WO2016052706A1 - タイヤ骨格体およびタイヤ - Google Patents
タイヤ骨格体およびタイヤ Download PDFInfo
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- WO2016052706A1 WO2016052706A1 PCT/JP2015/077966 JP2015077966W WO2016052706A1 WO 2016052706 A1 WO2016052706 A1 WO 2016052706A1 JP 2015077966 W JP2015077966 W JP 2015077966W WO 2016052706 A1 WO2016052706 A1 WO 2016052706A1
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- tire
- polyamide
- resin material
- acid
- caprolactam
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0041—Compositions of the carcass layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C5/00—Inflatable pneumatic tyres or inner tubes
- B60C5/01—Inflatable pneumatic tyres or inner tubes without substantial cord reinforcement, e.g. cordless tyres, cast tyres
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- 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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
Definitions
- the present invention relates to a tire mounted on a rim and a tire frame used in the tire, and more particularly to a tire in which at least a part of the tire frame (tire case) is formed of a resin material.
- pneumatic tires made of rubber, organic fiber materials, steel members, and the like are used for vehicles such as passenger cars.
- Conventional rubber materials conventionally used for tire skeletons of pneumatic tires have no problem in heat resistance.
- a plurality of processes such as kneading, sheeting, molding, and vulcanization are usually performed, and improvement in productivity has been demanded.
- thermoplastic resins have many advantages from the viewpoint of improving productivity, such as being capable of injection molding.
- Japanese Patent Application Laid-Open No. 2013-180621 has a polyamide-based thermoplastic elastomer as a thermoplastic polymer material and a group capable of bonding a hydrogen bond in the molecule, and has 3 or more carbon atoms.
- An annular tire skeleton formed of a thermoplastic resin material containing a low molecular weight compound having no glass transition temperature has been proposed.
- a tire using a thermoplastic polymer material is easier to manufacture and lower in cost than a conventional rubber tire.
- it is possible to assemble a rim even in a tire using a thermoplastic polymer material and it is required to ensure excellent rim assembling properties so that internal air does not leak when the rim is assembled.
- a method for adjusting the hard segment / soft segment ratio in the thermoplastic elastomer is a method for obtaining low loss while maintaining the rim assembly.
- rim assembly elastic modulus
- an object of the present invention is to provide a tire frame body that is formed by using a resin material and has both excellent rim assemblability and excellent low loss.
- An annular tire skeleton formed of a resin material containing a polyamide-based thermoplastic elastomer and caprolactam.
- a tire skeleton body that is formed using a resin material and has both excellent rim assemblability 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 skeleton of the present invention is formed of a resin material containing a polyamide-based thermoplastic elastomer and caprolactam (that is, formed using at least a resin material).
- polyamide-based thermoplastic elastomer means a polymer that forms part or all of a crystalline hard segment with a high melting point, and part or all of a soft segment that is amorphous and has a low glass transition temperature. And a copolymer thermoplastic resin material having an amide bond (—CONH—) in the main chain of the polymer constituting part or all of the hard segment.
- the polyamide-based thermoplastic elastomer may be simply referred to as “TPA” (ThermoPlastic Amid elastomer).
- the resin material in the present invention contains caprolactam (CL) in addition to the polyamide-based thermoplastic elastomer (TPA), thereby obtaining a tire skeleton body that achieves both excellent rim assembly and excellent low loss.
- CL caprolactam
- TPA polyamide-based thermoplastic elastomer
- the reason for this effect is not necessarily clear, but caprolactam (CL) plays the role of a plasticizer, so it is presumed that the loss can be reduced while suppressing the change in elastic modulus.
- the polymer viscosity at the time of melting can be reduced by blending caprolactam (CL), the injection moldability can be improved.
- the tire skeleton of the present invention is a tubular tire skeleton formed of a resin material containing a polyamide-based thermoplastic elastomer (TPA) and caprolactam (CL) (that is, formed at least using a resin material). is there.
- the resin material may contain a thermoplastic elastomer other than the polyamide-based thermoplastic elastomer or an arbitrary component.
- content of the polyamide-type thermoplastic elastomer in this invention with respect to the total amount of the said resin material is 30 mass% or more, It is further more preferable that it is 50 mass% or more, It is especially 70 mass% or more. preferable.
- “resin” is a concept including a thermoplastic resin and a thermosetting resin, but does not include natural rubber.
- polyamide thermoplastic elastomer As described above, as the polyamide-based thermoplastic elastomer (TPA) in the present invention, at least part of the polyamide is crystalline and has a high melting point, and other polymers (for example, polyester or polyether) are used. Is a material that constitutes a part or the whole of a soft segment that is amorphous and has a low glass transition temperature.
- the polyamide-based thermoplastic elastomer may use a chain extender such as dicarboxylic acid as a bonding part between the hard segment and the soft segment.
- 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, 2 to 100 is preferable, and 3 to 50 is more preferable.
- the polyamide thermoplastic elastomer has, as a hard segment, polyamide (polyamide 6) having a unit structure represented by — [CO— (CH 2 ) 5 —NH] —, or — [CO— (CH 2 ) 11 —NH It is preferable to have a polyamide (polyamide 12) having a unit structure represented by Furthermore, it is preferable to have a polyamide (polyamide 6) having a unit structure represented by — [CO— (CH 2 ) 5 —NH] —.
- polyamide 6 By having polyamide 6 in particular, a tire skeleton having excellent heat resistance can be obtained.
- polyester and polyether examples include polyester and polyether.
- polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (PTMG), polyether such as polyester polyol and polyester, ABA type triblock polyether diol, or the like can be given. These may be used alone or in combination of two or more.
- polyether diamine etc. which are obtained by reacting an anionia etc. with the terminal of polyether can be used, for example, ABA type
- examples of the “ABA type triblock polyether diol” include polyethers represented by the following general formula (3).
- x and z each independently represents an integer of 1 to 20.
- y represents an integer of 4 to 50.
- each of x and z is preferably an integer of 1 to 18, more preferably an integer of 1 to 16, particularly preferably an integer of 1 to 14, and most preferably an integer of 1 to 12.
- y is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, particularly preferably an integer of 7 to 35, and most preferably an integer of 8 to 30.
- examples of the “ABA type triblock polyether diamine” include polyether diamines represented by the following general formula (N).
- X N and Z N each independently represent an integer of 1 to 20.
- Y N represents an integer of 4 to 50.
- X N and Z N are each preferably an integer of 1 to 18, more preferably an integer of 1 to 16, particularly preferably an integer of 1 to 14, and an integer of 1 to 12 Most preferred.
- Y N is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, particularly preferably an integer of 7 to 35, and most preferably an integer of 8 to 30.
- 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.
- ⁇ -caprolactam ring-opening polycondensate / polyethylene glycol combination ⁇ -caprolactam ring-opening polycondensate / polypropylene glycol combination
- ⁇ -caprolactam ring-opening polycondensate / polytetramethylene ether glycol combination ⁇ -caprolactam ring-opening polycondensate / ABA type triblock polyether diol combination
- aminohexanoic acid polycondensate / polyethylene glycol combination aminohexanoic acid polycondensate / polypropylene glycol combination
- aminohexane An acid polycondensate / polytetramethylene ether glycol combination or an aminohexanoic acid polycondensate / ABA triblock polyether diol combination is 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. . However, it is preferably used in combination with the above-mentioned ABA type triblock polyether diol.
- Examples of the branched saturated diamine having 6 to 22 carbon atoms include 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, and 1,2- Examples include diaminopropane, 1,3-diaminopentane, 2-methyl-1,5-diaminopentane, and 2-methyl-1,8-diaminooctane.
- Examples of the branched alicyclic diamine having 6 to 16 carbon atoms include 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine and 5-amino-1,3,3-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.
- the polyamide-based thermoplastic elastomer may use a chain extender such as dicarboxylic acid in addition to the hard segment and the soft segment.
- a chain extender such as dicarboxylic acid
- dicarboxylic acid at least 1 type chosen from aliphatic, alicyclic, and aromatic dicarboxylic acid, or these derivatives can be used, for example.
- dicarboxylic acid examples include 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.
- Caprolactam refers to a lactam of amino caproic acid NH 2 (CH 2 ) 5 COOH, that is, a cyclic compound having a —NHCO— bond, and specifically includes ⁇ -caprolactam (6-aminocaproic acid lactam).
- the content of caprolactam (CL) in the resin material is preferably 0.1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and more preferably 3% by mass or more and 10% by mass with respect to the entire resin material. A mass% or less is more preferable.
- caprolactam (CL) content is 0.1% by mass or more, the disappearance of caprolactam due to volatilization during injection molding or in the vulcanization process is suppressed, and a desirable elastic modulus and excellent low loss properties are obtained. Effectively compatible.
- the content of caprolactam (CL) is 20% by mass or less, the viscosity is controlled within an appropriate range, and excellent injection moldability is obtained.
- caprolactam examples include ⁇ -caprolactam, N-Boc- ⁇ -caprolactam, 4-t-butylcaprolactam, ⁇ -aminocaprolactam, N-methylcaprolactam, N-acetylcaprolactam and the like manufactured by Aldrich. .
- Examples of the method of incorporating caprolactam (CL) into the resin material include a method of first synthesizing a polyamide-based thermoplastic elastomer and then adding caprolactam (CL) to a desired amount. If caprolactam is used as a raw material in the synthesis of the polyamide-based thermoplastic elastomer, a specific amount of caprolactam is added in advance, and the caprolactam as the raw material remains as it is after the polyamide-based thermoplastic elastomer is synthesized. You may adjust so that it may remain without superposing
- the polyamide thermoplastic elastomer in the present invention has a mass ratio (HS / SS, HS mass ratio) of the hard segment (HS) and the soft segment (SS) of the polyamide thermoplastic elastomer of 55/45 to 85/15. Preferably there is.
- the HS mass ratio is not less than the lower limit, the elastic modulus increases, shape retention is obtained, and good rim assembly is obtained. Further, when the HS mass ratio is less than or equal to the upper limit value, the elastic modulus does not become too high, and a good rim assembly property is obtained.
- the HS mass ratio can be adjusted to a desired range by setting the charge amount of the raw material constituting the hard segment and the raw material constituting the soft segment.
- the HS mass ratio can be measured by using 1 H-NMR and 13 C-NMR for polyamide-based thermoplastic elastomers.
- the content of the hard segment and the soft segment in the polyamide thermoplastic elastomer is preferably set as appropriate so that the HS mass ratio is in the above range.
- the content is preferably set so 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.
- the content of the hard segment, the soft segment and the chain extender used as necessary in the polyamide thermoplastic elastomer is appropriately selected so that the HS mass ratio is within the above range. For example, it can be set as desired content by setting each charging amount.
- the weight average molecular weight of the polyamide-based thermoplastic elastomer contained in the resin material is not particularly limited, but is preferably about 10,000 to 400,000.
- the polyamide thermoplastic elastomer preferably has a weight average molecular weight of 15,700 to 300,000, more preferably 22,000 to 200,000. Further preferred.
- the weight average molecular weight of the polyamide-based thermoplastic elastomer can be measured by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- HLC-8320GPC EcoSEC manufactured by Tosoh Corporation can be used.
- the number average molecular weight of the polymer (polyamide) constituting part or all of the hard segment is preferably 300 to 15000 from the viewpoint of melt moldability.
- the number average molecular weight of the polymer constituting part or all of the soft segment is preferably 200 to 6000 from the viewpoint of toughness and low temperature flexibility.
- the polyamide-based thermoplastic elastomer can be synthesized by copolymerizing 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.
- the polyamide 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, The ABA triblock polyether diol) and a chain extender (for example, adipic acid or decanedicarboxylic acid) can be polymerized in a container.
- 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
- ⁇ -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 polymerization average molecular weight of the polyamide thermoplastic elastomer to be synthesized and the polymerization temperature.
- the polymerization time 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.
- 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 )”).
- 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.
- 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 rim assembly property can be improved.
- the tensile elongation at break specified in JIS K7113: 1995 of the resin material (tire frame) itself is preferably 50% or more, preferably 100% or more, more preferably 150% or more, and particularly preferably 200% or more.
- the rim assembly property is good and it is possible to make it difficult to break against a collision.
- the deflection temperature under load (when loaded with 0.45 MPa) as defined in ISO 75-2 or ASTM D648 of the resin material (tire frame) itself is preferably 50 ° C. or more, preferably 50 ° C. to 150 ° C., and preferably 50 ° C. to 50 ° C. 130 ° C. is more preferable.
- the deflection temperature under load of the resin material is 50 ° C. or higher, deformation of the tire skeleton can be suppressed even when vulcanization is performed in the manufacture of the tire.
- FIG. 1A is a perspective view showing a partial cross section of a tire according to an embodiment of the present invention.
- FIG. 1B is a cross-sectional view of a bead portion attached to a rim.
- the tire 10 of the present embodiment has a cross-sectional shape 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.
- a resin material including, for example, a polyamide-based thermoplastic elastomer and caprolactam 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 body 17A formed using at least the resin material can be formed by, for example, vacuum forming, pressure forming, injection forming, measuring and tort casting. 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.
- a crown 30 made of a material having higher wear resistance than a resin material constituting part or all of the tire case 17, for example, rubber alone, is disposed.
- 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 crown 30 is disposed on the outer peripheral side of the reinforcing cord layer 28 in the tire radial direction.
- the rubber used for the crown 30 is preferably the same type of rubber used in conventional rubber pneumatic tires.
- a crown formed of another type of resin material that is more excellent in wear resistance than a resin material that constitutes part or all of the tire case 17 may be used.
- the crown 30 is formed with a crown pattern including a plurality of grooves on the ground contact surface with the road surface in the same manner as a conventional rubber pneumatic tire.
- the manufacturing method of the tire of this embodiment is explained.
- a tire case half is formed using a resin material containing the polyamide-based thermoplastic elastomer. These tire cases are preferably formed by injection molding.
- the tire case halves supported by the thin metal support ring face each other.
- a joining mold (not shown) is installed so as to be in contact with the outer peripheral surface of the abutting portion of the tire case half.
- die is comprised so that the periphery of the junction part (butting part) of the tire case half body 17A may be pressed with a predetermined pressure.
- the periphery of the joint portion of the tire case half is pressed at a temperature equal to or higher than the melting point (or softening point) of the resin material constituting part or all of the tire case.
- the joint portion of the tire case half is heated and pressed by the joining mold, the joint portion is melted and the tire case halves are fused together, and the tire case 17 is formed by integrating these members.
- the joining portion of the tire case half is heated using a joining mold, but the present invention is not limited to this.
- the joining portion is heated by a separately provided high-frequency heater or the like.
- the tire case halves may be joined by softening or melting in advance by irradiation with hot air, infrared rays, or the like, and pressurizing with a joining mold.
- FIG. 3 is an explanatory diagram for explaining an operation of embedding a reinforcing cord in a crown portion of a tire case using a cord heating device and rollers.
- the cord supply device 56 is disposed on the reel 58 around which the reinforcing cord 26 is wound, the cord heating device 59 disposed on the downstream side of the reel 58 in the cord transport direction, and the downstream side of the reinforcing cord 26 in the transport direction.
- the first roller 60, the first cylinder device 62 that moves the first roller 60 in the direction of contacting and separating from the outer peripheral surface of the tire, and the downstream side in the conveying direction of the reinforcing cord 26 of the first roller 60 A second roller 64, and a second cylinder device 66 that moves the second roller 64 in a direction in which the second roller 64 comes into contact with and separates from the tire outer peripheral surface.
- the second roller 64 can be used as a metal cooling roller.
- the surfaces of the first roller 60 and the second roller 64 are made of fluororesin (in this embodiment, Teflon (registered trademark)) in order to suppress adhesion of a molten or softened resin material. It is coated.
- the cord supply device 56 has two rollers, ie, the first roller 60 and the second roller 64, but the present invention is not limited to this configuration, and either one of the rollers. It is also possible to have only one (that is, one roller).
- the cord heating device 59 includes a heater 70 and a fan 72 that generate hot air. Further, the cord heating device 59 includes a heating box 74 through which the reinforcing cord 26 passes through an internal space in which hot air is supplied, and a discharge port 76 for discharging the heated reinforcing cord 26.
- the temperature of the heater 70 of the cord heating device 59 is raised, and the ambient air heated by the heater 70 is sent to the heating box 74 by the wind generated by the rotation of the fan 72.
- the reinforcing cord 26 unwound from the reel 58 is fed into a heating box 74 in which the internal space is heated with hot air (for example, the temperature of the reinforcing cord 26 is heated to about 100 to 200 ° C.).
- the heated reinforcing cord 26 passes through the discharge port 76 and is wound spirally around the outer peripheral surface of the crown portion 16 of the tire case 17 rotating in the direction of arrow R in FIG.
- the resin material at the contact portion melts or softens, and at least a part of the heated reinforcing cord 26 is embedded in the outer peripheral surface of the crown portion 16. Is done. At this time, since the heated reinforcing cord 26 is embedded in the molten or softened resin material, there is no gap between the resin material and the reinforcing cord 26, that is, a tight contact state. Thereby, the air entering to the portion where the reinforcing cord 26 is embedded is suppressed.
- the burying amount L of the reinforcing cord 26 can be adjusted by the heating temperature of the reinforcing cord 26, the tension applied to the reinforcing cord 26, the pressing force by the first roller 60, and the like.
- the embedding amount L of the reinforcing cord 26 is set to be 1/5 or more of the diameter D of the reinforcing cord 26.
- the burying amount L of the reinforcing cord 26 is more preferably more than 1/2 of the diameter D, and most preferably the entire reinforcing cord 26 is embedded.
- the reinforcing cord layer 28 is formed on the outer peripheral side of the crown portion 16 of the tire case 17 by winding the heated reinforcing cord 26 while being embedded in the outer peripheral surface of the crown portion 16.
- the vulcanized belt-shaped crown 30 is wound around the outer peripheral surface of the tire case 17 by one turn, and the crown 30 is bonded to the outer peripheral surface of the tire case 17 using an adhesive or the like.
- the crown 30 may be, for example, a precure crown that is used in conventionally known retreaded tires. This step is the same step as the step of bonding the precure crown to the outer peripheral surface of the base tire of the retreaded tire.
- the seal layer 24 made of 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 reinforcing cord 26 is heated, and the surface of the tire case 17 at the portion where the heated reinforcing cord 26 contacts is melted or softened.
- the present invention is not limited to this configuration.
- the reinforcing cord 26 may be embedded in the crown portion 16 after the outer peripheral surface of the crown portion 16 in which the reinforcing cord 26 is embedded is heated using a hot air generator without heating the reinforcing cord 26.
- the heat source of the cord heating device 59 is a heater and a fan.
- the present invention is not limited to this configuration, and the reinforcement cord 26 may be directly heated by radiant heat (for example, infrared rays). Good.
- the portion in which the resin material in which the reinforcing cord 26 is embedded is melted or softened is forcibly cooled by the metal second roller 64, but the present invention is not limited to this configuration. .
- 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.
- the tire of the present invention is an embodiment using a reinforcing cord member in which the cord member is coated with a resin material as shown in the second embodiment (FIGS. 4 and 5) of JP 2012-46030 A. Also good.
- Example 1 (Hard segment: Synthesis of PA6 (nylon (registered trademark) 6))
- a reaction vessel having a volume of 2 liters equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet was charged with 470 g of caprolactam made by Aldrich, 173 g of dodecanedioic acid, and 37 g of aminohexanoic acid.
- the temperature was raised to 0 ° 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, and a white solid which was a PA6 polymer having a desired number average molecular weight of about 1200 was obtained through a water washing step.
- PA6 polymer (HS) forming a hard segment
- PPG / PTMG / PPG polytetramethylene ether glycol (PTMG) -derived structural unit and polypropylene glycol (PPG) -derived structural unit
- PTMG polytetramethylene ether glycol
- PPG polypropylene glycol
- Example 2 Each type of polymer forming the hard segment (HS) and the soft segment, the hard segment HS / soft segment SS ratio [mass ratio], and the types and addition amounts of the additives are shown in Table 1 below. It was supposed to be. Moreover, HS was changed to PA6 having a molecular weight of 1860, and the amount of charge was changed to 200 g for PA6 (HS) having a molecular weight of 1860, 108 g for PPG / PTMG / PPG (SS), and 6.2 g for caprolactam, respectively. A polyamide elastomer was obtained in the same manner as in Example 1.
- Example 3 Each type of polymer forming the hard segment (HS) and the soft segment, the hard segment HS / soft segment SS ratio [mass ratio], and the types and addition amounts of the additives are shown in Table 1 below. It was supposed to be. Further, HS was changed to PA6 having a molecular weight of 2030, and the charging amount was changed to 200 g of PA6 (HS) having a molecular weight of 2030, 99 g of PPG / PTMG / PPG (SS), and the polymerization time to 8 hours. A polyamide elastomer was obtained in the same manner as in Example 1.
- Example 4 Each type of polymer forming the hard segment (HS) and the soft segment, the hard segment HS / soft segment SS ratio [mass ratio], and the types and addition amounts of the additives are shown in Table 1 below. It was supposed to be.
- HS was changed to PA6 having a molecular weight of 2030, and charged amounts were set to Examples except that PA6 (HS) having a molecular weight of 2030 was changed to 200 g, PPG / PTMG / PPG (SS) was changed to 99 g, and caprolactam was changed to 12 g.
- a polyamide elastomer was obtained.
- Example 5 Each type of polymer forming the hard segment (HS) and the soft segment, the hard segment HS / soft segment SS ratio [mass ratio], and the types and addition amounts of the additives are shown in Table 1 below. It was supposed to be.
- HS was changed to PA6 having a molecular weight of 2030, and charged amounts were changed to Examples except that PA6 (HS) having a molecular weight of 2030 was changed to 200 g, PPG / PTMG / PPG (SS) was changed to 99 g, and caprolactam was changed to 56 g.
- a polyamide elastomer was obtained.
- Example 6 Each type of polymer forming the hard segment (HS) and the soft segment, the hard segment HS / soft segment SS ratio [mass ratio], and the types and addition amounts of the additives are shown in Table 1 below. It was supposed to be. In addition, HS was changed to PA6 having a molecular weight of 2330, and charged amounts were changed to Examples except that PA6 (HS) having a molecular weight of 2330 was changed to 200 g, PPG / PTMG / PPG (SS) was changed to 86 g, and caprolactam was changed to 25 g. In the same manner as in Example 1, a polyamide elastomer was obtained.
- HS hard segment
- HS / soft segment SS ratio weight ratio
- the types and addition amounts of the additives are shown in Table 2 below. It was supposed to be. Further, HS is PA6 having a molecular weight of 4670, and the charging amount is 200 g of PA6 (HS) having a molecular weight of 4670, the soft segment is 86 g of PPG (diamine, ELASTAMINE (registered trademark) RP-2009 manufactured by HUNTSMAN), and caprolactam is used. A polyamide elastomer was obtained in the same manner as in Example 1 except that the amount was changed to 24 g.
- Example 8 Each type of polymer forming the hard segment (HS) and the soft segment, the hard segment HS / soft segment SS ratio [mass ratio], and the types and addition amounts of the additives are shown in Table 2 below. It was supposed to be. Further, HS was changed to PA6 having a molecular weight of 8000, and the amounts charged were the same as in Example 1 except that PA6 (HS) having a molecular weight of 8000 was changed to 200 g, PPG (SS) was changed to 50 g, and caprolactam was changed to 35 g. Thus, a polyamide elastomer was obtained.
- Example 9 Each type of polymer forming the hard segment (HS) and the soft segment, the hard segment HS / soft segment SS ratio [mass ratio], and the types and addition amounts of the additives are shown in Table 2 below. It was supposed to be.
- HS was changed to PA6 having a molecular weight of 5670
- the charge amount was changed to Example 6 except that PA6 (HS) having a molecular weight of 5670 was changed to 200 g, PPG / PTMG / PPG (SS) was changed to 35 g, and caprolactam was changed to 48 g.
- a polyamide elastomer was obtained.
- Example 10 Each type of polymer forming the hard segment (HS) and the soft segment, the hard segment HS / soft segment SS ratio [mass ratio], and the types and addition amounts of the additives are shown in Table 2 below. It was supposed to be.
- HS was changed to PA12 having a molecular weight of 3000, and the charged amounts were set to Examples except that PA12 (HS) having a molecular weight of 3000 was changed to 200 g, PPG / PTMG / PPG (SS) was changed to 67 g, and caprolactam was changed to 10 g.
- a polyamide elastomer was obtained.
- Example 11 Each type of polymer forming the hard segment (HS) and the soft segment, the hard segment HS / soft segment SS ratio [mass ratio], and the types and addition amounts of the additives are shown in Table 3 below. It was supposed to be.
- HS was changed to PA6 having a molecular weight of 2030, and charged amounts were set to Examples except that PA6 (HS) having a molecular weight of 2030 was changed to 200 g, PPG / PTMG / PPG (SS) was changed to 99 g, and caprolactam was changed to 5 g.
- a polyamide elastomer was obtained.
- the evaluation criteria are as follows. A: Moisture content is lower than 1.5% B: Moisture content is 1.5% or more and 2.0% or less C: Moisture content is higher than 2.0%
- Tables 1 to 3 The components shown in Tables 1 to 3 are as follows. -Polymer for soft segment- PPG / PTMG / PPG: manufactured by HUNTSMAN, trade name: JEFFAMINE (registered trademark) RT-1000 -PPG: manufactured by HUNTSMAN, trade name: ELASTAMINE (registered trademark) RP-2009
- PA6 PA6 synthesized in Example 1 (nylon (registered trademark) 6)
- PA12 PA12 synthesized by the following method (nylon (registered trademark) 12) (Hard segment: Synthesis of PA12 (nylon (registered trademark) 12))
- a reaction vessel having a volume of 2 liters equipped with a stirrer, a nitrogen gas inlet, and a condensed water outlet
- 40 g of Aldrich 12-aminododecanoic acid, 550 g of aminododecanolactam and 67 g of dodecanedioic acid were placed, and the inside of the vessel was sufficiently nitrogen
- the temperature was raised to 280 ° C., and the reaction was performed 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 as a PA12 polymer having a desired number average molecular weight of about
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Abstract
Description
尚、リム組性を維持しつつ低ロス性を得るための方法としては、熱可塑性エラストマー中のハードセグメント/ソフトセグメント比を調整する方法が挙げられる。しかし、一方を高めると他方が低下するというように、リム組性(弾性率)と低ロス性とは二律背反の関係にあり、この両者をともに向上させることは容易でなかった。
この効果が奏される理由は必ずしも明確ではないが、カプロラクタム(CL)が可塑剤の役割を果たすため、弾性率の変化を抑えつつも低ロス化を図ることができるものと推察される。
また、カプロラクタム(CL)配合により溶融時のポリマー粘度を下げることができるため、射出成形性の向上をも図ることができる。
本発明のタイヤ骨格体は、ポリアミド系熱可塑性エラストマー(TPA)と、カプロラクタム(CL)と、を含む樹脂材料で形成される(つまり少なくとも樹脂材料を用いて形成される)管状のタイヤ骨格体である。
前記樹脂材料は、ポリアミド系熱可塑性エラストマー以外の熱可塑性エラストマーや任意の成分を含んでいてもよい。なお、前記樹脂材料の総量に対する本発明におけるポリアミド系熱可塑性エラストマーの含有量が30質量%以上であることが好ましく、50質量%以上であることが更に好ましく、70質量%以上であることが特に好ましい。また、本明細書において「樹脂」とは、熱可塑性樹脂及び熱硬化性樹脂を含む概念であるが、天然ゴムは含まない。
上述のように本発明におけるポリアミド系熱可塑性エラストマー(TPA)としては、少なくともポリアミドが結晶性で融点の高いハードセグメント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。また、ポリアミド系熱可塑性エラストマーはハードセグメント及びソフトセグメントの結合部として、ジカルボン酸等の鎖長延長剤を用いてもよい。
前記ハードセグメント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。
更には、-[CO-(CH2)5-NH]-で表される単位構造を有するポリアミド(ポリアミド6)を有することが好ましい。特にポリアミド6を有することにより、耐熱性に優れたタイヤ骨格体とすることができる。
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。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)、又はポリエステルポリオール等のポリエーテル及びポリエステル、あるいはABA型トリブロックポリエーテルジオール等が挙げられる。これらを単独で又は2種以上を用いることができる。また、ポリエーテルの末端にアニモニア等を反応させることによって得られるポリエーテルジアミン等を用いることができ、例えば、ABA型トリブロックポリエーテルジアミンを用いることができる。
上述のジアミンは単独で使用してもよいし、2種類以上を適宜組合せて使用してもよい。
上述のように、ポリアミド系熱可塑性エラストマーはハードセグメント及びソフトセグメントの他に、ジカルボン酸等の鎖長延長剤を用いてもよい。前記ジカルボン酸としては、例えば、脂肪族、脂環式及び芳香族ジカルボン酸から選ばれる少なくとも一種又はこれらの誘導体を用いることができる。
本発明における樹脂材料には、添加剤として少なくともカプロラクタム(CL)を含有する。カプロラクタムとは、アミノカプロン酸NH2(CH2)5COOHのラクタムつまり-NHCO-結合をもつ環状化合物を指し、具体的にはε-カプロラクタム(6-アミノカプロン酸ラクタム)等が挙げられる。
樹脂材料中においてカプロラクタム(CL)の含有量は、樹脂材料全体に対し0.1質量%以上20質量%以下が好ましく、更には1質量%以上15質量%以下がより好ましく、3質量%以上10質量%以下が更に好ましい。カプロラクタム(CL)の含有量が0.1質量%以上であることで、射出成形の際や加硫プロセスでの揮発によるカプロラクタムの消失が抑制され、望ましい弾性率と優れた低ロス性とをより効果的に両立できる。一方、カプロラクタム(CL)の含有量が20質量%以下であることで、粘度が適正な範囲に制御され、優れた射出成形性が得られる。
また、ポリアミド系熱可塑性エラストマーの合成の際に原料としてカプロラクタムを用いる場合であれば、予め特定量のカプロラクタムを添加しておき、ポリアミド系熱可塑性エラストマーを合成した後にもこの原料であるカプロラクタムがそのまま重合されずに残るよう調整してもよい。この方法による場合、原料であるカプロラクタムの添加量や重合条件を、カプロラクタムが残るよう調整して行うことができる。また、ポリアミド系熱可塑性エラストマー合成後の洗浄(特に水洗浄)によって残存するカプロラクタムは除去されるため、洗浄の条件を調整して樹脂材料中のカプロラクタム(CL)量をコントロールすることができる。
本発明におけるポリアミド系熱可塑性エラストマーは、前記ポリアミド系熱可塑性エラストマーのハードセグメント(HS)とソフトセグメント(SS)との質量比(HS/SS、HS質量比)が55/45~85/15であることが好ましい。前記HS質量比が下限値以上であると、弾性率が高くなり、形状保持性が得られ、良好なリム組み性が得られる。また、前記HS質量比が上限値以下であると、弾性率が高くなり過ぎず、良好なリム組み性が得られる。前記HS質量比は、ハードセグメントを構成する原料及びソフトセグメントを構成する原料の仕込み量を設定することで所望の範囲に調整することができる。また、前記HS質量比は、ポリアミド系熱可塑性エラストマーは1H-NMR及び13C-NMRを用いることで、測定することができる。
前記鎖長延長剤を用いる場合、その含有量は前記ソフトセグメントの原料となるモノマーの水酸基又はアミノ基と、鎖長延長剤のカルボキシル基とがほぼ等モルになるように設定されることが好ましい。
前記ポリアミド熱可塑性エラストマー中のハードセグメント、ソフトセグメント及び必要に応じて用いられる鎖長延長剤の含有量は、HS質量比が上述の範囲内になるように適宜選定される。例えば各々の仕込み量を設定することで各々所望の含有量とすることができる。
本発明において、樹脂材料に含まれるポリアミド系熱可塑性エラストマーの重量平均分子量は、特に限定はないが、10,000~400,000程度であることが好ましい。リム組み性の更なる向上やタイヤの内圧に対する耐圧性を向上させる観点からは、前記ポリアミド系熱可塑性エラストマーの重量平均分子量が15,700~300,000が好ましく、22,000~200,000が更に好ましい。
前記ポリアミド系熱可塑性エラストマーの重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)により測定することができる。例えば、東ソー株式会社製の「HLC-8320GPC EcoSEC」等のGPC(ゲル浸透クロマトグラフィー)を用いることができる。
また、前記ポリアミド系熱可塑性エラストマーの製造においては、必要に応じて触媒を用いることができる。前記触媒としては、P、Ti、Ge、Zn、Fe、Sn、Mn、Co、Zr、V、Ir、La、Ce、Li、Ca、及び、Hfからなる群より選択される少なくとも1種を含む化合物が挙げられる。
例えば、無機系リン化合物、有機チタン化合物、有機ジルコニウム化合物、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。
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、上述のように前記ポリアミド系熱可塑性エラストマーを含む樹脂材料を用いて、タイヤケース半体を形成する。これらタイヤケースの形成は、射出成形で行うことが好ましい。次に、薄い金属の支持リングに支持されたタイヤケース半体同士を互いに向かい合わせる。次いで、タイヤケース半体の突き当て部分の外周面と接するように図を省略する接合金型を設置する。ここで、前記接合金型はタイヤケース半体17Aの接合部(突き当て部分)周辺を所定の圧力で押圧するように構成されている。次いで、タイヤケース半体の接合部周辺を、タイヤケース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及び加圧されると、前記接合部が溶融しタイヤケース半体同士が融着しこれら部材が一体となってタイヤケース17が形成される。尚、本実施形態においては接合金型を用いてタイヤケース半体の接合部を加熱したが、本発明はこれに限定されず、例えば、別に設けた高周波加熱機等によって前記接合部を加熱したり、予め熱風、赤外線の照射等によって軟化又は溶融させ、接合金型によって加圧して、タイヤケース半体を接合させてもよい。
次に、補強コード巻回工程について図3を用いて説明する。図3は、コード加熱装置、及びローラ類を用いてタイヤケースのクラウン部に補強コードを埋設する動作を説明するための説明図である。図3において、コード供給装置56は、補強コード26を巻き付けたリール58と、リール58のコード搬送方向下流側に配置されたコード加熱装置59と、補強コード26の搬送方向下流側に配置された第1のローラ60と、第1のローラ60をタイヤ外周面に対して接離する方向に移動する第1のシリンダ装置62と、第1のローラ60の補強コード26の搬送方向下流側に配置される第2のローラ64と、第2のローラ64をタイヤ外周面に対して接離する方向に移動する第2のシリンダ装置66と、を備えている。第2のローラ64は、金属製の冷却用ローラとして利用することができる。また、本実施形態において、第1のローラ60及び第2のローラ64の表面は、溶融又は軟化した樹脂材料の付着を抑制するためにフッ素樹脂(本実施形態では、テフロン(登録商標))でコーティングされている。なお、本実施形態では、コード供給装置56は、第1のローラ60及び第2のローラ64の2つのローラを有する構成としているが、本発明はこの構成に限定されず、何れか一方のローラのみ(即ち、ローラ1個)を有している構成でもよい。
(ハードセグメント:PA6(ナイロン(登録商標)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、アルドリッチ製カプロラクタム470g、ドデカン二酸173g、アミノヘキサン酸37gを入れ、容器内を十分窒素置換した後、250℃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、水洗工程を経て所望の数平均分子量約1200のPA6重合物である白色固体を得た。
前記PA6(ハードセグメントを形成するポリマー(HS))200gと、PPG/PTMG/PPG(ポリテトラメチレンエーテルグリコール(PTMG)由来の構成単位及びポリプロピレングリコール(PPG)由来の構成単位を含む三元共重合体のジアミン、ソフトセグメントを形成するポリマー、HUNTSMAN社製、商品名:JEFFAMINE(登録商標)RT-1000)164gと、を混合した。
この混合物を窒素気流下、230℃7時間撹拌を行い、その後カプロラクタム(アルドリッチ製)7.1gと、Irganox1010(BASF社製)1gと、を加え、白色のポリアミドエラストマーを得た。
得られたポリアミドエラストマーはペレット化し、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。
ハードセグメントを形成するポリマー(HS)、およびソフトセグメントを形成するポリマーの各種類、ハードセグメントHS/ソフトセグメントSS比[質量比]、並びに添加剤の種類および添加量を、下記表1に記載のものとした。また、HSを分子量1860のPA6にし、仕込み量についてはそれぞれ、分子量1860のPA6(HS)を200gに、PPG/PTMG/PPG(SS)を108gに、カプロラクタムを6.2gに変更した以外は、実施例1と同様にしてポリアミドエラストマーを得た。
ハードセグメントを形成するポリマー(HS)、およびソフトセグメントを形成するポリマーの各種類、ハードセグメントHS/ソフトセグメントSS比[質量比]、並びに添加剤の種類および添加量を、下記表1に記載のものとした。また、HSを分子量2030のPA6にし、仕込み量についてはそれぞれ、分子量2030のPA6(HS)を200gに、PPG/PTMG/PPG(SS)を99gに、重合時間を8時間に変更した以外は、実施例1と同様にしてポリアミドエラストマーを得た。
ハードセグメントを形成するポリマー(HS)、およびソフトセグメントを形成するポリマーの各種類、ハードセグメントHS/ソフトセグメントSS比[質量比]、並びに添加剤の種類および添加量を、下記表1に記載のものとした。また、HSを分子量2030のPA6にし、仕込み量についてはそれぞれ、分子量2030のPA6(HS)を200gに、PPG/PTMG/PPG(SS)を99gに、カプロラクタムを12gに変更した以外は、実施例1と同様にしてポリアミドエラストマーを得た。
ハードセグメントを形成するポリマー(HS)、およびソフトセグメントを形成するポリマーの各種類、ハードセグメントHS/ソフトセグメントSS比[質量比]、並びに添加剤の種類および添加量を、下記表1に記載のものとした。また、HSを分子量2030のPA6にし、仕込み量についてはそれぞれ、分子量2030のPA6(HS)を200gに、PPG/PTMG/PPG(SS)を99gに、カプロラクタムを56gに変更した以外は、実施例1と同様にしてポリアミドエラストマーを得た。
ハードセグメントを形成するポリマー(HS)、およびソフトセグメントを形成するポリマーの各種類、ハードセグメントHS/ソフトセグメントSS比[質量比]、並びに添加剤の種類および添加量を、下記表1に記載のものとした。また、HSを分子量2330のPA6にし、仕込み量についてはそれぞれ、分子量2330のPA6(HS)を200gに、PPG/PTMG/PPG(SS)を86gに、カプロラクタムを25gに変更した以外は、実施例1と同様にしてポリアミドエラストマーを得た。
ハードセグメントを形成するポリマー(HS)、およびソフトセグメントを形成するポリマーの各種類、ハードセグメントHS/ソフトセグメントSS比[質量比]、並びに添加剤の種類および添加量を、下記表2に記載のものとした。また、HSを分子量4670のPA6にし、仕込み量については、分子量4670のPA6(HS)を200gにし、ソフトセグメントをPPG(ジアミン、HUNTSMAN社製ELASTAMINE(登録商標)RP-2009)86gにし、カプロラクタムを24gに変更した以外は、実施例1と同様にしてポリアミドエラストマーを得た。
ハードセグメントを形成するポリマー(HS)、およびソフトセグメントを形成するポリマーの各種類、ハードセグメントHS/ソフトセグメントSS比[質量比]、並びに添加剤の種類および添加量を、下記表2に記載のものとした。また、HSを分子量8000のPA6にし、仕込み量についてはそれぞれ、分子量8000のPA6(HS)を200gに、PPG(SS)を50gに、カプロラクタムを35gに変更した以外は、実施例1と同様にしてポリアミドエラストマーを得た。
ハードセグメントを形成するポリマー(HS)、およびソフトセグメントを形成するポリマーの各種類、ハードセグメントHS/ソフトセグメントSS比[質量比]、並びに添加剤の種類および添加量を、下記表2に記載のものとした。また、HSを分子量5670のPA6にし、仕込み量についてはそれぞれ、分子量5670のPA6(HS)を200gに、PPG/PTMG/PPG(SS)を35gに、カプロラクタムを48gに変更した以外は、実施例1と同様にしてポリアミドエラストマーを得た。
ハードセグメントを形成するポリマー(HS)、およびソフトセグメントを形成するポリマーの各種類、ハードセグメントHS/ソフトセグメントSS比[質量比]、並びに添加剤の種類および添加量を、下記表2に記載のものとした。また、HSを分子量3000のPA12にし、仕込み量についてはそれぞれ、分子量3000のPA12(HS)を200gに、PPG/PTMG/PPG(SS)を67gに、カプロラクタムを10gに変更した以外は、実施例1と同様にしてポリアミドエラストマーを得た。
ハードセグメントを形成するポリマー(HS)、およびソフトセグメントを形成するポリマーの各種類、ハードセグメントHS/ソフトセグメントSS比[質量比]、並びに添加剤の種類および添加量を、下記表3に記載のものとした。また、HSを分子量2030のPA6にし、仕込み量についてはそれぞれ、分子量2030のPA6(HS)を200gに、PPG/PTMG/PPG(SS)を99gに、カプロラクタムを5gに変更した以外は、実施例1と同様にしてポリアミドエラストマーを得た。
ハードセグメントを形成するポリマー(HS)、およびソフトセグメントを形成するポリマーの各種類、ハードセグメントHS/ソフトセグメントSS比[質量比]、並びに添加剤の種類および添加量を、下記表2に記載のものとした。また、HSを分子量5670のPA6にし、仕込み量についてはそれぞれ、分子量5670のPA6(HS)を200gに、PPG(SS)を35gに、添加剤(アミノドデカン酸)を7.0gに変更した以外は、実施例1と同様にしてポリアミドエラストマーを得た。
ハードセグメントを形成するポリマー(HS)、およびソフトセグメントを形成するポリマーの各種類、ハードセグメントHS/ソフトセグメントSS比[質量比]、並びに添加剤の種類および添加量を、下記表3に記載のものとした。また、HSを分子量2330のPA6にし、仕込み量についてはそれぞれ、分子量2330のPA6(HS)を200gに、PPG/PTMG/PPG(SS)を86gに、カプロラクタムを0g(つまりカプロラクタムを添加しない)に変更した以外は、実施例1と同様にしてポリアミドエラストマーを得た。
[射出成形性]
前記射出成形の際、15t射出成形機で平板が成形できれば「A」、Aよりもハンドリングが劣る(計量不良)ものを「B」、充填不良(粘度が高い)が見られるものを「C」とした。
各実施例及び比較例で得られた重合体を用いて、それぞれ上述の第1の実施形態を参照し、タイヤを形成した。次いで、タイヤをリムに装着し、エアシール性が確保できた場合を「A」、リム組みの際に、硬くてハンドリング性に劣る場合を「B」、割れの発生や、エアシール性が確保できなかった場合を「C」とした。
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(TAインスツルメンツ社製)を使用し、温度30℃、歪み1%、周波数20Hzで損失正接(tanδ)を、23℃50RH%の環境下で調湿後に測定した。該tanδが0.08以下の場合を「A」、0.08より大きく0.12以下の場合を「B」、0.12より大きい場合を「C」として評価した。また、全実施例および比較例中で、最もロスが低いものを基準(100)とし、インデックス表記した。
得られたサンプルについて、以下の方法により吸湿性の試験を行った。
15t射出成形機にて作製した試験片を23℃50RH%の恒温恒湿環境下に放置し、重量変化が見られなくなった時点の飽和水分率をカールフィッシャー水分率測定計(三菱化学アナリテック社製)にて評価した。射出片を用い加硫を模擬した160℃熱プレスを実施した際に、評価基準がAの場合は、気泡発生、変形等が見られず、良好な形状を維持していた。評価基準がBの場合、気泡発生により射出片の一部に変形が見られる場合があった。評価基準がCの場合、気泡発生により射出片が大きく変形してしまった。
評価基準は以下の通りである。
A:水分率が1.5%より低い
B:水分率が1.5%以上2.0%以下
C:水分率が2.0%より高い
-ソフトセグメント用ポリマー-
・PPG/PTMG/PPG:HUNTSMAN社製、商品名:JEFFAMINE(登録商標)RT-1000
・PPG:HUNTSMAN社製、商品名:ELASTAMINE(登録商標)RP-2009
・カプロラクタム(CL):アルドリッチ製
・アミノドデカン酸:アルドリッチ製
・PA6:前記実施例1で合成したPA6(ナイロン(登録商標)6)
・PA12:下記方法で合成したPA12(ナイロン(登録商標)12)
(ハードセグメント:PA12(ナイロン(登録商標)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40g、アミノドデカノラクタム550g、ドデカン二酸67g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3,000のPA12重合物である白色固体を得た。
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 (4)
- ポリアミド系熱可塑性エラストマーと、カプロラクタムと、を含む樹脂材料で形成される環状のタイヤ骨格体。
- 前記樹脂材料中における前記カプロラクタムの含有量が0.1質量%以上20質量%以下である請求項1に記載のタイヤ骨格体。
- 前記ポリアミド系熱可塑性エラストマーが、ハードセグメントとしてポリアミド6を含む請求項1または請求項2に記載のタイヤ骨格体。
- 請求項1~請求項3のいずれか一項に記載のタイヤ骨格体を有するタイヤ。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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CN201580053143.1A CN107075252A (zh) | 2014-10-01 | 2015-10-01 | 轮胎骨架体和轮胎 |
JP2016514791A JP5989280B1 (ja) | 2014-10-01 | 2015-10-01 | タイヤ骨格体およびタイヤ |
US15/515,152 US20170233550A1 (en) | 2014-10-01 | 2015-10-01 | Tire frame and tire |
EP15847321.5A EP3202853B1 (en) | 2014-10-01 | 2015-10-01 | Tire frame and tire |
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JP2014203499 | 2014-10-01 | ||
JP2014-203499 | 2014-10-01 |
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WO2016052706A1 true WO2016052706A1 (ja) | 2016-04-07 |
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PCT/JP2015/077966 WO2016052706A1 (ja) | 2014-10-01 | 2015-10-01 | タイヤ骨格体およびタイヤ |
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US (1) | US20170233550A1 (ja) |
EP (1) | EP3202853B1 (ja) |
JP (1) | JP5989280B1 (ja) |
CN (1) | CN107075252A (ja) |
WO (1) | WO2016052706A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019082767A1 (ja) * | 2017-10-25 | 2019-05-02 | 株式会社ブリヂストン | タイヤ用金属樹脂複合部材及びタイヤ |
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JP2000095861A (ja) * | 1998-09-21 | 2000-04-04 | Unitika Ltd | ナイロン6樹脂組成物 |
JP2007217445A (ja) * | 2006-02-14 | 2007-08-30 | Toray Ind Inc | 制電性ポリ乳酸樹脂組成物およびそれからなる成形品 |
US20090186971A1 (en) * | 2008-01-21 | 2009-07-23 | Grant William E | Polyamide resin compositon and method of preparing |
JP2014009353A (ja) * | 2012-07-03 | 2014-01-20 | Asahi Kasei Chemicals Corp | 共重合ポリアミド |
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JP5328358B2 (ja) * | 2005-10-27 | 2013-10-30 | エクソンモービル ケミカル パテンツ,インコーポレイティド | 低透過性熱可塑性エラストマー組成物 |
US8283407B2 (en) * | 2005-12-16 | 2012-10-09 | Exxonmobil Chemical Patents Inc. | Processing aids for elastomeric compositions |
CA2701805C (en) * | 2007-10-11 | 2014-03-25 | Exxonmobil Chemical Patents Inc. | Efficient mixing process for producing thermoplastic elastomer composition |
WO2009093695A1 (ja) * | 2008-01-23 | 2009-07-30 | Ube Industries, Ltd. | ゴム組成物、ベーストレッド用ゴム組成物、チェーファー用ゴム組成物、及びサイドウォール用ゴム組成物、並びにそれらを用いたタイヤ |
RU2495064C2 (ru) * | 2008-12-17 | 2013-10-10 | Эксонмобил Кемикал Пэйтентс, Инк. | Стабилизированные композиции на основе термоэластопласта динамической вулканизации для использования в барьерных изделиях для текучих сред |
CN103189215B (zh) * | 2010-08-25 | 2018-12-18 | 株式会社普利司通 | 轮胎、及轮胎的制造方法 |
-
2015
- 2015-10-01 CN CN201580053143.1A patent/CN107075252A/zh active Pending
- 2015-10-01 WO PCT/JP2015/077966 patent/WO2016052706A1/ja active Application Filing
- 2015-10-01 JP JP2016514791A patent/JP5989280B1/ja not_active Expired - Fee Related
- 2015-10-01 EP EP15847321.5A patent/EP3202853B1/en not_active Not-in-force
- 2015-10-01 US US15/515,152 patent/US20170233550A1/en not_active Abandoned
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US2922727A (en) * | 1955-02-14 | 1960-01-26 | American Enka Corp | Method of treating polyamide tire cord with caprolactam oligomers |
JP2000095861A (ja) * | 1998-09-21 | 2000-04-04 | Unitika Ltd | ナイロン6樹脂組成物 |
JP2007217445A (ja) * | 2006-02-14 | 2007-08-30 | Toray Ind Inc | 制電性ポリ乳酸樹脂組成物およびそれからなる成形品 |
US20090186971A1 (en) * | 2008-01-21 | 2009-07-23 | Grant William E | Polyamide resin compositon and method of preparing |
JP2014009353A (ja) * | 2012-07-03 | 2014-01-20 | Asahi Kasei Chemicals Corp | 共重合ポリアミド |
Cited By (3)
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WO2019082767A1 (ja) * | 2017-10-25 | 2019-05-02 | 株式会社ブリヂストン | タイヤ用金属樹脂複合部材及びタイヤ |
JPWO2019082767A1 (ja) * | 2017-10-25 | 2020-11-19 | 株式会社ブリヂストン | タイヤ用金属樹脂複合部材及びタイヤ |
JP7162004B2 (ja) | 2017-10-25 | 2022-10-27 | 株式会社ブリヂストン | タイヤ用金属樹脂複合部材及びタイヤ |
Also Published As
Publication number | Publication date |
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CN107075252A (zh) | 2017-08-18 |
US20170233550A1 (en) | 2017-08-17 |
JPWO2016052706A1 (ja) | 2017-04-27 |
EP3202853B1 (en) | 2019-06-12 |
EP3202853A4 (en) | 2017-08-09 |
EP3202853A1 (en) | 2017-08-09 |
JP5989280B1 (ja) | 2016-09-07 |
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