WO2020171617A1 - Composition pour film isolant, et fil électrique isolé comprenant un film isolant formé à partir de celle-ci - Google Patents

Composition pour film isolant, et fil électrique isolé comprenant un film isolant formé à partir de celle-ci Download PDF

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Publication number
WO2020171617A1
WO2020171617A1 PCT/KR2020/002449 KR2020002449W WO2020171617A1 WO 2020171617 A1 WO2020171617 A1 WO 2020171617A1 KR 2020002449 W KR2020002449 W KR 2020002449W WO 2020171617 A1 WO2020171617 A1 WO 2020171617A1
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WO
WIPO (PCT)
Prior art keywords
insulating film
composition
diamine compound
bis
dianhydride
Prior art date
Application number
PCT/KR2020/002449
Other languages
English (en)
Korean (ko)
Inventor
서동진
Original Assignee
엘에스전선 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020200020168A external-priority patent/KR20200101867A/ko
Application filed by 엘에스전선 주식회사 filed Critical 엘에스전선 주식회사
Publication of WO2020171617A1 publication Critical patent/WO2020171617A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation

Definitions

  • the present invention relates to an insulating electric wire comprising a composition for an insulating film and an insulating film formed therefrom. Specifically, the present invention relates to an insulating wire comprising a composition for an insulating film having low relative dielectric constant and high partial discharge initiation voltage and excellent heat resistance, stable at high temperature, and excellent flexibility, and an insulating film formed therefrom.
  • Insulated wires applied as coils of rotating electric machines such as motors or electric devices such as transformers are made of resins such as polyimide, polyamideimide, and polyesterimide on the surface of a metal conductor with a circular or square cross-sectional shape. It can be produced by covering with an insulating paint dissolved in a solvent to form one or two or more insulating films.
  • inverter surge voltage generated by the inverter control is high, partial discharge occurs due to the inverter surge voltage in the insulated wire constituting the coil of the electric device and insulates it.
  • the insulating film of the electric wire may be deteriorated or damaged.
  • conventional insulated wires contain inorganic particles such as silica in the insulating film to prevent deterioration or damage of the insulating film due to inverter surge voltage, but these inorganic particles increase the relative dielectric constant of the insulating film, and as a result, the insulating wire
  • the partial discharge inception voltage of may be reduced, and flexibility may be greatly reduced.
  • an aromatic diamine component having three or more aromatic rings and an aromatic imide prepolymer containing an acid component have two or less aromatics.
  • a polyimide resin coating obtained by mixing an aromatic diisocyanate component having a ring was applied.
  • such a polyimide resin coating has low heat resistance and thus a stable insulating film at high temperature cannot be formed.
  • high-temperature stability of the insulating film is becoming important.
  • An object of the present invention is to provide a composition for an insulating film having a low relative dielectric constant, high partial discharge initiation voltage, and excellent flexibility, and an insulating wire including an insulating film formed therefrom.
  • Another object of the present invention is to provide an insulating wire comprising a composition for an insulating film stable at high temperature and an insulating film formed therefrom.
  • composition for an insulating film includes a polyimide resin formed through polymerization of a dianhydride compound and a diamine compound, the dianhydride compound includes a tetracarboxylic dianhydride or an isomer thereof, and the diamine compound is a first diamine A compound and a second diamine compound, wherein the first diamine compound is 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), bis[4-(4-aminophenoxy)phenyl ]Sulfone (BAPS), bis[4-(4-aminophenoxy)phenyl]ether (BAPE), 4,4'-bis(4-aminophenoxy)biphenyl (BAPB), 1,4-bis(4 -Aminophenoxy)benzene, 9,9-bis(4-aminophenyl)fluorene (FDA), 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,
  • BAPP
  • a molar ratio of the first diamine compound and the second diamine compound is greater than 50:50 and less than or equal to 95:5, providing a composition for an insulating film.
  • the tetracarboxylic dianhydride is 1 selected from the group consisting of pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and isomers thereof. It provides a composition for an insulating film, characterized in that it contains more than one species.
  • the pyromellitic dianhydride (PMDA) and 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) are 30:70 or more and 70:30 or less. It provides a composition for an insulating film, characterized in that mixed in a molar ratio of.
  • the polyimide resin provides a composition for an insulating film, characterized in that it has a molecular structure of the following formula (1).
  • n 5 to 200.
  • the polyimide resin provides a composition for an insulating film, characterized in that the number average molecular weight (Mn) is 10,000 to 200,000.
  • NMP N-methyl-2-pyrrolidone
  • DMAc N,N-dimethylacetamide
  • DMF N,N-dimethylformamide
  • DI dimethylimidazolidinone
  • cyclohexanone methylcyclohexanone and aromatic alkyl benzenes, characterized in that it comprises at least one solvent selected from the group consisting of, provides a composition for an insulating film.
  • the insulating film is formed on the surface of the conductor and includes a first insulating film comprising at least one resin selected from the group consisting of polyimide resin, polyamideimide resin, and polyesterimide resin; And a second insulating film formed on the first insulating film and formed from the composition for an insulating film of claim 1 or 2.
  • the second insulating film has a thickness of 85% or more of the total thickness of the insulating film.
  • an insulated wire characterized in that it further comprises at least one layer selected from the group consisting of an adhesion-improving layer formed on the surface of the conductor, a lubricating layer formed on the surface of the insulating film or the surface of the second insulating film, and a highly flexible layer Provides.
  • composition for an insulating film according to the present invention contains a polyimide resin having a specific molecular structure, the relative dielectric constant is low, the partial discharge initiation voltage is high, and the heat resistance is excellent, so that it is stable at high temperatures and has excellent flexibility.
  • FIG. 1 shows an embodiment of an insulated wire according to the present invention.
  • Figure 2 shows another embodiment of the insulated wire according to the present invention.
  • the composition for an insulating film according to the present invention may include a polyimide resin formed through polymerization of a dianhydride compound and a diamine compound, wherein the dianhydride compound is, for example, tetracarboxylic dianhydride, preferably fatigue.
  • a polyimide resin formed through polymerization of a dianhydride compound and a diamine compound, wherein the dianhydride compound is, for example, tetracarboxylic dianhydride, preferably fatigue.
  • the pyromellitic dianhydride (PMDA) and 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) are 30:70 or more and 70:30 or less. It can be mixed in a molar ratio of.
  • the insulated wire according to the present invention can be applied in automobiles, and oil resistance must be secured due to the environment exposed to engine oil, etc., and pyromellitic dianhydride (PMDA) and 3,3',4,4'-biphenyltetra
  • the carboxylic acid dianhydride (BPDA) is in the above range, sufficient oil resistance can be secured.
  • the diamine compound may include a first diamine compound and a second diamine compound
  • the first diamine compound is, for example, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP ), bis[4-(4-aminophenoxy)phenyl]sulfone (BAPS), bis[4-(4-aminophenoxy)phenyl] ether (BAPE), 4,4'-bis(4-aminophenoxy) ) Biphenyl (BAPB), 1,4-bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene (FDA), 2,2'-dimethyl-4,4'- Diaminobiphenyl, 4,4'-bis(4-aminophenyl)sulfide, etc. or isomers thereof
  • the second diamine compound is, for example, 1,4-diaminobenzene, 2,4- Diaminotoluene and the like
  • the first diamine compound is a compound having polarity and may lower the relative dielectric constant, but there is a problem in that heat resistance may decrease when excessively added. Therefore, it was confirmed that heat resistance can be secured by mixing the second diamine compound to compensate for this.
  • the molar ratio of the first diamine compound and the second diamine compound may be greater than 50:50 and not greater than 95:5.
  • the molar ratio of the first diamine compound and the second diamine compound is 50:50 or less, the relative dielectric constant of the composition for an insulating film increases, thereby reducing the partial discharge initiation voltage of the insulated wire having the insulating film formed therefrom.
  • the molar ratio is more than 95:5, heat resistance of the composition for insulating coating is lowered, and thus usability insulated wires cannot be manufactured under a high temperature environment.
  • composition for an insulating film according to the present invention may include a polyimide resin having a molecular structure represented by Formula 1 below.
  • n 5 to 200.
  • the polyimide resin may have a number average molecular weight (Mn) of 10,000 to 200,000, and preferably 13,000 to 80,000.
  • n and number average molecular weight are measures of molecular weight, and if the molecular weight is too small, sufficient viscosity may not be secured, making it difficult to form an insulating film, and if the molecular weight is too large, the viscosity increases and the coating operation is difficult. Sex problems can occur.
  • the composition for an insulating film according to the present invention has a low ratio of polar groups in the molecular structure of the polyimide resin, so that the relative dielectric constant of the composition can be lowered and the heat resistance can be improved, and since there is no need to contain inorganic particles, it has flexibility. great.
  • the polyimide resin is N-methyl-2-pyrrolidone (NMP), ⁇ -butyrolactone, N,N-dimethylacetamide (DMAc), N,N-dimethylform It may be dissolved in a solvent such as amide (DMF), dimethylimidazolidinone (DMI), cyclohexanone, methylcyclohexanone, and aromatic alkyl benzenes.
  • NMP N-methyl-2-pyrrolidone
  • DMAc N,N-dimethylacetamide
  • N,N-dimethylform N,N-dimethylform
  • a solvent such as amide (DMF), dimethylimidazolidinone (DMI), cyclohexanone, methylcyclohexanone, and aromatic alkyl benzenes.
  • FIG. 1 shows an embodiment of an insulated wire according to the present invention.
  • the insulated wire according to the present invention may include a conductor 10 and an insulating film 20 formed on the surface of the conductor 10 and formed from the composition for an insulating film as described above, ,
  • the thickness of the insulating film 20 may be, for example, 0.01 to 0.1 mm.
  • the conductor 10 may be made of copper, preferably oxygen-free copper or hypoxic copper, and the cross-sectional shape thereof is circular as shown in FIG. 1A or a cross-sectional shape as shown in FIG. It may be a curved square.
  • Figure 2 shows another embodiment of the insulated wire according to the present invention.
  • the insulated wire according to the present invention is formed on the surface of the conductor 10, the conductor 10, and is made of a conventional general polyimide resin, polyamideimide resin, polyesterimide resin, etc.
  • An insulating film 21 and a second insulating film 22 formed on the first insulating film 21 and formed from the composition for an insulating film as described above may be included.
  • the thickness of the second insulating film 22 may be 85% or more of the total thickness of the insulating film 20, for example, 85% or more and less than 100%.
  • the dielectric constant of the insulating film of the insulating wire according to the present invention increases, so that the partial discharge initiation voltage of the insulated wire decreases or heat resistance It is degraded and cannot be used under high temperature environments.
  • the insulated wire according to the present invention includes the conductor 10 and the insulating film or the first insulating film between the surface of the conductor 10 or between the first insulating film 21 and the second insulating film 22.
  • an adhesion-improving layer may be additionally included, or the surface of the insulating film 20 or the second insulating film 22 may have a lubricating layer, intrinsic It may further include a soft layer and the like.
  • the temperature at which a 10% mass loss occurs was measured as the decomposition temperature for the insulating film formed from the insulating film composition of each of the examples and comparative examples using TGA.
  • Each insulated wire of Examples and Comparative Examples was cut into 500 mm to prepare 10 insulated wire specimens of a twisted pair, and the insulating film was removed from the end of each of the insulated wires to a position of 10 mm to form a terminal treatment part.
  • the voltage was measured at the point where 10 pC discharge occurred 50 times per second on the insulated wire specimen while boosting the voltage of 50 Hz to 10 to 30 V/s under 25°C and 50% humidity, and this was measured by repeating 3 times.
  • the average value of the resulting voltage was described as the partial discharge start voltage.
  • Flexibility was evaluated according to the standard IEC 60851-3. Specifically, in order to make the insulated wire specimens of each of the Examples and Comparative Examples having a length of 400 mm in an elongated S shape, they were bent at 180° along a polishing mandrel having a diameter given in the corresponding standard in two directions and bent in a U shape. The part should be at least 150 mm. In this case, if no cracks occurred on the surface of the insulated wire specimen, it was marked as OK, and if cracks occurred, it was marked as NG.
  • Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Filming ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ permittivity 2.35 2.43 2.43 2.32 2.51 - - 4.7 Decomposition temperature(°C) 565 579 590 510 595 - - 420 Partial discharge start voltage (V) 1150 1130 1130 1140 1100 - - 910 flexibility OK OK OK OK OK OK NG - - OK
  • Comparative Example 1 it was confirmed that the molar ratio of the first diamine compound and the second diamine compound exceeded the standard, and the heat resistance was significantly lowered. It was confirmed that the partial discharge start voltage decreased due to the increase, and the flexibility decreased.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Insulated Conductors (AREA)

Abstract

La présente invention concerne une composition pour film isolant, et un fil électrique isolé comprenant un film isolant formé à partir de celle-ci. La présente invention concerne en particulier : une composition pour un film isolant, possédant une faible permittivité relative de façon à présenter une tension d'émission de décharge partielle élevée et, présentant simultanément une excellente résistance à la chaleur de façon à être stable à une température élevée, et possédant une excellente flexibilité ; et un fil électrique isolé comprenant un film isolant formé à partir de celle-ci.
PCT/KR2020/002449 2019-02-20 2020-02-20 Composition pour film isolant, et fil électrique isolé comprenant un film isolant formé à partir de celle-ci WO2020171617A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20190019667 2019-02-20
KR10-2019-0019667 2019-02-20
KR10-2020-0020168 2020-02-19
KR1020200020168A KR20200101867A (ko) 2019-02-20 2020-02-19 절연 피막용 조성물 및 이로부터 형성된 절연 피막을 포함하는 절연 전선

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WO2020171617A1 true WO2020171617A1 (fr) 2020-08-27

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110133001A (ko) * 2010-06-03 2011-12-09 엘에스전선 주식회사 절연전선
JP2012048922A (ja) * 2010-08-26 2012-03-08 Sumitomo Electric Wintec Inc 絶縁電線及びそれを用いた電機コイル、モータ
KR20120102712A (ko) * 2009-11-20 2012-09-18 이 아이 듀폰 디 네모아 앤드 캄파니 치수적으로 안정한 폴리이미드, 및 그 관련 방법
KR20150054707A (ko) * 2012-11-30 2015-05-20 후루카와 덴키 고교 가부시키가이샤 절연 전선 및 전기·전자기기
KR20160014651A (ko) * 2013-05-31 2016-02-11 가부시키가이샤 가네카 절연 피복 재료 및 그의 용도

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120102712A (ko) * 2009-11-20 2012-09-18 이 아이 듀폰 디 네모아 앤드 캄파니 치수적으로 안정한 폴리이미드, 및 그 관련 방법
KR20110133001A (ko) * 2010-06-03 2011-12-09 엘에스전선 주식회사 절연전선
JP2012048922A (ja) * 2010-08-26 2012-03-08 Sumitomo Electric Wintec Inc 絶縁電線及びそれを用いた電機コイル、モータ
KR20150054707A (ko) * 2012-11-30 2015-05-20 후루카와 덴키 고교 가부시키가이샤 절연 전선 및 전기·전자기기
KR20160014651A (ko) * 2013-05-31 2016-02-11 가부시키가이샤 가네카 절연 피복 재료 및 그의 용도

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