WO2020091147A1 - Vernis polyimide pour revêtement conducteur permettant d'améliorer la résistance à la chaleur d'un produit revêtu de polyimide, et produit revêtu de polyimide fabriqué à partir de ce dernier - Google Patents

Vernis polyimide pour revêtement conducteur permettant d'améliorer la résistance à la chaleur d'un produit revêtu de polyimide, et produit revêtu de polyimide fabriqué à partir de ce dernier Download PDF

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Publication number
WO2020091147A1
WO2020091147A1 PCT/KR2019/000910 KR2019000910W WO2020091147A1 WO 2020091147 A1 WO2020091147 A1 WO 2020091147A1 KR 2019000910 W KR2019000910 W KR 2019000910W WO 2020091147 A1 WO2020091147 A1 WO 2020091147A1
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polyimide
polyimide varnish
coating
varnish
conductor
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PCT/KR2019/000910
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English (en)
Korean (ko)
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황인환
이익상
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에스케이씨코오롱피아이 주식회사
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Publication of WO2020091147A1 publication Critical patent/WO2020091147A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/06—Insulating conductors or cables
    • 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
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat

Definitions

  • the present invention relates to a polyimide varnish for conductor coating for improving the heat resistance of a polyimide coating and a polyimide coating prepared therefrom.
  • the insulating layer (insulating coating) covering the conductor is required to have excellent insulation, adhesion to the conductor, heat resistance, mechanical strength, and the like.
  • a high voltage is applied to an insulated wire constituting the electric device, and partial discharge (corona discharge) is likely to occur on the surface of the insulating coating.
  • corona discharge may cause local temperature rise or generation of ozone or ions.
  • deterioration in the insulation coating of the insulated wire may cause premature insulation destruction and shorten the lifespan of electrical equipment. .
  • Examples of the resin that can be used for the insulating layer include polyimide resin, polyamideimide resin, and polyesterimide resin.
  • polyimide resin is a material having excellent heat resistance and insulation properties, and has excellent properties for use as a material for coating a conductor.
  • the polyimide resin refers to a high heat-resistant resin produced by solution polymerization of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to produce a polyamic acid derivative, followed by dehydration at high temperature by ring dehydration.
  • a polyimide varnish which is a precursor of a polyimide resin, is coated or coated around an electric wire made of a conductor, and then a curing furnace capable of heat treatment at a predetermined temperature.
  • the method of imidizing the polyimide varnish within can be used.
  • the method of forming the insulating coating may cause a difference in physical properties, productivity and manufacturing cost of the insulating coating prepared according to conditions such as the temperature of the curing furnace, the number of coating times of the polyimide varnish, and the coating speed. That is, forming an insulating coating at a high temperature may be advantageous for producing an insulating coating having excellent physical properties, and productivity may increase as the number of coatings is small or the coating speed is fast.
  • the general polyimide resin since the general polyimide resin has excellent adhesion to a conductor despite excellent physical properties, a problem in appearance defects may occur when forming an insulating coating.
  • An object of the present invention is to provide a polyimide varnish for coating a conductor comprising a surface modifier, a coupling agent and a curing agent and a polyimide coating prepared therefrom.
  • surface modifiers, coupling agents and curing agents are disclosed as essential factors for the implementation of polyimide coatings having excellent heat resistance, insulation, flexibility and adhesion to a substrate (conductor).
  • the present invention has a practical purpose to provide a specific embodiment thereof.
  • the present invention is a polyimide varnish for conductor coating
  • a polyamic acid solution prepared by polymerizing one or more dianhydride monomers and one or more diamine monomers in an organic solvent;
  • a polyimide varnish having a softening resistance of 500 ° C or higher of the coating prepared from the polyimide varnish.
  • the polyimide coating was prepared using the polyimide varnish, it was found that it has excellent heat resistance and insulation, and the flexibility of the coating and adhesion to the substrate are improved.
  • dianhydride dianhydride
  • dianhydride is intended to include its precursors or derivatives, which may not technically be dianhydrides, but nevertheless react with diamines to form polyamic acids. And this polyamic acid can be converted back to polyimide.
  • Diamine as used herein is intended to include precursors or derivatives thereof, which may not technically be diamines, but will nevertheless react with dianhydrides to form polyamic acids, which polyamic acids are again polydi Can be converted to mead.
  • the polyimide varnish according to the present invention is a polyimide varnish for conductor coating
  • a polyamic acid solution prepared by polymerizing one or more dianhydride monomers and one or more diamine monomers in an organic solvent;
  • the coating made from the polyimide varnish has a softening resistance of 500 ° C or higher.
  • the degree of softening of the coating made from the polyimide varnish may be 500 ° C or more and 900 ° C or less.
  • the polyimide varnish may have a solid content of 15 to 38% by weight, specifically 18 to 38% by weight based on the total weight of the polyimide varnish, and a viscosity at 23 ° C of 500 to 8,000 cP, in detail 500 to 5,000 cP.
  • the polyimide varnish having the viscosity has an advantage of easy handling in terms of fluidity, and may be advantageous in a process of coating on the conductor surface.
  • the process cost is required because a higher pressure must be applied by friction with the pipe when the polyimide varnish is moved through the pipe during the polyimide manufacturing process. This increases and handling can be deteriorated.
  • It may include 0.01 to 0.05 parts by weight of an alkoxy silane coupling agent with respect to 100 parts by weight of the solid content of the polyimide varnish.
  • the alkoxy silane coupling agent When the content of the alkoxy silane coupling agent exceeds the above range, mechanical properties may be deteriorated, and when heat treatment for imidization, the alkoxy silane coupling agent decomposes at a high temperature to decrease the adhesion between the polyimide coating and the conductor rather. It is not desirable because it can be done.
  • the content of the alkoxy silane coupling agent is less than the above range, it is not preferable because the effect of improving the adhesion between the polyimide coating and the conductor cannot be sufficiently exhibited.
  • the alkoxy silane coupling agent is, for example, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyl dimethoxysilane, 3-aminopropyl methyl diethoxysilane, 3- (2 -Aminoethyl) aminopropyl trimethoxysilane, 3-phenylaminopropyl trimethoxysilane, 2-aminophenyl trimethoxysilane, and 3-aminophenyl trimethoxysilane. It can, but is not limited to this.
  • the polyimide varnish may contain 0.01 to 0.05 parts by weight of a silicone-based additive with respect to 100 parts by weight of solids.
  • the content of the silicone-based additive exceeds the above range, the mechanical properties of the polyimide coating to be produced may be deteriorated, and when the heat treatment for imidization, the silicone-based additive is decomposed at a high temperature to improve adhesion between the polyimide coating and the conductor. Rather, it is not preferable because it may decrease.
  • the content of the silicone-based additive is less than the above range, it is not preferable because the effect of improving the adhesion between the polyimide coating and the conductor to be produced cannot be sufficiently exhibited.
  • the polyimide varnish may include 0.1 to 2 parts by weight of a low temperature curing agent relative to 100 parts by weight of the solid content.
  • the low temperature curing agent may include at least one selected from the group consisting of betapicoline, isoquinoline, triethylenediamine and pyridine.
  • the low temperature curing agent may include at least one selected from the group consisting of beta-picoline, isoquinoline and pyridine, and triethylenediamine.
  • the triethylenediamine serves to enable low temperature curing of the polyimide varnish and to improve the heat resistance of the prepared polyimide coating.
  • the content of the low-temperature curing agent exceeds the above range, there is a high possibility of appearance defects due to an increase in the curing rate, and physical properties such as heat resistance, insulation, and flexibility of the polyimide coating are lowered due to differences in local curing rates. Can be. Conversely, when the content of the low-temperature curing agent is less than the above range, it is not preferable because the effect of the present invention for improving the heat resistance of the polyimide coating cannot be sufficiently exhibited.
  • polyimide resins undergo chemical changes, ie oxidation reactions, in the presence of oxygen by light, heat, pressure, shear force, and the like.
  • This oxidation reaction causes a problem of deteriorating the heat resistance and mechanical properties of the polyimide resin produced by generating a change in physical properties by cutting, crosslinking, etc. of the molecular chain in the polyimide resin.
  • the polyimide varnish may further solve the problem by further including an antioxidant.
  • the antioxidant may have a 5% by weight decomposition temperature of 380 ° C or higher, and specifically, a 5% by weight decomposition temperature of 400 ° C or higher.
  • the antioxidant may include a compound represented by Formula 1 below.
  • R 1 to R 6 may each independently be selected from the group consisting of C1-C3 alkyl groups, aryl groups, carboxylic acid groups, hydroxy groups, fluoroalkyl groups, and sulfonic acid groups,
  • n is an integer from 1 to 4,
  • R 1 to R 6 are plural, they may be the same or different from each other,
  • n1 to m6 are each independently an integer of 0 to 3.
  • n in Formula 1 may be 1, m1 to m6 may be 0, and more specifically, the antioxidant may be a compound of Formula 1-1.
  • antioxidants Since these antioxidants have low volatility and excellent thermal stability, they do not decompose or volatilize during the manufacturing process of the polyimide coating, and thus can exert an effect of preventing oxidation of the amide group in the polyimide varnish or the imide group of the polyimide coating. have.
  • the antioxidant may be included in the range of 0.1 to 2 parts by weight based on 100 parts by weight of the solid content of the polyimide varnish.
  • the polyamic acid solution may be produced by polymerization of one or more dianhydride monomers and one or more diamine monomers.
  • the dianhydride monomer that can be used in the production of the polyamic acid of the present invention may be an aromatic tetracarboxylic dianhydride.
  • the aromatic tetracarboxylic dianhydride is pyromellitic dianhydride (or PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (or BPDA), 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (or a-BPDA), oxydiphthalic dianhydride (or ODPA), diphenylsulfone-3,4,3', 4'-tetracarboxylic Dianhydride (or DSDA), bis (3,4-dicarboxyphenyl) sulfide dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3- Hexafluoropropane dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride (
  • dianhydride monomers that can be particularly preferably used in the present invention include pyromellitic dianhydride (PMDA) and 3,3 ', It may be one or more selected from the group consisting of 4,4'-biphenyltetracarboxylic dianhydrid (BPDA).
  • PMDA pyromellitic dianhydride
  • BPDA 4,4'-biphenyltetracarboxylic dianhydrid
  • the diamine monomers that can be used in the production of the polyamic acid solution of the present invention are aromatic diamines, and are classified as follows.
  • 1,4-diaminobenzene or paraphenylenediamine, PDA
  • 1,3-diaminobenzene 2,4-diaminotoluene
  • 2,6-diaminotoluene 3,5-diaminobenzo Diamines having one benzene nucleus in the structure, such as diacid (or DABA), etc., which have a relatively rigid structure in diamine;
  • Diaminodiphenyl ethers such as 4,4'-diaminodiphenyl ether (or oxidianiline, ODA) and 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane (Or methylenedianiline, MDA), 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis ( Trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diamino Diphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis (4-aminophenyl) sulfide, 4,4'-
  • Second aspect a method for producing a polyimide varnish
  • the second composition In the dianhydride monomer component in excess, in the first composition when the dianhydride monomer component is excessive, in the second composition, the diamine monomer component in excess, the first and second compositions are mixed and used in these reactions So that the total diamine monomer component and the dianhydride monomer component become substantially equimolar It can be joined to the methods.
  • the organic solvent is not particularly limited as long as it is a solvent in which the polyamic acid can be dissolved, but as an example, the organic solvent may be an aprotic polar solvent.
  • Non-limiting examples of the aprotic polar solvent include amide solvents such as N, N'-dimethylformamide (DMF) and N, N'-dimethylacetamide (DMAc), p-chlorophenol, and o-chloro And phenol-based solvents such as phenol, N-methyl-pyrrolidone (NMP), gamma brotirolactone (GBL) and digrime, and these may be used alone or in combination of two or more.
  • amide solvents such as N, N'-dimethylformamide (DMF) and N, N'-dimethylacetamide (DMAc), p-chlorophenol, and o-chloro And phenol-based solvents such as phenol, N-methyl-pyrrolidone (NMP), gamma brotirolactone (GBL) and digrime, and these may be used alone or in combination of two or more.
  • the solubility of the polyamic acid may be adjusted by using auxiliary solvents such as xylene, toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, and water.
  • auxiliary solvents such as xylene, toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, and water.
  • organic solvents that can be particularly preferably used in the preparation of the polyimide varnish of the present invention may be amide-based solvents N, N'-dimethylformamide and N, N'-dimethylacetamide.
  • the polymerization method is not limited to the above examples, and it is needless to say that any known method can be used.
  • the dianhydride monomer may be appropriately selected from the examples described above, and in detail, pyromellitic dianhydride (PMDA) and 3,3 ', 4,4'-biphenyltetracarboxylic
  • PMDA pyromellitic dianhydride
  • BPDA dianhydrides
  • biphenyl-tetracarboxylic dianhydrid dianhydrides
  • the diamine monomer may be appropriately selected from the examples described above, and specifically, composed of 4,4'-diaminodiphenyl ether (or oxydianiline, ODA) and 4,4'-methylenedianiline (MDA).
  • ODA 4,4'-diaminodiphenyl ether
  • MDA 4,4'-methylenedianiline
  • the process (a) is performed at 30 to 80 ° C, and the polyamic acid solution may have a viscosity at 23 ° C in the range of 500 to 9,000 cP.
  • process (b) may further be performed by mixing an antioxidant in a polyamic acid solution and at 40 to 90 ° C.
  • the silicone-based additive and the alkoxy silane coupling agent included in the polyimide varnish can improve the adhesion between the polyimide coating and the conductor prepared therefrom, and the antioxidant included in the polyimide varnish is the polyimide coating prepared therefrom Changes in physical properties can be minimized.
  • the low-temperature curing agent included in the polyimide varnish can improve physical properties such as heat resistance, insulation, and flexibility of the polyimide coating prepared therefrom.
  • the physical properties of the polyimide coating may be changed even with a specific combination of the silicone-based additive, alkoxy silane coupling agent, antioxidant, and low temperature curing agent and slight content difference included in the polyimide varnish, and it is not easy to predict the change. .
  • the polyimide coating has a softening resistance of 500 ° C or higher.
  • the thickness of the polyimide varnish coated per repetition of the above steps (1) and (2) is 2 to 6 ⁇ m
  • the process (2) can be carried out at 300 to 750 °C.
  • the coating speed of the conductor may be 2 to 30 m / min.
  • the conductor may be a copper wire made of copper or a copper alloy, but a conductor made of another metal material such as a silver wire or various metal plating wires such as aluminum and tin-plated wire may also be included as conductors.
  • the cross-sectional shape of the conductor may be a circular line, a flat angle line, a hexagonal line, etc., but is not limited thereto.
  • the polyimide coating may be prepared through thermal imidization.
  • the thermal imidization method is a method of excluding chemical catalysts and inducing an imidization reaction with a heat source such as hot air or an infrared dryer.
  • the thermal imidization method may heat the polyimide varnish at a variable temperature in the range of 100 to 750 ° C to imidize the amic acid group present in the polyimide varnish, specifically 300 to 750 ° C, and more specifically Can be imidized by heat treatment at 500 to 700 ° C to amic acid groups present in the polyimide varnish.
  • the polyimide coating of the present invention manufactured according to the above-described manufacturing method has a thickness in the range of 16 to 50 ⁇ m, a softening resistance of 500 ° C. or higher, a tan ⁇ of 270 ° C. or higher, and an insulation breakdown voltage (BDV) of 8 kV / mm. It may be abnormal.
  • the present invention can also provide an electric wire including a polyimide coating prepared by coating and imidizing the polyimide varnish on the surface of the electric wire, and providing an electronic device including the electric wire.
  • the polyanyl having a molar ratio of dianhydride monomer of 100: 100, 0.01 parts by weight of an alkoxy silane coupling agent, 0.5 parts by weight of an antioxidant, 0.01 parts by weight of a silicone-based additive, and 0.5 parts by weight of a low temperature curing agent based on 100 parts by weight of solid content Mid varnish was prepared.
  • the polyimide varnish was adjusted to a copper wire having a conductor diameter of 1 mm between 2 to 6 ⁇ m per coating thickness, the maximum temperature of the coating curing furnace was adjusted to 500 ° C, and the coating speed of the copper wire was 12 m.
  • a process of coating, drying, and curing a total of 7 times was repeated to prepare an electric wire including a polyimide coating having a coating thickness of 35 ⁇ m.
  • Example 1 the electric wires were prepared in the same manner as in Example 1, except that the viscosity of the monomer, additive, and polyimide varnish was changed as shown in Table 1 below.
  • Example 1 an electric wire was prepared in the same manner as in Example 1, except that instead of the compound of Formula 1-1 as an antioxidant, a compound of Formula A having a 5 wt% decomposition temperature of about 377 ° C was added.
  • Example 1 a wire was prepared in the same manner as in Example 1, except that instead of the compound of Formula 1-1 as an antioxidant, a compound of Formula B having a 5 wt% decomposition temperature of about 338 ° C. was added.
  • Example 1 100 - 100 - Formula 1-1 0.5 0.01 0.01 0.5 3,100
  • Example 2 100 - 100 - Formula 1-1 0.5 0.01 0.01 2 3,100
  • Example 3 100 - 100 - Formula 1-1 0.5 0.05 0.01 0.5 3,100
  • Example 4 100 - 100 - Formula 1-1 0.5 0.01 0.05 0.5 3,100
  • Example 5 100 - 100 - Formula 1-1 2 0.01 0.01 0.5 3,100
  • Example 6 100 - 100 - Formula 1-1 0.1 0.01 0.01 0.5 3,100
  • Example 7 100 - 100 - Formula 1-1 0.5 0.01 0.01 0.1 3,100
  • Example 8 50 50 100 - Formula 1-1 0.5 0.01 0.01 0.5 5,500
  • Example 9 50 100 - Formula 1-1 0.5 0.05 0.05 0.5
  • 'O' when it is a coating of a good product, it is represented by 'O', and when an appearance defect such as pinhole or polyimide resin is carbonized, it is represented by 'X'.
  • Heat resistance shock was evaluated for the polyimide coatings of the electric wires produced in Examples 1 to 13 and Comparative Examples 1 to 16. Heat shock is an indicator of whether a wire can withstand temperature exposure in an extended state or in a state where it is wound or bent around the mandrel.
  • the polyimide coatings of the wires prepared in Examples 1 to 13 and Comparative Examples 1 to 16 were heated at a temperature of 200 ° C. for 30 minutes, and then taken out of the oven, the specimen was cooled to room temperature, and then 20 % The number of cracks in the polyimide coating upon elongation was determined and the results are shown in Table 2 below.
  • the coating of the polyimide coating may not be uniform, or partially carbonized, and heat shock Vulnerable to.
  • the tan ⁇ value of the polyimide coating was measured using a TSE300 Tan Delta Tester from DSE.
  • the specimen is connected to the bridge with the conductor as one electrode and the graphite coating as the other, and the temperature of the assembly is increased at a constant rate from ambient to a temperature that provides a clearly defined curve.
  • the temperature was taken through the detector in contact with the sample, and the result was plotted as a logarithmic or linear axis of the temperature versus the linear axis and tan ⁇ , and the tan ⁇ value of the polyimide coating was calculated from the values.
  • the degree of softening represents the decomposition temperature of an insulator, and is determined by measuring the temperature at which a short circuit occurs between two wires that cross each other at right angles when a specified load is applied to the intersection.
  • the wires are stacked so as to cross at right angles, placed on a flat plate, and in the state where 1000 g of load is applied to the overlapped portions, an AC voltage of 100 V is applied and the temperature is shorted by raising the temperature at a rate of about 2 ° C / min. Was measured.
  • the specimens were pretreated in an oven at 150 ° C. for 4 hours, and then placed in a pressure vessel.
  • the pressure vessel is filled with 1400 g of refrigerant and the pressure vessel is heated for 72 hours, then the pressure vessel is cooled, the specimen is transferred to a 150 ° C. oven and held for 10 minutes and cooled to room temperature.
  • BDV was measured by connecting both ends of the wire and increasing the AC voltage at the nominal frequency of the test voltage (60 Hz) between the wire conductors from 0 to a constant speed.
  • a pinhole test was performed to confirm whether there was a defect in the insulation of the polyimide coating of the electric wire. Specifically, a wire specimen having a length of about 1.5 m was taken and placed in an air circulation oven (125 ° C) for 10 minutes, and then cooled at room temperature without any bending or stretching. The cooled wire specimen was immersed in a sodium chloride electrolyte containing phenolphthalein alcohol while connected to an electric circuit having a direct current test voltage, and then taken out to check the number of pinholes visually.
  • a straight wire specimen having a free measuring length of 200-250 mm is quickly stretched to the breaking point or the elongation (20%) given in the standard. After stretching, inspect the specimen for the loss of adhesion or cracking at the specified magnification (1 to 6 times). The 2 mm length of the broken wire end should be neglected.
  • Example 1 320 543 10.3 0 0
  • Example 2 315 563 10.1 0 0
  • Example 3 325 555 10.2 0 0
  • Example 4 335 557 10.5 0 0
  • Example 5 550 9.8 0 0
  • Example 6 310 535 9.7 0 0
  • Example 7 300 530 9.8 0 0
  • Example 8 305 522 9.5
  • Example 9 310 530 9.6 One 0
  • Example 10 295 520 9.3 0 0
  • Example 11 300 528 9.5 2 0
  • Example 12 285 505 8.8 0 0
  • Example 13 290 515 8.9 One 0 Comparative Example 1 250 474 6.3 12 15 Comparative Example 2 260 490 7.5 4 3 Comparative Example 3 265 495 7.8 10 8 Comparative Example 4 265 480 7.9 11 7 Comparative Example 5 260 475 7.5 2 2 Comparative Example 6 285 4
  • the polyimide coatings of Examples 1 to 13 prepared from a polyimide varnish comprising a silicone-based additive and an alkoxy silane coupling agent, a low-temperature curing agent, and an antioxidant according to the present invention have tan ⁇ of 270 ° C. or higher and internal combustion It can be seen that the degree of chemical conversion is excellent at heat resistance of 500 ° C or higher, the insulation breakdown voltage is 8 kV / mm or higher, and the adhesion is excellent between the conductor and the coating through a pull test.
  • Comparative Examples 1 to 16 which differ from the examples at the highest temperature of the silicone-based additive, alkoxy silane coupling agent, low temperature curing agent, antioxidant and solids content, viscosity, and curing temperature, tan ⁇ compared to the example, It can be seen that at least one of the softening resistance and the breakdown voltage was decreased, and the number of pinholes according to the pinhole test, that is, a relatively large number of defects in the insulator was present. In addition, in some comparative examples, cracks were observed on the outer surface of the polyimide coating in the pulling test, and it can be confirmed that the adhesion between the conductor and the coating was lowered.
  • the alkoxy silane coupling agent and the silicone-based additive can improve the production yield by improving the adhesion between the polyimide coating and the conductor.
  • the low temperature curing agent included in the polyimide varnish achieves a high imidation rate even at a relatively low curing temperature and a small number of coatings or a low coating speed in the production process of the polyimide coating, such as heat resistance, insulation, flexibility, etc. At the same time as improving physical properties, it is possible to increase productivity and process efficiency.
  • the polyimide coating has the advantage of satisfying the heat resistance, insulation and flexibility required for the electronic device, and has an advantage of excellent adhesion between the polyimide coating and the conductor.

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Abstract

La présente invention concerne un vernis polyimide pour revêtement conducteur comprenant : une solution d'acide polyamique à préparer par la polymérisation d'un ou plusieurs types de monomères dianhydride et d'un ou plusieurs types de monomères diamine dans un solvant organique ; un additif à base de silicone ; un agent de couplage alcoxysilane ; et un agent de durcissement à basse température, la température de résistance au ramollissement d'un produit revêtu fabriqué à partir du vernis de polyimide étant de 500 °C ou plus.
PCT/KR2019/000910 2018-10-31 2019-01-22 Vernis polyimide pour revêtement conducteur permettant d'améliorer la résistance à la chaleur d'un produit revêtu de polyimide, et produit revêtu de polyimide fabriqué à partir de ce dernier WO2020091147A1 (fr)

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KR1020180131726A KR101992576B1 (ko) 2018-10-31 2018-10-31 폴리이미드 피복물의 내열성을 향상시키기 위한 도체 피복용 폴리이미드 바니쉬 및 이로부터 제조된 폴리이미드 피복물

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CN116622069A (zh) * 2023-07-24 2023-08-22 佳腾电业(赣州)股份有限公司 一种聚双醚醚酰亚胺粘结剂及其制备方法、应用

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WO2023200156A1 (fr) * 2022-04-15 2023-10-19 피아이첨단소재 주식회사 Précurseur de polyimide
WO2024005508A1 (fr) * 2022-06-29 2024-01-04 피아이첨단소재 주식회사 Vernis polyimide auto-lubrifiant et revêtement polyimide préparé à partir de celui-ci

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CN114628065B (zh) * 2022-03-15 2024-01-26 安徽华能电缆集团有限公司 一种耐低温屏蔽控制电缆
CN116622069A (zh) * 2023-07-24 2023-08-22 佳腾电业(赣州)股份有限公司 一种聚双醚醚酰亚胺粘结剂及其制备方法、应用
CN116622069B (zh) * 2023-07-24 2023-10-03 佳腾电业(赣州)股份有限公司 一种聚双醚醚酰亚胺粘结剂及其制备方法、应用

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