JPH0587923B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a heat-resistant insulated wire that can be subjected to solder stripping treatment, and more specifically, a novel polyesterimide resin/aromatic resin that has excellent solder stripping properties, softening temperature, heat resistance, and processability. This invention relates to a heat-resistant insulated wire coated with polyamide-imide resin. (Prior Art and its Problems) In recent years, electrical equipment such as motors and transformers have become significantly smaller and lighter. This means that
It plays a role in reducing the size and weight of not only home appliances but also automobiles and aircraft. Furthermore, there is a strong desire to improve the reliability of electrical equipment. From these viewpoints, materials with excellent heat resistance are required as coating materials for insulated wires used in electrical equipment such as motors and transformers. In addition, to make equipment smaller and lighter, it is necessary to make the wires thinner, and because the thinner insulated wires are subject to a higher load than before, naturally the insulated wires are required to have higher performance. It became like that. As a result, insulation materials have become more heat resistant, and H class (180°C) tris-(2-hydroxyethyl) isocyanurate (hereinafter referred to as
abbreviated as THEIC)-containing polyesterimide insulated wire, H class (180℃) THEIC-containing polyesteramideimide insulated wire, K class (200℃) aromatic polyamideimide insulated wire, and M class (220℃)
Polyimide insulated wire was developed. Furthermore, since insulated wires are used in harsh environments, they are required to have chemical resistance, solvent resistance, hydrolysis resistance, and alkali resistance. The aforementioned insulated wires generally have excellent chemical resistance. In summary, improvements in heat resistance, chemical resistance, and wire thinning have been desired for insulated wires, and insulating paint manufacturers have responded to these demands. Along with improvements in the heat resistance of insulated wires, electrical equipment manufacturers are striving to streamline processes by reducing labor costs, creating production lines and thinning wires, and are also seeking higher performance than ever before. An example of labor-saving and line-based processing is line-based processing for stripping the ends of insulated wires. Currently, this terminal peeling process consists of (1) mechanical peeling, (2)
There are various methods such as pyrolysis stripping, (3) chemical stripping, and (4) solder stripping, but considering the working time, keeping the thin conductor intact, continuous processing, etc., the solder stripping method (4) above is recommended. is said to be the most preferable. For this reason, electrical equipment manufacturers strongly desire insulated wires that can be subjected to solder removal treatment, so-called solder removal, and have heat resistance of class F (155°C) to class H (180°C). For this purpose, a dual structure line consisting of a desolder-stripping polyesterimide/aromatic polyamideimide coating was developed. It is a well-known fact that a solder-stripping processable insulating film can be formed on a conductor. In this field, the expression "solder stripping processing is possible" means that when an insulated wire is immersed in a heated solder bath, the insulation film is decomposed and removed in the immersed area, and at this point the conductor has solder attached to it. This makes soldering easier, but does not mean that soldering can be done directly. In addition, when soldering insulated wires made of many fine wires twisted together, such as the Ritsutsu wires used in the deflection yokes of high-definition televisions, and several twisted insulated wires, it is necessary to There has been an increase in the number of terminal treatments in which the insulation film is removed and soldered at the same time by immersing the wire with the film still covered in a solder bath. For this purpose, the insulating coating must be removed as quickly as possible, i.e. instantaneously, following immersion into the solder bath. It goes without saying that the shorter the immersion time in the solder bath, the better. An alloy of lead and tin is used as a solder bath for this purpose. Stripping and soldering are carried out in essentially the same manner as in the connection of printed circuits to conductors. On the other hand, as an insulated wire having solderability, a polyurethane insulated wire containing a compound having at least two hydroxyl groups and a blocked isocyanate having difunctionality or higher functionality is used. Polyurethane insulated wires, which have thermally depolymerizable groups such as urethane bonds and urea bonds with low bonding energy in their main chains, can be directly soldered in the low temperature range of 320°C to the high temperature range of 400°C. However, the heat resistance of polyurethane insulated wires was at most Class E (120°C). On the other hand, recently the Temperature Index is 130
A polyesterimide/polyisocyanate coated wire has been developed that has heat resistance of 155°C to 155°C and can be soldered in a 370°C solder bath. When stripping solder from an insulated wire, the higher the heat resistance, the higher the film decomposition temperature in the molten solder bath must be.In order to completely decompose the film and not leave a carbonized film on the conductor, It has become necessary to lengthen the immersion treatment time in the molten solder bath. The processing conditions for solder stripping on a certain line are as follows:
A high-temperature, short-time immersion method is used at 520° C. for 1 to 2 seconds. However, when the temperature of the molten solder bath exceeds 400° C., the oxidation deterioration of the solder bath progresses further, and the rate at which copper dissolves in the solder increases, resulting in the problem of thinning of the insulated wire. Therefore, it is preferable that the temperature of the solder bath is at least around 450° C. and the immersion treatment time is 10 seconds or less. However, the heat resistance of the aforementioned THEIC-containing polyesterimide insulated wire, THEIC-containing polyesteramide-imide insulated wire, aromatic polyamide-imide insulated wire, and polyimide insulated wire is
Although the temperature is higher than Class H (180°C), there is no solderability or solder removability. On the other hand, the requirements for the winding properties of insulated wires are becoming increasingly severe, and they are required to withstand mechanical loads during high-speed winding, and heat softening resistance is required to withstand rapid thermal loads during winding. Thermal shock resistance
In addition, crazing resistance and the like are also becoming necessary. It is well known that aromatic polyamide-imide insulated wires are the best in meeting these requirements;
It has excessive characteristics to satisfy the above-mentioned required characteristics, is very expensive, and does not have solder removability. Therefore, as an insulated wire that has these required characteristics and a reasonable price, a multi-structure insulated wire that combines the characteristics of each has been developed. The most commonly used insulated wires as multi-structure insulated wires with heat resistance of class F (155°C) or higher are glycerin-containing polyesterimide insulation paint of F class, and THEIC-containing polyester insulation paint of F to H classes. It is an insulated wire with a two-layer structure, in which the lower layer is an insulating layer coated with a THEIC-containing polyesterimide insulating paint and then baked, and the upper layer is coated with an aromatic polyamide-imide insulating paint and baked. However, since this multi-structure insulated wire uses an aromatic polyamide-imide insulating material, it is difficult to perform terminal peeling treatment. In particular, aromatic polyamide-imide insulation materials have excellent chemical resistance.
Further, since it is difficult to remove the solder even if the lower layer itself is used alone, a multi-layer insulated wire made of a combination of these does not generally have solder removal properties. As a result of intensive research in response to the above-mentioned demands, the present inventors have improved the solder removability of polyesterimide insulated wires with a multilayer structure using an aromatic polyamideimide insulating material in the upper layer, and We have discovered a new and superior insulated wire that has heat resistance (TI of 200°C or higher) and high softening temperature (340°C or higher). (Means for Solving the Problems) That is, the present invention provides a method for combining a divalent carboxylic acid containing a five-membered imide group, a derivative thereof, or a mixture thereof, and (B) a trivalent carboxylic acid, a derivative thereof, or a mixture thereof. (C) dihydric alcohol; (D)
trihydric aliphatic alcohol in the absence of other dihydric carboxylic acids, the above (A) is 5 to 20 equivalent %, and (B) is
10 to 30 equivalent%, (C) 25 to 60 equivalent%, and (D) 10
An insulating paint containing a polyesterimide resin obtained by reacting at a ratio of 40 to 40 equivalent % is applied and baked on the conductor, and an insulating paint containing an aromatic polyamide-imide resin is further applied and baked on top of the conductor. It is a heat-resistant insulated wire that can be soldered. (Function) The insulated wire of the present invention is a multilayer insulated wire that combines a specific polyesterimide-based insulating material and an aromatic polyamide-imide insulating material, and has excellent thermal, mechanical, electrical, and chemical properties. It also has good solder removability. Although the solder removability and heat resistance of insulated wires are completely contradictory characteristics, the inventor discovered that approximately 340
The present inventors have discovered a new polyesterimide/aromatic polyamideimide insulated wire that has a high softening temperature of 0.degree. C. or more, a TI limit temperature of 200.degree. C. or more, and a solder removability of 450.degree. In the present invention, the solder removability at 450°C or less is imparted by the polyesterimide insulating layer having a specific configuration, and an insulated wire that simultaneously has excellent solder removability and excellent heat resistance is provided. . (Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments. The polyesterimide resin, which is the main component for producing the polyesterimide insulating paint used in the present invention, contains the above-mentioned (A) component and the acid component.
Using component (B), as the alcohol component (C) above.
It is obtained by esterifying the components and (D) component according to a conventional method. Generally, the above raw materials are used as they are in most cases, but their precursors can also be used. As a constituent factor of polyesterimide resin
(A), (B), (C) and (D) contain 5 to 20 equivalent% of (A), (B)
is 10 to 30 equivalent%, (C) is 25 to 60 equivalent%, and (D) is
It is preferable that the main component is one obtained by reacting at 10 to 40 equivalent %. In the above usage amount, if (A) is less than 5 equivalent %, the solder removability and thermal shock resistance of the obtained insulated wire will be insufficient, while if it exceeds 20 equivalent %, it will be costly from the viewpoint of raw materials. This is not preferable because it increases the temperature and also reduces the flexibility of the coating. or,
If (B) is less than 10 equivalent%, the resulting insulated wire will have insufficient solder removability, while if it exceeds 30 equivalent%, it will be difficult to synthesize the resin and the flexibility will be reduced. This is not preferable because it reduces the Also, (C)
If it is less than 25 equivalent %, the flexibility of the resulting insulated wire coating will be significantly reduced, while if it exceeds 60 equivalent %, the solder removability will be reduced. Also, (D)
If it is less than 10 equivalent %, the softening temperature of the coating of the resulting insulated wire will be lowered, while if it exceeds 40 equivalent %, solder removability will deteriorate, which is not preferable. Therefore, in order to satisfy the solder releasability and softening temperature of this polyesterimide resin in a well-balanced manner, as well as the heat resistance properties of class F, it is most preferable that (A) and (B) be present in a total of 30 to 40 equivalent %, and (C ) and (D) is
A resin obtained by reaction such that the amount is 60 to 70% by weight is preferable. The divalent carboxylic acid containing a five-membered imide group, its derivative, or a mixture thereof (A) used in the present invention can be prepared by the following (a) and (b) or (i) by a conventionally known method. ) and (c) are reacted. (a) An aromatic carboxylic anhydride containing at least one other reactive group in addition to the five-membered carboxylic anhydride group. This latter reactive group is a carboxyl group, a carboxylic anhydride group, or a hydroxyl group. In place of the above five-membered ring carboxylic acid anhydride group,
Half-amides with primary amines listed in (b) below may also be used, as long as two carboxyl groups bonded to adjacent carbon atoms or their esters and half-esters and imide groups can be formed. . (b) A primary amine containing at least one other reactive group in addition to the primary amino group. This latter reactive group may be a carboxyl group, a hydroxyl group or even a primary amino group. Instead of primary amines, salts, amides, lactams or polyamides of the amines can also be used, insofar as the primary amino groups to which they are attached can form imide groups. (c) Polyisocyanate Examples of the compound (a) having a five-membered carboxylic anhydride group and other functional groups include tricarboxylic anhydride, such as trimellitic anhydride, hemimellitic anhydride, 1, 2,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,8,4-naphthalenetricarboxylic anhydride, 3,4,4'-diphenyltricarboxylic anhydride, 3 , 4,4'-diphenylmethanetricarboxylic anhydride, 3,4,4'-diphenyl ethertricarboxylic anhydride, 3,4,4'-benzophenonetricarboxylic anhydride, and the like. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, merophanic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 1,8,4,5-naphthalene. Tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4, 4'-Diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl methane tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride Examples include acid dianhydrides, and a particularly useful one is trimellitic anhydride. Examples of compounds (b) having primary amino groups and other functional groups include fats such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, and octamethylenediamine. group diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'- Diaminodiphenyl ether, 3,3'-diaminodiphenyl, 3,3'-diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-bisphenyldiamine, 1,4-diaminonaphthalene, 1, Aromatic diamines (particularly preferred are is an aromatic diamine), and further, for example, 3-(p-aminocyclohexyl)methanediaminopropyl, 3-methyl-heptanemethinediamine, 4,4'-dimethylheptamethinediamine, 2,5-dimethylhexamethylenediamine , 2,5-dimethylheptamethine diamine, further aliphatic diamines such as 1,4-diaminocyclohexane, 1,10-diamino-1,10-dimethyldecane, furthermore e.g. , monoethanolamine, monopropanolamine, dimethylethanolamine, and aminocarboxylic acids such as, for example, glycocol, aminopropionic acid, aminocaproic acid, aminobenzoic acid. Examples of polyisocyanate (c) compounds include:
Single-nuclear polyisocyanates include m-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, etc. Examples of aromatic polyisocyanate compounds having multiple nuclei include: Diphenyl ether-4,4'-diisocyanate, Diphenylmethane-4,4'-diisocyanate, Diphenylmethane-2,4'-diisocyanate, Diphenylmethane-2,2'-diisocyanate, Diphenylsulfone-4,4'-diisocyanate, Diphenyl sulfone-4,4'-diisocyanate Examples include enylthioether-4,4'-diisocyanate and naphthalene diisocyanate, and further examples include hexamethylene diisocyanate and xylene diisocyanate. In addition, so-called stabilized isocyanates in which the isocyanate groups of these polyisocyanates are stabilized with phenolic hydroxyl groups can also be used. Preferred dihydric carboxylic acids containing a five-membered imide group include 2 moles of trimellitic anhydride, 1 mole of 4,4'-diaminodiphenylmethane, 1 mole of 4,4'-diaminodiphenyl ether, and diphenylmethane. -4,
It is a dihydric carboxylic acid obtained from 1 mol of 4'-diisocyanate or 1 mol of dipnyl ether-4,4'-diisocyanate. These divalent carboxylic acids containing a five-membered imide group are usually obtained by reacting (a) and (b) or (a) and (c) in a solvent. Examples of solvents used when obtaining a divalent carboxylic acid containing a five-membered imide group in a solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N −
Diethylformamide, N,N-diethylacetamide, cresylic acid, phenol, o-cresol, m-cresol, p-cresol, 2,3
-xylenol, 2,4-xylenol, 2,5
-xylenol, 2,6-xylenol, 3,4
-xylenol, 3,5-xylenol, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, ketones and esters, examples of which include benzene, toluene, xylene, Examples include ethylbenzene, diethylbenzene, isopropylbenzene, petroleum naphtha, coal tar naphtha, solvent naphtha, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, and ethyl acetate. These solvents can be used not only alone but also as a mixed solvent. Examples of divalent carboxylic acid derivatives containing a five-membered imide group include esters and halides. Examples of the trivalent carboxylic acid or its derivative (B) include, in addition to trimellitic acid and trimemic acid, trimellitic anhydride, hemimellitic anhydride, 1,2,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,8,4-naphthalenetricarboxylic anhydride, 3,4,4'-diphenyltricarboxylic anhydride, 3,4,4'-diphenylmethane Examples include tricarboxylic anhydride, 3,4,4'-diphenyl ether tricarboxylic anhydride, and 3,4,4'-benzophenone tricarboxylic anhydride. Derivatives of these trivalent carboxylic acids include their esters, but particularly useful ones are trimellitic anhydride and trimellitic acid. Examples of dihydric alcohols (C) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,3-propanediol, various butanes, pentane, or hexanediol, such as 1,3- or 1,4-butanediol 1,5-pentanediol 1,6-hexanediol, butene-2-diol-1,4, 2,2-dimethylpropanediol-1, 3, 2-ethyl-2-butyl-propanediol-
1,3,1,4-dimethylolcyclohexane, 1,4-butenediol, water-added bisphenols (e.g., water-added P,
P'-dihydroxydiphenylpropane or its homologues), cyclic glycols such as 2,2,4,4-tetramethyl-1,3-cyclobutanediol, hydroquinone-di-β-hydroxyethyl-ether
1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, trimethylene glycol, hexylene glycol, octylene glycol, and the like. Particularly preferred are ethylene glycol and 1,6-hexanediol. The trihydric aliphatic alcohol referred to in the present invention refers to one that does not contain aromatic or heterocyclic rings at any position in the molecule. When a trihydric alcohol or a tetravalent or higher alcohol containing an aromatic or heterocyclic ring is used, it is not preferable to add it because the solder removability will be significantly impaired. Examples of these trivalent aliphatic alcohols (D) include glycerin, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, etc., and particularly preferred is glycerin. be. In the present invention, the following method may be mentioned as an embodiment of synthesizing a polyesterimide resin using these raw material compounds. (1) Divalent carboxylic acid containing a five-membered imide group
(A) is reacted with the raw materials (a) and (b) or (a) and (c) mentioned above in the section of the dihydric carboxylic acid containing a five-membered imide group (A) in a solvent. Let it form. In this system, other raw materials (B), (C) and
A method of synthesizing a polyesterimide resin solution by adding (D) and proceeding with an esterification reaction at 200 to 210°C for 3 to 7 hours. (2) Divalent carboxylic acid containing a five-membered imide group
(A) is reacted with the raw materials (a) and (b) or (a) and (c) mentioned in the section of the dihydric carboxylic acid containing a five-membered imide group (A) in a solvent. to form. In this system, other raw materials (B), (C) and
Adding the polyester intermediate synthesized from (D),
A method of synthesizing a polyesterimide resin solution by carrying out an esterification reaction at 200 to 210°C for 3 to 5 hours. (3) Into the system of the polyester intermediate obtained by the method (2) above, a five-membered ring imide group synthesized from the above raw materials (a) and (b) or (a) and (c) is added. A method of synthesizing a polyesterimide resin solution by adding the divalent carboxylic acid (A) contained therein and proceeding with an esterification reaction at 200 to 210°C for 3 to 5 hours. (4) The polyester intermediate solution obtained by the method (2) above is cooled to 100°C or less, and the polyester intermediate solution obtained by the method (2) above is cooled to 100°C or less, and the polyester intermediate solution obtained in the above (a), which is the starting material for the dihydric carboxylic acid (A) containing a five-membered imide group, is and (b) are added to form a divalent carboxylic acid (A) containing an imide group at 120 to 160°C, and at the same time, the temperature is raised to 200°C and the ester is heated at 200 to 210°C for 3 to 5 hours. A method of synthesizing a polyesterimide resin solution by proceeding with a chemical reaction. (5) The above raw materials (a) and (b) are the starting materials for the dicarboxylic acid (A) containing a five-membered imide group.
and other raw materials (B), (C), and (D) are mixed all at once, and an imidization reaction is carried out at 120 to 160°C in this system, and the temperature is raised to 200°C. There is a simultaneous reaction method in which a polyesterimide resin solution is synthesized by carrying out a direct esterification reaction at a temperature of 3 to 5 hours at a temperature of 210°C to 210°C. The polyesterimide resin obtained by the reaction of raw materials (A), (B), (C), and (D) is dissolved in a solvent or adjusted to an appropriate concentration, and then applied to the insulating paint used in the present invention. obtain. Examples of the solvent include solvents having phenolic hydroxyl groups, such as phenol, o-cresol, m
-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, o-n-propylphenol, 2,4,6-trimethylphenol, 2,3,5-trimethylphenol, 2,
4,5-trimethylphenol, 4-ethyl-2
-Methylphenol, 5-ethyl-2-methylphenol and their mixtures, cresylic acid, are preferably used. Others, N-methyl-
Polar solvents such as 2-pyrrolidone and N,N-dimethylacetamide can be used. In addition, examples of diluting solvents include aliphatic hydrocarbons, aromatic hydrocarbons, ethers, acetals, ketones,
Esters etc. can be used. Aliphatic hydrocarbons and aromatic hydrocarbons include:
For example, n-heptane, n-octane, cyclohexane, decalin, dipentene, pinene, p-menthane, decane, dodecane, tetradecane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, p-cymene, tetralin or Mixtures thereof include petroleum naphtha, coal tar naphtha, and solvent naphtha. The most useful solvent for the polyesterimide resin insulation coating used in this invention is cresylic acid. Cresylic acid has a boiling point range of 180-230°C and contains phenols, o-cresol, m-cresol, p-cresol, and xylenols. A process for manufacturing insulated wires by diluting a portion of this cresylic acid with aromatic hydrocarbons, such as petroleum naphtha, coal tar naphtha, solvent naphtha, etc., and applying and baking an insulating paint onto a conductor. can improve sex. These diluting solvents include, for example, xylene,
Examples include Solvent Naphtha No. 2, Solbetsuso #100, and Solbetsuso #150, and the amount used is 0 to 30% of the weight of the solvent, but preferably
It is 10 to 20%. When manufacturing insulated wires by coating and baking the insulating paint obtained in this way on conductors, using a small amount of metal desiccant improves the surface smoothness of the insulated wires and increases the take-up speed. This is preferable because it further improves the workability. As these metal desiccants, zinc, calcium or lead octoate, linoleate, etc. are useful, such as zinc octoate, calcium naphthenate, zinc naphthenate, lead naphthenate,
These include lead linonate, calcium linoleate, zinc resinate, and others such as manganese naphthenate and cobalt naphthenate. However, it is further advantageous to use compounds of titanic acid and zirconic acid instead of these metal desiccants. Typical titanic acid compounds include, for example, tetraalkyl titanates such as tetraisopropyl titanate, tetrabutyl titanate, tetrahexyl titanate, tetramethyl titamate, tetrapropyl titamate, and tetraoctyl titanate. Also useful are tetraalkyl titanium chelates obtained by reacting tetraalkyl titanates with octylene glycol, triethanolamine, 2,4-pentadiene, acetoacetate, and the like. Also useful are tetraalkyl titanium acylates obtained by reacting tetraalkyl titanates with stearic acid and the like. . Examples of zirconic acid compounds include tetraalkyl zirconates corresponding to the above titanic acid compounds,
Examples include zirconium chelates and zirconium acylates. The amount of these metal compounds added is 0.1 to 6.0% by weight, preferably 1 to 3% by weight, based on the solid content of the insulating coating. Further, as a curing agent, a stabilized polyisocyanate in which the isocyanate groups of polyisocyanate are blocked with phenol, cresol, etc. can be used. Examples of these include cyclic trimer of 2,4-tolylene diisocyanate, cyclic trimer of 2,6-tolylene diisocyanate, trimer of diphenylmethane-4,4'-diisocyanate, 3 mol. reaction product of diphenylmethane-4,4'-diisocyanate and 1 mole of trimethylolpropane, 3 moles of 2,4-tolylene diisocyanate and 1
reaction product with mol of trimethylolpropane, 3 mol of 2,4-tolylene diisocyanate and 1
reaction product with mol of trimethylolpropane, 3 mol of 2,6-tolylene diisocyanate and 1
reaction product with mol of trimethylolpropane, 3 mol of 2,4-tolylene diisocyanate and 1
reaction product with mol of trimethylolethane, 3 mol of 2,6-tolylene diisocyanate and 1
reaction product with mol of trimethylolethane, reaction product of 3 mol of mixed 2,4- and 2,6-tolylene diisocyanate and 1 mol of trimethylolpropane, 2,4- and 2,6- Examples include stabilized polyisocyanates in which a cyclic trimer containing tolylene diisocyanate is blocked with phenol or cresol. Furthermore, diphenylmethane
Stabilized isocyanates prepared by blocking 4,4'-diisocyanate with xylenol are also useful. Others: phenol-formaldehyde resin,
Melamine-formaldehyde resin, cresol-
By adding 1 to 5% by weight of formaldehyde resin, xylene-formaldehyde resin, epoxy resin, or silicone resin, the appearance and workability of the insulated wire can be further improved. If the content of these resins is less than 1% by weight, there is no effect on improving workability. If it is added in an amount of 5% by weight or more, it is not preferable because carbide will be formed significantly when the solder is peeled off. A particularly preferred resin is phenol-
Formaldehyde resin and xylene-formaldehyde resin, these resins are contained in an amount of 1 to 2% by weight.
By adding it, the appearance workability can be improved without impairing the solder removability of the insulated wire. The aromatic polyamide-imide insulating paint as used in the present invention is an insulating paint whose main component is aromatic polyamide-imide resin or aromatic polyamide-imide precursor resin. Regarding the manufacturing method of polyamide-imide resin which is the main component of polyamide-imide insulating paint, for example, Japanese Patent Publication No. 39-09698, Japanese Patent Publication No. 15637-1972, Japanese Patent Publication No. 18914-1972, Japanese Patent Publication No. 22998-1978. Publications, JP 43-30260, JP 44-19274, JP 44-27395, JP 44-29269, JP 45-02397, JP 45-09394, Special Publication No. 45-27611, Publication No. 35072, Special Publication No. 35073, Publication No. 37902, Special Publication No. 38574, Publication No. 02270, Special Publication No. 46-02270. Publication No. 46-29730, Publication No. 46-42385, Publication No. 03659-03659, Publication No. 33079-1979, Publication No. 10999-1979, Publication No. 17759-1975, Publication No. 17759, Publication No. 17759- No. 18117, Japanese Patent Publication No. 49-34455 and US Patent No. 3238181, US Patent No. 3260691, US Patent No. 3306771, US Patent No. 3314923, US Patent No. 3347828, US Patent No. 3360502 Specification, US Patent No. 3,392,144, US Patent No. 3,428,486, US Patent No. 3,440,215, US Patent No. 3,458,595, US Patent No. 3,562,217 and British Patent No. 1,032,649, British Patent No. 1,119,791 In the specification, GB 1155230 and GB 1160097. The most typical manufacturing method involves reacting an acid chloride of tricarboxylic anhydride with at least one diamine, or reacting a tricarboxylic anhydride with a diisocyanate, but the latter method is preferred. be. In the present invention, the resin is limited to polyamide-imide resin or polyamide-imide precursor resin, both of which are aromatic compounds. Among these, insulating paints whose main component is a polyamide-imide resin composed of trimellitic anhydride and diphenylmethane-4,4'-diisocyanate are useful. The above are the contents of the polyesterimide insulating paint and aromatic polyamideimide insulating paint used in the present invention, and the solderable heat-resistant insulated wire of the present invention is obtained by applying and baking the above polyesterimide insulating paint onto a conductor. It is provided by forming a predetermined film thickness, and then similarly applying and baking an aromatic polyamide-imide insulating paint thereon to obtain a predetermined film thickness. The conductor used in this case is, for example, copper, silver, or stainless steel wire, and the applicable conductor diameter may be any diameter from ultra-thin wire to thick wire, and is limited to a specific conductor diameter. It's not a thing. Generally, it is mainly applied to copper wires with a diameter of about 0.005 to 2.0 mm. The method of forming a different type of insulating film on the conductor may be based on a conventionally known method. For example, an insulating paint is applied by a method such as a felt drawing method or a die drawing method, and the coating is continuously heated at approximately 350 to 550°C. A desired insulating film is formed by passing the film through several or more than ten times in a baking oven or in a plurality of baking ovens at a temperature of . The thickness of the insulation film is JIS, NEMA or
The coating thickness is specified by standards such as IEC, and the inner and lower layers account for about 60 to 90% by weight, preferably about 70 to 80% by weight. If such a film thickness cannot be formed by one coating and baking, the coating and baking may be repeated as many times as necessary. (Effects) According to the present invention as described above, by forming the lower layer of the double-structured insulating film from a specific polyesterimide resin, the soldering temperature, softening temperature, solder releasability, and limit temperature are significantly improved. A possible heat-resistant insulated wire is provided economically. The content of the present invention will be specifically explained in the following reference examples, comparative examples, and examples, but the present invention is not limited to these examples. Reference Example 1 192 g (1.0 mol) of trimellitic anhydride was added to 600 g of cresol, then 99 g (0.5 mol) of 4,4'-diaminodiphenylmethane was added, and the mixture was reacted at 140°C for 6 hours. did. After cooling, a pale yellow, finely crystalline precipitate was obtained. This was washed several times with alcohol and separated by filtration to obtain a five-membered ring diimide dicarboxylic acid. Reference Example 2 192 g (1.0 mol) of trimellitic anhydride was added to 600 g of cresol, then 100 g (0.5 mol) of 4,4'-diaminodiphenyl ether was added, and the mixture was reacted at 180°C for 4 hours. . After cooling, a brown crystalline precipitate was obtained. This was washed several times with alcohol and separated by filtration to obtain a five-membered ring diimide dicarboxylic acid. Reference Example 3 192 g (1.0 mol) of trimellitic anhydride was added to 600 g of cresol, then 124 g (0.5 mol) of 4,4'-diaminodiphenylsulfone was added, and the mixture was heated at 160°C for 4 hours. I reacted. A white crystalline precipitate was obtained after cooling. This was washed several times with alcohol and separated by filtration to obtain a five-membered ring diimide dicarboxylic acid. Reference Example 4 192 g (1.0 mol) of trimellitic anhydride was added to 600 g of cresol, then 108 g (0.5 mol) of p-phenylenediamine was added, and this mixture was
The reaction was carried out at 180°C for 4 hours. After cooling, a greenish-brown crystalline precipitate was obtained. This was washed several times with alcohol and separated by filtration to obtain a five-membered ring diimide dicarboxylic acid. Reference Example 5 192 g (1.0 mol) of trimellitic anhydride was added to 600 g of cresol, then 58 g (0.5 mol) of hexamethylene diamine was added, and the mixture was heated to 180 g (0.5 mol).
The reaction was carried out at ℃ for 4 hours. A white crystalline precipitate was obtained after cooling. This was washed several times with alcohol and separated by filtration to obtain a five-membered ring diimide dicarboxylic acid. Reference Example 6 192 g (1.0 mol) of trimellitic anhydride and 137 g (1.0 mol) of p-aminobenzoic acid were added to 600 g of cresol.
and dispersed in it. This mixture was reacted at 150°C for 4 hours. After cooling, a fine precipitate of white powder was obtained. This was washed several times with alcohol and separated by filtration to obtain a five-membered ring diimide dicarboxylic acid. Reference example 7 192g (1.0 mol) of trimellitic anhydride and 125g of diphenylmethane-4,4'-diisocyanate
(0.5 mol) into 150 g of solvent naphtha (Nisseki Chemical Hysol #100), and this mixture was
The reaction was carried out at 150°C for 4 hours. As the reaction proceeded, significant foaming occurred and then solidification occurred. This solidified product was pulverized to obtain a five-membered diimide dicarboxylic acid. Reference example 8 192g (1.0 mol) of trimellitic anhydride and 126g of diphenyl ether-4,4'-diisocyanate
(0.5 mol) into 150 g of solvent naphtha (Nisseki Chemical Hysol #100), and this mixture was
The reaction was carried out at 150°C for 4 hours. As the reaction proceeded, significant foaming occurred and then solidification occurred. This solidified product was pulverized to obtain a five-membered diimide dicarboxylic acid. Reference example 9 185g (0.95 mol) of trimellitic anhydride and 250g of diphenylmethane-4,4'-diisocyanate
(1.0 mol) and 810 g of N-methyl-2-pyrrolidone
When added to a mixed solvent of 90 g of 140 more
The temperature was raised to .degree. C. and the reaction was continued for about 3 hours to obtain a polyamide-imide insulation coating. Example 1 In the same manner as in Reference Example 1, 192 g (0.1 mol) of trimellitic anhydride was placed in a 2000 c.c. four-necked flask equipped with a stirrer, nitrogen gas introduction tube, thermometer, and cooling tube.
was added to 600 g of cresol and dispersed. Next, 99g of 4,4′-diaminodiphenylmethane
(0.5 mol) to obtain 273 g (1.0 equivalent) of five-membered diimidodicarboxylic acid. Heat this mixture to 150℃
The reaction was carried out for 3 hours. After cooling this system to below 100°C, 96 g (1.5 equivalents) of trimellitic anhydride, 105 g (3.4 equivalents) of ethylene glycol and glycerin were added.
26 g (0.85 equivalent) was added, mixed and stirred, and the temperature was raised to 200° C. over 6 hours, and the reaction was continued at this temperature for 5 hours. This five-membered ring diimide dicarboxylic acid reacts with the produced polyester component to obtain a transparent resin solution. The degree of reaction was measured by the increase in viscosity, and samples were collected over time. The end point of the reaction is when the viscosity of the resin sample becomes Z ₃ (Gardner viscometer) in 40% cresol, then cresol is added to make the non-volatile content 40%, and the above-mentioned Nisseki Chemical Hysol #100 is added to this to make the non-volatile content 35%. % resin solution. Further, 2% of a phenol-formaldehyde resin containing 2% of tetrabutyl titanate and tert-butylphenol as main components was added to the resin content to prepare an insulating coating. Example 2 In a 1000 c.c. four-neck flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a cooling tube, 192 g (1.0 mol) of trimellitic anhydride was added and dispersed in 600 g of cresol. Next, 99 g (0.5 mol) of 4,4'-diaminodiphenylmethane is added to obtain 273 g (1.0 equivalent) of five-membered diimidodicarboxylic acid. This mixture is reacted at 150°C for 3 hours and then cooled to below 100°C. Separately, in the same 500c.c. reaction vessel as above, 96g of trimellitic anhydride (1.5 equivalents), 105g of ethylene glycol (3.4 equivalents), and 26g of glycerin.
(0.85 equivalent) and 30 g of xylene were mixed and stirred to give 200
The temperature was raised to .degree. C. over 6 hours, and the reaction was continued at this temperature for 5 hours. After cooling this polyester component to 80° C., it is added to the dispersion solution of the aforementioned five-membered ring diimide dicarboxylic acid and the reaction is started again. The reaction is carried out at 200°C for 5 to 7 hours.
The five-membered ring diimide dicarboxylic acid reacts with the polyester component to obtain a transparent resin solution. The degree of reaction was measured by the increase in viscosity, and samples were collected over time. At the end of the reaction, the viscosity of the resin sample is
When Z ₃ + (Gardner viscometer) is reached in 40% cresol, cresol is added to make the non-volatile content 40%, and Nisseki Chemical Hysol #100 is added to this to make a resin solution with a non-volatile content of 35%. The resin solution thus obtained was treated as in Example 1 to form an insulating coating. Example 3 96 g (1.5 equivalents) of trimellitic anhydride and 105 g of ethylene glycol were placed in a 2000 c.c. four-necked flask equipped with a stirrer, nitrogen gas inlet tube, thermometer, and cooling tube.
(3.4 equivalents), 26 g (0.85 equivalents) of glycerin, and 30 g of xylene were mixed and stirred and reacted at 200° C. over 6 hours to synthesize a polyester component. After adding 300g of cresol and cooling to 80℃, 192g (1.0 mol) of trimellitic anhydride was added.
and 96g of 4,4'-diaminodiphenylmethane
(0.5 mol) and the reaction temperature was raised to 200°C. During this time, five-membered ring diimidodicarboxylic acid (1.0 equivalent) is generated and precipitated at 140 to 150°C, making the system cloudy and highly viscous, but as the temperature rises, it is absorbed by the polyester component and becomes a solution. , followed by a clear resin solution. reaction temperature
Incubate at 200℃ for 1 to 2 hours. The degree of reaction is
Samples were collected over time to measure the increase in viscosity. The end point of the reaction is when the viscosity of the resin sample becomes Z ₂ (Gardner viscometer) in 40% cresol.
Cresol is added to make the non-volatile content 40%, and Nisseki Chemical Hysol #100 is added to this to make a resin solution with a non-volatile content of 35%. The resin solution thus obtained was treated as in Example 1 to form an insulating coating. Example 4 288 g (2.5 equivalents) of trimellitic anhydride and 99 g of 4,4'-diaminodiphenylmethane were placed in a 2000 c.c. four-necked flask equipped with a stirrer, nitrogen gas inlet tube, thermometer, and cooling tube. (0.5 mol), 105 g (3.4 equivalents) of ethylene glycol, 26 g (0.85 equivalents) of glycerin, and 300 g of cresol were mixed and stirred at 200°C.
Raise the temperature over 6 hours. During this time, a five-membered ring diimide dicarboxylic acid is produced at 140°C and precipitates, becoming cloudy and highly viscous. As the temperature rises, the five-membered ring diimide dicarboxylic acid precipitated is gradually absorbed into the polyester component. Continue the reaction at 200°C for 5 hours. The degree of reaction was measured by the increase in viscosity, and samples were collected over time. The end point of the reaction is when the viscosity of the resin sample becomes Z ₂ + (Gardner viscometer) in 40% cresol, then cresol is added to make the non-volatile content 40%, and the above-mentioned Nisseki Chemical Hysol #100 is added to this to reduce the non-volatile content. Make it a 35% resin solution. The resin solution thus obtained was treated as in Example 1 to form an insulating coating. Example 5 Ethylene glycol in the formulation example of Example 3
An insulating coating material was obtained in the same manner as in Example 3 using 200 g (3.4 equivalents) of 1,6-hexanediol instead of 105 g (3.4 equivalents). Example 6 Ethylene glycol in the formulation example of Example 3
Example 3 using 200 g (3.4 equivalents) of 1,6-hexanediol instead of 105 g (3.4 equivalents) and 38 g (0.85 equivalents) of 1,1,1-trimethylolpropane instead of 26 g (0.85 equivalents) of glycerin. Insulating paint was obtained in a similar manner. Example 7 58 g (0.9 eq.) of trimellitic anhydride, 93 g (3.0 eq.) of ethylene glycol, 92 g (3.0 eq.) of glycerin, 20 g of xylene, 900 g of cresol, 384 g (2.0 mol) of trimellitic anhydride, and 4,4'-diamino 198 g (1.0 mol) of diphenylmethane [ie, diimide dicarboxylic acid (2.0 equivalents)] was reacted in the same manner as in Example 3, and an insulating paint was obtained in the same manner. Example 8 Trimellitic anhydride 250g (3.9 equivalents), ethylene glycol 310g (10.0 equivalents), glycerin 92g
(3.0 equivalents), 20 g of xylene, 1100 g of cresol, 192 g (1.0 mol) of trimellitic anhydride and 4,4'-
Example 3: 99 g (0.5 mol) of diaminodiphenylmethane [i.e., diimidodicarboxylic acid (1.0 equivalent)]
The reaction was carried out in the same manner as above, and an insulating paint was obtained in the same manner. Examples 9 to 13 In place of 192 g (1.0 mol) of trimellitic anhydride and 99 g (0.5 mol) of 4,4'-diaminodiphenylmethane in the formulation example of Example 2, the five-membered ring of Reference Examples 2 to 6 was used. An insulating coating material was obtained in the same manner as in Example 2 using diimide dicarboxylic acid. Example 14 In place of 192 g (1.0 mol) of trimellitic anhydride and 99 g (0.5 mol) of 4,4'-diaminodiphenylmethane in the formulation example of Example 3, the five-membered ring diimidodicarboxylic acid of Reference Example 8 was used. An insulating paint was obtained in the same manner as in Example 3. Comparative Example 1 340 g (3.5 equivalents) of dimethyl terephthalate and ethylene glycol were placed in a 2000 c.c. four-necked flask equipped with a stirrer, nitrogen gas inlet tube, thermometer, and cooling tube.
155 g (5.0 equivalents), 154 g (5.0 equivalents) of glycerin, 0.4 g of litharge, and 300 g of xylene were added, mixed and stirred, heated to 180° C., and reacted at this temperature for 5 hours. 410 g (1.5 equivalents) of the five-membered ring diimide dicarboxylic acid obtained in Reference Example 7 was gradually added to this,
Raise the reaction temperature to 200°C. During this time, the five-membered ring diimide dicarboxylic acid reacts with the polyester component to obtain a transparent resin solution. Next, the reaction temperature was raised to 240°C and the temperature was kept for 1 to 2 hours, followed by distillation under reduced pressure. When the mixture became sufficiently viscous, cresol was added to make the non-volatile content 40%, and Nisseki Kagaku Hysol #100 was added to this. A resin solution with a non-volatile content of 35%. Furthermore, tetrabutyl titanate with a fat content of 3% was added to form an insulating paint. Comparative Example 2 340 g (3.5 equivalents) of dimethyl terephthalate and ethylene glycol were placed in a 2000 c.c. four-necked flask equipped with a stirrer, nitrogen gas inlet tube, thermometer, and cooling tube.
155 g (5.0 equivalents), 154 g (5.0 equivalents) of glycerin, 0.4 g of litharge, and 300 g of xylene were added, mixed and stirred, heated to 180° C., and reacted at this temperature for 5 hours. After cooling this to 80°C, 288 g (1.5 mol) of trimellitic anhydride and 149 g (0.75 mol) of 4,4'-diaminodiphenylmethane were added.
Raise the reaction temperature to 200°C. During this time 140~
The five-membered ring diimide dicarboxylic acid produced at 150°C reacts with the polyester component to obtain a transparent resin solution. Next, the reaction temperature was raised to 240° C. and maintained for 1 to 2 hours, followed by distillation under reduced pressure, and when the mixture became sufficiently viscous, cresol was added to make the nonvolatile content 40%. This was treated in the same manner as in Comparative Example 1 to obtain an insulating paint. Comparative Example 3 155g (5.0 equivalent) of ethylene glycol from Comparative Example 2
295g (5.0g) of 1,6-hexanediol instead of
An insulating coating material was obtained in the same manner as in Comparative Example 2 using (equivalent amount). In performing performance tests on these insulating paints, insulated wires of the present invention and comparative examples were manufactured by coating and baking under the following conditions. Conductor diameter: 0.32m/m Baking furnace: Horizontal baking furnace with effective furnace length of 2.5m Baking temperature: 500℃ (maximum temperature) Squeezing method: Die method Number of applications: Lower layer 6 times + upper layer 3 times Lower layer: Polyester imide insulation Paint Upper layer: Aromatic polyamide-imide insulating paint prepared in Reference Example 9 Film thickness: 0.025 to 0.030 m/m The test method was conducted according to the test method for enameled copper wire and enamelled aluminum wire of JIS C 3003-1984. The test results are shown in Table 1. As is clear from the above test results, when the polyesterimide insulating paint according to the present invention is used, the softening temperature, solder releasability, and limit temperature (TI) are lower than those using the conventional polyesterimide insulating paint. It is clear that there has been a significant improvement. In addition, TI (Temperature Index) is IEC 251−
1978 Methods of testing for winding wires
Partl: Compliant with Enamelled round wires.

【table】

[Table] : Limit temperature

Claims (1)

[Claims] 1 (A) a divalent carboxylic acid containing a five-membered imide group, a derivative thereof, or a mixture thereof, and (B)
A trihydric carboxylic acid, a derivative thereof, or a mixture thereof, (C) a dihydric alcohol, and (D) a trihydric aliphatic alcohol in the absence of other dihydric carboxylic acid, the above (A) 5 to 20 equivalent%, (B) 10 to 30 equivalent%, (C) 25 to 60 equivalent%, and (D) 10 to 40 equivalent%
A soldering process characterized by applying and baking an insulating paint containing a polyesterimide resin obtained by reacting at a ratio of Heat resistant insulated wire possible.