WO2012008378A1 - 電気絶縁性樹脂組成物、及び、積層シート - Google Patents
電気絶縁性樹脂組成物、及び、積層シート Download PDFInfo
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- WO2012008378A1 WO2012008378A1 PCT/JP2011/065683 JP2011065683W WO2012008378A1 WO 2012008378 A1 WO2012008378 A1 WO 2012008378A1 JP 2011065683 W JP2011065683 W JP 2011065683W WO 2012008378 A1 WO2012008378 A1 WO 2012008378A1
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- resin composition
- resin
- laminated sheet
- polyamide
- electrically insulating
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- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
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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
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
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- 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
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- 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
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- 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
- B32B27/286—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 polysulphones; polysulfides
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/06—Polysulfones; Polyethersulfones
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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
- H01B3/301—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen or carbon in the main chain of the macromolecule, not provided for in group H01B3/302
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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
- H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
- H01B3/305—Polyamides or polyesteramides
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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
- H01B3/308—Wires with resins
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- 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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0261—Polyamide fibres
- B32B2262/0269—Aromatic polyamide fibres
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- 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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- 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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
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- 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
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- 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
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- 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
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/08—Polysulfonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- 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
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2848—Three or more layers
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- 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]
- Y10T428/31533—Of polythioether
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- 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
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/674—Nonwoven fabric with a preformed polymeric film or sheet
Definitions
- the present invention relates to an electrically insulating resin composition.
- the present invention also relates to a laminated sheet in which a plurality of sheet materials are bonded together via a resin composition layer in which the resin composition is formed into a sheet shape.
- this type of electrically insulating resin composition includes, for example, a polyphenylene sulfide resin having an aromatic hydrocarbon and a plurality of sulfide bonds (—S—) in the molecule, and a vinyl copolymer. What was formed in the sheet form is proposed (patent document 1).
- such an electrically insulating resin composition has a tracking resistance as an electrical insulating property required between a coil wire of a motor and the like, but has a tensile strength or the like due to heat generated from the coil wire or the like. There is a problem that the heat resistance may not be sufficient. That is, such an electrically insulating resin composition has a problem that it is relatively difficult to have both excellent heat resistance and excellent tracking resistance.
- a laminated sheet for example, a sheet in which a plurality of sheet materials are bonded through an electrically insulating resin composition layer formed in a sheet shape is known.
- This type of laminated sheet can be used, for example, arranged around a coil wire in a motor as described above.
- this type of laminated sheet for example, two polyamide papers as a sheet material formed of aromatic polyamide fibers are bonded through a resin layer containing polyphenylene sulfide (PPS) resin.
- PPS polyphenylene sulfide
- Patent Document 2 the sheet material is suppressed from peeling from the resin layer due to the adhesiveness between the sheet material and the resin layer.
- such a laminated sheet has a problem that mechanical properties such as tensile strength can be lowered by heat generated from a coil wire or the like in a motor, and heat resistance is not always sufficient. That is, such a laminated sheet has a problem that it is relatively difficult to simultaneously satisfy the suppression of delamination between the sheet material and the resin layer and the excellent heat resistance.
- the present invention has been made in view of the above-described problems, and an object thereof is to provide an electrically insulating resin composition having excellent heat resistance and excellent electrical insulation.
- An object of the present invention is to provide a laminated sheet having excellent heat resistance and delamination is suppressed.
- the electrically insulating resin composition of the present invention comprises a polysulfone resin containing a plurality of sulfonyl groups (—SO 2 —) in the molecule and a polyamide resin, and the content ratio of the polyamide resin is 1 to 45% by mass. It is characterized by that.
- the electrically insulating resin composition having the above-described structure is excellent in tracking resistance and heat resistance by containing the polysulfone resin and a polyamide resin having a content ratio of 1 to 45% by mass. Can be.
- the polysulfone resin is a polyethersulfone resin further including a plurality of ether bonds in the molecule, or a polyphenyl further including a plurality of aromatic hydrocarbons in the molecule.
- a sulfone resin is preferred.
- the moldability of the electrical insulating resin composition is improved and the electrical insulating resin composition has excellent tracking resistance. And there is an advantage of having heat resistance.
- the polyamide resin preferably contains an aromatic hydrocarbon.
- the electrically insulating resin composition can be more excellent in heat resistance while having excellent tracking resistance.
- the electrically insulating resin composition according to the present invention preferably has a CTI value in a tracking resistance test of 130 V or more. Moreover, it is preferable that an end tear resistance value is 20 MPa or more. Moreover, it is preferable that the intensity
- the electrically insulating resin composition according to the present invention is preferably formed in a sheet shape. Further, it is preferably used for electrical insulation.
- the laminated sheet of the present invention comprises a plurality of sheet materials via a resin composition layer containing a polysulfone resin containing a plurality of sulfonyl groups in the molecule and a polyamide resin, and the content ratio of the polyamide resin is 1 to 45% by mass. It is characterized by being bonded together.
- the laminated sheet having the above structure is formed by laminating a plurality of sheet materials through a resin composition layer containing the polysulfone resin and the polyamide resin and having a polyamide resin content of 1 to 45% by mass. Therefore, delamination can be suppressed and heat resistance can be improved.
- the sheet material preferably contains wholly aromatic polyamide.
- the sheet material contains wholly aromatic polyamide, there is an advantage that the heat resistance of the laminated sheet can be further improved.
- the said sheet material is the paper produced by the wet papermaking method. Further, it is preferably a wholly aromatic polyamide paper containing fibers of wholly aromatic polyamide.
- the sheet material is wholly aromatic polyamide paper containing fibers of wholly aromatic polyamide, there is an advantage that the heat resistance of the laminated sheet can be further improved.
- the sheet material is preferably a nonwoven fabric.
- the sheet material is a nonwoven fabric, there is an advantage that delamination between the sheet material and the resin composition layer can be further suppressed.
- the laminated sheet according to the present invention is preferably subjected to corona treatment on at least the resin composition layer side of the sheet material.
- corona treatment By performing the corona treatment, there is an advantage that delamination between the sheet material and the resin composition layer can be further suppressed.
- the polysulfone resin is a polyethersulfone resin further including a plurality of ether bonds in the molecule or a polyphenylsulfone resin further including a plurality of aromatic hydrocarbons in the molecule.
- the said polyamide resin is a polyamide resin which contains an aromatic hydrocarbon in a molecule
- the laminated sheet according to the present invention preferably further comprises an adhesive sheet-like adhesive layer, and the adhesive layer is preferably disposed on at least one outermost surface. Further, it is preferable that the adhesive layer has flame retardancy that satisfies the VTM-O standard of the UL94 standard.
- the laminated sheet according to the present invention is preferably used for electrical insulation.
- the electrically insulating resin composition of the present invention has the effect of having excellent heat resistance and excellent electrical insulation.
- the laminated sheet of the present invention has excellent heat resistance and has the effect that delamination is suppressed.
- disconnected the lamination sheet in the thickness direction Sectional drawing which showed typically the cross section which cut
- the electrically insulating resin composition according to this embodiment includes a polysulfone resin containing a plurality of sulfonyl groups in the molecule and a polyamide resin, and the content ratio of the polyamide resin is 1 to 45% by mass.
- the electrical insulating resin composition if the content ratio of the polyamide resin exceeds 45% by mass, the electrical insulating resin composition may be inferior in heat resistance. Moreover, there exists a possibility that the tracking resistance of an electrically insulating resin composition may become inadequate that the content rate of a polyamide resin is less than 1 mass%.
- the content of the polyamide resin is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 8% by mass or more. 15% by mass or more is most preferable.
- the content rate of the said polyamide resin is 40 mass% or less, It is more preferable that it is 35 mass% or less, It is further more preferable that it is 32 mass% or less.
- the content ratio of the polyamide resin is 3% by mass or more, there is an advantage that the tracking resistance as the electric insulation in the electric insulating resin composition can be further improved.
- the content rate of the said polyamide resin is 40 mass% or less, there exists an advantage that the heat resistance of an electrically insulating resin composition can become more excellent.
- the polysulfone resin has a molecular structure including a plurality of sulfonyl groups (—SO 2 —).
- the polysulfone resin include a polyethersulfone resin further including a plurality of ether bonds (—O—) in the molecule, and a polyphenylsulfone resin further including a plurality of aromatic hydrocarbons in the molecule.
- the polyether polyphenyl sulfone resin which further contains a some ether bond and a some aromatic hydrocarbon in a molecule
- the moldability of the electrically insulating resin composition becomes good, and the electrically insulating resin composition has excellent tracking resistance and more excellent heat resistance.
- the polyether polyphenyl sulfone resin is preferable in that it is obtained.
- n is a positive integer representing the degree of polymerization and is usually in the range of 10 to 5000.
- polyether polyphenylsulfone resin commercially available products can be used. For example, “Ultra Zone E Series” manufactured by BASF, “Radel A Series” manufactured by Solvay, “ “Sumika Excel series”.
- the polyamide resin is obtained by polymerizing at least a polyamine compound and a polycarboxylic acid compound by dehydration condensation.
- the polyamide resin examples include a polyamide resin having an aromatic hydrocarbon in the molecule and an aliphatic polyamide resin having only an aliphatic hydrocarbon as a hydrocarbon in the molecule.
- numerator is preferable at the point that the said electrically insulating resin composition can become what was excellent in heat resistance, while having the outstanding tracking resistance.
- the polyamide resin having an aromatic hydrocarbon in the molecule includes a wholly aromatic polyamide resin having only an aromatic hydrocarbon as a hydrocarbon in the molecule, an aliphatic hydrocarbon and an aromatic hydrocarbon as a hydrocarbon in the molecule.
- semi-aromatic polyamide resins having both of the above As the polyamide resin having an aromatic hydrocarbon in the molecule, the semi-aromatic polyamide resin is preferable in that the tracking resistance and the heat resistance can be balanced.
- polyamine compound used in the polymerization of the polyamide resin include a diamine compound.
- diamine compound include aliphatic diamines containing linear or branched hydrocarbon groups, alicyclic diamines containing cyclic saturated hydrocarbon groups, and aromatic diamines containing aromatic hydrocarbon groups. .
- Examples of the aliphatic diamine, the alicyclic diamine, or the aromatic diamine include those represented by the following formula (2).
- R 1 in the following formula (2) represents an aliphatic hydrocarbon group having 4 to 12 carbon atoms, or an alicyclic hydrocarbon group having 4 to 12 carbon atoms including a cyclic saturated hydrocarbon, or Represents a hydrocarbon group containing an aromatic ring.
- nonanediamine having 9 carbon atoms in R 1 in formula (2) is preferable in that the polyamide resin can have better tracking resistance, and 1,9-nonanediamine and 2 More preferred is a mixture of -methyl-1,8-octanediamine.
- aromatic diamine include phenylenediamine and xylylenediamine.
- polycarboxylic acid compound used in the polymerization of the polyamide resin include a dicarboxylic acid compound.
- dicarboxylic acid compound examples include an aliphatic dicarboxylic acid containing a linear or branched hydrocarbon group, an alicyclic dicarboxylic acid containing a cyclic saturated hydrocarbon group, and an aromatic dicarboxylic acid containing an aromatic hydrocarbon group. Etc.
- R 2 in the following formula (3) represents an aliphatic hydrocarbon group having 4 to 25 carbon atoms, or an alicyclic hydrocarbon group having 4 to 12 carbon atoms including a cyclic saturated hydrocarbon, or Represents a hydrocarbon group containing an aromatic ring.
- R 2 in the following formula (3) represents an aliphatic hydrocarbon group having 4 to 25 carbon atoms, or an alicyclic hydrocarbon group having 4 to 12 carbon atoms including a cyclic saturated hydrocarbon, or Represents a hydrocarbon group containing an aromatic ring.
- Examples of the aliphatic dicarboxylic acid include adipic acid and sebacic acid.
- Examples of the aromatic dicarboxylic acid include terephthalic acid, methyl terephthalic acid, and naphthalene dicarboxylic acid.
- terephthalic acid can be used because the heat resistance of the polyamide resin can be further improved. Acid is preferred.
- the polyamide resin may be obtained by polymerizing one kind of the diamine compound and one kind of dicarboxylic acid compound, and is obtained by polymerizing a combination of plural kinds of the respective compounds. Also good. Further, the polyamide resin may be obtained by further polymerizing other than the diamine compound and the dicarboxylic acid compound, if necessary.
- the semi-aromatic polyamide resin is preferable as the polyamide resin, and as the semi-aromatic polyamide resin, an aliphatic diamine as a diamine compound and an aromatic dicarboxylic acid as a dicarboxylic acid compound are polymerized. More preferably, nonanediamine as an aliphatic diamine and terephthalic acid as an aromatic dicarboxylic acid are polymerized (PA9T).
- additives may be blended.
- additives include alkylphenol resins, alkylphenol-acetylene resins, xylene resins, coumarone-indene resins, terpene resins, rosin and other tackifiers, brominated flame retardants such as polybromodiphenyl oxide and tetrabromobisphenol A, Chlorinated flame retardants such as chlorinated paraffin and perchlorocyclodecane, phosphorus flame retardants such as phosphate esters and halogen-containing phosphate esters, boron flame retardants, oxide flame retardants such as antimony trioxide, aluminum hydroxide Hydrated metal compounds such as magnesium hydroxide, phenolic, phosphorus, sulfur antioxidants, silica, clay, calcium carbonate, barium carbonate, strontium carbonate, aluminum oxide, magnesium oxide, boron nitride, silicon nitride, nitride Inorganic fibers such
- aromatic polyamide fibers montmorillonite having a particle size of several nm to several hundred nm, and the like can be mentioned.
- These additives can be used in an amount of, for example, 0.1 to 5 parts by weight with respect to 100 parts by weight of the electrically insulating resin composition.
- the CTI value of the tracking resistance test measured by the method described in the examples is 130 V or more in that the electrical insulating resin composition can have better tracking resistance as electrical insulation. Is preferred.
- the electrical insulating resin composition has a tensile strength residual ratio of 55 after 250 hours at 240 ° C., measured by the method described in Examples, in that it can be more excellent in heat resistance. % Or more is preferable.
- the electrical insulating resin composition preferably has an end tear resistance value of 20 MPa or more as measured by the method described in the Examples in that it can be more excellent in tear resistance.
- the electrical insulating resin composition is produced by mixing at least a polysulfone resin and a polyamide resin using a general mixing and stirring means such as a kneader, a pressure kneader, a kneading roll, a Banbury mixer, a twin screw extruder, and the like.
- a general mixing and stirring means such as a kneader, a pressure kneader, a kneading roll, a Banbury mixer, a twin screw extruder, and the like.
- a general mixing and stirring means such as a kneader, a pressure kneader, a kneading roll, a Banbury mixer, a twin screw extruder, and the like.
- it can manufacture by carrying out mixing and stirring in the cylinder of an extruder by dry blending.
- the electrical insulating resin composition can be formed into a sheet shape by, for example, an extruder equipped with a T die, an injection molding machine, or the like. Also, for example, a laminated sheet can be produced by sticking a sheet material such as paper formed of aromatic amide resin fibers on both surfaces of the electrically insulating resin composition formed into a sheet shape.
- the produced laminated sheet can be suitably used in applications requiring electrical insulation and heat resistance.
- the laminated sheet is an electric insulating sheet material used in the periphery of a coil wire that is a heating element in a motor, an electric insulating sheet material used in a transformer, a bus bar, a capacitor, a cable, and the like. It can be used for applications such as insulating films on electronic circuit boards.
- FIG.1 and FIG.2 is sectional drawing which showed typically the cross section which cut
- the laminated sheet 1 includes a polysulfone resin having a plurality of sulfonyl groups in the molecule and a polyamide resin, and the content of the polyamide resin is 1 to 45% by mass.
- a plurality of sheet materials 3 are bonded together through the resin composition layer 2.
- the resin composition layer 2 is formed by forming a resin composition containing the polysulfone resin and the polyamide resin into a sheet shape so that the content of the polyamide resin is 1 to 45% by mass. That is, the resin composition layer 2 is formed by forming the above-described electrically insulating resin composition into a sheet shape.
- the resin composition layer 2 When the content ratio of the polyamide resin exceeds 45% by mass, the resin composition layer 2 may be inferior in heat resistance. Moreover, there exists a possibility that the delamination between the resin composition layer 2 and the sheet
- seat material 3 may arise easily that the content rate of the said polyamide resin is less than 1 mass%.
- the content ratio of the polyamide resin is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and 15% by mass. % Or more is most preferable. Moreover, it is preferable that the content rate of the said polyamide resin is 40 mass% or less, It is more preferable that it is 35 mass% or less, It is further more preferable that it is 32 mass% or less.
- the content ratio of the polyamide resin is 3% by mass or more, there is an advantage that delamination between the resin composition layer 2 and the sheet material 3 can be less likely to occur.
- the content ratio of the polyamide resin is 40% by mass or less, there is an advantage that the heat resistance of the resin composition layer 2 can be more excellent, and the flame retardancy is more excellent. There are advantages.
- the thickness of the resin composition layer 2 is not particularly limited, and is usually 1 ⁇ m to 500 ⁇ m.
- polysulfone resin and the polyamide resin examples include those described above.
- the polyamide resin is preferably a polyamide resin having an aromatic hydrocarbon in the molecule in that the resin composition layer 2 can be more excellent in heat resistance.
- the said semi-aromatic polyamide resin is preferable at the point that the delamination between the sheet
- the aliphatic diamine used in the polymerization of the polyamide resin has a carbon number of 9 in R 1 in the above formula (2) in that delamination between the sheet material and the resin composition layer can be further suppressed.
- Nonanediamine is preferable, and a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is more preferable.
- terephthalic acid is preferable in that the polyamide resin can be more excellent in heat resistance.
- the polyamide resin is preferably the semi-aromatic polyamide resin.
- the semi-aromatic polyamide resin an aliphatic diamine as a diamine compound and an aromatic dicarboxylic acid as a dicarboxylic acid compound are polymerized. More preferred are those obtained by polymerizing nonanediamine as an aliphatic diamine and terephthalic acid as an aromatic dicarboxylic acid (PA9T).
- the resin composition layer 2 may contain various additives as described above.
- the sheet material 3 is not particularly limited as long as it is a sheet. Further, the thickness is not particularly limited, and is usually 10 to 100 ⁇ m. In addition, as shown in FIG. 1, the sheet material 3 is usually provided in two sheets in a laminated sheet.
- Examples of the sheet material 3 include paper, nonwoven fabric, and film.
- the sheet material 3 is preferably paper or non-woven fabric in that delamination between the sheet material and the resin composition layer can be further suppressed.
- Examples of the sheet material 3 include those produced by a wet papermaking method and those produced by a dry method in the air.
- the sheet material 3 is preferably paper made by a wet papermaking method in that delamination between the sheet material and the resin composition layer can be further suppressed.
- Examples of the material of the sheet material 3 include synthetic polymer compounds such as polyamide and polyester, natural polymer compounds such as cellulose, and the like, and delamination between the sheet material and the resin composition layer can be further suppressed.
- polyamide is preferable.
- the polyamide includes a wholly aromatic polyamide in which all of the constituent monomers have aromatic hydrocarbons, an aliphatic polyamide in which all of the constituent monomers have only aliphatic hydrocarbons as hydrocarbons, and some of the constituent monomers are aromatic hydrocarbons
- semi-aromatic polyamides are preferable, and wholly aromatic polyamides are preferable in that delamination between the sheet material and the resin composition layer can be further suppressed. That is, it is preferable that the sheet material 3 contains the wholly aromatic polyamide.
- the sheet material 3 it is possible to further suppress delamination between the sheet material and the resin composition layer, and it is possible to further suppress all of the fibers including wholly aromatic polyamide fibers from the viewpoint of excellent flame retardancy.
- Aromatic polyamide paper is more preferable, and wholly aromatic polyamide paper produced by wet papermaking using fibers of wholly aromatic polyamide is more preferable.
- the wholly aromatic polyamide paper examples include, for example, a wholly aromatic polyamide fiber obtained by fiberizing a condensation polymerization product (fully aromatic polyamide) of phenylenediamine and phthalic acid, which includes a benzene ring except for an amide group. Are formed as the main constituent material.
- the wholly aromatic polyamide paper preferably has a basis weight of 5 g / m 2 or more in terms of excellent mechanical properties and good handling in the production process of the laminated sheet. When the basis weight is 5 g / m 2 or more, an insufficient mechanical strength is suppressed, and there is an advantage that it is difficult to break during the production of the laminated sheet.
- the wholly aromatic polyamide paper may contain other components.
- Examples of the other components include polyphenylene sulfide fiber, polyether ether ketone fiber, polyester fiber, arylate fiber, liquid crystal polyester fiber, and polyethylene.
- Examples thereof include organic fibers such as naphthalate fiber, or inorganic fibers such as glass fiber, rock wool, asbestos, boron fiber, and alumina fiber.
- Examples of the wholly aromatic polyamide paper include those commercially available from DuPont under the trade name “NOMEX”.
- the sheet material 3 is preferably subjected to a corona treatment on the resin composition layer 2 side.
- a corona treatment is a treatment in which one surface of the sheet material 3 in contact with the resin composition layer 2 is subjected to a discharge treatment to generate a carboxyl group or a hydroxyl group having polarity to be roughened.
- a conventionally known general method can be employed as the corona treatment.
- the laminated sheet 1 may further include a sheet-like adhesive layer 4 having adhesiveness, and the adhesive layer 4 may be disposed on at least one outermost surface.
- the adhesive layer 4 may be provided only on one side of the laminated sheet 1 or may be provided on both sides as shown in FIG. Since the laminated sheet 1 includes the adhesive layer 4 on the outermost surface, the adhesive layer 4 can be attached to an adherend and used.
- the laminated sheet 1 is a sheet-like material, for example, in a state where the adhesive layer 4 is attached to a metal plate-like conductor in an application where heat resistance and electrical insulation are required. It can be used as an electrical insulating material.
- the pressure-sensitive adhesive layer 4 that can be provided in the laminated sheet 1 includes at least a pressure-sensitive adhesive containing a conventionally known general polymer.
- a pressure-sensitive adhesive an acrylic pressure-sensitive adhesive containing an acrylic polymer having a (meth) acrylic acid ester as a basic structural unit, an acrylic pressure-sensitive adhesive, a rubber pressure-sensitive adhesive containing an elastomeric polymer such as synthetic rubber or natural rubber, Examples include silicone-based pressure-sensitive adhesives containing silicone polymers, polyester-based pressure-sensitive adhesives containing polyester polymers, and polyurethane-based pressure-sensitive adhesives containing polyurethane polymers. System adhesives are preferred.
- the pressure-sensitive adhesive layer 4 preferably contains a cross-linking agent that can cross-link the polymer in the pressure-sensitive adhesive in that the pressure-sensitive adhesive strength and durability are more excellent.
- the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, an oxazoline crosslinking agent, a carbodiimide crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent.
- the adhesive layer 4 is composed of a rosin resin, a terpene resin, an aliphatic petroleum resin, an aromatic petroleum resin, a copolymer petroleum resin, in that the adhesive strength and durability are further improved. It is more preferable to further include a tackifier resin such as an alicyclic petroleum resin, a xylene resin, or an elastomer resin.
- the pressure-sensitive adhesive layer 4 includes a dispersant, an anti-aging agent, an antioxidant, a processing aid, a stabilizer, an antifoaming agent, a thickener, and a pigment in addition to the above-described pressure-sensitive adhesive, crosslinking agent, and tackifying resin.
- a dispersant an anti-aging agent, an antioxidant, a processing aid, a stabilizer, an antifoaming agent, a thickener, and a pigment in addition to the above-described pressure-sensitive adhesive, crosslinking agent, and tackifying resin.
- General additives added to rubber and plastics can be included as appropriate.
- the pressure-sensitive adhesive layer 4 may have, for example, a configuration in which a mixture obtained by mixing a flame retardant described later and the pressure-sensitive adhesive is formed into a sheet shape.
- the pressure-sensitive adhesive layer 4 has, for example, a sheet-like base material that enhances the shape retention of the pressure-sensitive adhesive layer, and a layered body containing at least the pressure-sensitive adhesive is disposed on both sides of the base material. May be.
- stacked these base materials are mentioned.
- the laminated base material those including at least the plastic base material such as a laminate of a plurality of the plastic base materials are preferable.
- the material of the plastic base material examples include olefins containing ⁇ -olefin as a monomer component such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), and the like.
- olefins containing ⁇ -olefin as a monomer component such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), and the like.
- Polyester resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); polyvinyl chloride (PVC) resin; vinyl acetate resin; polyphenylene sulfide (PPS) resin; aliphatic Examples thereof include polyamide resins such as polyamide and wholly aromatic polyamide; polyimide resins; polyether ether ketone (PEEK) resins.
- the material for the plastic base material one kind may be used alone, or two or more kinds may be used in combination.
- the laminated sheet 1 preferably has flame retardancy that satisfies the VTM-O standard of the UL94 standard in that it can be used in applications such as terminal insulating materials that require relatively high flame retardancy. Since the laminated sheet 1 has such flame retardancy, it can be used in, for example, an insulating material for a terminal of a power module such as an IGBT (Insulated Gate Bipolar Transistor) module.
- the UL94 standard is a combustion test standard established by Underwriters Laboratories of the United States and is generally known. The flame retardancy satisfying the VTM-O standard of the UL94 standard is specifically determined to be acceptable by the method described in the examples.
- the adhesive layer 4 has flame retardancy that satisfies the standard.
- the pressure-sensitive adhesive layer 4 can have flame retardancy satisfying the VTM-O standard of the UL94 standard, for example, by including an appropriate amount of a conventionally known general flame retardant.
- the flame retardant is not particularly limited, and examples thereof include chlorinated paraffin, chlorinated diphenyl, chlorinated ethane, chlorinated polyethylene, chlorinated polyphenyl, chlorinated diphenyl, perchlorocyclopentadecanone, and tetrachloro.
- Chlorinated compounds such as bisphenol A; brominated paraffin, brominated polyphenyl, tetrabromoethane, tetrabromobenzene, decabromodiphenyl oxide, octabromodiphenyl oxide, hexabromocyclododecane, bis (tribromophenoxy) ethane, bis ( Tribromophenoxy) ethane, ethylenebistetrabromophthalimide, hexabromobenzene, polydibromophenylene oxide, tetrabromobisphenol A, tris (2,3-dibromopropyl-1) isocyanurate Bromine compounds such as tribromophenol allyl ether, brominated polystyrene, tribromoneopentyl alcohol, dibromodichloropropane, dibromotetrafluoroethane; triphenyl phosphate (TPP), tricresy
- the amount of the flame retardant contained in the pressure-sensitive adhesive layer 4 is not particularly limited. Preferably, it is 1 to 250 parts by weight, more preferably 5 to 200 parts by weight. When the flame retardant is contained in an amount of 250 parts by weight or less with respect to 100 parts by weight of the pressure-sensitive adhesive, there is an advantage that the flame retardant bleeds out and the adhesiveness is reduced.
- the laminated sheet 1 preferably has a tensile strength remaining ratio of 50% or more after 250 hours at 240 ° C. measured by the method described in the examples.
- a sheet material 3 is arranged so as to be in contact with both surfaces of the resin composition layer 2, and the resin composition layer 2 and the resin composition layer 2 and the sheet material 3 have a cohesive failure force. It is preferable that the interlayer adhesive strength with the sheet material 3 is increased. With such a configuration, delamination between the resin composition layer 2 and the sheet material 3 is suppressed.
- the laminated sheet 1 can be manufactured, for example, by sandwiching the resin composition layer 2 between two sheet materials 3 and pressing the sheet materials 3 together.
- the resin composition layer 2 is obtained by mixing the polysulfone resin and the polyamide resin by a general mixing means such as a kneader, a pressure kneader, a kneading roll, a Banbury mixer, a twin screw extruder, and the like. And by extruding the resin composition into a sheet by an extruder equipped with a T-die.
- the laminated sheet 1 provided with the adhesive layer 4 is, for example, sandwiching and pressing the resin composition layer 2 between the two sheet materials 3 as described above, and at least one surface of the pressed sheet, It can manufacture by sticking the adhesion layer of a commercially available adhesive tape.
- the laminated sheet 1 has an electrical insulation property.
- an electrical insulation sheet for a motor in an automobile an electrical insulation sheet for a transformer, an electrical insulation sheet for a bus bar, etc. Can be used.
- the electrically insulating resin composition and laminated sheet of the present embodiment are as illustrated above, but the present invention is not limited to the above-exemplified laminated sheet. Moreover, in this invention, the various aspect used in a general electrically insulating resin composition and a lamination sheet is employable.
- Example 1 As the polysulfone resin, a polyether polyphenylsulfone resin (PES) resin (trade name “RADEL A-300A” manufactured by Solvay) containing a plurality of sulfonyl groups and further containing a plurality of ether bonds and a plurality of aromatic hydrocarbons was used. .
- a polyamide (PA) resin (trade name “Genesta N1000A” manufactured by Kuraray Co., Ltd.) composed of terephthalic acid units and nonanediamine units was used as the polyamide resin.
- PEN polyethylene naphthalate
- Example 6 Two sheets of wholly aromatic polyamide paper (trade name “NOMEX T410”, 50 ⁇ m thick, manufactured by DuPont) were used as the sheet material.
- a polysulfone resin a polyether polyphenylsulfone resin (PES) resin (trade name “Radel A-300A” manufactured by Solvay) including a plurality of sulfonyl groups and further including a plurality of ether bonds and a plurality of aromatic hydrocarbons is used.
- PES polyether polyphenylsulfone resin
- polyamide resin a polyamide (PA) resin (trade name “Genesta N1000A” manufactured by Kuraray Co., Ltd.) containing a terephthalic acid unit and a nonanediamine unit was used.
- PA polyamide
- the resin composition was formed into a sheet having a thickness of 100 ⁇ m by extrusion molding at 310 ° C. to form a resin composition layer, and wholly aromatic polyamide papers were arranged on both sides thereof.
- it was pressed for 60 seconds at a pressure of 200 N / cm 2 by a hot press machine sandwiched between two metal plates and heated to 350 ° C. to produce a laminated sheet (about 200 ⁇ m thick).
- the corona treatment was performed under the conditions of an output of 500 W, a treatment speed of 4 m / min, and a sample width of 0.4 m under atmospheric pressure using a “500 series” manufactured by PILLAR TECHNOLOGIES as a device.
- Adhesive layer A Flame Retardant Acrylic Adhesive Double-sided Tape (Nitto Denko Corporation, trade name “No. 5011N”) From which the release material is peeled off (thickness 150 ⁇ m) (A non-woven fabric with an adhesive layer containing an acrylic adhesive on both sides) (Meets UL94 VTM-O standard)
- Adhesive layer B Acrylic adhesive double-sided tape (Nitto Denko, trade name “No. 500”) From which the release material is peeled off (thickness 170 ⁇ m) (A non-woven fabric with an adhesive layer containing an acrylic adhesive on both sides) (Does not meet UL94 VTM-O standard)
- Example 6 A laminated sheet was produced in the same manner as in Example 6 except that the resin composition layer was formed only with the PES resin.
- Example 7 A laminated sheet was produced in the same manner as in Example 6 except that the resin composition layer was formed only with the PES resin and a sheet material subjected to corona treatment similar to that in Example 7 was used.
- Example 10 Comparative Example 10 Except for using a polyethylene naphthalate (PEN) film (trade name “Teonex 100 ⁇ m” manufactured by Teijin DuPont Films Japan Ltd.) instead of the resin composition layer, and using a sheet material subjected to corona treatment similar to Example 7. Produced a laminated sheet in the same manner as in Example 6.
- PEN polyethylene naphthalate
- Example 11 (Comparative Example 11) Implemented except for using a polyphenylene sulfide (PPS) film (trade name “Torelina 100 ⁇ m” manufactured by Toray Industries, Inc.) instead of the resin composition layer, and using a sheet material subjected to corona treatment similar to Example 7. A laminated sheet was produced in the same manner as in Example 6.
- PPS polyphenylene sulfide
- a flame test was conducted in accordance with UL94 standard to evaluate flame retardancy. Specifically, first, the laminated sheets produced in each Example and Comparative Example were cut into a size of 50 mm ⁇ 200 mm to obtain five test pieces each. The test piece was wound in a cylindrical shape, arranged so as to extend in the vertical direction, suspended by fixing the upper end, and a marked line was put at a position of 125 mm from the lower end. Absorbent cotton was placed directly under the test piece, and a flame was applied to the lower end of the test piece for 3 seconds to perform an ignition operation. The ignition operation was performed twice. And what satisfy
- Total flammable burning time for each specimen (burning time after applying the first flame, The total combustion time after applying the second flame is within 10 seconds. 2. The total of the total flammable burning times for each test piece is within 50 seconds. 3. The flame burning time and flameless burning time of each test piece after applying the flame for the second time is within 30 seconds. 4). Combustion dripping material falls from any specimen and does not ignite the cotton placed underneath. 5. Flame does not reach the 125mm mark from the bottom.
- Tables 3 and 4 show the evaluation results of long-term heat resistance (strength residual rate) and peelability in each Example and each Comparative Example.
- the electrically insulating resin composition of the present invention can be suitably used as a raw material for an electrically insulating sheet material that requires heat resistance and electrical insulation.
- the laminated sheet of the present invention can be suitably used as a sheet material for electrical insulation that requires heat resistance and electrical insulation.
- an electrical insulating sheet material arranged around the coil wire of a motor, a transformer, a bus bar, a capacitor, an electrical insulating sheet material for a cable, or an insulating film of an electronic circuit board is preferred.
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Abstract
Description
即ち、斯かる電気絶縁性樹脂組成物は、優れた耐熱性と、優れた耐トラッキング性とを併せ持つことが比較的困難であるという問題がある。
即ち、斯かる積層シートは、シート材と樹脂層との間における層間剥離を抑制すること、及び、優れた耐熱性を有することを同時に満足することが比較的困難であるという問題がある。
本発明は、優れた耐熱性を有し、しかも層間剥離が抑制された積層シートを提供することを課題とする。
本発明の電気絶縁性樹脂組成物は、前記ポリスルホン樹脂が、分子中に複数のエーテル結合をさらに含むポリエーテルスルホン樹脂であること、又は、分子中に複数の芳香族炭化水素をさらに含むポリフェニルスルホン樹脂であることが好ましい。
前記ポリスルホン樹脂が前記ポリエーテルスルホン樹脂又は前記ポリフェニルスルホン樹脂であることにより、前記電気絶縁性樹脂組成物の成形性が良好なものになるとともに前記電気絶縁性樹脂組成物が優れた耐トラッキング性及び耐熱性を有するという利点がある。
上記構成からなる積層シートは、前記ポリスルホン樹脂と前記ポリアミド樹脂とを含み前記ポリアミド樹脂の含有割合が1~45質量%である樹脂組成物層を介して、複数のシート材が貼り合わされてなることにより、層間剥離が抑制され且つ耐熱性に優れたものになり得る。
また、前記シート材が、湿式抄紙法により作製された紙であることが好ましい。また、全芳香族ポリアミドの繊維を含む全芳香族ポリアミド紙であることが好ましい。前記シート材が、全芳香族ポリアミドの繊維を含む全芳香族ポリアミド紙であることにより、積層シートの耐熱性がより優れたものになり得るという利点がある。
また、本発明に係る積層シートにおいては、前記ポリアミド樹脂が分子中に芳香族炭化水素を含むポリアミド樹脂であることが好ましい。前記ポリアミド樹脂が分子中に芳香族炭化水素を含むポリアミド樹脂であることにより、積層シートの耐熱性がより優れたものになり得るという利点がある。
本発明の積層シートは、優れた耐熱性を有し、しかも層間剥離が抑制されているという効果を奏する。
前記ポリアミド樹脂の含有割合が3質量%以上であることにより、電気絶縁性樹脂組成物における電気絶縁性としての耐トラッキング性が、より優れたものになり得るという利点がある。また、前記ポリアミド樹脂の含有割合が40質量%以下であることにより、電気絶縁性樹脂組成物の耐熱性がより優れたものになり得るという利点がある。
該ポリスルホン樹脂としては、分子中に複数のエーテル結合(-O-)をさらに含むポリエーテルスルホン樹脂、又は、分子中に複数の芳香族炭化水素をさらに含むポリフェニルスルホン樹脂などが挙げられる。また、該ポリスルホン樹脂としては、分子中に複数のエーテル結合と複数の芳香族炭化水素とをさらに含むポリエーテルポリフェニルスルホン樹脂が挙げられる。
分子中に芳香族炭化水素を有するポリアミド樹脂としては、耐トラッキング性と耐熱性とをバランス良く兼ね備えることができるという点で、前記半芳香族ポリアミド樹脂が好ましい。
該ジアミン化合物としては、直鎖状又は分岐鎖状の炭化水素基を含む脂肪族ジアミン、環状の飽和炭化水素基を含む脂環族ジアミン、芳香族炭化水素基を含む芳香族ジアミンなどが挙げられる。
H2N-R1-NH2 ・・・(2)
前記芳香族ジアミンとしては、フェニレンジアミン、キシリレンジアミンなどが挙げられる。
該ジカルボン酸化合物としては、直鎖状又は分岐鎖状の炭化水素基を含む脂肪族ジカルボン酸、環状の飽和炭化水素基を含む脂環族ジカルボン酸、芳香族炭化水素基を含む芳香族ジカルボン酸などが挙げられる。
HOOC-R2-COOH ・・・(3)
前記芳香族ジカルボン酸としては、テレフタル酸、メチルテレフタル酸、ナフタレンジカルボン酸などが挙げられ、該芳香族ジカルボン酸としては、前記ポリアミド樹脂の耐熱性がより優れたものになり得るという点で、テレフタル酸が好ましい。
該添加剤としては、例えば、アルキルフェノール樹脂、アルキルフェノール-アセチレン樹脂、キシレン樹脂、クマロン-インデン樹脂、テルペン樹脂、ロジンなどの粘着付与剤、ポリブロモジフェニルオキサイド、テトラブロモビスフェノールAなどの臭素系難燃剤、塩素化パラフィン、パークロロシクロデカンなどの塩素系難燃剤、リン酸エステル、含ハロゲンリン酸エステルなどのリン系難燃剤、ホウ素系難燃剤、三酸化アンチモンなどの酸化物系難燃剤、水酸化アルミニウム、水酸化マグネシウムなどの水和金属化合物、フェノール系、リン系、硫黄系の酸化防止剤、シリカ、クレー、炭酸カルシウム、炭酸バリウム、炭酸ストロンチウム、酸化アルミ、酸化マグネシウム、窒化硼素、窒化珪素、窒化アルミニウムといった無機フィラー、熱安定剤、光安定剤、紫外線吸収剤、滑剤、顔料、架橋剤、架橋助剤、シランカップリング剤、チタネートカップリング剤などの一般的なプラスチック用配合成分などが挙げられる。また、芳香族ポリアミド繊維、数nm~数百nmの粒径のモンモリロナイトなどが挙げられる。これら添加剤は、電気絶縁性樹脂組成物100重量部に対して、例えば0.1~5重量部用いることができる。
前記電気絶縁性樹脂組成物は、耐熱性がより優れたものになり得るという点で、実施例に記載した方法で測定した、240℃で250時間経過した後の引張強度の強度残率が55%以上であることが好ましい。
前記電気絶縁性樹脂組成物は、耐引き裂き性がより優れたものになり得るという点で、実施例に記載した方法で測定した端裂抵抗値が20MPa以上であることが好ましい。
前記ポリアミド樹脂の含有割合が3質量%以上であることにより、樹脂組成物層2とシート材3との間の層間剥離がより生じにくくなり得るという利点がある。また、前記ポリアミド樹脂の含有割合が40質量%以下であることにより、樹脂組成物層2の耐熱性がより優れたものになり得るという利点があり、難燃性がより優れたものになるという利点がある。
前記シート材3としては、シート材と樹脂組成物層との間における層間剥離がより抑制され得るという点で、湿式抄紙法により作製された紙が好ましい。
前記全芳香族ポリアミド紙は、力学的特性に優れ、積層シートの製造工程におけるハンドリングが良好であるという点で、坪量が5g/m2以上であることが好ましい。坪量が5g/m2以上であることにより、力学的強度の不足が抑制され積層シートの製造中に破断しにくいという利点がある。
なお、前記全芳香族ポリアミド紙には、他の成分が配合されていてもよく、該他の成分としては、ポリフェニレンスルフィド繊維、ポリエーテルエーテルケトン繊維、ポリエステル繊維、アリレート繊維、液晶ポリエステル繊維、ポリエチレンナフタレート繊維などの有機繊維、又は、ガラス繊維、ロックウール、アスベスト、ボロン繊維、アルミナ繊維などの無機繊維が挙げられる。
前記全芳香族ポリアミド紙としては、例えば、デュポン社より商品名「ノーメックス」で市販されているもの等を用いることができる。
前記コロナ処理は、樹脂組成物層2と接するシート材3の一方の面に放電処理を行い、極性を持つカルボキシル基や水酸基を生成させ粗面化する処理である。前記コロナ処理としては、従来公知の一般的な方法を採用することができる。
前記積層シート1は、最表面に粘着層4を備えていることにより、粘着層4を被着物に貼り付けて使用することができる。具体的には、前記積層シート1は、耐熱性と電気絶縁性とが必要とされる用途において、例えば、前記粘着層4を金属製の板状の導体に貼り付けた状態で、シート状の電気絶縁材として使用することができる。
該粘着剤としては、(メタ)アクリル酸エステルを基本構成単位として有するアクリルポリマーを含有するアクリル系粘着剤アクリル系粘着剤、合成ゴムや天然ゴムなどのエラストマー性ポリマーを含有するゴム系粘着剤、シリコーンポリマーを含有するシリコーン系粘着剤、ポリエステルポリマーを含有するポリエステル系粘着剤、ポリウレタンポリマーを含有するポリウレタン系粘着剤等が挙げられ、なかでも、粘着特性や耐候性に優れるという点で、前記アクリル系粘着剤が好ましい。
また、前記粘着層4は、例えば、粘着層の保形性を高めるシート状の基材を有し、該基材の両面側に、少なくとも前記粘着剤を含む層状体が配された構成であってもよい。
なお、UL94規格は、米国のUnderwriters Laboratories社によって制定された燃焼試験の規格であり、一般的に知られているものである。また、UL94規格のVTM-O基準を満たす難燃性は、具体的には、実施例に記載された方法によって合格と判断されたものである。
前記樹脂組成物層2は、前記ポリスルホン樹脂と前記ポリアミド樹脂とを、例えば、ニーダー、加圧ニーダー、混練ロール、バンバリーミキサー、二軸押し出し機などの一般的な混合手段により混合して樹脂組成物を調製すること、及び、該樹脂組成物をT-ダイを取り付けた押出機によってシート状に押し出すことを行うことにより作製することができる。
また、前記粘着層4を備えた積層シート1は、例えば、上記のごとく2枚のシート材3で樹脂組成物層2を挟み込んで押圧すること、及び、該押圧したものの少なくとも一方の表面に、市販の粘着テープの粘着層を貼り付けることを行うことにより製造することができる。
また、本発明においては、一般の電気絶縁性樹脂組成物及び積層シートにおいて用いられる種々の態様を採用することができる。
ポリスルホン樹脂として、スルホニル基を複数含み複数のエーテル結合と複数の芳香族炭化水素とをさらに含むポリエーテルポリフェニルスルホン樹脂(PES)樹脂(ソルベイ社製 商品名「レーデルA-300A」)を用いた。
一方、ポリアミド樹脂として、テレフタル酸単位とノナンジアミン単位とからなるポリアミド(PA)樹脂(PA9T クラレ社製 商品名「ジェネスタN1000A」)を用いた。
PES樹脂とPA樹脂とをPES/PA=95/5の質量比になるように2軸混練機(テクノベル社製)を用いて310℃で混合し、電気絶縁性樹脂組成物を製造した。
PES樹脂とPA樹脂との質量比をPES/PA=90/10となるようにした点以外は、実施例1と同様にして電気絶縁性樹脂組成物を製造した。
PES樹脂とPA樹脂との質量比をPES/PA=80/20となるようにした点以外は、実施例1と同様にして電気絶縁性樹脂組成物を製造した。
PES樹脂とPA樹脂との質量比をPES/PA=70/30となるようにした点以外は、実施例1と同様にして電気絶縁性樹脂組成物を製造した。
PES樹脂とPA樹脂との質量比をPES/PA=60/40となるようにした点以外は、実施例1と同様にして電気絶縁性樹脂組成物を製造した。
電気絶縁性樹脂組成物に代えて、PES樹脂のみを用いた。
PES樹脂とPA樹脂との質量比がPES/PA=50/50となるようにした点以外は、実施例1と同様にして電気絶縁性樹脂組成物を製造した。
PES樹脂とPA樹脂との質量比がPES/PA=30/70となるようにした点以外は、実施例1と同様にして電気絶縁性樹脂組成物を製造した。
電気絶縁性樹脂組成物に代えて、ポリエチレンナフタレート(PEN)フィルム(帝人デュポンフィルム社製 商品名「テオネックス100μm」)を用意した。
電気絶縁性樹脂組成物に代えて、ポリフェニレンサルファイド(PPS)フィルム(東レ社製 商品名「トレリナ100μm」)を用意した。
製造した電気絶縁性樹脂組成物、又は樹脂を押出成形により310℃で100μm厚のシート状に成形し、シート体を作製した。
次に、シート体成形時の流れ方向に沿って15mm幅で切断した試験サンプルを作製した。作製した試験サンプルを240℃に加熱した恒温槽に250時間放置した。恒温槽に放置する前と後の試験サンプルについて、200mm/分、標線100mmの試験条件で引張試験を行い、引張強度を測定した。そして、下記の式により、強度残率を算出した。
強度残率(%)={(放置後の引張強度)/(放置前の引張強度)}×100
なお、比較例4及び5におけるフィルムに対しても同様にして上記評価を行った。
JIS C2134に準じて、シート体又はフィルムにおけるCTI(Comparative Tracking Index)値を測定した。
JIS C2111に準じて、シート体又はフィルムの縦(MD)方向と横(TD)方向の端裂抵抗値をそれぞれ測定した。
2枚の全芳香族ポリアミド紙(デュポン社製 商品名「ノーメックスT410」厚さ50μm)をシート材として用いた。
一方、ポリスルホン樹脂として、スルホニル基を複数含み複数のエーテル結合と複数の芳香族炭化水素とをさらに含むポリエーテルポリフェニルスルホン樹脂(PES)樹脂(ソルベイ社製 商品名「レーデルA-300A」)を用いた。
また、ポリアミド樹脂として、テレフタル酸単位とノナンジアミン単位とを含むポリアミド(PA)樹脂(PA9T クラレ社製 商品名「ジェネスタN1000A」)を用いた。
次に、PES樹脂とPA樹脂とをPES/PA=95/5の質量比になるように混合し、2軸混練機(テクノベル社製)を用いて310℃で混合し、樹脂組成物を調製した。
続いて、樹脂組成物を押出成形により310℃で100μm厚のシート状に成形して樹脂組成物層を形成し、その両面側にそれぞれ全芳香族ポリアミド紙を配置した。そして、2枚の金属板で挟み350℃に加熱した熱プレス機により、圧力200N/cm2で60秒間プレスし、積層シート(約200μm厚)を製造した。
樹脂組成物層におけるPES樹脂とPA樹脂との質量比がPES/PA=90/10となるように樹脂組成物層を形成した点、シート材にコロナ処理を施しコロナ処理面が樹脂組成物層と接するようにした点以外は、実施例6と同様にして積層シートを製造した。
なお、コロナ処理は、機器としてPILLAR TECHNOLOGIES社製「500シリーズ」を用いて、大気圧下で、出力500W、処理速度4m/分、試料幅0.4mの条件により行った。
樹脂組成物層におけるPES樹脂とPA樹脂との質量比がPES/PA=90/10となるように樹脂組成物層を形成した点以外は、実施例6と同様にして積層シートを製造した。
樹脂組成物層におけるPES樹脂とPA樹脂との質量比がPES/PA=80/20となるように樹脂組成物層を形成した点以外は、実施例6と同様にして積層シートを製造した。
樹脂組成物層におけるPES樹脂とPA樹脂との質量比がPES/PA=80/20となるように樹脂組成物層を形成した点、実施例7と同様なコロナ処理を施したシート材を用いた点以外は、実施例6と同様にして積層シートを製造した。
樹脂組成物層におけるPES樹脂とPA樹脂との質量比がPES/PA=70/30となるように樹脂組成物層を形成した点以外は、実施例6と同様にして積層シートを製造した。
樹脂組成物層におけるPES樹脂とPA樹脂との質量比がPES/PA=60/40となるように樹脂組成物層を形成した点以外は、実施例6と同様にして積層シートを製造した。
実施例10で製造した積層シートの片面側に、さらに下記の粘着層Aを貼り付け、粘着層を備えた積層シートを製造した。
粘着層A:
難燃性アクリル系粘着両面テープ(日東電工社製、商品名「No.5011N」)
から剥離材を剥がしたもの(厚み150μm)
(不織布の両面側にアクリル系粘着剤を含む粘着性の層が積層されたもの)
(UL94規格のVTM-O基準を満たす)
実施例10で製造した積層シートの片面側に、さらに下記の粘着層Bを貼り付け、粘着層を備えた積層シートを製造した。
粘着層B:
アクリル系粘着両面テープ(日東電工社製、商品名「No.500」)
から剥離材を剥がしたもの(厚み170μm)
(不織布の両面側にアクリル系粘着剤を含む粘着性の層が積層されたもの)
(UL94規格のVTM-O基準を満たさない)
PES樹脂のみで樹脂組成物層を形成した点以外は、実施例6と同様にして積層シートを製造した。
PES樹脂のみで樹脂組成物層を形成した点、実施例7と同様なコロナ処理を施したシート材を用いた点以外は、実施例6と同様にして積層シートを製造した。
樹脂組成物層におけるPES樹脂とPA樹脂との質量比がPES/PA=50/50となるように樹脂組成物層を形成した点以外は、実施例6と同様にして積層シートを製造した。
樹脂組成物層におけるPES樹脂とPA樹脂との質量比がPES/PA=30/70となるように樹脂組成物層を形成した点以外は、実施例6と同様にして積層シートを製造した。
樹脂組成物層に代えてポリエチレンナフタレート(PEN)フィルム(帝人デュポンフィルム社製 商品名「テオネックス100μm」)を用いた点、実施例7と同様なコロナ処理を施したシート材を用いた点以外は、実施例6と同様にして積層シートを製造した。
樹脂組成物層に代えてポリフェニレンサルファイド(PPS)フィルム(東レ社製 商品名「トレリナ100μm」)を用いた点、実施例7と同様なコロナ処理を施したシート材を用いた点以外は、実施例6と同様にして積層シートを製造した。
比較例10で製造した積層シートの片面側に、さらに上記の粘着層Aを貼り付け、粘着層を備えた積層シートを製造した。
製造した積層シートにおける樹脂組成物層の流れ方向に沿って15mm幅で切断した試験サンプルを作製した。また、作製した試験サンプルを240℃に加熱した恒温槽に250時間放置した。恒温槽に放置する前と後の試験サンプルについて、200mm/分、標線100mmの試験条件で引張試験を行い、引張強度を測定した。そして、下記の式により、強度残率を算出した。
強度残率(%)={(放置後の引張強度)/(放置前の引張強度)}×100
製造した積層シートを、樹脂組成物層の成形時の流れ方向に沿って10mm幅で切断して試験サンプルを用意した。また、製造した積層シートを23℃で24時間純水に浸漬した後、同様に10mm幅で切断して作製した試験サンプルを用意した。
これら試験サンプルにおいて、シート材(全芳香族ポリアミド紙)を樹脂組成物層に対して90℃の角度及び200mm/分の速さで引っ張ることにより25℃で剥離させ、剥離時の状態を観察した。そして、結果を下記の3段階で評価した。
○:シート材の破壊により剥離するもの
△:シート材の部分的な破壊により剥離するもの
×:シート材と樹脂組成物層との間で層間剥離するもの
UL94規格に準じて燃焼試験を行い、難燃性を評価した。
詳しくは、まず、各実施例、比較例で製造した積層シートを50mm×200mmの大きさにカットし、各々5つの試験片を得た。
試験片を円筒状に巻き、上下方向に延在するように配置し、上端を固定することによりつり下げ、下端から125mmの位置に標線をいれた。試験片の真下に脱脂綿を置き、試験片の下端に炎を3秒間あてて着火操作を行った。なお、着火操作は計2回行った。
そして、下記事項を全て満たしたものを合格(○)と判断した。即ち、VTM-Oの基準を満たすものを合格と判断した。一方、下記事項のいずれかを満たさないものを不合格(×)とした。
1.各試験片の合計有炎燃焼時間(最初の炎をあてた後の燃焼時間と、
2回目の炎をあてた後の燃焼時間の合計)が10秒以内である。
2.各試験片5つの合計有炎燃焼時間の総計が50秒以内である。
3.2回目に炎をあてた後の各試験片の有炎燃焼時間及び無炎燃焼時間が
30秒以内である。
4.いずれかの試験片から燃焼滴下物が落下して下に配置された綿に着火し
ない。
5.有炎が下端から125mmの標線に達しない。
本発明の積層シートは、耐熱性と電気絶縁性とを要する電気絶縁用シート材などとして好適に用いられ得る。具体的には、例えば、モーターのコイル線の周囲に配される電気絶縁用シート材、トランス、バスバー、コンデンサ、ケーブル用の電気絶縁用シート材、又は、電子回路基板の絶縁膜などの用途に好適である。
Claims (22)
- 分子中に複数のスルホニル基を含むポリスルホン樹脂と、ポリアミド樹脂とを含み、前記ポリアミド樹脂の含有割合が1~45質量%であることを特徴とする電気絶縁性樹脂組成物。
- 前記ポリスルホン樹脂が、分子中に複数のエーテル結合をさらに含むポリエーテルスルホン樹脂、又は、分子中に複数の芳香族炭化水素をさらに含むポリフェニルスルホン樹脂である請求項1記載の電気絶縁性樹脂組成物。
- 前記ポリアミド樹脂が芳香族炭化水素を含む請求項1又は2記載の電気絶縁性樹脂組成物。
- 耐トラッキング試験のCTI値が130V以上である請求項1~3のいずれか1項に記載の電気絶縁性樹脂組成物。
- 端裂抵抗値が20MPa以上である請求項1~4のいずれか1項に記載の電気絶縁性樹脂組成物。
- 240℃で250時間経過した後の引張強度の強度残率が55%以上である請求項1~5のいずれか1項に記載の電気絶縁性樹脂組成物。
- シート状に形成されている請求項1~6いずれか1項に記載の電気絶縁性樹脂組成物。
- 電気絶縁用途で使用する請求項1~7のいずれか1項に記載の電気絶縁性樹脂組成物。
- 分子中に複数のスルホニル基を含むポリスルホン樹脂とポリアミド樹脂とを含み前記ポリアミド樹脂の含有割合が1~45質量%である樹脂組成物層を介して、複数のシート材が貼り合わされてなることを特徴とする積層シート。
- 前記シート材が全芳香族ポリアミドを含んでいる請求項9に記載の積層シート。
- 前記シート材が、湿式抄紙法により作製された紙である請求項9又は10に記載の積層シート。
- 前記シート材が、全芳香族ポリアミドの繊維を含む全芳香族ポリアミド紙である請求項9~11のいずれか1項に記載の積層シート。
- 前記シート材が不織布である請求項9又は10に記載の積層シート。
- 前記シート材の少なくとも樹脂組成物層側には、コロナ処理が施されている請求項9~13のいずれか1項に記載の積層シート。
- 前記ポリスルホン樹脂が、分子中に複数のエーテル結合をさらに含むポリエーテルスルホン樹脂である請求項9~14のいずれか1項に記載の積層シート。
- 前記ポリスルホン樹脂が、分子中に複数の芳香族炭化水素をさらに含むポリフェニルスルホン樹脂である請求項9~15のいずれか1項に記載の積層シート。
- 前記ポリアミド樹脂が、分子中に芳香族炭化水素を有するポリアミド樹脂である請求項9~16のいずれか1項に記載の積層シート。
- 粘着性を有するシート状の粘着層をさらに備え、該粘着層が少なくとも一方側の最表面に配されている請求項9~17のいずれか1項に記載の積層シート。
- 前記粘着層が、UL94規格のVTM-O基準を満たす難燃性を有する請求項18に記載の積層シート。
- 前記樹脂組成物層の両面に接するように前記シート材が配され、前記樹脂組成物層及び前記シート材の各凝集破壊力より、前記樹脂組成物層と前記シート材との間の層間接着力が大きくなるように構成されている請求項9~19のいずれか1項に記載の積層シート。
- 240℃で250時間経過した後の引張強度の強度残率が50%以上である請求項9~20のいずれか1項に記載の積層シート。
- 電気絶縁用途で使用する請求項9~21のいずれか1項に記載の積層シート。
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CN201180034970.8A CN103003363B (zh) | 2010-07-16 | 2011-07-08 | 电绝缘性树脂组合物及层叠片 |
US13/810,013 US20130115844A1 (en) | 2010-07-16 | 2011-07-08 | Electrically insulating resin composition and laminate sheet |
EP11806708.1A EP2594610B1 (en) | 2010-07-16 | 2011-07-08 | Electrically insulating resin composition, and laminate sheet |
KR1020137003894A KR101771769B1 (ko) | 2010-07-16 | 2011-07-08 | 전기 절연성 수지 조성물, 및 적층 시트 |
US15/191,683 US11331876B2 (en) | 2010-07-16 | 2016-06-24 | Electrically insulating resin composition and laminate sheet |
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JP2010-161731 | 2010-07-16 | ||
JP2011143157A JP5710399B2 (ja) | 2010-07-16 | 2011-06-28 | 積層シート |
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US13/810,013 A-371-Of-International US20130115844A1 (en) | 2010-07-16 | 2011-07-08 | Electrically insulating resin composition and laminate sheet |
US15/191,683 Division US11331876B2 (en) | 2010-07-16 | 2016-06-24 | Electrically insulating resin composition and laminate sheet |
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JP5695927B2 (ja) * | 2011-02-09 | 2015-04-08 | 日東電工株式会社 | 電気絶縁性樹脂シート |
JP5964627B2 (ja) * | 2011-04-18 | 2016-08-03 | 日東シンコー株式会社 | 電気絶縁用立体形状物及び電気絶縁性シート材 |
WO2015070209A1 (en) | 2013-11-11 | 2015-05-14 | General Cable Technologies Corporation | Data cables having an intumescent tape |
CN103804903A (zh) * | 2014-02-27 | 2014-05-21 | 苏州市涵信塑业有限公司 | 一种改良性聚酰胺9t |
US9327923B1 (en) * | 2014-11-17 | 2016-05-03 | Quintin S. Marx | Portable heated ramp and method |
WO2018114681A1 (en) * | 2016-12-19 | 2018-06-28 | Abb Schweiz Ag | Laminated busbar with protective earth |
JP6811647B2 (ja) * | 2017-03-03 | 2021-01-13 | 住友化学株式会社 | 不織布 |
KR20200008835A (ko) * | 2018-07-17 | 2020-01-29 | 현대자동차주식회사 | 차량 구동모터의 코일 결선 유닛 및 이의 제조 방법 |
WO2023094231A1 (en) | 2021-11-23 | 2023-06-01 | Basf Se | Compositions comprising polyarylene(ether)sulfones |
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US20160303821A1 (en) | 2016-10-20 |
EP2594610A1 (en) | 2013-05-22 |
EP2594610B1 (en) | 2018-11-07 |
KR101771769B1 (ko) | 2017-08-25 |
KR20130037719A (ko) | 2013-04-16 |
US11331876B2 (en) | 2022-05-17 |
EP2594610A4 (en) | 2016-09-07 |
CN103003363B (zh) | 2015-02-04 |
CN103003363A (zh) | 2013-03-27 |
US20130115844A1 (en) | 2013-05-09 |
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