WO2014157559A1 - タイヤ - Google Patents
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- WO2014157559A1 WO2014157559A1 PCT/JP2014/058981 JP2014058981W WO2014157559A1 WO 2014157559 A1 WO2014157559 A1 WO 2014157559A1 JP 2014058981 W JP2014058981 W JP 2014058981W WO 2014157559 A1 WO2014157559 A1 WO 2014157559A1
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- WIPO (PCT)
- Prior art keywords
- tire
- polyamide
- resin material
- acid
- thermoplastic elastomer
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0041—Compositions of the carcass layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C5/00—Inflatable pneumatic tyres or inner tubes
- B60C5/01—Inflatable pneumatic tyres or inner tubes without substantial cord reinforcement, e.g. cordless tyres, cast tyres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/0678—Injection moulding specially adapted for tyres or parts thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
- B60C9/20—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel
- B60C9/22—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre
- B60C9/2204—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre obtained by circumferentially narrow strip winding
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/08—Building tyres
- B29D30/20—Building tyres by the flat-tyre method, i.e. building on cylindrical drums
- B29D30/32—Fitting the bead-rings or bead-cores; Folding the textile layers around the rings or cores
- B29D2030/3285—Placing a cushioning element, e.g. a ring, aside or around the beads
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2380/00—Tyres
Definitions
- the present invention relates to a tire mounted on a rim, and particularly relates to a tire in which at least a part of a tire case is formed of a resin material.
- pneumatic tires made of rubber, organic fiber materials, steel members, and the like are used for vehicles such as passenger cars.
- Conventional rubber materials conventionally used for pneumatic tires have no problem in heat resistance.
- a plurality of processes such as kneading, sheeting, molding, and vulcanization are usually performed, and improvement in productivity has been demanded.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2003-104008 discloses a pneumatic tire molded using a thermoplastic polymer material.
- thermoplastic polymer materials thermoplastic resins
- thermoplastic resins have many advantages from the viewpoint of improving productivity, such as being capable of injection molding.
- Patent Document 2 Japanese Patent Laid-Open No. 2012-46030
- a tire using a thermoplastic polymer material is easier to manufacture and less expensive than a conventional rubber tire.
- a rim assembly is possible even in a tire using a thermoplastic polymer material, and it is required to secure an excellent rim assembly property so that internal air does not leak when the rim assembly is performed.
- an object of the present invention is to provide a tire that is formed using a resin material and has excellent rim assemblability and low rolling resistance.
- the resin material includes a polyamide-based thermoplastic elastomer containing an ester bond in a molecule, and the hard segment (HS) of the polyamide-based thermoplastic elastomer A tire having a mass ratio (HS / SS) of 54/46 to 90/10 with respect to the soft segment (SS).
- FIG. 1 is a perspective view showing a partial cross section of a tire according to an embodiment of the present invention. It is sectional drawing of the bead part with which the rim
- the tire of the present invention is formed of a resin material and has an annular tire skeleton, and the resin material includes a polyamide-based thermoplastic elastomer containing an ester bond in a molecule, and the hard segment of the polyamide-based thermoplastic elastomer
- the mass ratio (HS / SS) between (HS) and the soft segment (SS) is 54/46 to 90/10.
- the tire skeleton in the present invention includes a polyamide-based thermoplastic elastomer containing an ester bond in the molecule.
- the “polyamide thermoplastic elastomer” is a heat composed 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 a plastic resin material having an amide bond (—CONH—) in the main chain of the polymer constituting the hard segment.
- the polyamide-based thermoplastic elastomer may be simply referred to as “TPA” (ThermoPlastic Amid elastomer).
- the polyamide-based thermoplastic elastomer has a mass ratio (HS / SS) between the hard segment (HS) and the soft segment (SS) (hereinafter sometimes simply referred to as “HS mass ratio”) of 54/46. Since it is ⁇ 90 / 10, the inner air is difficult to escape when the rim is assembled, and the rim assembly property is excellent. Further, the tire of the present invention is excellent in productivity because it is possible to form a tire frame body by injection molding.
- the tire has a tire frame body using a resin material.
- the resin material has a mass ratio of 54/46 to 90/10 at least and a polyamide-based thermoplastic elastomer containing an ester bond (hereinafter, simply referred to as “polyamide-based thermoplastic elastomer in the present invention”). )including.
- the resin material may contain a thermoplastic elastomer other than the polyamide-based thermoplastic elastomer or an optional component, but the content of the polyamide-based thermoplastic elastomer in the present invention relative to the total amount of the resin material is 30% by mass or more. It is preferably 50% by mass or more, particularly preferably 70% by mass or more.
- “resin” is a concept including a thermoplastic resin and a thermosetting resin, but does not include natural rubber.
- polyamide thermoplastic elastomer As described above, as the polyamide-based thermoplastic elastomer in the present invention, at least the polyamide is crystalline and constitutes a hard segment having a high melting point, and other polymers (for example, polyester or polyether) are amorphous and have a glass transition temperature. The material which comprises the low soft segment 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.
- polyamide forming the hard segment examples include polyamides synthesized using monomers represented by the following general formula (1) or general formula (2).
- R 1 represents a hydrocarbon molecular chain having 2 to 20 carbon atoms or an alkylene group having 2 to 20 carbon atoms.
- R 2 represents a hydrocarbon molecular chain having 3 to 20 carbon atoms or an alkylene group having 3 to 20 carbon atoms.
- 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.
- An alkylene group having 15 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.
- 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 hydrocarbon molecular chain having 4 to 15 carbon atoms or carbon.
- alkylene group having 4 to 15 carbon atoms is more preferable, and a hydrocarbon molecular chain having 10 to 15 carbon atoms or an alkylene group having 10 to 15 carbon atoms is particularly preferable.
- the monomer represented by the general formula (1) or the general formula (2) include ⁇ -aminocarboxylic acid and lactam.
- the polyamide forming the hard segment include polycondensates of these ⁇ -aminocarboxylic acids and lactams, and copolycondensation polymers of diamines and dicarboxylic acids.
- Examples of the ⁇ -aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.
- Examples of the lactam include aliphatic lactams having 5 to 20 carbon atoms such as lauryl lactam, ⁇ -caprolactam, undecane lactam, ⁇ -enantolactam, and 2-pyrrolidone.
- diamine examples 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.
- the dicarboxylic acid can be represented by HOOC- (R 3 ) m-COOH (R 3 : a hydrocarbon molecular chain having 3 to 20 carbon atoms, m: 0 or 1).
- R 3 a hydrocarbon molecular chain having 3 to 20 carbon atoms, m: 0 or 1.
- 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.
- polyamide (polyamide 6) obtained by ring-opening polycondensation of ⁇ -caprolactam
- polyamide (polyamide 11) obtained by ring-opening polycondensation of undecane lactam
- polyamide (polyamide) obtained by ring-opening polycondensation of lauryl lactam 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).
- n is preferably 2 to 100 3 to 50 are more preferable.
- the amide MX having meta-xylenediamine as a structural unit can be represented, for example, by the following structural unit (A-1) [in (A-1), n represents an arbitrary number of repeating units], for example, 2 to 100 is preferable, and 3 to 50 is more preferable.
- the polyamide-based thermoplastic elastomer preferably has a polyamide (polyamide 12) having a unit structure represented by — [CO— (CH 2 ) 11 —NH] — as a hard segment.
- the polyamide 12 can be obtained by ring-opening polycondensation of lauryl lactam or polycondensation of 12-aminododecanoic acid.
- polyesters and polyethers examples include polyesters such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (PTMG), polyester polyol, and ABA type triblocks.
- polyesters such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (PTMG), polyester polyol, and ABA type triblocks.
- polyether diols examples include polyether diols, and these may be used alone or in combination of two or more.
- polyether diamine etc. which are obtained by reacting an anionia etc. with the terminal of polyether can be used, for example, ABA type
- examples of the “ABA type triblock polyether diol” include polyethers represented by the following general formula (3).
- x and z each independently represents an integer of 1 to 20.
- y represents an integer of 4 to 50.
- 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.
- 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).
- X N and Z N each independently represent an integer of 1 to 20.
- Y N represents an integer of 4 to 50.
- 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.
- 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.
- 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 polyconden
- 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.
- 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.
- These branched saturated diamines having 6 to 22 carbon atoms, branched alicyclic diamines having 6 to 16 carbon atoms, or norbornane diamines may be used alone or in combination. However, it is preferably used in combination with the above-mentioned ABA type triblock polyether diol.
- 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.
- the polymer which comprises the said soft segment may contain other diamine compounds other than the above as a monomer unit.
- diamine compounds include ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2, Aliphatic diamines such as 2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 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 diamine
- the polyamide-based thermoplastic elastomer may use a chain extender such as dicarboxylic acid in addition to the hard segment and the soft segment.
- a chain extender such as dicarboxylic acid
- dicarboxylic acid at least 1 type chosen from aliphatic, alicyclic, and aromatic dicarboxylic acid, or these derivatives can be used, for example.
- dicarboxylic acid examples 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, dodecanedioic acid and the like.
- Aliphatic dicarboxylic acids dimerized aliphatic dicarboxylic acids having 14 to 48 carbon atoms obtained by dimerizing unsaturated fatty acids obtained by fractionation of triglycerides, and aliphatic dicarboxylic acids such as 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.
- the polyamide-based thermoplastic elastomer in the present invention has an ester bond in the molecule. Since the tire of the present invention has an ester bond, the rolling resistance can be lowered.
- the ester bond may be in any of the hard segment and soft segment of the polyamide-based thermoplastic elastomer, but as the soft segment, a copolymer containing polyester such as polyester polyol may be used, or as the soft segment.
- polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (PTMG), or a diol compound having hydroxyl groups at both ends, such as the above-described ABA type triblock polyether diol, and a polyvalent carboxylic acid ( Dicarboxylic acid) may be used and may have an ester bond contained in a structural unit derived from these condensation polymers.
- the polyamide-based thermoplastic elastomer in the present invention includes a diol compound as a soft segment, and is used for bonding a hydroxyl group of the diol compound and a carboxyl group (for example, in a hard segment or a chain length extender). It preferably contains an ester bond derived from it.
- diol compound there is no limitation in particular as said diol compound.
- the above-mentioned glycols and diols can be mentioned.
- a diol having hydroxyl groups at both ends selected from polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (PTMG), and ABA type triblock polyether diol represented by the above general formula (3)
- PTMG polytetramethylene ether glycol
- ABA type triblock polyether diol represented by the above general formula (3)
- ABA type triblock polyether diol and PTMG can be used.
- the amount of ester bonds generated in the polymerization reaction between the raw materials can be controlled.
- the amount of ester bonds generated in the polymerization reaction between the raw materials can be controlled.
- ring-opening polycondensation or 12-aminododecanoic acid is used as a raw material for the hard segment
- PTG, PTMG is used as the raw material for the soft segment.
- the polyamide thermoplastic elastomer in the present invention has a mass ratio (HS / SS) of 54/46 to 90/10 between the hard segment (HS) and the soft segment (SS) of the polyamide thermoplastic elastomer.
- HS mass ratio is less than 54/46, the elastic modulus is low, the shape retention is poor, and the rim assembly property is deteriorated. Further, if the HS mass ratio exceeds 90/10, the elastic modulus is high and the rim cannot be assembled well, and the rim assembly performance is deteriorated.
- the HS mass ratio can be adjusted to a desired range by setting the charge amount of the raw material constituting the hard segment and the raw material constituting the soft segment.
- the HS mass ratio can be measured by using 1 H-NMR. From the viewpoint of durability, the HS mass ratio is preferably 54/46 to 88/12.
- the content of the hard segment and the soft segment in the polyamide-based thermoplastic elastomer is preferably set as appropriate so that the HS mass ratio is in the above range.
- the content thereof is preferably set so that the hydroxyl group or amino group of the monomer constituting the soft segment and the carboxyl group of the chain extender are approximately equimolar.
- the hard segment, the soft segment and the content of the chain extender used as necessary in the polyamide-based thermoplastic elastomer are appropriately selected so that the HS mass ratio is within the above range. By setting, each of the desired contents can be obtained.
- 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.
- the polyamide thermoplastic elastomer preferably has a weight average molecular weight of 15,700 to 300,000, more preferably 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).
- GPC gel permeation chromatography
- GPC gel permeation chromatography
- the number average molecular weight of the polymer (polyamide) constituting the hard segment is preferably 300 to 15000 from the viewpoint of melt moldability.
- the number average molecular weight of the polymer constituting the soft segment is preferably 200 to 6000 from the viewpoint of toughness and low temperature flexibility.
- the polyamide-based thermoplastic elastomer can be synthesized by copolymerizing the polymer that forms the hard segment and the polymer that forms the soft segment by a known method.
- the polyamide-based thermoplastic elastomer includes a monomer constituting a hard segment (for example, an ⁇ -aminocarboxylic acid such as 12-aminododecanoic acid and a lactam such as lauryl lactam) and a monomer constituting a soft segment (for example, The ABA triblock polyether diol) and a chain extender (for example, adipic acid or decanedicarboxylic acid) can be polymerized in a container.
- a monomer constituting a hard segment for example, an ⁇ -aminocarboxylic acid such as 12-aminododecanoic acid and a lactam such as lauryl lactam
- a monomer constituting a soft segment for example, The ABA triblock polyether di
- ⁇ -aminocarboxylic acid when used as a 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.
- lactam When used as the monomer constituting the hard segment, an appropriate amount of water can coexist, and from melt polymerization under pressure of 0.1 to 5 MPa, followed by normal pressure melt polymerization and / or reduced pressure melt polymerization.
- 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.
- the polymerization temperature is preferably 150 to 300 ° C, more preferably 160 to 280 ° C.
- the polymerization time can be appropriately determined depending on the relationship between the polymerization average molecular weight of the polyamide-based thermoplastic elastomer to be synthesized and the polymerization temperature. For example, it is preferably 0.5 to 30 hours, and more preferably 0.5 to 20 hours.
- 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.
- 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 include inorganic phosphorus compounds, organic titanium compounds, organic zirconium compounds, and organic tin compounds.
- 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 )”).
- 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.
- polyamide-based thermoplastic elastomer examples 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.
- 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.
- 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.
- the tire frame in the present invention uses the above-mentioned resin material.
- the melting point (or softening point) of the resin material (tire frame) itself is usually 100 ° C. to 350 ° C., preferably about 100 ° C. to 250 ° C., but from the viewpoint of tire productivity, 120 ° C. to 250 ° C. The degree is preferable, and 120 ° C. to 200 ° C. is more preferable.
- 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.
- 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.
- the resin material can be obtained by adding various additives as necessary and mixing them appropriately by a known method (for example, melt mixing).
- the resin material obtained by melt mixing can be used in the form of pellets if necessary.
- the tensile yield strength defined in JIS K7113: 1995 of the resin material (tire frame) itself is preferably 5 MPa or more, preferably 5 MPa to 20 MPa, and more preferably 5 MPa to 17 MPa.
- the resin material can withstand deformation against a load applied to the tire during traveling.
- the tensile yield elongation defined by JIS K7113: 1995 of the resin material (tire frame) itself is preferably 10% or more, preferably 10% to 70%, and more preferably 15% to 60%.
- 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.
- the rim assembly property is good and it is possible to make it difficult to break against a collision.
- the deflection temperature under load (when loaded with 0.45 MPa) as defined in ISO 75-2 or ASTM D648 of the resin material (tire frame) itself is preferably 50 ° C. or more, preferably 50 ° C. to 150 ° C., and preferably 50 ° C. to 50 ° C. 130 ° C. is more preferable.
- 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.
- FIG. 1A is a perspective view showing a partial cross section of a tire according to an embodiment of the present invention.
- FIG. 1B is a cross-sectional view of a bead portion attached to a rim.
- the tire 10 of the present embodiment has a cross-sectional shape that is substantially the same as a conventional general rubber pneumatic tire.
- the tire 10 includes a pair of bead portions 12 that contact the bead seat 21 and the rim flange 22 of the rim 20 shown in FIG. 1B, and side portions 14 that extend outward from the bead portion 12 in the tire radial direction.
- a tire case 17 is provided that includes a crown portion 16 (outer peripheral portion) that connects an outer end in the tire radial direction of one side portion 14 and an outer end in the tire radial direction of the other side portion 14.
- the tire case 17 of the present embodiment includes, as a resin material, for example, a polyamide-based thermoplastic elastomer having an ester bond and an HS mass ratio of 54/46 to 90/10 including each additive. Can be used.
- a resin material for example, a polyamide-based thermoplastic elastomer having an ester bond and an HS mass ratio of 54/46 to 90/10 including each additive. Can be used.
- the tire case 17 is formed of a single resin material.
- 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.
- 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 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.
- 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.
- an annular bead core 18 made of a steel cord is embedded in the bead portion 12, similar to a conventional general pneumatic tire.
- 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.
- an organic fiber cord, a resin-coated organic fiber cord, or a hard resin may be used.
- 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.
- 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.
- thermoplastic resin thermoplastic elastomer
- 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.
- 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.
- a reinforcement 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.
- FIG. 2 is a cross-sectional view along the tire rotation axis showing a state where a reinforcing cord is embedded in the crown portion of the tire case of the tire of the first embodiment.
- the reinforcing cord 26 is spirally wound in a state in which at least a part is embedded in the crown portion 16 in a sectional view along the axial direction of the tire case 17.
- a reinforcing cord layer 28 indicated by a broken line portion in FIG. 2 is formed together with a part of the outer peripheral portion 17.
- 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).
- a monofilament 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
- a steel cord is used as the reinforcing cord 26.
- 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.
- the reinforcing cord layer 28 corresponds to a belt disposed on the outer peripheral surface of the carcass of a conventional rubber pneumatic tire.
- the crown 30 is disposed on the outer peripheral side of the reinforcing cord layer 28 in the tire radial direction.
- the rubber used for the crown 30 is preferably the same type of rubber used in conventional rubber pneumatic tires.
- a crown formed of another type of resin material that is more excellent in wear resistance than the resin material constituting the tire case 17 may be used.
- the crown 30 is formed with a crown pattern including a plurality of grooves on the ground contact surface with the road surface in the same manner as a conventional rubber pneumatic tire.
- the manufacturing method of the tire of this embodiment is explained.
- a tire case half is formed using a resin material containing the polyamide-based thermoplastic elastomer. These tire cases are preferably formed by injection molding.
- the tire case halves supported by the thin metal support ring face each other.
- 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.
- 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.
- 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.
- the joint portion of the tire case half is heated and pressed by the joining mold, the joint portion is melted and the tire case halves are fused together, and the tire case 17 is formed by integrating these members.
- the joining portion of the tire case half is heated using a joining mold, but the present invention is not limited to this.
- the joining portion is heated by a separately provided high-frequency heater or the like.
- 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.
- FIG. 3 is an explanatory diagram for explaining an operation of embedding a reinforcing cord in a crown portion of a tire case using a cord heating device and rollers.
- the cord supply device 56 is disposed on the reel 58 around which the reinforcing cord 26 is wound, the cord heating device 59 disposed on the downstream side of the reel 58 in the cord transport direction, and the downstream side of the reinforcing cord 26 in the transport direction.
- the first roller 60, the first cylinder device 62 that moves the first roller 60 in the direction of contacting and separating from the outer peripheral surface of the tire, and the downstream side in the conveying direction of the reinforcing cord 26 of the first roller 60 A second roller 64, and a second cylinder device 66 that moves the second roller 64 in a direction in which the second roller 64 comes in contact with and separates from the tire outer peripheral surface.
- the second roller 64 can be used as a metal cooling roller.
- the surface of the first roller 60 or the second roller 64 is made of fluororesin (in this embodiment, Teflon (registered trademark)) in order to suppress adhesion of a molten or softened resin material. It is coated.
- 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 26 passes through an internal space in which hot air is supplied, and a discharge port 76 for discharging the heated reinforcing cord 26.
- 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.
- the reinforcing cord 26 unwound from the reel 58 is fed into a heating box 74 in which the internal space is heated with hot air (for example, the temperature of the reinforcing cord 26 is heated to about 100 to 200 ° C.).
- the heated reinforcing cord 26 passes through the discharge port 76 and is wound spirally around the outer peripheral surface of the crown portion 16 of the tire case 17 rotating in the direction of arrow R in FIG.
- the resin material at the contact portion melts or softens, and at least a part of the heated reinforcing cord 26 is embedded in the outer peripheral surface of the crown portion 16. Is done. At this time, since the heated reinforcing cord 26 is embedded in the molten or softened resin material, there is no gap between the resin material and the reinforcing cord 26, that is, a tight contact state. Thereby, the air entering to the portion where the reinforcing cord 26 is embedded is suppressed.
- the burying amount L of the reinforcing cord 26 can be adjusted by the heating temperature of the reinforcing cord 26, the tension applied to the reinforcing cord 26, the pressing force by the first roller 60, and the like.
- the embedding amount L of the reinforcing cord 26 is set to be 1/5 or more of the diameter D of the reinforcing cord 26.
- the burying amount L of the reinforcing cord 26 is more preferably more than 1/2 of the diameter D, and most preferably the entire reinforcing cord 26 is embedded.
- the reinforcing cord layer 28 is formed on the outer peripheral side of the crown portion 16 of the tire case 17 by winding the heated reinforcing cord 26 while being embedded in the outer peripheral surface of the crown portion 16.
- the vulcanized belt-shaped crown 30 is wound around the outer peripheral surface of the tire case 17 by one turn, and the crown 30 is bonded to the outer peripheral surface of the tire case 17 using an adhesive or the like.
- the crown 30 may be, for example, a precure crown that is used in conventionally known retreaded tires. This step is the same step as the step of bonding the precure crown to the outer peripheral surface of the base tire of the retreaded tire.
- the seal layer 24 made of vulcanized rubber is bonded to the bead portion 12 of the tire case 17 using an adhesive or the like, the tire 10 is completed.
- the tire case 17 is formed of a resin material that includes an ester bond and includes a polyamide-based thermoplastic elastomer having an HS mass ratio of 54/46 to 90/10, the rolling resistance is low. It is low and the rim assembly property can be improved.
- the tire 10 is light in weight because it has a simple structure as compared with a conventional rubber tire. For this reason, the tire 10 of this embodiment has high friction resistance and durability. Further, since the tire case 17 can be injection-molded, the productivity is very excellent.
- 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.
- the reinforcing cord 26 is embedded in the outer peripheral surface of the crown portion 16 of the tire case 17 made of a resin material in a cross-sectional view along the axial direction of the tire case 17 (cross section shown in FIG. 1).
- the reinforcing cord 26 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 crown 30, and the durability of the tire 10 is improved.
- the reinforcing cord layer 28 is configured to include a resin material in this way, the difference in hardness between the tire case 17 and the reinforcing cord layer 28 is reduced as compared with the case where the reinforcing cord 26 is fixed with cushion rubber. Therefore, the reinforcing cord 26 can be further adhered or fixed to the tire case 17. Thereby, the above-mentioned air entering can be prevented effectively, and it can control effectively that a reinforcement cord member moves at the time of driving. Furthermore, when the reinforcing cord 26 is a steel cord, the reinforcing cord 26 can be easily separated and collected from the resin material by heating at the time of disposal of the tire, which is advantageous in terms of recyclability of the tire 10.
- the resin material has a lower loss coefficient (tan ⁇ ) than vulcanized rubber, if the reinforcing cord layer 28 contains a large amount of the resin material, the rolling property of the tire can be improved. Furthermore, the resin material has an advantage that the in-plane shear rigidity is larger than that of the vulcanized rubber, and the handling property and wear resistance during running of the tire are excellent.
- the embedding amount L of the reinforcement cord 26 is 1/5 or more of the diameter D as shown in FIG. 2, the air entry at the time of manufacture is suppressed effectively, the input at the time of driving, etc. This further suppresses the movement of the reinforcing cord 26.
- the crown 30 in contact with the road surface is made of a rubber material that is more resistant to wear than the resin material constituting the tire case 17, the wear resistance of the tire 10 is improved. 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 like the conventional rubber pneumatic tire. Retained.
- the tire case 17 uses a polyamide-based thermoplastic elastomer that includes an ester bond and has an HS mass ratio of 54/46 to 90/10, the tire case 17 is attached to a portion that contacts the rim 20 of the bead portion 12.
- the sealing layer 24 made of a rubber material having a sealing property rather than the resin material to be configured, the rim assembly property between the tire 10 and the rim 20 can be further improved.
- the reinforcing cord 26 is heated and the surface of the tire case 17 where the heated reinforcing cord 26 contacts is melted or softened.
- the present invention is not limited to this configuration, and the reinforcing cord is used. It is also possible to use a hot air generating device without heating 26 and heat the outer peripheral surface of the crown portion 16 in which the reinforcing cord 26 is embedded, and then embed the reinforcing cord 26 in the crown portion 16.
- the heat source of the cord heating device 59 is a heater and a fan.
- the present invention is not limited to this configuration, and the reinforcement cord 26 may be directly heated by radiant heat (for example, infrared rays). Good.
- the portion in which the resin material in which the reinforcing cord 26 is embedded is melted or softened is forcibly cooled by the metal second roller 64, but the present invention is limited to this configuration.
- a configuration may be adopted in which cold air is directly blown onto a portion where the resin material is melted or softened to forcibly cool and solidify the melted or softened portion of the resin material.
- the reinforcing cord 26 is heated.
- 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.
- 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.
- 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 tire of the present invention is an embodiment using a reinforcing cord member in which the cord member is coated with a resin material as shown in the second embodiment (FIGS. 4 and 5) of JP 2012-46030 A. Also good.
- ABA type triblock polyether diol was a transparent and slightly yellow viscous liquid.
- Examples 1 to 5 In the synthesis of the polyamide of Comparative Example 1, the amounts of aminododecanoic acid and adipic acid were changed to those shown in Table 1 below. Further, in the synthesis of the polyamide elastomer, the amounts of nylon 12 and ABA triblock polyether diol were changed as follows. Except having changed into the thing of Table 1, it carried out similarly to the comparative example 1, and obtained the polymer of each Example.
- PA12 means polyamide 12 (nylon 12)
- ABA type TPEG means ABA type triblock polyether diol
- Zr (Obu) 4 is Zr (O—C 4).
- H 8 ) means 4 .
- PA12 means polyamide 12 (nylon 12)
- PTMG means polytetramethylene ether glycol
- Zr (Obu) 4 means Zr (O—C 4 H 8 ). 4 means.
- PPG polypropylene glycol
- PTMG polytetramethylene ether glycol
- the comparative example in which the HS mass ratio of the polyamide-based thermoplastic elastomer contained in the tire case is out of the range of 54/46 to 90/10 is inferior to the examples in terms of rim assembly. I understand that.
- A represents “HO-PPG-PTMG-PPG-OH”
- B represents “PTMG”
- C represents “H 2 N-PPG-PTMG-PPG-NH 2 ”.
- Comparative Example 4 using a polyamide-based thermoplastic elastomer having no ester bond in the molecule is compared with an example using a polyamide-based thermoplastic elastomer having an ester bond in the molecule. It can be seen that the tire rolling resistance index is high.
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Abstract
Description
[先行技術文献]
[特許文献1]特開2003-104008号公報
[特許文献2]特開2012-46030号公報
上述のように前記タイヤは、樹脂材料を用いたタイヤ骨格体を有する。前記樹脂材料は、少なくともHS質量比が54/46~90/10であり、且つ、エステル結合を含むポリアミド系熱可塑性エラストマー(以下、単に「本発明におけるポリアミド系熱可塑性エラストマー」と称することがある)を含む。前記樹脂材料は、ポリアミド系熱可塑性エラストマー以外の熱可塑性エラストマーや任意の成分を含んでいてもよいが、前記樹脂材料の総量に対する本発明におけるポリアミド系熱可塑性エラストマーの含有量が30質量%以上であることが好ましく、50質量%以上であることが更に好ましく、70質量%以上であることが特に好ましい。また、本明細書において「樹脂」とは、熱可塑性樹脂及び熱硬化性樹脂を含む概念であるが、天然ゴムは含まない。
上述のように本発明におけるポリアミド系熱可塑性エラストマーとしては、少なくともポリアミドが結晶性で融点の高いハードセグメントを構成し、他のポリマー(例えば、ポリエステル又はポリエーテル等)が非晶性でガラス転移温度の低いソフトセグメントを構成している材料が挙げられる。また、ポリアミド系熱可塑性エラストマーはハードセグメント及びソフトセグメントの結合部として、ジカルボン酸等の鎖長延長剤を用いてもよい。
前記ハードセグメントを形成するポリアミドとしては、例えば、下記一般式(1)又は一般式(2)で表されるモノマーを用いて合成されるポリアミドを挙げることができる。
前記一般式(1)又は一般式(2)で表されるモノマーとしては、ω-アミノカルボン酸やラクタムが挙げられる。また、前記ハードセグメントを形成するポリアミドとしては、これらω-アミノカルボン酸やラクタムの重縮合体や、ジアミンとジカルボン酸との共縮重合体等が挙げられる。
前記ジアミンとしては、例えば、エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン、2,2,4-トリメチルヘキサメチレンジアミン、2,4,4-トリメチルヘキサメチレンジアミン、3-メチルペンタメチレンジアミン、メタキシレンジアミンなどの炭素数2~20の脂肪族ジアミンなどのジアミン化合物を挙げることができる。また、ジカルボン酸は、HOOC-(R3)m-COOH(R3:炭素数3~20の炭化水素の分子鎖、m:0又は1)で表すことができ、例えば、シュウ酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸などの炭素数2~22の脂肪族ジカルボン酸を挙げることができる。
前記ポリアミド11は、例えば、{CO-(CH2)10-NH}n(nは任意の繰り返し単位数を表す)で表すことができ、例えば、nとしては2~100が好ましく、3~50が更に好ましい。
前記ポリアミド12は、例えば、{CO-(CH2)11-NH}n(nは任意の繰り返し単位数を表す)で表すことができ、例えば、nとしては2~100が好ましく、3~50が更に好ましい。
前記ポリアミド66は、例えば、{CO(CH2)4CONH(CH2)6NH}n(nは任意の繰り返し単位数を表す)で表すことができ、例えば、nとしては2~100が好ましく、3~50が更に好ましい。
前記ソフトセグメントを形成するポリマーとしては、例えば、ポリエステルや、ポリエーテルが挙げられ、更に、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコール(PTMG)、ポリエステルポリオール等のポリエステル、ABA型トリブロックポリエーテルジオール等が挙げられ、これらを単独で又は2種以上を用いることができる。また、ポリエーテルの末端にアニモニア等を反応させることによって得られるポリエーテルジアミン等を用いることができ、例えば、ABA型トリブロックポリエーテルジアミンを用いることができる。
上述のジアミンは単独で使用してもよいし、2種類以上を適宜組合せて使用してもよい。
上述のように、ポリアミド系熱可塑性エラストマーはハードセグメント及びソフトセグメントの他に、ジカルボン酸等の鎖長延長剤を用いてもよい。前記ジカルボン酸としては、例えば、脂肪族、脂環式及び芳香族ジカルボン酸から選ばれる少なくとも一種又はこれらの誘導体を用いることができる。
本発明におけるポリアミド系熱可塑性エラストマーは、分子中にエステル結合を有する。本発明のタイヤはエステル結合を有することで、転がり抵抗を下げることができる。前記エステル結合は、ポリアミド系熱可塑性エラストマーのハードセグメントやソフトセグメント中のいずれにあってもよいが、ソフトセグメントとして、ポリエステルポリオール等のポリエステルを含む共重合体を用いてもよいし、ソフトセグメントとしてポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコール(PTMG)、又は、上述のABA型トリブロックポリエーテルジオール等の両末端に水酸基を有するジオール化合物を用い、更に鎖長延長剤として多価カルボン酸(ジカルボン酸)を用い、これらの縮重合体に由来する構成単位に含まれるエステル結合を有していてもよい。以上の観点から、本発明におけるポリアミド系熱可塑性エラストマーとしては、ソフトセグメントとしてジオール化合物を含み、前記ジオール化合物の水酸基と、(例えば、ハードセグメントや鎖長延長剤中の)カルボキシル基との結合に由来するエステル結合を含むことが好ましい。前記ジオール化合物としては、特に限定はなく上述のグリコール類やジオール類を挙げることができる。具体的には、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコール(PTMG)、及び、上述の一般式(3)で表されるABA型トリブロックポリエーテルジオールから選ばれる両末端に水酸基を有するジオール化合物を挙げることができ、例えば、ABA型トリブロックポリエーテルジオールやPTMG用いることができる。
本発明におけるポリアミド系熱可塑性エラストマーは、前記ポリアミド系熱可塑性エラストマーのハードセグメント(HS)とソフトセグメント(SS)との質量比(HS/SS)が54/46~90/10である。前記HS質量比が54/46未満であると、弾性率が低く、形状保持性が劣り、リム組み性が低下する。また、前記HS質量比が90/10を超えると、弾性率が高く、うまくリムに組めず、リム組み性が低下する。前記HS質量比は、ハードセグメントを構成する原料及びソフトセグメントを構成する原料の仕込み量を設定することで所望の範囲に調整することができる。また、前記HS質量比は、1H-NMRを用いることで、測定することができる。また、耐久性の観点からHS質量比としては54/46~88/12であることが好ましい。
前記鎖長延長剤を用いる場合、その含有量は前記ソフトセグメントを構成するモノマーの水酸基又はアミノ基と、鎖長延長剤のカルボキシル基とがほぼ等モルになるように設定されることが好ましい。
前記ポリアミド系熱可塑性エラストマー中のハードセグメント、ソフトセグメント及び必要に応じて用いられる鎖長延長剤の含有量は、HS質量比が上述の範囲内になるように適宜選定され、例えば各々の仕込み量を設定することで各々所望の含有量とすることができる。
本発明において、樹脂材料に含まれるポリアミド系熱可塑性エラストマーの重量平均分子量は、特に限定はないが、10,000~400,000程度であることが好ましい。リム組み性の更なる向上やタイヤの内圧に対する耐圧性を向上させる観点からは、前記ポリアミド系熱可塑性エラストマーの重量平均分子量が15,700~300,000が好ましく、22,000~200,000が更に好ましい。前記ポリアミド系熱可塑性エラストマーの重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)により測定することができ、例えば、東ソー株式会社製の「HLC-8320GPC EcoSEC」等のGPC(ゲル浸透クロマトグラフィー)を用いることができる。
また、前記ポリアミド系熱可塑性エラストマーの製造においては、必要に応じて触媒を用いることができる。前記触媒としては、P、Ti、Ge、Zn、Fe、Sn、Mn、Co、Zr、V、Ir、La、Ce、Li、Ca、及び、Hfからなる群より選択される少なくとも1種を含む化合物が挙げられる。
例えば、無機系リン化合物、有機チタン化合物、有機ジルコニウム化合物、有機スズ化合物等が挙げられる。
具体的には、無機系リン化合物としては、リン酸、ピロリン酸、ポリリン酸、亜リン酸、次亜リン酸等のリン含有酸、リン含有酸のアルカリ金属塩、リン含有酸のアルカリ土類金属塩等が挙げられる。
有機チタン化合物としては、チタンアルコキシド〔チタンテトラブトキシド、チタンテトライソプロポキシド等〕等が挙げられる。
有機ジルコニウム化合物としては、ジルコニウムアルコキシド〔ジルコニウムテトラブトキシド(「Zr(OBu)4」または「Zr(OC4H8)4」とも称される)等〕等が挙げられる。
有機スズ化合物としては、ジスタノキサン化合物〔1-ヒドロキシ-3-イソチオシアネート-1,1,3,3-テトラブチルジスタノキサン等〕、酢酸スズ、ジラウリン酸ジブチルスズ、ブチルチンヒドロキシドオキシドヒドレート等が挙げられる。
触媒添加量及び触媒添加時期は、目的物を速やかに得られる条件であれば特に制限されない。
次に、タイヤ骨格体を構成する樹脂材料の好ましい物性について説明する。本発明におけるタイヤ骨格体は、上述の樹脂材料を用いるものである。
このように、融点が120℃~250℃の樹脂材料を用いることで、例えばタイヤの骨格体を、その分割体(骨格片)を融着して形成する場合に、120℃~250℃の周辺温度範囲で融着された骨格体であってもタイヤ骨格片同士の接着強度が十分である。このため、本発明のタイヤは耐パンク性や耐摩耗性など走行時における耐久性に優れる。尚、前記加熱温度は、タイヤ骨格片を形成する樹脂材料の融点(又は軟化点)よりも10℃~150℃高い温度が好ましく、10℃~100℃高い温度が更に好ましい。
溶融混合して得られた樹脂材料は、必要に応じてペレット状にして用いることができる。
以下に、図面に従って本発明のタイヤの第1の実施形態に係るタイヤを説明する。
本実施形態のタイヤ10について説明する。図1Aは、本発明の一実施形態に係るタイヤの一部の断面を示す斜視図である。図1Bは、リムに装着したビード部の断面図である。図1Aに示すように、本実施形態のタイヤ10は、従来一般のゴム製の空気入りタイヤと略同様の断面形状を呈している。
また、本実施形態では、タイヤケース半体17Aは左右対称形状、即ち、一方のタイヤケース半体17Aと他方のタイヤケース半体17Aとが同一形状とされているので、タイヤケース半体17Aを成形する金型が1種類で済むメリットもある。
以下、本実施形態のタイヤの製造方法について説明する。
まず、上述のように前記ポリアミド系熱可塑性エラストマーを含む樹脂材料を用いて、タイヤケース半体を形成する。これらタイヤケースの形成は、射出成形で行うことが好ましい。次に、薄い金属の支持リングに支持されたタイヤケース半体同士を互いに向かい合わせる。次いで、タイヤケース半体の突き当て部分の外周面と接するように図を省略する接合金型を設置する。ここで、前記接合金型はタイヤケース半体17Aの接合部(突き当て部分)周辺を所定の圧力で押圧するように構成されている。次いで、タイヤケース半体の接合部周辺を、タイヤケースを構成する樹脂材料の融点(又は軟化点)以上で押圧する。タイヤケース半体の接合部が接合金型によって加熱及び加圧されると、前記接合部が溶融しタイヤケース半体同士が融着しこれら部材が一体となってタイヤケース17が形成される。尚、本実施形態においては接合金型を用いてタイヤケース半体の接合部を加熱したが、本発明はこれに限定されず、例えば、別に設けた高周波加熱機等によって前記接合部を加熱したり、予め熱風、赤外線の照射等によって軟化又は溶融させ、接合金型によって加圧して、タイヤケース半体を接合させてもよい。
次に、補強コード巻回工程について図3を用いて説明する。図3は、コード加熱装置、及びローラ類を用いてタイヤケースのクラウン部に補強コードを埋設する動作を説明するための説明図である。図3において、コード供給装置56は、補強コード26を巻き付けたリール58と、リール58のコード搬送方向下流側に配置されたコード加熱装置59と、補強コード26の搬送方向下流側に配置された第1のローラ60と、第1のローラ60をタイヤ外周面に対して接離する方向に移動する第1のシリンダ装置62と、第1のローラ60の補強コード26の搬送方向下流側に配置される第2のローラ64と、及び第2のローラ64をタイヤ外周面に対して接離する方向に移動する第2のシリンダ装置66と、を備えている。第2のローラ64は、金属製の冷却用ローラとして利用することができる。また、本実施形態において、第1のローラ60又は第2のローラ64の表面は、溶融又は軟化した樹脂材料の付着を抑制するためにフッ素樹脂(本実施形態では、テフロン(登録商標))でコーティングされている。なお、本実施形態では、コード供給装置56は、第1のローラ60又は第2のローラ64の2つのローラを有する構成としているが、本発明はこの構成に限定されず、何れか一方のローラのみ(即ち、ローラ1個)を有している構成でもよい。
本実施形態のタイヤ10では、タイヤケース17が、エステル結合を含み且つHS質量比が54/46~90/10であるポリアミド系熱可塑性エラストマーを含む樹脂材料によって形成されているため、転がり抵抗が低く、また、リム組み性を向上させることができる。また、タイヤ10は従来のゴム製のタイヤに比して構造が簡易であるため重量が軽い。このため、本実施形態のタイヤ10は、耐摩擦性及び耐久性が高い。更に、タイヤケース17を射出成形できることから生産性にも非常に優れる。
更に、補強コード26がスチールコードの場合に、タイヤ処分時に補強コード26を加熱によって樹脂材料から容易に分離や回収が可能であるため、タイヤ10のリサイクル性の点で有利である。また、樹脂材料は加硫ゴムに比して損失係数(tanδ)が低いため、補強コード層28が樹脂材料を多く含んでいると、タイヤの転がり性を向上させることができる。更には、樹脂材料は加硫ゴムに比して、面内せん断剛性が大きく、タイヤ走行時の操安性や耐摩耗性にも優れるといった利点がある。
さらに、ビード部12には、金属材料からなる環状のビードコア18が埋設されていることから、従来のゴム製の空気入りタイヤと同様に、リム20に対してタイヤケース17、すなわちタイヤ10が強固に保持される。
-ポリアミドの合成-
攪拌機、温度計、トルクメーター、圧力計、窒素ガス導入口、圧力調整装置及びポリマー取り出し口を備えた50リットルの圧力容器にALDRICH製の12-アミノドデカン酸17.75kg、ALDRICH製のアジピン酸0.25kgを仕込んだ。
次いで、容器内を十分に窒素で置換した後、窒素ガスを供給しながら容器内の圧力を0.05MPaに調整し、室温から240℃まで昇温した。さらに容器内の圧力を0.05MPaに調整しながら240℃で4時間重合(重合反応A)を行い両末端カルボン酸のナイロン12(上述のポリアミド12)を得た(ナイロンは登録商標)。
攪拌機、温度計、圧力計、窒素ガス導入口、原料投入口、圧力調整装置、生成物取り出し口を備えた50Lの圧力容器にALDRICH製「TERATHANE650」(PTMG:ポリテトラメチレングリコール)8.6kg及び水酸化カリウム50gを仕込み、容器内を十分窒素ガスで置換した後、窒素ガスを100ml/分で供給しながら、攪拌し、ALDRICH製プロピレンオキシド9.9kgを徐々に滴下した。次に、窒素ガス導入口のバルブを閉めて窒素ガスの導入を止め、約3時間かけて120℃まで昇温し、更に120℃で4時間反応させた。その後反応物を室温まで冷却し、容器の下部の取り出し口から生成物を取り出した。生成物にクエン酸水溶液を加えて中和し、水溶液相と生成物相を分離した後、生成物相を水で7回洗浄し、ABAトリブロックポリエーテルジオールを合成した。得られたABA型トリブロックポリエーテルジオールは透明で僅かに黄色の粘調な液状物であった。
攪拌機、温度計、トルクメーター、圧力計、窒素ガス導入口、圧力調整装置及びポリマー取り出し口を備えた50リットルの圧力容器に、上記から得られた両末端カルボン酸のナイロン12を16.38kgと、ABA型トリブロックポリエーテルジオール1.62kgとを容器内に仕込み、200℃まで昇温して攪拌を開始し、ALDRICH製の触媒(Zr(O-C4H8)4)を1.8g投入し、その後、容器内を260℃まで昇温し、更に真空ポンプにより容器内を真空にした。更に2時間攪拌して重合反応を行い重合体を得た。
比較例1のポリアミドの合成において、アミノドデカン酸及びアジピン酸の量を下記表1に記載のものに変更し、更に、ポリアミドエラストマーの合成において、ナイロン12及びABAトリブロックポリエーテルジオールの量を下記表1に記載のものに変更した以外は比較例1と同様にして各実施例の重合体を得た。
-ポリアミドの合成-
攪拌機、温度計、トルクメーター、圧力計、窒素ガス導入口、圧力調整装置及びポリマー取り出し口を備えた50リットルの圧力容器にALDRICH製のラウリロラクタム19.47kg、ALDRICH製の12-アミノドデカン酸0.69kg、ALDRICH製のデカンジカルボン酸7.84kgを仕込んだ。
次いで、容器内を280℃まで昇温し、2時間攪拌した。更に、窒素ガスを供給して280℃で2時間重合を行い、両末端カルボン酸のナイロン12(上述のポリアミド12)を得た(ナイロンは登録商標)。
攪拌機、温度計、トルクメーター、圧力計、窒素ガス導入口、圧力調整装置及びポリマー取り出し口を備えた50Lの圧力容器に、上記から得られた両末端カルボン酸のナイロン12を7.31kgと、和光純薬(株)製のPTMG(重量平均分子量:650)10.69kgとを容器内に仕込み、200℃まで昇温して攪拌を開始し、ALDRICH製の触媒(Zn(O-C4H8)4)を1.62g投入し、その後、容器内を260℃まで昇温し、更に真空ポンプにより容器内を真空にした。更に3時間攪拌して重合反応を行い、重合体を得た。
比較例2のポリアミドの合成において、ラウリロラクタム及びアミノドデカン酸及びデカンジカルボン酸の量を下記表2に記載のものに変更し、更に、ポリアミドエラストマーの合成において、ナイロン12(PA12)、PTMG及びZr(O-C4H8)4の量を下記表1に記載のものに変更した以外は比較例1と同様にして各実施例及び比較例の重合体を得た。
各実施例及び比較例で得られた重合体を用いて、それぞれ上述の第1の実施形態を参照し、タイヤを形成した。次いで、タイヤをリムに装着し、リムに組め、空気抜けがあるか否かを測定した。リムに組めて空気抜けが認められなかったものを「A」、リムに組めなかったもの、又は、空気抜けが認められたものを「C」として評価した。
攪拌機、温度計、トルクメーター、圧力計、窒素ガス導入口、圧力調整装置及びポリマー取り出し口を備えた50リットルの圧力容器に12-アミノドデカン酸11.24kg、ABA型のトリブロックポリエーテルジアミン(HUNTSMAN社製の「XTJ-542)3.21kg、アジピン酸0.67kgを仕込んだ。
次いで、圧力容器内を十分窒素置換した後、窒素ガスを供給しながら、圧力容器内の圧力を0.05MPaに調整し、室温から240℃まで昇温した。圧力容器内の圧力を0.05MPaに調整しながら240℃で2時間重合を行った。
実施例4、実施例7及び比較例4で得られた重合体を用いて、それぞれ上述の第1の実施形態を参照し、タイヤを形成した。各タイヤを標準リムに装着し、内圧を230kPaに調整した後、鉄板表面を持つドラム試験機(速度:80km/h)を用いて、車軸の転がり抵抗力を求めた。転がり抵抗の測定はJIS D4234に準拠し、スムースドラム、フォース式にて実施したものである。
Claims (5)
- 樹脂材料で形成され且つ環状のタイヤ骨格体を有し、
前記樹脂材料は、分子中にエステル結合を含むポリアミド系熱可塑性エラストマーを含み、
前記ポリアミド系熱可塑性エラストマーのハードセグメント(HS)とソフトセグメント(SS)との質量比(HS/SS)が54/46~90/10であるタイヤ。 - 前記ポリアミド系熱可塑性エラストマーのハードセグメント(HS)とソフトセグメント(SS)との質量比(HS/SS)が54/46~88/12である請求項1に記載のタイヤ。
- 前記ポリアミド系熱可塑性エラストマーが、ソフトセグメントとしてジオール化合物を含み、カルボキシル基と、前記ジオール化合物の水酸基との結合に由来するエステル結合を含む請求項1又は2に記載のタイヤ。
- 前記ポリアミド系熱可塑性エラストマーが、前記ハードセグメントとして、-[CO-(CH2)11-NH]-で表される構成単位を有するポリアミドを有する請求項1~4のいずれか1項に記載のタイヤ。
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