WO2020255360A1 - 樹脂組成物、樹脂組成物の製造方法及び絶縁電線 - Google Patents
樹脂組成物、樹脂組成物の製造方法及び絶縁電線 Download PDFInfo
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- WO2020255360A1 WO2020255360A1 PCT/JP2019/024609 JP2019024609W WO2020255360A1 WO 2020255360 A1 WO2020255360 A1 WO 2020255360A1 JP 2019024609 W JP2019024609 W JP 2019024609W WO 2020255360 A1 WO2020255360 A1 WO 2020255360A1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—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 C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08G73/00—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 C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C08G73/00—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 C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- H01B3/306—Polyimides or polyesterimides
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/22—Expandable microspheres, e.g. Expancel®
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- C—CHEMISTRY; METALLURGY
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2427/08—Homopolymers or copolymers of vinylidene chloride
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
- C08L2205/20—Hollow spheres
Definitions
- the present disclosure relates to a resin composition, a method for producing the resin composition, and an insulated electric wire.
- the resin composition according to one aspect of the present disclosure is a resin composition containing a polyamic acid and a solvent, and the polyamic acid has a repeating unit represented by the following general formula (1) in the molecular chain.
- One end or both ends of the molecular chain is a structure represented by the following general formula (2), and a structure represented by the following general formula (2) for 1 mol of the repeating unit represented by the following general formula (1).
- the ratio is 0.001 mol or more and 0.1 mol or less.
- R 1 is a tetravalent organic group.
- R 2 is a divalent organic group.
- R 1 has the same meaning as R 1 in the general formula (1).
- R 1 in the general formula (2) is identical to R 1 in the general formula (1) It may or may be different.
- R 3 is an organic group having 15 or less carbon atoms. When both ends of the molecular chain have the structure of the general formula (2), two R 1 and two R Each of 3 may be the same or different. * Indicates a binding site with a portion of the molecular chain different from the structure represented by the general formula (2).)
- the present disclosure has been made based on the above circumstances, and an object of the present disclosure is to provide a resin composition containing a high concentration of polyamic acid having excellent physical properties of a coating film after curing and high productivity.
- the resin composition of the present disclosure has excellent physical properties of the coating film after curing, high productivity, and can be increased in concentration. Therefore, the resin composition can be suitably used for forming an insulating layer of an insulated electric wire.
- the resin composition according to one aspect of the present disclosure is a resin composition containing a polyamic acid and a solvent, and the polyamic acid has a repeating unit represented by the following general formula (1) in the molecular chain.
- One end or both ends of the molecular chain is a structure represented by the following general formula (2), and a structure represented by the following general formula (2) for 1 mol of the repeating unit represented by the following general formula (1).
- the ratio is 0.001 mol or more and 0.1 mol or less.
- R 1 is a tetravalent organic group.
- R 2 is a divalent organic group.
- R 1 has the same meaning as R 1 in the general formula (1).
- R 1 in the general formula (2) is identical to R 1 in the general formula (1) It may or may be different.
- R 3 is an organic group having 15 or less carbon atoms. When both ends of the molecular chain have the structure of the general formula (2), two R 1 and two R Each of 3 may be the same or different. * Indicates a binding site with a portion of the molecular chain different from the structure represented by the general formula (2).
- the resin composition a high molecular weight polyamic acid can be easily obtained by setting the ratio of the structure represented by the above general formula (2) to 1 mol of the repeating unit within the above range. Therefore, the resin composition can be easily and surely increased in concentration. Moreover, since the resin composition is obtained in a one-step reaction step, the productivity is high.
- the "organic group” means a group containing at least one carbon atom.
- the "ratio of the structure represented by the above general formula (2) to 1 mol of the repeating unit” is an amount obtained as follows. First, the resin composition is diluted with N-methyl-2-pyrrolidone (NMP) and added dropwise to acetone while stirring with a stirrer. The solid content thus obtained is recovered and dried under vacuum for 12 hours or more. About 30 mg of the above solid content is taken, dissolved in dimethyl sulfoxide-d6 (DMSO-d6), and measured by 1 H NMR in a quantitative mode to obtain a spectrum.
- NMP N-methyl-2-pyrrolidone
- DMSO-d6 dimethyl sulfoxide-d6
- A the number of protons derived from the benzene ring
- B the number of protons derived from R 3 appearing in the spectrum
- the ratio of the structure represented by the above general formula (2) to 1 mol of the repeating unit is determined by (B / NB) / (A / NA).
- the ratio of the weight average molecular weight to the number average molecular weight of the polyamic acid is preferably 2.3 or less.
- weight average molecular weight and number average molecular weight are defined as JIS-K7252-1: 2008 "How to obtain the average molecular weight and molecular weight distribution of a polymer by plastic-size exclusion chromatography-Part 1: General rules". Refers to the value measured in polystyrene conversion by gel permeation chromatography in accordance with.
- the weight average molecular weight of the polyamic acid is preferably 15,000 or more.
- the number average molecular weight of the polyamic acid is preferably 8,000 or more.
- the polyamic acid is preferably a repeating unit polymer in which R 1 is a benzene-1,2,4,5-tetrayl group.
- the polyamic acid is a repeating unit in which R 1 is a benzene-1,2,4,5-tetrayl group and a repeating unit in which R 1 is a biphenyl-3,3', 4,4'-tetrayl group. It is preferable that it is a copolymer. By using the polyamic acid as the copolymer in this way, the heat resistance and the heat deterioration resistance after curing are improved.
- the average molar ratio of the repeating unit in which R 1 is a benzene-1,2,4,5-tetrayl group and the repeating unit in which R 1 is a biphenyl-3,3', 4,4'-tetrayl group is 2: 8 or more and 4: 6 or less is preferable.
- the average molar ratio is a repeating unit in which R 1 is a benzene-1,2,4,5-tetrayl group in the entire resin composition and the above R 1 is biphenyl-3,3', 4,4. '-The ratio to the repeating unit which is a tetrayl group.
- the average molar ratio can be determined by analyzing the spectrum measured in the quantitative mode by 1 1 H NMR.
- the polyamic acid and the free diamine compound having amino groups at both ends of the molecular chain are substantially not contained.
- the "free diamine compound” refers to an unreacted diamine compound contained in the resin composition.
- the concentration of the polyamic acid is preferably 25% by mass or more.
- concentration of the polyamic acid is a concentration calculated by Wa / Wb ⁇ 100 [mass%] from the mass Wb before drying and the mass Wa after drying after drying the resin composition at 250 ° C. for 2 hours. To say.
- the above solvent is an aprotic polar solvent.
- This aprotic polar solvent does not react with the acid dianhydride and the diamine compound which are the raw materials of the polyamic acid, and can function as a suitable solvent for the polyamic acid.
- the resin composition may contain a pore forming agent.
- a pore forming agent By containing the pore-forming agent in this way, pores can be included in the insulating layer when used as a resin composition for forming an insulating layer. Therefore, the dielectric constant of the insulating layer can be lowered, and the corona discharge starting voltage is improved. Therefore, it is possible to prevent dielectric breakdown of the insulating layer from occurring.
- the pore-forming agent is a chemical foaming agent.
- the pore-forming agent is a chemical foaming agent.
- the pore-forming agent is a heat-expandable microcapsule having a core material containing a heat-expanding agent and an outer shell surrounding the core material.
- the main component of the core material azobisisobutyronitrile and azodicarbonamide are preferable. Azobisisobutyronitrile and azo radical Boji amides, since generates N 2 gas by heating, while maintaining the chemical stability of the thermally expandable microcapsules may be thermally expanded.
- the "main component” is a component having the highest content, for example, a component contained in an amount of 50% by mass or more.
- a vinylidene chloride-acrylonitrile copolymer As the main component of the outer shell, a vinylidene chloride-acrylonitrile copolymer is preferable.
- the vinylidene chloride-acrylonitrile copolymer has excellent stretchability and expands without breaking when the thermally expandable microcapsules are expanded, and easily forms microballoons containing the generated gas.
- the pore-forming agent is hollow-forming particles having a core-shell structure. Since the hollow-forming particles having a core-shell structure have pores and an outer shell obtained by thermal decomposition of the core after the resin composition is cured, the communication of pores is suppressed even when the pores are formed. Therefore, when used as a resin composition for forming an insulating layer, it is easy to increase the dielectric breakdown voltage of the insulating layer.
- the "core-shell structure” refers to a structure in which the material forming the core of the particles and the material of the shell surrounding the core are different.
- the core of the hollow-forming particles contains a pyrolyzable resin as a main component, and the thermal decomposition temperature of the main component of the shell of the hollow-forming particles is higher than the thermal decomposition temperature of the thermally decomposable resin.
- the thermal decomposition temperature of the main component of the shell of the hollow-forming particles is higher than the thermal decomposition temperature of the thermally decomposable resin.
- Silicone is preferable as the main component of the shell of the hollow-forming particles.
- silicone By using silicone as the main component of the shell of the hollow-forming particles in this way, it is easy to impart elasticity to the shell and improve the insulating property and heat resistance, and as a result, it becomes easier to maintain independent pores due to the hollow-forming particles. ..
- the pore forming agent is a high boiling point solvent having a boiling point higher than that of the solvent.
- the boiling point of the high boiling point solvent is preferably 180 ° C. or higher and 300 ° C. or lower.
- the resin composition may contain a thermosetting resin.
- a thermosetting resin When used as a resin composition for forming an insulating layer by containing the thermosetting resin in this way, the pyrolyzable resin is thermally decomposed by heating at the time of curing, and the thermosetting resin is formed at the time of forming the insulating layer. Pore can be easily formed in the portion where the resin was present.
- thermosetting resin is a crosslinked product of a (meth) acrylic polymer.
- the (meth) acrylic polymer tends to be evenly distributed in the sea phase of polyamic acid as an island phase of fine particles. Further, by forming it as a crosslinked product, it is excellent in compatibility with polyamic acid and easily organized in a spherical shape. Therefore, by using the thermosetting resin as a crosslinked product of the (meth) acrylic polymer, spherical pores can be evenly distributed after curing.
- the thermosetting resin is preferably spherical resin particles, and the average particle diameter of the resin particles is preferably 0.1 ⁇ m or more and 50 ⁇ m or less.
- the average particle size of the resin particles By setting the average particle size of the resin particles within the above range, it is easy to obtain pores having a uniform distribution.
- the "average particle size” means a particle size indicating the highest volume content ratio in the particle size distribution measured by a laser diffraction type particle size distribution measuring device.
- the resin composition may contain a hollow filler.
- a hollow filler By containing the hollow filler in this way, when it is used as a resin composition for forming an insulating layer, the hollow portion inside the hollow filler becomes pores. In addition, the flexibility and mechanical strength of the obtained insulating layer can be easily controlled.
- the hollow filler may be an organic resin balloon, a glass balloon, or a combination thereof.
- the organic resin balloon tends to increase the flexibility of the obtained insulating layer.
- the glass balloon tends to increase the mechanical strength of the obtained insulating layer. Therefore, by using the hollow filler as an organic resin balloon, a glass balloon, or a combination thereof, the flexibility and mechanical strength controllability of the obtained insulating layer can be enhanced.
- the method for producing a resin composition according to another aspect of the present disclosure contains a polyamic acid and a solvent, and the polyamic acid has a repeating unit represented by the following general formula (1) in the molecular chain.
- a step of polymerizing the diamine compound represented by (4) in the presence of an aprotic polar solvent and a reaction control agent is provided, and the content of the reaction control agent is adjusted to the acid dianhydride in the polymerization step.
- the amount is 0.1 mol or more and 300 mol or less with respect to 100 mol.
- R 1 is a tetravalent organic group.
- R 2 is a divalent organic group.
- R 1 has the same meaning as R 1 in the general formula (1).
- R 1 in the general formula (2) is identical to R 1 in the general formula (1) It may or may be different.
- R 3 is an organic group having 15 or less carbon atoms. When both ends of the molecular chain have the structure of the general formula (2), two R 1 and two R Each of 3 may be the same or different.
- R 1 is synonymous with R 1 in the general formula (1).
- R 2 is synonymous with R 2 in the general formula (1).
- the production can be carried out in one step and the productivity is high.
- the manufacturing method of the resin composition is sealed in a structure represented by the above general formula (2) containing R 3 derived from the molecular chain ends in an appropriate amount of the reaction controlling agent. Therefore, in the method for producing the resin composition, the molecular weight can be increased while easily controlling the molecular weight of the polyamic acid.
- the acid dianhydride and the diamine compound may be substantially equimolar.
- the acid dianhydride and the diamine compound substantially equimolar in the step of polymerizing in this way, the molecular weight of the polyamic acid can be further increased.
- the "substantially equimolar amount” means a range in which the ratio of the two is 99: 101 or more and 101: 99 or less, preferably 99.9: 100.1 or more and 100.1: 99.9 or less.
- R 1 is a benzene-1,2,4,5-tetrayl group.
- R 1 is a benzene-1,2,4,5-tetrayl group and a biphenyl-3,3', 4,4'-tetrayl group.
- R 1 a benzene-1,2,4,5-tetrayl group and a biphenyl-3,3', 4,4'-tetrayl group.
- the above R 1 becomes a benzene-1 as a polyamic acid.
- 2,4,5 repeating units tetrayl a group the R 1 is 3,3 ', copolymer of repeating units is 4,4'-tetrayl groups are obtained.
- the polyamic acid as the copolymer, the heat resistance and moisture heat deterioration resistance of the obtained resin composition after curing can be improved.
- the ratio is preferably 2: 8 or more and 4: 6 or less.
- a step of dispersing the pore forming agent in the reaction mixture after the above-mentioned polymerization step.
- thermosetting resin it is preferable to include a step of mixing the thermosetting resin with the reaction mixture after the above-mentioned polymerization step.
- the thermally decomposable resin in the resin composition thus obtained, when it is used as a resin composition for forming an insulating layer, the thermally decomposable resin is thermally decomposed by heating at the time of curing to form an insulating layer. Pore can be easily formed in the portion where the pyrolytic resin was sometimes present.
- the insulated wire according to still another aspect of the present disclosure is an insulated wire having a linear conductor and an insulating layer that covers the conductor directly or via another layer, and the insulating layer is It is formed of the resin composition of the present disclosure.
- the productivity is high and the film elongation of the insulating layer is excellent.
- the resin composition is a resin composition containing a polyamic acid and a solvent.
- the resin composition contains a pore-forming agent.
- the upper limit of the viscosity of the resin composition at 30 ° C. is preferably 100,000 cps, more preferably 80,000 cps. If the viscosity of the resin composition at 30 ° C. is less than the above lower limit, it becomes difficult to uniformly apply the resin composition, and the coating of the insulated wire may be insufficient. On the other hand, if the viscosity of the resin composition at 30 ° C. exceeds the above upper limit, coating of the resin composition may become difficult.
- the viscosity of the resin composition can be controlled by adjusting the amount of the reaction control agent and the reaction temperature at the time of the reaction of the acid dianhydride and the diamine compound in the method for producing the resin composition described later.
- the resin composition does not substantially contain a polyamic acid and a free diamine compound having amino groups at both ends of the molecular chain.
- the polyamic acid has a repeating unit represented by the following general formula (1) in the molecular chain, and one end or both ends of the molecular chain has a structure represented by the following general formula (2).
- R 1 is a tetravalent organic group.
- R 1 include benzene-1,2,4,5-tetrayl group, biphenyl-3,3', 4,4'-tetrayl group, benzophenone-2,2', 3,3'-tetrayl group, and the like.
- R 1 may be used alone or in combination of two or more. That is, in the above general formula (1) and the above general formula (2), R 1 of the molecular chain may be an organic group different between the molecular chains, and one molecular chain is different within the molecular chain. It may be an organic group.
- R 2 is a divalent organic group.
- examples of R 2 include m-phenylene group, p-phenylene group, 2,2-diphenylpropane-4,4'-diyl group, 2,2-diphenylpropane-3,3'-diyl group, 2,2.
- R 2 may be used alone or in combination of two or more. That is, in the above general formula (1), R 2 of the molecular chain may be an organic group different between the molecular chains, or one molecular chain may be an organic group different within the molecular chain. ..
- R 3 is an organic group having 1 or more and 15 or less carbon atoms.
- R 3 include monovalent hydrocarbon groups such as ethyl group, methyl group, n-propyl group, i-propyl group, t-butyl group, n-butyl group and n-pentyl group, and hydrocarbons thereof.
- Examples of a group obtained by substituting a part or all of the hydrogen atom of the group with a hydroxyl group such as a hydroxylethyl group, a hydroxypropyl group, a 1,3-dihydroxypropyl group, and a 1,2-dihydroxypropyl group, can be mentioned. ..
- an ethyl group and a methyl group are preferable from the viewpoint of reactivity and cost.
- the polyamic acid may be a polymer of repeating units in which R 1 is a benzene-1,2,4,5-tetrayl group.
- the polyamic acid is a repeating unit in which the R 1 is a benzene-1,2,4,5-tetrayl group, and the R 1 is a biphenyl-3,3', 4,4'.
- -It is preferable that it is a copolymer with a repeating unit which is a tetrayl group.
- the upper limit of the average molar ratio 40:60 is preferable, and 50:50 is more preferable. If the average molar ratio is less than the above lower limit, the moisture resistance and heat deterioration resistance of the insulating layer formed by curing the resin composition may be insufficient. On the contrary, if the average molar ratio exceeds the upper limit, the heat resistance of the insulating layer formed by curing the resin composition may be insufficient.
- the structure represented by the general formula (2) seals the molecular chain end of the polyamic acid having a repeating unit represented by the general formula (1). By sealing the end of the molecular chain of the polyamic acid in this way, the molecular weight of the polyamic acid can be controlled.
- the lower limit of the ratio of the structure represented by the general formula (2) to 1 mol of the repeating unit represented by the general formula (1) is 0.001 mol, more preferably 0.002 mol.
- the upper limit of the ratio of the structure represented by the general formula (2) is 0.1 mol, more preferably 0.07 mol. If the proportion of the structure represented by the general formula (2) is less than the above lower limit, the molecular chain may become long and the viscosity of the resin composition may become too high. On the contrary, if the ratio of the structure represented by the general formula (2) exceeds the above upper limit, the chain extension reaction at the time of curing the resin composition may be inhibited and a sufficient high molecular weight substance may not be obtained. ..
- the molecular weight of the polyamic acid can be controlled by adjusting the amount of the reaction control agent and the reaction temperature at the time of the reaction of the acid dianhydride and the diamine compound.
- the lower limit of the weight average molecular weight (Mw) of the polyamic acid 15,000 is preferable, and 16,000 is more preferable.
- the upper limit of the weight average molecular weight of the polyamic acid is preferably 100,000, more preferably 50,000. If the weight average molecular weight of the polyamic acid is less than the above lower limit, the film elongation when forming the insulating layer of the insulated wire may be insufficient. On the other hand, if the weight average molecular weight of the polyamic acid exceeds the upper limit, the viscosity of the resin composition may become too high.
- the lower limit of the number average molecular weight (Mn) of the polyamic acid is preferably 8,000, more preferably 10,000, and even more preferably 15,000.
- the upper limit of the number average molecular weight of the polyamic acid is preferably 100,000, more preferably 50,000. If the number average molecular weight of the polyamic acid is less than the above lower limit, the low molecular weight component increases, so that the mechanical strength of the obtained insulating layer may decrease or the coating strength of the insulating layer may not be maintained in a high thermal environment. is there. On the other hand, if the number average molecular weight of the polyamic acid exceeds the upper limit, the viscosity of the resin composition may become too high.
- the upper limit of the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polyamic acid 2.3 is preferable, and 2.1 is more preferable.
- the above ratio (Mw / Mn) is an index showing the polydispersity of the molecular weight of the polyamic acid.
- the lower limit of the concentration of the polyamic acid with respect to the entire resin composition is preferably 25% by mass, more preferably 26% by mass.
- the upper limit of the concentration of the polyamic acid is preferably 35% by mass, more preferably 34% by mass. If the concentration of the polyamic acid is less than the above lower limit, the workability when used as a resin composition for an insulating layer of an insulated wire may decrease. On the other hand, if the concentration of the polyamic acid exceeds the upper limit, the viscosity of the resin composition may become too high.
- solvent Various organic solvents can be used as the solvent, and it is preferable that the solvent is an aprotic polar solvent. This aprotic polar solvent does not react with the acid dianhydride and the diamine compound which are the raw materials of the polyamic acid, and can function as a suitable solvent for the polyamic acid.
- the upper limit of the amount of the aprotic polar solvent is preferably 1500 mol, more preferably 1200 mol. If the amount of the aprotic polar solvent is less than the above lower limit, the polymerization reaction between the acid dianhydride which is the raw material of the polyamic acid and the diamine compound proceeds rapidly, and the viscosity of the resin composition may become too high. ..
- the amount of the aprotic polar solvent exceeds the above upper limit, it is necessary to volatilize a large amount of solvent when used as a resin composition for an insulating layer of an insulating electric wire, and it takes time to form the insulating layer. It may take.
- aprotic polar solvent examples include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), dimethylformamide (DMF) and the like. These may be used alone or as a mixture of two or more.
- pores forming agent By containing the pore-forming agent in the resin composition, pores can be included in the insulating layer when the resin composition is used as the resin composition for forming the insulating layer. Therefore, the dielectric constant of the insulating layer can be lowered, and the corona discharge starting voltage is improved. Therefore, it is possible to prevent dielectric breakdown of the insulating layer from occurring.
- pore-forming agent examples include chemical foaming agents, heat-expandable microcapsules, hollow-forming particles having a core-shell structure, and high boiling point solvents.
- ⁇ Chemical foaming agent> When the insulating layer of the insulated wire is formed by applying and curing the resin composition to the conductor, the chemical foaming agent foams by heating during curing by baking to generate pores in the insulating layer.
- the pore-forming agent As a chemical foaming agent in this way, pores can be easily formed when the resin composition is cured by baking.
- azobisisobutyronitrile which produces nitrogen gas (N 2 gas)
- a substance having a thermal decomposition property such as azo radical Boji amide is preferably used by heating.
- the lower limit of the foaming temperature of the chemical foaming agent is preferably 180 ° C., more preferably 210 ° C.
- the upper limit of the foaming temperature 300 ° C. is preferable, and 260 ° C. is more preferable. If the foaming temperature is less than the above lower limit, foaming is likely to occur before baking, and it may be difficult to adjust the thickness of the insulating layer. On the contrary, if the foaming temperature exceeds the upper limit, the baking temperature may rise and the baking time may be lengthened, which may increase the manufacturing cost of the insulated wire.
- the "foaming temperature” is the temperature at which the foaming agent starts foaming.
- the “baking time” is a time for holding the conductor coated with the resin composition at the baking temperature.
- the heat-expandable microcapsules have a core material containing a heat-expanding agent and an outer shell that encloses the core material.
- the heat-expanding agent contained in the core material expands or foams by the heating of the baking, and the outer shell is expanded to form pores. Therefore, by using the heat-expandable microcapsules as the pore-forming agent, the controllability of the pore size can be enhanced.
- the thermal expansion agent may be any one that expands or generates a gas by heating, and the principle thereof is not limited.
- a low boiling point liquid for example, a low boiling point liquid, a chemical foaming agent, or a mixture thereof can be used.
- the low boiling point liquid include alkanes such as butane, i-butane, n-pentane, i-pentane, and neopentane, and chlorofluorocarbons such as trichlorofluoromethane.
- the chemical blowing agent azobisisobutyronitrile that generates N 2 gas by heating, it includes materials having a thermal decomposition property such as azo radical Boji amide.
- the core material may contain the thermal expansion agent as a main component, and azobisisobutyronitrile and azodicarbonamide are preferable as the main components of the core material.
- Azobisisobutyronitrile and azo radical Boji amides since generates N 2 gas by heating, while maintaining the chemical stability of the thermally expandable microcapsules may be thermally expanded.
- the expansion start temperature of the thermal expansion agent that is, the boiling point of the low boiling point liquid or the thermal decomposition temperature of the chemical foaming agent is set to be equal to or higher than the softening temperature of the outer shell of the thermal expansion microcapsule described later. More specifically, as the lower limit of the expansion start temperature of the thermal expansion agent, 60 ° C. is preferable, and 70 ° C. is more preferable. On the other hand, the upper limit of the expansion start temperature of the thermal expansion agent is preferably 200 ° C., more preferably 150 ° C. If the expansion start temperature of the thermal expansion agent is less than the above lower limit, the thermal expansion microcapsules may unintentionally expand during formation, transportation, or storage of the insulating layer. On the contrary, if the expansion start temperature of the thermal expansion agent exceeds the upper limit, the energy cost required for expanding the thermal expansion microcapsules may become excessive.
- the material of the outer shell is a stretchable material capable of forming a microballoon containing the generated gas by expanding without breaking when the thermal expansion agent expands.
- a resin composition such as a thermoplastic resin is usually used.
- the thermoplastic resin include a polymer formed from monomers such as vinyl chloride, vinylidene chloride, acrylonitrile, acrylic acid, methacrylic acid, acrylate, methacrylate, and styrene, or two or more kinds of monomers. Examples thereof include the formed copolymers.
- a vinylidene chloride-acrylonitrile copolymer is preferable as the main component of the outer shell.
- the vinylidene chloride-acrylonitrile copolymer has excellent stretchability and expands without breaking when the thermally expandable microcapsules are expanded, and easily forms microballoons containing the generated gas.
- the expansion start temperature of the thermal expansion agent is 80 ° C. or higher and 150 ° C. or lower.
- Hollow particles having a core-shell structure are obtained by gasifying and removing the core by heating the above-mentioned baking. Since the hollow-forming particles have pores and an outer shell obtained by thermal decomposition of the core after the resin composition is cured, the communication of the pores is suppressed even when the pores are formed. Therefore, when used as a resin composition for forming an insulating layer, it is easy to increase the dielectric breakdown voltage of the insulating layer.
- the core of the hollow-forming particles should be mainly composed of a thermosetting resin.
- the thermodegradable resin is not particularly limited, and is, for example, a compound in which one or both ends or a part of polyethylene glycol, polypropylene glycol or the like is alkylated, (meth) acrylated or epoxidized; methyl poly (meth) acrylate.
- a polymer of a (meth) acrylic acid ester having an alkyl group having 1 to 6 carbon atoms is preferable in that pores are easily formed in the insulating layer.
- the polymer of such a (meth) acrylic acid ester include polymethylmethacrylate (PMMA).
- the shape of the core is preferably spherical.
- spherical thermosetting resin particles may be used as the core.
- the lower limit of the average particle diameter of the resin particles is not particularly limited, but for example, 0.1 ⁇ m is preferable, 0.5 ⁇ m is more preferable, and 1 ⁇ m is further preferable.
- the upper limit of the average particle size of the resin particles is preferably 15 ⁇ m, more preferably 10 ⁇ m. If the average particle size of the resin particles is less than the above lower limit, it may be difficult to produce hollow-forming particles having the resin particles as a core.
- the average particle diameter of the resin particles exceeds the upper limit, the hollow-forming particles having the resin particles as the core become too large, so that the distribution of pores in the insulating layer becomes difficult to be uniform, and the dielectric constant becomes high. There is a risk that the distribution will be biased.
- the main component of the shell it is preferable to use one having a thermal decomposition temperature higher than the thermal decomposition temperature of the thermosetting resin.
- the hollow particles can be formed only by the outer shell whose inside is hollow by heating, so that pores can be easily formed.
- the main component of the shell one having a low dielectric constant and high heat resistance is preferable.
- resins such as polystyrene, silicone, fluororesin, and polyimide.
- the "fluorine resin” is an organic group in which at least one hydrogen atom bonded to a carbon atom constituting a repeating unit of a polymer chain has a fluorine atom or a fluorine atom (hereinafter, also referred to as "fluorine atom-containing group”). ) Replaced with.
- the fluorine atom-containing group is one in which at least one of the hydrogen atoms in the linear or branched organic group is substituted with a fluorine atom, and examples thereof include a fluoroalkyl group, a fluoroalkoxy group, and a fluoropolyether group. Can be done.
- the shell may contain a metal as long as the insulating property is not impaired.
- silicone is preferable as the main component of the shell.
- silicone is preferable as the main component of the shell.
- silicone is easy to impart elasticity to the shell and improve the insulating property and heat resistance, and as a result, it is easy to maintain independent pores by the hollow-forming particles. Become.
- the lower limit of the average thickness of the shell is not particularly limited, but for example, 0.01 ⁇ m is preferable, and 0.02 ⁇ m is more preferable.
- the upper limit of the average thickness of the shell is preferably 0.5 ⁇ m, more preferably 0.4 ⁇ m. If the average thickness of the shell is less than the above lower limit, the effect of suppressing the communication of pores may not be sufficiently obtained. On the contrary, if the average thickness of the shell exceeds the upper limit, the volume of the pores becomes too small, and the porosity of the insulating layer may not be increased more than a predetermined value.
- the shell may be formed of one layer or a plurality of layers. When the shell is formed of a plurality of layers, the average of the total thicknesses of the plurality of layers may be within the above range.
- the upper limit of the CV value of the hollow-forming particles is preferably 30%, more preferably 20%.
- the insulating layer contains a plurality of pores having different sizes, so that the distribution of the dielectric constant may be easily biased.
- the lower limit of the CV value of the above-mentioned air-forming particles is not particularly limited, but is preferably 1%, for example. If the CV value of the hollow-forming particles is less than the above lower limit, the production cost of the hollow-forming particles may become too high.
- the “CV value” means a variable variable defined in JIS-Z8825 (2013).
- the hollow-forming particles may be configured such that the core is formed of one thermosetting resin particle, or the core is formed of a plurality of thermosetting resin particles, and the shell forms these plurality of heats. It may be configured to cover the decomposable resin particles.
- the surface of the hollow-forming particles may be smooth without unevenness, or unevenness may be formed.
- the high boiling point solvent has a higher boiling point than the solvent of the above resin composition and is used for bubble formation.
- the lower limit of the boiling point of the high boiling point solvent is preferably 180 ° C., more preferably 210 ° C.
- the upper limit of the boiling point of the high boiling point solvent is preferably 300 ° C., more preferably 260 ° C. If the boiling point of the high boiling point solvent is less than the above lower limit, the amount of volatilization when the solvent of the resin composition is volatilized increases, and bubbles may not be sufficiently formed. On the contrary, when the boiling point of the high boiling point solvent exceeds the above upper limit, the high boiling point solvent is difficult to volatilize, and bubbles may not be sufficiently formed.
- diethylene glycol dimethyl ether diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol monomethyl ether and the like can be used.
- Triethylene glycol dimethyl ether is preferable because the variation in bubble diameter is small.
- dipropylene glycol dimethyl ether diethylene glycol ethyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, tri Ethethylene glycol monomethyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, propylene glycol monomethyl ether and the like can also be used.
- the above-mentioned high boiling point solvent may be used alone, but it is preferable to use two or more in combination because the effect of generating bubbles in a wide temperature range can be obtained.
- preferred combinations are tetraethylene glycol dimethyl ether and diethylene glycol dibutyl ether, diethylene glycol dibutyl ether and triethylene glycol dimethyl ether, triethylene glycol monomethyl ether and tetraethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether.
- a combination containing tetraethylene glycol dimethyl ether is a combination containing diethylene glycol dibutyl ether and triethylene glycol dimethyl ether, and triethylene glycol monomethyl ether and tetraethylene glycol dimethyl ether.
- the high boiling point solvent has a higher boiling point than the solvent of the resin composition, but when one kind of high boiling point solvent is used, the lower limit of the difference in boiling points is preferably 10 ° C. It is known that the high boiling point solvent has the roles of both a bubble nucleating agent and a foaming agent when used alone. On the other hand, when two or more kinds of high boiling point solvents are used, the high boiling point solvent having the highest boiling point (hereinafter, also referred to as "highest boiling point solvent”) acts as a foaming agent, and the other high boiling point solvents are used as bubble nucleating agents. It works.
- the lower limit of the difference in boiling point between the highest boiling point solvent and the solvent of the resin composition is preferably 20 ° C., more preferably 30 ° C.
- the upper limit of the difference in boiling points is preferably 60 ° C.
- the lower limit of the difference in boiling point between the other high boiling point solvent and the solvent of the resin composition is preferably 10 ° C.
- the lower limit of the ratio of the highest boiling point solvent to another high boiling point solvent is preferably 1:99 in terms of mass ratio, and is preferably 1:10. Is more preferable.
- the upper limit of the ratio is preferably 99: 1 and more preferably 10: 1.
- the solubility of the polyamic acid in another high boiling point solvent is larger than the solubility of the polyamic acid in the highest boiling point solvent.
- the resin composition can easily obtain a high molecular weight polyamic acid having a controlled molecular weight. .. Therefore, the resin composition can be easily and surely increased in concentration. Moreover, since the resin composition is obtained in a one-step reaction step, the productivity is high.
- the method for producing the resin composition contains a polyamic acid and a solvent, and the polyamic acid has a repeating unit represented by the following general formula (1) in the molecular chain, and one end or both ends of the molecular chain.
- a resin composition having a structure represented by the following general formula (2) that is, the resin composition can be produced.
- the method for producing the resin composition includes a step of polymerizing and a step of dispersing the pore-forming agent.
- R 1 is a tetravalent organic group.
- R 2 is a divalent organic group.
- R 1 has the same meaning as R 1 in the general formula (1).
- R 1 in the general formula (2) is identical to R 1 in the general formula (1) It may or may be different.
- R 3 is an organic group having 15 or less carbon atoms. When both ends of the molecular chain have the structure of the general formula (2), two R 1 and two R Each of 3 may be the same or different. * Indicates a binding site with a portion of the molecular chain different from the structure represented by the general formula (2).)
- acid dianhydride examples include pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 3,.
- PMDA pyromellitic dianhydride
- BPDA biphenyltetracarboxylic dianhydride
- 2,2', 3,3'-benzophenonetetracarboxylic dianhydride 3,.
- the acid dianhydride is a pyromellitic dianhydride, that is, R 1 is a benzene-1,2,4,5-tetrayl group.
- R 1 is a benzene-1,2,4,5-tetrayl group.
- the acid dianhydride is pyromellitic dianhydride and biphenyltetracarboxylic dianhydride, that is, R 1 is a benzene-1,2,4,5-tetrayl group and biphenyl-3. , 3', 4,4'-Tetrayl group is preferable.
- R 1 is a benzene-1,2,4,5-tetrayl group and a biphenyl-3,3', 4,4'-tetrayl group in this way, the above R 1 becomes a benzene-1 as a polyamic acid.
- the pyromellitic dianhydride in which R 1 is a benzene-1,2,4,5-tetrayl group and the biphenyltetracarboxylic dianhydride in which R 1 is a biphenyl-3,3', 4,4'-tetrayl group As the lower limit of the molar ratio with the anhydride, 2: 8 is preferable, and 1: 3 is more preferable. On the other hand, as the upper limit of the average molar ratio, 4: 6 is preferable, and 1: 2 is more preferable. If the average molar ratio is less than the above lower limit, the moisture resistance and heat deterioration resistance of the insulating layer formed by curing the obtained resin composition may be insufficient. On the contrary, if the average molar ratio exceeds the upper limit, the heat resistance of the insulating layer formed by curing the obtained resin composition may be insufficient.
- diamine compound an aromatic diamine or a derivative thereof is used.
- examples of such a diamine compound include m-phenylenediamine, p-phenylenediamine, 4,4'-diamino-diphenylpropane, 3,3'-diamino-diphenylpropane, and 2,2-bis [4- (4- (4- (4- (4- (4- (4-) Aminophenoxy) phenyl] propane, 4,4'-diamino-diphenylmethane, 3,3'-diamino-diphenylmethane, 4,4'-diamino-diphenylsulfide, 3,3'-diamino-diphenylsulfide, 4,4'- Diamino-diphenylsulfone, 3,3′-diamino-diphenylsulfone, 4,4′-diamino-diphenylether, 3,3′-diamino-dipheny
- reaction control agent examples include alcohols having 1 or more and 15 or less carbon atoms.
- monohydric alcohols such as ethanol, methanol, n-propyl alcohol, i-propyl alcohol, t-butyl alcohol, n-butyl alcohol and n-pentyl alcohol, and polyhydric such as ethylene glycol, propylene glycol and glycerin. Alcohol and the like can be mentioned. Among these, ethanol and methanol are preferable from the viewpoint of reactivity and cost.
- aprotic polar solvent can be the same as the aprotic polar solvent of the resin composition described above, detailed description thereof will be omitted.
- this polymerization step can be performed by, for example, the following procedure. First, the aprotic polar solvent and the reaction control agent are mixed, and the diamine compound is dissolved in the aprotic polar solvent and the reaction control agent. Next, the acid dianhydride is added to the solution in which the diamine compound is dissolved in the aprotic polar solvent and the reaction control agent to polymerize the acid dianhydride and the diamine compound.
- the acid dianhydride is added to a solution in which the diamine compound is dissolved in the aprotic polar solvent and the reaction control agent.
- the acid dianhydride is added to the aprotic polar solvent and the reaction control agent. It can also be polymerized by adding a diamine compound to the dissolved solution.
- the acid dianhydride is added at a constant speed while stirring the solution.
- the polymerization reaction can be easily controlled by adding the acid dianhydride at a constant rate.
- the temperature at the time of the polymerization reaction and the charging time of the acid dianhydride are appropriately determined according to the amount of the resin composition to be produced and the like.
- the lower limit of the content of the reaction control agent with respect to 100 mol of the acid dianhydride is 0.1 mol.
- the upper limit of the content of the reaction control agent is 300 mol.
- the content of the reaction control agent is less than the above lower limit, the reaction of the acid dianhydride and the diamine compound proceeds excessively until the terminal of the molecular chain of the polyamic acid has a structure represented by the general formula (2). , The viscosity of the resin composition may become too high.
- the content of the reaction control agent exceeds the above upper limit, the molecular chain terminal of the polyamic acid quickly becomes a structure represented by the above general formula (2) too much, and the chain when the resin composition is cured. The elongation reaction may be inhibited and a sufficient high molecular weight substance may not be obtained.
- the acid dianhydride and the diamine compound may be substantially equimolar.
- the molecular weight of the polyamic acid can be further increased.
- the step of dispersing the pore-forming agent may include a step of mixing a thermosetting resin with the reaction mixture after the polymerization step.
- a thermosetting resin By including the thermally decomposable resin in the resin composition thus obtained, when it is used as a resin composition for forming an insulating layer, the thermally decomposable resin is thermally decomposed by heating at the time of curing to form an insulating layer. Pore can be easily formed in the portion where the pyrolytic resin was sometimes present.
- the pore-forming agent can be the same as the pore-forming agent of the resin composition described above, detailed description thereof will be omitted.
- the content of the pore-forming agent is appropriately determined based on the solid content of the resin composition so that the porosity of the insulating layer to be formed becomes a desired value.
- the lower limit of the porosity of the insulating layer to be formed 5% by volume is preferable, and 10% by volume is more preferable.
- the upper limit of the porosity 80% by volume is preferable, and 50% by volume is more preferable. If the porosity is less than the above lower limit, the dielectric constant of the insulating layer may not be sufficiently lowered, and the corona discharge starting voltage may not be sufficiently improved. On the contrary, if the porosity exceeds the upper limit, the mechanical strength of the insulating layer may not be maintained.
- the method for producing the resin composition since the acid dianhydride and the diamine compound are polymerized in the presence of an aprotic polar solvent and a reaction control agent, the production can be carried out in one step and the productivity is high.
- the manufacturing method of the resin composition is sealed in a structure represented by the above general formula (2) containing R 3 derived from the molecular chain ends in an appropriate amount of the reaction controlling agent. Therefore, in the method for producing the resin composition, the molecular weight can be increased while easily controlling the molecular weight of the polyamic acid.
- the insulated wire has a linear conductor and an insulating layer that covers the conductor directly or via another layer.
- the conductor usually contains a metal as a main component.
- the metal is not particularly limited, but copper, a copper alloy, aluminum, or an aluminum alloy is preferable. By using the above metal for the conductor, an insulated wire having good workability, conductivity and the like can be obtained.
- the conductor may contain other components such as known additives in addition to the metal as the main component.
- the cross-sectional shape of the conductor is not particularly limited, and various shapes such as a circle, a square, and a rectangle can be adopted. Further, the size of the cross section of the conductor is not particularly limited, and the diameter (short side width) can be, for example, 0.2 mm or more and 2.0 mm or less.
- the insulating layer is laminated on the peripheral surface side of the conductor so as to cover the conductor.
- the insulating layer may be coated via another layer.
- the coating layer of the conductor may have a multilayer structure including a layer other than the insulating layer.
- the insulating layer can be formed by applying and curing (baking) the resin composition. That is, the insulating layer is formed of the resin composition of the present disclosure. Since the insulating layer of the insulated wire is formed of the resin composition of the present disclosure, the insulating wire has high productivity and excellent film elongation of the insulating layer.
- the average thickness of the insulating layer is not particularly limited, but is usually 2 ⁇ m or more and 200 ⁇ m or less.
- the insulated wire can be effectively obtained by a manufacturing method including a step of applying and a step of forming an insulating layer.
- the resin composition is applied directly to the outer circumference of the conductor or via another layer.
- a method of applying the resin composition to the outer peripheral surface side of the conductor for example, a method using a coating device including a liquid composition tank for storing the resin composition and a coating die can be mentioned.
- the resin composition adheres to the outer peripheral surface side of the conductor when the conductor is inserted into the liquid composition tank, and then passes through the coating die to make the resin composition substantially uniform in thickness. It is applied.
- the resin composition coated on the conductor in the coating step is heated to be cured to form the insulating layer.
- the solvent in the resin composition is volatilized, the polyamic acid is cured, and polyimide is formed. In this way, an insulating layer having excellent electrical characteristics, mechanical characteristics, thermal characteristics, and the like can be obtained.
- the device used in the step of forming the insulating layer is not particularly limited, but for example, a tubular baking furnace long in the traveling direction of the conductor can be used.
- the heating method is not particularly limited, but can be performed by a conventionally known method such as hot air heating, infrared heating, and high frequency heating.
- the heating temperature can be, for example, 350 ° C. or higher and 500 ° C. or lower, and the heating time can be 5 seconds or longer and 1 minute or lower. If the heating temperature or the heating time is less than the above lower limit, the vaporization of the solvent and the formation of the insulating layer become insufficient, and the appearance, electrical characteristics, mechanical characteristics, thermal characteristics, etc. of the insulated wire may be deteriorated. On the contrary, if the heating temperature exceeds the upper limit, excessive rapid heating may cause foaming of the insulating layer and deterioration of mechanical properties. Further, if the heating time exceeds the upper limit, the productivity of the insulated wire may decrease.
- the coating process and the insulating layer forming process are usually repeated a plurality of times. By doing so, the thickness of the insulating layer can be increased. At this time, the hole diameter of the coating die is appropriately adjusted according to the number of repetitions.
- the resin composition is a resin composition containing a polyamic acid and a solvent.
- the resin composition contains a thermosetting resin.
- the viscosity of the resin composition at 30 ° C. can be the same as that of the resin composition of the first embodiment. Further, it is preferable that the resin composition does not substantially contain a polyamic acid and a free diamine compound having amino groups at both ends of the molecular chain.
- the polyamic acid has a repeating unit represented by the following general formula (1) in the molecular chain, and one end or both ends of the molecular chain has a structure represented by the following general formula (2).
- the polyamic acid can be the same as the polyamic acid of the first embodiment, detailed description thereof will be omitted.
- solvent Since the solvent can be the same as the solvent of the first embodiment, detailed description thereof will be omitted.
- thermosetting resin When the resin composition is used as a resin composition for forming an insulating layer by containing the thermally decomposable resin, the thermally decomposable resin is thermally decomposed by heating during curing, and heat is generated when the insulating layer is formed. Pore can be formed in the portion where the degradable resin was present.
- thermosetting resin a resin that thermally decomposes at a temperature lower than the heating temperature at the time of curing of the resin composition is preferably used.
- the thermally decomposable resin is not particularly limited, but for example, one of polyethylene glycol, polypropylene glycol and the like, a compound in which one or both ends or a part of the resin is alkylated, (meth) acrylated or epoxidized, or poly (meth) acrylic acid.
- (meth) acrylates such as methyl, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, and butyl poly (meth) acrylate.
- thermosetting resin a crosslinked product of a (meth) acrylic polymer is preferable.
- the (meth) acrylic polymer tends to be evenly distributed in the sea phase of polyamic acid as an island phase of fine particles. Further, by forming it as a crosslinked product, it is excellent in compatibility with polyamic acid and easily organized in a spherical shape. Therefore, by using the thermosetting resin as a crosslinked product of the (meth) acrylic polymer, spherical pores can be evenly distributed after curing.
- the crosslinked poly (meth) acrylic polymer can be obtained, for example, by polymerizing a (meth) acrylic monomer and a polyfunctional monomer by emulsion polymerization, suspension polymerization, solution polymerization or the like.
- Examples of the (meth) acrylic monomer include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, dodecyl acrylate, stearyl acrylate, and 2-ethylhexyl acrylate.
- polyfunctional monomer examples include divinylbenzene, ethylene glycol di (meth) acrylate, and trimethylolpropane triacrylate.
- the constituent monomer of the crosslinked poly (meth) acrylic polymer other monomers may be used in addition to the (meth) acrylic monomer and the polyfunctional monomer.
- Other monomers include glycol esters of (meth) acrylic acid such as ethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl acetate, vinyl butyrate and the like.
- N-alkyl substituted (meth) acrylamides such as N-methylacrylamide, N-ethylacrylamide, N-methylmethacrylate, N-ethylmethacrylate, nitriles such as acrylonitrile and metaacrylonitrile, styrene, p.
- styrene-based monomers such as -methylstyrene, p-chlorostyrene, chloromethylstyrene, and ⁇ -methylstyrene.
- the thermosetting resin is spherical resin particles.
- the lower limit of the average particle size of the resin particles is preferably 0.1 ⁇ m, more preferably 0.5 ⁇ m, and even more preferably 1 ⁇ m.
- the upper limit of the average particle size of the resin particles is preferably 100 ⁇ m, more preferably 50 ⁇ m, further preferably 30 ⁇ m, and particularly preferably 10 ⁇ m.
- the resin particles are thermally decomposed when forming the insulating layer to form pores in the existing portion. Therefore, if the average particle size of the resin particles is less than the above lower limit, it may be difficult for pores to be formed in the insulating layer. On the contrary, when the average particle diameter of the resin particles exceeds the upper limit, the distribution of pores in the insulating layer is difficult to be uniform, and the distribution of dielectric constant may be easily biased.
- the method for producing the resin composition contains a polyamic acid and a solvent, and the polyamic acid has a repeating unit represented by the following general formula (1) in the molecular chain, and one end or both ends of the molecular chain.
- a resin composition having a structure represented by the following general formula (2) that is, the resin composition can be produced.
- the method for producing the resin composition includes a step of polymerizing and a step of mixing the thermosetting resin.
- R 1 is a tetravalent organic group.
- R 2 is a divalent organic group.
- R 1 has the same meaning as R 1 in the general formula (1).
- R 1 in the general formula (2) is identical to R 1 in the general formula (1) It may or may be different.
- R 3 is an organic group having 15 or less carbon atoms. When both ends of the molecular chain have the structure of the general formula (2), two R 1 and two R Each of 3 may be the same or different. * Indicates a binding site with a portion of the molecular chain different from the structure represented by the general formula (2).)
- thermosetting resin (Step of mixing thermosetting resin) In the step of mixing the thermosetting resin, the thermosetting resin is mixed with the reaction mixture after the polymerization step.
- thermosetting resin can be the same as the thermosetting resin of the resin composition described above, so detailed description thereof will be omitted.
- the content of the thermosetting resin is appropriately determined based on the solid content of the resin composition so that the porosity of the insulating layer to be formed becomes a desired value.
- the porosity can be the same as the porosity described in the step of dispersing the pore-forming agent of the first embodiment.
- the thermally decomposable resin is heated by heating during curing. Is thermally decomposed, and pores can be easily formed in the portion where the thermally decomposable resin was present at the time of forming the insulating layer.
- the resin composition is a resin composition containing a polyamic acid and a solvent.
- the resin composition contains a hollow filler.
- the viscosity of the resin composition at 30 ° C. can be the same as that of the resin composition of the first embodiment. Further, it is preferable that the resin composition does not substantially contain a polyamic acid and a free diamine compound having amino groups at both ends of the molecular chain.
- the polyamic acid has a repeating unit represented by the following general formula (1) in the molecular chain, and one end or both ends of the molecular chain has a structure represented by the following general formula (2).
- the polyamic acid can be the same as the polyamic acid of the first embodiment, detailed description thereof will be omitted.
- solvent Since the solvent can be the same as the solvent of the first embodiment, detailed description thereof will be omitted.
- the resin composition contains the hollow filler and is used as a resin composition for forming an insulating layer
- the hollow portion inside the hollow filler becomes pores. Further, by incorporating the hollow filler in the resin composition, the flexibility and mechanical strength of the obtained insulating layer can be easily controlled.
- the hollow filler examples include shirasu balloons, glass balloons, ceramic balloons, organic resin balloons and the like. Above all, it is preferable that the hollow filler is an organic resin balloon, a glass balloon, or a combination thereof.
- the organic resin balloon tends to increase the flexibility of the obtained insulating layer. Further, the glass balloon tends to increase the mechanical strength of the obtained insulating layer. Therefore, by using the hollow filler as an organic resin balloon, a glass balloon, or a combination thereof, the flexibility and mechanical strength controllability of the obtained insulating layer can be enhanced.
- the lower limit of the average particle size of the hollow filler 1 ⁇ m is preferable, and 5 ⁇ m is more preferable.
- the upper limit of the average particle size of the hollow filler is preferably 100 ⁇ m, more preferably 50 ⁇ m, and even more preferably 30 ⁇ m. If the average particle size of the hollow filler is less than the above lower limit, the volume of the cavity portion that becomes a pore in each hollow filler becomes small, so that it may be difficult to secure the porosity in the insulating layer. On the contrary, when the average particle size of the hollow filler exceeds the upper limit, it becomes difficult for the pores to be uniformly distributed in the insulating layer, and the dielectric constant distribution may be easily biased.
- the method for producing the resin composition contains a polyamic acid and a solvent, and the polyamic acid has a repeating unit represented by the following general formula (1) in the molecular chain, and one end or both ends of the molecular chain.
- a resin composition having a structure represented by the following general formula (2) that is, the resin composition can be produced.
- the method for producing the resin composition includes a step of polymerizing and a step of dispersing the hollow filler.
- R 1 is a tetravalent organic group.
- R 2 is a divalent organic group.
- R 1 has the same meaning as R 1 in the general formula (1).
- R 1 in the general formula (2) is identical to R 1 in the general formula (1) It may or may be different.
- R 3 is an organic group having 15 or less carbon atoms. When both ends of the molecular chain have the structure of the general formula (2), two R 1 and two R Each of 3 may be the same or different. * Indicates a binding site with a portion of the molecular chain different from the structure represented by the general formula (2).
- Step to disperse hollow filler In the step of dispersing the hollow filler, the hollow filler is dispersed in the reaction mixture after the polymerization step.
- the hollow filler can be the same as the hollow filler of the resin composition described above, detailed description thereof will be omitted.
- the content of the hollow filler is appropriately determined based on the solid content of the resin composition so that the porosity of the insulating layer to be formed becomes a desired value.
- the porosity can be the same as the porosity described in the step of dispersing the pore-forming agent of the first embodiment.
- the flexibility and mechanical strength of the insulating layer obtained when the resin composition is used as a resin composition for forming an insulating layer by including a hollow filler in the resin composition Is easy to control.
- thermosetting resin and the hollow filler alone has been described, but two or all three of them may be contained. ..
- a resin composition containing neither a pore forming agent, a thermosetting resin nor a hollow filler is also intended by the present invention.
- a resin composition for forming an insulating layer a solid insulating layer containing no pores is formed.
- a linear conductor and an insulated wire having an insulating layer that directly or via another layer have been described, but a topcoat layer may be further provided on the outer peripheral side of the insulating layer. ..
- a topcoat layer for imparting lubricity it is possible to reduce stress caused by friction between insulated wires during compression processing for increasing the number of coil turns and occupancy, and damage to the insulating layer due to this stress.
- the resin constituting the topcoat layer may be any resin having lubricity, and examples thereof include paraffins such as liquid paraffin and solid paraffin, and various waxes.
- the method of manufacturing the insulating layer of the insulated wire by coating and baking the resin composition has been described, but when the insulating layer has a multi-layer structure, it can also be manufactured by coextrusion.
- the insulating layer By manufacturing the insulating layer by coextrusion, it is possible to manufacture a multi-layered insulating layer at a time, so that the manufacturing efficiency is high.
- N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent and methanol as a reaction control agent were mixed at room temperature using a 1 L flask equipped with a stirring blade, and this solution was mixed with a diamine compound 4 , 4'-Diamino-diphenyl ether (ODA) was dissolved.
- PMDA which is an acid dianhydride
- ODA 4'-Diamino-diphenyl ether
- the mixing ratio (molar ratio) of PMDA and ODA is as shown in Table 1, and the mixing ratio of the reaction control agent was 60.
- the amount of NMP was adjusted so that the concentration of the obtained polyamic acid was 26% by mass.
- the resin composition thus obtained was applied and baked on the surface of a conductor having an average conductor diameter (average diameter) of 1 mm by a conventional method to form an insulating layer having an average thickness of 40 ⁇ m, and an insulated electric wire was produced.
- Table 1 shows the concentration of polyamic acid, and the mixing ratios of the reaction control agents were 70 (No. 2), 100 (No. 3), 310 (No. 6), and 120 (No. 9). No. An insulated wire was produced in the same manner as in 1.
- aprotic polar solvent was a mixed solvent of NMP and DMAc (mixing ratio 20:80)
- concentration of polyamic acid was as shown in Table 1
- the mixing ratio of the reaction control agent was 100.
- An insulated wire was produced in the same manner as in 1.
- the acid dianhydride was a mixture of PMDA and BPDA (mixing ratio 35:65), the concentration of polyamic acid was as shown in Table 1, and the mixing ratios of the reaction control agents were 100 (No. 11) and 210 (No. 12). ), 300 (No. 13), No. An insulated wire was produced in the same manner as in 1.
- the diamine compound was a mixture of ODA and 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) (mixing ratio 70:30), and the concentration of polyamic acid was as shown in Table 1 for the reaction. No. except that the mixing ratios of the control agents were 30 (N0.14), 60 (No.15), 100 (No.16), and 200 (No.17).
- An insulated wire was produced in the same manner as in 1.
- the resin composition thus obtained was applied and baked on the surface of a conductor having an average conductor diameter (average diameter) of 1 mm by a conventional method to form an insulating layer having an average thickness of 40 ⁇ m, and an insulated electric wire was produced.
- spherical hollow-forming particles (average particle diameter 3 ⁇ m, core: (meth) acrylic polymer crosslinked product, shell: silicone) are dispersed at a ratio of 30 phr, and the concentration of polyamic acid obtained is high. No. except that the amount of NMP was adjusted to be 28% by mass. An insulated wire was produced in the same manner as in 21.
- the resin composition thus obtained was applied and baked on the surface of a conductor having an average conductor diameter (average diameter) of 1 mm by a conventional method to form an insulating layer having an average thickness of 40 ⁇ m, and an insulated electric wire was produced.
- ⁇ Viscosity> The viscosity was measured using a B-type viscometer (“RB-80L” manufactured by Toki Sangyo Co., Ltd.) as the viscosity when rotated at a measurement temperature of 30 ° C. and a rotation speed of 6 rpm for 3 minutes.
- Mn number average molecular weight
- Mw weight average molecular weight
- Mw / Mn molecular weight distribution
- the target resin composition was diluted with N-methyl-2-pyrrolidone (NMP) and added dropwise to acetone while stirring with a stirrer.
- NMP N-methyl-2-pyrrolidone
- the solid content thus obtained was recovered and dried under vacuum for 12 hours or more.
- About 30 mg of the above solid content was taken, dissolved in dimethyl sulfoxide-d6 (DMSO-d6), and measured by 1 H NMR ("AVANCE III HD using Ascend 500" manufactured by Bruker) in a quantitative mode to obtain a spectrum. ..
- the number of protons per mole of the repeating unit and the terminal structure is calculated (NA [mol] and NB [mol], respectively), and the ratio of the terminal structure to 1 mol of the repeating unit (NA and NB, respectively).
- the ratio of the structure represented by the above general formula (2)) was calculated by (B / NB) / (A / NA).
- the chemical shift ⁇ [ppm] used in the present specification is a value based on the proton of tetramethylsilane.
- the number of protons NA appearing in ⁇ 6 or more and ⁇ 9 or less per mole of repeating unit was calculated as follows.
- the number of protons derived from the benzene ring of BPDA and appearing in ⁇ 6 or more and ⁇ 9 or less is 6 per molecule of BPDA.
- the number of protons derived from the benzene ring of BAPP and appearing in ⁇ 6 or more and ⁇ 9 or less is 16 per molecule of BAPP.
- ⁇ Film elongation> For film elongation, a tubular insulating layer was obtained by removing the conductor from the obtained insulated wire, and a tensile tester (Autograph AGS-X manufactured by Shimadzu Corporation) was used to obtain a chuck-to-chuck distance of 20 mm, 10 mm / min. A tensile test was carried out at the speed of, and the film elongation (break elongation) was measured.
- the glass transition temperature was set in a temperature range of 20 ° C. using a dynamic viscoelasticity measuring device (DMS) (EXSTAR DMS6100 manufactured by Yamato Scientific Co., Ltd.) in which a conductor was removed from the obtained insulated wire to form a tubular insulating layer.
- the glass transition temperature was measured at ⁇ 500 ° C. and a heating rate of 10 ° C./min.
- the molar ratios of acid anhydride, diamine, and reaction control agent represent relative values when the total molar amount of acid dianhydride is 100.
- "-" in the insulation wire evaluation result in Table 1 means that it has not been measured or cannot be measured.
- the resin composition of 20 has an appropriate viscosity while having a high concentration, and the insulating layer of the insulated wire using the resin composition has an excellent film elongation of 100% or more. Further, since the insulating layer of the insulated wire using these resin compositions does not show a decrease in the glass transition temperature, it can be seen that the decrease in the performance of the polyimide after curing is small.
- the ratio of the structure represented by the above general formula (2) to 1 mol of the repeating unit represented by the above general formula (1) of the polyamic acid of the resin composition is 0.001 mol or more and 0.1.
- the resin composition can have an appropriate viscosity while having a high concentration, and it can be said that the insulating layer of the insulated wire using the resin composition has an excellent film elongation of 100% or more.
- a pore-forming agent or a hollow filler is added to include pores inside the insulating layer. 21-No.
- the 24 resin compositions also have an appropriate viscosity while having a high concentration, and it can be seen that the insulating layer of the insulated wire using this has an excellent film elongation of 90% or more.
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Abstract
Description
特許文献1に記載の方法ではワニス合成が多段階となるため、ポリアミック酸を含有する樹脂組成物の生産性が劣る。また、特許文献1に記載の方法で製造された樹脂組成物は、分子量が比較的低く、絶縁電線等の製造効率を高めるために高濃度化することが難しい。
本開示の樹脂組成物は、硬化後の塗膜物性に優れ生産性が高く、高濃度化が可能である。従って、当該樹脂組成物は、絶縁電線の絶縁層の形成に好適に用いることができる。
本開示の一態様に係る樹脂組成物は、ポリアミック酸と溶媒とを含有する樹脂組成物であって、上記ポリアミック酸が分子鎖中に下記一般式(1)で表される繰り返し単位を有し、上記分子鎖の一端又は両端が下記一般式(2)で表される構造であり、下記一般式(1)で表される繰り返し単位1モルに対する下記一般式(2)で表される構造の割合が0.001モル以上0.1モル以下である。
以下、本開示に係る樹脂組成物、樹脂組成物の製造方法及び絶縁電線の実施形態について詳説する。
<樹脂組成物>
当該樹脂組成物は、ポリアミック酸と溶媒とを含有する樹脂組成物である。また、当該樹脂組成物は、空孔形成剤を含有する。
上記溶媒としては、各種の有機溶剤を用いることができるが、上記溶媒が非プロトン性極性溶媒であるとよい。この非プロトン性極性溶媒は、ポリアミック酸の原料となる酸二無水物及びジアミン化合物と反応せず、上記ポリアミック酸に対して好適な溶媒として機能できる。
当該樹脂組成物に上記空孔形成剤を含有させることで、絶縁層を形成する樹脂組成物として当該樹脂組成物を用いた際、絶縁層に気孔を含めることができる。このため、絶縁層の低誘電率化を実現でき、コロナ放電開始電圧が向上する。従って、絶縁層の絶縁破壊を発生し難くすることができる。
当該樹脂組成物の導体への塗布及び硬化により絶縁電線の絶縁層を形成する際、化学発泡剤は、焼付けによる硬化時の加熱により発泡し、絶縁層中に気孔を生じさせる。このように上記空孔形成剤を化学発泡剤とすることで、焼付けによる当該樹脂組成物の硬化時に容易に気孔を形成することができる。
調整が困難となるおそれがある。逆に、上記発泡温度が上記上限を超えると、焼付け温度の上昇や焼付け時間の長大化を招き、絶縁電線の製造コストが増加するおそれがある。ここで「発泡温度」とは、発泡剤が発泡を開始する温度である。また、「焼付け時間」とは、当該樹脂組成物が塗布された導体を焼付け温度で保持する時間である。
熱膨張性マイクロカプセルは、熱膨張剤を含む芯材と上記芯材を包む外殻とを有する。熱膨張性マイクロカプセルは、上述の焼付けの加熱により上記芯材に含まれる上記熱膨張剤が膨張又は発泡し、上記外殻を押し広げることで気孔が形成される。従って、上記空孔形成剤を熱膨張性マイクロカプセルとすることで、気孔の大きさの制御性を高められる。
コアシェル構造の中空形成粒子は、上述の焼付けの加熱によりコアをガス化し除去することで、中空粒子を得る。上記中空形成粒子は、当該樹脂組成物の硬化後にコアの熱分解により得られる気孔及び外殻を備えるため、気孔の形成時にも気孔の連通が抑制される。このため、絶縁層を形成する樹脂組成物として用いた際、絶縁層の絶縁破壊電圧を高め易い。
上記高沸点溶媒は、上述の当該樹脂組成物の溶媒より沸点が高く、気泡形成用に用いられる。上記高沸点溶媒の沸点の下限としては、180℃が好ましく、210℃がより好ましい。一方、上記高沸点溶媒の沸点の上限としては、300℃が好ましく、260℃がより好ましい。上記高沸点溶媒の沸点が上記下限未満であると、当該樹脂組成物の溶媒を揮発させる際に揮発する量が増加し、気泡が十分に形成できないおそれがある。逆に、上記高沸点溶媒の沸点が上記上限を超えると、上記高沸点溶媒が揮発し難くなり、気泡が十分に形成できないおそれがある。
当該樹脂組成物は、繰り返し単位1モルに対する上記一般式(2)で表される構造の割合を上記範囲内とすることにより、分子量が制御された高分子量のポリアミック酸を容易に得ることができる。従って、当該樹脂組成物は、容易かつ確実に高濃度化することができる。また、当該樹脂組成物は、一段階の反応工程で得られるため生産性が高い。
当該樹脂組成物の製造方法は、ポリアミック酸と溶媒とを含有し、上記ポリアミック酸が、分子鎖中に下記一般式(1)で表される繰り返し単位を有し、上記分子鎖の一端又は両端が下記一般式(2)で表される構造である樹脂組成物、すなわち当該樹脂組成物を製造することができる。当該樹脂組成物の製造方法は、重合する工程と、空孔形成剤を分散させる工程とを備える。
上記重合する工程では、下記一般式(3)で表される酸二無水物及び下記一般式(4)で表されるジアミン化合物を、非プロトン性極性溶媒及び反応制御剤の存在下で重合する。
上記空孔形成剤を分散させる工程では、上記重合する工程後の反応混合物に、熱分解性樹脂を混合する工程を備えるとよい。このように得られる樹脂組成物に熱分解性樹脂を含めることで、絶縁層を形成する樹脂組成物として用いた際、硬化時の加熱により上記熱分解性樹脂が熱分解し、絶縁層の形成時に熱分解性樹脂が存在していた部分に気孔を容易に形成することができる。
当該樹脂組成物の製造方法は、非プロトン性極性溶媒及び反応制御剤の存在下、酸二無水物及びジアミン化合物を重合するので、製造を一工程で行うことができ、生産性が高い。また、当該樹脂組成物の製造方法は、分子鎖末端を適量の反応制御剤に由来するR3を含む上記一般式(2)で表される構造で封止する。このため、当該樹脂組成物の製造方法では、ポリアミック酸の分子量を容易に制御しつつ、分子量を高めることができる。
当該絶縁電線は、線状の導体と、この導体を直接又は他の層を介して被覆する絶縁層とを有する。
上記導体は、通常金属を主成分とする。上記金属としては、特に限定されないが、銅、銅合金、アルミニウム、又はアルミニウム合金が好ましい。導体に上記金属を用いることで、良好な加工性や導電性等を兼ね備えた絶縁電線を得ることができる。
上記絶縁層は、上記導体を被覆するように上記導体の周面側に積層される。上記絶縁層は、他の層を介して被覆してもよい。具体的には、導体の被覆層が上記絶縁層以外の層を含む多層構造であってもよい。
当該絶縁電線は、塗布する工程及び絶縁層を形成する工程を備える製造方法により効果的に得ることができる。
<樹脂組成物>
当該樹脂組成物は、ポリアミック酸と溶媒とを含有する樹脂組成物である。また、当該樹脂組成物は、熱分解性樹脂を含有する。
上記溶媒は、第1実施形態の溶媒と同様とできるので、詳細説明を省略する。
当該樹脂組成物に上記熱分解性樹脂を含有させることで、絶縁層を形成する樹脂組成物として用いた際、硬化時の加熱により上記熱分解性樹脂が熱分解し、絶縁層の形成時に熱分解性樹脂が存在していた部分に気孔を形成することができる。
当該樹脂組成物の製造方法は、ポリアミック酸と溶媒とを含有し、上記ポリアミック酸が、分子鎖中に下記一般式(1)で表される繰り返し単位を有し、上記分子鎖の一端又は両端が下記一般式(2)で表される構造である樹脂組成物、すなわち当該樹脂組成物を製造することができる。当該樹脂組成物の製造方法は、重合する工程と、熱分解性樹脂を混合する工程とを備える。
上記重合する工程では、下記一般式(3)で表される酸二無水物及び下記一般式(4)で表されるジアミン化合物を、非プロトン性極性溶媒及び反応制御剤の存在下で重合する。
上記熱分解性樹脂を混合する工程では、上記重合する工程後の反応混合物に、熱分解性樹脂を混合する。
当該樹脂組成物及び当該樹脂組成物の製造方法では、樹脂組成物に熱分解性樹脂を含めることで、絶縁層を形成する樹脂組成物として用いた際、硬化時の加熱により上記熱分解性樹脂が熱分解し、絶縁層の形成時に熱分解性樹脂が存在していた部分に気孔を容易に形成することができる。
<樹脂組成物>
当該樹脂組成物は、ポリアミック酸と溶媒とを含有する樹脂組成物である。また、当該樹脂組成物は、中空フィラーを含有する。
上記溶媒は、第1実施形態の溶媒と同様とできるので、詳細説明を省略する。
当該樹脂組成物に上記中空フィラーを含有させることで、絶縁層を形成する樹脂組成物として用いた際、この中空フィラーの内部の空洞部分が気孔となる。また、当該樹脂組成物に上記中空フィラーを含有させることで、得られる絶縁層の可撓性及び機械的強度が制御し易い。
当該樹脂組成物の製造方法は、ポリアミック酸と溶媒とを含有し、上記ポリアミック酸が、分子鎖中に下記一般式(1)で表される繰り返し単位を有し、上記分子鎖の一端又は両端が下記一般式(2)で表される構造である樹脂組成物、すなわち当該樹脂組成物を製造することができる。当該樹脂組成物の製造方法は、重合する工程と、中空フィラーを分散させる工程とを備える。
上記重合する工程では、下記一般式(3)で表される酸二無水物及び下記一般式(4)で表されるジアミン化合物を、非プロトン性極性溶媒及び反応制御剤の存在下で重合する。
上記中空フィラーを分散させる工程では、上記重合する工程後の反応混合物に、中空フィラーを分散させる。
当該樹脂組成物及び当該樹脂組成物の製造方法では、樹脂組成物に中空フィラーを含めることで、絶縁層を形成する樹脂組成物として用いた際、得られる絶縁層の可撓性及び機械的強度が制御し易い。
今回開示された実施の形態はすべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は、上記実施形態の構成に限定されるものではなく、請求の範囲によって示され、請求の範囲と均等の意味及び範囲内での全ての変更が含まれることが意図される。
まず撹拌翼を備えた1Lフラスコを用いて非プロトン性極性溶媒としてのN-メチル-2-ピロリドン(NMP)と反応制御剤としてのメタノールとを室温で混合し、この溶液にジアミン化合物である4,4’-ジアミノ-ジフェニルエーテル(ODA)を溶解した。その後、上記溶液を200rpmで撹拌しながら酸二無水物であるPMDAをほぼ等量に2分割し、分割したそれぞれのPMDAを10分の間隔を空けて、すなわち投入時間10分で加え、上記溶液を2時間室温で放置した。なお、PMDA及びODAの混合比(モル比)は表1に示すとおりであり、反応制御剤の混合比は、60とした。また、得られるポリアミック酸の濃度が26質量%となるようにNMPの量を調整した。
ポリアミック酸の濃度を表1のとおりとし、反応制御剤の混合比を70(No.2)、100(No.3)、310(No.6)、120(No.9)とした以外は、No.1と同様にして絶縁電線を作製した。
反応制御剤を用いず(混合比0)、ポリアミック酸の濃度を表1のとおりとした以外は、No.1と同様にして樹脂組成物を得た。No.4の樹脂組成物は粘度が高過ぎたため、塗工を行うことができず、絶縁電線は作製できなかった。また、No.5の樹脂組成物はゲル化したため、塗工を行うことができず、絶縁電線は作製できなかった。
反応制御剤をエタノールとし、エタノールの混合比を60(No.7)、350(No.8)、100(No.18)とした以外は、No.1と同様にして絶縁電線を作製した。
非プロトン性極性溶媒をNMPとDMAcとの混合溶媒(混合比20:80)とし、ポリアミック酸の濃度を表1のとおりとし、反応制御剤の混合比を100とした以外は、No.1と同様にして絶縁電線を作製した。
酸二無水物をPMDAとBPDAとの混合物(混合比35:65)とし、ポリアミック酸の濃度を表1のとおりとし、反応制御剤の混合比を100(No.11)、210(No.12)、300(No.13)とした以外は、No.1と同様にして絶縁電線を作製した。
ジアミン化合物をODAと、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン(BAPP)との混合物(混合比70:30)とし、ポリアミック酸の濃度を表1のとおりとし、反応制御剤の混合比を30(N0.14)、60(No.15)、100(No.16)、200(No.17)とした以外は、No.1と同様にして絶縁電線を作製した。
反応制御剤を1-プロパノールとし、混合比を100とした以外は、No.1と同様にして絶縁電線を作製した。
反応制御剤を1-ブタノールとし、混合比を100とした以外は、No.1と同様にして絶縁電線を作製した。
No.1と同様の組成で同様の方法で重合して得られる反応混合物に、空孔形成剤としての化学発泡剤(アゾジカルボジアミド)を10phrの割合で分散させ、化学発泡剤を含む樹脂組成物を得た。なお、上記樹脂組成物において、得られるポリアミック酸の濃度が29質量%となるようにNMPの量を調整した。ここで「phr」とは樹脂100質量部当たりの質量部をいう。
化学発泡剤に代えて、熱膨張性マイクロカプセル(芯材:アゾジカルボジアミド、外殻:塩化ビニリデン―アクリロニトリル共重合体)を10phrの割合で分散させた以外は、No.21と同様にして絶縁電線を作製した。
化学発泡剤に代えて、球状の中空形成粒子(平均粒子径3μm、コア:(メタ)アクリル系重合体架橋物、シェル:シリコーン)を30phrの割合で分散させ、また得られるポリアミック酸の濃度が28質量%となるようにNMPの量を調整した以外は、No.21と同様にして絶縁電線を作製した。
No.1と同様の組成で同様の方法で重合して得られる反応混合物に、中空フィラーとしてのガラスバルーン(平均粒子径18μm)を30phrの割合で分散させ、ガラスバルーンを含む樹脂組成物を得た。なお、上記樹脂組成物において、得られるポリアミック酸の濃度が28質量%となるようにNMPの量を調整した。
上記No.1~No.24で得られた樹脂組成物について、粘度、平均分子量及び末端構造割合を測定した。なお、ゲル化したNo.5については粘度及び平均分子量は測定していない。
粘度は、B型粘度計(東機産業株式会社の「RB-80L」)を用いて測定温度30℃、回転数6rpmで3分間回転させたときの粘度として測定した。
樹脂組成物を東ソー株式会社の「GPCシステム」で分析することによりポリアミック酸の数平均分子量(Mn)、重量平均分子量(Mw)及び分子量分布(Mw/Mn)を算出した。分析時の展開溶媒としては、リン酸30mモル及びリチウムブロマイド10mモルを溶解させたN-メチル2-ピロリドンを用い、標準物質としては、ポリスチレンを用いた。また、分析時のカラムは、東ソー株式会社の「TSKgeI GMH HR-H」を2本直列接続したものを用い、ガードカラムとしては「TSK Guard Colum HHR-Hを用いた。測定は、流速0.5mL/分、測定時間60分で行った。
まず、対象の樹脂組成物をN-メチル-2-ピロリドン(NMP)で希釈し、スターラーで撹拌させながらアセトン中に滴下した。これにより得られた固形分を回収し、真空下で12時間以上乾燥させた。上記固形分を約30mg取り、ジメチルスルホキシド-d6(DMSO-d6)に溶解させ、1H NMR(ブルカー社製の「Ascend500を用いたAVANCE III HD」)により定量モードで測定し、スペクトルを得た。なお、測定条件としては、Flip Angle=13.0μs、PD=70s、積算回数=64回とした。
PMDAのベンゼン環に由来し、δ6以上δ9以下に現れるプロトン数は、PMDA1分子当たり2個である。また、ODAのベンゼン環に由来し、δ6以上δ9以下に現れるプロトン数は、ODA1分子当たり8個である。繰り返し単位1モル当たりには、PMDA及びODAが1モルずつ含まれるから、繰り返し単位1モル当たりのプロトン数NAは、2+8=10モルである。
BPDAのベンゼン環に由来し、δ6以上δ9以下に現れるプロトン数は、BPDA1分子当たり6個である。PMDA及びODAについては上述の通りである。繰り返し単位1モル当たりには、PMDAが0.35モル、BPDAが0.65モル、ODAが1モル含まれるから、繰り返し単位1モル当たりのプロトン数NAは、0.35×2+0.65×6+8=12.6モルである。
BAPPのベンゼン環に由来し、δ6以上δ9以下に現れるプロトン数は、BAPP1分子当たり16個である。PMDA及びODAについては上述の通りである。繰り返し単位1モル当たりには、PMDAが1モル、ODAが0.7モル、BAPPが0.3モル含まれるから、繰り返し単位1モル当たりのプロトン数NAは、2+8×0.7+16×0.3=12.4モルである。
皮膜伸びは、得られた絶縁電線から導体を取り除いてチューブ状の絶縁層としたものを引張試験機(株式会社島津製作所製のオートグラフAGS-X)を用いてチャック間距離20mm、10mm/分の速度で引張試験を行い、皮膜伸び(破断伸び)を測定した。
ガラス転移温度は、得られた絶縁電線から導体を取り除いてチューブ状の絶縁層としたものを動的粘弾性測定装置(DMS)(ヤマト科学株式会社製のEXSTAR DMS6100)を用いて温度範囲20℃~500℃、昇温速度10℃/分でガラス転移温度を測定した。
皮膜伸び、ガラス転移温度及び巻線外観観察から絶縁電線について以下の基準で判定を行った。
A:皮膜伸び、ガラス転移温度共に良好で巻線外観も正常である。
B:皮膜伸び、ガラス転移温度共に良好であるが、巻線外観に発泡が見られる。
C:皮膜伸び又はガラス転移温度が不十分である。
Claims (34)
- ポリアミック酸と溶媒とを含有する樹脂組成物であって、
上記ポリアミック酸が分子鎖中に下記一般式(1)で表される繰り返し単位を有し、
上記分子鎖の一端又は両端が下記一般式(2)で表される構造であり、
下記一般式(1)で表される繰り返し単位1モルに対する下記一般式(2)で表される構造の割合が0.001モル以上0.1モル以下である樹脂組成物。
- 上記ポリアミック酸の数平均分子量に対する重量平均分子量の比が2.3以下である請求項1に記載の樹脂組成物。
- 上記ポリアミック酸の重量平均分子量が15,000以上である請求項1又は請求項2に記載の樹脂組成物。
- 上記ポリアミック酸の数平均分子量が8,000以上である請求項1、請求項2又は請求項3に記載の樹脂組成物。
- 上記ポリアミック酸が上記R1がベンゼン-1,2,4,5-テトライル基である繰り返し単位の重合体である請求項1から請求項4のいずれか1項に記載の樹脂組成物。
- 上記ポリアミック酸が上記R1がベンゼン-1,2,4,5-テトライル基である繰り返し単位と、上記R1がビフェニル-3,3’,4,4’-テトライル基である繰り返し単位との共重合体である請求項1から請求項4のいずれか1項に記載の樹脂組成物。
- 上記R1がベンゼン-1,2,4,5-テトライル基である繰り返し単位と上記R1がビフェニル-3,3’,4,4’-テトライル基である繰り返し単位との平均モル比が、2:8以上4:6以下である請求項6に記載の樹脂組成物。
- 上記分子鎖の両端がアミノ基であるポリアミック酸及び遊離ジアミン化合物が実質的に含まれない請求項1から請求項7のいずれか1項に記載の樹脂組成物。
- 上記ポリアミック酸の濃度が25質量%以上である請求項1から請求項8のいずれか1項に記載の樹脂組成物。
- 上記溶媒が非プロトン性極性溶媒である請求項1から請求項9のいずれか1項に記載の樹脂組成物。
- 空孔形成剤を含有する請求項1から請求項10のいずれか1項に記載の樹脂組成物。
- 上記空孔形成剤が化学発泡剤である請求項11に記載の樹脂組成物。
- 上記空孔形成剤が熱膨張剤を含む芯材と上記芯材を包む外殻とを有する熱膨張性マイクロカプセルである請求項11に記載の樹脂組成物。
- 上記芯材の主成分がアゾビスイソブチロニトリル又はアゾジカルボジアミドである請求項13に記載の樹脂組成物。
- 上記外殻の主成分が塩化ビニリデン―アクリロニトリル共重合体である請求項13又は請求項14に記載の樹脂組成物。
- 上記空孔形成剤がコアシェル構造の中空形成粒子である請求項11に記載の樹脂組成物。
- 上記中空形成粒子のコアが熱分解性樹脂を主成分とし、
上記中空形成粒子のシェルの主成分の熱分解温度が上記熱分解性樹脂の熱分解温度より高い請求項16に記載の樹脂組成物。 - 上記中空形成粒子のシェルの主成分がシリコーンである請求項17に記載の樹脂組成物。
- 上記空孔形成剤が上記溶媒より沸点の高い高沸点溶媒である請求項11に記載の樹脂組成物。
- 上記高沸点溶媒の沸点が180℃以上300℃以下である請求項19に記載の樹脂組成物。
- 熱分解性樹脂を含有する請求項1から請求項10のいずれか1項に記載の樹脂組成物。
- 上記熱分解性樹脂が(メタ)アクリル系重合体の架橋物である請求項21に記載の樹脂組成物。
- 上記熱分解性樹脂が球状の樹脂粒子であり、
上記樹脂粒子の平均粒子径が0.1μm以上50μm以下である請求項21又は請求項22に記載の樹脂組成物。 - 中空フィラーを含有する請求項1から請求項10のいずれか1項に記載の樹脂組成物。
- 上記中空フィラーが有機樹脂バルーン、ガラスバルーン又はそれらの組み合わせである請求項24に記載の樹脂組成物。
- ポリアミック酸と溶媒とを含有し、上記ポリアミック酸が、分子鎖中に下記一般式(1)で表される繰り返し単位を有し、上記分子鎖の一端又は両端が下記一般式(2)で表される構造である樹脂組成物の製造方法であって、
下記一般式(3)で表される酸二無水物及び下記一般式(4)で表されるジアミン化合物を、非プロトン性極性溶媒及び反応制御剤の存在下で重合する工程を備え、
上記重合する工程で、上記反応制御剤の含有量を、上記酸二無水物100モルに対して0.1モル以上300モル以下とする樹脂組成物の製造方法。
- 上記重合する工程で、上記酸二無水物及び上記ジアミン化合物を実質的に等モル量とする請求項26に記載の樹脂組成物の製造方法。
- 上記R1がベンゼン-1,2,4,5-テトライル基である請求項26又は請求項27に記載の樹脂組成物の製造方法。
- 上記R1がベンゼン-1,2,4,5-テトライル基及びビフェニル-3,3’,4,4’-テトライル基である請求項26又は請求項27に記載の樹脂組成物の製造方法。
- 上記R1がベンゼン-1,2,4,5-テトライル基である酸二無水物と上記R1がビフェニル-3,3’,4,4’-テトライル基である酸二無水物とのモル比が、2:8以上4:6以下である請求項29に記載の樹脂組成物の製造方法。
- 上記重合する工程後の反応混合物に、空孔形成剤を分散させる工程を備える請求項26から請求項30のいずれか1項に記載の樹脂組成物の製造方法。
- 上記重合する工程後の反応混合物に、熱分解性樹脂を混合する工程を備える請求項26から請求項30のいずれか1項に記載の樹脂組成物の製造方法。
- 上記重合する工程後の反応混合物に、中空フィラーを分散させる工程を備える請求項26から請求項30のいずれか1項に記載の樹脂組成物の製造方法。
- 線状の導体と、上記導体を直接又は他の層を介して被覆する絶縁層とを有する絶縁電線であって、
上記絶縁層が請求項1に記載の樹脂組成物により形成されている絶縁電線。
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CN201980097642.9A CN114008139B (zh) | 2019-06-20 | 2019-06-20 | 树脂组合物、树脂组合物的制造方法以及绝缘电线 |
KR1020217040380A KR20220007135A (ko) | 2019-06-20 | 2019-06-20 | 수지 조성물, 수지 조성물의 제조 방법 및 절연 전선 |
TW109120952A TWI839535B (zh) | 2019-06-20 | 2020-06-20 | 樹脂組成物、樹脂組成物之製造方法及絕緣電線 |
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WO2023058288A1 (ja) * | 2021-10-05 | 2023-04-13 | 住友電気工業株式会社 | 樹脂組成物及び絶縁電線 |
WO2023233558A1 (ja) * | 2022-05-31 | 2023-12-07 | 住友電気工業株式会社 | プレポリマー溶液の製造方法及び絶縁電線の製造方法 |
WO2024157378A1 (ja) * | 2023-01-25 | 2024-08-02 | 住友電気工業株式会社 | 樹脂組成物、絶縁電線および絶縁電線の製造方法 |
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TWI839535B (zh) | 2024-04-21 |
US20230017427A1 (en) | 2023-01-19 |
JPWO2020255360A1 (ja) | 2020-12-24 |
CN114008139A (zh) | 2022-02-01 |
CN114008139B (zh) | 2023-10-20 |
TW202108662A (zh) | 2021-03-01 |
KR20220007135A (ko) | 2022-01-18 |
JP7157879B2 (ja) | 2022-10-20 |
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