Insulated wires, coils and cables containing insulated wires

Abstract

To provide an insulated wire including a coat that is thin but has excellent insulation performance and a method for producing the same, and a production method that can produce such an insulated wire at a firing temperature of 250°C or lower while reducing the environmental load and cost.SOLUTION: An insulated wire includes a conductor wire, and an insulation film that coats the conductor wire. The insulation film comprises a cured product of an aromatic (poly)ether compound comprising bisphenol A and benzophenone.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to insulated wires, coils and cables including insulated wires, motors and generators equipped with the coils, and electronic and electrical equipment equipped with the coils or cables. [Background technology]

[0002] An insulated wire comprises a wire and an insulating film covering the surface of the wire. Coils obtained by winding the insulated wire, and cables obtained by protecting the surface of the insulated wire with an outer sheath, are used as components in electronic and electrical equipment, etc.

[0003] It is known that resins with excellent heat resistance, such as polyimide and polyamideimide, are used as materials to form the aforementioned insulating film. Patent Document 1 describes that insulating films made of polyimide or polyamideimide with a thickness of 40 to 65 μm have excellent insulating performance and adhesion to conductor wires.

[0004] The aforementioned insulating film is manufactured by applying an insulating paint containing a precursor of polyimide or polyamide-imide and a solvent to a conductor wire, and then firing the resulting coating. Since water is generated during sintering of the precursors of polyimide or polyamide-imide, when the insulating paint is applied thickly and fired, the vaporized water is difficult to expel to the outside, and voids and pinholes tend to occur in the insulating film. Therefore, in order to form an insulating film with a thickness of 40 to 65 μm, it is necessary to repeat the process of applying the insulating paint thinly, to a thickness of about 1 μm, and firing it about 40 to 65 times, which has been problematic in terms of environmental impact and cost.

[0005] Furthermore, it is stated that NMP and DMAc should be used as solvents to dissolve polyimide and polyamide-imide precursors. However, the problem is that NMP and DMAc are substances that can have adverse effects on human health and the environment, and their use is restricted. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2018-147582 [Overview of the project] [Problems that the invention aims to solve]

[0007] Therefore, the object of this disclosure is to provide an insulated wire having a coating that is thin yet has excellent insulating performance. Another object of this disclosure is to provide a manufacturing method that enables the production of insulated wires having a coating with excellent insulating properties while reducing environmental impact and costs. Another object of this disclosure is to provide a manufacturing method for producing insulated wires having a coating with excellent insulating properties at a firing temperature of 250°C or lower. Another object of this disclosure is to provide coils and cables including insulated wires having a thin coating that provides excellent insulating performance. Another object of this disclosure is to provide a motor or generator comprising the coil. Another object of this disclosure is to provide an electronic or electrical device comprising the coil or cable. [Means for solving the problem]

[0008] As a result of diligent research to solve the above problems, the inventors have found the following: 1. The compound represented by the following formula (1) (hereinafter sometimes referred to as "compound (1)") does not generate water during sintering, and therefore, even when applied thickly and fired, it is possible to form a hardened product that does not have voids or pinholes caused by the aforementioned water. 2. The cured product of compound (1) has a lower dielectric constant and better insulating properties than polyimide or polyamideimide. Therefore, if an insulating film is formed with the cured product, it is possible to create a thinner film compared to when an insulating film is formed with polyimide or polyamideimide. 3. In addition to NMP and DMAc, Compound (1) is soluble in relatively low-boiling toluene, and safer cyclohexanone, cyclopentanone, etc., so it has excellent workability. 4. Toluene, cyclohexanone, or cyclopentanone has a boiling point lower than that of NMP and DMAc, and a large difference from the curing start temperature of Compound (1). Therefore, it can be volatilized while suppressing the curing of Compound (1). 5. When a radical polymerization initiator is used in combination, the curing start temperature of Compound (1) can be lowered (for example, lowered to a temperature of 250 °C or lower), and a cured product can be formed without special temperature-raising equipment. This disclosure has been completed based on these findings.

[0009] That is, this disclosure provides an insulated wire including a conductor wire and an insulating film covering the conductor wire, wherein the insulating film contains a cured product of a compound represented by the following formula (1). [Chemical formula] [In the formula, R 1 , R 2 represents a group represented by the following formula (r-1) [Chemical formula] (In the formula, Q represents C or CH. Two Qs in the formula are bonded via a single bond or a double bond. R 3 to R 6 represent the same or different hydrogen atoms or hydrocarbon groups. R 3 and R 4 may be bonded to each other to form a ring. n' represents an integer of 0 or more. The wavy bond in the formula is bonded to D 1 or D 2 ). D 1 , D 2 represent the same or different single bonds or linking groups. L represents a structure represented by the following formula (I) and the following formula (II) [Chemical formula] (In the formula, Ar 1 ~Ar 3 X represents a group obtained by removing two hydrogen atoms from the structural formula of an aromatic ring, or a group obtained by removing two hydrogen atoms from a structural formula in which two or more aromatic rings are linked by a single bond or a linking group. X represents -CO-, -S-, or -SO2-, and Y represents -S-, -SO2-, -O-, -CO-, -COO-, or -CONH-, either identical or different. n represents an integer of 0 or greater. [This represents a divalent group having repeating units including the structure represented by ]

[0010] This disclosure also relates to D in formula (1). 1 , D 2 However, they may be the same or different, as shown in the following equations (d-1) to (d-4) [ka] The present invention provides an insulated wire which is a base selected from bases including a structure represented by the given name.

[0011] This disclosure also relates to R in formula (1). 1 , R 2 However, the present invention provides an insulated wire that is a base represented by the following formula (r-1'). [ka] (In the formula, Q represents C or CH. The two Qs in the formula are connected by a single or double bond. R 3 , R 4 R represents the same or different hydrogen atom or hydrocarbon group. 3 and R 4 They may be joined to each other to form a ring. The bond indicated by the wavy line in the formula is D 1 or D 2 (Combine)

[0012] The present disclosure also provides an insulated wire wherein L in formula (1) is a divalent base represented by the following formula (L-1-1) or (L-1-2). [ka] (In the formula, m1 and m2 represent numbers between 2 and 50.)

[0013] The disclosure also provides an insulated wire having a relative permittivity of 2.7 or less at 10 GHz for a cured product of the compound represented by formula (1).

[0014] This disclosure also provides a method for manufacturing an insulated wire, comprising applying an insulating paint containing a compound represented by the following formula (1) and a solvent to a conductor wire and heating it to produce the insulated wire. [ka] [In the formula, R 1 , R 2 The following equation (r-1) [ka] (In the formula, Q represents C or CH. The two Qs in the formula are connected by a single or double bond. R 3 ~R 6 R represents the same or different hydrogen atom or hydrocarbon group. 3 and R 4 The elements may be joined together to form a ring. n' represents a non-negative integer. The underlined connections in the equation are D 1 or D 2 (Combine) This indicates the group represented by D. 1 , D 2 These are identical or different, and represent a single bond or a linking group. L is the structure represented by the following formula (I) and the following formula (II) [ka] (In the formula, Ar 1 ~Ar 3 X represents a group obtained by removing two hydrogen atoms from the structural formula of an aromatic ring, or a group obtained by removing two hydrogen atoms from a structural formula in which two or more aromatic rings are linked by a single bond or a linking group. X represents -CO-, -S-, or -SO2-, and Y represents -S-, -SO2-, -O-, -CO-, -COO-, or -CONH-, either identical or different. n represents an integer of 0 or greater. [This represents a divalent group having repeating units including the structure represented by ]

[0015] This disclosure also provides a coil including the insulated wire.

[0016] This disclosure also provides a motor comprising the coil.

[0017] This disclosure also provides a generator comprising the coil.

[0018] This disclosure also provides an electronic or electrical device comprising the coil.

[0019] This disclosure also provides a cable including the insulated wire.

[0020] This disclosure also provides an electronic and electrical device comprising the cable. [Effects of the Invention]

[0021] The insulated wire of this disclosure is free from voids and pinholes and has an insulating film with high insulating properties. Therefore, using the insulated wire can suppress the occurrence of short circuits, ground faults, leakage currents, etc., and is safe. The insulated wire can be used, for example, in coils and cables. Furthermore, coils containing the insulated wire can be suitably used in motors, generators, etc. Cables containing the insulated wire can be suitably used as connecting components in electronic and electrical equipment.

[0022] The insulated wires of this disclosure can be manufactured in a short process, thereby reducing manufacturing costs. Furthermore, they can also reduce environmental impact. Moreover, the insulating film of the insulated wires can maintain high insulation performance even when its thickness is reduced compared to conventional wires. Therefore, using these insulated wires can meet the demands for further miniaturization and weight reduction of electronic and electrical equipment. [Modes for carrying out the invention]

[0023] [Insulated wire] The insulated wire of this disclosure is an insulated wire comprising a conductor wire and an insulating film covering the conductor wire.

[0024] The insulating film contains a cured product of the compound represented by formula (1). The proportion of the cured product of the compound represented by formula (1) in the total amount of the insulating film is, for example, 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, particularly preferably 80% by weight or more, most preferably 90% by weight or more, and especially preferably 95% by weight or more. The upper limit is 100% by weight. In other words, the insulating film may consist only of the cured product of the compound represented by formula (1).

[0025] Insulated wires are obtained, for example, by applying an insulating coating containing compound (1) and a solvent to the surface of a conductor wire, and then firing the resulting thin film to form an insulating film. In other words, the cured product of the compound represented by formula (1) is a sintered body of the insulating coating.

[0026] The insulating paint contains compound (1) and a solvent. The content of compound (1) in the insulating paint is, for example, 10% by weight or more, preferably 15% by weight or more, more preferably 20% by weight or more, more preferably 30% by weight or more, more preferably 50% by weight or more, even more preferably 60% by weight or more, and particularly preferably 65% ​​by weight or more, of the total amount of compound (1) and solvent (100% by weight). The upper limit of the content of compound (1) is, for example, 95% by weight, preferably 90% by weight, and particularly preferably 80% by weight. In addition to compound (1) and the solvent, the insulating paint may contain other components as needed. Other components include, for example, radical polymerization initiators. Adding a radical polymerization initiator to the insulating paint has the effect of lowering the firing temperature of the insulating paint (for example, lowering it to a temperature of 250°C or lower).

[0027] The insulating coating can be prepared by mixing compound (1) and a solvent and heating and stirring it at a temperature of, for example, 80°C or lower, preferably 40-80°C, and particularly preferably 50-70°C.

[0028] The method for applying insulating paint to a conductor wire is not particularly limited as long as a thin film of insulating paint can be formed on the surface of the conductor wire. For example, dip coating is one such method. Dip coating is a method in which the conductor wire is immersed in insulating paint to adhere the insulating paint to the surface of the conductor wire and form a thin film.

[0029] When applying the insulating coating to a conductor wire, it is preferable to maintain the temperature of the insulating coating at a temperature lower than the exothermic onset temperature of compound (1). At this temperature, the curing reaction of compound (1) does not proceed, so the coating can be applied to the conductor wire while suppressing viscosity increase, and a thin film of uniform thickness can be formed.

[0030] Furthermore, the application of the insulating coating to the conductor wire can be repeated multiple times until the desired thickness of the thin film is achieved. Compound (1) does not generate water during curing. Therefore, even if the thin film is laminated to the desired thickness and then fired, voids and pinholes caused by water will not occur. Also, firing after laminating the thin film reduces the number of firings, resulting in power saving and energy efficiency. After applying the insulating coating, it is preferable to dry the coating film between applications. Drying of the coating film can be done, for example, by heating it at a temperature above room temperature but below the exothermic onset temperature of compound (1).

[0031] The dried thin film can be fired, specifically by heating it to a temperature above the exothermic onset temperature of compound (1), thereby initiating the curing of compound (1) and forming an insulating film containing the cured compound (1).

[0032] The exothermic onset temperature of compound (1) is, for example, 220°C or higher, more particularly 230°C or higher, even more specifically 240°C or higher, and especially 250°C or higher. The upper limit of the exothermic onset temperature is, for example, 320°C. The exothermic onset temperature of compound (1) can be determined by DSC measurement (heating rate: 20°C / min, in nitrogen).

[0033] If it is required to lower the firing temperature to a temperature below the exothermic onset temperature (for example, a temperature of 250°C or lower), a radical polymerization initiator may be added to the insulating paint. The amount of radical polymerization initiator added is, for example, 0.1 to 5 parts by weight per 100 parts by weight of compound (1).

[0034] Furthermore, by using an inert gas atmosphere (e.g., nitrogen atmosphere, argon atmosphere, etc.) during firing, the radical polymerization reaction can be promoted, and the firing temperature can be further reduced.

[0035] The relative permittivity at 10 GHz of the cured compound (1) obtained in this way (or an insulating film containing the cured compound (1)) is, for example, 2.70 or less, preferably 2.65 or less, and particularly preferably 2.60 or less. The lower limit of the relative permittivity is, for example, 2.20. Because the cured compound (1) has the above relative permittivity, the insulating film containing the cured compound (1) has excellent insulating properties.

[0036] Because the insulating film containing the cured compound (1) has excellent insulating properties, it can exhibit sufficient insulating function even if the insulating film is thin (for example, with a thickness of 30 μm or less). The lower limit of the insulating film thickness is, for example, 10 μm.

[0037] Furthermore, the cured compound (1) exhibits high adhesion to the conductor wire. For example, even when the insulated wire (thickness of the cured compound (1): 30 μm, conductor wire diameter: 1.0 mm) is wrapped around a mandrel (diameter: 1 mm), no cracks occur.

[0038] The 5% weight loss temperature (T) of the cured compound (1) is measured at a heating rate of 20°C / min (in nitrogen). d5 The temperature is 300°C or higher, preferably 400°C or higher, and particularly preferably 500°C or higher. 5% weight loss temperature (T d5 The upper limit of the temperature is, for example, 600°C. Therefore, the insulating film containing the cured material has excellent heat resistance, and an insulated wire equipped with such an insulating film has excellent heat resistance is solderable and versatile.

[0039] (Compound (1)) Compound (1) is represented by the following formula (1). [ka] [In the formula, R 1 , R 2 This is expressed by the following formula (r-1 [ka] (In the formula, Q represents C or CH. The two Qs in the formula are connected by a single or double bond. R 3 ~R 6 R represents the same or different hydrogen atom or hydrocarbon group. 3 and R 4 The elements may be joined together to form a ring. n' represents a non-negative integer. The underlined connections in the equation are D 1 or D 2 (Combine) This indicates the group represented by D. 1 , D 2 These are identical or different, and represent a single bond or a linking group. L is the structure represented by the following formula (I) and the following formula (II) [ka] (In the formula, Ar 1 ~Ar 3 X represents a group obtained by removing two hydrogen atoms from the structural formula of an aromatic ring, either identical or different, or a group obtained by removing two hydrogen atoms from a structural formula in which two or more aromatic rings are linked by a single bond or linking group (more specifically, from the aromatic ring portion of a structural formula in which two or more aromatic rings are linked by a single bond or linking group). X represents -CO-, -S-, or -SO2-, and Y represents -S-, -SO2-, -O-, -CO-, -COO-, or -CONH-, either identical or different. n represents an integer of 0 or greater. [This represents a divalent group having repeating units including the structure represented by ]

[0040] R 3 ~R 6Examples of hydrocarbon groups in this context include saturated or unsaturated aliphatic hydrocarbon groups (preferably alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, or alkynyl groups having 2 to 10 carbon atoms), aromatic hydrocarbon groups (preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups or naphthyl groups), or groups formed by bonding two or more groups selected from the saturated or unsaturated aliphatic hydrocarbon group and aromatic hydrocarbon groups.

[0041] R 3 and R 4 These may be bonded to each other and form a ring with adjacent carbon atoms. Examples of such rings include alicyclic rings having 3 to 20 carbon atoms and aromatic rings having 6 to 14 carbon atoms. Examples of alicyclic rings having 3 to 20 carbon atoms include cycloalkane rings with 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members) such as cyclopropane rings, cyclobutane rings, cyclopentane rings, and cyclohexane rings; cycloalkene rings with 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members) such as cyclopentene rings and cyclohexene rings; perhydronaphthalene rings, norbornane rings, norbornene rings, adamantane rings, tricyclo[5.2.1.0 2,6 ] Decane ring, tetracyclo[4.4.0.1 2,5 .1 7,10 This includes cross-linked cyclic hydrocarbon groups such as dodecane rings. The aforementioned aromatic rings with 6 to 14 carbon atoms include benzene rings, naphthalene rings, and the like.

[0042] n' is a non-negative integer, for example, an integer between 0 and 3, preferably 0 or 1.

[0043] Among the groups represented by the above formula (r-1), a group selected from the groups represented by the following formulas (r-1-1) to (r-1-6) is preferred. [ka] (The bond extending from the nitrogen atom in the formula is D in formula (1) 1 or D 2 (Combines with)

[0044] The groups represented by formulas (r-1-1) to (r-1-6) may have one or more substituents attached to them. Examples of such substituents include C1-C6 alkyl groups, C1-C6 alkoxy groups, and halogen atoms.

[0045] The group represented by the above formula (r-1) is particularly preferably a group selected from the groups represented by the above formulas (r-1-1) to (r-1-5), and especially preferably a group represented by the above formula (r-1-1) or (r-1-5).

[0046] Among the groups represented by the above formula (r-1), the group represented by the following formula (r-1') is preferred. [ka] (In the formula, Q, R 3 , R 4 (The same as above)

[0047] In formula (1), D 1 , D 2 These represent a single bond or a linking group, which may be the same or different. Examples of such linking groups include a divalent hydrocarbon group, a divalent heterocyclic group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, an imide bond, and groups formed by linking multiple such groups.

[0048] The aforementioned D 1 , D 2 In particular, groups containing divalent aromatic hydrocarbon groups are preferred because they yield cured products with excellent heat resistance, and especially arylene groups having 6 to 14 carbon atoms, such as 1,4-phenylene, 1,3-phenylene, 4,4'-biphenylene, 3,3'-biphenylene, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,8-naphthalenediyl, and anthracenediyl groups.

[0049] The aforementioned D 1 , D 2The group is preferably selected from the groups represented by the following formulas (d-1) to (d-4), and is particularly preferably the group represented by the following formula (d-1) (1,2-phenylene group, 1,3-phenylene group, or 1,4-phenylene group), with the 1,4-phenylene group being especially preferred. [ka]

[0050] Also, the above D 1 , D 2 Preferably, the group is formed by linking the divalent aromatic hydrocarbon group with at least one group selected from the group consisting of a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, and an imide bond, and in particular, a group in which an ether bond is linked to the divalent aromatic hydrocarbon group is preferred.

[0051] Therefore, R in equation (1) 1 -D 1 -Base, and R 2 -D 2 -The preferred base is one represented by the following formula (rd-1'-1) or (rd-1'-2). [ka] (In the formula, Q, R 3 , R 4 (The same as above)

[0052] The aforementioned Ar 1 ~Ar 3 This refers to a group that is identical or different, obtained by removing two hydrogen atoms from the structural formula of an aromatic ring, or a group obtained by removing two hydrogen atoms from a structural formula in which two or more aromatic rings are linked by a single bond or a linking group.

[0053] Examples of the aromatic ring (=aromatic hydrocarbon ring) include aromatic rings having 6 to 14 carbon atoms, such as benzene, naphthalene, anthracene, and phenanthrene. Among these, aromatic rings having 6 to 10 carbon atoms, such as benzene and naphthalene, are preferred.

[0054] Examples of the linking group include a divalent hydrocarbon group having 1 to 5 carbon atoms, or a group in which one or more hydrogen atoms of a divalent hydrocarbon group having 1 to 5 carbon atoms are substituted with halogen atoms.

[0055] Therefore, the Ar 1 ~Ar 3 Preferably, the group is the same or different group obtained by removing two hydrogen atoms from the structural formula of an aromatic ring having 6 to 14 carbon atoms, or a group obtained by removing two hydrogen atoms from a structural formula in which two or more aromatic rings having 6 to 14 carbon atoms are bonded via a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched alkylene group having 1 to 5 carbon atoms in which one or more hydrogen atoms are substituted with halogen atoms.

[0056] The aforementioned Ar 1 ~Ar 3 In particular, groups selected from the groups represented by the following formulas (a-1) to (a-5), either identical or different, are preferred. The attachment positions of the bonds in the following formulas are not particularly limited. [ka]

[0057] Ar in equation (I) 1 Ar 2 Among these, a group obtained by removing two hydrogen atoms from the structural formula of an aromatic ring having 6 to 14 carbon atoms is preferred, and in particular, the group represented by the above formula (a-1) or (a-2) is preferred. Furthermore, as X, -CO- or -SO2- is preferred.

[0058] Ar in equation (II) 3 Among these, a group selected from the groups represented by the above formulas (a-1), (a-4), and (a-5) is preferred. Furthermore, as for Y, -S-, -O-, or -SO2- are preferred.

[0059] In equation (II), n represents an integer greater than or equal to 0, for example, an integer between 0 and 5, preferably an integer between 1 and 5, and particularly preferably an integer between 1 and 3.

[0060] In formula (1), L is preferably a divalent group represented by the following formulas (L-1-1) or (L-1-2). [ka]

[0061] In the above formula, m1 and m2 represent the number of repeating units shown in parentheses in the molecular chain (= the divalent group represented by the above formula (L-1-1) or (L-1-2)), i.e., the average degree of polymerization, which is, for example, 2 to 50, preferably 3 to 40, more preferably 4 to 30, particularly preferably 5 to 20, and most preferably 5 to 10. The values ​​of m1 and m2 can be determined by GPC measurement or NMR spectral analysis.

[0062] The number of moles of the group represented by formula (r-1) per gram of compound (1) (hereinafter sometimes referred to as "functional group concentration") is, for example, 0.5 × 10⁻⁶. -4 ~20×10 -4 The value is moles / g. The upper limit of the functional group concentration is preferably 15 × 10⁻⁶. -4 moles / g, most preferably 10 × 10 -4 The concentration is expressed as moles / g. The lower limit of the functional group concentration is preferably 1.0 × 10⁻⁶. -4 moles / g, most preferably 1.5 × 10⁻⁶ -4 The concentration is expressed as moles / g. When the functional group concentration of compound (1) is within the above range, a cured product with excellent solvent solubility, toughness, and heat resistance can be formed. On the other hand, if the functional group concentration falls below the above range, solvent solubility tends to decrease. Furthermore, if the functional group concentration exceeds the above range, it tends to become difficult to form a cured product with excellent toughness.

[0063] The concentration of the functional group is of compound (1) 1 The area of ​​each peak is determined from the H-NMR spectrum, and these values ​​are then calculated and added to the following formula. Functional group concentration = [Peak area of ​​the group represented by formula (r-1) / Number of protons of the group represented by formula (r-1)] / Σ[(Peak area of ​​each peak / Number of protons of the group to which each peak belongs) × Chemical formula weight corresponding to each peak]

[0064] The number average molecular weight (Mn; standard polystyrene conversion) of the compound (1) is, for example, 1000 to 15000, preferably 1500 to 12000, more preferably 2000 to 10000, particularly preferably 2200 to 8000, and most preferably 2500 to 7500.

[0065] The weight average molecular weight (Mw; standard polystyrene conversion) of the compound (1) is, for example, 1000 to 45000. The lower limit value of the weight average molecular weight (Mw) is preferably 1500, more preferably 2500, particularly preferably 3000, and most preferably 4000. The upper limit value of the weight average molecular weight (Mw) is preferably 40000, more preferably 35000, and still more preferably 25000.

[0066] The above Mn and Mw are determined by gel permeation chromatography (GPC) measurement (solvent: chloroform, standard polystyrene conversion). Since the compound (1) has the above molecular weight, it has excellent solvent solubility.

[0067] The compound (1) has excellent solvent solubility, and the solubility is 1 g or more, preferably 5 g or more, and particularly preferably 10 g or more per 100 g of the solvent at 23°C.

[0068] The compound (1) is, for example, the following formula (2)

Chemical formula

Chemical formula

[0069] Among the compounds represented by the above formula (2), for example, the compound represented by the following formula (2-1) can be produced through the following steps [1-1] and [1-2]. Step [1-1]: React the compound represented by the following formula (4) with the compound represented by the following formula (5) in the presence of a base to obtain the compound represented by the following formula (6). Step [1-2]: React the compound represented by the following formula (6) with an amino alcohol (the compound represented by the following formula (7)).

[0070] [Chemical formula]

[0071] In the above formulas, Ar 1 ~Ar 3 , X, Y, and n are the same as above. D represents a linking group, and examples similar to the linking groups in D 1 , D 2 can be given. m is the average degree of polymerization of the repeating unit, and for example, it is 3 to 50, preferably 4 to 30, and particularly preferably 5 to 20. Z represents a halogen atom.

[0072] (Step [1-1]) Examples of the compound represented by the formula (4) include halides of bisaryl compounds such as benzophenone and 2-naphthyl phenyl ketone, and derivatives thereof.

[0073] Examples of the compound represented by the formula (5) include hydroquinone, resorcinol, bisphenol A, etc.

[0074] Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate; organic bases such as pyridine and triethylamine. The amount of the base used can be appropriately adjusted according to the type of the base. For example, the amount of a dibasic base such as calcium hydroxide used is about 1.0 to 2.0 moles per 1 mole of the compound represented by the formula (5).

[0075] Furthermore, this reaction can be carried out in the presence of a solvent. Examples of such solvents include organic solvents such as N-methyl-2-pyrrolidone, dimethylformamide, and dimethyl sulfoxide, or a mixture of two or more of these solvents.

[0076] The reaction atmosphere is not particularly limited as long as it does not inhibit the reaction, and may be any atmosphere such as a nitrogen atmosphere or an argon atmosphere.

[0077] The reaction temperature is, for example, around 100-200°C.

[0078] (Process [1-2]) Examples of compounds represented by formula (7) above include 4-aminophenol, 2-amino-6-hydroxynaphthalene, and their positional isomers and derivatives.

[0079] Furthermore, this reaction can be carried out in the presence of a solvent. The same solvent used in step [1] can be used.

[0080] The reaction temperature is, for example, around 100-200°C.

[0081] (solvent) Solvents used in insulating paints include, for example, chain ketones such as methyl ethyl ketone and methyl isobutyl ketone; cyclic ketones such as cyclopentanone and cyclohexanone; amides such as formamide, acetamide, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide, and N,N-dimethylacetamide (DMAc); halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, benzotrifluoride, and hexafluoro-2-propanol; sulfoxides such as dimethyl sulfoxide (DMSO), diethyl sulfoxide, and benzylphenyl sulfoxide; tetrahydrofuran (THF); aromatic hydrocarbons such as benzene, toluene, and xylene; and mixtures of two or more of these.

[0082] Among the solvents, those with a large difference between the exothermic onset temperature of compound (1) and the boiling point of the solvent (= boiling point under normal pressure) are preferable because they can volatilize the solvent while suppressing the progress of the curing reaction of compound (1). Furthermore, using a solvent with a boiling point of 150°C or lower is preferable because it can suppress the decomposition of the radical polymerization initiator.

[0083] Among the solvents, at least one solvent selected from the aromatic hydrocarbons, cyclic ketones, and amides is preferred, and at least one solvent selected from the aromatic hydrocarbons and cyclic ketones is particularly preferred.

[0084] (Radical polymerization initiator) The radical polymerization initiators include photoradical polymerization initiators and thermal radical polymerization initiators.

[0085] Examples of the aforementioned photoradical polymerization initiators include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfite, orthobenzoyl methyl benzoate, 4-dimethylaminobenzoate ethyl (manufactured by Nippon Kayaku Co., Ltd., trade name "KayaCure EPA", etc.), 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name "KayaCure DETX", etc.), 2-methyl-1-[4-(methyl)phenyl]-2-morpholinopropanone-1 (manufactured by Ciba-Gaigi Co., Ltd., trade name "Irgacure 907", etc.), 1-hydroxycyclohexylphenyl ketone (manufactured by Ciba-Gaigi Co., Ltd., trade name "Irgacure 184", etc.), and 2-dimethylamino-2 Examples include 2-amino-2-benzoyl-1-phenylalkane compounds such as -(4-morpholino)benzoyl-1-phenylpropane, aminobenzene derivatives such as tetra(t-butylperoxycarbonyl)benzophenone, benzyl, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 4,4'-bis(diethylamino)benzophenone, imidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole (manufactured by Hodogaya Chemical Co., Ltd., trade name "B-CIM", etc.), halomethylated triazine compounds such as 2,6-bis(trichloromethyl)-4-(4-methoxynaphthalen-1-yl)-1,3,5-triazine, and halomethyloxadiazole compounds such as 2-trichloromethyl-5-(2-benzofuran-2-ylethenyl)-1,3,4-oxadiazole. These can be used individually or in combination of two or more. Additionally, a photosensitizer can be added as needed.

[0086] Examples of thermal radical polymerization initiators include azo compounds such as azobisisobutyronitrile and organic peroxides. Examples of the above organic peroxides include hydroperoxides, dialkylperoxides, peroxyesters, diacylperoxides, peroxydicarbonates, peroxyketals, ketone peroxides, etc. (specifically, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoyl)peroxyhexane, t-butylperoxybenzoate, t-butylperoxide, cumene hydroperoxide, dicumyl peroxide, di-t-butylperoxide, 2,5-dimethyl-2,5-dibutylperoxyhexane, 2,4-dichlorobenzoyl peroxide, 1,4-di(2-t-butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, etc.). These can be used individually or in combination of two or more types.

[0087] (Conducting wire) A conductor wire is a wire formed from a conductive material. Examples of such conductive materials include copper, copper alloys, aluminum, aluminum alloys, and stainless steel. Among these, copper is preferred because it provides high conductivity. Therefore, copper wire is preferred as the conductor wire.

[0088] The conductor wire may have a plating layer (for example, a tin plating layer) on its surface to suppress corrosion.

[0089] The diameter of the conductor wire is, for example, 0.5 to 2.0 mm.

[0090] The cross-sectional shape of the conductor wire is not particularly limited and can be appropriately selected depending on the application. Examples include circular, rectangular, and square shapes.

[0091] [coil] The coil of this disclosure includes the insulated wire described above. More specifically, it has a configuration in which the insulated wire is wound. The coil is suitably used in electronic and electrical equipment [for example, equipment equipped with devices that convert electrical energy to mechanical energy, such as motors (for example, motors in hybrid vehicles and electric vehicles) and generators].

[0092] The insulating film of the above-mentioned insulated wire has excellent insulating properties, ensuring high insulation even when thinned. Therefore, by thinning the insulating film, the coil of this disclosure can be made smaller and lighter while maintaining its insulating properties.

[0093] Furthermore, the insulated wire exhibits high adhesion between the insulating film and the conductor wire, and does not peel off due to the load during coil winding. Therefore, the coil of this disclosure, including the insulated wire, has high reliability in its electrical characteristics.

[0094] [cable] The cable of this disclosure includes the insulated wire described above. More specifically, it has a configuration in which one or several of the insulated wires are bundled together and a protective outer covering (=sheath) is applied to the surface thereof. The cable can be suitably used as a connecting component for electronic and electrical equipment (for example, a charger cord for a smartphone, a LAN cable for an electronic device, a cord for a home appliance, etc.).

[0095] The insulating film of the above-mentioned insulated wire has excellent insulating properties and can ensure high insulating performance even when thinned. Therefore, by thinning the insulating film, the cable of this disclosure can be made smaller and lighter while maintaining insulating properties.

[0096] Furthermore, since the insulating film and conductor wire have high adhesion, the cable of this disclosure, including the insulating wire, has high reliability in its electrical characteristics.

[0097] Furthermore, the electronic and electrical equipment equipped with the cable also has high reliability in electrical characteristics. The electronic and electrical equipment is, for example, equipment equipped with connection parts such as cords and LAN cables, and includes chargers such as smartphones, electronic devices such as smartphones including the charger, and household appliances.

[0098] As described above, each configuration of the present disclosure and their combinations are examples, and additions, omissions, substitutions, and changes to the configuration can be made as appropriate without departing from the gist of the present disclosure.

Examples

[0099] Hereinafter, the present disclosure will be described more specifically by way of examples, but the present disclosure is not limited to these examples.

[0100] In addition, the measurements were carried out under the following conditions. <NMR measurement> Measurement device: JEOL ECA500 or BRUKER AVANCE600MHz Measurement solvent: heavy DMSO, heavy chloroform, or a mixed solution of heavy chloroform / pentafluorophenol = 2 / 1 (wt / wt) Chemical shift: Based on TMS <GPC measurement> Device: Pump "LC-20AD" (manufactured by Shimadzu Corporation) Detector: RID-10A (manufactured by Shimadzu Corporation) or MODEL302TDA (manufactured by Viscotek), and UV2501 (manufactured by Viscotek) Solvent: THF or chloroform Column: (Shodex KF-803)×1, (Shodex KF802)×1, and (Shodex KF801)×2 Flow rate: 1.0 mL / min Temperature: 40°C Sample concentration: 0.1% (wt / vol) In terms of standard polystyrene conversion <DSC measurement> Device: DSC Q2000 (manufactured by TA Instruments) Heating rate: 20 °C / min Atmosphere: Nitrogen atmosphere <TGA measurement> Apparatus: TG / DTA6200 (manufactured by Seiko Instruments Inc.) Heating rate: 20 °C / min Atmosphere: Nitrogen atmosphere

[0101] Preparation Example 1 (Preparation of Compound (1-1)) (Step 1-1) Into a reactor equipped with a stirrer, a nitrogen inlet tube, and a Dean-Stark apparatus, 37.25 g of 4,4'-difluorobenzophenone, 32.48 g of bisphenol A, 29.50 g of potassium carbonate anhydrous, 214.4 g of N-methylpyrrolidone, and 90.4 g of toluene were added. It was heated with stirring under a nitrogen atmosphere, and toluene was refluxed at 130 - 140 °C for 4 hours. Then, it was further heated to distill off toluene at 170 - 180 °C. Furthermore, after continuing stirring at 170 - 180 °C for 10 hours, it was returned to room temperature.

[0102] (Step 1-2) Thereafter, 6.520 g of 4-aminophenol, 8.260 g of potassium carbonate anhydrous, 27.9 g of N-methylpyrrolidone, and 117.4 g of toluene were added to the reactor containing the reaction product. It was heated again with stirring under a nitrogen atmosphere, and toluene was refluxed at 130 - 140 °C for 3 hours. Then, it was heated to distill off toluene at 170 - 180 °C, and stirring was continued for 4 hours while maintaining the above temperature. Then, it was cooled to room temperature, and the reaction solution was added to 3000 mL of methanol and filtered to obtain a powdery solid. This powdery solid was repeatedly washed with methanol and water, and then dried under reduced pressure at 80 °C overnight to obtain a powdery solid of diamine-1 (Diamine-1, a compound represented by the following formula).

[0103] [Chemical formula]

[0104] (Step 2) In a reactor equipped with a stirrer, a nitrogen inlet tube, and a Dean-Stark apparatus, 49.70 g of diamine-1 obtained in step 1, 6.03 g of maleic anhydride, 316.0 g of N-methylpyrrolidone, and 178.3 g of toluene were added and stirred at room temperature under a nitrogen atmosphere for 5 hours. Then, 1.086 g of p-toluenesulfonic acid was added as a catalyst, the temperature was raised to 140°C, and stirring was continued for 8 hours, during which the toluene was refluxed to remove water. After the reaction mixture was returned to room temperature, a powdered solid was obtained by adding the reaction mixture to 3000 mL of methanol. This powdered solid was repeatedly washed with methanol and water, and then dried under reduced pressure at 80°C overnight to obtain 48.8 g of compound (1-1) (the compound represented by the following formula (1-1)).

[0105] [ka]

[0106] Regarding the obtained compound (1-1), 1 The functional group concentration was calculated from the integrated intensity ratio of the signals in the 1H-NMR spectrum. The number-average molecular weight and weight-average molecular weight were determined by GPC measurement. Furthermore, the exothermic onset temperature was determined by DSC measurement, and the 5% thermogravimetric loss temperature (TGA) was determined by TGA measurement. d5 The following was calculated. The results are summarized in Table 1 below.

[0107] [Table 1]

[0108] The solvent solubility of the obtained compound (1-1) was measured by the following method. Compound (1-1) and the solvents shown in the table below were mixed in a ratio such that the concentration of compound (1-1) was 20% by weight. The mixture was stirred at 60°C for 1.5 hours, and the solvent solubility of compound (1-1) was evaluated. As a result, compound (1-1) was completely dissolved in all solvents. Furthermore, no precipitate formed during storage for 30 days after dissolution. In other words, it was confirmed that compound (1-1) has good solvent solubility (○).

[0109] The results are summarized in the table below. [Table 2]

[0110] Preparation Example 2 (Preparation of insulating paint) Compound (1-1) obtained in Preparation Example 1 and cyclohexanone were mixed in a ratio such that the concentration of compound (1-1) was 20% by weight, and the mixture was stirred at 60°C and 400 rpm for 1.5 to 2 hours to dissolve compound (1-1). Then, 1% by weight of a radical polymerization initiator (trade name "Parkmil D", manufactured by Nippon Oil & Fats Co., Ltd.) was added, and the mixture was stirred at room temperature for 3 minutes to obtain insulating paint 1.

[0111] Preparation Example 3 (Preparation of insulating paint) Insulating paint 2 was obtained in the same manner as in preparation example 2, except that cyclopentanone was used instead of cyclohexanone.

[0112] Example 1 <Pre-treatment> The copper wire was cleaned of dust, oil, and other contaminants using an alkaline aqueous solution, then rinsed with water, chemically polished with an acidic aqueous solution, rinsed again with water, and finally, the surface of the copper was cleaned with alcohol to remove any remaining moisture.

[0113] <First immersion> In the insulating paint 1 obtained in Preparation Example 2, the pre-treated copper wire was gently immersed vertically in the paint 1, ensuring that no bubbles formed on the surface, and held for 6 to 8 seconds.

[0114] <Primary drying> The copper wire was removed from the insulating coating and dried at 150°C for 5 minutes under normal pressure.

[0115] <Second immersion> After the initial drying, the copper wire was cooled to room temperature and then immersed again in insulating paint 1 for 6-8 seconds. This formed a 30 μm thick coating on the surface of the copper wire.

[0116] <Main drying> The coated copper wire was removed from the insulating paint and dried at 150°C for 5 minutes under normal pressure.

[0117] <Firing> The coated copper wire was heated under reduced pressure at 230°C for 2 hours to burn off the coating. This resulted in an insulated wire 1 in which the surface of the copper wire was covered with an insulating film made of a cured compound (1-1).

[0118] Example 2 An insulated wire 2 was obtained in the same manner as in Example 1, except that insulating paint 2 was used instead of insulating paint 1.

[0119] [Evaluation of insulated wires] Insulated wires 1 and 2 obtained in the examples were subjected to visual inspection, adhesion evaluation, and insulation performance evaluation. <External observation> The surface of the insulating film was observed using a CCD camera, and it was confirmed that there were no voids or density variations in any of the films. <Adhesion Evaluation> Mandrel tests were conducted. In all cases, no cracks occurred in the bent areas, confirming excellent adhesion. <Insulation Performance Evaluation> The dielectric constant of the insulating film was measured to evaluate its insulating performance. To measure the dielectric constant, a 1.5 mm wide test specimen was prepared by cutting a molded body, and the dielectric constant was measured using the cavity resonator perturbation method (according to ASTM D2520). The measurement frequency was 10 GHz. As a result, the relative permittivity was found to be 2.60, confirming superior insulating performance compared to polyimide and polyamide-imide. For reference, the relative permittivity of polyimide is 3.34, and that of polyamide-imide is over 2.7.

Claims

1. An insulated electric wire comprising a conductor wire and an insulating film covering the conductor wire, The thickness of the insulating film is 10 to 30 μm. The insulating film comprises a cured product of a compound represented by the following formula (1), An insulated wire having a weight-average molecular weight of 5,900 to 45,000 of the compound represented by formula (1). 【Chemistry 1】 [In the formula, R １ , R ２ The following formula (r-1) 【Chemistry 2】 (In the formula, Q represents C or CH. The two Qs in the formula are connected by a single or double bond. R ３ ~R ６ R represents the same or different hydrogen atom or hydrocarbon group. ３ and R ４ The elements may be joined together to form a ring. n' represents a non-negative integer. The underlined connections in the equation are D １ Or D ２ (Combine) represents a group represented by D １ , D ２ is, the same or different, a group containing a divalent aromatic hydrocarbon group. L is a divalent group represented by the following formula (L-1-1) 【Transformation 6】 (In the formula, m1 represents a number between 2 and 50.)

2. D in equation (1) １ , D ２ However, they may be the same or different, as shown in the following formulas (d-1) to (d-4) 【Chemistry 4】 The insulated wire according to claim 1, wherein the base is selected from a base that includes a structure represented by the above.

3. R in equation (1) １ , R ２ The insulated wire according to claim 1 or 2, wherein the base is represented by the following formula (r-1'). 【Transformation 5】 (In the formula, Q represents C or CH. The two Qs in the formula are connected by a single or double bond. R ３ , R ４ R represents the same or different hydrogen atom or hydrocarbon group. ３ and R ４ They may be joined to each other to form a ring. The bond indicated by the wavy line in the formula is D １ Or D ２ (Combine)

4. An insulated wire according to any one of claims 1 to 3, wherein the relative permittivity at 10 GHz of the cured product of the compound represented by formula (1) is 2.7 or less.

5. A method for manufacturing an insulated wire, comprising applying an insulating paint containing a compound having a weight-average molecular weight of 5,900 to 45,000, represented by the following formula (1), and a solvent, to a conductor wire, and heating it to produce an insulated wire according to any one of claims 1 to 4. 【Transformation 7】 [In the formula, R １ , R ２ The following formula (r-1) 【Transformation 8】 (In the formula, Q represents C or CH. The two Qs in the formula are connected by a single or double bond. R ３ ~R ６ R represents the same or different hydrogen atom or hydrocarbon group. ３ and R ４ The elements may be joined together to form a ring. n' represents a non-negative integer. The underlined connections in the equation are D １ Or D ２ (Combine) This indicates the group represented by D. １ , D ２ L is a group containing a divalent aromatic hydrocarbon group, either identical or different. L is a divalent group represented by the following formula (L-1-1). 【Transformation 6】 (In the formula, m1 represents a number between 2 and 50.)

6. A coil comprising an insulated wire as described in any one of claims 1 to 4.

7. A motor comprising the coil described in claim 6.

8. A generator comprising the coil described in claim 6.

9. An electronic or electrical device comprising the coil described in claim 6.

10. A cable including an insulated wire as described in any one of claims 1 to 4.

11. An electronic or electrical device comprising the cable described in claim 10.

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