[go: up one dir, main page]

WO2019208798A1 - Composite résine-caoutchouc, pneu, et procédé de production de composite résine-caoutchouc - Google Patents

Composite résine-caoutchouc, pneu, et procédé de production de composite résine-caoutchouc Download PDF

Info

Publication number
WO2019208798A1
WO2019208798A1 PCT/JP2019/018013 JP2019018013W WO2019208798A1 WO 2019208798 A1 WO2019208798 A1 WO 2019208798A1 JP 2019018013 W JP2019018013 W JP 2019018013W WO 2019208798 A1 WO2019208798 A1 WO 2019208798A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
resin
rubber
tire
based thermoplastic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/018013
Other languages
English (en)
Japanese (ja)
Inventor
啓之 筆本
福島　敦
正洋 本間
雄司 大久保
和也 山村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bridgestone Corp
University of Osaka NUC
Original Assignee
Bridgestone Corp
Osaka University NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bridgestone Corp, Osaka University NUC filed Critical Bridgestone Corp
Priority to JP2020515616A priority Critical patent/JP7312411B2/ja
Publication of WO2019208798A1 publication Critical patent/WO2019208798A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • 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
    • B60C15/00—Tyre beads, e.g. ply turn-up or overlap
    • B60C15/04—Bead cores
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present disclosure relates to a resin rubber composite, a tire, and a method for manufacturing the resin rubber composite.
  • Patent Document 1 discloses a tire that is formed of at least a thermoplastic resin material and has an annular tire frame, and is wound around the outer periphery of the tire frame to form a reinforcing cord layer.
  • a tire including a reinforcing cord member that includes the thermoplastic resin material including at least a polyamide-based thermoplastic elastomer.
  • an adhesive for example, an organic solvent-based adhesive
  • Patent Document 2 the surface temperature of a molded body containing an organic polymer compound is set to a melting point of the organic polymer compound of ⁇ 120 ° C. or higher, and atmospheric pressure plasma treatment is performed on the surface of the molded body to perform peroxidation.
  • a method for producing a surface-modified molded body in which a product radical is introduced is disclosed.
  • Patent Document 1 JP 2012-46030
  • Patent Document 2 JP 2016-56363
  • Patent Document 2 a surface-modified molded body with improved adhesion to other members such as a rubber member by performing atmospheric pressure plasma treatment on the surface of the molded body that is a resin material. Even so, there is still room for improvement in adhesion, and further excellent adhesion is required.
  • the present disclosure provides a resin rubber composite excellent in adhesiveness between a resin member and a rubber member in direct contact with the resin member, a tire having the resin rubber composite, and manufacture of the resin rubber composite. It is an object to provide a method.
  • the gist of the present disclosure is as follows. ⁇ 1> A reactive inorganic compound that has been subjected to a first surface treatment by plasma treatment and further contains an organic reactive group and at least one group selected from a hydroxyl group and an alkoxy group on the surface that has been subjected to the plasma treatment. A resin member having a treated surface subjected to a second surface treatment; A rubber member that includes a rubber that is in contact with the treated surface of the resin member and contains a functional group that exhibits reactivity with the organic reactive group; A resin rubber composite having:
  • a resin rubber composite excellent in adhesiveness between a resin member and a rubber member in direct contact with the resin member, a tire having the resin rubber composite, and a method for manufacturing the resin rubber composite are provided. can do.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the resin rubber composite according to the first embodiment includes a resin member and a rubber member in contact with the resin member.
  • the resin member is subjected to a first surface treatment by plasma treatment, and an organic reactive group, a hydroxyl group (—OH), and an alkoxy group (—OR: R represents an alkyl group) on the surface subjected to the plasma treatment.
  • the rubber member includes a rubber containing a functional group that is in contact with the treated surface of the resin member and exhibits reactivity with the organic reactive group.
  • the present inventors performed a first surface treatment by a plasma treatment on the resin member, and further provided an organic reactive group, a hydroxyl group (—OH), and an alkoxy group on the surface subjected to the plasma treatment.
  • R represents an alkyl group
  • a second surface treatment with a reactive inorganic compound containing at least one group selected from the group, and the reactivity of the rubber member with the organic reactive group It has been found that the adhesiveness between the resin member and the rubber member is improved by including a rubber containing the functional group shown and placing the rubber member in contact with the treated surface of the resin member. The reason is guessed as follows.
  • the surface of the resin member is activated by the first surface treatment by plasma treatment, and an active group (for example, peroxy radical, hydroperoxide group, carbonyl group, aldehyde group, carboxy group, hydroxyl group, etc.) is introduced into the surface. .
  • an active group for example, peroxy radical, hydroperoxide group, carbonyl group, aldehyde group, carboxy group, hydroxyl group, etc.
  • the active group introduced into the surface of the resin member reacts with the hydroxyl group or alkoxy group in the reactive inorganic compound by the second surface treatment with the reactive inorganic compound. That is, the active group and the reactive inorganic compound react with each other on the surface of the resin member to introduce the organic reactive group.
  • a functional group showing reactivity with the organic reactive group is contained in the rubber member in contact with the treated surface subjected to the first surface treatment and the second surface treatment, so that the organic reactive group And a functional group in the rubber in the rubber member are bonded. That is, in the resin rubber composite according to the first embodiment, the treated surface of the resin member and the surface of the rubber member are bonded by the organic reactive group, and the formation of this bond between the resin member and the rubber member. It is presumed that the adhesion is improved.
  • the resin rubber composite according to the second embodiment includes a resin member and a rubber member in contact with the resin member.
  • the rubber member includes a rubber containing a functional group that exhibits reactivity with the organic reactive group of the reactive inorganic compound.
  • At the interface between the resin member and the rubber member at least one selected from a peroxy radical, a hydroperoxide group, a carbonyl group, an aldehyde group, a carboxy group, and a hydroxyl group, an organic reactive group, and a hydroxyl group (—OH) and
  • the surface of the resin member and the surface of the rubber member are bonded to each other by cross-linking formed by a reaction with a reactive inorganic compound containing at least one selected from an alkoxy group (—OR: R represents an alkyl group).
  • the inventors have found that the adhesiveness between the resin member and the rubber member is improved by the configuration of the second embodiment. The reason is guessed as follows.
  • At least one selected from a peroxy radical, a hydroperoxide group, a carbonyl group, an aldehyde group, a carboxy group, and a hydroxyl group and a hydroxyl group or an alkoxy group in the reactive inorganic compound are reacted with each other.
  • a peroxy radical a hydroperoxide group
  • a carbonyl group an aldehyde group
  • a carboxy group a hydroxyl group and a hydroxyl group or an alkoxy group in the reactive inorganic compound
  • the organic reactive group in the cross-linking group is bonded to a functional group contained in the rubber member, whereby the surface of the resin member and the surface of the rubber member are bonded by the cross-linking group. The formation of this bond is presumed to improve the adhesion between the resin member and the rubber member.
  • the first member having a resin member having a treated surface subjected to the first surface treatment and the second surface treatment, and a rubber member containing a rubber containing a functional group showing reactivity with the organic reactive group.
  • the resin rubber composite according to the embodiment preferably further includes the configuration of the resin rubber composite according to the second embodiment.
  • the resin rubber composite according to the present embodiment includes a resin member and a rubber member in contact with the resin member.
  • the aspect which has the 2nd rubber member which touches this rubber member may be sufficient.
  • the method for producing the resin rubber composite according to the first embodiment and the second embodiment is not particularly limited.
  • the first surface treatment by the plasma treatment and the surface subjected to the plasma treatment are further selected from an organic reactive group, a hydroxyl group (—OH), and an alkoxy group (—OR: R represents an alkyl group).
  • the term “process” includes not only an independent process but also a process that can be clearly distinguished from other processes as long as the purpose is achieved. Included in this term.
  • the resin rubber composite according to the present embodiment is applied to various fields in which a resin member and a rubber member are used. , Seismic isolation rubber, sealing materials, caulking materials, bicycles and other fields.
  • examples of the combination of the resin member and the rubber member include the following combinations.
  • the layer is a resin rubber composite).
  • a combination of a bead wire as a resin member, a wire coating layer covering the bead wire as a rubber member, and at least one member selected from a rubber sheet bonded to the surface of the bead wire (that is, a bead core) Is a resin rubber composite).
  • tire frame as a rubber member is a member constituting a tire frame such as a carcass corresponding to a rubber member (for example, a carcass made only of a carcass ply in which a plurality of wires are covered with rubber). It may be replaced.
  • the resin rubber composite has a resin member, a rubber member in contact with the resin member, and a second rubber member in contact with the rubber member
  • the following combinations may be mentioned.
  • a combination of a belt cord as a resin member, a rubber sheet as a rubber member, and a cord covering layer as a second rubber member that is, the belt layer is a resin rubber composite.
  • a combination of a bead wire as a resin member, a rubber sheet as a rubber member, and a wire coating layer as a second rubber member is a resin rubber composite).
  • the “tire frame as the second rubber member” is a tire frame such as a carcass corresponding to the second rubber member (for example, a carcass made only of a carcass ply in which a plurality of wires are covered with rubber). You may replace with the member which comprises.
  • the resin member according to the first embodiment is subjected to the first surface treatment by the plasma treatment, and further, an organic reactive group, a hydroxyl group (—OH), and an alkoxy group (—OR: R has a treated surface that has been subjected to a second surface treatment with a reactive inorganic compound containing at least one group selected from:
  • At the interface with the rubber member at least one selected from the group represented by the following group [P] and the cross-linking group formed by the reaction of the reactive inorganic compound shown below are used.
  • the surface and the surface of the rubber member are combined.
  • the surface which gave the 1st surface treatment by plasma treatment with respect to the resin member introduce
  • a group capable of binding to at least one of a hydroxyl group (—OH) and an alkoxy group (—OR: R represents an alkyl group) is introduced to the surface of the resin member by the first surface treatment by plasma treatment.
  • groups introduced by the first surface treatment by plasma treatment include peroxy radical (—O—O.), Hydroperoxide group (—O—OH), carbonyl group (—C ( ⁇ O) —), aldehyde Examples thereof include an oxidizing group such as a group (—C ( ⁇ O) —H), a carboxy group (—C ( ⁇ O) —OH), and a hydroxyl group (—OH).
  • peroxy radical (—O—O.), Hydroperoxide group (—O—OH), carbonyl group (—C ( ⁇ O) —), aldehyde group (—C ( More preferably, at least one group selected from O) —H), a carboxy group (—C ( ⁇ O) —OH), and a hydroxyl group (—OH) is introduced.
  • the conditions for performing the plasma treatment as the first surface treatment on the surface of the resin member are not particularly limited as long as the surface after the treatment is activated, and can be performed by a known method. In other words, conditions capable of generating plasma can be appropriately employed.
  • the temperature of the environment in plasma processing is preferably 0 ° C. or higher and 240 ° C. or lower from the viewpoint of improving adhesiveness and simplifying the plasma processing. More preferably, the temperature is from 150 ° C. to 220 ° C., more preferably from 15 ° C. to 200 ° C. Further, the atmospheric pressure in the plasma treatment is preferably 5 hPa or more and 2000 hPa or less, more preferably 10 hPa or more and 1500 hPa or less, and further preferably 10 hPa or more and 1300 hPa or less, from the viewpoint of improving adhesiveness and simplifying the plasma treatment.
  • a high-frequency power source having an applied voltage frequency of 50 Hz to 2.45 GHz.
  • the output power per unit area (that is, the irradiation density) is, for example, 1 W / cm 2 or more, preferably 3 W / cm 2 or more, more preferably 5 W / cm 2 or more, while the upper limit is not particularly limited. However, it is good to set it as 50 W / cm ⁇ 2 > or less, for example.
  • a pulse modulation frequency of 1 kHz to 50 kHz (preferably 5 kHz to 30 kHz), a pulse duty of 5% to 99% (preferably 15% to 80%, more preferably 25). % To 70%).
  • the counter electrode is preferably made of a cylindrical or flat metal whose one side is coated with a dielectric.
  • the distance between the counter electrode and the resin member is not particularly limited, but is preferably 10 mm or less, more preferably 3 mm or less, still more preferably 1.2 mm or less, and particularly preferably 1 mm or less. Although the minimum of distance is not specifically limited, For example, it is 0.5 mm or more.
  • the time during which the plasma treatment is performed (that is, the irradiation time) is preferably 2 seconds or longer and 30 minutes or shorter, more preferably 30 seconds or longer and 20 minutes or shorter, from the viewpoint of improving adhesiveness and simplifying the plasma processing, and more preferably 1 minute More preferably, it is 10 minutes or less.
  • a rare gas such as helium, argon, or neon
  • a reactive gas such as oxygen, nitrogen, hydrogen, or ammonia
  • these gases may use only 1 type, or 2 or more types of noble gases, or use the mixed gas of 1 type, or 2 types or more of noble gases, and 1 type, or 2 or more types of reactive gas of appropriate amount. Also good.
  • the generation of the plasma may be performed under the above-described conditions in which the gas atmosphere is controlled using a chamber, or may be performed under a completely open atmosphere condition in which, for example, a rare gas is flowed to the electrode portion.
  • the surface of the resin member that has been subjected to the first surface treatment is further selected from at least an organic reactive group, a hydroxyl group (—OH), and an alkoxy group (—OR: R represents an alkyl group).
  • a second surface treatment with a reactive inorganic compound containing a kind of group is performed. By the second surface treatment, a bond is formed between at least one group selected from the hydroxyl group and alkoxy group of the reactive inorganic compound and the group introduced to the surface of the resin member by the plasma treatment.
  • a reactive inorganic compound has at least 1 type of group selected from a hydroxyl group and an alkoxy group.
  • the group include a hydroxyl group (—OH), a methoxy group (—OCH 3 ), an ethoxy group (—OC 2 H 5 ), an isopropoxy group (—OC 3 H 7 ), a t-butoxy group (—OC 4 H). 9 ) and the like.
  • a hydroxyl group (—OH), a methoxy group (—OCH 3 ), or an ethoxy group (—OC 2 H 5 ) is preferable.
  • the reactive inorganic compound only needs to have one of the above groups in one molecule, and may have two or more.
  • a reactive inorganic compound contains the organic reactive group which shows the reactivity with the functional group which the rubber
  • organic reactive groups include polysulfide groups, vinyl groups, thiol groups, amino groups, epoxy groups, isocyanate groups, isocyanurate groups, styryl groups (that is, vinylphenyl groups), acrylic groups, methacrylic groups, ureido groups (—NHCONH). 2 ), a hydroxyl group, an aldehyde group, and the like.
  • polysulfide groups vinyl groups, thiol groups, amino groups, epoxy groups, and isocyanate groups are preferred from the viewpoint of satisfactorily forming a bond between the reactive inorganic compound and the rubber in the rubber member. More preferred are groups, vinyl groups, and thiol groups.
  • the reactive inorganic compound preferably has at least one organic reactive group in one molecule.
  • the reactive inorganic compound has an inorganic element in the molecule.
  • an inorganic element Si atom etc. are mentioned, for example, Si atom is especially preferable.
  • the reactive inorganic compound preferably has at least one inorganic element in one molecule.
  • the reactive inorganic compound for example, at least one group selected from a hydroxyl group and an alkoxy group is directly bonded to an inorganic element (preferably an Si atom), and an organic reaction is further performed on the inorganic element. And a compound having a group having a functional group bonded thereto.
  • Examples of the reactive inorganic compound include the following compounds.
  • (Compound having Si atom) Polysulfide silane coupling agents having two or more sulfur (eg, bis- (3- (triethoxysilyl) propyl) -disulfide, bis- (3- (triethoxysilyl) propyl) -tetrasulfide, and bis- ( Bis- (trialkoxysilylalkyl) -polysulfide) such as triethoxysilylpropyl) -polysulfide), N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3- Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, 11-aminounde
  • the reactive inorganic compound the following compounds are preferable from the viewpoint of improving adhesiveness.
  • Bis- (3- (triethoxysilyl) propyl) -disulfide, bis- (3- (triethoxysilyl) propyl) -tetrasulfide, bis- (triethoxysilylpropyl) -polysulfide, 3-mercaptopropyltriethoxysilane preferable.
  • one type of reactive inorganic compound may be used alone, or two or more types may be used in combination.
  • Second surface treatment method The method of performing the second surface treatment using a reactive inorganic compound on the surface of the resin member that has been subjected to the first surface treatment (that is, plasma treatment) is a hydroxyl group possessed by the reactive inorganic compound. And a method in which a bond is formed between at least one group selected from alkoxy groups and a group introduced on the surface of the resin member by plasma treatment, is not particularly limited. For example, there is a method in which a reactive inorganic compound is added to a liquid to prepare a surface treatment liquid, and a resin member subjected to plasma treatment is immersed in the surface treatment liquid.
  • liquid used for the surface treatment liquid examples include organic solvents and aqueous solutions. Specifically, water, methanol, ethanol, acetone, methyl ethyl ketone, acetonitrile, toluene, xylene and the like are preferable. Moreover, you may mix and use water and the said organic solvent by arbitrary ratios.
  • the liquid used for the surface treatment liquid is adjusted to be acidic (for example, pH 2 or more and 10 or less, preferably pH 3 or more and 9 or less) before adding the reactive inorganic compound. It is preferable for suppressing the speed and efficiently promoting the reaction between the alkoxide of the reactive inorganic compound and the functional group present on the resin surface.
  • the concentration of the reactive inorganic compound contained in the surface treatment liquid is 0.5 mass from the viewpoint of favorably forming a bond between the reactive inorganic compound and a group introduced to the surface of the resin member by plasma treatment. % To 50% by mass is preferable, and 1% to 30% by mass is more preferable.
  • the time for immersing the resin member subjected to the first surface treatment in the surface treatment liquid is not particularly limited, but it is between the reactive inorganic compound and the group introduced to the surface of the resin member by the plasma treatment. 10 seconds to 3600 seconds, and more preferably 60 seconds to 600 seconds, from the viewpoint of forming a good bond.
  • treatment such as washing and drying may be performed as necessary.
  • the treated surface of the resin member subjected to the first surface treatment and the second surface treatment in the resin rubber composite of the first embodiment has a contact angle of water from the viewpoint of improving adhesiveness. It is preferably 20 ° or more and 98 ° or less, more preferably 50 ° or more and 96 ° or less, and further preferably 60 ° or more and 95 ° or less.
  • the surface of the resin member side at the interface between the resin member and the rubber member preferably has a water contact angle in the above range from the viewpoint of improving adhesiveness. .
  • the contact angle of water on the treated surface of the resin member or the surface on the resin member side at the interface between the resin member and the rubber member is an automatic minimum contact angle manufactured by Kyowa Interface Science Co., Ltd. by dropping pure water at 25 ° C. Measurement is performed by observing the shape of the droplet using a meter (MCA-3).
  • the resin member preferably contains a resin as a main component.
  • the resin content is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 75% by mass or more with respect to the total amount of the resin members.
  • thermoplastic resin means a polymer compound that softens and flows as the temperature rises and becomes relatively hard and strong when cooled, but does not have rubbery elasticity.
  • Thermoplastic elastomer means a copolymer having a hard segment and a soft segment.
  • the hard segment refers to a component that is relatively harder than the soft segment, and is preferably a molecular constraining component that serves as a crosslinking point of the crosslinked rubber that prevents plastic deformation.
  • the soft segment refers to a component that is relatively softer than the hard segment, and is preferably a flexible component that exhibits rubber elasticity.
  • the thermoplastic elastomer for example, a crystalline polymer having a high melting point hard segment or a polymer constituting a hard segment having a high cohesive force, and a polymer constituting an amorphous soft segment having a low glass transition temperature, And a copolymer having.
  • the thermoplastic elastomer includes, for example, a polymer compound that softens and flows as the temperature rises, becomes relatively hard and strong when cooled, and has rubbery elasticity.
  • the hard segment is, for example, a structure having a rigid group such as an aromatic group or an alicyclic group in the main skeleton, or a structure enabling intermolecular packing by intermolecular hydrogen bonding or ⁇ - ⁇ interaction, etc. Can be mentioned.
  • the soft segment includes, for example, a segment having a long chain group (for example, a long chain alkylene group) in the main chain, a high degree of molecular rotation freedom, and a stretchable structure.
  • thermoplastic resin contained in the resin material examples include polyester-based thermoplastic resins, polyamide-based thermoplastic resins, polystyrene-based thermoplastic resins, polyurethane-based thermoplastic resins, polyolefin-based thermoplastic resins, and vinyl chloride-based thermoplastic resins. Can be illustrated.
  • thermoplastic elastomer contained in the resin material examples include polyester-based thermoplastic elastomer (TPEE), polyamide-based thermoplastic elastomer (TPA), polystyrene-based thermoplastic elastomer (TPS), and polyurethane-based thermoplastic as defined in JIS K6418.
  • TPEE polyester-based thermoplastic elastomer
  • TPA polyamide-based thermoplastic elastomer
  • TPS polystyrene-based thermoplastic elastomer
  • polyurethane-based thermoplastic as defined in JIS K6418.
  • examples include elastomers (TPU), polyolefin-based thermoplastic elastomers (TPO), crosslinked thermoplastic rubber (TPV), and other thermoplastic elastomers (TPZ).
  • thermosetting resin contained in the resin material examples include phenol-based thermosetting resins, urea-based thermosetting resins, melamine-based thermosetting resins, and epoxy-based thermosetting resins.
  • the resin contained in the resin material includes polyester-based thermoplastic elastomer, polyester-based thermoplastic resin, polyamide-based thermoplastic elastomer, polyamide-based thermoplastic resin, polystyrene-based thermoplastic elastomer, polystyrene-based thermoplastic resin, polyurethane.
  • a thermoplastic thermoplastic elastomer, a polyurethane thermoplastic resin, a polyolefin thermoplastic elastomer, or a polyolefin thermoplastic resin is preferable, and a polyester thermoplastic elastomer or a polyester thermoplastic resin is more preferable.
  • thermoplastic elastomer Poly(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol dimethacrylate), poly(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol)-(ethylene glycol
  • aromatic polyester can be used, for example.
  • the aromatic polyester can be formed, for example, from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol.
  • the aromatic polyester is preferably polybutylene terephthalate derived from at least one of terephthalic acid and dimethyl terephthalate and 1,4-butanediol.
  • the aromatic polyester includes, for example, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5
  • a dicarboxylic acid component such as sulfoisophthalic acid or an ester-forming derivative thereof and a diol having a molecular weight of 300 or less (for example, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, etc.
  • Aliphatic diols such as: 1,4-cyclohexanedimethanol, tricyclodecane dimethylol and other alicyclic diols; xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2- Bi [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4′- And diol components such as aromatic diols such as dihydroxy-p-terphenyl and 4,4′-dihydroxy-p-quarterphenyl; and the like.
  • polyester forming the hard segment examples include polyethylene terephthalate, polybutylene terephthalate, polymethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like, and polybutylene terephthalate is preferable.
  • 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) And ethylene oxide addition polymer of glycol, and a copolymer of ethylene oxide and tetrahydrofuran.
  • the aliphatic polyester include poly ( ⁇ -caprolactone), polyenantlactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate.
  • poly (tetramethylene oxide) glycol poly (propylene oxide) glycol are polymers that form soft segments from the viewpoint of the elastic properties of the resulting polyester block copolymer.
  • Preferred are ethylene oxide adducts, poly ( ⁇ -caprolactone), polybutylene adipate, polyethylene adipate and the like.
  • the number average molecular weight of the polymer forming the soft segment is preferably 300 to 6000 from the viewpoint of toughness and low temperature flexibility. Furthermore, the mass ratio (x: y) between the hard segment (x) and the soft segment (y) is preferably 99: 1 to 20:80, more preferably 98: 2 to 30:70, from the viewpoint of moldability. .
  • the combination of the hard segment and the soft segment described above examples include, for example, combinations of the hard segment and the soft segment mentioned above.
  • the combination of the hard segment and the soft segment described above is preferably a combination in which the hard segment is polybutylene terephthalate, the soft segment is an aliphatic polyether, and the hard segment is polybutylene terephthalate. More preferred is a combination wherein is poly (ethylene oxide) glycol.
  • polyester-based thermoplastic elastomers examples include “Hytrel” series (for example, 3046, 5557, 6347, 4047N, 4767N, etc.) manufactured by Toray DuPont Co., Ltd., and “Perprene” series manufactured by Toyobo Co., Ltd. (For example, P30B, P40B, P40H, P55B, P70B, P150B, P280B, P450B, P150M, S1001, S2001, S5001, S6001, S9001, etc.) can be used.
  • Hytrel for example, 3046, 5557, 6347, 4047N, 4767N, etc.
  • Perprene manufactured by Toyobo Co., Ltd.
  • the polyester-based thermoplastic elastomer can be synthesized by copolymerizing a polymer that forms a hard segment and a polymer that forms a soft segment by a known method.
  • the polyamide-based thermoplastic elastomer is a thermoplastic polymer composed only of a copolymer having a crystalline polymer having a high melting point and a non-crystalline polymer having a low glass transition temperature. It means a resin material having an amide bond (—CONH—) in the main chain of the polymer forming the hard segment.
  • the polyamide-based thermoplastic elastomer for example, at least a polyamide is a crystalline hard crystalline segment with a high melting point, and other polymers (for example, polyester, polyether, etc.) are amorphous and have a soft glass transition temperature low soft segment. The material which forms is mentioned.
  • the polyamide-based thermoplastic elastomer may be formed using a chain extender such as dicarboxylic acid in addition to the hard segment and the soft segment.
  • a chain extender such as dicarboxylic acid
  • Specific examples of polyamide-based thermoplastic elastomers include amide-based thermoplastic elastomers (TPA) defined in JIS K6418: 2007, polyamide-based elastomers described in JP-A No. 2004-346273, and the like. it can.
  • examples of the polyamide forming the hard segment include polyamides produced by monomers represented by the following general formula (1) or general formula (2).
  • R 1 represents a molecular chain of a hydrocarbon having 2 to 20 carbon atoms (for example, an alkylene group having 2 to 20 carbon atoms). ]
  • R 2 represents a hydrocarbon molecular chain 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 or lactam.
  • the polyamide forming the hard segment include polycondensates of these ⁇ -aminocarboxylic acids or lactams, and co-condensation polymers of diamines and dicarboxylic acids.
  • Examples of the ⁇ -aminocarboxylic acid include those having 5 to 20 carbon atoms such as 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. Examples thereof include aliphatic ⁇ -aminocarboxylic acids.
  • Examples of the lactam include aliphatic lactams having 5 to 20 carbon atoms such as lauryl lactam, ⁇ -caprolactam, udecan lactam, ⁇ -enantolactam, and 2-pyrrolidone.
  • diamine examples include ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2, 2, 4
  • diamine compounds such as aliphatic diamines having 2 to 20 carbon atoms such as trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 3-methylpentamethylenediamine, and metaxylenediamine.
  • the dicarboxylic acid can be represented by HOOC- (R 3 ) m —COOH (R 3 : a hydrocarbon molecular chain having 3 to 20 carbon atoms, m: 0 or 1).
  • R 3 a hydrocarbon molecular chain having 3 to 20 carbon atoms, m: 0 or 1.
  • oxalic acid, succinic acid And aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid.
  • a polyamide obtained by ring-opening polycondensation of lauryl lactam, ⁇ -caprolactam, or udecan lactam can be preferably used.
  • polyester, polyether, etc. are mentioned, for example.
  • Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and ABA type triblock polyether. These can 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 also be used.
  • the “ABA type triblock polyether” means a polyether represented by the following general formula (3).
  • each of x and z is preferably an integer of 1 to 18, more preferably an integer of 1 to 16, still more preferably an integer of 1 to 14, and particularly preferably an integer of 1 to 12.
  • y is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, still more preferably an integer of 7 to 35, and particularly preferably an integer of 8 to 30.
  • combinations of the hard segment and the soft segment include a combination of a ring-opening polycondensate of lauryl lactam and polyethylene glycol, a combination of a ring-opening polycondensate of lauryl lactam and polypropylene glycol, and a ring opening of lauryl lactam.
  • a combination of a polycondensate and a polytetramethylene ether glycol, or a ring-opening polycondensate of lauryl lactam and an ABA type triblock polyether is preferred, and a ring opening polycondensate of lauryl lactam and an ABA type triblock polyether The combination with is more preferable.
  • the number average molecular weight of the polymer forming the hard segment is preferably 300 to 15000 from the viewpoint of melt moldability.
  • the number average molecular weight of the polymer forming the soft segment is preferably 200 to 6000 from the viewpoint of toughness and low temperature flexibility.
  • the mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 50:50 to 90:10, and more preferably 50:50 to 80:20, from the viewpoint of moldability.
  • the polyamide-based thermoplastic elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method.
  • polyamide-based thermoplastic elastomers examples include UBE Kosan's “UBESTA XPA” series (for example, XPA9068X1, XPA9063X1, XPA9055X1, XPA9048X2, XPA9048X1, XPA9040X1, XPA9040X2XPA9044), Daicel Eponic Co., Ltd. “Vestamide” series (for example, E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, EX9200, E50-R2, etc.) can be used.
  • polystyrene-based thermoplastic elastomer for example, at least polystyrene forms a hard segment, and other polymers (for example, polybutadiene, polyisoprene, polyethylene, hydrogenated polybutadiene, hydrogenated polyisoprene, etc.) are not. Examples thereof include materials that form a soft segment having a crystallinity and a low glass transition temperature.
  • the polystyrene forming the hard segment for example, those obtained by a known radical polymerization method, ionic polymerization method and the like are preferably used, and specifically, polystyrene having anion living polymerization can be mentioned.
  • the polymer that forms the soft segment include polybutadiene, polyisoprene, poly (2,3-dimethyl-butadiene), and the like.
  • the combination of the hard segment and the soft segment mentioned above can be mentioned.
  • the combination of the hard segment and the soft segment is preferably a combination of polystyrene and polybutadiene or a combination of polystyrene and polyisoprene.
  • the soft segment is preferably hydrogenated.
  • the number average molecular weight of the polymer forming the hard segment is preferably from 5,000 to 500,000, more preferably from 10,000 to 200,000. Further, the number average molecular weight of the polymer forming the soft segment is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 800,000, and even more preferably from 30,000 to 500,000. Furthermore, the volume ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 5:95 to 80:20, more preferably 10:90 to 70:30, from the viewpoint of moldability.
  • the polystyrene-based thermoplastic elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method.
  • the polystyrene-based thermoplastic elastomer include styrene-butadiene copolymers [eg, SBS (polystyrene-poly (butylene) block-polystyrene), SEBS (polystyrene-poly (ethylene / butylene) block-polystyrene)], styrene- Isoprene copolymer (polystyrene-polyisoprene block-polystyrene), styrene-propylene copolymer [eg SEP (polystyrene- (ethylene / propylene) block), SEPS (polystyrene-poly (ethylene / propylene)
  • thermoplastic elastomer As a commercially available product of polystyrene-based thermoplastic elastomer, for example, “Tough Tech” series (for example, H1031, H1041, H1043, H1051, H1052, H1053, H1062, H1082, H1141, H1221, H1272, etc.) manufactured by Asahi Kasei Corporation, “SEBS” series (8007, 8076, etc.) and “SEPS” series (2002, 2063, etc.) manufactured by Kuraray Co., Ltd. can be used.
  • “Tough Tech” series for example, H1031, H1041, H1043, H1051, H1052, H1053, H1062, H1082, H1141, H1221, H1272, etc.
  • SEBS 8007, 8076, etc.
  • SEPS 2002, 2063, etc.
  • thermoplastic elastomer As polyurethane-based thermoplastic elastomers, for example, at least polyurethane forms a hard segment in which pseudo-crosslinking is formed by physical aggregation, and other polymers form a soft segment with a low glass transition temperature that is amorphous. Material.
  • Specific examples of the polyurethane-based thermoplastic elastomer include a polyurethane-based thermoplastic elastomer (TPU) defined in JIS K6418: 2007.
  • TPU polyurethane-based thermoplastic elastomer
  • the polyurethane-based thermoplastic elastomer can be represented as a copolymer including a soft segment including a unit structure represented by the following formula A and a hard segment including 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 or long-chain aliphatic polyester represented by P for example, those having a molecular weight of 500 to 5000 can be used.
  • P is derived from a diol compound containing a long-chain aliphatic polyether represented by P or a long-chain aliphatic polyester.
  • diol compounds include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, poly (butylene adipate) diol, poly- ⁇ -caprolactone diol, poly (hexamethylene carbonate) having a molecular weight within the above range.
  • Diol, ABA type triblock polyether, etc. are mentioned. These can be used alone or in combination of two or more.
  • R is a partial structure introduced using a diisocyanate compound containing an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon represented by R.
  • the aliphatic diisocyanate compound containing an aliphatic hydrocarbon represented by R include 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate, 1,6-hexamethylene diisocyanate, and the like.
  • Examples of the diisocyanate compound containing an alicyclic hydrocarbon represented by R include 1,4-cyclohexane diisocyanate and 4,4-cyclohexane diisocyanate.
  • examples of the aromatic diisocyanate compound containing an aromatic hydrocarbon represented by R include 4,4′-diphenylmethane diisocyanate and tolylene diisocyanate. These can be used alone or in combination of two or more.
  • 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.
  • ethylene glycol, propylene glycol, trimethylene glycol, 1, 4 -Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- A decanediol etc. are mentioned.
  • 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 thereof include 1-di (4-hydroxyphenyl) cyclohexane, 1,2-bis (4-hydroxyphenoxy) ethane, 1,4-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. These can be used alone or in combination of two or more.
  • the number average molecular weight of the polymer forming the hard segment is preferably 300 to 1500 from the viewpoint of melt moldability.
  • the number average molecular weight of the polymer forming the soft segment is preferably 500 to 20000, more preferably 500 to 5000, and particularly preferably 500 to 3000, from the viewpoints of flexibility and thermal stability of the polyurethane-based thermoplastic elastomer.
  • the mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 15:85 to 90:10, and more preferably 30:70 to 90:10, from the viewpoint of moldability.
  • the polyurethane-based thermoplastic elastomer can be synthesized by copolymerizing a polymer forming a hard segment and a polymer forming a soft segment by a known method.
  • thermoplastic polyurethane described in JP-A-5-331256 can be used.
  • thermoplastic elastomer specifically, a combination of a hard segment consisting only of an aromatic diol and an aromatic diisocyanate and a soft segment consisting only of a polycarbonate ester is preferable, and more specifically, tolylene Isocyanate (TDI) / polyester polyol copolymer, TDI / polyether polyol copolymer, TDI / caprolactone polyol copolymer, TDI / polycarbonate polyol copolymer, 4,4′-diphenylmethane diisocyanate (MDI) / Polyester polyol copolymer, MDI / polyether polyol copolymer, MDI / caprolactone polyol copolymer, MDI / polycarbonate polyol copolymer, and MDI + hydroquinone / polyhe At least one selected from Sa methylene carbonate copolymer.
  • TDI tolylene Isocyanate
  • MDI polyester polyol
  • TDI / polyester polyol copolymer TDI / polyether polyol copolymer
  • MDI / polyester polyol copolymer MDI / polyether polyol copolymer
  • MDI + hydroquinone / polyhexamethylene carbonate copolymer At least one selected from is more preferable.
  • thermoplastic elastomers examples include, for example, “Elastolan” series (for example, ET680, ET880, ET690, ET890, etc.) manufactured by BASF, and “Clamiron U” series (manufactured by Kuraray Co., Ltd.). For example, 2000 series, 3000 series, 8000 series, 9000 series, etc., “Milactolan” series (for example, XN-2001, XN-2004, P390RSUP, P480RSUI, P26MRNAT, E490, E590, P890, etc.) manufactured by Japan Miraclan ) Etc. can be used.
  • “Elastolan” series for example, ET680, ET880, ET690, ET890, etc.
  • Clamiron U” series manufactured by Kuraray Co., Ltd.
  • “Milactolan” series for example, XN-2001, XN-
  • thermoplastic elastomer examples include, for example, a hard segment in which at least polyolefin is crystalline and having a high melting point, and other polymers (for example, other polyolefins, polyvinyl compounds, etc.) are amorphous and have a low glass transition temperature. The material which forms the segment is mentioned.
  • polyolefin forming the hard segment examples include polyethylene, polypropylene, isotactic polypropylene, polybutene, and the like.
  • polyolefin-based thermoplastic elastomers include olefin- ⁇ -olefin random copolymers and olefin block copolymers.
  • propylene block copolymer ethylene-propylene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, propylene-1-butene copolymer, ethylene- 1-hexene copolymer, ethylene-4-methyl-pentene copolymer, ethylene-1-butene copolymer, 1-butene-1-hexene copolymer, 1-butene-4-methyl-pentene, ethylene- Methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl
  • polyolefin-based thermoplastic elastomers include propylene block copolymers, ethylene-propylene copolymers, propylene-1-hexene copolymers, propylene-4-methyl-1-pentene copolymers, propylene-1- Butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-pentene copolymer, ethylene-1-butene copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer , Ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, propylene-methacrylic acid copolymer , Propylene-methyl methacrylate copolymer, Lopylene
  • olefin resins such as ethylene and propylene may be used in combination.
  • 50 mass% or more and 100 mass% or less of the olefin resin content rate in polyolefin-type thermoplastic elastomer are preferable.
  • the number average molecular weight of the polyolefin-based thermoplastic elastomer is preferably 5,000 to 10,000,000.
  • the number average molecular weight of the polyolefin-based thermoplastic elastomer is 5,000 to 10,000,000, the mechanical properties of the thermoplastic resin material are sufficient, and the processability is also excellent.
  • the number average molecular weight of the polyolefin-based thermoplastic elastomer is more preferably 7,000 to 1,000,000, and particularly preferably 10,000 to 1,000,000. Thereby, the mechanical properties and processability of the thermoplastic resin material can be further improved.
  • the number average molecular weight of the polymer forming the soft segment is preferably 200 to 6000 from the viewpoint of toughness and low temperature flexibility.
  • the mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 50:50 to 95:15, and more preferably 50:50 to 90:10, from the viewpoint of moldability.
  • the polyolefin-based thermoplastic elastomer can be synthesized by copolymerization by a known method.
  • polyolefin-based thermoplastic elastomer those obtained by acid-modifying a polyolefin-based thermoplastic elastomer may be used.
  • a product obtained by acid-modifying a polyolefin-based thermoplastic elastomer refers to a product obtained by bonding an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfuric acid group, or a phosphoric acid group to a polyolefin-based thermoplastic elastomer.
  • Examples of bonding an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfuric acid group, or a phosphoric acid group to a polyolefin-based thermoplastic elastomer include, for example, an unsaturated compound having an acidic group as a polyolefin-based thermoplastic elastomer, Examples include bonding (for example, graft polymerization) an unsaturated bonding site of an unsaturated carboxylic acid (for example, generally maleic anhydride).
  • an unsaturated compound having an acidic group an unsaturated compound having a carboxylic acid group which is a weak acid group is preferable from the viewpoint of suppressing deterioration of the polyolefin-based thermoplastic elastomer.
  • the unsaturated compound having an acidic group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and the like.
  • thermoplastic elastomers Commercially available products of polyolefin-based thermoplastic elastomers include, for example, “Tuffmer” series (for example, A0550S, A1050S, A4050S, A1070S, A4070S, A35070S, A1085S, A4085S, A7090, A70090, MH7007, MH7010, manufactured by Mitsui Chemicals, Inc.
  • “Tuffmer” series for example, A0550S, A1050S, A4050S, A1070S, A4070S, A35070S, A1085S, A4085S, A7090, A70090, MH7007, MH7010, manufactured by Mitsui Chemicals, Inc.
  • E-2900H, F-3900H, E-2900, F-3900, J-5900, E-2910, F-3910, J-5910, E-2710 F-3710, J-5910, E-2740, F-3740, R110MP, R110E, can be used T310E, also M142E, etc.) and the like.
  • polyester-based thermoplastic resin examples include polyester that forms the hard segment of the above-described polyester-based thermoplastic elastomer.
  • Specific examples of the polyester-based thermoplastic resin include polylactic acid, polyhydroxy-3-butylbutyric acid, polyhydroxy-3-hexylbutyric acid, poly ( ⁇ -caprolactone), polyenantlactone, polycaprylolactone, and polybutylene.
  • Examples include aliphatic polyesters such as adipate and polyethylene adipate, and aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate.
  • polybutylene terephthalate is preferable as the polyester-based thermoplastic resin.
  • polyester thermoplastic resins examples include “Duranex” series (for example, 2000, 2002, etc.) manufactured by Polyplastics Co., Ltd., and “Novaduran” series (for example, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) 5010R5, 5010R3-2, etc.), “Toraycon” series (for example, 1401X06, 1401X31, etc.) manufactured by Toray Industries, Inc. can be used.
  • polyamide-based thermoplastic resin examples include polyamides that form the hard segments of the aforementioned polyamide-based thermoplastic elastomer.
  • polyamide-based thermoplastic resins include polyamide (amide 6) obtained by ring-opening polycondensation of ⁇ -caprolactam, polyamide (amide 11) obtained by ring-opening polycondensation of undecane lactam, and ring-opening polycondensation of lauryl lactam.
  • the amide 6 can be represented by, for example, ⁇ CO— (CH 2 ) 5 —NH ⁇ n .
  • the amide 11 can be represented by ⁇ CO— (CH 2 ) 10 —NH ⁇ n , for example.
  • the amide 12 can be represented by, for example, ⁇ CO— (CH 2 ) 11 —NH ⁇ n .
  • the amide 66 can be represented by ⁇ CO (CH 2 ) 4 CONH (CH 2 ) 6 NH ⁇ n , for example.
  • Amide MX can be represented, for example, by the following structural formula (A-1). Here, n represents the number of repeating units.
  • amide 6 As a commercially available product of amide 6, for example, “UBE nylon” series (for example, 1022B, 1011FB, etc.) manufactured by Ube Industries, Ltd. can be used. As a commercially available product of amide 11, for example, “Rilsan B” series manufactured by Arkema Co., Ltd. can be used. As a commercially available product of amide 12, for example, “UBE nylon” series (for example, 3024U, 3020U, 3014U, etc.) manufactured by Ube Industries, Ltd. can be used. As a commercially available product of amide 66, for example, “Leona” series (for example, 1300S, 1700S, etc.) manufactured by Asahi Kasei Corporation can be used. As a commercially available product of amide MX, for example, “MX nylon” series (for example, S6001, S6021, S6011, etc.) manufactured by Mitsubishi Gas Chemical Co., Ltd. can be used.
  • MX nylon for example, S6001, S
  • the polyamide-based thermoplastic resin may be a homopolymer consisting only of the above structural unit, or may be a copolymer of the above structural unit and another monomer. In the case of a copolymer, it is preferable that the content rate of the said structural unit in each polyamide-type thermoplastic resin is 40 mass% or more.
  • polyolefin-based thermoplastic resin examples include polyolefins that form the hard segment of the aforementioned polyolefin-based thermoplastic elastomer.
  • polyolefin-based thermoplastic resin examples include a polyethylene-based thermoplastic resin, a polypropylene-based thermoplastic resin, and a polybutadiene-based thermoplastic resin.
  • a polypropylene-based thermoplastic resin is preferable as the polyolefin-based thermoplastic resin.
  • polypropylene-based thermoplastic resin examples include a propylene homopolymer, a propylene- ⁇ -olefin random copolymer, a propylene- ⁇ -olefin block copolymer, and the like.
  • Examples of the ⁇ -olefin include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, Examples thereof include ⁇ -olefins having about 3 to 20 carbon atoms such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicocene.
  • the resin member may contain other components such as an additive in addition to the resin as long as the effect is not impaired.
  • other components include rubber, various fillers (for example, silica, calcium carbonate, clay, etc.), anti-aging agents, oils, plasticizers, color formers, weathering agents, and the like.
  • the rubber member is a rubber containing a functional group that is in contact with the treated surface of the resin member and exhibits reactivity with the organic reactive group contained in the reactive inorganic compound.
  • the rubber member includes a rubber containing a functional group that exhibits reactivity with the organic reactive group contained in the reactive inorganic compound, and at the interface with the resin member, The surface of the resin member and the surface of the rubber member are bonded by a cross-linking group formed by a reaction between at least one group selected from the group represented by the group [P] and the reactive inorganic compound.
  • the rubber member in the present embodiment includes a rubber containing a functional group showing reactivity with an organic reactive group contained in the reactive inorganic compound.
  • Examples of the functional group contained in the rubber include a diene group, a vinyl group, an isocyanate group, an amino group, a hydroxyl group, a carboxy group, an epoxy group, a thiol group, and a polysulfide.
  • polysulfide, thiol group, vinyl group, isocyanate group, amino group, hydroxyl group, carboxy group, or epoxy group are preferred from the viewpoint of satisfactorily forming a bond between the organic reactive group and the rubber in the reactive inorganic compound.
  • Vinyl group, amino group, carboxy group, or epoxy group is more preferable.
  • a good bond is formed between the two by using a rubber containing a functional group such as a diene group as the rubber.
  • a good bond is formed between the two by using a rubber containing a functional group such as a diene group or a vinyl group as the rubber.
  • a good bond is formed between the two by using a rubber containing a functional group such as an isocyanate group, a carboxy group or an epoxy group as the rubber.
  • the reactive inorganic compound has an epoxy group as the organic reactive group
  • a rubber containing a functional group such as an amino group, a hydroxyl group, or a carboxy group
  • a good bond is formed between the two.
  • a rubber containing a functional group such as an amino group, a hydroxyl group, a carboxy group, or a thiol group is used as a rubber, so that a good bond is formed between the two.
  • the rubber containing a functional group showing reactivity with an organic reactive group include the following. Natural rubber (NR / example of functional group: diene group, etc.) Butadiene rubber (example of BR / functional group: diene group, vinyl group, etc.) Styrene-butadiene rubber (SBR / example of functional group: diene group, etc.) Styrene, butadiene, styrene rubber (SBS / examples of functional groups: diene groups, etc.) Polyisoprene rubber (example of functional group: diene group, etc.) Chloroprene rubber (Examples of functional groups: diene group, vinyl group, etc.) Acrylonitrile butadiene rubber (examples of functional groups: diene group, vinyl group, etc.) Epoxidized natural rubber (examples of functional groups: diene groups, epoxy groups, etc.) Epoxidized styrene-butadiene rubber (
  • natural rubber SBR, BR, and polyisoprene rubber are preferable as the rubber containing a functional group that exhibits reactivity with an organic reactive group.
  • the rubber member may be used in combination with a rubber that does not contain a functional group showing reactivity with an organic reactive group.
  • the rubber component contains a functional group showing reactivity with the organic reactive group in all rubber components.
  • the proportion of rubber is preferably 0.5% by mass or more, more preferably 30% by mass or more, and further preferably 100% by mass or more.
  • the content of the rubber with respect to the total amount of the rubber member is not particularly limited, but is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more.
  • 90 mass% or less is preferable, 80 mass% or less is more preferable, and 70 mass% or less is further more preferable.
  • the rubber member preferably contains a filler having a silanol group and a silane coupling agent in addition to rubber.
  • a filler having a silanol group and a silane coupling agent in addition to rubber.
  • a filler which has a silanol group contained in a rubber member particles, such as silica and glass (for example, glass fiber, glass bead, etc.), are mentioned, for example.
  • a silica particle is preferable from a viewpoint of adhesive improvement.
  • Silica includes not only silicon dioxide (SiO 2 ) in a narrow sense but also silicate compounds, and silicates such as hydrous silicate, calcium silicate, and aluminum silicate in addition to anhydrous silicate.
  • silicates such as hydrous silicate, calcium silicate, and aluminum silicate in addition to anhydrous silicate.
  • hydrous silicate such as hydrous silicate, calcium silicate, and aluminum silicate in addition to anhydrous silicate.
  • hydrous silicate such as hydrous silicate, calcium silicate, and aluminum silicate in addition to anhydrous silicate.
  • hydrous silicate such as hydrous silicate, calcium silicate, and aluminum silicate in addition to anhydrous silicate.
  • the aggregation state of the silica is not particularly limited, and includes precipitated silica, gel silica, dry silica, colloidal silica, and the like.
  • hydrophilic silica from the viewpoint of the number of silanol groups on the surface.
  • silica is “hydrophilic” means that the moisture content (that is, loss on drying) specified in JIS-K1150 (1994) is 10% by mass or less.
  • the content of the filler having a silanol group in the rubber member is preferably 20 phr or more and 100 phr or less, and more preferably 30 phr or more and 90 phr or less, with respect to the total amount of rubber contained, from the viewpoint of improving adhesiveness. .
  • silane coupling agent As a silane coupling agent, the group provided with the reactive group which shows the reactivity with an organic material, for example, and the compound which the alkoxy group couple
  • the alkoxy group include a methoxy group and an ethoxy group.
  • reactive groups include vinyl groups, epoxy groups, styryl groups (that is, vinyl phenyl groups), acrylic groups, methacryl groups, amino groups, ureido groups, isocyanate groups, isocyanurate groups, mercapto groups, triazine dithiol groups, vinyl groups. , Etc.
  • silane coupling agent contained in the rubber member examples include the following compounds.
  • Polysulfide silane coupling agents having two or more sulfur eg, bis- (3- (triethoxysilyl) propyl) -disulfide, bis- (3- (triethoxysilyl) propyl) -tetrasulfide, and bis- ( Bis- (trialkoxysilylalkyl) -polysulfide) such as triethoxysilylpropyl) -polysulfide
  • N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane N-2- (aminoethyl) -3- Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, 11-aminoundecyltrie
  • silane coupling agent it is preferable to use the polysulfide type
  • the silane coupling agent the following compounds are preferable from the viewpoint of improving adhesiveness.
  • Bis- (3- (triethoxysilyl) propyl) -disulfide, bis- (3- (triethoxysilyl) propyl) -tetrasulfide, bis- (triethoxysilylpropyl) -polysulfide, 3-mercaptopropyltriethoxysilane preferable.
  • silane coupling agents may be used alone or in combination of two or more.
  • the content of the silane coupling agent in the rubber member is preferably 5 parts by mass or more and 15 parts by mass or less, and 7 parts by mass or more and 12 parts by mass or less with respect to 100 parts by mass of the filler from the viewpoint of improving adhesiveness. More preferably.
  • additives include reinforcing materials such as carbon black, fillers, vulcanizing agents, vulcanization accelerators, fatty acids or salts thereof, metal oxides, process oils, anti-aging agents, and the like. can do.
  • the rubber member is in an unvulcanized state, and is preferably a vulcanized rubber that is molded into a required shape and crosslinked by heating.
  • the resin rubber composite according to the present embodiment may have a second rubber member in contact with the rubber member.
  • the second rubber member includes rubber. Examples of the rubber used include those listed as the rubber contained in the rubber member.
  • other components such as additives may be added to the second rubber member depending on the purpose. Examples of this additive include those listed as the additives contained in the rubber member described above. It is mentioned in.
  • the tire according to this embodiment has the resin rubber composite according to the above-described embodiment.
  • a resin rubber composite when used for a tire, the following combinations are mentioned as a combination of a resin member and a rubber member.
  • the resin member is a “belt layer”
  • examples of the rubber member include at least one member selected from “tread, tire frame, and rubber sheet bonded to the surface of the belt layer”.
  • examples of the rubber member include at least one member selected from “a tire frame body and a rubber sheet bonded to the surface of the bead member”.
  • the rubber member includes at least one member selected from “tread, belt layer, bead member, and rubber sheet bonded to the surface of the tire frame”. It is done.
  • the rubber member When the resin member is a “belt cord”, the rubber member includes at least one member selected from “a cord covering layer covering the belt cord and a rubber sheet bonded to the surface of the belt cord”. .
  • the resin member When the resin member is “bead wire”, the rubber member includes at least one member selected from “a wire coating layer covering the bead wire and a rubber sheet bonded to the surface of the bead wire”.
  • the “tire frame” as the rubber member is a member that forms a tire frame such as a carcass corresponding to the rubber member (for example, a carcass made of only a carcass ply in which a plurality of wires are covered with rubber). It may be replaced.
  • the resin rubber composite is an aspect having a resin member, a rubber member in contact with the resin member, and a second rubber member in contact with the rubber member.
  • the resin member is a “belt layer”
  • the rubber member includes “rubber sheet”
  • the second rubber member includes at least one member selected from “tread, tire frame body, and side rubber”.
  • the resin member is a “bead member”
  • the rubber member includes “rubber sheet”
  • the second rubber member includes at least one member selected from “tire frame and side rubber”.
  • the resin member is a “tire frame”
  • the rubber member includes “rubber sheet”
  • the second rubber member is at least one selected from “tread, belt layer, bead member, and side rubber”
  • the “tire skeleton body” as the second rubber member is a skeleton of a tire such as a carcass (for example, a carcass made only of a carcass ply in which a plurality of wires are covered with rubber) corresponding to the second rubber member. You may replace with the member which comprises.
  • a tire skeleton body and a belt layer will be described by taking a tire corresponding to a resin member as an example.
  • FIG. 1 is a cross-sectional view along the tire width direction of the tire of the first embodiment.
  • the tire case 17 (an example of a tire skeleton) corresponds to a resin member.
  • the tire 200 includes a belt layer in which a belt in which a belt cord 26 ⁇ / b> A is covered with a coating resin 26 ⁇ / b> B is wound in the circumferential direction on the outer peripheral surface of a crown portion 16 of a tire case 17. 26 is formed, and this belt layer 26 also corresponds to a resin member.
  • the belt layer 26 constitutes the outer peripheral portion of the tire case 17 and reinforces the circumferential rigidity of the crown portion 16.
  • the tire case 17 and the belt layer 26 corresponding to the resin member are treated surfaces in which at least the surface in contact with the cushion rubber 28 is treated by the above-described surface treatment.
  • the melting point of the resin is, for example, about 100 ° C. to 350 ° C., and from the viewpoint of tire durability and productivity, about 100 ° C. to 250 ° C. is preferable, and 120 ° C. to 250 ° C. is more preferable.
  • the tensile modulus of elasticity defined in JIS K7113: 1995 of the tire frame body (for example, the tire case 17) itself is preferably 50 MPa to 1000 MPa, more preferably 50 MPa to 800 MPa, and particularly preferably 50 MPa to 700 MPa.
  • the tensile modulus is 50 MPa to 1000 MPa, the rim can be assembled efficiently while maintaining the shape of the tire frame.
  • the tensile strength specified in JIS K7113 (1995) of the tire frame body is usually about 15 MPa to 70 MPa, preferably 17 MPa to 60 MPa, and more preferably 20 MPa to 55 MPa.
  • the tensile yield strength defined in JIS K7113 (1995) of the tire frame body (for example, the tire case 17) itself is preferably 5 MPa or more, more preferably 5 MPa to 20 MPa, and particularly preferably 5 MPa to 17 MPa.
  • the tensile yield strength is 5 MPa or more, it is possible to withstand deformation against a load applied to the tire during traveling or the like.
  • the tensile yield elongation defined by JIS K7113 (1995) of the tire frame body (for example, the tire case 17) itself is preferably 10% or more, more preferably 10% to 70%, and particularly preferably 15% to 60%.
  • the tensile yield elongation is 10% or more, the elastic region is large, and the rim assembly property can be improved.
  • the tensile elongation at break stipulated in JIS K7113 (1995) of the tire frame (for example, the tire case 17) itself is preferably 50% or more, more preferably 100% or more, particularly preferably 150% or more, most preferably 200% or more. preferable.
  • the tensile elongation at break is 50% or more, the rim assemblability is good and it is difficult to break against collision.
  • the load deflection temperature (at 0.45 MPa load) specified in ISO 75-2 or ASTM D648 of the tire frame body (for example, the tire case 17) itself is preferably 50 ° C. or more, more preferably 50 ° C. to 150 ° C., 50 C. to 130.degree. C. is particularly preferable.
  • the deflection temperature under load is 50 ° C. or higher, deformation of the tire skeleton can be suppressed even when vulcanization is performed in the manufacture of the tire.
  • the belt layer 26 is formed by coating a belt cord 26A having higher rigidity than the resin forming the tire case 17 with a coating resin 26B separate from the resin forming the tire case 17.
  • the belt layer 26 is joined to the belt layer 26 and the tire case 17 at the contact portion with the crown portion 16 (for example, bonded by welding or an adhesive).
  • a cushion rubber 28 is joined so as to contact a region of the outer peripheral surface of the belt layer 26 and the outer peripheral surface of the tire case 17 that is not covered with the belt layer 26, and rubber is further applied on the outer peripheral surface of the cushion rubber 28.
  • the tread layer 30 including it is joined.
  • the cushion rubber 28 and the tread layer 30 form a rubber tread, and the cushion rubber 28 corresponds to a rubber member.
  • the tread layer 30 is formed with a tread pattern (not shown) including a plurality of grooves on the ground contact surface with the road surface.
  • a tire case half body (namely, one half of the tire case which has the shape where the tire case was cut
  • the tire case halves are joined to each other by a method such that the tire case halves face each other and are pressed at a melting point or higher of the resin material constituting the tire case.
  • Belt layer winding step As a method of forming the belt layer 26 on the crown portion 16 of the tire case 17, for example, a belt wound around a reel while rotating the tire case 17 (that is, the belt cord 26A is applied to the coating resin 26B).
  • the belt member 26 is unwound and this belt is wound around the crown portion 16 a predetermined number of times to form the belt layer 26.
  • the coating resin 26B may be welded to the tire case 17 by heating and pressurizing.
  • the timing for performing the surface treatment is not particularly limited.
  • the tire case 17 and the belt layer 26 may be collectively treated after the belt layer 26 is formed.
  • the tire case 17 may be first processed before the belt layer 26 is formed, and then the belt layer 26 may be processed again after the belt layer 26 is formed.
  • the cushion rubber 28 in an unvulcanized state is provided for one round so as to come into contact with the outer peripheral surface of the belt layer 26 and the outer peripheral surface of the tire case 17 not covered with the belt layer 26. Wrap.
  • the cushion rubber 28 corresponding to the rubber member contains a filler having a silanol group.
  • the vulcanized, semi-vulcanized or unvulcanized tread layer 30 is wound on the cushion rubber 28 for one turn.
  • the tire of the first embodiment is obtained by vulcanization.
  • the bead portion 12 of the tire case 17 may be provided with a seal layer 24 that is softer than the resin material used for the tire case 17 using an adhesive or the like.
  • the cushion rubber 28 corresponding to the rubber member contains a filler having a silanol group
  • the tire case 17 corresponding to the resin member and the region in contact with the cushion rubber 28 of the belt layer 26 are described above.
  • Surface treatment by the method of is performed. Therefore, the tire case 17 and the belt layer 26 and the cushion rubber 28 constituting the tread are excellent without using an adhesive between the tire case 17 and the cushion rubber 28 and between the belt layer 26 and the cushion rubber 28. Adhesiveness can be obtained.
  • the tread is formed on the outer peripheral surface of the tire case 17 by laminating the cushion rubber 28 and the tread layer 30, but the present invention is not limited thereto, and the cushion rubber 28 is not disposed. It is good also as a structure.
  • the tread layer 30 constituting the tread corresponds to a rubber member, and the tread layer 30 contains a filler having a silanol group.
  • the cushion rubber 28 is in direct contact with the tire case 17 and the belt layer 26.
  • the present invention is not limited thereto, and the cushion rubber 28, the tire case 17, and the belt are not limited thereto.
  • a rubber sheet corresponding to a rubber member may be interposed between the layer 26 and the layer 26.
  • the rubber sheet corresponds to a rubber member, and the rubber sheet contains a filler having a silanol group.
  • the cushion rubber 28 corresponds to the second rubber member, and the cushion rubber 28 may not contain a filler having a silanol group.
  • the thickness of the rubber sheet is as follows. Is preferably 0.1 ⁇ m or more and 100 mm or less, and more preferably 1 ⁇ m or more and 2 mm or less.
  • a bead member a belt cord, and a bead wire will be described as an example of a tire corresponding to a resin member.
  • FIG. 2 is a tire half sectional view showing one side of a cut surface cut along the tire width direction of the tire 110 of the second embodiment.
  • an arrow TW indicates the width direction of the tire 110 (tire width direction)
  • an arrow TR indicates the radial direction of the tire 110 (tire radial direction).
  • the tire 110 includes a pair of left and right bead portions 112 (only one bead portion 112 is shown in FIG. 2), and a pair of tires extending from the pair of bead portions 112 outward in the tire radial direction.
  • a side portion 114 and a tread portion 116 extending from one tire side portion 114 to the other tire side portion 114 are provided.
  • a tire 110 shown in FIG. 2 includes a tire case 140 corresponding to a tire skeleton.
  • the tire case 140 corresponds to a rubber member, and is formed using rubber and contains a filler having a silanol group.
  • the tire case 140 includes a bead portion 112, a tire side portion 114, and a tread portion 116.
  • a tire case 140 corresponding to a rubber member is a member constituting a tire skeleton such as a carcass corresponding to a rubber member (for example, a carcass made only of a carcass ply in which a plurality of wires are covered with rubber). It may be replaced.
  • a protective layer 122 is provided on the tire side portion 114 and the bead portion 112 in the tire width direction outer side, the bead portion 112 in the tire radial direction inner side, and the bead portion 112 on the tire width direction inner side.
  • the bead portion 112, the tire side portion 114, and the tread portion 116 may be integrally formed in the same process, or may be a combination of members formed in different processes. However, it is preferably formed integrally from the viewpoint of production efficiency.
  • a bead filler 120 extending along the protective layer 122 from the bead core 118 to the outer side in the tire radial direction is embedded in the bead portion 112.
  • the bead filler 120 corresponds to a resin member, and the surface in contact with the tire case 140 is a treated surface treated by the surface treatment described above.
  • the bead portion 112 is a part that contacts a rim (not shown), and an annular bead core 118 extending along the tire circumferential direction is embedded.
  • the forms that the bead core 118 can take will be described later.
  • the protective layer 122 is provided for the purpose of increasing the airtightness between the tire case 140 and the rim, and is made of a material such as rubber that is softer and weatherproof than the tire case 140. , May be omitted.
  • the tread portion 116 is a portion corresponding to the ground contact surface of the tire 110, and is provided with a belt layer 124A. Further, a tread layer 130 is provided on the belt layer 124A via a cushion rubber 124B. The forms that the belt layer 124A can take will be described later.
  • the manufacturing method of the tire case 140 is not particularly limited.
  • the tire case halves in a state where the tire case 140 is divided by the equator plane are respectively produced by an extrusion molding method (for example, an injection molding method) or the like, You may produce by joining in an equatorial plane.
  • a carcass produced by a conventionally known method may be used.
  • a method of forming the belt layer 124A on the tread portion 116 of the tire case 140 for example, a belt wound around a reel while the tire case 140 is rotated (the belt cord 1 shown in FIG.
  • the cord covering layer 3A is coated on the cord covering layer 3).
  • the belt layer 124A is formed by winding the belt around the crown portion 16 a predetermined number of times.
  • the cord covering layer 3 may be welded to the tire case 140 by heating and pressurizing.
  • a preformed bead filler 120 and an annular member for the bead core 118 are embedded in the bead portion 112 by a known method. May be formed.
  • a tire case 140 corresponding to a rubber member contains a filler having a silanol group, and a bead filler 120 (an example of a bead member) corresponding to a resin member is in contact with the tire case 140.
  • a bead filler 120 an example of a bead member
  • the tire case 140 is shown in a form in which the tire case 140 is in direct contact with the bead filler 120.
  • the present invention is not limited thereto, and the rubber member is interposed between the tire case 140 and the bead filler 120.
  • a corresponding rubber sheet may be interposed.
  • the rubber sheet corresponds to a rubber member, and the rubber sheet contains a filler having a silanol group.
  • the tire case 140 corresponds to the second rubber member, and the tire case 140 may not contain a filler having a silanol group.
  • the thickness of the rubber sheet is, for example, 0. 1 ⁇ m or more and 100 mm or less is preferable, and 1 ⁇ m or more and 2 mm or less is more preferable.
  • FIG. 3A is a diagram schematically illustrating a cross section when a part of the bead core 118 is cut perpendicularly to the length direction of the bead wire 1.
  • the wire coating layer 3 is provided so as to be in direct contact with the three bead wires 1.
  • the bead wire 1 corresponds to a resin member, and the surface in contact with the wire coating layer 3 is a treated surface treated by the surface treatment described above.
  • the wire coating layer 3 corresponds to a rubber member, and is formed using rubber and contains a filler having a silanol group. Therefore, excellent adhesiveness between the bead wire 1 and the wire coating layer 3 can be obtained without using an adhesive between the bead wire 1 and the wire coating layer 3. In addition, you may produce by carrying out the horizontal and vertical stepping of the one bead wire 1 while heat-welding.
  • the bead core 118 may have the rubber sheet 2 disposed between the bead wire 1 and the wire covering layer 3.
  • a part of the bead core 118 shown in FIG. 3B is provided with the rubber sheet 2 bonded to the surface of each of the three bead wires 1, and the wire coating layer 3 is further provided on the surface.
  • the rubber sheet 2 corresponds to a rubber member, and the rubber sheet 2 contains a filler having a silanol group.
  • the wire coating layer 3 corresponds to a second rubber member, and the wire coating layer 3 may not contain a filler having a silanol group. Thereby, even if it does not interpose an adhesive agent between bead wire 1 and rubber sheet 2, the superior adhesiveness of bead wire 1 and rubber sheet 2 is obtained.
  • the bead core 118 shown in FIG. 2 is formed by laminating three layers of the three bead wires 1 and the wire covering layer 3 shown in any of FIG. 3A and FIG. 3B (and the rubber sheet 2 in FIG. 3B). It has a form.
  • the bead core 118 may be used as a single layer or may be used as a laminate of two or more layers. In that case, it is preferable to weld the wire coating layers.
  • the form which the bead core 118 can take was demonstrated referring FIG. 3A and FIG. 3B, it is not limited to this structure.
  • the method for producing the bead core 118 is not particularly limited.
  • the rubber material for forming the rubber sheet 2 after the above-described surface treatment is performed on the bead wire 1 which is a resin member (the rubber material is silanol) Containing a filler having a group) and a rubber material for forming the wire coating layer 3 can be produced by an extrusion molding method.
  • the belt layer 124A shown in FIG. 2 can take will be described.
  • a configuration similar to that of the bead core 118 illustrated in FIG. 3A can be given, that is, a configuration in which a cord covering layer is provided so as to be in direct contact with three belt cords.
  • the belt cord corresponds to a resin member, and the surface in contact with the cord covering layer is the treated surface treated by the surface treatment described above.
  • the cord covering layer corresponds to a rubber member, and contains a filler that is formed using rubber and has a silanol group. Therefore, excellent adhesiveness between the belt cord and the cord covering layer can be obtained without using an adhesive between the belt cord and the cord covering layer.
  • the belt layer 124A may have a rubber sheet disposed between the belt cord and the cord covering layer.
  • the same configuration as the bead core 118 shown in FIG. 3B can be mentioned, that is, a rubber sheet is adhered to each surface of the three belt cords, and a cord covering layer is further provided on the surface.
  • a configuration is mentioned.
  • the rubber sheet corresponds to a rubber member, and the rubber sheet contains a filler having a silanol group.
  • the cord coating layer corresponds to the second rubber member, and the cord coating layer may not contain a filler having a silanol group. As a result, excellent adhesion between the belt cord and the rubber sheet can be obtained without using an adhesive between the belt cord and the rubber sheet.
  • the number of belt cords may be two or less, or four or more, as well as a mode in which three belt cords are arranged in parallel.
  • the belt layer 124A shown in FIG. 2 has a configuration in which three belt cords and a cord covering layer (and, if necessary, a rubber sheet) are laminated.
  • the belt layer 124A may be used by stacking two or more layers. In this case, it is preferable to weld the cord coating layers.
  • the form which 124A can take was demonstrated as mentioned above, it is not limited to this structure.
  • a resin member having a treated surface subjected to a second surface treatment A rubber member that includes a rubber that is in contact with the treated surface of the resin member and contains a functional group that exhibits reactivity with the organic reactive group; There is provided a resin rubber composite having ⁇ 2>
  • the treated surface of the resin member is subjected to peroxy radical (—O—O.), Hydroperoxide group (—O—OH), carbonyl group (—C ( ⁇ O) —), aldehyde group (—
  • the resin rubber according to the first aspect which is a surface into which at least one selected from C ( ⁇ O) —H), a carboxy group (—C ( ⁇ O) —OH), and a hydroxyl group (—OH) is introduced.
  • a complex is provided.
  • the resin rubber composite according to the first or second aspect in which a contact angle of water on the treated surface of the resin member is 20 ° or more and 98 ° or less, is provided.
  • a resin member, and a rubber member in contact with the resin member At the interface between the resin member and the rubber member, the surface of the resin member and the rubber member are formed by a crosslinking group formed by a reaction of at least one selected from the group represented by the following group [P] with the following reactive inorganic compound.
  • the surface of the The rubber member includes a rubber containing a functional group showing reactivity with an organic reactive group included in the following reactive inorganic compound.
  • a resin rubber composite is provided.
  • ⁇ Group [P] Peroxy radical (—O—O.), Hydroperoxide group (—O—OH), carbonyl group (—C ( ⁇ O) —), aldehyde group (—C ( ⁇ O) —H), carboxy group (—C ( O) -OH) and hydroxyl group (-OH)
  • Reactive inorganic compound Reactive inorganic compound containing an organic reactive group and at least one group selected from a hydroxyl group and an alkoxy group ⁇ 5>
  • the resin rubber composite according to the fourth aspect in which the contact angle of water on the surface on the resin member side at the interface between the resin member and the rubber member is 20 ° to 98 °, is provided.
  • the organic reactive group contained in the reactive inorganic compound is at least one group selected from a polysulfide group, a vinyl group, a thiol group, an amino group, an isocyanate group, and an epoxy group.
  • a resin rubber composite according to any one of the fifth aspects is provided.
  • the resin rubber composite according to any one of the first to sixth aspects is provided, wherein the reactive inorganic compound contains Si atoms as inorganic elements.
  • the functional group contained in the rubber is at least one group selected from a diene group, a vinyl group, an isocyanate group, an amino group, a hydroxyl group, a carboxy group, an epoxy group, a thiol group, and a polysulfide.
  • a resin rubber composite according to any one of the first to seventh aspects is provided.
  • the resin rubber composite according to any one of the first to eighth aspects is provided, wherein the rubber member further contains a filler having a silanol group.
  • the resin rubber composite according to the ninth aspect is provided, wherein the filler having a silanol group is silica. ⁇ 11> According to the eleventh aspect of the present disclosure, The resin rubber composite according to the tenth aspect is provided, wherein the silica is hydrophilic silica. ⁇ 12> According to the twelfth aspect of the present disclosure, The resin rubber composite according to any one of the ninth to eleventh aspects is provided, wherein the rubber member further contains a silane coupling agent.
  • the resin rubber composite according to any one of the first to twelfth aspects which has a second rubber member in contact with the rubber member, is provided.
  • the resin member is polyester-based thermoplastic elastomer, polyester-based thermoplastic resin, polyamide-based thermoplastic elastomer, polyamide-based thermoplastic resin, polystyrene-based thermoplastic elastomer, polystyrene-based thermoplastic resin, polyurethane-based thermoplastic elastomer, polyurethane-based thermoplastic
  • a resin rubber composite according to any one of the first to thirteenth aspects is provided, which contains at least one resin selected from a plastic resin, a polyolefin-based thermoplastic elastomer, and a polyolefin-based thermoplastic resin.
  • the resin rubber composite according to the fourteenth aspect is provided, wherein the resin member contains at least one resin selected from polyester-based thermoplastic elastomers and polyester-based thermoplastic resins.
  • the resin member contains at least one resin selected from polyester-based thermoplastic elastomers and polyester-based thermoplastic resins.
  • a tire having a resin rubber composite according to any one of the first to fifteenth aspects is provided.
  • a tire according to the aspect is provided.
  • a bead member as the resin member including a bead member as the resin member, a tire skeleton as the rubber member, and at least one member selected from a rubber sheet bonded to the surface of the bead member.
  • Tires are provided.
  • the resin rubber composite is at least one selected from a belt cord as the resin member, a cord covering layer covering the belt cord as the rubber member, and a rubber sheet bonded to the surface of the belt cord.
  • a tire according to the sixteenth aspect is provided.
  • the resin rubber composite is at least one selected from a bead wire as the resin member, a wire coating layer covering the bead wire as the rubber member, and a rubber sheet bonded to the surface of the bead wire.
  • the tire according to the sixteenth aspect is a bead core having a member.
  • First surface treatment by plasma treatment, and second surface by a reactive inorganic compound further containing an organic reactive group and at least one group selected from a hydroxyl group and an alkoxy group on the surface subjected to the plasma treatment A surface treatment step of performing treatment on at least a part of the surface of the resin member;
  • a rubber member containing a rubber containing a functional group having a reactivity with the organic reactive group is disposed on the surface of the resin member that has been subjected to the first surface treatment and the second surface treatment, and heated. Bonding process for bonding the resin member and the rubber member;
  • a method for producing a resin rubber composite having the following is provided.
  • Example 1 ⁇ Preparation of test piece> 1.
  • Resin member As a resin composition, Hytrel 4767N manufactured by Toray DuPont was used as a commercially available polyester-based thermoplastic elastomer to obtain a resin square plate having a thickness of 0.6 mm.
  • Rubber member As the rubber member, the rubber and various compounding agents shown in Table 1 were mixed and stirred at 110 ° C. for 3 minutes with a lab plast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and a rubber sheet having a thickness of 2.5 mm was obtained with a roll It was.
  • the plasma generator (the product name K2X02L023 by the Mingchang machine company) was used for the plasma irradiation apparatus which surface-treats to a resin member.
  • a high frequency power source for the plasma generator an applied voltage having a frequency of 13.56 MHz is used.
  • an electrode a copper tube having an inner diameter of 1.8 mm, an outer diameter of 3 mm, and a length of 165 mm is outer diameter of 5 mm, thickness of 1 mm, and length.
  • a resin member was placed on the upper surface of the sample holder, and the distance between the resin member surface and the electrode was set to 1.0 mm.
  • the chamber was sealed, and the pressure was reduced to 10 Pa or less with a rotary pump, and then helium gas was introduced until atmospheric pressure (that is, 1013 hPa). Thereafter, the high frequency power source was set so that the output power density (that is, the irradiation density) was 5.7 W / cm 2, and the moving speed of the scanning stage was set to 2 mm / second. Thereafter, while moving the scanning stage, the surface of the resin member (that is, the square plate) was irradiated with plasma in a helium atmosphere, and the scanning stage was reciprocated twice to perform the first surface treatment.
  • the output power density that is, the irradiation density
  • Table 1 below shows the contact angle of water on the treated surface subjected to the first surface treatment and the second surface treatment.
  • the first surface treatment is performed using a plasma generator having a specification different from that of the plasma generator, and the second surface treatment with the silane coupling agent is performed. It is the predicted value obtained from the simulation based on the water contact angle of the resin member obtained in this way.
  • a rubber member that is, a sheet
  • a resin member that is, a square plate
  • Examples 2 to 6, Comparative Examples 1 to 3 The composition of the rubber member (that is, the sheet) was changed to the composition shown in Table 1, and the presence or absence of the first surface treatment by the plasma treatment for the resin member (that is, the square plate), the second surface by the silane coupling agent Except that the presence or absence of the treatment and the type of the silane coupling agent used for the second surface treatment were changed to those shown in Table 1, a test piece was prepared in the same manner as in Example 1, and a peel test was performed.
  • Comparative Example 4 The composition of the rubber member (that is, the sheet) was changed to the composition shown in Table 1, and the presence or absence of the first surface treatment by the plasma treatment for the resin member (that is, the square plate), the second surface by the silane coupling agent A test piece is prepared in the same manner as in Example 1 except that the presence or absence of the treatment and the type of the silane coupling agent used for the second surface treatment are changed to those shown in Table 1, and a peel test is performed. In addition, about the comparative example 4, it is the estimated value obtained from simulation.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Tires In General (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un composite résine-caoutchouc comprenant : un élément en résine qui a une surface traitée à laquelle un premier traitement de surface à l'aide d'un traitement par plasma a été appliqué et à laquelle un second traitement de surface utilisant un composé inorganique réactif contenant au moins un groupe choisi parmi des groupes réactifs organiques, des groupes hydroxyle et des groupes alcoxy a été appliqué sur la surface traitée au plasma ; et un élément en caoutchouc qui est en contact avec la surface traitée de l'élément en résine et comprend un groupe fonctionnel qui est réactif avec le groupe réactif organique.
PCT/JP2019/018013 2018-04-26 2019-04-26 Composite résine-caoutchouc, pneu, et procédé de production de composite résine-caoutchouc Ceased WO2019208798A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020515616A JP7312411B2 (ja) 2018-04-26 2019-04-26 樹脂ゴム複合体、タイヤ、及び樹脂ゴム複合体の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018085710 2018-04-26
JP2018-085710 2018-04-26

Publications (1)

Publication Number Publication Date
WO2019208798A1 true WO2019208798A1 (fr) 2019-10-31

Family

ID=68294164

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/018013 Ceased WO2019208798A1 (fr) 2018-04-26 2019-04-26 Composite résine-caoutchouc, pneu, et procédé de production de composite résine-caoutchouc

Country Status (2)

Country Link
JP (1) JP7312411B2 (fr)
WO (1) WO2019208798A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06143914A (ja) * 1992-11-02 1994-05-24 Bridgestone Corp 空気入りラジアルタイヤ
JPH09300924A (ja) * 1996-05-13 1997-11-25 Yokohama Rubber Co Ltd:The 空気入りタイヤ
JP2003205553A (ja) * 2002-01-11 2003-07-22 Toyo Tire & Rubber Co Ltd 可とう管の製造方法と組合せ芯材と可とう管
WO2008044884A1 (fr) * 2006-10-13 2008-04-17 Sunwoo Amc Co., Ltd. Pellicule de revêtement de plastique/téflon-silicium et procédé de préparation correspondant
JP2011224954A (ja) * 2010-03-30 2011-11-10 Bridgestone Corp タイヤの製造方法及びタイヤ
JP2011242279A (ja) * 2010-05-19 2011-12-01 Yokohama Rubber Co Ltd:The 歪み計測構造および歪み計測方法
JP2012035435A (ja) * 2010-08-04 2012-02-23 Bridgestone Corp タイヤの製造方法及びタイヤ
JP2013216828A (ja) * 2012-04-11 2013-10-24 Kaneka Corp イソブチレン系熱可塑性エラストマーシート

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2732364A1 (fr) * 1995-03-29 1996-10-04 Michelin & Cie Procede pour traiter un corps en acier inoxydable de facon a favoriser son adhesion a une composition de caoutchouc
US6620517B2 (en) * 2000-03-09 2003-09-16 Toyo Tire & Rubber Co., Ltd. Method for producing rubber-resin composite
JP2006167919A (ja) * 2004-12-10 2006-06-29 Bridgestone Corp 積層体、その製造方法及びそれを用いたタイヤ
KR100635261B1 (ko) * 2005-08-12 2006-10-23 주식회사 나노텍세라믹스 폴리머 배합물 기재의 접착개선제 및 이를 포함하는 폴리머배합조성물
JP5376112B2 (ja) * 2008-06-02 2013-12-25 宇部興産株式会社 多層構造体
WO2010047315A1 (fr) * 2008-10-21 2010-04-29 宇部興産株式会社 Composition de caoutchouc et stratifié de polyamide
JPWO2011027703A1 (ja) * 2009-09-04 2013-02-04 宇部興産株式会社 ポリエーテルポリアミドエラストマー及びポリアミド積層体
JP5993545B2 (ja) * 2010-08-25 2016-09-14 株式会社ブリヂストン タイヤ
JP6369313B2 (ja) * 2014-12-09 2018-08-08 コニカミノルタ株式会社 中間転写ベルトおよびその製造方法
DE102015001902A1 (de) * 2015-02-18 2016-08-18 Continental Reifen Deutschland Gmbh Verfahren zur Verbesserung der Haftung zwischen einem Verstärkungselement und einem elastomeren Matrixmaterial

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06143914A (ja) * 1992-11-02 1994-05-24 Bridgestone Corp 空気入りラジアルタイヤ
JPH09300924A (ja) * 1996-05-13 1997-11-25 Yokohama Rubber Co Ltd:The 空気入りタイヤ
JP2003205553A (ja) * 2002-01-11 2003-07-22 Toyo Tire & Rubber Co Ltd 可とう管の製造方法と組合せ芯材と可とう管
WO2008044884A1 (fr) * 2006-10-13 2008-04-17 Sunwoo Amc Co., Ltd. Pellicule de revêtement de plastique/téflon-silicium et procédé de préparation correspondant
JP2011224954A (ja) * 2010-03-30 2011-11-10 Bridgestone Corp タイヤの製造方法及びタイヤ
JP2011242279A (ja) * 2010-05-19 2011-12-01 Yokohama Rubber Co Ltd:The 歪み計測構造および歪み計測方法
JP2012035435A (ja) * 2010-08-04 2012-02-23 Bridgestone Corp タイヤの製造方法及びタイヤ
JP2013216828A (ja) * 2012-04-11 2013-10-24 Kaneka Corp イソブチレン系熱可塑性エラストマーシート

Also Published As

Publication number Publication date
JP7312411B2 (ja) 2023-07-21
JPWO2019208798A1 (ja) 2021-05-13

Similar Documents

Publication Publication Date Title
CN108367596B (zh) 轮胎
US20200115599A1 (en) Resin-metal composite member for tire, and tire
US11135875B2 (en) Resin-metal composite member for tire, and tire
JP7221951B2 (ja) タイヤ用樹脂金属複合部材、及びその製造方法、並びにタイヤ
US20200115515A1 (en) Resin-metal composite member for tire, and tire
JP7269573B2 (ja) 樹脂ゴム複合体、タイヤ、及び樹脂ゴム複合体の製造方法
JP7312411B2 (ja) 樹脂ゴム複合体、タイヤ、及び樹脂ゴム複合体の製造方法
JP7306638B2 (ja) 樹脂ゴム複合体、タイヤ、及び樹脂ゴム複合体の製造方法
JP6785195B2 (ja) タイヤ用樹脂金属複合部材、及びタイヤ
JP7331316B2 (ja) タイヤ
JP2019001357A (ja) タイヤ用樹脂金属複合部材、及びタイヤ
CN110785289B (zh) 轮胎用树脂金属复合构件和轮胎
JP2020062935A (ja) タイヤ用ワイヤー樹脂複合部材、及びタイヤ

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19793136

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020515616

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19793136

Country of ref document: EP

Kind code of ref document: A1