WO2013008646A1 - 自己修復性積層構造体及び自己融着絶縁電線 - Google Patents

自己修復性積層構造体及び自己融着絶縁電線 Download PDF

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Publication number
WO2013008646A1
WO2013008646A1 PCT/JP2012/066654 JP2012066654W WO2013008646A1 WO 2013008646 A1 WO2013008646 A1 WO 2013008646A1 JP 2012066654 W JP2012066654 W JP 2012066654W WO 2013008646 A1 WO2013008646 A1 WO 2013008646A1
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Prior art keywords
self
resin
healing
laminated structure
thermosetting resin
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Ceased
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PCT/JP2012/066654
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English (en)
French (fr)
Japanese (ja)
Inventor
康太郎 荒谷
悟 天羽
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Hitachi Ltd
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Hitachi Ltd
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Priority to US14/131,095 priority Critical patent/US20140141254A1/en
Priority to EP12811308.1A priority patent/EP2749410B1/en
Publication of WO2013008646A1 publication Critical patent/WO2013008646A1/ja
Anticipated expiration legal-status Critical
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    • 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
    • H01B3/40—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 epoxy resins
    • 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
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific 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
    • B32B27/08—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 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
    • 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
    • H01B3/42—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 polyesters; polyethers; polyacetals
    • H01B3/427—Polyethers
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/762—Self-repairing, self-healing
    • 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
    • B32B2457/00—Electrical equipment
    • 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
    • H01B3/308—Wires with resins
    • 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
    • H01B7/02—Disposition of insulation
    • H01B7/0208—Cables with several layers of insulating material
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31515—As intermediate layer

Definitions

  • the present invention relates to a self-healing laminated structure and a self-bonding insulated wire.
  • the resin material products that can be applied in this way are widely considered to have a large need for self-healing resin materials such as electronic devices such as mobile phones, electric devices such as refrigerators and washing machines, and drive motors such as automobiles and wind power generation.
  • An object of the present invention is to provide a laminated structure excellent in self-repairing property which can be manufactured by a simple and inexpensive method, and a self-sealing insulated wire using it and the insulated wire To provide electrical equipment.
  • the present invention is a laminated structure in which a thermosetting resin top coat is formed on a self-repairing resin layer and its outer layer on a substrate, and the self-repairing resin layer is uncured and crosslinkable or cured.
  • a thermosetting resin top coat comprises a crosslinker or a curing agent or a curing catalyst of the crosslinkable thermoplastic resin. is there.
  • a self-healing resin layer and a top coat of an uncured self-adhesive thermosetting resin are formed on the outer layer of the conductor, and the self-healing resin layer is crosslinkable without curing.
  • a thermosetting resin top coat comprising a curable thermoplastic resin, wherein the thermosetting resin top coat comprises a crosslinking agent or curing agent for the crosslinkable or curable thermoplastic resin or a curing catalyst; It is provided.
  • the laminated structure excellent in the self-repairing property which can be manufactured by cheap and a simple method can be provided, and the self-fusion-insulated electric wire and electrical equipment which used it can be provided.
  • FIG. 1 is a schematic view for explaining a schematic configuration of a self-repairing laminated structure according to the present invention.
  • the self-repairing resin layer 3 is provided on the base material 1, and the thermosetting resin layer 2 (top coat) is provided on the upper layer thereof.
  • FIG. 4 shows a laminated structure without the self-repairing resin layer shown here.
  • the thickness of each of the self-repairing resin layer 3 and the thermosetting resin layer 2 formed thereon is preferably 10 to 100 ⁇ m.
  • FIG. 2 is a schematic view for explaining a schematic configuration of a self-repairing laminated structure according to the present invention.
  • the self-repairing resin layer 3 is provided on the base material 1, and the thermosetting resin layer 2 is provided on the upper layer thereof. Furthermore, the barrier layer 4 is provided between the self-repairing resin layer and the thermosetting resin layer.
  • FIG. 3 is an explanatory view of a schematic configuration of a self-bonding insulated wire using the self-repairing laminated structure according to the present invention.
  • An insulating coating layer 6 is formed on the conductor 5, and further, a self-repairing resin layer 3 is provided on the upper layer, and a thermosetting resin layer 2 is provided on the upper layer.
  • FIG. 5 shows a self-bonding insulated wire without the self-repairing resin layer shown here.
  • the material of the substrate according to the present invention is not particularly limited as long as it is solid such as plastic, glass, metal, and ceramics. Moreover, the base material with which these materials were mixed may be used.
  • the shape of the substrate according to the present invention is also not particularly limited as long as it can be coated with a laminated structure such as flat, linear, block or spherical.
  • thermosetting resin used for the thermosetting resin layer concerning this invention, an epoxy resin, a phenoxy resin, an acrylic resin, a phenol resin, a melamine resin, a thermosetting polyimide etc. are mention
  • phenoxy resin is preferable as the thermosetting resin for the self-bonding insulated wire.
  • phenoxy resins bisphenol A-type and bisphenol S-type phenoxy resins are particularly preferable.
  • the thermosetting resin layer (top coat) according to the present invention may contain, in addition to the thermosetting resin and its curing agent or curing catalyst, a curing agent for the self-healing resin layer, a crosslinking agent or a curing catalyst. Good.
  • the curing agent, crosslinking agent or curing catalyst is used to cure the self-healing resin of the underlying self-healing resin layer.
  • a curing agent, a crosslinking agent or a curing catalyst which reacts with the one or more components is previously added to the thermosetting resin layer.
  • the amount of the curing agent, the crosslinking agent or the curing catalyst is 10 parts by weight or less with respect to the thermosetting resin layer.
  • any resin such as a thermoplastic resin can be used as long as it exhibits fluidity at high temperature.
  • examples include butyral resin, phenoxy resin and polyamide resin.
  • phenoxy resin bisphenol A type and bisphenol S type phenoxy resin are mentioned. It may be a thermoplastic resin obtained by adding an epoxy resin to these phenoxy resins.
  • Various polyamide resins can be used as the polyamide resin. This self-healing resin exhibits fluidity under heating, flows into the defects generated in the thermosetting resin layer of the upper layer thereof, and the curing agent, crosslinking agent or curing catalyst contained in the thermosetting resin layer. It reacts and hardens, and the above-mentioned thermosetting resin layer is repaired.
  • the barrier layer according to the present invention is provided for the purpose of suppressing the diffusion of the curing agent of the thermosetting resin layer into the self-repairing resin layer at normal temperature or low temperature (for example, 100 ° C. or less). Any material may be used as long as it suppresses the diffusion of the curing agent. In general, non-polar materials incompatible with the curing agent are particularly preferable because the curing agent has high polarity. Polyethylene resin, polypropylene resin, polystyrene resin, etc. are mentioned.
  • a barrier layer is spontaneously formed by using a surfactant such as polyethylene glycol or polyvinyl alcohol in the preparation of the self-healing resin layer.
  • the thickness of the barrier layer is preferably 1 to 5 ⁇ m. This thickness is a thickness that can be coated in a single coating process.
  • the self-healing resin layer contains an epoxy resin
  • amine catalysts, acid anhydrides, imidazoles and the like can be used.
  • the self-healing resin layer is a phenoxy resin
  • a latent curing agent or the like can be used.
  • imidazoles such as metaxylenediamine and trimethylhexamethylenediamine as an amine catalyst
  • acid anhydrides include tetrahydrophthalic anhydride and hexahydrophthalic anhydride.
  • the latent curing agent may, for example, be a blocked isocyanate or an aromatic sulfonium salt. The former is converted by heat and the latter by light to a curing agent.
  • the self-bonding insulated wire according to the present invention is a self-bonding wire having an insulating coating, and is a wire provided with an enamel layer on the surface of a copper wire and provided with a self-bonding layer on this enamel layer. is there.
  • the enamel layer is formed by applying and baking a polyester imide varnish and a polyimide imide varnish.
  • the electric device in which the self-bonding insulated wire according to the present invention is used is, for example, an electronic device such as a mobile phone in which a speaker voice coil is mounted, a refrigerator or a laundry in which a motor for household appliances such as a compressor motor is mounted. Electric appliances such as electric machines, electric motors such as industrial motors for transformers and wind power generators and rotary motors, and electric motors for automobiles.
  • Example 1 The self-healing laminated structure shown in FIG. 1 will be described.
  • a substrate 1 a glass substrate having a size of 20 mm ⁇ 40 mm and a thickness of 1 mm was used.
  • thermosetting resin layer 2 bisphenol A epoxy resin (grade name “1001” made by Japan Epoxy Resin) was used.
  • the self-healing resin layer 3 a blend resin of phenoxy resin (YP-55: manufactured by Toto Kasei Co., Ltd.) and bisphenol A epoxy resin (manufactured by Japan Epoxy Resin, grade name “1001”) was used.
  • thermosetting resin varnish for forming the top coat is mainly composed of bisphenol A epoxy resin as a main component, methyl hexahydrophthalic anhydride (HN-5500, manufactured by Hitachi Chemical Co., Ltd.) which is a curing agent, and an imidazole type curing catalyst (a catalyst) P-200 (manufactured by Japan Epoxy Resin) was used. Each of 72 parts by weight, 26 parts by weight and 2 parts by weight was added to tetrahydrofuran to obtain a thermosetting resin varnish having a solid content weight concentration of 20%.
  • HN-5500 methyl hexahydrophthalic anhydride
  • P-200 imidazole type curing catalyst
  • a phenoxy resin and a bisphenol A epoxy resin were used as the self-healing resin varnish. 50 parts by weight of each was added to tetrahydrofuran to obtain a self-healing resin varnish having a solid content weight concentration of 20%.
  • the imidazole curing catalyst has a role as a curing agent for the self-healing resin.
  • the glass substrate surface was washed with acetone, and after drying, a self-healing resin varnish was applied with a bar coater. After air-drying the solvent at room temperature, the solvent was completely removed over 1 hour at 150 ° C. Thus, a self-healing resin layer having a thickness of about 40 ⁇ m was produced.
  • thermosetting resin varnish was applied by a bar coater on the self-healing resin layer prepared above. After air-drying the solvent at room temperature, the solvent was completely removed over 2 hours at 150 ° C., and at the same time the curing reaction of the epoxy resin was terminated. Thus, a thermosetting resin top coat having a film thickness of about 40 ⁇ m was produced, and a self-healing laminated structure A was obtained.
  • thermosetting resin varnish of Example 1 was used for preparation of the thermosetting resin layer 2, and the laminated structure A was obtained.
  • FIG. 6A shows a schematic view of the cross section of the self-repairing laminated structure A after incision
  • FIG. 6B shows the laminated structure A after incision.
  • the state of these incisions 7 can be easily observed with a stereomicroscope. Since the substrate of the laminated structure is a glass substrate, it can be observed even with a transmission microscope.
  • a blend resin of phenoxy resin and bisphenol A epoxy resin is used for the self-healing resin layer, and the weight part ratio thereof is selected because it melts and flows at 160 ° C.
  • the self-healing temperature is set to 160 ° C. or less, the weight part of the epoxy resin may be increased.
  • the self-healing temperature is set to 160 ° C. or more, the weight part of the phenoxy resin may be increased.
  • the self-repairing laminated structure of the present invention is characterized in that the temperature for self-repairing can be set arbitrarily.
  • thermosetting resin such as urea resin, melamine resin, phenol resin or unsaturated polyester resin. It will also be clear that
  • thermosetting resin layer and the self-healing resin layer can obtain the self-healing effect even if there is an additive material such as glass fiber or alumina filler as well as the resin component.
  • Example 2 The self-healing laminated structure shown in FIG. 2 will be described.
  • the substrate an aluminum substrate having a size of 20 mm ⁇ 40 mm and a thickness of 1 mm was used.
  • thermosetting resin layer 2 bisphenol A epoxy resin (grade name “1001” made by Japan Epoxy Resin) was used.
  • the self-healing resin layer 3 a blend resin of phenoxy resin (YP-55: manufactured by Toto Kasei Co., Ltd.) and bisphenol A epoxy resin (grade name "1001” manufactured by Japan Epoxy Resin) was used.
  • the barrier layer cycloolefin polymer resin (manufactured by Nippon Zeon, Zeonex 480) was used.
  • thermosetting resin varnishes bisphenol A epoxy resin as the main component, methyl hexahydrophthalic anhydride (HN-5500, manufactured by Hitachi Chemical Co., Ltd.) as a curing agent, and imidazole based curing catalyst (P-200, Japan) Stabilized isocyanate (made by Showa Denko, Karen MOI-BM) was used as a curing agent for a self-healing resin.
  • HN-5500 methyl hexahydrophthalic anhydride
  • P-200 imidazole based curing catalyst
  • Stabilized isocyanate made by Showa Denko, Karen MOI-BM
  • a phenoxy resin and a bisphenol A epoxy resin were used as the self-healing resin varnish. 70 parts by weight and 30 parts by weight of each were added to tetrahydrofuran to obtain a self-healing resin varnish having a solid content weight concentration of 20%.
  • the varnish for barrier layers added cycloolefin polymer resin to toluene, and obtained the varnish for barrier layers with 5% of solid content weight concentration.
  • the aluminum substrate surface was washed with acetone, and after drying, a self-healing resin varnish was applied by a bar coater. After air-drying the solvent at room temperature, the solvent was completely removed over 1 hour at 150 ° C. Thus, a self-healing resin layer having a thickness of about 40 ⁇ m was produced.
  • thermosetting resin varnish was applied on the barrier layer by a bar coater.
  • the ultraviolet irradiation is to improve the adhesion between the barrier layer and the thermosetting resin film.
  • the solvent was completely removed over 2 hours at 150 ° C. to complete the curing reaction of the epoxy resin.
  • a thermosetting resin layer having a thickness of about 40 ⁇ m was produced to obtain a self-repairing laminated structure B.
  • thermosetting resin varnish As a comparative example, a laminated structure B composed of the aluminum base 1, the self-repairing resin layer 3 and the thermosetting resin layer 2 shown in FIG. 1 was produced. Although the self-healing varnish was used as the self-healing resin layer 3 and the thermosetting resin varnish was used as the thermosetting resin layer 2, curing of the thermosetting resin varnish was performed at 180 ° C. for 4 hours As a result, the stabilized isocyanate added to the thermosetting resin varnish was diffused into the self-healing resin varnish, and the phenoxy resin as the self-healing resin was cured.
  • FIG. 6C shows a schematic view of a cross section of the self-repairing laminated structure B after incision and FIG. 6A shows the laminated structure B after incision. The state of these incisions 7 can be easily observed with a stereomicroscope.
  • the cut scar 8 of the thermosetting resin layer 2 was changed to a form buried by the flow of the self-repairing resin.
  • no flow was observed to the surface of the thermosetting resin layer. It is presumed that this is because the phenoxy resin reacts with the stabilized isocyanate contained in the thermosetting resin layer 2 to be cured and the flowability decreases.
  • a blend resin of phenoxy resin (polymer) and bisphenol A epoxy resin (low molecular weight) is used for the self-healing resin layer, but the melt flow ratio is 180 ° C. It is selected from When the self-healing temperature is set to 180 ° C. or more, the weight part of the high molecular weight phenoxy resin may be increased. These are also advantages when using a blend resin.
  • a similar self-healing is achieved using a single thermoplastic resin with a defined melt flow temperature directly. For example, when a thermoplastic resin such as unsaturated polyester resin or modified polyamide resin is used, it becomes possible to achieve the thermoplastic resin at a set temperature according to the thermoplastic resin used.
  • thermosetting resin layer which intrudes into a defect of the thermosetting resin layer (top coat) by the flow of the self-healing resin and exists in the thermosetting resin layer in that portion Reacts with a catalyst (which is added in excess to the thermosetting resin so that it also functions as a crosslinking agent or curing agent for a self-healing resin) to self-heal the defect and the repair portion It is characterized in that the fluidity of the self-healing resin layer can be adjusted so as not to protrude from the surface of the thermoplastic resin layer.
  • a substance that acts as a curing agent or a crosslinking agent for a self-healing resin can be added to the thermosetting resin layer, which is a substance different from the curing agent or curing catalyst for the thermosetting resin.
  • thermosetting resin such as urea resin, melamine resin, phenol resin or unsaturated polyester resin. It will also be clear that
  • thermosetting resin layer and the self-healing resin layer can obtain the self-healing effect even if there is an additive material such as glass fiber or alumina filler as well as the resin component.
  • the barrier layer was prepared by adding cycloolefin polymer resin to toluene and applying a barrier layer varnish.
  • a cycloolefin polymer resin is dissolved in tetrahydrofuran when producing a self-healing resin varnish
  • the cycloolefin polymer phase-separates on the surface of the self-healing resin layer when the self-healing resin layer is formed.
  • means for spontaneously forming a barrier layer can also be used, and the same self-repairing effect as in this embodiment can be obtained.
  • stabilized isocyanates can be used (description of the example).
  • urea resin urea resin + hydrazodicarbonamide
  • stabilized isocyanates can be used.
  • melamine resin (melamine resin + hydrazodicarbum amide)
  • stabilized isocyanate can be used.
  • a stabilized isocyanate can be used.
  • Example 3 The self-bonding insulated wire shown in FIG. 3 will be described.
  • a polyamide imide enameled wire was used as a substrate.
  • the polyamide imide film thickness to be the insulating film 6 is 10 ⁇ m, and the conductor diameter of the copper wire to be the conductor 5 is ⁇ 0.8 mm.
  • a phenoxy resin (YP-50: manufactured by Tohto Kasei Co., Ltd.) was used for the thermosetting resin layer 2.
  • a blend resin of phenoxy resin (YP-55: manufactured by Toto Kasei Co., Ltd.) and bisphenol A epoxy resin (grade name "1001" manufactured by Japan Epoxy Resin) was used.
  • thermosetting resin varnish For the thermosetting resin varnish, a phenoxy resin as a main component and a stabilized isocyanate (Kalens MOI-BP, manufactured by Showa Denko K.K.) which is a crosslinking curing agent were used. Each 80 parts by weight and 20 parts by weight were added to tetrahydrofuran to obtain a thermosetting resin varnish having a solid content weight concentration of 20%.
  • a phenoxy resin and a bisphenol A epoxy resin were used as the self-healing resin varnish. 80 parts by weight and 20 parts by weight of each were added to tetrahydrofuran to obtain a self-healing resin varnish having a solid content weight concentration of 20%.
  • a self-healing resin varnish was applied to a polyamideimide enameled wire and baked to prepare a self-healing resin layer having a thickness of about 30 ⁇ m. Further, a thermosetting resin varnish was applied to and baked on this self-healing resin layer, whereby a thermosetting resinous resin layer having a film thickness of about 40 ⁇ m was produced, and a self-bonding insulated wire C was obtained.
  • the top coat Before curing the top coat 2 of the outermost layer thermosetting resin, the top coat has self-adhesiveness. After the self-bonding insulating wire is molded into a coil or the like, and then the top coat is fused and cured, a part of the self-healing resin 6 at a certain heating temperature is caused by defects generated in the top coat. It flows into the defect and reacts with the crosslinking agent or curing agent or curing catalyst present in the top coat 2 to repair the defect and convert it into a thermosetting resin.
  • thermosetting resin varnish was used for preparation of the thermosetting resin layer 2, and the self-bonding insulated wire D was obtained.
  • thermosetting bonding film forcibly provided on the outer periphery of the insulated conductor by the bending operation.
  • a varnish for a barrier layer having a solid content weight concentration of 5% obtained by adding a cycloolefin polymer resin to toluene
  • a stabilizing isocyanate which is a crosslinking curing agent of a phenoxy resin may be added to the thermosetting resin layer in a slight excess over the equivalent relationship.
  • an amine-based curing agent for the bisphenol A epoxy resin may be added to the thermosetting resin layer.
  • the self-healing resin is cured at the crack site to suppress the flow.
  • a blend resin of phenoxy resin and bisphenol A type epoxy resin is used for the self-healing resin layer, but the ratio by weight of the blend resin is selected because it melts and flows at the set temperature.
  • the self-bonding insulated wire of the present invention is characterized in that the temperature for self-repairing can be set arbitrarily.
  • Example 4 The self-healing laminated structure shown in FIG. 1 will be described.
  • a substrate a glass substrate having a size of 20 mm ⁇ 40 mm and a thickness of 1 mm was used.
  • thermosetting resin layer 2 bisphenol A epoxy resin (grade name “1001” made by Japan Epoxy Resin) was used.
  • polyvinyl butyral resin BM-1: manufactured by Sekisui Chemical Co., Ltd.
  • thermosetting resin varnishes bisphenol A epoxy resin as the main component, methyl hexahydrophthalic anhydride (HN-5500, manufactured by Hitachi Chemical Co., Ltd.) as a curing agent, and imidazole based curing catalyst (P-200, Japan) Stabilized isocyanate (made by Showa Denko, Karen MOI-BM) was used as a curing agent for a self-healing resin.
  • HN-5500 methyl hexahydrophthalic anhydride
  • P-200 imidazole based curing catalyst
  • Stabilized isocyanate made by Showa Denko, Karen MOI-BM
  • a polyvinyl butyral resin was used as the self-healing resin varnish.
  • a 20% solid weight concentration self-healing resin varnish was obtained.
  • the glass substrate surface was washed with acetone, and after drying, a self-healing resin varnish was applied with a bar coater. After air-drying the solvent at room temperature, the solvent was completely removed over 1 hour at 80 ° C. Thus, a self-healing resin layer having a thickness of about 40 ⁇ m was produced.
  • thermosetting resin varnish was applied by a bar coater on the self-healing resin layer prepared above. After air-drying the solvent at room temperature, the solvent was completely removed over 2 hours at 150 ° C., and at the same time the curing reaction of the epoxy resin was terminated. Thus, a thermosetting resin layer having a thickness of about 40 ⁇ m was produced, and a self-repairing laminated structure A was obtained.
  • thermosetting resin varnish was used for preparation of the thermosetting resin layer 2, and the laminated structure A was obtained.
  • FIG. 6A shows a schematic view of the cross section of the self-repairing laminated structure A after incision
  • FIG. 6B shows the laminated structure A after incision.
  • the state of these incisions 7 can be easily observed with a stereomicroscope. Since the base material of these laminated structures is a glass base material, it can observe also with a transmission microscope.
  • the self-healing of the incision perpendicular to the surface of the self-healing laminated structure has been described, but it is of course clear that the invention can also cope with the peeling between the thermoplastic resin layer and the self-healing resin layer.
  • thermosetting resin such as urea resin, melamine resin, phenol resin or unsaturated polyester resin. It will also be clear that
  • thermosetting resin layer and the self-healing resin layer can obtain the self-healing effect even if there is an additive material such as glass fiber or alumina filler as well as the resin component.
  • Example 5 The self-healing laminated structure shown in FIG. 1 will be described.
  • a substrate a glass substrate having a size of 20 mm ⁇ 40 mm and a thickness of 1 mm was used.
  • a thermosetting acrylic resin (made by Mitsui Chemicals, Inc.) was used for the thermosetting resin layer 2.
  • a blend resin of phenoxy resin (YP-55: manufactured by Tohto Kasei Co., Ltd.) and bisphenol A epoxy resin (grade name "1001" manufactured by Japan Epoxy Resins Co., Ltd.) was used.
  • thermosetting resin varnish thermosetting acrylic resin as a main component, isophorone diisocyanate (made by Bayer) which is a curing agent, and stabilized isocyanate as a curing agent of a self-healing resin (manufactured by Showa Denko, Karen MOI-BM) )It was used. 72 parts by weight, 26 parts by weight and 2 parts by weight were added to methyl ethyl ketone to obtain a thermosetting resin varnish having a solid content weight concentration of 20%.
  • a phenoxy resin and a bisphenol A epoxy resin were used as the self-healing resin varnish. 50 parts by weight of each was added to tetrahydrofuran to obtain a self-healing resin varnish having a solid content weight concentration of 20%.
  • the glass substrate surface was washed with acetone, and after drying, a self-healing resin varnish was applied with a bar coater. After air-drying the solvent at room temperature, the solvent was completely removed over 1 hour at 150 ° C. Thus, a self-healing resin layer having a thickness of about 40 ⁇ m was produced.
  • thermosetting resin varnish was applied by a bar coater on the self-healing resin layer prepared above. After air-drying the solvent at room temperature, the solvent was completely removed over 1 hour at 120 ° C., and at the same time the curing reaction of the acrylic resin was terminated. Thus, a thermosetting resin layer having a thickness of about 40 ⁇ m was produced, and a self-repairing laminated structure A was obtained.
  • thermosetting resin varnish was used for preparation of the thermosetting resin layer 2, and the laminated structure A was obtained.
  • FIG. 6A shows a schematic view of the cross section of the self-repairing laminated structure A after incision
  • FIG. 6B shows the laminated structure A after incision.
  • the state of these incisions 7 can be easily observed with a stereomicroscope. Since the substrate of the laminated structure is a glass substrate, it can be observed even with a transmission microscope.
  • the self-healing of the incision perpendicular to the surface of the self-healing laminated structure has been described, but it is of course clear that the invention can also cope with the peeling between the thermoplastic resin layer and the self-healing resin layer.
  • isophorone diisocyanate is described as a curing agent for the thermosetting resin layer, but the same self-healing effect can be obtained by using a curing agent such as tolylene diisocyanate, diphenylmethane dicisocyanate, and trimethylhexamethylene diisocyanate. It will also be clear that it can be obtained.
  • thermosetting resin layer and the self-healing resin layer can obtain the self-healing effect even if there is an additive material such as glass fiber or alumina filler as well as the resin component.
  • the present invention was concretely explained based on the above-mentioned example, the present invention is not limited to the above-mentioned example, It can be variously changed in the range which does not deviate from the gist Of course.
  • SYMBOLS 1 Base material, 2 ... Thermosetting resin layer, 3 ... Self-healing resin layer, 4 ... Barrier layer, 5 ... Conductor, 6 ... Insulating film, 7 ... Crack, 8 ... Flowing self-healing resin.

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  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Laminated Bodies (AREA)
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PCT/JP2012/066654 2011-07-08 2012-06-29 自己修復性積層構造体及び自己融着絶縁電線 Ceased WO2013008646A1 (ja)

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JP6331219B2 (ja) * 2014-08-08 2018-05-30 株式会社安川電機 可動電機、コイルの製造方法
KR20180090255A (ko) * 2015-12-04 2018-08-10 후루카와 덴키 고교 가부시키가이샤 자기 융착성 절연 전선, 코일 및 전기·전자 기기
CN113261393A (zh) * 2019-03-15 2021-08-13 深圳市柔宇科技股份有限公司 导线、电子设备及导线的制作方法
US11446915B2 (en) * 2019-06-14 2022-09-20 Ut-Battelle, Llc Roll-to-roll slot die coating method to create interleaving multi-layered films with chemical slurry coatings
CN110619974B (zh) * 2019-08-22 2020-12-18 百通赫思曼工业（苏州）有限公司 一种基于自修复的自检测高强度超薄抗弯曲胶带电线电缆
DE102021100950A1 (de) 2021-01-19 2022-07-21 Audi Aktiengesellschaft Komponentengehäuseanordnung, elektrische Komponente und Verfahren zum Verschließen einer Beschädigungsöffnung in einem Komponentengehäuse
CN113527983B (zh) * 2021-07-30 2022-05-31 中山大学 一种免修饰可回收的光热驱动自修复环氧防腐涂层材料的制备方法
CN113845313B (zh) * 2021-09-17 2023-11-03 成都拓米双都光电有限公司 复合涂层及制备方法、超薄玻璃及制备方法、终端设备
CN120913935A (zh) * 2025-08-11 2025-11-07 百州电缆集团有限公司 一种交联聚乙烯绝缘耐腐蚀电力电缆

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EP2749410A4 (en) 2015-04-15
EP2749410A1 (en) 2014-07-02

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