 75-2 or ASTM D648 of the resin material (tire frame) itself, 50 ° C. or more is preferable, 50 ° C. to 150 ° C. is preferable, and 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.

  In the laminate, the shape, dimensions, and the like of the resin layer can be appropriately set according to the use of the laminate.

(String)
In the laminate of the present invention, at the interface between the rubber layer and the resin layer, a part of the resin material becomes a string-like portion having a length of 30 nm or more and a width of 5 nm to 40 nm, and from the resin layer surface to the rubber layer. I'm stuck in. Here, the “string-like portion” is a string-like portion in which a part of the resin material in the resin layer protrudes from the surface of the resin layer. The shape of the string-like portion is not particularly limited as long as it has a length of 30 nm or more and a width of 5 nm to 40 nm, and includes a straight shape, a spiral shape, a fishhook shape, and the like. The “interface” means a boundary line that can be observed between the rubber layer and the resin layer with an electron microscope or the like. The interface does not include the surface of the string-like portion. For example, in FIG. 1B described later, the interface 5 is represented as a straight line passing through the root (point F and point G) of the string-like portion 4. The relationship among the rubber layer, the resin layer, and the string-like portion will be described with reference to FIG. FIG. 1A shows a cross-sectional view for explaining the structure of the laminate of the present invention, and FIG. 1B shows an enlarged view of the region M. FIG.

  As shown in FIG. 1A, the laminate 3 of the present invention has a shape in which a rubber layer 1 and a resin layer 2 are laminated. The rubber layer 1 and the resin layer 2 may be in contact with each other at least partially, but may be in contact with the entire surface of one side as shown in FIG. The rubber layer 1 and the resin layer 2 may each be a single layer or may be composed of a plurality of layers.

  On the surface of the resin layer 2, a part of the resin material of the resin layer 2 is a string-like portion 4 having a length of 30 nm or more and a width of 5 nm to 40 nm. A plurality of string-like portions 4 are formed on the surface of the resin layer 2 on the side in contact with the rubber layer 1. As shown in FIG. 1A, the string-like portion 4 protruding from the resin layer 2 enters the rubber layer 1. As shown in FIG. 1B, which is an enlarged view of the region M in FIG. 1A, the string-like portion 4 has a certain length and width. As described above, the interface 5 between the rubber layer 1 and the resin layer 2 in FIG. 1 is represented as a straight line passing through the root (point H and point G) of the string-like portion 4.

  The length of the string-like part 4 is 30 nm or more. Here, the “length” of the string-like portion 4 is a line passing through the center of the string-like portion 4 extending from the interface 5 between the rubber layer 1 and the resin layer 2 (dotted line W in FIG. 1B), It means the length to reach the tip of the string-like part. That is, in FIG. 1B, the length of the string-like portion 4 means the length of the dotted line W. If the length of the string-like portion 4 is less than 30 nm, the string-like portion cannot sufficiently enter the rubber layer, and the adhesive force between the rubber layer and the resin layer cannot be sufficiently increased. The upper limit of the length of the string-like part 4 is not particularly limited, but is preferably 300 nm or less from the viewpoint of the time required to form the string-like part. The length of the string-like portion 4 is preferably 30 nm to 300 nm, more preferably 40 nm to 250 nm, and particularly preferably 50 nm to 200 nm.

  The string-like portion 4 has a width of 5 nm to 40 nm. Here, the “width” of the string-like portion 4 is the three points arbitrarily selected from the root of the string-like portion (the line segment HG in FIG. 1 (B)) to the tip of the string-like portion 4. It means the average value of the lengths of lines that intersect perpendicularly to the line (dotted line W) passing through the center of the string-like part. That is, when the straight line X, the straight line Y, and the straight line Z in FIG. 1B intersect perpendicularly with the dotted line W at each part, the line segment AB on the straight line X, the line segment CD on the straight line Y, and the straight line Z The average value of the length of the upper line segment EF is the width of the string-like portion 4 in FIG. If the width of the string-like part 4 is less than 5 nm, the durability of the string-like part 4 is low and the adhesive force at the interface between the rubber layer and the resin layer cannot be sufficiently exhibited. Moreover, since the brittleness of the string-like part 4 will become high when the width | variety of the string-like part 4 exceeds 40 nm, the adhesive force of the interface of a rubber layer and a resin layer cannot fully be exhibited. As a width | variety of the string-like part 4, 10 nm-30 nm are preferable from a viewpoint for obtaining sufficient peeling resistance, and 15 nm-20 nm are still more preferable.

  The aspect ratio of the string-like portion 4 is preferably 0.75 to 60, more preferably 1 to 30, and particularly preferably 1 to 10 from the viewpoint of sufficiently withstanding the force estimated to act on the peeling interface. The aspect ratio (L / D) of the string-like part 4 can be obtained by dividing the length (L) of the string-like part 4 by the width (D).

The number of the string-like portions 4 on the surface of the resin layer 2 is not particularly limited, but from the viewpoint of increasing the adhesive force between the rubber layer 1 and the resin layer 2, 1 × 10 ⁹ to 8 × 10 ¹⁰ per 1 mm ^2. Preferably, 3 × 10 ¹⁰ to 5 × 10 ¹⁰ are more preferable.

[Manufacturing method of laminate]
The laminate of the present invention can be formed by applying a resin material on a rubber layer before vulcanization to form a resin layer, and performing a heat treatment step at a temperature of 180 ° C to 220 ° C.
For example, the rubber layer is formed using a rubber composition containing unvulcanized tin-modified SBR (for example, “JSR SL563” described above), a vulcanizing agent, carbon black, and the like. Next, an amide-based thermoplastic resin elastomer (for example, “Pebax 5533” described above), which is a copolymer of polyamide and polyether, is applied on the rubber layer to form a resin layer. When a heat treatment step is added after the resin layer is formed on the rubber layer, the resin material in the resin layer is first softened. Next, the unvulcanized rubber composition in the rubber composition is vulcanized. When the rubber layer is vulcanized and then cooled, a laminated body having a rubber layer in which the string-like portion of the resin layer enters (invades) the interface can be formed.

As the conditions in the heat treatment step, the above vulcanization conditions (temperature, pressure, and time) of the rubber composition can be applied. That is, when the unvulcanized rubber layer and the resin layer are subjected to a heat treatment step, a string-like portion is formed in the resin layer in the course of vulcanizing the unvulcanized rubber layer, and the string-like portion is placed in the rubber layer. Therefore, the laminate of the present invention can be formed.
The means for forming the resin layer by applying a resin material to the surface of the rubber layer is not particularly limited, and a known method such as a known coating method, dipping method, or injection molding can be appropriately employed. Further, in the above production method, it is not necessary to form the resin layer directly on the surface of the rubber layer by coating or the like, and a mode in which a resin layer is formed separately from the rubber layer and installed on the rubber layer surface may be employed. .

[tire]
The tire of the present invention can be formed by using the laminate of the present invention as a member. For example, the tire of the present invention can be formed by using the rubber layer of the laminate as an exterior member and the resin layer as a tire skeleton. The rubber layer of the laminate may be used as an intervening layer provided between the exterior member and the tire frame.
Specifically, the tire of the present invention includes an exterior member formed of a rubber composition containing a diene rubber, and an annular tire skeleton body that is in contact with the exterior member at least partially and formed of a resin material. And at the interface between the exterior member and the tire frame body, a string-like portion having a length of 30 nm or more and a width of 5 nm to 40 nm of the resin material enters the exterior member from the tire frame body. Can be configured.

(Tire frame)
The tire has an annular tire skeleton formed of a resin material. As said resin material, the thing similar to the resin material in the above-mentioned laminated body of this invention can be used, and the preferable range regarding a characteristic, a physical property, etc. is also the same.

(Exterior material)
The tire of the present invention can have an exterior member together with a tire skeleton. In the present invention, the “exterior member” means a member that is installed outside the tire frame body and covers at least a part of the outer surface of the tire frame body. The exterior member may be installed so as to be in direct contact with the surface of the tire frame body, or may be installed on an intervening layer or the like provided on the surface of the tire frame body. In the case of using the laminate of the present invention as a member, from the viewpoint of increasing production efficiency as a simple structure, the rubber layer of the laminate may be used as an exterior member and a tire may be formed using the resin layer as a tire skeleton. preferable. Examples of the exterior member include a tread member installed at the crown portion of the tire frame body, a side member installed at the side portion of the tire frame body, and the like. 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.

  The exterior member can be formed of a rubber composition containing a diene rubber. As said rubber composition, the thing similar to the rubber composition in the above-mentioned laminated body of this invention can be used, and the preferable range regarding a characteristic, a physical property, etc. is also the same.

  The rubber composition used for the exterior member may use other rubber components in addition to the above-described diene rubber as long as the effects of the present invention are not impaired. Moreover, you may add another additive to the exterior member according to the objective. As said additive, well-known things, such as fillers, such as carbon black, and anti-aging agent, can be suitably selected according to the objective, for example.

[First Embodiment]
A tire according to a first embodiment of the tire of the present invention will be described below with reference to the drawings.
The tire 10 of this embodiment will be described. FIG. 2A is a perspective view showing a partial cross section of the tire according to the first embodiment. FIG. 2B is a cross-sectional view of the bead portion attached to the rim. As shown in FIG. 2, the tire 10 of the present embodiment has a cross-sectional shape that is substantially the same as a conventional general rubber pneumatic tire.

  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.

  Here, the tire case 17 of the present embodiment uses, as a resin material, a resin composition including, for example, a polyamide-based thermoplastic resin elastomer (for example, the above-mentioned “Pebax 5533”) including each additive. Can do.

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

  In the present invention, the tire frame body in the present invention is formed of a single resin material, but the tire frame body is configured by combining a plurality of materials for the crown part, the side part, etc. of the tire frame body in the present invention. You can also.

  At this time, the thickness of the crown portion of the tire skeleton can be appropriately selected in order to adjust the bending elastic modulus. However, in consideration of the tire weight and the like, 0.5 mm to 10 mm is preferable, and 1 mm to 5 mm is preferable. Further preferred is 1 mm to 4 mm. Similarly, the thickness of the side portion of the tire skeleton is more preferably 0.5 mm to 10 mm, and particularly preferably 1 mm to 5 mm. About the thickness of the crown part and side part of these tire frame bodies, it can be based on the average thickness of the test piece at the time of measuring the above-mentioned bending elastic modulus. In addition, you may measure the thickness of a tire frame body suitably using a well-known method and apparatus.

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

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

  In this embodiment, as shown in FIG. 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 present 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, rubber An annular seal layer 24 made of 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. Further, if the sealing property between the rim 20 can be ensured only by the resin material forming the tire case 17, the rubber seal layer 24 may be omitted, and other thermoplastic resins having a sealing property superior to the resin material. (Thermoplastic resin elastomer) may be used. Examples of such other thermoplastic resins include polyurethane resins, polyolefin resins, polystyrene thermoplastic resins, polyester resins, and the like, and blends of these resins with rubbers or elastomers. Also, a thermoplastic resin elastomer can be used. For example, a polyester-based thermoplastic resin elastomer, a polyurethane-based thermoplastic resin elastomer, a polystyrene-based thermoplastic resin elastomer, a polyolefin-based thermoplastic resin elastomer, or a combination of these elastomers And blends with rubber.

  As shown in FIG. 2, a reinforcing cord 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 26 is wound spirally in a state in which at least a part thereof is embedded in the crown portion 16 in a cross-sectional view along the axial direction of the tire case 17, thereby forming a reinforcing cord layer 28. A tread 30 made of a rubber composition obtained by adding an additive such as carbon black to a diene rubber (for example, “JSR SL563” described above) is disposed on the outer circumferential side of the reinforcing cord layer 28 in the tire radial direction.

  The reinforcing cord layer 28 formed by the reinforcing cord 26 will be described with reference to FIG. FIG. 3 is a cross-sectional view along the tire rotation axis showing a state where a reinforcing cord is embedded in a crown portion of the tire case of the tire of the first embodiment. As shown in FIG. 3, the reinforcing cord 26 is spirally wound in a state in which at least a part is embedded in the crown portion 16 in a sectional view along the axial direction of the tire case 17. A reinforcing cord layer 28 indicated by a broken line portion in FIG. 3 is formed together with a part of the outer peripheral portion 17. The portion embedded in the crown portion 16 of the reinforcing cord 26 is in close contact with the resin material constituting the crown portion 16 (tire case 17). As the reinforcing cord 26, a monofilament (single wire) such as a metal fiber or an organic fiber, or a multifilament (twisted wire) obtained by twisting these fibers such as a steel cord twisted with a steel fiber can be used. In the present embodiment, a steel cord is used as the reinforcing cord 26.

  Further, in FIG. 3, the burying amount L indicates the burying amount of the reinforcing cord 26 in the tire rotation axis direction with respect to the tire case 17 (crown portion 16). The embedding amount L of the reinforcing cord 26 in the crown portion 16 is preferably 1/5 or more of the diameter D of the reinforcing cord 26, and more preferably more than 1/2. Most preferably, the entire reinforcing cord 26 is embedded in the crown portion 16. When the embedment amount L of the reinforcing cord 26 exceeds 1/2 of the diameter D of the reinforcing cord 26, it is difficult to jump out of the embedded portion due to the size of the reinforcing cord 26. Further, when the entire reinforcing cord 26 is embedded in the crown portion 16, the surface (outer peripheral surface) becomes flat, and even if a member is placed on the crown portion 16 where the reinforcing cord 26 is embedded, Air can be prevented from entering. The reinforcing cord layer 28 corresponds to a belt disposed on the outer peripheral surface of the carcass of a conventional rubber pneumatic tire.

A tread 30 is disposed on the outer circumferential side of the reinforcing cord layer 28 in the tire radial direction. Diene rubber is used for the tread 30. As shown in FIG. 3, in the present embodiment, the tread 30 is in direct contact with the crown portion 16 of the tire case 17. The tread 30 and the crown portion 16 are bonded at the interface. The tread 30 is preferably superior in wear resistance to the resin material constituting the tire case 17. 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 molding process)
First, a tire case half is formed using a resin material containing a resin composition containing a polyamide-based thermoplastic resin elastomer as described above. These tire cases are preferably formed by injection molding. Next, the tire case halves supported by the thin metal support ring face each other. Next, a joining mold (not shown) is installed so as to be in contact with the outer peripheral surface of the abutting portion of the tire case half. Here, the said joining metal mold | die is comprised so that the periphery of the junction part (butting part) of the tire case half body 17A may be pressed with a predetermined pressure. Next, the periphery of the joint portion of the tire case half is pressed at a temperature equal to or higher than the melting point (or softening point) of the resin material constituting the tire case. When the joint portion of the tire case half is heated or pressed by the joining mold, the joint portion is melted and the tire case halves are fused together, and the tire case 17 is formed by integrating these members. In the present embodiment, the joining portion of the tire case half is heated using a joining mold, but the present invention is not limited to this. For example, the joining portion is heated by a separately provided high-frequency heater or the like. Or softened or melted beforehand by hot air, infrared irradiation, etc., and pressed by a joining mold. The tire case halves may be joined.

(Reinforcement cord member winding process)
Next, although not shown in the drawings, the heated reinforcing cord 26 is wound while being embedded in the outer peripheral surface of the crown portion 16 using a reel, a cord heating device, and a cord supply device provided with various rollers. Thus, the reinforcing cord layer 28 can be formed on the outer peripheral side of the crown portion 16 of the tire case 17.

(Exterior member installation process / heat treatment process)
Next, the unvulcanized belt-like tread 30 is wound around the outer peripheral surface of the tire case 17 by one turn. Next, for example, a heat treatment process is performed for 3 minutes under the conditions of a temperature of 200 ° C. and a pressure of 10 MPa. By performing the heat treatment step, first, the surface of the tire case 17 is melted to form a string-like portion. Next, the string-like portion enters the tread 30 and the unvulcanized tread 30 is vulcanized. As described above, after the unvulcanized tread 30 is installed in the tire case 17, a heat treatment process is performed so that the tread 30 is vulcanized and a plurality of string-like portions are formed on the surface of the tire case 17. The shaped portion can enter the tread 30.

  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.

(Function)
In the tire 10 of the present embodiment, a string-like portion of a resin material is formed on the surface of a crown portion 16 of a tire case 17 formed of a resin material containing a polyamide-based thermoplastic resin elastomer, and the string-like portion is a tire. Since it has penetrated into the tread 30 installed in the crown portion 16 of the case 17, the adhesive force between the tire case 17 and the tread 30 is high. In particular, in the tire 10 of the present embodiment, the tread 30 (exterior member) is difficult to peel from the tire case 17 without using an adhesive between the tread 30 and the tire case 17. Further, since the tread 30 is directly bonded to the tire case 17, the step of applying an adhesive can be omitted when the tread 30 is attached to the tire case 17. For this reason, the tire 10 of this embodiment is very excellent in productivity.

  The tire 10 is light in weight because it has a simple structure as compared with a conventional rubber tire. For this reason, the tire 10 of this embodiment has high friction resistance and durability.

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

  Further, at least a part of the reinforcing cord 26 is embedded in the outer peripheral surface of the crown portion 16 of the tire case 17 formed of a resin material in a cross-sectional view along the axial direction of the tire case 17 (cross section shown in FIG. 2). In addition, since it is in close contact with the resin material, entry of air at the time of manufacture is suppressed, and movement of the reinforcing cord 26 due to input during travel is suppressed. Thereby, it is suppressed that peeling etc. arise in the reinforcement cord 26, the tire case 17, and the tread 30, and durability of the tire 10 improves.

  And since the embedding amount L of the reinforcement cord 26 is 1/5 or more of the diameter D as shown in FIG. 3, the air entry at the time of manufacture is suppressed effectively, the input at the time of driving, etc. This further suppresses the movement of the reinforcing cord 26.

  Further, since an annular bead core 18 made of a metal material is embedded in the bead portion 12, the tire case 17, that is, the tire 10 is strong against the rim 20 in the same manner as a conventional rubber pneumatic tire. Retained.

  Furthermore, since a seal layer 24 made of a rubber material having a sealing property than the resin material constituting the tire case 17 is provided at a portion of the bead portion 12 that contacts the rim 20, the tire 10 and the rim 20 The sealing performance between the two is improved. For this reason, compared with the case where it seals only with the rim | limb 20 and the resin material which comprises the tire case 17, the air leak in a tire is suppressed further. Further, the rim fit property is improved by providing the seal layer 24.

  In the first embodiment, the reinforcing cord 26 is heated. However, for example, the outer periphery of the reinforcing cord 26 may be covered with the same resin material as the tire case 17. In this case, the covering reinforcing cord is used. When the wire is wound around the crown portion 16 of the tire case 17, the resin material covered with the reinforcing cord 26 is also heated, so that the air can be effectively suppressed when being embedded in the crown portion 16.

  Further, although it is easy to manufacture the reinforcing cord 26 in a spiral manner, a method of making the reinforcing cord 26 discontinuous in the width direction can be considered.

  The tire 10 of the first embodiment is a so-called tubeless tire in which an air chamber is formed between the tire 10 and the rim 20 by attaching the bead portion 12 to the rim 20, but the present invention is limited to this configuration. It may be a complete tube shape.

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

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

(Example 1)
A plate-shaped rubber layer having a size (30 mm × 30 mm × 3 mm) was formed using the rubber composition shown in Table 1 below in an unvulcanized state. Subsequently, the resin material shown in the following Table 1 was applied on the rubber layer to form a resin layer having a thickness of 6 mm to obtain a laminate (unvulcanized).
Next, the obtained laminate (unvulcanized) was subjected to a heat treatment step while pressing under the conditions described in Table 1, and the rubber layer was vulcanized to obtain a laminate. The SEM image of the cross section of the obtained laminated body is shown in FIG.

(Comparative Examples 1 and 2)
A plate-shaped rubber layer having a size (30 mm × 30 mm × 3 mm) was formed using the rubber composition shown in Table 1 below in an unvulcanized state. Subsequently, a 6 mm thick laminate (unvulcanized) was obtained by forming a plate-shaped resin layer having a size (30 mm × 30 mm × 3 mm) on the rubber layer using the resin material described in Table 1 below. .
Next, the obtained laminate (unvulcanized) was subjected to a heat treatment step under the conditions described in Table 1, and the rubber layer was vulcanized to obtain a laminate. The SEM image of the cross section of the obtained laminated body is shown in FIG.

(Adhesion test)
The adhesive strength of the obtained laminate was measured according to the following.
Samples corresponding to each of the examples and comparative examples were prepared such that a 30 × 40 mm chuck portion was formed on the rubber layer and the resin layer of the laminate in each of the examples and comparative examples. Next, the sample was pulled at a rate of 0 mm / min using an autograph manufactured by Shimadzu Corporation, and the shear peeling force (adhesive force: N / 9 cm ² ) was calculated.

(Destruction state of peeled surface)
After the adhesion test, the fracture state of the peeled surface of each laminate was visually confirmed and evaluated according to the following criteria.
<Standard>
Interface: The base material (rubber layer and resin layer) was not destroyed, and both layers were peeled at the interface between the rubber layer and the resin layer.
Base material: At least the rubber layer or the resin layer itself was broken on the release surface.

Abbreviations in the table mean the following.
Resin A: polyamide-based thermoplastic elastomer, Pebax 5533 (trade name of Arkema: copolymer of polyamide and polyether, viscosity 238 Pa · s at 200 ° C.)
Resin B: polyamide-based thermoplastic elastomer (“UBESTA XPA9055X1” manufactured by Ube Industries, Ltd., viscosity 302 Pa · s at 200 ° C.)
-Rubber A: ("JSR SL563" tin-modified SBR manufactured by JSR Corporation)
Rubber B: (Natural rubber (TSR20): 90%, SBR (trade name “JSR 0202”: manufactured by JSR Corporation, 10%))

  As shown in Table 1, the laminated body of the comparative example has the rubber layer and the resin layer peeled at the interface, whereas the laminated body of Example 1 has a base material when the rubber layer and the resin layer are peeled off. It can be seen that the adhesive strength is high.

  In each cross-sectional photograph in FIG. 4, the layer on the left side of the paper is a resin layer, and the layer on the right side is a rubber layer. In the cross-sectional view of Example 1 in FIG. 4, it is recognized that a plurality of string-like portions have entered the rubber layer from the resin layer. On the other hand, as shown in FIG. 4, in the laminates of Comparative Example 1 and Comparative Example 2, there was no evidence that the string-like portion of the resin layer entered the rubber layer.

DESCRIPTION OF SYMBOLS 1 Rubber layer, 2 resin layer, 3 laminated body, 4 string-like part, 5 interface, 10 tire, 12 bead part, 14 side part, 15 side member, 16 crown part (outer peripheral part), 18 bead core, 20 rim, 21 Bead sheet, 22 rim flange, 17 tire case (tire frame), 24 seal layer (seal part), 26 reinforcement cord (reinforcement cord member), 28 reinforcement cord layer, 30 tread, D diameter of reinforcement cord (reinforcement cord member) Diameter), L Reinforcement amount of reinforcement cord (reduction amount of reinforcement cord member)

Claims (6)

A rubber layer formed of a rubber composition containing a diene rubber, and a resin layer that is at least partially in contact with the rubber layer and formed of a resin material,
A laminate in which a part of the resin material becomes a string-like portion having a length of 30 nm or more and a width of 5 nm to 40 nm at the interface between the rubber layer and the resin layer, and enters the rubber layer from the surface of the resin layer.   The laminate according to claim 1, wherein the string-like portion has an aspect ratio of 0.75 to 60.   The laminate according to claim 1 or 2, wherein the resin material includes a polyamide-based thermoplastic resin elastomer.   The laminate according to any one of claims 1 to 3, wherein the diene rubber includes a styrene-butadiene copolymer rubber.   The tire which used the laminated body of any one of Claims 1-4 as a member. An exterior member formed of a rubber composition containing a diene rubber;
An annular tire frame body that is in contact with the exterior member at least partially and formed of a resin material,
At the interface between the exterior member and the tire frame body, a part of the resin material becomes a string-like portion having a length of 30 nm or more and a width of 5 nm to 40 nm, and enters the exterior member from the tire frame body. tire.