WO2016052564A1 - タイヤ - Google Patents
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- WO2016052564A1 WO2016052564A1 PCT/JP2015/077612 JP2015077612W WO2016052564A1 WO 2016052564 A1 WO2016052564 A1 WO 2016052564A1 JP 2015077612 W JP2015077612 W JP 2015077612W WO 2016052564 A1 WO2016052564 A1 WO 2016052564A1
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- WIPO (PCT)
- Prior art keywords
- thermoplastic elastomer
- tire
- molecular weight
- acid
- resin material
- Prior art date
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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
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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
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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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
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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 an excellent low-loss property while having durability.
- 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 structure in which a hard segment (HS) and a soft segment (SS) are alternately repeated, and the hard segment (HS) and the soft segment (SS) in one molecular chain are combined.
- a thermoplastic elastomer having 2 to 10 repeating units and a number average molecular weight of 45,000 to 160,000 is included.
- the number of repeating units (number of repeating units) in which one set of the hard segment (HS) and the soft segment (SS) in one molecular chain is a hard segment (HS) and a soft segment (SS).
- the number of repetitions of a set of one hard segment (HS) and one soft segment (SS) in one molecular chain of a thermoplastic elastomer having a structure in which the structure is alternately repeated is “1 unit”.
- the said repeating unit number represents the average value in the thermoplastic elastomer contained in the said resin material.
- the thermoplastic elastomer contained in the resin material has a hard segment and a soft segment, whereby the characteristics of these segments can be obtained.
- the number average molecular weight of the thermoplastic elastomer is in the range of 45,000 or more and 160,000 or less, excellent rim assembly property and productivity can be obtained, and further durability 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 tire of the present invention is a thermoplastic elastomer having a number average molecular weight within the above range, and further has a structure in which hard segments (HS) and soft segments (SS) are alternately repeated, and one molecule.
- a thermoplastic elastomer having a structure in which the number of repeating units of the hard segment (HS) and the soft segment (SS) in the chain is 2 to 10 is included.
- the length per one hard segment (HS) is longer than that of the case where only the thermoplastic elastomer having the same overall molecular weight and the number of repeating units exceeding 10 is included.
- the compatibility with the segment (SS) decreases, and the intermediate phase in which HS and SS are mixed can be reduced.
- the crystallinity of HS that affects the elastic modulus increases, the elastic modulus improves, and the loss can also be reduced.
- thermoplastic elastomer used as the resin material has a structure in which hard segments (HS) and soft segments (SS) are alternately repeated.
- the number of repeating units of the hard segment (HS) and the soft segment (SS) in one molecular chain as a set is 2 to 10, and the number average molecular weight is 45,000 to 160,000. is there.
- the resin material may contain a thermoplastic elastomer other than the thermoplastic elastomer or any 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.
- thermoplastic elastomer The number of repeating units in the thermoplastic elastomer is controlled to 2 to 10. If it exceeds 10, the length per one hard segment (HS) becomes relatively shorter when the total molecular weight is equal, it becomes difficult to control the elastic modulus within a desired range, and the loss also increases. On the other hand, if it is less than 2, the elastomeric properties are lowered, the required rubber elasticity cannot be obtained, and the elasticity and elongation required for the tire cannot be obtained.
- the number of repeating units in the thermoplastic elastomer is preferably 2 or more as a lower limit, and more preferably 3 or more. Moreover, as an upper limit, 8 or less is preferable and 6 or less is more preferable.
- the number of repeating units (average value) of hard segment (HS) and soft segment (SS) as a set is the average molecular weight of thermoplastic elastomer, hard segment (HS), soft segment (SS) by NMR. It can be calculated by measuring the average molecular weight of each. For example, if the thermoplastic elastomer consists of only one hard segment (HS) and one soft segment (SS), one of the following equations (1) to (3) should hold: is there.
- thermoplastic elastomer may include a bonding portion, that is, the “repeating unit” including one unit of one hard segment (HS) and one soft segment (SS) as the unit A mode in which HS and SS are coupled by a coupling portion may be employed.
- a bond portion is included in addition to the hard segment (HS) and the soft segment (SS)
- each of the thermoplastic elastomer, the hard segment (HS), the soft segment (SS), and the bond portion is analyzed by NMR as described above.
- the number of repeating units (average value) of HS and SS can be calculated by measuring the average molecular weight.
- the measuring method of average molecular weights such as a thermoplastic elastomer by NMR, a hard segment (HS), a soft segment (SS), and a coupling
- 1 H-NMR and 13 C-NMR are measured according to a conventional method by dissolving the thermoplastic elastomer to be measured in deuterated trifluoroacetic acid.
- attribution of each functional group is performed, HS, SS, and the structure of a coupling
- the number of repeating units of HS and SS is controlled so that the number average molecular weight in the thermoplastic elastomer and the number of repeating units in one molecule are the target values, and the molecular weight of the hard segment (HS) in one unit. And adjusting the molecular weight of the soft segment (SS). Moreover, it can also carry out by adjusting the polymerization degree (namely, the number of superposition
- thermoplastic elastomer has a number average molecular weight in the range of 45,000 to 160,000. If it is less than 45,000, the rim assemblability will deteriorate. On the other hand, if it exceeds 160,000, the melt viscosity becomes high and there is a possibility that insufficient filling occurs 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 more preferably 80,000 to 160,000, and more preferably 100,000 to 160,000.
- 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 of the hard segment (HS) and the soft segment (SS) in the repeating unit (that is, one unit including one hard segment (HS) and one soft segment (SS)).
- the average value of (HS / SS) is preferably 20/80 to 90/10. Further, 20/80 to 80/20 is more preferable, 30/70 to 80/20 is still more preferable, and 40/60 to 75/25 is still more preferable.
- the average mass ratio of HS in the repeating unit is 20 or more (that is, the average mass ratio of SS is 80 or less)
- necessary rigidity can be imparted to the tire.
- the average mass ratio of HS in the repeating unit is 90 or less (that is, the average mass ratio of SS is 10 or more)
- 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) and a polyester-based thermoplastic elastomer (Thermoplastic polymer elastomer, TPC) defined in JIS K6418: 2007.
- TPA polyamide-based thermoplastic elastomer
- TPC polyester-based thermoplastic elastomer
- thermoplastic elastomer Thermoplastic Polyolefin, TPO
- Polystyrene thermoplastic elastomer Styrenic Thermoplastic Elastomer, TPS
- Polyurethane thermoplastic elastomer Thermoplastic Polythane, TPU
- Thermo-crosslinked thermoplastic rubber lcanizates TPV
- TPZ thermoplastic elastomers
- a polyurethane-based thermoplastic elastomer (TPU), a polyamide-based thermoplastic elastomer (TPA), and a polyester-based thermoplastic elastomer (TPC) are polymers having a bond portion by a polyaddition reaction, and this bond It is a polymer that can change the physical properties of a thermoplastic elastomer only by changing the structure of the part, and is preferable because its method has been established.
- the polyamide-based thermoplastic elastomer (TPA) is more preferable from the viewpoint of hydrolyzability.
- polyamide thermoplastic elastomer (TPA), polyurethane thermoplastic elastomer (TPU), and polyester thermoplastic elastomer (TPC) 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.
- 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.
- 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 that is a raw material for a hard segment (for example, an ⁇ -aminocarboxylic acid such as 12-aminododecanoic acid and a lactam such as lauryl lactam) and a monomer that is a raw material for a soft segment (for example, it can be obtained by polymerizing the ABA triblock polyether or the ABA triblock polyether diamine) and, if necessary, a chain extender (for example, adipic acid or decanedicarboxylic acid) in a container. it can.
- a monomer that is a raw material for a hard segment for example, an ⁇ -aminocarboxylic acid such as 12-aminododecanoic acid and a lactam such as lauryl lactam
- a monomer that is a raw material for a soft segment for example, it can be obtained by polymerizing the ABA triblock polyether or the
- ⁇ -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.
- 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.
- lauryl lactam ring-opening polycondensate / ABA type triblock polyether / adipic acid combination aminododecanoic acid polycondensate / ABA type triblock polyether / adipic acid combination, aminododecanoic acid polycondensate / ABA type triblock polyether diamine / decane dicarboxylic acid combination, aminododecanoic acid polycondensate / polytetramethylene ether glycol / adipic acid combination, or aminododecanoic acid polycondensate / polytetramethylene ether glycol / decane
- a combination of dicarboxylic acids is particularly preferred.
- polyamide-type thermoplastic elastomer what combined the preferable aspect mentioned above about the combination of a structural unit, the structural ratio, molecular weight, etc. can be used.
- polyester thermoplastic elastomer is a soft segment having at least a part of or the entire hard segment having a crystalline polyester and a high melting point, and other polymers (for example, polyester or polyether) being amorphous and having a low glass transition temperature.
- polymers for example, polyester or polyether
- An aromatic polyester can be used as the crystalline polyester that forms part or all of the hard segment in the polyester-based thermoplastic elastomer.
- the aromatic polyester can be formed using, for example, an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol.
- Examples of the aromatic polyester that forms part or all of the hard segment include polyethylene terephthalate, polybutylene terephthalate, polystyrene terephthalate, polyethylene naphthalate, and polybutylene naphthalate, and polybutylene terephthalate is preferable.
- One suitable aromatic polyester that forms part or all of the hard segment includes terephthalic acid and / or polybutylene terephthalate derived from dimethyl terephthalate and 1,4-butanediol, and further includes isophthalic acid , Phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or their ester forming properties
- a dicarboxylic acid component such as a derivative and a diol having a molecular weight of 300 or less (for example, an aliphatic diol such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, 1,4-cyclone) Alicyclic diols such as
- -Soft segment- Examples of the polymer that forms part or all of the soft segment include polymers selected from aliphatic polyesters and aliphatic polyethers.
- Aliphatic polyethers include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, poly (propylene oxide)
- An ethylene oxide addition polymer of glycol or a copolymer of ethylene oxide and tetrahydrofuran can be used.
- the aliphatic polyester include poly ( ⁇ -caprolactone), polyenantlactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate.
- poly (tetramethylene oxide) glycol poly (propylene oxide) glycol ethylene oxide adducts, poly ( ⁇ -caprolactone) from the viewpoint of the elastic properties of the resulting copolymer
- polybutylene adipate polyethylene adipate, and the like are preferable.
- binding part examples include a part bound by a chain extender.
- chain extender examples include those described above for the polyamide-based thermoplastic elastomer.
- the polyester-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.
- 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.
- 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.
- polyurethane-based thermoplastic elastomers include tolylene diisocyanate (TDI) / polyester-based polyol copolymers, TDI / polyether-based polyol copolymers, TDI / caprolactone-based polyol copolymers, and TDI / polycarbonate-based polyols.
- TDI tolylene diisocyanate
- 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 includes, for example, a structure having a hard segment (HS) and a soft segment (SS) that are alternately repeated as a resin material, and the hard segment (HS) in one molecular chain.
- the soft segment (SS) as a set, the number of repeating units is 2 to 10, and the number average molecular weight is 45,000 to 160,000, and each additive is added to the thermoplastic elastomer. 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.
- a tire case half is formed using the resin material containing the thermoplastic resin elastomer according to the present invention. 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.
- the tire 10 of the present embodiment has a structure in which a part or all of the tire case 17 has a structure in which a hard segment (HS) and a soft segment (SS) are alternately repeated, and the hard segment (HS in one molecular chain).
- a hard segment (HS) and a soft segment (SS) are alternately repeated, and the hard segment (HS in one molecular chain).
- the soft segment (SS) as a set, the number of repeating units is 2 to 10, and the number average molecular weight is 45,000 to 160,000. .
- 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 PA12 (nylon 12) having a number average molecular weight of 3,800 In a 2-liter reaction vessel equipped with a stirrer, nitrogen gas inlet, and condensed water outlet, 12-aminododecane manufactured by Aldrich 43.7 g of acid, 600 g of aminododecanolactam, and 38.3 g of dodecanedioic acid (amount of molecular weight corresponding to the HS molecular weight shown in Table 1 below) were added, and the interior of the container was sufficiently purged with nitrogen. And reacted for 4 h (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 3,800.
- PA12 number average molecular weight 3,800
- SS polyoxypropylenediamine having a molecular weight of 2000 (corresponding to SS molecular weight described in Table 1 below)
- a polyamide-based thermoplastic elastomer having a controlled number of repeating units was obtained.
- the obtained polyamide-based thermoplastic elastomer was pelletized and injection molded at 220 ° 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 dodecanedioic acid was changed to 24.5 g (a molecular weight corresponding to the HS molecular weight described in Table 1 below), and SS was a molecular weight of 3000 (corresponding to the SS molecular weight described in Table 1 below). Except for changing to 168 g of propylenediamine (manufactured by Wako Pure Chemical Industries, Ltd.) (amount in which the mass ratio of HS / SS is the value described in Table 1 below) to obtain a polyamide-based thermoplastic elastomer having a number average molecular weight of about 54,000, It was produced by the same method as in Example 1.
- Example 3 In Example 1, the dodecanedioic acid was changed to 18.8 g (the molecular weight is the amount that makes the HS molecular weight described in Table 1 below), and the SS is a polyoxy having a molecular weight of 4000 (corresponding to the SS molecular weight described in Table 1 below). Except for changing to 156 g of propylenediamine (manufactured by Wako Pure Chemical Industries, Ltd.) (amount in which the mass ratio of HS / SS is the value shown in Table 1 below) to obtain a polyamide-based thermoplastic elastomer having a number average molecular weight of about 59,000, It was produced by the same method as in Example 1.
- Example 4 In Example 1, the dodecanedioic acid was changed to 12 g (the molecular weight of which is the HS molecular weight described in Table 1 below), and the SS was a polyoxypropylenediamine having a molecular weight of 6000 (corresponding to the SS molecular weight described in Table 1 below).
- Example except for Wako Pure Chemical Industries, Ltd. except that a polyamide-based thermoplastic elastomer having a number average molecular weight of about 72,000 was obtained by changing to 150 g (amount in which the mass ratio of HS / SS is the value shown in Table 1 below). 1 in the same manner.
- Example 5 In Example 1, dodecanedioic acid was changed to 38.8 g (a molecular weight corresponding to the HS molecular weight described in Table 1 below), and SS was a polyoxy having a molecular weight of 1000 (corresponding to the SS molecular weight described in Table 1 below). Except for changing to 80 g of propylenediamine (Jeffamine RT-1000 manufactured by HUNTSMAN) (amount in which the mass ratio of HS / SS is the value shown in Table 1 below) to obtain a polyamide-based thermoplastic elastomer having a number average molecular weight of about 45,505 was produced by the same method as in Example 1.
- Example 6 In Example 1, aminododecanolactam was changed to 500 g of caprolactam, dodecanedioic acid was changed to 184 g of hexanedioic acid (a molecular weight corresponding to the HS molecular weight shown in Table 1 below), and 12-aminododecanoic acid was changed to adipine. The acid was changed to 38.7 g, the amount of PA6 obtained (number average molecular weight 630) was changed to 100 g, and SS was a polyoxypropylenediamine having a molecular weight of 12000 (corresponding to the SS molecular weight described in Table 1 below) (manufactured by Asahi Glass).
- Example 2 The same method as in Example 1 except that the polyamide-based thermoplastic elastomer having a number average molecular weight of about 50,520 was obtained by changing to 886 g (amount at which the HS / SS mass ratio is the value shown in Table 1 below). Manufactured by.
- Example 7 In Example 1, the dodecanedioic acid was changed to 18.2 g (amount of molecular weight corresponding to the HS molecular weight described in Table 1 below), and SS was a polyoxygen having a molecular weight of 12000 (corresponding to the SS molecular weight described in Table 1 below). Except that a polyamide-based thermoplastic elastomer having a number average molecular weight of about 160,000 was obtained by changing to 450 g of propylenediamine (manufactured by Asahi Glass) (amount at which the mass ratio of HS / SS is the value shown in Table 1 below). 1 in the same manner.
- Hard segment (HS) Synthesis of PA6 (nylon 6) having a number average molecular weight of 3,500 In a reaction vessel having a volume of 2 liters equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet, 570 g of ⁇ -caprolactam manufactured by Aldrich , 44 g of adipic acid and 25 g of hexanedioic acid (the molecular weight is the amount that makes the HS molecular weight shown in Table 2 below), the inside of the container was sufficiently purged with nitrogen, then the temperature was raised to 260 ° C., and the pressure was 0.6 MPa For 4 hours (hours). After releasing the pressure, the mixture was further reacted under a nitrogen stream for 2 hours to obtain a white solid which was a PA6 polymer having a desired number average molecular weight of about 3,500.
- thermoplastic elastomer To 300 g of the obtained PA6 (number average molecular weight 3,500), 120 g of polypropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) having a molecular weight of 1400 (corresponding to SS molecular weight described in Table 2 below) is added, and the temperature is 230 ° C. After stirring for 5 hours, 1 g of Irganox 1010 (manufactured by BASF) was added to complete the reaction. The obtained polyamide-based thermoplastic elastomer was pelletized and subjected to Soxhlet extraction with hot water for 8 hours, followed by injection molding at 220 ° C. to obtain a sample piece. Various measurements were carried out using a sample obtained by punching a test piece from this sample piece.
- Hard segment (HS) Synthesis of PA612 (nylon 612) having a number average molecular weight of 3,100
- a reaction vessel having a volume of 2 liters equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet
- 207 g (molecular weight) of dodecanedioic acid Is the amount of HS molecular weight described in Table 2 below
- 95 g of hexamethylenediamine, and 100 g of purified water are added, the inside of the container is sufficiently purged with nitrogen, and the temperature is raised to 280 ° C. Reacted for hours.
- the mixture After releasing the pressure, the mixture is further reacted for 1 hour under a nitrogen stream, taken out from the container, and subjected to Soxhlet extraction with ethanol for 24 hours to obtain a white solid which is a PA612 polymer having a desired number average molecular weight of about 3,100. It was.
- thermoplastic elastomer PA612TPA To 200 g of the obtained nylon 612 (PA612) polymer, polyoxypropylenediamine (Elastamine RP-2009, manufactured by HUNTSMAN, number average molecular weight: 2000 (SS molecular weight described in Table 2 below) was used as a soft segment. 129) (the amount by which the mass ratio of HS / SS becomes the value described in Table 2 below) was added, and the mixture was stirred at 230 ° C. for 7 hours. Further, 1 g of Irganox 1010 was added to obtain a white polyamide-based thermoplastic elastomer. Then, the sample piece was manufactured by the same method as Example 1.
- Example 10 In Example 1, the dodecanedioic acid was changed to 47 g (the amount of molecular weight corresponding to the HS molecular weight shown in Table 2 below), the amount of PA12 (number average molecular weight 3,100) obtained was changed to 150 g, SS Is changed to 580 g of polypropylene glycol (manufactured by Asahi Glass Co., Ltd.) having a molecular weight of 12000 (corresponding to SS molecular weight described in Table 2 below), the reaction time at 230 ° C. is changed to 8 hours, and a polyamide having a number average molecular weight of 120,800 This was produced in the same manner as in Example 1 except that a thermoplastic elastomer was obtained.
- SS Is changed to 580 g of polypropylene glycol (manufactured by Asahi Glass Co., Ltd.) having a molecular weight of 12000 (corresponding to SS molecular weight described in Table 2 below)
- Example 1 is the same as Example 1 except that the reaction time at 230 ° C. at the time of production of the thermoplastic elastomer was changed to 7 h (hours) to obtain a polyamide-based thermoplastic elastomer having a number average molecular weight of about 70,800. The same method was used.
- Example 7 the reaction time at 230 ° C. during the production of the thermoplastic elastomer was changed to 10 h (hours) to obtain a polyamide-based thermoplastic elastomer having a number average molecular weight of about 190,000. The same method was used.
- Example 3 the dodecanedioic acid was changed to 19.5 g (the amount of molecular weight corresponding to the HS molecular weight described in Table 2 below), and the reaction time at 230 ° C. during the production of the thermoplastic elastomer was set to 2 h (hours). This was produced in the same manner as in Example 1 except that a polyamide-based thermoplastic elastomer having a number average molecular weight of about 28,750 was obtained by modification.
- Example 4 In Example 1, the reaction time at 230 ° C. during the production of the thermoplastic elastomer was changed to 6 hours and 45 minutes (15 minutes shorter than that of Comparative Example 1), and a polyamide-based thermoplastic elastomer having a number average molecular weight of about 64,900. It was manufactured by the same method as in Example 1 except that
- Example 6 the reaction time at 230 ° C. during the production of the thermoplastic elastomer was changed to 4 hours and 40 minutes (20 minutes shorter than that of Example 6), and a polyamide-based thermoplastic elastomer having a number average molecular weight of about 39,200. This was prepared in the same manner as in Example 6 except that
- Example 6 In Example 4, the reaction time at 230 ° C. during the production of the thermoplastic elastomer was changed to 10 hours (5 hours longer than Example 4) to obtain a polyamide-based thermoplastic elastomer having a number average molecular weight of about 183,600. Except for the above, it was produced by the same method as in Example 4.
- the number of repeating units of hard segments (HS) and soft segments (SS) in one molecular chain is 2 to 10, and the number average molecular weight is 45,000 to 160,000.
- the embodiment is provided with both durability and excellent elastic modulus and low loss performance.
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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、耐久性を損なうことなく、弾性率および低ロス性が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。
尚、上記繰り返し単位数は、前記樹脂材料に含まれる熱可塑性エラストマーにおける平均値を表す。
一方で、これらのセグメントの界面において存在する、ハードセグメントとソフトセグメントとが混合している領域(以下、「中間相」と称する)により、それぞれのセグメントが有する特性が期待通りに十分に得られない場合がある。
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)とを交互に繰り返し有する構造を備える。また、1分子鎖中における前記ハードセグメント(HS)と前記ソフトセグメント(SS)とを一組とした繰り返し単位の数が2~10であり、且つ数平均分子量が45,000~160,000である。
上記熱可塑性エラストマーにおける上記繰り返し単位の数は2~10に制御される。10を超えると、全体の分子量が等しい場合に相対的にハードセグメント(HS)1つ当たりの長さがより短くなり、弾性率を望ましい範囲に制御することが難しくなり、更にロスも増加する。一方、2未満となると、エラストマー性が低下し、必要なゴム弾性が得られなくなり、タイヤに必要な弾性や伸びが得られない。
ハードセグメント(HS)とソフトセグメント(SS)とを一組とした繰り返し単位数(平均値)は、NMRによって、熱可塑性エラストマーの平均分子量やハードセグメント(HS)、ソフトセグメント(SS)それぞれの平均分子量などを測定することで算出できる。
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、下記式(1)~(3)の何れかの等式が成り立つはずである。
(1)熱可塑性エラストマー平均分子量=HS平均分子量×X+SS平均分子量×X
(2)熱可塑性エラストマー平均分子量=HS平均分子量×X+SS平均分子量×(X-1)
(3)熱可塑性エラストマー平均分子量=HS平均分子量×X+SS平均分子量×(X+1)
(上記式(1)~(3)におけるXは1以上の整数を表す。)
そして、成り立つ式におけるXの値を算出することで、HSとSSの繰り返し単位数(平均値)が計算される。
ハードセグメント(HS)、及びソフトセグメント(SS)に加えて結合部を含む場合にも、上記と同じくNMRによって、熱可塑性エラストマーやハードセグメント(HS)、ソフトセグメント(SS)、および結合部それぞれの平均分子量を測定することで、HSとSSの繰り返し単位数(平均値)が算出できる。
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、すなわち繰り返し単位あたりの平均分子量に相当する。
尚、HSとSSの繰り返し単位数の制御は、熱可塑性エラストマーにおける数平均分子量および一分子中における繰り返し単位数が目的の値になるよう、1単位中のハードセグメント(HS)の分子量、およびソフトセグメント(SS)の分子量を調整することで行うことができる。また、これらHSやSSの重合度(つまり重合箇所の数)等を調整することでも行うことができる。
上記熱可塑性エラストマーは数平均分子量が45,000~160,000の範囲である。45,000未満であると、リム組み性が低下してしまう。一方160,000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、繰り返し単位(つまり1つのハードセグメント(HS)と1つのソフトセグメント(SS)とを一組とした1単位)中における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)の平均値は、20/80~90/10が好ましい。また、20/80~80/20がより好ましく、30/70~80/20が更に好ましく、40/60~75/25が更に好ましい。
前記繰り返し単位中におけるHSの平均質量比が20以上(つまりSSの平均質量比が80以下)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、繰り返し単位中におけるHSの平均質量比が90以下(つまりSSの平均質量比が10以上)であることで、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)、ポリアミド系熱可塑性エラストマー(TPA)、及びポリエステル系熱可塑性エラストマー(TPC)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)、ポリアミド系熱可塑性エラストマー(TPA)、及びポリエステル系熱可塑性エラストマー(TPC)の中でも、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)、ポリウレタン系熱可塑性エラストマー(TPU)、及びポリエステル系熱可塑性エラストマー(TPC)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。
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、12-アミノドデカン酸などのω-アミノカルボン酸や、ラウリルラクタムなどのラクタム)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、必要により鎖長延長剤(例えば、アジピン酸又はデカンジカルボン酸)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。
ポリエステル系熱可塑性エラストマーは、少なくともポリエステルが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の一部又は全部を構成している材料が挙げられる。
ポリエステル系熱可塑性エラストマーにおけるハードセグメントの一部又は全部を形成する結晶性のポリエステルとしては、芳香族ポリエステルを用いることができる。芳香族ポリエステルは、例えば、芳香族ジカルボン酸又はそのエステル形成性誘導体と脂肪族ジオールを用いて形成することができる。
ハードセグメントの一部又は全部を形成する芳香族ポリエステルとしては、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリスチレンテレフタレート、ポリエチレンナフタレート、又はポリブチレンナフタレート等が挙げられ、ポリブチレンテレフタレートが好ましい。
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、脂肪族ポリエステル及び脂肪族ポリエーテルから選択されたポリマーが挙げられる。
脂肪族ポリエーテルとしては、ポリ(エチレンオキシド)グリコール、ポリ(プロピレンオキシド)グリコール、ポリ(テトラメチレンオキシド)グリコール、ポリ(ヘキサメチレンオキシド)グリコール、エチレンオキシドとプロピレンオキシドの共重合体、ポリ(プロピレンオキシド)グリコールのエチレンオキシド付加重合体、又はエチレンオキシドとテトラヒドロフランの共重合体等が挙げられる。
脂肪族ポリエステルとしては、ポリ(ε-カプロラクトン)、ポリエナントラクトン、ポリカプリロラクトン、ポリブチレンアジペート、又はポリエチレンアジペートなどが挙げられる。
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。
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。
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、上述のように本発明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)とを交互に繰り返し有する構造を備え、且つ1分子鎖中における前記ハードセグメント(HS)と前記ソフトセグメント(SS)とを一組とした繰り返し単位の数が2~10であり、且つ数平均分子量が45,000~160,000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):数平均分子量3,800のPA12(ナイロン12)の合成
攪拌機、窒素ガス導入口、及び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、及びドデカン二酸38.3g(分子量が下記表1に記載のHS分子量となる量)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4h(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3,800のPA12重合物である白色固体を得た。
得られたPA12(HS、数平均分子量3,800)300gに、SSとして、分子量2000(下記表1に記載のSS分子量に相当)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(HS/SS質量比が下記表1に記載の値となる量)を加え、230℃5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、繰り返し単位数の制御されたポリアミド系熱可塑性エラストマーを得た。
得られたポリアミド系熱可塑性エラストマーをペレット化し、220℃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、ドデカン二酸を24.5g(分子量が下記表1に記載のHS分子量となる量)に変更し、SSを分子量3000(下記表1に記載のSS分子量に相当)のポリオキシプロピレンジアミン(和光純薬製)168g(HS/SS質量比が下記表1に記載の値となる量)に変更して数平均分子量約54,000のポリアミド系熱可塑性エラストマーを得た以外は、実施例1と同様の方法により製造した。
実施例1において、ドデカン二酸を18.8g(分子量が下記表1に記載のHS分子量となる量)に変更し、SSを分子量4000(下記表1に記載のSS分子量に相当)のポリオキシプロピレンジアミン(和光純薬製)156g(HS/SS質量比が下記表1に記載の値となる量)に変更して数平均分子量約59,000のポリアミド系熱可塑性エラストマーを得た以外は、実施例1と同様の方法により製造した。
実施例1において、ドデカン二酸を12g(分子量が下記表1に記載のHS分子量となる量)に変更し、SSを分子量6000(下記表1に記載のSS分子量に相当)のポリオキシプロピレンジアミン(和光純薬製)150g(HS/SS質量比が下記表1に記載の値となる量)に変更して数平均分子量約72,000のポリアミド系熱可塑性エラストマーを得た以外は、実施例1と同様の方法により製造した。
実施例1において、ドデカン二酸を38.8g(分子量が下記表1に記載のHS分子量となる量)に変更し、SSを分子量1000(下記表1に記載のSS分子量に相当)のポリオキシプロピレンジアミン(HUNTSMAN製 Jeffamine RT-1000)80g(HS/SS質量比が下記表1に記載の値となる量)に変更して数平均分子量約45,505のポリアミド系熱可塑性エラストマーを得た以外は、実施例1と同様の方法により製造した。
実施例1において、アミノドデカノラクタムをカプロラクタム500gに変更し、ドデカン二酸をヘキサン二酸184g(分子量が下記表1に記載のHS分子量となる量)に変更し、12-アミノドデカン酸をアジピン酸38.7gに変更し、得られたPA6(数平均分子量630)の量を100gに変更し、SSを分子量12000(下記表1に記載のSS分子量に相当)のポリオキシプロピレンジアミン(旭硝子製)886g(HS/SS質量比が下記表1に記載の値となる量)に変更して数平均分子量約50,520のポリアミド系熱可塑性エラストマーを得た以外は、実施例1と同様の方法により製造した。
実施例1において、ドデカン二酸を18.2g(分子量が下記表1に記載のHS分子量となる量)に変更し、SSを分子量12000(下記表1に記載のSS分子量に相当)のポリオキシプロピレンジアミン(旭硝子製)450g(HS/SS質量比が下記表1に記載の値となる量)に変更して数平均分子量約160,000のポリアミド系熱可塑性エラストマーを得た以外は、実施例1と同様の方法により製造した。
・ハードセグメント(HS):数平均分子量3,500のPA6(ナイロン6)の合成
攪拌機、窒素ガス導入口、及び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ε-カプロラクタム570g、アジピン酸44g、及びヘキサン二酸25g(分子量が下記表2に記載のHS分子量となる量)を入れ、容器内を十分窒素置換した後、260℃まで昇温し、0.6MPaの加圧下で4h(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2時間反応させ、所望の数平均分子量約3,500のPA6重合物である白色固体を得た。
得られたPA6(数平均分子量3,500)300gに、分子量1400(下記表2に記載のSS分子量に相当)のポリプロピレングリコール(和光純薬製)120gを加え、230℃5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。
得られたポリアミド系熱可塑性エラストマーをペレット化し、熱水にて8時間ソックスレー抽出した後、220℃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。
・ハードセグメント(HS):数平均分子量3,100のPA612(ナイロン612)の合成
攪拌機、窒素ガス導入口、及び縮合水排出口を備えた容積2リットルの反応容器に、ドデカン二酸207g(分子量が下記表2に記載のHS分子量となる量)、ヘキサメチレンジアミン95g、及び精製水100g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、容器から取り出し、エタノールにて24時間ソックスレー抽出することで、所望の数平均分子量約3,100のPA612重合物である白色固体を得た。
得られたナイロン612(PA612)重合物200gに、ソフトセグメントとして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、数平均分子量:2000(下記表2に記載のSS分子量に相当))129g(HS/SS質量比が下記表2に記載の値となる量)を加え、230℃で7時間撹拌を行った。さらにIrganox1010を1g加え、白色のポリアミド系熱可塑性エラストマーを得た。
その後、実施例1と同様の方法によりサンプル片を製造した。
実施例1において、ドデカン二酸を47g(分子量が下記表2に記載のHS分子量となる量)に変更し、得られたPA12(数平均分子量3,100)の量を150gに変更し、SSを分子量12000(下記表2に記載のSS分子量に相当)のポリプロピレングリコール(旭硝子製)580gに変更して、230℃での反応時間を8時間に変更して、数平均分子量120,800のポリアミド系熱可塑性エラストマーを得た以外は、実施例1と同様の方法により製造した。
実施例1において、熱可塑性エラストマーの製造時の230℃での反応時間を7h(時間)に変更して数平均分子量約70,800のポリアミド系熱可塑性エラストマーを得た以外は、実施例1と同様の方法により製造した。
実施例7において、熱可塑性エラストマーの製造時の230℃での反応時間を10h(時間)に変更して数平均分子量約190,000のポリアミド系熱可塑性エラストマーを得た以外は、実施例1と同様の方法により製造した。
実施例3において、ドデカン二酸を19.5g(分子量が下記表2に記載のHS分子量となる量)に変更し、熱可塑性エラストマーの製造時の230℃での反応時間を2h(時間)に変更して数平均分子量約28,750のポリアミド系熱可塑性エラストマーを得た以外は、実施例1と同様の方法により製造した。
実施例1において、熱可塑性エラストマーの製造時の230℃での反応時間を6時間45分(比較例1より15分短い時間)に変更して数平均分子量約64,900のポリアミド系熱可塑性エラストマーを得た以外は、実施例1と同様の方法により製造した。
実施例6において、熱可塑性エラストマーの製造時の230℃での反応時間を4時間40分(実施例6より20分短い時間)に変更して数平均分子量約39,200のポリアミド系熱可塑性エラストマーを得た以外は、実施例6と同様の方法により製造した。
実施例4において、熱可塑性エラストマーの製造時の230℃での反応時間を10時間(実施例4より5時間長い時間)に変更して数平均分子量約183,600のポリアミド系熱可塑性エラストマーを得た以外は、実施例4と同様の方法により製造した。
尚、前述のNMRによって分子量を測定する方法により、HSとSSの繰り返し単位数(平均値)を算出した。結果を表1及び表2に示す。
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(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。次に、上記測定方法で得られた弾性率の実測値に対して、比較例1の値を100として計算を行い、換算値を求めた。なお、弾性率は高い方が好ましい。
JIS K7113:1995に規定される引張破断伸びEbを測定した。次に、上記測定方法で得られた破断伸びの実測値に対して、比較例1の値を100として計算を行い、換算値を求めた。なお、Ebは大きいほど耐破壊特性(耐久性)に優れ、目安としては比較例1に対して10%以上低いものは耐破壊特性(耐久性)に劣る。
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。
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 (6)
- 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)とを交互に繰り返し有する構造を備え、1分子鎖中における前記ハードセグメント(HS)と前記ソフトセグメント(SS)とを一組とした繰り返し単位の数が2~10であり、且つ数平均分子量が45,000~160,000である熱可塑性エラストマーを含むタイヤ。 - 前記繰り返し単位の数が2~8である請求項1に記載のタイヤ。
- 前記繰り返し単位の数が2~6である請求項1に記載のタイヤ。
- 前記繰り返し単位中における、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20/80~80/20である請求項1~請求項3の何れか一項に記載のタイヤ。
- 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、ポリアミド系熱可塑性エラストマー、及びポリエステル系熱可塑性エラストマーから選択される少なくとも1種である請求項1~請求項4の何れか一項に記載のタイヤ。
- 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~請求項4の何れか一項に記載のタイヤ。
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WO2017146069A1 (ja) * | 2016-02-22 | 2017-08-31 | 株式会社ブリヂストン | タイヤ |
WO2018211734A1 (ja) * | 2017-05-18 | 2018-11-22 | 株式会社ブリヂストン | タイヤ |
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JP6648024B2 (ja) | 2014-09-24 | 2020-02-14 | 株式会社ブリヂストン | タイヤ |
WO2016047708A1 (ja) | 2014-09-24 | 2016-03-31 | 株式会社ブリヂストン | タイヤ |
WO2016052565A1 (ja) | 2014-09-29 | 2016-04-07 | 株式会社ブリヂストン | タイヤ |
US10703139B2 (en) | 2014-09-29 | 2020-07-07 | Bridgestone Corporation | Tire |
JP6517572B2 (ja) * | 2015-04-10 | 2019-05-22 | 株式会社ブリヂストン | ポリアミド系熱可塑性エラストマー及びタイヤ |
CN110655646B (zh) * | 2019-09-16 | 2021-01-19 | 北京化工大学 | 一种长碳链尼龙弹性体的制备方法 |
JP6969596B2 (ja) * | 2019-10-08 | 2021-11-24 | 住友ゴム工業株式会社 | 空気入りタイヤ |
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CN107075113A (zh) | 2017-08-18 |
EP3202819A4 (en) | 2017-08-09 |
US10611190B2 (en) | 2020-04-07 |
EP3202819A1 (en) | 2017-08-09 |
JPWO2016052564A1 (ja) | 2017-04-27 |
JP6001811B2 (ja) | 2016-10-05 |
US20170232796A1 (en) | 2017-08-17 |
EP3202819B1 (en) | 2019-05-08 |
CN107075113B (zh) | 2019-11-22 |
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