WO2023032899A1 - 架橋性高分子組成物、架橋高分子材料、絶縁電線ならびにワイヤーハーネス - Google Patents

架橋性高分子組成物、架橋高分子材料、絶縁電線ならびにワイヤーハーネス Download PDF

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WO2023032899A1
WO2023032899A1 PCT/JP2022/032374 JP2022032374W WO2023032899A1 WO 2023032899 A1 WO2023032899 A1 WO 2023032899A1 JP 2022032374 W JP2022032374 W JP 2022032374W WO 2023032899 A1 WO2023032899 A1 WO 2023032899A1
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Prior art keywords
component
polymer composition
cross
crosslinked
crosslinkable polymer
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PCT/JP2022/032374
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English (en)
French (fr)
Japanese (ja)
Inventor
正史 佐藤
武広 細川
保之 大塚
達也 嶋田
達也 長谷
誠 溝口
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Sumitomo Wiring Systems Ltd
Kyushu University NUC
AutoNetworks Technologies Ltd
Sumitomo Electric Industries Ltd
Original Assignee
Sumitomo Wiring Systems Ltd
Kyushu University NUC
AutoNetworks Technologies Ltd
Sumitomo Electric Industries Ltd
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Priority to DE112022003180.8T priority Critical patent/DE112022003180T5/de
Priority to JP2023545548A priority patent/JP7706557B2/ja
Priority to US18/682,368 priority patent/US20240352161A1/en
Priority to CN202280058361.4A priority patent/CN117881750A/zh
Publication of WO2023032899A1 publication Critical patent/WO2023032899A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/442—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from aromatic vinyl compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/0045—Cable-harnesses
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/08—Flat or ribbon cables
    • H01B7/0823—Parallel wires, incorporated in a flat insulating profile
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/08—Flat or ribbon cables

Definitions

  • the present disclosure relates to crosslinkable polymer compositions, crosslinked polymer materials, insulated wires, and wire harnesses.
  • thermoplastic polymer compositions are often used as insulating members such as insulating coatings that cover the outer periphery of wire conductors.
  • a molding technique such as extrusion molding is applied after making it fluid by heating.
  • the polymer composition acquire fluidity without being heated to an extremely high temperature.
  • the polymer composition, including the insulating coating, placed near the energized part is required to have high heat resistance.
  • the polymer composition does not undergo irreversible deformation due to heat generation during energization.
  • the insulating coating of electric wires for automobiles does not undergo reversible deformation at temperatures of 190° C. or less.
  • polymer compositions used for insulated wires and wire harnesses are required to be relatively easily moldable by heating and to have high heat resistance after molding.
  • a method to achieve both of these characteristics it is conceivable to adjust the flow start temperature of the thermoplastic polymer material used, but polymer materials with a high flow start temperature require heating to a high temperature during molding.
  • polymer materials with a low flow initiation temperature are unlikely to have high heat resistance, and this method has limitations. Therefore, a method using cross-linking of polymer materials is also adopted. In other words, a technique is adopted in which an uncrosslinked polymer composition is formed into a desired shape by extrusion molding or the like, and then the molecular chains are crosslinked to improve the heat resistance.
  • Cross-linking methods include electron beam cross-linking (for example, Patent Document 1) in which electron beams are irradiated to a material molded from polyolefin or the like to cross-link polymer molecular chains in the form of a three-dimensional network, and active silane groups are introduced.
  • Silane cross-linking for example, Patent Document 2 or the like is used in which a thermoplastic resin that has been stored is molded and then cross-linked by contact with moisture or the like.
  • cross-linking by vulcanization can be used.
  • a polymer composition that is crosslinked by electron beam crosslinking, silane crosslinking, or vulcanization is a material that acquires high heat resistance by undergoing crosslinking after being molded into a desired shape. It is difficult to re-mold it into another shape after molding it into one shape. Strong covalent bonds are irreversibly formed by cross-linking, and while these cross-links have the effect of improving heat resistance, the fluidity of the molecular chains is increased again, making it possible to re-mold. because it interferes.
  • the cross-sectional shape of the insulated wire may be deformed into a shape different from a circular shape, such as a flat shape, due to restrictions on the wiring space.
  • an insulated wire that has been formed to have a cross-sectional shape different from a circular shape, such as a flat shape is required to be deformed into a circular cross-sectional shape.
  • the insulating coating can be remolded by heating or the like, the insulating coating can also be deformed following the deformation of the wire conductor.
  • a crosslinkable polymer composition that provides a crosslinked body capable of achieving both heat resistance and remoldability, a crosslinked polymer material capable of achieving both heat resistance and remoldability, and such a crosslinked polymer composition
  • An object of the present invention is to provide an insulated wire and a wire harness comprising a polymer material.
  • the crosslinkable polymer composition according to the present disclosure includes an A component that liberates metal ions by heat, and a B component composed of an organic polymer having a side chain, and the B component is attached to the side chain.
  • the crosslinked product containing an electron-withdrawing substituent capable of forming an ionic bond with the metal ions released from the A component, and the B component crosslinked by the metal ions released from the A component is heated at 190° C. or higher. It has a flow initiation temperature in the range of 300°C or less.
  • the crosslinked polymer material according to the present disclosure includes a crosslinked body of the crosslinkable polymer composition, which is configured as a crosslinked body in which the B component is crosslinked by the metal ions liberated from the A component.
  • An insulated wire according to the present disclosure includes a wire conductor and an insulating coating made of the crosslinked polymer material and covering the outer periphery of the wire conductor.
  • a wire harness according to the present disclosure includes the insulated wire.
  • the crosslinkable polymer composition according to the present disclosure provides a crosslinked body capable of achieving both heat resistance and remoldability.
  • the crosslinked polymer material according to the present disclosure can achieve both heat resistance and remoldability.
  • insulated wires and wire harnesses according to the present disclosure are provided with such a crosslinked polymeric material.
  • FIGS. 1A to 1C are diagrams for explaining behavior when a crosslinked body contained in a crosslinked polymer material according to an embodiment of the present disclosure is heated. It shows an elevated state.
  • M2 + represents a metal ion and R represents a side chain.
  • FIG. 2 is a cross-sectional view showing the structure of an insulated wire according to an embodiment of the present disclosure;
  • FIG. 3 is a diagram showing an infrared absorption spectrum measured while heating the crosslinked polymer material.
  • the crosslinkable polymer composition according to the present disclosure includes an A component that liberates metal ions by heat, and a B component composed of an organic polymer having a side chain, and the B component is attached to the side chain.
  • the crosslinked product containing an electron-withdrawing substituent capable of forming an ionic bond with the metal ions released from the A component, and the B component crosslinked by the metal ions released from the A component is heated at 190° C. or higher. It has a flow initiation temperature in the range of 300°C or less.
  • the B component By heating the crosslinkable polymer composition according to the present disclosure, the B component can be crosslinked via metal ions liberated from the A component. Therefore, in the uncrosslinked state of the composition, high moldability can be obtained when it is molded into a desired shape by extrusion molding, etc., while a polymer having high heat resistance can be obtained by forming a crosslinked body through heating. material.
  • the flow initiation temperature of the crosslinked body By setting the flow initiation temperature of the crosslinked body to 190° C. or higher, it is ensured that the polymer material after crosslinked has high heat resistance.
  • a highly heat-resistant material having a flow initiation temperature of 190° C. or more can be suitably used to form an insulating coating, particularly for electric wires for automobiles.
  • the crosslinked structure is formed through ionic bonds between the substituents of the organic polymer of component B and the metal ions.
  • the reversibility of ionic bonds can be used to reshape the polymer material after cross-linking. This is because reheating the already formed crosslinked body causes movement of the crosslinked points due to ionic bonding, thereby causing fluidization of the material. Since the substituent introduced into the organic polymer of the B component is an electron-withdrawing group, the crosslinked structure is stably formed and the crosslinked body exhibits high heat resistance.
  • the introduction of the substituents into the side chains of the organic polymer increases the degree of freedom of thermal movement of the cross-linked sites, making it easier for the cross-linked sites to migrate during heating, resulting in poor remoldability.
  • the flexibility of the crosslinked body is increased. In particular, by suppressing the flow initiation temperature of the crosslinked body to 300° C. or less, the re-moldability by heating at a temperature of 300° C. or less is ensured.
  • the B component preferably has a flow start temperature in the range of 50°C or higher and 190°C or lower. Then, through cross-linking by metal ions derived from component A, it is easy to obtain a cross-linked product having a flow initiation temperature of 190° C. or higher and 300° C. or lower as described above. In addition, high moldability can be obtained when the uncrosslinked crosslinkable polymer composition is molded into a desired shape by extrusion molding or the like.
  • the B component preferably has a Shore D hardness of less than 50. Then, through the cross-linking of the B component by the metal ions derived from the A component, it becomes easy to obtain a highly flexible cross-linked body that can be suitably used for applications involving bending, such as insulating coating of insulated wires.
  • the A component preferably has a decomposition point or a phase transition point at 50°C or higher and 300°C or lower. Then, during the preparation of the crosslinkable polymer composition or before the use of the crosslinkable polymer composition, the liberation of metal ions from the A component is suppressed, thereby suppressing the progress of cross-linking. High storage stability can be obtained in the crosslinkable polymer composition, such as suppression of quality change of the crosslinkable polymer composition in.
  • the A component decomposes or undergoes a phase transition at an appropriate temperature, whereby metal ions are easily released from the A component, and the cross-linking reaction can proceed at a temperature at which the B component is not degraded.
  • the A component preferably has a decomposition point or a phase transition point at a temperature equal to or higher than the flow initiation temperature of the B component. Then, in a state in which the B component has already acquired fluidity, liberation of metal ions from the A component and accompanying cross-linking of the B component occur. Therefore, by utilizing the flow of the B component, the dispersibility of the A component in the B component can be enhanced, and a crosslinked body in which the crosslink points are formed with high spatial uniformity can be obtained. In addition, unintentional liberation of metal ions from component A and subsequent cross-linking of component B are less likely to occur during the preparation or molding of the crosslinkable polymer composition.
  • the A component is preferably a metal complex containing a ligand having the structure of formula (1) below.
  • R 1 and R 2 each independently represent a hydrocarbon group having 1 to 8 carbon atoms
  • R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
  • the ⁇ -diketonato ligand represented by formula (1) is a bidentate ligand, and stabilizes metal ions more than monodentate ligands and ligands that form a bridged coordination structure.
  • release of metal ions from component A is suppressed, and particularly high storage stability is obtained.
  • the metal ions released from the A component are preferably ions of at least one of alkaline earth metals, aluminum, zinc, titanium, and zirconium. All of the metal ions have a valence of 2 or more, and easily form a stable crosslinked structure between the polymer chains of the B component. Furthermore, the above metal ions belong to the hard acids in the HSAB rule, and correspond to having a high ionization tendency, forming stable bonds with the substituents of the B component. For this reason as well, it is suitable as a metal for forming a crosslinked body.
  • the metal ions liberated from the A component are preferably ions of at least one of aluminum and zirconium. When those metal ions are liberated from the A component, they tend to form a particularly stable crosslinked structure with the B component. In addition, in a relatively low temperature state before cross-linking, high storage stability is provided.
  • the substituent of the B component is preferably at least one of a carboxylic acid group, an acid anhydride group, and a phosphoric acid group. These substituents tend to form ionic bonds with metal ions liberated from the A component. In addition, since it is an acidic group with relatively low polarity, it is possible to form a crosslinked structure with high spatial uniformity without causing phase separation with respect to the main chain and side chains of the B component.
  • the substituent of the B component is preferably bonded to the main chain via an alkyl group or alkylene group having 1 or more carbon atoms.
  • the B component should not contain an electron-withdrawing group in the main chain. Then, competition with the electron-withdrawing group in the main chain prevents the side chain substituent from forming an ionic bond with the metal ion derived from the A component. Due to steric hindrance, it is difficult for the substituents in the main chain to form a stable crosslinked structure with the metal ion. It is difficult to obtain high remoldability, and flexibility tends to be low.
  • the main chain of the B component is preferably an olefin-based polymer or a styrene-based polymer. Then, the formation of cross-linking points in the side chains of component B and the movement of those cross-linking points are less likely to be affected by the main chain, and the high heat resistance and re-moldability brought about by these phenomena in the side chain portions are advantageous for the material. It is effectively exhibited as an overall characteristic.
  • the crosslinkable polymer composition preferably contains 0.1 parts by mass or more and 30 parts by mass or less of the A component, with the total of the A component and the B component being 100 parts by mass. Then, by containing a sufficient amount of component A, the crosslink density is increased, and the crosslinkable polymer composition becomes excellent in crosslinkability. On the other hand, it is easy to avoid the influence of containing a large amount of component A in the material before and after cross-linking.
  • the crosslinked polymer material according to the present disclosure includes a crosslinked body of the crosslinkable polymer composition according to the present disclosure, which is configured as a crosslinked body in which the B component is crosslinked by the metal ions liberated from the A component.
  • the cross-linked body formed by cross-linking the B component via the metal ions released from the A component has a cross-linking point at the position of the electron-withdrawing substituent introduced into the side chain of the B component, and at 190° C. or higher. Since it has a flow initiation temperature in the range of 300° C. or less, the crosslinked polymer material has both high heat resistance and remoldability by heating. In addition, it becomes a material having high flexibility.
  • An insulated wire according to the present disclosure includes a wire conductor and an insulating coating that is composed of the crosslinked polymer material according to the present disclosure and covers the outer circumference of the wire conductor.
  • the insulating coating is made of the crosslinked polymer material according to the present disclosure, so that it exhibits high heat resistance, and even if the wire conductor heats up when energized, it does not deform irreversibly. unlikely to occur.
  • the insulating coating is heated to a sufficient temperature, the insulating coating can be re-fluidized and reshaped to change the shape of the insulating coating. For example, when the wire conductor is deformed, the insulating coating also follows the shape of the wire conductor, making it easier to deform.
  • the electric wire conductor is formed by twisting a plurality of strands, and the insulated electric wire has a flat portion in which a cross section of the electric wire conductor perpendicular to the axial direction has a flat shape.
  • An electric wire having a flat portion is required from the viewpoint of space saving.
  • the flat part can be easily formed by applying a force to compress the insulating coating into a flat shape while the insulating coating is heated to a normal insulated wire with a circular cross section by utilizing the re-moldability of the insulating coating. can do.
  • the electric wire can be made to have a different cross-sectional shape such as a circular cross-section. Insulated wires can be deformed.
  • an insulated wire comprising a wire conductor that is made by twisting a plurality of strands and is easily deformed by the application of force, and an insulating coating that can be reversibly reshaped by heating.
  • deformation between a low flatness state such as a circular cross section and a flat state can be easily performed in both directions.
  • a common insulated wire it is possible to obtain a variety of insulated wires that are deformed into a desired shape such as a flat shape or the like depending on the routing location or application.
  • a wire harness according to the present disclosure includes the insulated wire according to the present disclosure. Since the insulated wire according to the present disclosure has an insulating coating with excellent heat resistance and re-moldability as described above, these characteristics can also be used in wire harnesses.
  • crosslinkable polymer composition and crosslinked polymer material The crosslinkable polymer composition according to the embodiment of the present disclosure includes component A from which metal ions are released by heat, and metal ions and ions released from component A. and a B component composed of an organic polymer having an electron-withdrawing substituent capable of forming a bond on the side chain.
  • the crosslinkable polymer composition according to the present embodiment is heated to form a crosslinked body in which the B component is crosslinked by the metal ions liberated from the A component, thereby forming the crosslinked polymer material according to the embodiment of the present disclosure.
  • the crosslinked body has a flow initiation temperature of 190°C or higher and 300°C or lower.
  • the crosslinkable polymer composition according to this embodiment contains an A component from which metal ions are liberated by heat, and a B component having a substituent capable of forming an ionic bond with the metal ions.
  • a component from which metal ions are liberated by heat contains metal ions and a B component having a substituent capable of forming an ionic bond with the metal ions.
  • metal ions are liberated from the A component.
  • FIG. 1A the liberated metal ions form ionic bonds with the substituents of component B, and the organic polymer chains of component B are crosslinked via the ionic bonds.
  • FIG. 1A the liberated metal ions form ionic bonds with the substituents of component B, and the organic polymer chains of component B are crosslinked via the ionic bonds.
  • a divalent metal ion M 2+ is assumed as the metal ion, and a carboxylic acid group (COO ⁇ ) in an anionic state is assumed as the substituent of the B component. are doing.
  • a polymer chain of the B component is indicated by a broken line.
  • the A component liberates metal ions by heat, and until the A component reaches a temperature at which the A component releases metal ions due to decomposition or phase transition, the release of metal ions from the A component does not occur, and ionic bonds are formed.
  • Crosslinking of the organic polymer of the B component does not proceed. Therefore, the crosslinkable polymer composition according to the present embodiment is in a state of relatively high fluidity at a low temperature at which metal ions are not liberated from the A component and the resulting crosslinking of the B component does not occur, and is extruded. etc., it can be easily molded into a desired shape.
  • the metal ions are liberated from the A component by heating, and the B component is crosslinked to form a crosslinked body.
  • the adjacent polymer chains of the B component are crosslinked, so that the heat resistance is improved compared to the state before crosslinking.
  • the organic polymer chains of the B component are crosslinked via ionic bonds, and the bonding force is stronger than the van der Waals force, effectively enhancing the heat resistance and mechanical toughness of the crosslinked product. It will improve.
  • the crosslinkable polymer composition according to the present embodiment forms a crosslinked polymer material having high heat resistance because the flow initiation temperature of the formed crosslinked body is 190°C or higher.
  • the crosslinked polymeric material formed through crosslinking is less likely to cause an increase in fluidity and accompanying irreversible deformation at a temperature of 190° C. or less.
  • a heat resistance temperature of 190° C. is generally desired for insulating coatings of insulated wires for automobiles, and the crosslinkable polymer composition according to the present embodiment, as described in detail later, It can be suitably used to form an insulation coating for insulated wires for automobiles.
  • the flow initiation temperature of the crosslinked body is preferably 200° C. or higher, more preferably 220° C. or higher.
  • the flow initiation temperature of the crosslinked body and the B component described later refers to the temperature at which the material begins to exhibit fluidity when the solid material is heated. can be measured as the temperature at which the indenter can penetrate the material. Alternatively, the material's melting point or pour point (whichever is lower if it has both) can be considered the flow initiation temperature.
  • the crosslinked structure between the polymer chains of the B component is not an irreversible covalent bond formed in the case of electron beam crosslinking or silane crosslinking, Since it is formed by ionic bonds with metal ions, which are reversible bonds, the formed crosslinked polymeric material has remoldability.
  • the crosslinked polymer material becomes fluid again, and can be molded into a shape different from that before heating by applying an external force or the like.
  • crosslinked polymer materials can be explained by the following mechanism.
  • the cross-linked product obtained by cross-linking the polymer chains of component B with metal ions is not heated, at room temperature or in a state close to it, as shown in FIG. , is localized at a certain position.
  • the molecular motion of the B component becomes active due to heat, and as shown in FIG. Vigorous thermal motion also occurs in the vicinity.
  • the crosslinked body is further heated to a high temperature, the molecular motion of the B component is further activated, and the crosslinked point via the metal ion can move to a nearby different site (position of another substituent), Cross-linking points are delocalized.
  • one metal ion is simultaneously coordinated with multiple substituents in the same molecular chain of component B (multiple substituents). sitting).
  • Activation of thermal motion in the B component and subsequent movement of the cross-linking point enable the cross-linked body to flow.
  • the crosslinked polymeric material can be reshaped by appropriately applying an external force to the material.
  • Activation of thermal motion of crosslinked sites and delocalization of crosslinked points are reversible phenomena.
  • the reshaped crosslinked polymer material is cooled, the localized state of the crosslinked points is restored and thermally returns to a stable crosslinked state. By repeating heating and cooling, the crosslinked polymeric material can be repeatedly reshaped.
  • Activation of the thermal motion of the cross-linking site and delocalization of the cross-linking site by heating can be confirmed by, for example, an infrared absorption spectrum.
  • the absorption peak broadening of the substituents forming the structure and the delocalization of the cross-linking points appear on the spectrum as the growth of new peaks corresponding to the polydentation.
  • the substituent capable of forming an ionic bond with a metal ion is contained in the side chain instead of the main chain of the polymer.
  • a crosslinked structure is formed via ions, a high degree of freedom of movement can be obtained at the crosslinked sites. Therefore, in the crosslinked body, the thermal motion of the crosslinked sites and the movement of the crosslinked points are likely to occur particularly actively. Therefore, the crosslinked polymeric material exhibits high remoldability when heated. In addition, the crosslinked polymer material has high flexibility.
  • the flow initiation temperature of the formed crosslinked body is suppressed to 300°C or less, so that if the crosslinked polymer material is heated up to 300°C at most, , remolding becomes possible, and remolding can be performed easily.
  • the flow initiation temperature of the crosslinked body is preferably 280° C. or lower, more preferably 250° C. or lower.
  • the crosslinkable polymer composition according to the present embodiment includes an A component that liberates metal ions by heat and a B component that includes a substituent capable of forming an ionic bond with the metal ion in the side chain.
  • the crosslinked body obtained by cross-linking the B component with the metal ions liberated from the A component has a flow initiation temperature in the range of 190° C. or higher and 300° C. or lower, thereby achieving both high heat resistance and remoldability.
  • a crosslinked polymeric material is provided. Therefore, the crosslinkable polymer composition is formed into a desired shape by extrusion molding or the like, and then crosslinked to obtain a crosslinked polymer material having high heat resistance, while the crosslinked polymer material is heated again.
  • the remoldability can be utilized. Since the crosslinkable polymer composition according to the present embodiment has the above properties, it can be used as a member that is required to have high heat resistance, such as an insulating coating for an insulated wire, and is advantageous because of its remoldability. It can be preferably used to configure Furthermore, as another index indicating that the heat resistance improvement effect due to crosslinking is sufficiently manifested in the crosslinked polymer material, the flow initiation temperature of the crosslinked polymer material is 5°C or higher than the flow initiation temperature of the B component alone. , and more preferably 10° C. or higher.
  • the movement of the crosslinked sites and the delocalization of the crosslinked points described above as the behavior when the crosslinked body is heated can occur to some extent even at relatively low temperatures such as room temperature.
  • the motion of the cross-linked sites and the delocalization of the cross-linked sites at relatively low temperatures reduce the elastic modulus of the cross-linked polymer material and increase the flexibility. Therefore, the crosslinked polymer material according to the present embodiment can maintain high flexibility even after cross-linking, unlike general cross-linked polymer materials subjected to electronic cross-linking or silane cross-linking. Since the crosslinked polymer material obtained through crosslinking has high flexibility, it can be suitably used for constructing members that are frequently bent, such as insulating coatings of insulated wires.
  • the tensile elastic modulus of the crosslinked polymer material is preferably 30 MPa or less, or preferably 20 MPa or less.
  • the tensile modulus of the crosslinked polymeric material does not increase by more than 30% compared to the tensile modulus of the B component that is not crosslinked. Furthermore, it is preferable not to increase by 20% or more.
  • the crosslinked body flows within a predetermined range. Having an onset temperature is important.
  • the flow initiation temperature of the crosslinked product is determined by the type of metal ions liberated from the A component, the polymeric main chain and side chains of the B component, the type and structure of the substituents, the ratio of the A component to the B component, and the like. Preferred structures and properties of each component are described below in order.
  • Component A is a component that liberates metal ions by heat. By heat, it is assumed to heat, and assumes a temperature higher than room temperature. Liberation of metal ions means release of metal ions from the A component due to decomposition or phase transition of the A component. Metal ions liberated from the A component cause cross-linking of the B component.
  • the A component preferably has a decomposition point or phase transition point of 50°C or higher. Then, during the preparation of the crosslinkable polymer composition and before the use of the crosslinkable polymer composition (before cross-linking), the liberation of metal ions from the A component is likely to be suppressed, and the progress of the cross-linking of the B component is suppressed. As a result, the crosslinkable polymer composition has excellent storage stability. That is, at a low temperature such as less than 50 ° C., when the A component and the B component are mixed to prepare a crosslinkable polymer composition, when the prepared crosslinkable polymer composition is stored, or by extrusion molding etc.
  • component A has a decomposition point or phase transition point of 60° C. or higher, or 70° C. or higher, the effect of improving storage stability is further enhanced.
  • the A component preferably has a decomposition point or phase transition point at 300°C or lower. Then, at a temperature lower than the temperature at which metal ions are liberated from the A component, the B component is unlikely to be degraded, and the undegraded B component is easily crosslinked by the metal ions. In addition, when the A component decomposes or undergoes a phase transition at an appropriate temperature, metal ions are easily released from the A component, and the crosslinkable polymer composition has an excellent crosslinking rate. From these points of view, the A component more preferably has a decomposition point or phase transition point at 200° C. or lower, further 150° C. or lower, or 120° C. or lower.
  • the A component preferably has a decomposition point or a phase transition point at a temperature equal to or higher than the flow initiation temperature of the B component, which will be described later. Then, at the temperature at which the A component liberates metal ions, the crosslinking of the B component by the metal ions liberated from the A component can proceed while the B component has already acquired fluidity. Therefore, by utilizing the flow of the B component, the cross-linking can proceed in a state in which the metal ions are well dispersed in the B component. It becomes easy to obtain a crosslinked polymeric material with high uniformity.
  • the A component has a decomposition point or a phase transition point at a temperature higher than the flow initiation temperature of the B component, and the A component is 10°C or more higher than the flow initiation temperature of the B component. It is preferable that the temperature has a decomposition point or a phase transition point.
  • the decomposition point or phase transition point of component A is represented by the baseline change start temperature by differential scanning calorimetry (DSC) (measurement temperature range: 25° C. to 200° C., measured in air).
  • phase transition point does not include the melting point, and the phase transition does not include melting. If the A component has both a phase transition point and a decomposition point, or if it has a plurality of phase transition points, the lower one (the lowest one) shall be treated as the "decomposition point or phase transition point". do.
  • the metal species of the metal ion liberated from component A is not particularly limited, but alkaline earth metals, aluminum, zinc, titanium, zirconium, etc. can be suitably used.
  • the metal ions liberated from the A component are preferably ions of at least one of these metals.
  • the ions of these metals have a valence of 2 or more, and by forming an ionic bond with the substituent of the B component, it is easy to form a stable crosslinked structure between the polymer chains of the B component.
  • the metals listed above belong to hard acids according to the HSAB rule, and are metals with a relatively high ionization tendency. It is suitable as a metal for constructing the body.
  • the metal ions liberated from the A component are preferably ions of at least one of aluminum and zirconium.
  • the A component containing aluminum or zirconium has a certain degree of high stability, and when mixed with the B component, the formation of a crosslinked structure does not proceed easily, and the crosslinkable polymer composition exhibits high storage stability. will give.
  • the metal ions are released relatively easily to form a crosslinked product.
  • the phase transition initiation temperature of zirconium (IV) acetylacetonate (Zr-AA) is 180° C., which is a high temperature among various acetylacetonate complexes.
  • the phase transition start temperature (DSC baseline change start temperature) is not so high at 112°C, but this compound is said to undergo a gradual change in the amount of heat from the start of the phase transition.
  • a characteristic and significant change in calorific value occurs around 170°C. That is, at a relatively high temperature around 170° C., the phase transition progresses remarkably.
  • the flow initiation temperature of the crosslinked product becomes higher than when titanium is used, for example, and the crosslinked polymer material is , excellent in heat resistance.
  • titanium aluminum and zirconium are not easily oxidized, and thus the existence of oxidation pathways is unlikely to reduce the efficiency of the cross-linking reaction.
  • aluminum and zirconium are not as hard as alkaline earth metals as acids compared to alkaline earth metals such as calcium, so they can be dispersed more uniformly in the B component.
  • aluminum and zirconium tend to have a higher decomposition temperature of component A formed in the form of a metal complex or the like, and provide higher storage stability.
  • the metal species contained in the crosslinkable polymer composition is the main component of the metal member. If it is the same as the metal species, the influence caused by the presence of the metal member on the formation and stable maintenance of the crosslinked structure at the interface between the metal member and the polymer material can be easily suppressed.
  • the metal ions liberated from the component A are replaced with aluminum should be set as
  • the B component is crosslinked by forming an ionic bond with the substituent of the B component, and the flow initiation temperature is 190 ° C. or higher and Any metal ion that can be liberated from the A component can be applied as long as it can give a crosslinked product at 300° C. or lower.
  • transition metals such as iron, nickel, and copper tend to give a crosslinked body with a flow initiation temperature higher than the above range.
  • the metal ions liberated from component A may be not only monoatomic ions of metal, but also polyatomic ions (metal-containing ions) in which metal atoms and other atoms are combined. However, from the viewpoint of forming a stable ionic bond with the substituent of component B, it is preferably a monoatomic metal ion.
  • the A component may be any chemical species as long as it liberates metal ions by heat, but a metal complex can be mentioned as a suitable chemical species.
  • a metal complex is composed of a central metal ion coordinated with a ligand having a lone pair of electrons. When using a metal complex, the effect of stabilizing the metal ion by the ligand is excellent, and the crosslinkable polymer composition is desired during preparation of the crosslinkable polymer composition or before use of the crosslinkable polymer composition. In addition, when the crosslinkable polymer composition is crosslinked, metal ions are easily liberated from the A component by heat.
  • Ligands constituting the metal complex include monodentate ligands having one coordination site and multidentate ligands having two or more coordination sites.
  • Metal complexes formed by multidentate ligands are metal complexes formed by monodentate ligands and metal formed by ligands with bridged coordination structures such as alkoxide ligands due to the chelate effect. They are more stable than complexes. Therefore, the A component is preferably a metal complex containing a polydentate ligand. Coordination by multidentate ligands is more effective in stabilizing metal ions than coordination by monodentate ligands or ligands with a cross-linked coordination structure. Liberation of metal ions from the A component is more effectively suppressed during preparation of the composition, before use of the crosslinkable polymer composition, and during molding.
  • ⁇ -diketonato ligands (1,3-diketonato ligands), which are bidentate ligands, can be preferably used.
  • a ⁇ -diketonato ligand is particularly effective in stabilizing metal ions.
  • the metal complex having a ⁇ -diketonato ligand is easily dispersed well in the organic polymer, it is suitable for dispersing the A component in the B component and forming the cross-linking points with high uniformity.
  • the ⁇ -diketonato ligand is represented by the following general formula (1).
  • R 1 and R 2 each independently represent a hydrocarbon group
  • R 3 represents a hydrogen atom or a hydrocarbon group.
  • the ligand may take the structure of formula (1) due to the resonance structure.
  • R 1 , R 2 and R 3 may be aliphatic hydrocarbon groups or hydrocarbon groups containing aromatic rings. In addition, it may contain a heteroatom such as an oxygen atom.
  • hydrocarbon groups constituting R 1 , R 2 and R 3 include alkyl groups, alkoxy groups, aromatic groups and condensed aromatic groups. Although the number of carbon atoms in R 1 , R 2 and R 3 is not particularly limited, it is preferably 1 or more and 8 or less.
  • Specific ⁇ -diketonato ligands include acetylacetonato ligand (acac), 2,2,6,6-tetramethyl-3,5-heptanedionato ligand (dpm), 3-methyl-2 ,4-pentadionato ligand, 3-ethyl-2,4-pentadionato ligand, 3,5-heptanedionato ligand, 2,6-dimethyl-3,5-heptanedionato ligand, 1,3-diphenyl -1,3-propanedionato ligands and the like.
  • acetylacetonato ligands in which R 1 and R 2 are methyl groups and R 3 is a hydrogen atom in the above formula (1) are particularly preferable from the viewpoint of structural simplicity.
  • the content of component A is preferably 0.1 parts by mass or more, with the total of component A and component B being 100 parts by mass. Then, since the A component is contained in a sufficiently large amount with respect to the B component, the crosslinked product has a high crosslink density and is highly effective in improving heat resistance. From the viewpoint of enhancing the effect of improving heat resistance, the content of component A is more preferably 1.0 parts by mass or more, more preferably 2.0 parts by mass or more per 100 parts by mass. On the other hand, the content of component A is preferably 30 parts by mass or less per 100 parts by mass.
  • the content of component A is more preferably 20 parts by mass or less, more preferably 10 parts by mass or less per 100 parts by mass.
  • Component B is a component composed of an organic polymer having a side chain, and the side chain contains an electron-withdrawing substituent capable of forming an ionic bond with a metal ion liberated from Component A. I'm in. Even if the substituent is not necessarily electron-withdrawing, it can form an ionic bond with the metal ion liberated from the A component. It can form stable ionic bonds. Therefore, in the crosslinkable polymer composition, when component B is crosslinked with metal ions, a crosslinked structure is stably formed, and the crosslinked product tends to exhibit high heat resistance.
  • Suitable examples of electron-withdrawing substituents capable of forming ionic bonds with metal ions include acidic groups other than hydroxyl groups, such as carboxylic acid groups, acid anhydride groups, and phosphoric acid groups.
  • the number of substituents may be one, or two or more, and preferably at least one of the substituents listed above.
  • an acid anhydride group such as a maleic anhydride group can be preferably employed.
  • the substituents listed above are excellent in that they easily form ionic bonds with metal ions liberated from the A component.
  • substituents listed above are acidic groups with relatively low polarity, phase separation is unlikely to occur with respect to the main chain and side chains of the B component, and in the structure of the B component, It has high uniformity and can form a crosslinked structure.
  • a sulfonic acid group is also an electron-withdrawing substituent that easily forms an ionic bond with a metal ion. It cannot be suitably employed as a substituent of the B component.
  • the substituents that form ionic bonds with metal ions are contained in the side chains rather than in the main chain of the polymer. Maintain freedom of movement. As a result, the polymer material after cross-linking has high remoldability and excellent flexibility.
  • the structure and length of the side chain are not particularly limited, but from the viewpoint of enhancing their effects, a substituent is bound to the main chain via an alkyl group or alkylene group having 1 or more carbon atoms. Good to have.
  • the substituent may be attached to the main chain through a heteroatom such as an oxygen atom.
  • the substituent may be introduced at the end of the side chain or at the intermediate portion, but is preferably introduced at the end from the viewpoint of effectively increasing the degree of freedom of movement of the crosslinked portion.
  • the upper limit of the number of carbon atoms in the side chain is not particularly limited, but from the viewpoint of minimizing the influence of the main chain on physical properties, the number of carbon atoms connecting the main chain and the substituent is preferably 4 or less.
  • the substituents are a carboxylic acid group and a phosphoric acid group, particularly preferred side chain structures are represented by the following formulas (2) and (3), respectively.
  • R4 is the main chain
  • R5 is an oxygen atom or an alkyl group having 1 or more carbon atoms or an alkylene group
  • R6 is an alkyl group or alkylene group having 1 or more carbon atoms.
  • Multiple electron-withdrawing substituents may be attached to the backbone via a common R5 or R6 .
  • an anhydride may be formed by a plurality of electron-withdrawing substituents.
  • the electron-withdrawing substituent may be included in the side chain, may be included in the main chain, or may not be included in the main chain.
  • the backbone preferably does not contain electron-withdrawing groups. This is because if an electron-withdrawing group is contained in the main chain, it may prevent the electron-withdrawing group in the side chain from forming a crosslinked structure through an ionic bond with a metal ion. Since the electron-withdrawing group in the main chain is likely to undergo large steric hindrance, it is difficult to effectively contribute to cross-linking through the formation of ionic bonds with metal ions, and the effect of cross-linking to improve heat resistance is poor.
  • electron-withdrawing groups that should not be contained in the main chain of component B include a carbonyl group when the main chain is composed of a copolymer of (meth)acrylic acid, and an ester structure such as a vinyl acetate main chain.
  • a hydrolyzable group, a halogen atom, etc. in the case of containing can be mentioned.
  • the content of the substituent contained in the side chain is not particularly limited, but from the viewpoint of ensuring physical properties by crosslinking, etc., it is 0.01% by mass or more with respect to the total mass of component B. % or less is preferable. It is more preferably 0.1% by mass or more and 5% by mass or less, and still more preferably 0.2% by mass or more and 3% by mass or less.
  • the content of the above substituents in component B can be determined by comparing the size of the peak specific to the substituent in the infrared absorption spectrum with the size of the spectral peak of a material with a known content.
  • the organic polymer of component B is an organic polymer such as resin, rubber, or elastomer.
  • the B component is composed of a thermoplastic resin or elastomer.
  • the main chain of component B is preferably configured as an olefin polymer.
  • the olefin-based polymer may be a homopolymer such as polyethylene or polypropylene, or a copolymer such as an ethylene- ⁇ -olefin copolymer.
  • a form in which the main chain of component B is configured as a styrenic polymer such as a hydrogenated styrenic thermoplastic elastomer (SEBS) is also preferred.
  • SEBS hydrogenated styrenic thermoplastic elastomer
  • elastomers having main chains of polyurethane, polyester, and polyamide can be exemplified as organic polymers that can be applied as the B component.
  • the main chain having these structures is less likely to affect the formation of cross-linking points in the side chains, the activation of molecular motion at the cross-linking sites by heating, and the movement of the cross-linking points.
  • High heat resistance, remoldability, and flexibility are effectively exhibited as the overall characteristics of the crosslinked product of the B component.
  • the main chain of component B is composed of an olefinic polymer, these effects are highly obtained.
  • the B component preferably has a flow start temperature in the range of 50°C or higher and 190°C or lower. Then, a crosslinked product having a flow initiation temperature of 190° C. or more and 300° C. or less is likely to be obtained through crosslinking by metal ions liberated from the A component. In addition, high moldability can be obtained when the crosslinkable polymer composition before crosslinking is molded into a desired shape by extrusion molding or the like. More preferably, component B has a flow initiation temperature of 80°C or higher and 160°C or lower.
  • the hardness of the B component is kept low.
  • the Shore D hardness of the B component measured according to JIS K6253 is preferably less than 50.
  • the crosslinked polymer material containing the crosslinked body can be suitably used for forming a member that requires bending, such as an insulating coating for an insulated wire. More preferably, the D hardness of the B component is 45 or less, or 40 or less.
  • the lower limit of the D hardness of the B component is not particularly set, but from the viewpoint of ensuring the strength of the material, it is preferable to set it to, for example, 10 or more, or even 20 or more.
  • the crosslinkable polymer composition according to the present embodiment contains additives such as a flame retardant, a copper damage inhibitor, an antioxidant, and a coloring agent in addition to the above components A and B within a range that does not interfere with the function of the material. It may be included as appropriate. Further, as a polymer component, a polymer other than the B component may be contained, but the content thereof is preferably suppressed to be less than the content of the B component. More preferably, the crosslinkable polymer composition contains only the B component as a polymer component. Furthermore, the following compounds (a) to (f) can be mentioned as components that should not be included in the crosslinkable polymer composition.
  • silane coupling agent (b) epoxy compound, (c) isocyanate, isothiocyanate compound, (d) photoradical generator, thermal radical generator, (e) chlorine compound, bromine compound, (f) Volatile organic solvents may be mentioned.
  • the compounds of groups (a) to (d) when contained in the crosslinkable polymer composition, when heated, the B component is crosslinked by a reaction other than the crosslinking reaction mediated by the metal ions liberated from the A component, and the B component is crosslinked. Unintended chemical reactions may occur, such as cleavage of the backbone of the component. As a result, the heat resistance and remoldability of the crosslinkable polymer composition may not be exhibited sufficiently.
  • the compound of group (e) when the compound of group (e) is contained in the crosslinkable polymer composition, heating may cause coloring or generation of corrosive gas. If the compound of group (f) is contained in the crosslinkable polymer composition, ignition or air bubbles may occur during molding of the composition.
  • the crosslinkable polymer composition can be prepared by mixing the A component, the B component, and additional components added as necessary. Mixing may be performed, for example, by heating and kneading each component, or by dissolving each component in an organic solvent and heating and stirring. Moreover, when using a crosslinkable polymer composition, the crosslinkable polymer composition may be appropriately heated and then molded into an arbitrary shape by extrusion molding or the like. At this time, the heating temperature should be higher than the flow initiation temperature of the B component and lower than the temperature at which the A component liberates metal ions by decomposition or phase transition.
  • component B is crosslinked by the metal released from component A, resulting in a crosslinked product. It becomes a crosslinked polymer material containing. Then, if the formed crosslinked polymer material is heated to a temperature equal to or higher than the flow initiation temperature of the crosslinked body, the crosslinked polymer material acquires fluidity and can be remolded. Reshaping can be reversibly repeated. Since the crosslinkable polymer composition according to the present embodiment can form a crosslinked structure only by heating, the crosslinking process can be performed with simple equipment compared to the case of using electron beam crosslinking or silane crosslinking. can be implemented. The remolding process can also be performed by applying an appropriate external force while heating, and thus can be performed with simple equipment.
  • the crosslinked polymer material formed from the crosslinkable polymer composition according to the present embodiment can be used to construct any member. However, by utilizing its high heat resistance, re-moldability, and flexibility, it can be suitably used as a constituent material for insulated wires and wire harnesses for automobiles and the like. In insulated wires and wire harnesses, heat generation is likely to occur when metal members such as wire conductors are energized, and polymeric materials placed near these metal members do not undergo irreversible deformation when heated. such as high heat resistance is required. In addition, there are cases where it is required to re-mold a polymer material that has been once molded into a predetermined shape due to requests such as deformation of insulated wires and changes in the configuration of wire harnesses.
  • the specific locations to which the crosslinked polymer material according to the embodiment of the present disclosure is applied are not particularly limited, and the insulating coating covering the outer circumference of the wire conductor of the insulated wires, the wire An exterior material for bundling a plurality of insulated wires in a harness, a wire protection material, and the like can be mentioned.
  • a form in which the insulating coating of the insulated wire is composed of the crosslinked polymer material according to the embodiment of the present disclosure is preferable.
  • FIG. 2 An example of the insulated wire according to the embodiment of the present disclosure is shown in FIG. 2 in a cross section perpendicular to the axial direction.
  • the insulated wire 1 shown in FIG. 2 has a wire conductor 2 and an insulating coating 3 covering the outer periphery of the wire conductor 2 .
  • the configuration of the electric wire conductor 2 is not particularly limited, it is configured as a twisted wire conductor in which a plurality of strands 21 are twisted together.
  • the insulated wire 1 is configured to have a flat portion, and the cross section of the wire conductor 2 has a flat shape (a shape elongated in the width direction).
  • the insulating coating 3 is composed of the crosslinked polymeric material according to the embodiments of the present disclosure described above.
  • the insulating coating 3 also has a flat cross-sectional shape that follows the shape of the wire conductor 2 .
  • the insulating coating 3 In the insulated wire 1, heat is generated when the electric wire conductor 2 is energized, and the insulating coating 3 is also heated. and has high heat resistance. Therefore, if the temperature is 190° C. or less, for example, even if the insulating coating 3 is heated, the influence of heat such as irreversible deformation is unlikely to occur.
  • the insulated wire 1 has a flat portion, so that the space required for wiring can be reduced and space saving can be improved.
  • the insulated wire 1 having a flat portion is replaced with a conventional insulated wire having a substantially circular cross section (round wire) by utilizing the fact that the crosslinked polymer material constituting the insulating coating 3 has remoldability.
  • a round wire having an insulating coating 3 made of a crosslinked polymer material that has been crosslinked according to the embodiment of the present disclosure is heated to a temperature at which the crosslinked body starts to flow, and a compressive force is applied in one direction. By doing so, the flat portion can be easily formed.
  • the wire conductor 2 is configured as a stranded wire conductor, it can be easily deformed by the application of force, and the insulating coating 3 is also in a fluid state by heating, so that the wire conductor 2 is deformed. This is because it can be easily deformed by following the .
  • the insulating coating 3 is allowed to cool to return to the original stable crosslinked state.
  • the insulating coating 3 is heated to a temperature equal to or higher than the flow start temperature of the cross-linking body, and a force is applied so as to compress the flat portion from both sides in the width direction. It can be returned to a shape, or a less flattened shape close to it. Also in this case, the insulating coating 3 is deformed into a shape having a low degree of flatness following the deformation of the electric wire conductor 2 .
  • the insulated wire 1 can be formed into any shape, such as bi-directional deformation between a flat cross-sectional shape and a substantially circular cross-sectional shape. Deformation can be easily performed while deforming the insulating coating 3 following the wire conductor 2 .
  • a common electric wire as a raw material it is possible to produce various insulated electric wires having flat portions at different locations.
  • the insulated wire may be used alone, or may be used in the form of a wire harness including an insulated wire by connecting a member such as a connection terminal or bundling it with another insulated wire.
  • sample preparation and evaluation were performed at room temperature in air.
  • ⁇ Ca-AA Calcium (II) acetylacetonate (110°C) ⁇ Zn-AA: Zinc (II) acetylacetonate (105°C) ⁇ Al-AA: Aluminum (III) acetylacetonate (112°C) ⁇ Zr-AA: Zirconium (IV) acetylacetonate (180°C) ⁇ Ti-AA: Titanium (IV) acetylacetonate (125°C) ⁇ TiO-AA: Titanium (IV) oxyacetylacetonate (158°C) ⁇ Cu-AA: Copper (II) acetylacetonate (205°C) ⁇ Ni-AA: nickel (II) acetylacetonate (200°C) ⁇ Li-AA: Lithium ace
  • Flow start temperature A test piece of 10 mm x 10 mm x 2 mmt was prepared using the above sample sheet. This test piece was placed on a temperature-variable hot plate, and a 2 mm ⁇ cylindrical indenter with a dial gauge attached to the top was pressed against the center of the test piece with a force of 1N. The distance that the indenter penetrated into the sample was recorded while the temperature of the hot plate was increased at a rate of 5° C./min.
  • the temperature when the penetration of the indenter reached 2.0 mm (when it penetrated) was taken as the flow start temperature. It can be considered that the samples whose flow initiation temperature is 5° C. or more higher than that of the B component, which does not contain the A component, have undergone cross-linking by metal ions and have improved heat resistance.
  • Samples A1 to A10 are raw materials, A component from which metal ions are liberated by heat, and organic high molecular weight organic compounds containing electron-withdrawing substituents capable of forming ionic bonds with metal ions in side chains.
  • a sample sheet obtained by cross-linking at the time of press molding, which contains the B component composed of molecules, has a flow initiation temperature of 190° C. or more and 300° C. or less.
  • the flow start temperature of these samples A1 to A10 is higher than the flow start temperature of the B component by 5° C. or more, and it can be said that high heat resistance is obtained by cross-linking.
  • the molding temperature of general thermoplastic resins is about 300° C.
  • the samples A1 to A10 have a flow initiation temperature of 300° C. or less, it can be said that they have high re-moldability.
  • the elastic modulus is suppressed to 30 MPa or less, and the increase rate of the tensile elastic modulus of the B component that has not undergone cross-linking is less than 30%, and each sample maintains high flexibility even after cross-linking. ing.
  • samples B1 to B3, B12, and B13 did not contain the A component, and the flow initiation temperature was lower than 190°C, corresponding to the fact that the cross-linking of the B component by metal ions could not proceed.
  • Samples B4 and B5 use zinc oxide and calcium stearate, respectively, as the A component instead of a metal complex. These compounds do not liberate metal ions even when heated, so they cannot crosslink the B component.
  • the flow start temperature of samples B4 and B5 is also much lower than 190° C., which is almost the same as that of sample B1.
  • the B component does not have a substituent capable of forming an ionic bond with a metal ion, and the metal ion derived from the A component cannot form a crosslinked structure in the B component.
  • the flow initiation temperature is much lower than 190° C., which is almost the same as that of sample B1.
  • Sample B7 has a carboxylic acid group, which is an electron-withdrawing group, in the polymer main chain of component B, but does not have an electron-withdrawing substituent in the side chain.
  • a carboxylic acid group in the main chain cannot effectively form a crosslinked structure via an ionic bond with a metal ion due to steric hindrance of adjacent methacryloyl groups.
  • the flow initiation temperature is much lower than 190°C.
  • the degree of freedom of movement of the crosslinked portion is considered to be low, and correspondingly, the elastic modulus is also high.
  • the flow start temperature is below 190°C. This is probably because the metal contained in the A component is lithium, which is a monovalent metal, and a stable crosslinked structure cannot be formed in the B component.
  • the flow start temperature exceeds 300°C. This is because copper and nickel, which are metals with a large number of possible oxidation numbers and relatively low ionization tendency, are used as the metal of the A component, and when the crosslinked body is heated, the crosslink point moves. It is thought that this is because it is difficult to cause fluidization due to Furthermore, in these samples, due to the low fluidity of the crosslinked body, it was not possible to produce a sample sheet for measuring the elastic modulus by press molding. If the temperature during press molding is increased further, partial decomposition of the B component begins, resulting in significant discoloration and deterioration.
  • the A component is configured as a metal complex, but the titanium atoms are in the state of TiO(II), and heat liberates TiO 2+ ions.
  • the substituents on the side chains of component B cause cross-linking. ing.
  • the reason why a strong ionic bond is not formed is considered to be that the three-dimensional structure of the metal coordination state of the cross-linked site becomes bulky and the molecular aggregation density of the cross-linked site becomes low.
  • samples A1 to A10 are compared with each other.
  • Samples A1 to A4 and A9 differ in the type of metal contained in the A component.
  • the flow start temperature of sample A9 is lower than the flow start temperature of the other samples, and is exactly 190°C. It has become. This is probably because even if titanium ions are liberated from the A component, they are easily oxidized and become in a state of low activity, making it difficult to increase the cross-linking efficiency.
  • calcium, zinc, aluminum, and zirconium contained in component A contribute to the formation of a crosslinked structure in component B while free metal ions remain highly active.
  • samples A1 to A4 which contain aluminum and zirconium as the A component, have particularly high flow initiation temperatures exceeding 230°C. In other words, it can be said that particularly high heat resistance can be obtained in the crosslinked product if a component that liberates aluminum or zirconium ions is used as the A component.
  • sample A1 in which component A contains calcium, which is an alkaline earth metal, slight non-uniformity was observed when component A and component B were kneaded.
  • the sample A2 containing zinc in the A component has a higher flow start temperature than the samples A3 and A4 due to the fact that the phase transition start temperature of the A component is lower than that of the samples A3 and A4. It is considered that it will not be possible.
  • the type of B component is different in each of the set of samples A1, A5, A10 and the set of samples A2, A6. Comparing each set of samples with each other, it is found that the main chain of the olefin-based polymer is used rather than the samples A1, A10 and A2, which use the styrene-based polymer of the main chain as the B component. In Samples A5 and A6, the range of increase in flow initiation temperature due to cross-linking is large. In other words, it can be seen that the use of component B whose main chain is an olefin-based polymer is highly effective in improving heat resistance due to the formation of a crosslinked structure via metal ions.
  • sample A10 Comparing sample A1 and sample A10, both of which use component B whose main chain is a styrene-based polymer, sample A10 has a higher flow initiation temperature. This is presumably because MAHA-SBBS used as the B component in sample A10 is slightly amine-modified and contains an inner salt domain in the polymer chain.
  • Samples A1, A7, and A8 differ from each other in the content of component A within the range of 0.1 to 30 parts by mass with respect to the total of 100 parts by mass of components A and B.
  • a flow initiation temperature of 190° C. or higher and 300° C. or lower is obtained, and the elastic modulus is suppressed to 30 MPa or lower, but the flow initiation temperature increases as the content of component A increases.
  • the lower the content of the A component the lower the elastic modulus and the higher the flexibility.
  • FIG. 3 shows an infrared absorption spectrum (ATR-IR spectrum) of Sample A1 measured while heating the vacuum-dried composition. The measurement was started from 100°C.
  • the metal ions released from component A already crosslinked the component B at 100°C, and the peak near 1600 cm -1 was as shown in Fig. 1A.
  • it can be attributed to the C O antisymmetric expansion and contraction of the carboxylic acid group in a state in which the metal ion (calcium ion) released from the A component is monodentately bonded to the carboxylic acid group of the B component.
  • the peak near 1600 cm ⁇ 1 is broadened as the temperature rises. This broadening indicates that the molecular motion is activated in the vicinity of the carboxylic acid group. In other words, as shown in FIG. 1B, it is suggested that the thermal motion is activated in the vicinity of the crosslinked site including the side chains of the B component.

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PCT/JP2022/032374 2021-08-30 2022-08-29 架橋性高分子組成物、架橋高分子材料、絶縁電線ならびにワイヤーハーネス Ceased WO2023032899A1 (ja)

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JP2023545548A JP7706557B2 (ja) 2021-08-30 2022-08-29 絶縁電線およびワイヤーハーネス
US18/682,368 US20240352161A1 (en) 2021-08-30 2022-08-29 Crosslinkable polymer composition, crosslinked polymer material, insulated wire, and wiring harness
CN202280058361.4A CN117881750A (zh) 2021-08-30 2022-08-29 交联性高分子组合物、交联高分子材料、绝缘电线和线束

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WO2024167025A1 (ja) * 2023-02-10 2024-08-15 株式会社オートネットワーク技術研究所 架橋性高分子組成物、架橋高分子材料、絶縁電線ならびにワイヤーハーネス
WO2024167026A1 (ja) * 2023-02-10 2024-08-15 株式会社オートネットワーク技術研究所 架橋性高分子組成物、架橋高分子材料、絶縁電線ならびにワイヤーハーネス
US12509570B2 (en) 2020-12-11 2025-12-30 Autonetworks Technologies, Ltd. Metal-containing additive, crosslinkable polymer composition, crosslinked polymer material, metal member, and wire harness

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CN117881750A (zh) 2024-04-12

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