WO2016052565A1 - タイヤ - Google Patents
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- WO2016052565A1 WO2016052565A1 PCT/JP2015/077613 JP2015077613W WO2016052565A1 WO 2016052565 A1 WO2016052565 A1 WO 2016052565A1 JP 2015077613 W JP2015077613 W JP 2015077613W WO 2016052565 A1 WO2016052565 A1 WO 2016052565A1
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- WIPO (PCT)
- Prior art keywords
- tire
- thermoplastic elastomer
- acid
- resin material
- molecular weight
- 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
- B60C5/00—Inflatable pneumatic tyres or inner tubes
- B60C5/007—Inflatable pneumatic tyres or inner tubes made from other material than rubber
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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
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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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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- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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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.
- thermoplastic polymer materials such as thermoplastic elastomers and thermoplastic resin materials
- JP 2012-46030 A proposes a tire using a polyamide-based thermoplastic elastomer as the thermoplastic polymer material.
- a tire using a thermoplastic polymer material is easier to manufacture and lower in cost than a conventional rubber tire.
- an object of the present invention is to provide a tire that is formed using a resin material and has both a desirable elastic modulus and excellent low-loss properties.
- 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 (that is, formed of at least a resin material) and has an annular tire skeleton.
- the resin material has a hard segment (HS) and a soft segment (SS), the soft segment (SS) contained in one molecular chain is one unit, and both ends of the one molecular chain are A thermoplastic elastomer which is the hard segment (HS) and has a number average molecular weight of 12,000 to 24,000 is included.
- the thermoplastic elastomer contained in the resin material has a hard segment and a soft segment, so that the characteristics of these segments can be obtained.
- the characteristics of each segment are sufficiently obtained as expected by the region where the hard segment and the soft segment are mixed (hereinafter referred to as “intermediate phase”) existing at the interface of these segments. There may not be.
- the thermoplastic elastomer contained in the resin material of the tire of the present invention first has a structure in which the soft segment (SS) is one unit and both ends of one molecular chain are hard segments (HS). That is, a hard segment (HS) exists at both ends in one molecular chain, and a soft segment (SS) that does not include any hard segment (HS) between the two (2 units) hard segments (HS). ) Has a triblock structure of HS-SS-HS (including the case where soft segments (SS) or hard segments (HS) are connected by a chain extender).
- the intermediate phase in which HS and SS are mixed can be reduced, so that the crystallinity of HS that affects the elastic modulus is increased and the elastic modulus is improved. Further, as the degree of crystallinity increases, the whole becomes hard and the elastic modulus increases, and both ends are HS. Since HS at both ends is crystallized, the effect of reducing the free ends can be obtained and the loss is reduced. . As a result, it is possible to achieve both a desirable elastic modulus and an excellent low-loss property.
- thermoplastic elastomer used as the resin material has a hard segment (HS) and a soft segment (SS), and the soft segment (SS) contained in one molecular chain is one unit, and the one molecular chain Both ends of are the hard segment (HS).
- the number average molecular weight is 12,000 to 24,000.
- the resin material may contain a thermoplastic elastomer other than the thermoplastic elastomer and an optional component.
- resin is a concept including a thermoplastic resin and a thermosetting resin, but does not include natural rubber.
- the thermoplastic elastomer may have a joint between the hard segment (HS) and the soft segment (SS).
- the “joining part” is a joining part that joins two or more segments, that is, a joining part of a hard segment and a soft segment.
- the binding part include a part bound by a chain extender described later.
- a method for realizing a thermoplastic elastomer having a bonding portion will be described.
- the soft segment (SS) which has 2 units of hard segments (HS) which have one reactive functional group in a molecule
- thermoplastic elastomer has a structure in which a soft segment (SS) contained in one molecular chain is one unit and both ends of one molecular chain are hard segments (HS), that is, a triblock structure of HS-SS-HS.
- the confirmation method is to measure the average molecular weight of the thermoplastic elastomer by gel permeation chromatography (GPC) and to measure the average molecular weight of structural units such as hard segments (HS) and soft segments (SS) by NMR. It can be carried out.
- thermoplastic elastomer consists of only one hard segment (HS) and one soft segment (SS)
- Thermoplastic elastomer average molecular weight HS average molecular weight ⁇ 2 + SS average molecular weight ⁇ 1
- thermoplastic elastomer may include a bonding portion, and in the case where the bonding portion is included in addition to the hard segment (HS) and the soft segment (SS), the hard segment (HS), By measuring the average molecular weight of each of the soft segment (SS) and the binding portion, it can be confirmed whether or not the triblock structure of HS-SS-HS is provided.
- the number average molecular weight of the thermoplastic elastomer is in the range of 12,000 to 24,000. If it is less than 12,000, the rim assemblability will deteriorate. On the other hand, if it exceeds 24,000, the melt viscosity becomes high and there is a risk that insufficient filling will occur in the case of a tire skeleton, so it is necessary to increase the molding temperature and the mold temperature. For this reason, since cycle time becomes long, productivity is inferior.
- the number average molecular weight of the thermoplastic elastomer is preferably 15,000 to 24,000, more preferably 15,000 to 22,000.
- the number average molecular weight of the thermoplastic elastomer can be measured by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- HEC gel permeation chromatography
- the mass ratio (HS / SS) of the hard segment (HS) and the soft segment (SS) is preferably 5/95 to 50/50, more preferably 15/85 to 45/55, and 20 / 80 to 40/60 is more preferable. From the viewpoint of tire rigidity, 20/80 to 50/50 is preferable.
- the thermoplastic elastomer when the hard segment content in the mass ratio (HS / SS) of the hard segment (HS) and the soft segment (SS) is 5% by mass or more, the tire can have necessary rigidity. it can. On the other hand, when it is 50% by mass or less, the rim assembly property can be ensured by having a certain amount of SS.
- the content thereof is such that the hydroxyl group or amino group of the monomer that is the raw material of the soft segment and the carboxyl group of the chain extender are approximately equimolar. It is preferable to set to.
- thermoplastic elastomer examples include, for example, a polyamide-based thermoplastic elastomer (Thermoplastic Amid elastomer (TPA), a polyolefin-based thermoplastic elastomer (Thermoplastic Polyolefin, TPO), polystyrene, as defined in JIS K6418: 2007.
- Thermoplastic elastomers Styrenic Thermoplastic Elastomer, TPS
- polyurethane thermoplastic elastomers Thermoplastic Polyethane, TPU
- thermoplastic rubber crosslinks Thermoplastic Vulcanizates, Tplastic
- TPZ thermoplastic Vulcanizates
- the polyurethane-based thermoplastic elastomer (TPU) and the polyamide-based thermoplastic elastomer (TPA) are polymers having a bond portion due to the reaction of polyaddition, and only the structure of the bond portion is changed. It is a polymer that can change the physical properties of a thermoplastic elastomer, and is preferable because its technique has been established.
- a polyamide-based thermoplastic elastomer (TPA) is more preferable from the viewpoint of hydrolysis resistance.
- polyamide thermoplastic elastomer (TPA) and polyurethane thermoplastic elastomer (TPU) which are preferable thermoplastic elastomers in the present invention, will be described.
- the “polyamide thermoplastic elastomer” means a part or all of a soft segment having a low crystalline and low glass transition temperature and a polymer constituting part or all of a crystalline hard segment having a high melting point. It is a thermoplastic elastomer of a copolymer having a polymer that has an amide bond (—CONH—) in the main chain of the polymer constituting a part or all of the hard segment.
- the polyamide-based thermoplastic elastomer at least part of the polyamide is crystalline and constitutes a hard segment having a high melting point (preferably all), and other polymers (for example, polyester or polyether) are amorphous. And materials constituting part or all (preferably all) soft segments having a low glass transition temperature.
- the polyamide that forms part or all of the hard segment will be described.
- the polyamide is, for example, a polyamide synthesized using a monomer represented by the following general formula (1) or general formula (2), and polymerization is performed so that no reactive functional group remains at one end. Mention may be made of polyamides synthesized using a monomer that plays the role of stopping (hereinafter referred to as “stopper”).
- R 1 represents a hydrocarbon molecular chain having 2 to 20 carbon atoms (for example, an alkylene group having 2 to 20 carbon atoms).
- R 2 represents a molecular chain of a hydrocarbon having 3 to 20 carbon atoms (for example, an alkylene group having 3 to 20 carbon atoms).
- R 1 is preferably a hydrocarbon molecular chain having 3 to 18 carbon atoms (for example, an alkylene group having 3 to 18 carbon atoms), and a hydrocarbon molecular chain having 4 to 15 carbon atoms (for example, (Alkylene group having 4 to 15 carbon atoms) is more preferable, and a molecular chain of a hydrocarbon having 10 to 15 carbon atoms (for example, an alkylene group having 10 to 15 carbon atoms) is particularly preferable.
- R 2 is preferably a hydrocarbon molecular chain having 3 to 18 carbon atoms (eg, an alkylene group having 3 to 18 carbon atoms), and a hydrocarbon molecular chain having 4 to 15 carbon atoms.
- an alkylene group having 4 to 15 carbon atoms is more preferable, and a molecular chain of a hydrocarbon having 10 to 15 carbon atoms (for example, an alkylene group having 10 to 15 carbon atoms) is particularly preferable.
- the monomer represented by the general formula (1) or the general formula (2) include ⁇ -aminocarboxylic acid and lactam.
- the polyamide forming part or all of the hard segment include polycondensates of these ⁇ -aminocarboxylic acids and lactams, and co-condensation 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, or metaxylenediamine.
- the dicarboxylic acid can be represented by HOOC- (R 3 ) m —COOH (R 3 : a hydrocarbon molecular chain having 3 to 20 carbon atoms, m: 0 or 1).
- 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, or dodecanedioic acid.
- Examples of the terminator include “R A —COOH (R A is a hydrocarbon chain having 2 to 20 carbon atoms, an alkylene group having 2 to 20 carbon atoms, or a cyclic structure having 3 to 20 carbon atoms. And a monomer having a structure of “a functional group”.
- Specific examples of the terminator include saturated fatty acids such as dodecanoic acid, caproic acid, lauric acid, and stearic acid, unsaturated fatty acids such as linoleic acid, and oleic acid. By polymerizing these terminators together, it is possible to play a role of terminating the polymerization so that no reactive functional group remains at one end, and a polyamide in which only one end is modified is obtained.
- the molecular weight of the obtained hard segment can be controlled by adjusting the addition amount of the terminator.
- Polyamides that form part or all of the hard segment include polyamides obtained by ring-opening polycondensation of ⁇ -caprolactam (polyamide 6), polyamides obtained by ring-opening polycondensation of undecane lactam (polyamide 11), and lauryl lactams.
- 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, n is preferably 2 to 100, and more preferably 3 to 50.
- 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.
- polyester and polyether examples of the polymer that forms part or all of the soft segment include polyester and polyether.
- polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (PTMG), ABA type triblock polyether and the like can be mentioned. These may be used alone or in combination of two or more.
- polyether diamine etc. which are obtained by making ammonia etc. react with the terminal of polyether can be used, for example, ABA type
- examples of the “ABA type triblock polyether” 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.
- the combination of the hard segment and the soft segment the combination of the hard segment and the soft segment mentioned above can be given.
- 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 combination, Lauryl lactam ring-opening polycondensate / ABA type triblock polyether diamine combination, aminododecanoic acid polycondensate / polyethylene glycol combination, aminododecane Acid polycondensate / polypropylene glycol combination, aminododecanoic acid polycondensate / polytetramethylene ether glycol combination, aminododecanoic acid polycondensate / ABA type triamine combination, amino
- lauryl lactam ring-opening polycondensate / ABA type triblock polyether lauryl lactam ring opening polycondensate / ABA type triblock polyether diamine combination, aminododecanoic acid polycondensate / ABA type triblock polyether
- a combination of block polyethers or a polycondensate of aminododecanoic acid / ABA type triblock polyether diamine is particularly preferred.
- the polymer that forms part or all of the soft segment contains, as a monomer unit, a branched saturated diamine having 6 to 22 carbon atoms, a branched alicyclic diamine having 6 to 16 carbon atoms, or a diamine such as norbornane diamine. May be. These branched saturated diamines having 6 to 22 carbon atoms, branched alicyclic diamines having 6 to 16 carbon atoms, or norbornane diamines may be used alone or in combination. . Moreover, you may use in combination with the above-mentioned ABA type
- Examples of the branched saturated diamine having 6 to 22 carbon atoms include 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, and 1,2- Examples include diaminopropane, 1,3-diaminopentane, 2-methyl-1,5-diaminopentane, and 2-methyl-1,8-diaminooctane.
- Examples of the branched alicyclic diamine having 6 to 16 carbon atoms include 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine and 5-amino-1,3,3-trimethylcyclohexanemethyl.
- An amine etc. can be mentioned.
- These diamines may be either cis isomers or trans isomers, or may be a mixture of these isomers.
- Examples of the norbornane diamine include 2,5-norbonane dimethylamine, 2,6-norbonane dimethylamine, and mixtures thereof.
- the polymer which comprises a part or all of 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, or 3-methylpentanemethylenediamine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane Alicyclic diamines such as 1,3-bisaminomethylcyclohexane or 1,4-bisaminomethylcyclohexane, metaxylylenediamine, paraxylylenediamine, etc. And aromatic diamines.
- bond part of a polyamide-type thermoplastic elastomer includes the part couple
- the chain extender include dicarboxylic acid, diol, and diisocyanate.
- dicarboxylic acid at least 1 type chosen from aliphatic, alicyclic, and aromatic dicarboxylic acid, or these derivatives can be used, for example.
- diol include aliphatic diols, alicyclic diols, and aromatic diols.
- diisocyanate aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, and a mixture thereof can be used, for example.
- dicarboxylic acid examples include adipic acid, decanedicarboxylic acid, oxalic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.
- Chain aliphatic dicarboxylic acids dimerized aliphatic dicarboxylic acids having 14 to 48 carbon atoms obtained by dimerization of unsaturated fatty acids obtained by fractionation of triglycerides, and aliphatic dicarboxylic acids such as hydrogenated products thereof, 1,4-cyclohexane Mention may be made of alicyclic dicarboxylic acids such as dicarboxylic acids and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid. Among these, dodecanedioic acid, eicosanedioic acid, phenyldiacetic acid, terephthalic acid, and adipic acid are preferable.
- diisocyanate examples include 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2 , 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone Diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2,6-dii Propyl phenyl isocyanate, and 1,3,
- diol examples include ethylene oxide addition of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, and bisphenol A. Or a propylene oxide adduct of bisphenol A.
- aliphatic diols are preferable and butanediol is more preferable.
- the polyamide-based thermoplastic elastomer can be synthesized by copolymerizing a polymer forming part or all of the hard segment and a polymer forming part or all of the soft segment by a known method.
- the polyamide-based thermoplastic elastomer includes a monomer (for example, a monomer having a reactive functional group only at one end) and a monomer (for example, the ABA-type tri-material) that is a soft segment material. It can be obtained by polymerizing a block polyether or the ABA triblock polyether diamine) in a container.
- ⁇ -aminocarboxylic acid when used as a monomer that is a raw material for the hard segment, it can be synthesized by performing a normal pressure melt polymerization or a normal pressure melt polymerization followed by a low pressure melt polymerization.
- lactam When used as a monomer as a raw material for the hard segment, an appropriate amount of water can coexist, melt polymerization under a pressure of 0.1 to 5 MPa, followed by normal pressure melt polymerization and / or reduced pressure melt polymerization. It can manufacture by the method which has this.
- These synthesis reactions can be carried out either batchwise or continuously. In the above synthesis reaction, a batch type reaction vessel, a single tank type or multi-tank type continuous reaction apparatus, a tubular continuous reaction apparatus or the like may be used alone or in appropriate combination.
- 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 number 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 such as laurylamine, stearylamine, hexamethylenediamine, and metaxylylenediamine or the like for the purpose of adjusting the molecular weight and stabilizing the melt viscosity at the time of molding as necessary.
- Additives such as monocarboxylic acids such as diamine, acetic acid, benzoic acid, stearic acid, adipic acid, sebacic acid, and dodecanedioic acid, or dicarboxylic acids may be added. These additives can be appropriately selected in relation to the molecular weight and viscosity of the resulting polyamide-based thermoplastic elastomer within a range that does not adversely affect the effects of the present invention.
- 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 phosphorus-containing acids such as phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphorous acid, and hypophosphorous acid, alkali metal salts of phosphorus-containing acids, or alkalis of phosphorus-containing acids.
- Examples include earth metal salts.
- Examples of the organic titanium compound include titanium alkoxide [titanium tetrabutoxide, titanium tetraisopropoxide, or the like].
- Examples of the organic zirconium compound include zirconium alkoxide (zirconium tetrabutoxide (also referred to as “Zr (OBu) 4 ” or “Zr (OC 4 H 8 ) 4 )”).
- Examples of organotin compounds include distannoxane compounds [1-hydroxy-3-isothiocyanate-1,1,3,3-tetrabutyldistanoxane, etc.], tin acetate, dibutyltin dilaurate, or butyltin hydroxide oxide hydrate, etc. Is mentioned.
- the catalyst addition amount and the catalyst addition timing are not particularly limited as long as the target product can be obtained quickly.
- a polyurethane-based thermoplastic elastomer constitutes at least a part of a hard segment in which polyurethane forms pseudo-crosslinks due to physical aggregation, and other polymers are amorphous and have a low glass transition temperature.
- the material which comprises a part or all is mentioned. For example, it can be expressed as a copolymer containing a soft segment containing a unit structure represented by the following formula A and a hard segment containing a unit structure represented by the following formula B.
- P represents a long-chain aliphatic polyether or a long-chain aliphatic polyester.
- R represents an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon.
- P ′ represents a short-chain aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon.
- the long-chain aliphatic polyether and long-chain aliphatic polyester represented by P for example, those having a molecular weight of 500 to 5000 can be used.
- the P is derived from a diol compound containing a long-chain aliphatic polyether represented by the P and a long-chain aliphatic polyester.
- Examples of such a diol compound include polyethylene glycol, prepropylene glycol, polytetramethylene ether glycol, poly (butylene adipate) diol, poly- ⁇ -caprolactone diol, poly (hexamethylene) having a molecular weight within the above range.
- Carbonate) diol, the ABA type triblock polyether, and the like may be used alone or in combination of two or more.
- R is derived from a diisocyanate compound containing an aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon represented by R.
- aliphatic diisocyanate compound containing an aliphatic hydrocarbon represented by R include 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate, and 1,6-hexamethylene diisocyanate. Is mentioned.
- Examples of the diisocyanate compound containing an alicyclic hydrocarbon represented by R include 1,4-cyclohexane diisocyanate and 4,4-cyclohexane diisocyanate.
- aromatic diisocyanate compound containing an aromatic hydrocarbon represented by R include 4,4′-diphenylmethane diisocyanate and tolylene diisocyanate. These may be used alone or in combination of two or more.
- alicyclic hydrocarbon or aromatic hydrocarbon represented by P ′ for example, those having a molecular weight of less than 500 can be used.
- P ′ is derived from a diol compound containing a short-chain aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon represented by P ′.
- Examples of the aliphatic diol compound containing a short-chain aliphatic hydrocarbon represented by P ′ include glycol and polyalkylene glycol.
- Examples of the alicyclic diol compound containing an alicyclic hydrocarbon represented by P ′ include cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, Examples include cyclohexane-1,4-diol and cyclohexane-1,4-dimethanol.
- examples of the aromatic diol compound containing an aromatic hydrocarbon represented by P ′ include hydroquinone, resorcin, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4,4′- Dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxydiphenylmethane, bisphenol A, 1, Examples include 1-di (4-hydroxyphenyl) cyclohexane, 1,2-bis (4-hydroxyphenoxy) ethane, 1,4-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. These may be used alone or in combination of two or more.
- R in formula B
- binding part examples include a part bound by a chain extender.
- chain extender examples include those described above for the polyamide-based thermoplastic elastomer. Among these, dodecanedioic acid, eicosanedioic acid, phenyldiacetic acid, terephthalic acid, and adipic acid are preferable as the chain extender of the polyurethane-based thermoplastic elastomer.
- the polyurethane-based thermoplastic elastomer can be synthesized by copolymerizing a polymer that forms part or all of the hard segment and a polymer that forms part or all of the soft segment by a known method.
- various additives such as rubber, various fillers (for example, silica, calcium carbonate, clay), anti-aging agent, oil, plasticizer, colorant, weathering agent, and reinforcing material may be used as desired. May be included.
- the content of the additive in the resin material (tire frame) is not particularly limited, and can be appropriately used as long as the effects of the present invention are not impaired.
- 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 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 part or all of the tire frame piece, and more preferably 10 ° C. to 100 ° C.
- the resin material can be obtained by adding various additives as necessary and mixing them appropriately by a known method (for example, melt mixing).
- the resin material obtained by melt mixing can be used in the form of pellets if necessary.
- the tensile yield strength defined in JIS K7113: 1995 of the resin material (tire frame) itself is preferably 5 MPa or more, preferably 5 MPa to 20 MPa, and more preferably 5 MPa to 17 MPa.
- 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 air sealability can be improved.
- the tensile elongation at break specified in JIS K7113: 1995 of the resin material (tire frame) itself is preferably 50% or more, preferably 100% or more, more preferably 150% or more, and particularly preferably 200% or more.
- 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 substantially similar to that of 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 having a crown portion 16 (outer peripheral portion) for connecting a tire radial direction outer end of one side portion 14 and a tire radial direction outer end of the other side portion 14 is provided.
- the tire case 17 of the present embodiment has, for example, a hard segment (HS) and a soft segment (SS) as a resin material, and the soft segment (SS) included in one molecular chain is one unit.
- a thermoplastic elastomer having both ends of the one molecular chain being the hard segment (HS) and having a number average molecular weight of 12,000 to 24,000 and including each additive can be used. .
- the tire case 17 is formed of only a single resin material, but the present invention is not limited to this configuration, and each tire case 17 is similar to a conventional general rubber pneumatic tire. You may use the thermoplastic resin material which has a different characteristic for every site
- the tire case 17 of the present embodiment is obtained by joining a pair of tire case halves (tire frame pieces) 17A formed only of a resin material.
- the tire case half 17A is formed by injection molding or the like so that one bead portion 12, one side portion 14, and a half-width crown portion 16 are integrated with each other so as to face each other. It is formed by joining at the tire equator part.
- the tire case 17 is not limited to the one formed by joining two members, and may be formed by joining three or more members.
- the tire case half 17A formed using at least the resin material can be formed by, for example, vacuum forming, pressure forming, injection forming, melt casting, or the like. For this reason, it is not necessary to perform vulcanization compared to the case where the tire case is molded with rubber as in the prior art, the manufacturing process can be greatly simplified, and the molding time can be omitted.
- 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 only a steel cord is embedded in the bead portion 12 as in 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.
- the portion that contacts the rim 20 of the bead portion 12 and at least the portion that contacts the rim flange 22 of the rim 20 are more excellent in sealing performance than the resin material that forms part or all of the tire case 17.
- An annular sealing layer 24 made of only a material such as rubber is formed.
- the seal layer 24 may also be formed at a portion where the tire case 17 (bead portion 12) and the bead sheet 21 are in contact with each other.
- a material having a better sealing property than a resin material constituting part or all of the tire case 17 a softer material can be used than a resin material constituting part or all of the tire case 17.
- thermoplastic resin thermoplastic elastomer
- examples of such other thermoplastic resins include polyurethane resins, polyolefin resins, polystyrene thermoplastic resins, resins such as polyester resins, blends of these resins with rubbers or elastomers, and the like.
- Thermoplastic elastomers can also be used, for example, polyester-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polystyrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers, combinations of these elastomers, and blends with rubber. Thing etc. are mentioned.
- a reinforcing cord 26 having higher rigidity than a resin material constituting part or all of the tire case 17 is wound 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 a state of being in close contact with a resin material that constitutes a part or all of the crown portion 16 (tire case 17).
- 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.
- 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 tread 30 is disposed on the outer peripheral side of the reinforcing cord layer 28 in the tire radial direction.
- the rubber used for the tread 30 is preferably the same type of rubber as that used in conventional rubber pneumatic tires.
- a crown formed of another type of resin material that is more excellent in wear resistance than a resin material that constitutes part or all of the tire case 17 may be used.
- 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.
- the manufacturing method of the tire of this embodiment is explained.
- the tire case half is formed using the resin material containing the thermoplastic resin elastomer in the present embodiment. 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 part or all of the tire case.
- 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.
- 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. Or softened or melted beforehand by hot air, infrared irradiation, etc., and pressed by a joining mold.
- the tire case halves may be joined.
- 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.
- the reinforcing cord layer 28 can be formed on the outer peripheral side of the crown portion 16 of the tire case 17.
- 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-like tread 30 is wound around the outer peripheral surface of the tire case 17 by one turn, and the tread 30 is bonded to the outer peripheral surface of the tire case 17 using an adhesive or the like.
- the tread 30 can use the precure crown used for the retread tire conventionally known, for example. This step is the same step as the step of bonding the precure crown to the outer peripheral surface of the base tire of the retreaded tire.
- the seal layer 24 made of only vulcanized rubber is bonded to the bead portion 12 of the tire case 17 using an adhesive or the like, the tire 10 is completed.
- a part or all of the tire case 17 has a hard segment (HS) and a soft segment (SS), and the soft segment (SS) included in one molecular chain is one unit. And both ends of the one molecular chain are the hard segments (HS), and are formed of a resin material containing a thermoplastic elastomer having a number average molecular weight of 12,000 to 24,000. For this reason, the tire 10 of this embodiment has a desirable elastic modulus and is excellent in low-loss property.
- the 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 using at least the 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 using at least a resin material is prevented by improving the circumferential rigidity of the tire 10.
- the reinforcing cord 26 is formed on the outer peripheral surface of the crown portion 16 of the tire case 17 formed using at least a resin material in a cross-sectional view along the axial direction of the tire case 17 (cross section shown in FIG. 1). Is embedded and is in close contact with the resin material, air entry 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.
- 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.
- annular bead core 18 made of only a metal material is embedded in the bead portion 12, the tire case 17, that is, the tire 10 is mounted on the rim 20 in the same manner as a conventional rubber pneumatic tire. Firmly held.
- a portion of the bead portion 12 that contacts the rim 20 is provided with a sealing layer 24 made of only a rubber material that has a sealing property rather than a resin material that constitutes part or all of the tire case 17,
- the sealing performance between the tire 10 and the rim 20 is improved. For this reason, compared with the case where it seals only with the resin material which comprises a part or all of the rim
- 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.
- the resin material covered together with the reinforcing cord 26 is also heated, thereby effectively suppressing air entry when embedded in the crown portion 16. can do.
- 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.
- Hard segment (HS) Synthesis of one-end modified PA12 (nylon 12) In a reaction vessel with a volume of 2 liters equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet, 58.2 g of 12-aminododecanoic acid made by Aldrich, After putting 800 g of aminododecanolactam and 80 g of dodecanoic acid, the inside of the container was sufficiently substituted with nitrogen, the temperature was raised to 280 ° C., and the reaction was carried out for 4 hours under a pressure of 0.6 MPa. After releasing the pressure, the mixture was further reacted for 1 hour under a nitrogen stream to obtain a white solid which was a one-end modified PA12 polymer having a desired number average molecular weight of about 2,000.
- SS Soft segment: Synthesis of polypropylene glycol having a number average molecular weight of 8,000 200 g of polypropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) having a number average molecular weight of 4,000 and 23 g of dodecanedioic acid are the same as the synthesis of the hard segment (HS). Then, a catalytic amount of zirconium tetrachloride was added at 200 ° C. under a nitrogen stream and reacted for 6 hours. Unreacted polypropylene glycol was removed by preparative GPC to obtain polypropylene glycol having a number average molecular weight of about 8,000. The yield was 76%.
- thermoplastic elastomer 300 g of the obtained one-end modified PA12 (number average molecular weight 2,000) and 200 g of polypropylene glycol having a number average molecular weight of 8,000 were introduced into a reaction vessel similar to the synthesis of the hard segment (HS). Then, after stirring at 200 ° C. for 1 hour under a nitrogen stream, the temperature was raised to 230 ° C., a catalytic amount of zirconium tetrachloride was added, and the reaction was performed for 6 hours. An excess amount of polypropylene glycol was removed by washing with methanol to obtain a thermoplastic elastomer.
- thermoplastic elastomer had an HS-SS-HS structure, that is, a TPA with a triblock structure.
- the obtained thermoplastic elastomer was pelletized and injection molded at 260 ° C. to obtain a sample piece. Various measurements were carried out using a sample obtained by punching a test piece from this sample piece.
- Example 2 Example 1 Example 1 except that the amount of dodecanoic acid in the synthesis of the hard segment: one-end modified PA12 was changed to 53.3 g to obtain a one-end modified PA12 having a number average molecular weight of about 3,000.
- a thermoplastic elastomer was obtained in the same manner as above. The obtained thermoplastic elastomer had an HS-SS-HS structure, that is, a TPA with a triblock structure.
- thermoplastic elastomer of Example 1 In the production of the thermoplastic elastomer of Example 1, a thermoplastic elastomer was obtained in the same manner as in Example 1 except that polypropylene glycol having a number average molecular weight of 12,000 (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the soft segment.
- the obtained thermoplastic elastomer had an HS-SS-HS structure, that is, a TPA with a triblock structure.
- Example 4 In Example 1, the amount of dodecanoic acid in the synthesis of the hard segment: one-end modified PA12 was changed to 40 g to obtain one-end modified PA12 having a number average molecular weight of about 4,000, and in the production of a thermoplastic elastomer, A thermoplastic elastomer was obtained in the same manner as in Example 1 except that polypropylene glycol having a number average molecular weight of 12,000 (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the soft segment. The obtained thermoplastic elastomer had an HS-SS-HS structure, that is, a TPA with a triblock structure.
- Example 5 In Example 1, the amount of dodecanoic acid in the synthesis of the hard segment: one-end modified PA12 was changed to 53.3 g to obtain one-end modified PA12 having a number average molecular weight of about 3,000, and production of a thermoplastic elastomer
- a thermoplastic elastomer was obtained in the same manner as in Example 1 except that polypropylene glycol having a number average molecular weight of 12,000 (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the soft segment.
- the obtained thermoplastic elastomer had an HS-SS-HS structure, that is, a TPA with a triblock structure.
- Example 6 In Example 1, the amount of dodecanoic acid in the synthesis of the hard segment: one-end modified PA12 was changed to 26.7 g to obtain one-end modified PA12 having a number average molecular weight of about 6,000, and production of a thermoplastic elastomer
- a thermoplastic elastomer was obtained in the same manner as in Example 1 except that polypropylene glycol having a number average molecular weight of 12,000 (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the soft segment.
- the obtained thermoplastic elastomer had an HS-SS-HS structure, that is, a TPA with a triblock structure.
- Example 7 In Example 1, the amount of dodecanoic acid in the synthesis of the hard segment: one-end modified PA12 was changed to 106.7 g to obtain one-end modified PA12 having a number average molecular weight of about 1,500, and production of a thermoplastic elastomer
- a thermoplastic elastomer was obtained in the same manner as in Example 1 except that polypropylene glycol having a number average molecular weight of 12,000 (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the soft segment.
- the obtained thermoplastic elastomer had an HS-SS-HS structure, that is, a TPA with a triblock structure.
- Hard segment (HS) Synthesis of one-end modified PA6 Into a reaction vessel with a volume of 2 liters equipped with a stirrer, nitrogen gas inlet, and condensed water outlet, 400 g of Aldrich caprolactam, 53 g of dodecanoic acid and 51 g of aminohexanoic acid were placed. After sufficiently substituting the inside of the container with nitrogen, the temperature was raised to 280 ° C., and the reaction was carried out under a pressure of 0.6 MPa for 4 hours. After releasing the pressure, the mixture was further reacted for 1 hour under a nitrogen stream, and the water washing step was performed to obtain a white solid which was a one-end modified PA6 polymer having a desired number average molecular weight of about 1,500.
- the reaction vessel was introduced into the same reaction vessel as in the synthesis, stirred at 200 ° C. for 1 hour in a nitrogen stream, heated to 230 ° C., added with a catalytic amount of zirconium tetrachloride, and reacted for 6 hours. An excess amount of polypropylene glycol was removed by washing with methanol to obtain a thermoplastic elastomer.
- thermoplastic elastomer In the obtained thermoplastic elastomer, the number of hard segment (HS) units in one molecule (average value) and the number of soft segment (SS) units (average value) are both 25, It was a TPA having a structure in which a terminal having a hard segment (HS) and a soft segment (SS) were mixed.
- the obtained thermoplastic elastomer was pelletized and injection molded at 260 ° C. to obtain a sample piece. Various measurements were carried out using a sample obtained by punching a test piece from this sample piece.
- Example 2 In Example 1, the amount of dodecanoic acid in the synthesis of the hard segment: one-end modified PA12 was changed to 47.2 g to obtain one-end modified PA12 having a number average molecular weight of about 3,900, and production of a thermoplastic elastomer , A polyether having a number average molecular weight of 4,000 (HUNSTMAN, Elastamine D-4000) was used as a soft segment, and the amount of one-end modified PA12 (number average molecular weight 3,900) was 300 g, and the amount of Elastamine D-4000 A thermoplastic elastomer was obtained in the same manner as in Example 1 except that 307 g was used. The obtained thermoplastic elastomer had an HS-SS-HS structure, that is, a TPA with a triblock structure.
- Hard segment (HS) Synthesis of PA12 with both ends modified In a reaction vessel having a volume of 2 liters equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet, 43.7 g of 12-aminododecanoic acid made by Aldrich, aminododecanolactam 600 g and 19.5 g of dodecanedioic acid were added, and after the inside of the container was sufficiently substituted with nitrogen, the temperature was raised to 280 ° C. and reacted for 4 hours under a pressure of 0.6 MPa. After releasing the pressure, the mixture was further reacted for 1 hour under a nitrogen stream to obtain a white solid which was a PA12 polymer having a desired number average molecular weight of about 7,500.
- thermoplastic elastomer To 300 g of the obtained both-end modified PA12 (number average molecular weight 7,500), 147 g of polyoxypropylenediamine having a number average molecular weight of 2,000 (Elastamine RP-2009, manufactured by HUNTSMAN) was added, and 230 After stirring for 2 hours at 1 ° C., 1 g of Irganox 1010 (manufactured by BASF) was added to complete the reaction. By extracting unreacted materials in a mixed solvent of isopropanol and hexafluoroisopropanol, a polyamide-based thermoplastic elastomer having a number average molecular weight of about 19,000 was obtained.
- thermoplastic elastomer In the obtained thermoplastic elastomer, the number of hard segment (HS) units in one molecule (average value) and the number of soft segment (SS) units (average value) are both two. It was a TPA having a structure in which a terminal having a hard segment (HS) and a soft segment (SS) were mixed.
- the obtained thermoplastic elastomer was pelletized and injection molded at 260 ° C. to obtain a sample piece. Various measurements were carried out using a sample obtained by punching a test piece from this sample piece.
- Elastic modulus The tensile modulus of elasticity defined in JIS K7113: 1995 (hereinafter referred to as “elastic modulus” in this specification unless otherwise specified) was measured. If the elastic modulus is in the range of 300 to 700, it is suitable for use as a tire skeleton, and if it exceeds 700, the riding comfort may deteriorate, and if it is less than 300, the rim assembly property may deteriorate. is there.
- Softening point Tm The softening point Tm was measured by DSC (manufactured by TA Instruments) in accordance with JIS K7121: 2012.
- Examples having an HS-SS-HS structure that is, a triblock structure, and having an average molecular weight in the range of 12,000 to 24,000 have at least any one of them.
- the outstanding elasticity modulus and low loss performance are compatible.
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Abstract
Description
近年では、軽量化や、成形の容易さ、リサイクルのしやすさから、樹脂材料、特に熱可塑性樹脂や熱可塑性エラストマーなどをタイヤ材料として用いることが検討されている。これら熱可塑性の高分子材料(熱可塑性エラストマー、熱可塑性樹脂材料等)は、射出成形が可能であるなど、生産性の向上の観点から有利な点が多い。例えば、特開2012-46030号公報には、前記熱可塑性の高分子材料としてポリアミド系熱可塑性エラストマーを用いたタイヤが提案されている。
そして、タイヤの性能としての弾性率および低ロス性は、いずれも優れており両立されていることが、熱可塑性エラストマーを用いたタイヤにおいて求められている。
このトリブロック構造を取ることで、HSとSSとが混ざり合った中間相を減らすことが出来るため、弾性率に影響するHSの結晶化度が増し、弾性率が向上する。
また、結晶化度が増えることで全体が固くなり弾性率が上がるとともに、両末端がHSであり、この末端のHS同士が結晶化するため、自由末端が減る効果も得られ、ロスが低下する。
これにより、望ましい弾性率と優れた低ロス性との両立が実現される。
<熱可塑性エラストマー>
前記樹脂材料として用いられる熱可塑性エラストマーは、ハードセグメント(HS)とソフトセグメント(SS)とを有し、1分子鎖中に含まれる前記ソフトセグメント(SS)が1単位であり、前記1分子鎖の両末端が前記ハードセグメント(HS)である。また、数平均分子量が12,000~24,000である。
1分子鎖中に含まれるソフトセグメント(SS)が1単位であり且つ1分子鎖の両末端がハードセグメント(HS)である構造、即ちHS-SS-HSのトリブロック構造(但しハードセグメント(HS)とソフトセグメント(SS)との間に結合部を有していてもよい)を有する熱可塑性エラストマーを実現する方法について説明する。該方法としては、特に限定されるものではないが、反応性官能基を分子中に1つ有するハードセグメント(HS)を2単位、反応性官能基を分子中に2つ有するソフトセグメント(SS)を1単位、重合する方法が挙げられる。
熱可塑性エラストマーにおいて1分子鎖中に含まれるソフトセグメント(SS)が1単位であり且つ1分子鎖の両末端がハードセグメント(HS)である構造、即ちHS-SS-HSのトリブロック構造を有するか否かの確認について説明する。該確認方法は、ゲルパーミエーションクロマトグラフィー(GPC)によって熱可塑性エラストマーの平均分子量を測定し、且つNMRによってハードセグメント(HS)やソフトセグメント(SS)等の構成単位の平均分子量を測定することで行うことができる。
例えば、熱可塑性エラストマーが1種のハードセグメント(HS)および1種のソフトセグメント(SS)のみからなる場合であれば、下記の等式が成り立つはずである。
熱可塑性エラストマー平均分子量=HS平均分子量×2+SS平均分子量×1
1H-NMR、13C-NMRを、測定対象の熱可塑性エラストマーを重水素化したトリフルオロ酢酸に溶解して、定法に従って測定する。次に、それぞれの官能基の帰属を行い、HS、SS、及び結合部の構造を同定し、分子量を求める。それぞれの部位の分子量を足しあわせた数値が、すなわち繰り返しあたりの平均分子量に相当する
熱可塑性エラストマーの数平均分子量は12,000~24,000の範囲である。12,000未満であると、リム組み性が低下してしまう。一方24,000を超えると、溶融粘度が高くなり、タイヤ骨格体の際に充填不足が発生するおそれがあるため、成形温度、金型温度を高くする必要がある。このため、サイクルタイムが長くなる為、生産性が劣る。
熱可塑性エラストマーにおいて、前記ハードセグメント(HS)及びソフトセグメント(SS)の質量比(HS/SS)は、5/95~50/50が好ましく、15/85~45/55がより好ましく、20/80~40/60が更に好ましい。尚、タイヤの剛性の観点では20/80~50/50が好ましい。
前記熱可塑性エラストマーにおいてハードセグメント(HS)及びソフトセグメント(SS)の質量比(HS/SS)におけるハードセグメントの含有量が5質量%以上であることにより、タイヤに必要な剛性を付与することができる。一方50質量%以下であることにより、SSを一定量有することにより、リム組性を確保できる。
これらの中でも、ポリウレタン系熱可塑性エラストマー(TPU)、及びポリアミド系熱可塑性エラストマー(TPA)は、重付加の反応による結合部を有する重合体であって、この結合部の構造等を変化させるだけで熱可塑性エラストマーの物性を変化できる重合体であり、その手法も確立されているため、好ましい。
そして、ポリウレタン系熱可塑性エラストマー(TPU)、及びポリアミド系熱可塑性エラストマー(TPA)の中でも、耐加水分解性の観点から、ポリアミド系熱可塑性エラストマー(TPA)がより好ましい。
以下、本発明において好ましい熱可塑性エラストマーである、ポリアミド系熱可塑性エラストマー(TPA)、及びポリウレタン系熱可塑性エラストマー(TPU)について説明する。
本発明において、「ポリアミド系熱可塑性エラストマー」とは、結晶性で融点の高いハードセグメントの一部又は全部を構成するポリマーと非晶性でガラス転移温度の低いソフトセグメントの一部又は全部を構成するポリマーとを有する共重合体の熱可塑性エラストマーであって、ハードセグメントの一部又は全部を構成する前記ポリマーの主鎖にアミド結合(-CONH-)を有するものを意味する。
前記ハードセグメントの一部又は全部を形成するポリアミドについて説明する。該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であって、且つその片末端に反応性官能基が残存しないよう重合を停止させる役割を担うモノマー(以下、「停止剤」と称す)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の一部又は全部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、又は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、又は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。
停止剤の具体例としては、例えば、ドデカン酸、カプロン酸、ラウリン酸、又はステアリン酸などの飽和脂肪酸、リノール酸、又はオレイン酸などの不飽和脂肪酸等が挙げられる。
これらの停止剤を共に重合させることで、片末端に反応性官能基が残存しないよう重合を停止させる役割を担わせることができ、片末端のみが修飾されたポリアミドが得られる。
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の一部又は全部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る。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)、又はABA型トリブロックポリエーテル等が挙げられる。なお、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ン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。
上述の通り、ポリアミド系熱可塑性エラストマーの結合部は、例えば、鎖長延長剤により結合された部分が挙げられる。
前記鎖長延長剤としては、例えば、ジカルボン酸、ジオール、及びジイソシアネート等が挙げられる。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。前記ジオールとしては、例えば、脂肪族ジオール、脂環式ジオール、及び芳香族ジオールが挙げられる。前記ジイソシアネートとしては、例えば、芳香族ジイソシアネート、脂肪族ジイソシアネート、及び脂環族ジイソシアネートやこれらの混合物を用いることができる。
前記ポリアミド系熱可塑性エラストマーは、前記ハードセグメントの一部又は全部を形成するポリマー及びソフトセグメントの一部又は全部を形成するポリマーを公知の方法によって共重合することで合成することができる。例えば、前記ポリアミド系熱可塑性エラストマーは、ハードセグメントの原料となるモノマー(例えば、前述の片末端のみに反応性官能基を有するモノマー)と、ソフトセグメントの原料となるモノマー(例えば、前記ABA型トリブロックポリエーテルや前記ABA型トリブロックポリエーテルジアミン)とを容器内で重合させることで得ることができる。特に、ハードセグメントの原料となるモノマーとしてω-アミノカルボン酸を使用する場合、常圧溶融重合又は常圧溶融重合に、更に減圧溶融重合を行って合成することができる。ハードセグメントの原料となるモノマーとしてラクタムを用いる場合には、適量の水を共存させることができ、0.1~5MPaの加圧下での溶融重合とそれに続く常圧溶融重合及び/又は減圧溶融重合を有する方法で製造することができる。また、これら合成反応は、回分式及び連続式のいずれでも実施することができる。また、上述の合成反応には、バッチ式反応釜、一槽式若しくは多槽式の連続反応装置、管状連続反応装置などを単独であるいは適宜組み合わせて用いてもよい。
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、及び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、及び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、又は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、又は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、又は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。
ポリウレタン系熱可塑性エラストマーは、少なくともポリウレタンが物理的な凝集によって疑似架橋を形成しているハードセグメントの一部又は全部を構成し、他のポリマーが非晶性でガラス転移温度の低いソフトセグメントの一部又は全部を構成している材料が挙げられる。例えば、下記式Aで表される単位構造を含むソフトセグメントと、下記式Bで表される単位構造を含むハードセグメントとを含む共重合体として表すことができる。
式A中、Pは、長鎖脂肪族ポリエーテル又は長鎖脂肪族ポリエステルを表す。式A又は式B中、Rは、脂肪族炭化水素、脂環族炭化水素、又は芳香族炭化水素を表す。式B中、P’は、短鎖脂肪族炭化水素、脂環族炭化水素、又は、芳香族炭化水素を表す。
これらは単独で使用されてもよく、また2種以上が併用されてもよい。
また、Rで表される脂環族炭化水素を含むジイソシアネート化合物としては、例えば、1,4-シクロヘキサンジイソシアネート及び4,4-シクロヘキサンジイソシアネート等が挙げられる。更に、Rで表される芳香族炭化水素を含む芳香族ジイソシアネート化合物としては例えば、4,4’-ジフェニルメタンジイソシアネート、及びトリレンジイソシアネートが挙げられる。
これらは単独で使用されてもよく、また2種以上が併用されてもよい。
式B中、P’で表される短鎖脂肪族炭化水素、脂環族炭化水素、又は、芳香族炭化水素としては、例えば、分子量500未満のものを使用することができる。また、P’は、P’で表される短鎖脂肪族炭化水素、脂環族炭化水素又は芳香族炭化水素を含むジオール化合物に由来する。P’で表される短鎖脂肪族炭化水素を含む脂肪族ジオール化合物としては、グリコール及びポリアルキレングリコールが挙げられる。例えば、エチレングリコール、プロピレングリコール、トリメチレングリコール、1,4-ブタンジオール、1,3-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、1,7-ヘプタンジオール、1,8-オクタンジオール、1,9-ノナンジオール及び1,10-デカンジオールが挙げられる。
また、P’で表される脂環族炭化水素を含む脂環族ジオール化合物としては、例えば、シクロペンタン-1,2-ジオール、シクロヘキサン-1,2-ジオール、シクロヘキサン-1,3-ジオール、シクロヘキサン-1,4-ジオール、及びシクロヘキサン-1,4-ジメタノール等が挙げられる。
更に、P’で表される芳香族炭化水素を含む芳香族ジオール化合物としては、例えば、ヒドロキノン、レゾルシン、クロロヒドロキノン、ブロモヒドロキノン、メチルヒドロキノン、フェニルヒドロキノン、メトキシヒドロキノン、フェノキシヒドロキノン、4,4’-ジヒドロキシビフェニル、4,4’-ジヒドロキシジフェニルエーテル、4,4’-ジヒドロキシジフェニルサルファイド、4,4’-ジヒドロキシジフェニルスルホン、4,4’-ジヒドロキシベンゾフェノン、4,4’-ジヒドロキシジフェニルメタン、ビスフェノールA、1,1-ジ(4-ヒドロキシフェニル)シクロヘキサン、1,2-ビス(4-ヒドロキシフェノキシ)エタン、1,4-ジヒドロキシナフタリン、及び2,6-ジヒドロキシナフタリン等が挙げられる。
これらは単独で使用されてもよく、また2種以上が併用されてもよい。
また、式B中のRは、式A中のRと同じである。
結合部は、例えば、鎖長延長剤により結合された部分が挙げられる。鎖長延長剤としては、ポリアミド系熱可塑性エラストマーにおいて上述したものが挙げられる。これらの中でも、ポリウレタン系熱可塑性エラストマーの鎖延長剤としては、ドデカン二酸、エイコサン二酸、フェニル二酢酸、テレフタル酸、アジピン酸が好ましい。
次に、タイヤ骨格体の一部又は全部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、タイヤ骨格片の一部又は全部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1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、上述のように本実施形態における熱可塑性樹脂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、タイヤケースの一部又は全部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や加圧されると、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、図を省略するが、補強コード26を巻き付けたリール、コード加熱装置、各種ローラ等を備えたコード供給装置を用い、加熱した補強コード26をクラウン部16の外周面に埋設しながら巻き付けることで、タイヤケース17のクラウン部16の外周側に補強コード層28を形成することができる。
本実施形態のタイヤ10は、タイヤケース17の一部又は全部が、ハードセグメント(HS)とソフトセグメント(SS)とを有し、1分子鎖中に含まれる前記ソフトセグメント(SS)が1単位であり、前記1分子鎖の両末端が前記ハードセグメント(HS)であり、且つ数平均分子量が12,000~24,000である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る。このため、本実施形態のタイヤ10は、望ましい弾性率を有し且つ低ロス性に優れる。
・ハードセグメント(HS):片末端修飾PA12(ナイロン12)の合成
攪拌機、窒素ガス導入口、縮合水排出口を備えた容積2リットルの反応容器に、アルドリッチ製12-アミノドデカン酸58.2g、アミノドデカノラクタム800g、ドデカン酸80gを入れ、容器内を十分窒素置換した後、280℃まで昇温し、0.6MPaの加圧下で4時間反応させた。圧力を解放したあと、窒素気流下でさらに1時間反応させ、所望の数平均分子量約2,000の片末端修飾PA12重合物である白色固体を得た。
数平均分子量4,000のポリプロピレングリコール(和光純薬製)200gとドデカン二酸23gを前記ハードセグメント(HS)の合成と同様の反応容器に導入し、窒素気流下200℃でジルコニウムテトラクロライドを触媒量加え、6時間反応を行った。未反応ポリプロピレングリコールは、分取GPCで除去し、数平均分子量約8,000のポリプロピレングリコールを得た。収率76%であった。
得られた片末端修飾PA12(数平均分子量2,000)300g、数平均分子量8,000のポリプロピレングリコール200gを前記ハードセグメント(HS)の合成と同様の反応容器に導入し、窒素気流下200℃1時間撹拌後、230℃に昇温し、ジルコニウムテトラクロライドを触媒量加えて、6時間反応を行った。過剰量のポリプロピレングリコールをメタノールで洗浄除去し、熱可塑性エラストマーを得た。
得られた熱可塑性エラストマーは、HS-SS-HSの構造、即ちトリブロック構造のTPAであった。
得られた熱可塑性エラストマーはペレット化し、260℃で射出成形し、サンプル片を得た。各種測定は、このサンプル片から試験片を打ち抜いたサンプルを用いて実施した。
実施例1において、ハードセグメント:片末端修飾PA12の合成の際のドデカン酸の量を53.3gに変更して数平均分子量約3,000の片末端修飾PA12を得た以外は、実施例1と同様の方法により熱可塑性エラストマーを得た。
得られた熱可塑性エラストマーは、HS-SS-HSの構造、即ちトリブロック構造のTPAであった。
実施例1の熱可塑性エラストマーの製造において、ソフトセグメントとして数平均分子量12,000のポリプロピレングリコール(和光純薬製)を用いた以外は、実施例1と同様の方法により熱可塑性エラストマーを得た。
得られた熱可塑性エラストマーは、HS-SS-HSの構造、即ちトリブロック構造のTPAであった。
実施例1において、ハードセグメント:片末端修飾PA12の合成の際のドデカン酸の量を40gに変更して数平均分子量約4,000の片末端修飾PA12を得、且つ熱可塑性エラストマーの製造において、ソフトセグメントとして数平均分子量12,000のポリプロピレングリコール(和光純薬製)を用いた以外は、実施例1と同様の方法により熱可塑性エラストマーを得た。
得られた熱可塑性エラストマーは、HS-SS-HSの構造、即ちトリブロック構造のTPAであった。
実施例1において、ハードセグメント:片末端修飾PA12の合成の際のドデカン酸の量を53.3gに変更して数平均分子量約3,000の片末端修飾PA12を得、且つ熱可塑性エラストマーの製造において、ソフトセグメントとして数平均分子量12,000のポリプロピレングリコール(和光純薬製)を用いた以外は、実施例1と同様の方法により熱可塑性エラストマーを得た。
得られた熱可塑性エラストマーは、HS-SS-HSの構造、即ちトリブロック構造のTPAであった。
実施例1において、ハードセグメント:片末端修飾PA12の合成の際のドデカン酸の量を26.7gに変更して数平均分子量約6,000の片末端修飾PA12を得、且つ熱可塑性エラストマーの製造において、ソフトセグメントとして数平均分子量12,000のポリプロピレングリコール(和光純薬製)を用いた以外は、実施例1と同様の方法により熱可塑性エラストマーを得た。
得られた熱可塑性エラストマーは、HS-SS-HSの構造、即ちトリブロック構造のTPAであった。
実施例1において、ハードセグメント:片末端修飾PA12の合成の際のドデカン酸の量を106.7gに変更して数平均分子量約1,500の片末端修飾PA12を得、且つ熱可塑性エラストマーの製造において、ソフトセグメントとして数平均分子量12,000のポリプロピレングリコール(和光純薬製)を用いた以外は、実施例1と同様の方法により熱可塑性エラストマーを得た。
得られた熱可塑性エラストマーは、HS-SS-HSの構造、即ちトリブロック構造のTPAであった。
・ハードセグメント(HS):片末端修飾PA6の合成
攪拌機、窒素ガス導入口、縮合水排出口を備えた容積2リットルの反応容器に、アルドリッチ製カプロラクタム400g、ドデカン酸53g、アミノヘキサン酸51gを入れ、容器内を十分窒素置換した後、280℃まで昇温し、0.6MPaの加圧下で4時間反応させた。圧力を解放したあと、窒素気流下でさらに1時間反応させ、水洗工程をへて所望の数平均分子量約1,500の片末端修飾PA6重合物である白色固体を得た。
得られた片末端修飾PA6(数平均分子量1,500)を200gとり、更に実施例3で用いたソフトセグメント(SS、数平均分子量12,000のポリプロピレングリコール、和光純薬製)800gを加え、230℃6時間撹拌を行った。Irganox1010(BASF社製)1gを加え、白色の熱可塑性エラストマー(ポリアミドエラストマー)を得た。
得られた熱可塑性エラストマーは、HS-SS-HSの構造、即ちトリブロック構造のTPAであった。
得られた熱可塑性エラストマーはペレット化し、260℃で射出成形し、サンプル片を得た。各種測定は、このサンプル片から試験片を打ち抜いたサンプルを用いて実施した。
・熱可塑性エラストマーの製造
ハードセグメントとして両末端修飾のナイロン12(数平均分子量3,000)120g、ソフトセグメントとして数平均分子量1,000のポリプロピレングリコール37gを前記実施例1のハードセグメント(HS)の合成と同様の反応容器に導入し、窒素気流下200℃1時間撹拌後、230℃に昇温し、ジルコニウムテトラクロライドを触媒量加えて、6時間反応を行った。過剰量のポリプロピレングリコールをメタノールで洗浄除去し、熱可塑性エラストマーを得た。
得られた熱可塑性エラストマーは、一分子中におけるハードセグメント(HS)の単位の数(平均値)及びソフトセグメント(SS)の単位の数(平均値)がいずれも25個であり、分子鎖の末端がハードセグメント(HS)であるものとソフトセグメント(SS)であるものとが混在した構造のTPAであった。
得られた熱可塑性エラストマーはペレット化し、260℃で射出成形し、サンプル片を得た。各種測定は、このサンプル片から試験片を打ち抜いたサンプルを用いて実施した。
実施例1において、ハードセグメント:片末端修飾PA12の合成の際のドデカン酸の量を47.2gに変更して数平均分子量約3,900の片末端修飾PA12を得、且つ熱可塑性エラストマーの製造において、ソフトセグメントとして数平均分子量4,000のポリエーテル(HUNTSMAN社製、エラスタミンD-4000)を用い、片末端修飾PA12(数平均分子量3,900)の量を300g、エラスタミンD-4000の量を307gとした以外は、実施例1と同様の方法により熱可塑性エラストマーを得た。
得られた熱可塑性エラストマーは、HS-SS-HSの構造、即ちトリブロック構造のTPAであった。
・ハードセグメント(HS):両末端修飾PA12の合成
攪拌機、窒素ガス導入口、縮合水排出口を備えた容積2リットルの反応容器に、アルドリッチ製12-アミノドデカン酸43.7g、アミノドデカノラクタム600g、ドデカン二酸19.5gを入れ、容器内を十分窒素置換した後、280℃まで昇温し、0.6MPaの加圧下で4時間反応させた。圧力を解放したあと、窒素気流下でさらに1時間反応させ、所望の数平均分子量約7,500のPA12重合物である白色固体を得た。
得られた両末端修飾PA12(数平均分子量7,500)300gに、数平均分子量2,000のポリオキシプロピレンジアミン(HUNTSMAN社製、エラスタミンRP-2009)147gを加え、230℃2時間撹拌を行ったのち、Irganox1010(BASF社製)を1g加え反応を終了した。イソプロパノールとヘキサフルオロイソプロパノール混合溶媒中で未反応物を抽出することで、数平均分子量約19,000のポリアミド系熱可塑性エラストマーを得た。
得られた熱可塑性エラストマーは、一分子中におけるハードセグメント(HS)の単位の数(平均値)及びソフトセグメント(SS)の単位の数(平均値)がいずれも2個であり、分子鎖の末端がハードセグメント(HS)であるものとソフトセグメント(SS)であるものとが混在した構造のTPAであった。
得られた熱可塑性エラストマーはペレット化し、260℃で射出成形し、サンプル片を得た。各種測定は、このサンプル片から試験片を打ち抜いたサンプルを用いて実施した。
実施例及び比較例から得た熱可塑性エラストマーを用いて、以下の項目について評価した。結果を表1及び表2に示す。
JIS K7113:1995に規定される引張弾性率(以下、特に特定しない限り本明細書で「弾性率」とは引張弾性率を意味する。)を測定した。
なお、弾性率は300~700の範囲であればタイヤ骨格体として用いるのに適しており、700を超えると乗心地が悪化する恐れがあり、300未満であるとリム組性が悪くなることがある。
2mm厚のサンプル片から、φ8mmの円盤状に打ち抜いた試験片を測定に用いた。粘弾性測定装置(レオメトリックス社製)を使用し、温度30℃、歪み1%、周波数20Hzで損失正接(tanδ)を測定した。次に、上記測定方法で得られたtanδの実測値に対して、比較例1の値を100として計算を行い、換算値を求めた。尚、値が小さい程低ロス性に優れている。
軟化点Tmを、JIS K7121:2012に則って、DSC(TAインスルメント社製)で測定を実施した。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
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、ハードセグメント(HS)とソフトセグメント(SS)とを有し、1分子鎖中に含まれる前記ソフトセグメント(SS)が1単位であり、前記1分子鎖の両末端が前記ハードセグメント(HS)であり、且つ数平均分子量が12,000~24,000である熱可塑性エラストマーを含むタイヤ。 - 前記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20/80~50/50である請求項1に記載のタイヤ。
- 前記熱可塑性エラストマーが、ポリウレタン系熱可塑性エラストマー、及びポリアミド系熱可塑性エラストマーからなる群より選択される少なくとも1種である請求項1又は請求項2に記載のタイヤ。
- 前記熱可塑性エラストマーが、ポリアミド系熱可塑性エラストマーである請求項1又は請求項2に記載のタイヤ。
- 前記熱可塑性エラストマーが、反応性官能基を分子中に1つ有する2単位のハードセグメント(HS)と、反応性官能基を分子中に2つ有する1単位のソフトセグメント(SS)と、が重合されてなる重合体である請求項1~請求項4の何れか一項に記載のタイヤ。
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