Classifications

• • 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
• • 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

Definitions

• the present disclosure relates to a resin composition, an insulated wire, and a method for producing an insulated wire.
• Patent Document 1 describes an insulating varnish that contains a coating resin and a thermally decomposable resin that decomposes at a temperature lower than the baking temperature of the coating resin.
• the resin composition according to one embodiment of the present disclosure contains a polyimide precursor that is a reaction product of an aromatic tetracarboxylic dianhydride and an aromatic diamine, an organic solvent, and an alkyl phthalate ester having a boiling point of 290°C or higher.
• the problem to be solved by the present disclosure is to provide a resin composition capable of forming an insulating layer having pores.
• an insulating layer having pores can be formed.
• Item 1 a polyimide precursor which is a reaction product of an aromatic tetracarboxylic dianhydride and an aromatic diamine; An organic solvent; A resin composition comprising an alkyl phthalate ester having a boiling point of 290°C or higher.
• Item 2. The resin composition according to item 1, wherein the boiling point of the alkyl phthalate is 380° C. or lower.
• Item 3. The resin composition according to item 1 or 2, wherein the alkyl phthalate is diisopropyl phthalate or diisobutyl phthalate.
• Item 5. The resin composition according to any one of items 1 to 4, wherein the organic solvent has a boiling point of 150° C. or higher.
• Item 6. The resin composition according to any one of items 1 to 5, further comprising thermally decomposable resin-containing particles.
• Item 7. The resin composition according to any one of items 1 to 6, which is used for forming an insulating layer for an insulated wire.
• An insulated wire wherein the insulating layer is formed from the resin composition according to any one of items 1 to 7.
• Item 9. A method for producing an insulated electric wire according to claim 8, applying the resin composition to an outer peripheral surface of the conductor; and heating the resin composition applied in the applying step.
• the resin composition contains a polyimide precursor which is a reaction product of an aromatic tetracarboxylic dianhydride and an aromatic diamine, an organic solvent, and an alkyl phthalate ester having a boiling point of 290° C. or higher.
• the resin composition contains an alkyl phthalate ester with a boiling point of 290°C or higher, and is therefore capable of forming an insulating layer with pores.
• an insulating layer is formed using the resin composition, pores can be formed by phase separation between the polyimide precursor and the alkyl phthalate ester, and it is presumed that the boiling point of the alkyl phthalate ester plays a role in whether or not pores are formed by the phase separation.
• the resin composition can be suitably used as a resin composition (resin varnish) for forming an insulating layer for an insulated electric wire.
• the polyimide precursor is a reaction product obtained by a polymerization condensation reaction between an aromatic tetracarboxylic dianhydride and an aromatic diamine.
• the polyimide precursor is a compound also called polyamic acid (polyamide acid).
• the polyimide precursor forms a cyclic imide by a dehydration cyclization reaction, becoming a polyimide.
• the aromatic tetracarboxylic dianhydride contains pyromellitic dianhydride (PMDA), the heat resistance of the insulating layer can be improved. This is because PMDA has a rigid and linear molecular structure.
• the aromatic tetracarboxylic dianhydride may contain aromatic tetracarboxylic dianhydrides other than PMDA (hereinafter also referred to as "other aromatic tetracarboxylic dianhydrides").
• aromatic tetracarboxylic dianhydrides include, for example, 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BDPA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BDPA), 2,2',3,3'-biphenyltetracarboxylic dianhydride (i-BDPA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2- Examples of the other aromatic tetracarboxylic dianhydrides include bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane
• the lower limit of the PMDA content relative to 100 mol% of the aromatic tetracarboxylic dianhydride may be 0 mol%, 10 mol%, 20 mol%, or 30 mol%.
• the upper limit of the PMDA content relative to 100 mol% of the aromatic tetracarboxylic dianhydride may be 100 mol%, 90 mol%, 80 mol%, or 70 mol%.
• the content of the other aromatic tetracarboxylic dianhydrides relative to 100 mol% of the aromatic tetracarboxylic dianhydride can be appropriately determined within a range that does not impair the effects of the present disclosure.
• the upper limit of the content may be 30 mol% or 20 mol%.
• the lower limit of the content may be 0 mol% or 10 mol%.
• diaminodiphenyl ether examples include 4,4'-diaminodiphenyl ether (4,4'-ODA), 3,4'-diaminodiphenyl ether (3,4'-ODA), 3,3'-diaminodiphenyl ether (3,3'-ODA), 2,4'-diaminodiphenyl ether (2,4'-ODA), and 2,2'-diaminodiphenyl ether (2,2'-ODA).
• 4,4'-diaminodiphenyl ether (4,4'-ODA) can improve the film elongation of the insulating layer.
• the lower limit of the content of ODA relative to 100 mol% of the aromatic diamine may be 50 mol%, 60 mol%, or 70 mol%.
• the upper limit of the content of ODA relative to 100 mol% of the aromatic diamine may be 100 mol%, or 90 mol%.
• the aromatic diamine may further contain an aromatic diamine other than ODA (hereinafter also referred to as "other aromatic diamine”).
• the other aromatic diamine include 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 4,4'-bis(4-aminophenoxy)biphenyl (BAPB), 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 2,4'-diaminodiphenylsulfone, 2,2'-diamino
• the content of the other aromatic diamine relative to 100 mol% of the aromatic diamine can be appropriately determined within a range that does not impair the effects of the present disclosure.
• the upper limit of the content may be 40 mol% or 30 mol%.
• the lower limit of the content may be 0 mol% or 10 mol%.
• the polyimide precursor may have a glass transition temperature of 250°C or higher as measured by the following method.
• the lower limit of the glass transition temperature may be 280°C or 300°C. Although no limiting interpretation is desired, if the glass transition temperature is above 280°C, the softening of the polyimide during pore formation can be suppressed, and the porosity tends to be improved.
• the upper limit of the glass transition temperature is not particularly limited, and is, for example, 400°C.
• the glass transition temperature is a value measured by applying a thin film of the resin composition to a glass plate and heating it at 350°C for 1 hour to prepare a film-like test specimen, using a dynamic viscoelasticity measuring device under the conditions of 1 Hz and 10°C/min temperature rise. The glass transition temperature can be adjusted by the type of monomer constituting the polyimide precursor.
• the lower limit of the concentration of the polyimide precursor in the resin composition may be 25% by mass or 27% by mass.
• the upper limit of the concentration may be 40% by mass or 35% by mass.
• the molar ratio of the aromatic tetracarboxylic dianhydride and aromatic diamine used as raw materials for the polyimide precursor may be, for example, 95:105 or more and 105:95 or less, 97:103 or more and 103:97 or less, or 99:101 or more and 101:99 or less, from the viewpoint of ease of synthesis of the polyimide precursor.
• the aromatic tetracarboxylic dianhydride and aromatic diamine may be substantially equimolar amounts. In this case, the molecular weight of the polyimide precursor can be easily increased.
• Substantially equimolar amounts refers to a molar ratio of the aromatic tetracarboxylic dianhydride and aromatic diamine (aromatic tetracarboxylic dianhydride:aromatic diamine) in the range of 99:101 or more and 101:99 or less.
• the polyimide precursor can be obtained by the polymerization condensation reaction of the aromatic tetracarboxylic dianhydride and the aromatic diamine described above.
• the method of the polymerization condensation reaction can be the same as that of the conventional synthesis of polyimide precursors.
• a specific method of the polymerization condensation reaction can be, for example, a method of mixing an aromatic tetracarboxylic dianhydride and an aromatic diamine in an organic solvent. By this method, the aromatic tetracarboxylic dianhydride and the aromatic diamine are polymerized, and a solution in which the polyimide precursor is dissolved in an organic solvent can be obtained.
• the polymerization condensation reaction can be carried out in the presence of a reaction inhibitor to control the degree of polymerization (weight average molecular weight).
• reaction inhibitor examples include water (H 2 O) and alcohols having 1 to 15 carbon atoms.
• alcohols having 1 to 15 carbon atoms include monohydric alcohols such as ethanol, methanol, propanol, butanol, and pentanol; and polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin.
• the reaction conditions for the above polymerization can be set appropriately depending on the raw materials used, etc.
• the reaction temperature can be set to 10°C or higher and 100°C or lower
• the reaction time can be set to 0.5 hours or higher and 24 hours or lower.
• the organic solvent used in the above polymerization condensation reaction may be the same as the organic solvent described below.
• organic solvent examples include aprotic polar organic solvents such as N-methyl-2-pyrrolidone (NMP, boiling point: 202° C.), N,N-dimethylacetamide (DMAc, boiling point: 165° C.), N,N-dimethylformamide (boiling point: 153° C.), dimethylsulfoxide (boiling point: 189° C.), and ⁇ -butyrolactone (boiling point: 204° C.).
• NMP N-methyl-2-pyrrolidone
• DMAc N,N-dimethylacetamide
• N,N-dimethylformamide boiling point: 153° C.
• dimethylsulfoxide bisulfoxide
• ⁇ -butyrolactone bioiling point: 204° C.
• the organic solvents may be used alone or in combination of two or more.
• aprotic polar organic solvent refers to a polar organic solvent that does not have a group that releases a
• boiling point of the organic solvent is 150°C or higher, unintended drying before baking can be suppressed during the process of forming the insulating layer. If there is a large difference (boiling point difference) between the boiling point of the organic solvent and the boiling point of the alkyl phthalate, pores tend to form more easily. Note that the boiling point of the alkyl phthalate is usually higher than that of the organic solvent.
• the content of the organic solvent is not particularly limited as long as it is an amount that can uniformly dissolve or disperse the aromatic tetracarboxylic dianhydride and aromatic diamine, but if the amount is too large, a large amount of the organic solvent must be volatilized when forming the insulating layer of the insulated electric wire, and it may take a long time to form the insulating layer. Therefore, the content of the organic solvent can be, for example, 100 parts by mass or more and 1,000 parts by mass or less per 100 parts by mass of the total of the aromatic tetracarboxylic dianhydride and aromatic diamine.
• alkyl phthalate esters have a boiling point of 290° C. or higher.
• alkyl ester refers to an ester containing a linear or branched alkyl group.
• phthalic acid refers to phthalic acid in the narrow sense, i.e., the ortho form of benzenedicarboxylic acid. Phthalic acid is clearly distinguished from isophthalic acid, which is the meta form, and terephthalic acid, which is the para form.
• the boiling point of the alkyl phthalate is 290°C or higher.
• an alkyl phthalate with a boiling point of 290°C or higher an insulating layer with pores can be formed.
• the alkyl phthalate ester volatilizes before phase separation between the polyimide precursor and the alkyl phthalate occurs during the heating step in forming the insulating layer, and therefore pores cannot be formed.
• the lower limit of the boiling point of the alkyl phthalate may be 300°C, 310°C, or 320°C. If the boiling point is 300°C or higher, an insulating layer with high porosity can be formed.
• the upper limit of the boiling point may be 410°C, 400°C, 390°C, 380°C, 340°C, 330°C, or 320°C. If the boiling point is 380°C or lower, the residue of the alkyl phthalate in the insulating layer can be suppressed. If the boiling point is 330°C or lower, the dielectric breakdown voltage and film elongation of the insulating layer can be improved. If the boiling point is 320°C or lower, the dielectric breakdown voltage and film elongation of the insulating layer can be further improved.
• alkyl phthalates examples include diethyl phthalate (boiling point: 298°C), diisopropyl phthalate (boiling point: 313°C), dipropyl phthalate (boiling point: 317°C), diisobutyl phthalate (boiling point: 327°C), dibutyl phthalate (boiling point: 340°C), dioctyl phthalate (boiling point: 385°C), bis(2-ethylhexyl) phthalate (boiling point: 384°C), and diisononyl phthalate (boiling point: 403°C). Dimethyl phthalate (boiling point: 282°C) does not fall under the category of alkyl phthalates.
• the content of the alkyl phthalate in the resin composition can be appropriately set within the range in which the effects of the present disclosure are exhibited. Since the porosity of the insulating layer formed increases as the content of the alkyl phthalate increases, the porosity of the insulating layer can be adjusted by adjusting the content of the alkyl phthalate.
• the upper limit of the content of the alkyl phthalate may be 12 parts by mass, 10 parts by mass, 9 parts by mass, 8 parts by mass, or 7 parts by mass, relative to 100 parts by mass of the polyimide precursor and the organic solvent in total. When the content is 12 parts by mass or less, the insulating layer formed has a good shape without foaming in appearance.
• the content is 12 parts by mass or less, the balance between the island portion and the sea portion of the sea-island structure generated by phase separation between the polyimide precursor and the alkyl phthalate is appropriately adjusted, thereby suppressing the occurrence of poor appearance such as foaming, swelling, and peeling of the insulating layer.
• the content is 10 parts by mass or less, the dielectric breakdown voltage and film elongation can be further improved. If the content is 8 parts by mass or less, the dielectric breakdown voltage and film elongation can be further improved.
• the lower limit of the content of the alkyl phthalate may be 1 part by mass, 2 parts by mass, 4 parts by mass, or 6 parts by mass per 100 parts by mass of the polyimide precursor and the organic solvent combined.
• the resin composition further contains heat-decomposable resin-containing particles
• an insulating layer having a good appearance can be formed even when the porosity is high.
• the particles are gasified, and pores are formed in the insulating layer in the area where the particles containing the thermally decomposable resin were present. In this case, the particles are uniformly distributed as islands of fine particles in the sea phase of the resin matrix that forms the insulating layer. This allows the formation of independent pores.
• the thermally decomposable resin contained in the thermally decomposable resin-containing particles is preferably a resin that thermally decomposes at a temperature lower than the baking temperature of the polyimide, which is the main component of the resin matrix of the insulating layer.
• the baking temperature is set appropriately depending on the type of polyimide, but is usually about 200°C to 600°C.
• “Thermal decomposition temperature” refers to the temperature at which the mass reduction rate reaches 50% when the temperature is increased from room temperature at 10°C/min in an air atmosphere.
• the thermal decomposition temperature can be measured by measuring the thermogravimetry using a thermogravimetry-differential thermal analyzer ("TG/DTA" from SII NanoTechnology, Inc.).
• thermally decomposable resins include compounds such as polyethylene glycol and polypropylene glycol that have one or both ends or a portion thereof alkylated, (meth)acrylated, or epoxidized; polymers of (meth)acrylic acid esters having an alkyl group with 1 to 6 carbon atoms, such as polymethyl (meth)acrylate, polyethyl (meth)acrylate, polypropyl (meth)acrylate, and polybutyl (meth)acrylate; polymers of modified (meth)acrylates, such as urethane oligomers, urethane polymers, urethane (meth)acrylates, epoxy (meth)acrylates, and ⁇ -caprolactone (meth)acrylate; poly(meth)acrylic acid; crosslinked products thereof; polystyrene; and crosslinked polystyrene.
• polymers of (meth)acrylic acid esters having an alkyl group with 1 to 6 carbon atoms such as polymethyl (me
• Polymers of (meth)acrylic acid esters having an alkyl group with 1 to 6 carbon atoms are easily thermally decomposed at the above baking temperature, and are likely to form pores in the insulating layer.
• An example of the above polymers of (meth)acrylic acid esters is polymethyl methacrylate (PMMA).
• PMMA polymethyl methacrylate
• (meth)acrylic acid” includes both "acrylic acid” and "methacrylic acid.”
• the above-mentioned heat-decomposable resin-containing particles may be particles consisting only of the above-mentioned heat-decomposable resin, or may be particles with a core-shell structure having a core mainly composed of the above-mentioned heat-decomposable resin and a shell mainly composed of a resin having a heat decomposition temperature higher than that of the above-mentioned heat-decomposable resin. In this case, it is possible to suppress the communication of pores and reduce the variation in pore size.
• the main component of the shell is not particularly limited as long as it is a material with a higher thermal decomposition temperature than the core, and is preferably a synthetic resin with a low dielectric constant and high heat resistance.
• examples include polystyrene, silicone, fluororesin, and polyimide. Silicone tends to increase elasticity, which in turn tends to improve the dispersion of pores in the insulating layer, resulting in excellent insulation and heat resistance.
• the resin composition may contain other components in addition to the above components.
• the other components are not particularly limited as long as they are additives to be blended in a resin varnish for forming an insulating layer of an insulated electric wire, and examples of the other components include a filler, an antioxidant, a leveling agent, a curing agent, and an adhesion aid.
• the insulated wire includes a conductor and an insulating layer that covers the conductor.
• the insulated wire can be suitably used as a winding for a coil (magnet wire).
• the conductor generally contains a metal as a main component.
• the metal is not particularly limited, but if the metal is copper, a copper alloy, aluminum, or an aluminum alloy, an insulated electric wire having good workability, electrical conductivity, etc. can be obtained.
• the conductor may contain other components such as known additives in addition to the main metal component.
• the cross-sectional shape of the conductor is not particularly limited, and various shapes such as circular, square, rectangular, etc. can be adopted.
• the size of the cross-section of the conductor is also not particularly limited, and the diameter (short side width) can be, for example, 0.2 mm or more and 8.0 mm or less.
• the insulating layer is laminated on the peripheral surface of the conductor so as to cover the conductor.
• the insulating layer may cover the conductor directly or indirectly.
• indirectly covering the conductor for example, a multi-layer structure in which the covering layer of the conductor includes a layer other than the insulating layer can be mentioned.
• the insulating layer is formed from the resin composition described above. Therefore, the insulating layer has a plurality of pores.
• 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 may further have another layer laminated on the outer peripheral surface of the insulating layer.
• Another layer is a surface lubricating layer.
• the lower limit of the porosity in the insulating layer may be 20 volume %, 25 volume %, or 30 volume %.
• the upper limit of the porosity may be 70 volume %, 60 volume %, or 50 volume %.
• “Porosity” refers to the percentage of the volume of the pores relative to the volume of the insulating layer including the pores.
• the thermally decomposable resin-containing particles are particles with the core-shell structure
• the pores have an outer shell at their periphery that originates from the shell of the particles with the core-shell structure.
• the insulating layer may contain other components in addition to the above components.
• the other components There are no particular limitations on the other components, so long as they are additives that are blended into the insulating layer of the insulated wire, and examples of such components include fillers, antioxidants, leveling agents, curing agents, and adhesive aids.
• the insulated wire can be produced, for example, by a method including a step of applying the above-mentioned resin composition to the outer peripheral surface of a conductor (hereinafter referred to as the "applying step") and a step of heating the resin composition applied to the conductor (hereinafter referred to as the "heating step").
• the resin composition is applied to the outer peripheral surface of the conductor.
• One method for applying the resin composition to the outer peripheral surface of the conductor is to use a coating device equipped with a liquid composition tank that stores the resin composition and a coating die. With this coating device, the resin composition adheres to the outer peripheral surface of the conductor as the conductor passes through the liquid composition tank, and the resin composition is then applied to a uniform thickness as the conductor passes through the coating die.
• the resin composition applied to the conductor in the application step is heated. This heating causes the solvent in the resin composition to volatilize and the polyimide precursor to harden, forming polyimide.
• the apparatus used in the heating step is not particularly limited, and for example, a cylindrical baking furnace that is long in the direction in which the conductor travels can be used.
• the heating method is not particularly limited, and can be any conventionally known method such as hot air heating, infrared heating, or high-frequency heating.
• the heating temperature can be, for example, 300°C or higher and 800°C or lower.
• the heating time can be, for example, 5 seconds or higher and 1 minute or lower.
• the coating process and the heating process are usually repeated multiple times. By repeating the process multiple times, the thickness of the insulating layer can be increased.
• the hole diameter of the coating die can be adjusted appropriately according to the number of repetitions.
• Test Example 1 In Test Example 1, the influence of differences in boiling points of alkyl phthalates on pore formation was tested.
• the dielectric constant of the insulating layer was measured for the insulated wires No. 1-1 to No. 1-6 prepared above.
• a measurement sample was prepared by applying silver paste to three points on the surface of the insulated wire and peeling off the insulating layer on one end of the insulated wire to expose the conductor.
• the application lengths of the silver paste applied to the three points on the surface of the insulated wire in the longitudinal direction of the insulated wire were 10 mm, 100 mm, and 10 mm, respectively, along the longitudinal direction.
• the two silver pastes applied at a length of 10 mm were grounded, and the electrostatic capacitance between the silver paste applied at a length of 100 mm between these two silver pastes and the exposed conductor was measured with an LCR meter.
• Test Example 2 In Test Example 2, the influence of different contents of alkyl phthalate on the characteristics of the insulated wire was tested.
• Test Example 3 In Test Example 3, the effects on the characteristics of the insulated wire due to the difference in boiling point between the alkyl phthalate ester and the organic solvent and the difference in glass transition temperature of the polyimide precursor were tested.
• the resin compositions No. 3-1 to No. 3-3 prepared above were thinly coated on a glass plate and heated at 350° C. for 1 hour to obtain film-like test specimens.
• the glass transition temperatures of the obtained test specimens were measured using a dynamic viscoelasticity measuring device (Seiko Instruments Inc.'s "DMS6100") under conditions of 1 Hz and a temperature increase rate of 10° C./min.
• acid anhydride means “aromatic tetracarboxylic dianhydride.”
• Diamine means “aromatic diamine.”
• the units of values in the “acid anhydride” and “diamine” rows are mol%, and “-” indicates that the corresponding component is not used.
• the units of values in the "polyimide precursor solution,” “DIBP,” and “DEP” rows are parts by mass. The “-” in the "glass transition temperature [°C]” row indicates that no measurement was performed.
• Table 3 shows that when resin composition No. 3-1 is used, an insulating layer with a higher porosity and a lower relative dielectric constant can be formed compared to when resin composition No. 3-3 is used. This shows that the glass transition temperature of the polyimide precursor affects the porosity.
• Test Example 4 In Test Example 4, the effect on pore formation when an alkyl phthalate ester and particles containing a thermally decomposable resin were used in combination was tested.

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• 2023
  • 2023-01-25 JP JP2024572588A patent/JPWO2024157378A1/ja active Pending
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