JPS63289712A - Soldering-handleable heat resistant insulated wire - Google Patents

Abstract

PURPOSE:To secure such an electric wire that is ease of solder handling by making both bivalent and tervalent carboxylic acids, dihydric alcohol and aliphatic alcohol react under the existence of an organic solvent, and applying and baking insulating varnish containing polyester resin to be obtained and linear polyester amidoimide resin on a conductor in order. CONSTITUTION:A bivalent carboxylic acid containing an imido group of five- membered ring or its derivative or their mixture, and a tervalent carboxylic acid or its derivative or their mixture as well as dihydric alcohol and trihydric alcohol are made to react on each other under the existence of an organic solvent such as phenol or the like, and insulating varinish containing polyester imido resin is applied and baked on a conductor. After another insulating varnish containing cresol soluble linear polyester amide imido resin is further applied on this top, it is dried up. Thus, such a wire that is good in softening temperature, solder peelability and critical temperature and soldering- handleability is formable in low cost.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a heat-resistant insulated wire that can be subjected to solder removal treatment, and more specifically to a new heat-resistant insulated wire that has excellent solder removal properties, softening temperature, heat resistance, and workability. The present invention relates to a heat-resistant insulated wire coated with a polyesterimide resin/linear polyesteramideimide resin.

(Prior Art and its Problems) In recent years, electrical equipment such as motors and transformers have become significantly smaller and lighter. This plays a role in reducing the size and weight of not only home appliances but also automobiles and aircraft.

Furthermore, reliability of electrical equipment is strongly desired, and materials with excellent heat resistance are required 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, the insulation material has improved heat resistance and is a thermally stable material. Electric wire, H class (180
A TIIEIG-containing polyesteramide-imide insulated wire 7 (class K) (200°C), and a polyimide insulated wire (class M (220°C)) were developed.

Since these insulated wires are used in harsh environments, they are required to have chemical resistance, solvent resistance, hydrolysis resistance, and alkali resistance. The insulated wires mentioned above 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, there are various methods for this terminal stripping process, such as (1) mechanical stripping, (2) thermal decomposition stripping, (3) chemical stripping, and (4) solder stripping, but these methods take a long time to process, leave the thin wire conductor intact, and In consideration of continuous processing, etc., the solder stripping method (4) of -F 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, multilayer wires consisting of desolder-stripping polyesterimide/linear polyesteramide-imide coatings have been developed.

It is a known fact that it is possible to form an insulating film on one of the conductors that can be treated to remove solder. In this field, the expression "possible solder stripping" means that insulated wires are placed in a heated solder bath? -2 When the insulation film is washed, the insulating film is decomposed and removed at the immersed part, and at this point the conductor has solder attached to it, making it easier to solder, and it can be soldered directly. Nowadays, insulated wires made by twisting together many ultra-fine wires such as the Litz wires used in the deflection yokes of high-definition televisions, as well as several wires twisted together, are soldered together. In some cases, there has been an increase in terminal processing in which the wire with the insulation film still covered is immersed in a solder bath to remove the insulation film and solder the wire at the same time.

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. As a solder bath for this purpose,
An alloy of lead and tin is used.

Stripping and soldering are carried out in essentially the same way as in the connection of so-called printed circuit conductors.

On the other hand, polyurethane insulated wires containing a compound having at least two hydroxyl groups and a blocked isocyanate having difunctionality or higher functionality are used as insulated wires that can be soldered.

Polyurethane insulated wires have thermally depolymerizable groups such as urethane bonds and urea bonds with low bond energy in their main chains.
Direct soldering is possible in a low temperature range of 320°C to a high temperature range of 400''C.

However, the heat resistance of polyurethane insulated wires was at most IJJl (120° C.).

On the other hand, recently Temperature In
A polyesterimide/polyisocyanate coated wire has been developed that has a heat resistance of dex of 130 to 155°C and can be soldered in a 370°C solder bath.

When stripping the solder from the wire, the higher the heat resistance, the better
It is necessary to raise the film decomposition temperature in the molten solder bath,
In addition, in order to completely decompose the film and not leave a carbonized film on the conductor, it has become necessary to lengthen the immersion time in the molten solder bath.

The processing conditions for solder removal in this line are a high temperature short-time dipping method, at 520° C. and 1 to 2 seconds. However, the temperature of the molten solder bath is 400℃
If this value is exceeded, the oxidation deterioration of the solder bath will further progress, and the rate at which copper will dissolve into the solder will increase, resulting in the problem of thinning of the insulated wire.

Therefore, the temperature of the solder bath is at least around 450℃,
The immersion treatment time is preferably within 10 seconds.

However, although the heat resistance of the above-mentioned EIG-containing polyesterimide insulated wire, TIIEIG-containing polyesteramide-imide insulated wire, aromatic polyamide-imide insulated wire, and polyimide insulated wire is higher than class H (180°C), the solder There is no solder removability or solder removability.

On the other hand, the requirements for the winding characteristics of insulated wires are becoming increasingly severe, and in order to withstand the mechanical load of high-speed winding, and to withstand the sudden thermal load of winding, heat softening resistance is required. Thermal shock resistance and crazing resistance are also becoming necessary.

It is well known that aromatic polyamide-imide insulated wires are the best in meeting these requirements;
J' Ancient polyamideimide M! The edge wire has excessive characteristics to meet the required characteristics described in +iit, is very expensive, and does not have solder removability. Therefore,
As an insulated wire having these required characteristics and a reasonable price, a multi-structure insulated wire that combines the characteristics of each has been developed.

F
The lower layer is an insulating layer coated and baked with a glycerin-containing polyesterimide insulating paint, a TIIEIC-containing polyester insulating paint of F to H classes, or a H-class 'rllEr (: I-containing polyesterimide insulating paint), and an aromatic upper layer. This is a double-layer insulated wire coated and baked with polyamide-imide insulation paint.

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 insulating materials have excellent chemical resistance, and since it is difficult to remove solder even if the lower layer itself is used alone, multilayer insulated wires that combine stiffness are generally used to remove solder. It does not have gender.

As a result of intensive research in response to the above-mentioned needs, the present inventors have developed a multi-structure insulated wire using an inexpensive and resol-soluble aromatic polyesteramide-imide insulating paint as an upper layer as an alternative to the aromatic polyamide-imide insulating material. In addition to improving solder removability, F to HJI heat resistance (71200℃ or higher) and high softening temperature (330℃ or higher)
We have discovered a new and excellent insulated wire that has the following properties.

(Means for Solving the Problems) That is, the present invention comprises (A) a divalent carboxylic acid containing a five-membered imide group, a derivative thereof, or a mixture thereof, and (B) a trivalent carboxylic acid or its derivative. Applying an insulating paint containing a polyesterimide resin obtained by reacting a derivative or a mixture thereof, (C) dihydric alcohol, and (D) trivalent aliphatic alcohol in the presence of an organic solvent onto the conductor. and baking, and then apply an insulating paint containing a cresol-soluble linear polyester amide-imide resin on it.
This is a heat-resistant insulated wire that can be subjected to solder removal treatment and is characterized by being Hi and baked.

(Function) The insulated wire of the present invention is a multilayer insulated wire that combines a specific polyesterimide-based insulating material and a cresol-soluble linear polyesteramide-imide insulating material, and has excellent thermal, mechanical, and electrical properties. It has good solder removability while having good physical and chemical properties.

Although the solder removability and heat resistance of an insulated wire are completely contradictory characteristics, the present inventor has found that the insulated wire has a high softening temperature of about 330°C or higher, a Tl limit temperature of 200°C or higher, and a Tl of 450°C or lower. A novel polyesterimide/linear polyesteramide-imide insulated wire having solder removability has been discovered. 450°C in the above invention
The solder removability described below is imparted by the polyesterimide insulating layer having a specific configuration, and an insulated wire having both 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, uses the above-mentioned (A) and (B) components as acid components, and (C) in Section F as the alcohol component. Ingredients and (D)
It is obtained by esterifying these components 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.

(A) as a constituent factor of polyesterimide resin, (
B), (C) and (D) contain 5 to 20 equivalents of (A), 10 to 30 equivalents of (B), and 25 to 6 equivalents of (C).
It is preferable that the main component be obtained by reacting 0 equivalent % and (D) at 10 to 40 equivalent %.

In the above usage amount, if (A) is less than 5%,
The solder removability and thermal shock resistance of the insulated wire subjected to 1++ will be insufficient. On the other hand, if it exceeds 20 equivalent %, the cost will increase from the viewpoint of raw materials, and the flexibility of the coating will also decrease, which is undesirable. .

In addition, if (B) is less than 10 equivalent %, the solder removability of the 1:t twisted insulated wire will be insufficient, while if it exceeds 30 equivalent %, F will be difficult to synthesize during resin synthesis. To,
This is not preferable because flexibility decreases. Also, (C) is 25
If it is less than 60 equivalent %, the flexibility of the resulting insulated wire coating will be significantly reduced, while if it exceeds 60 equivalent %,
Solder removability deteriorates. Moreover, if (D) 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 as well as the heat resistance properties of the F sleeve in a well-balanced manner, it is most preferable that (A) and (B) in total be 30 to 40 equivalent %, and (C) A resin obtained by reacting so that the total of (D) and (D) becomes 60 to 70 equivalent % 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 (a) by a conventionally known method. Examples include those obtained by reacting with (c).

(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 acid anhydride group, or a hydroxyl group.

As long as two carboxyl groups bonded to adjacent carbon atoms or their esters, half esters, and imide groups can be formed in place of the five-membered ring carboxylic acid anhydride group, the following (b) Half-amides with primary amines may also be used.

(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 acid anhydride group and other functional groups include tricarboxylic anhydrides, 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 and 3.4.4'-hensiphenontricarboxylic anhydride.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, merophadiic dianhydride, 2.3,6.7-naphthalenetetracarboxylic dianhydride, and 1.8,4.5-naphthalene. Tetracarboxylic dianhydride, 1.2.5.6-naphthalene tetracarboxylic dianhydride, 3.3', 4.4''-diphenyltetracarboxylic dianhydride, 3.3', 4.4 '-Diphenyl ether tetracarboxylic dianhydride, 3.3',4.4'-diphenylmethanetetracarboxylic dianhydride, 3.3',4.4'-benzophenonetetracarboxylic dianhydride A particularly useful one is trimerisol l-acid anhydride.

Examples of compounds (b) that convert primary amino groups and other 'l'1° functional groups to 4T include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, Aliphatic diamines such as octamethylene 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 1.3.3'-
Dimethyl-4,4'-bisphenyldiamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 1-isopropyl Aromatic diamines such as -2,4-metaphenylene diamine (particularly preferred is aromatic cyamine), furthermore, for example, 3-(p-aminocyclohexyl)methane diaminopropyl, 3-methyl-heptanemethine diamine, 74 .4
Branched aliphatic diamines such as '-dimethylhexamethylene diamine, 2,5-dimethylhexamethylene diamine, 2,5-dimethylhexamethylene diamine, and also, for example, 1,4-diaminocyclohexane, 1.10 -Alicyclic diamines such as -diamino-1,10-dimethyldecane; furthermore, amino alcohols such as monoethanolamine, monopropanolamine, dimethylethanolamine; and also aminoalcohols such as glycocol, aminopropionic acid, aminocaproic acid, Aminocarboxylic acids such as aminobenzoic acid may also be used.

Examples of the compound of polyisocyanate (c) include polyisocyanates with a single nucleus, such as m-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, etc.; Examples of aromatic polyisocyanate compounds having the following include: diphenyl ether-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-2,2'-diisocyanate, diphenylsulfone- Examples include 4,4'-diisocyanate, diphenylthioether-4,4'-diisocyanate, naphthalene diisocyanate, and further examples include hexamethylene diisocyanate, xylene diisocyanate, and the like.

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 dicarboxylic 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, 4 diphenylmethane, 4'-1 mol of diisocyanate or diphenyl ether-4,4'-
It is a dihydric carboxylic acid obtained from 1 mole of 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 the solvent 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, 0-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 can also be used, Examples of these include benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, petroleum naphtha, coal tar naphtha, solvent naphtha, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Examples include 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 trivalent carboxylic acids or derivatives thereof (B) include:
For example, in addition to trimellitic acid and trimemic acid, there are also 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 and 3.4.4'-benzophenonetricarboxylic 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, and pentane-1. or hexanediol,
For example, 1,3- or 1,4-butanediol 1,5-bentanediol 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-butynediol, 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 -Cyclohexane dimetatool, 1,4-cyclohexane jetanol, trimethylene glycol, hexylene glycol, octylene glycol and the like.

Particularly preferred are ethylene glycol and 1,6-
It is hexanediol.

The trihydric aliphatic alcohol used 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 tetrahydric 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) are:
For example, glycerin, 1.1. -trimethylolethane, 1.1.1-)limethylolbroban, etc., and particularly preferred is glycerin.

In the present invention, the following method may be mentioned as an embodiment of synthesizing a polyesterimide resin using these raw material compounds.

(1) Dihydric 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 (A) containing a five-membered imide group in a solvent. 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) Dihydric carboxylic acid containing a five-membered imide group (A
) is formed by reacting the raw materials (a) and (b) or (a) and (c) mentioned in the section of the dihydric carboxylic acid (A) containing a five-membered imide group in a solvent. do.

In this system, other raw materials (B), (C) and (
D) Add the polyester intermediate synthesized from 200
A method of synthesizing a polyesterimide resin solution by carrying out an esterification reaction at a temperature of 3 to 5 hours at 210°C to 210°C.

(3) In the system of the polyester intermediate obtained by the method (2) above, the above raw materials (a) and (b) or (a) and (
A polyesterimide resin solution is synthesized by adding the dihydric carboxylic acid (A) containing a five-membered imide group synthesized from c) and proceeding with the esterification reaction at 200 to 210°C for 3 to 5 hours. Method.

(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 above (2) is cooled to 100°C or less, and the polyester intermediate solution obtained by the above (2)
A) and (B) are added to form a dihydric carboxylic acid (A) containing an imide group at 120 to 160°C, and the temperature is raised to 200°C, and 3 to 5 A method of synthesizing a polyesterimide resin solution by proceeding with a time esterification reaction.

(5) Dihydric carboxylic acid containing a five-membered imide group (A
) The starting materials (a) and (b) and the other raw materials (B), (C) and (D) are simultaneously mixed and heated to 120 to 160°C in this system. At the same time, the temperature was raised to 200℃, and the temperature was increased to 200 to 21
There is a simultaneous reaction method in which a polyesterimide resin solution is synthesized by carrying out a direct esterification reaction at 0° C. for 3 to 5 hours.

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 to obtain the insulating coating used in the present invention.

Examples of solvents 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
．． It is preferred to use cresylic acid, which is 5-trimethylphenol, 4-ethyl-2-methylphenol, 5-ethyl-2-methylphenol, and mixtures thereof. In addition, polar solvents such as N-methyl-2-pyrrolidone and N,N-dimethylacetamide can be used. Further, as the diluting solvent, for example, aliphatic hydrocarbons, aromatic hydrocarbons, ethers, acetals, ketones, esters, etc. can be used.

Examples of aliphatic hydrocarbons and aromatic hydrocarbons include:
n-hebutane, n-octane, cyclohexane, decalin, dipentene, pinene, p-menthane, decane, dodecane, tetradecane, Hensen, toluene, xylene,
Examples include ethylhenzene, diethylbenzene, isopropylbenzene, amylbenzene, p-cymene, tetralin or a mixture thereof, 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 is 1
It has a boiling point range of 80 to 230°C and contains phenol, o-cresol, m-cresol, p-cresol, and xylenols.

By diluting a portion of this cresylic acid with an aromatic hydrocarbon such as petroleum naphtha, coal tar naphtha, solvent naphtha, etc., the workability of manufacturing insulated wires by coating and baking an insulating paint on a conductor is improved. can be improved.

These diluting solvents include, for example, xylene, solvent naphtha No. 2, Tsurupetz #100, and Tsurupetz #
150, etc., and the amount used is based on the weight of the solvent.
The content ranges from 30% to 30%, preferably from 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, lyruto, etc. are useful, such as zinc octoate, calcium naphthinate, zinc naphthinate, lead naphthinate, lead tinonate, calcium lylate, zinc resinate, etc. Others include manganese naphthinate, cobalt naphthinate, etc.

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 titanate, tetrapropyl titanate, 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 the zirconic acid compound include tetraalkyl zirconates, zirconium chelates, and zirconium acylates corresponding to the above titanic acid compounds.

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.
Weight%.

Furthermore, a stabilized polyisocyanate in which the isocyanate group of a polyisocyanate is blocked with phenol, cresol, etc. can be used as the isthening agent. 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 moles of Reaction product of diphenylmethane-4,4'-diisocyanate and 1 mole of trimethylolpropane, Reaction product of 3 moles of 2,4-tolylene diisocyanate and 1 mole of trimethylolpropane, 3 moles of 2 ．．
Reaction product of 6-tolylene diisocyanate and 1 mole of trimethylolpropane, reaction product of 3 moles of 2.4-tolylene diisocyanate and 1 mole of trimethylolethane, 3 moles of 2.6 - reaction product of tolylene diisocyanate and 1 mol of trimethylolethane, reaction product of 3 mol of mixed 2,4- and 2.6-1 lylene diisocyanate and 1 mol of trimethylolpropane, 2.4 - and 2,6-tolylene diisocyanate mixed cyclic trimer, etc., blocked with phenol or cresol, and the like can be mentioned. Also useful are stabilized isocyanates prepared by blocking diphenylmethane-4,4'-diisocyanate with xylenol.

In addition, the appearance and workability of the insulated wire can be further improved by adding 1 to 5% by weight of phenol-formaldehyde resin, melamine-formaldehyde resin, cresol-formaldehyde resin, xylene-formaldehyde resin, epoxy resin, and silicone resin. can. 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. Particularly preferred resins are phenol-formaldehyde resin and xylene-formaldehyde resin, and by adding 1 to 2% by weight of these resins, the appearance and workability of the insulated wire can be improved without impairing the solder removability of the insulated wire.

The linear polyester amide-imide insulating paint as used in the present invention is an insulating paint whose main component is a linear polyester amide-imide resin or a linear polyester amide-imide precursor resin.

Cresol soluble linear polyester amitomite M
Regarding the manufacturing method of the linear polyester amitomite resin or its precursor resin, which constitutes the main component of the paint, for example, Japanese Patent Publication No. 11624/1982, Japanese Patent Publication No. 13597/1982, and Japanese Patent Publication No. 18316/1989. , JP 45-18678, JP 46-05089, JP 47-23920, JP 47-26116, JP 47-40717, JP 47-46480, PT. JP 48-03717, JP 49-04709, JP 50-21676, JP 50-21677, JP 50-23409, JP 50-23410, JP 1972 -35555 Publication, Japanese Patent Publication No. 51-07689, Japanese Patent Publication No. 15859, Japanese Patent Publication No. 51-15859, Publication No. 51-23999 '-+, Japanese Patent Publication No. 51-4
6155 Publication, Japanese Patent Publication No. 51-46156, Japanese Patent Publication No. 52-07032, Japanese Patent Publication No. 52-31543, Japanese Patent Publication No. 52-39718, Japanese Patent Publication No. 54-20661, Japanese Patent Publication No. 54-38296 It is shown in the official gazette.

The most typical manufacturing method is to react trimellitic anhydride, a dibasic acid, and diphenylmethane-4゜4'-diisocyanate, and convert the terminal group of a dicarboxylic acid containing an amide group and an imide group into diphenyl carbonate. A cresol-soluble linear polyester amide resin-based paint that is a reaction product of a masked intermediate and a linear polyester composition is useful.

The above are the contents of the polyesterimide insulating paint and the cresol-soluble polyesteramide-imide insulating paint used in the present invention, and the solderable heat-resistant insulated wire of the present invention is obtained by coating and baking the above polyesterimide insulating paint on a conductor. The polyester amide-imide insulating paint is similarly coated and baked thereon to obtain a predetermined film thickness.

The conductor used in this case is, for example, copper, silver, or stainless steel W4 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 the diameter is about 0.050
It is mainly used for copper wires of about 2.0 mm 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 about 350 to 550°C. A desired insulating film is formed by passing it through a baking furnace or a plurality of baking furnaces several times or several times at a temperature of . The thickness of the insulation film is JIS,
The coating thickness is specified by standards such as NEMA or 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, solder processing is possible with significantly improved softening temperature, solder releasability, and limit temperature. A heat-resistant insulated wire is economically provided.

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 heated at 140°C. The reaction was carried out for 6 hours. After cooling, a pale yellow, fine crystal 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,
This 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. The reaction was carried out 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 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 0°C for 4 hours. A brown 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 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.
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 filtered 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 mixed into cresol 6.
00g and dispersed. This mixture was heated to 150°C.
The reaction was carried out 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 7 192 g (1.0 mol) of trimellitic anhydride and 125 g (1.0 mol) of diphenylmethane-4,4'-diisocyanate (
0.5 mol) was added to 150 g of solvent naphtha (11 Stone Chemical Hysol 5lop), and the mixture was reacted 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 8 192 g (1.0 mol) of trimellitic anhydride and 126 g of diphenyl ether-4,4'-diisocyanate
(0.5 mol) was added to 150 g of solvent naphtha (8 Stone Chemical Hysol #1OO), and the mixture was reacted 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 9 125 g (0.65 mol) of trimellitic anhydride, 42 g (0.25 mol) of isophthalic acid, and 130 g of cresol were heated to 100°C, and diphenylmethane-4,4'-dite was added under stirring. Kichi isocyanate 200g
(0.8 mol) is added. Thereafter, the reaction was carried out at 240°C for 3 hours. 20 g of diphenyl carbonate and 1 g of tetrabutyl titanate were added to this and reacted for 2 hours. After the reaction, 480 g of cresol was added. Separately, 200g of polyethylene terephthalate and 1g of diphenyl carbonate.
00g and 2g of tetrabutyl titanate were added thereto and reacted at 240°C for 2 hours. 80 g of this oligomer was added to the reaction product described in 11η and reacted at 180° C. for 1 hour. Next, 8 g of tetrabutyl titanate was added, and a linear polyesteramide-imit insulating paint with a non-volatile content of 30% was obtained using a mixed solvent of 7/3 cresol/xylene.

Example 1 2 equipped with a stirrer, nitrogen gas introduction pipe, thermometer and cooling pipe
In the same manner as in Reference Example 1, 192 g (1.0 mol) of Trimerit S=hydrate was added to 600 g of cresol and dispersed in a .000 cc four-hole flask. Next, 4,
99 g (0.5 mol) of 4'-diaminodiphenylmethane was added, and 273 g of five-membered diimidodicarboxylic acid (
1.0 equivalents). This mixture was reacted at 150°C for 3 hours. After cooling the system to below 100°C, 96 g (1,5 equivalents) of trimellitic anhydride, 105 g (3,4 equivalents) ethylene glycol and 26 g (0
, 85 equivalents) 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 reaches 23 (Gardner viscometer) in 40% cresol, then cresol is added to make the non-volatile content 40%, and to this the above-mentioned 8 Stone Chemical Hysol #100 is added to make the non-volatile content 35%. resin solution. Further, 2% of a phenol-formaldehyde resin containing 2% of tetrabutyl titanate and tcrt-butylphenol as main components was added to the resin content to prepare an insulating paint.

Example 2 192 g (1.0 mol) of trimellitic anhydride was added to 600 g of cresol in a 1.0 OOcc fourth flask equipped with a stirring J'P machine, a nitrogen gas inlet tube, a thermometer, and a cooling tube. Additionally, it was dispersed. Next, 99 g (0.5 mol) of 4°4'-diaminodiphenylmethane was added to obtain 273 g (1.0 equivalents! 1k) of five-membered diimidodicarboxylic acid. After reacting this mixture at 150°C for 3 hours, 10
Cool to below 0°C. Separately, in the same 500 cc reaction vessel as above, mix 96 g (1.5 equivalents) of trimellitic acid anhydride, 105 g (1.4 equivalents) of ethylene glycol, 26 g (0.85 equivalents) of glycerin, and 30 g of xylene. The mixture was stirred and heated to 200°C over 6 hours, and reacted at this temperature for 5 hours. This polyester component was heated at 80°C.
After the solution is cooled to a temperature of 100.degree. C., the solution is added to the dispersion solution of the 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. The end point of the reaction is when the viscosity of the resin sample reaches 40% and becomes Z3+ (Gardner viscometer), then cresol is added to make the non-volatile content 40%, and to this is added Hysol #100 to make the non-volatile content 35%. resin solution.

The resin solution thus obtained was treated as in Example 1 to form an insulating coating.

Example 3 2 equipped with a stirrer, nitrogen gas introduction pipe, thermometer and cooling pipe
, 000 cc [1 flask], 96 g (1,5 equivalents) of trimellitic acid anhydride, 105 ml of ethylene glycol
(3.4 equivalents), 26 g (0.85 equivalents) of glycerin, and 30 g of xylene were mixed and stirred and reacted at 200° C. for 6 hours to synthesize a polyester component. After adding 300 g of cresol and cooling to 80°C, 192 g (1.0 mol) of trimellitic anhydride and 96 g (4°4'-diaminodiphenylmethane)
0.5 mol) and the reaction temperature is raised to 200°C. During this time, at 140 to 150°C, membered ring diimide dicarboxylic acid (1.0 equivalent) is generated and precipitated, 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. The reaction temperature is maintained at 200° C. for 1 to 2 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 22 (Gardner viscometer) in 40% cresol, then cresol is added to make one shot of non-Pi 40%.
Add 8 Stone Chemical Hysol #100 to this and the non-volatile content is 35.
% resin solution.

The resin solution thus obtained was treated as in Example 1 to form an insulating coating.

Example 4 2 equipped with a stirrer, nitrogen gas introduction pipe, thermometer and cooling pipe
, 288 g (2,5 equivalents) of trimellitic anhydride, 99 g (0,5 mol) of 4゜4'-diaminodiphenylmethane, and 5 g (3,4" 5 amounts) of ethylene glycol in a 000 cc four-bottle flask. , glycerin 26g (
0.85 equivalents) and 300 g of cresol were added, mixed and stirred, and the temperature was raised to 200° C. over 6 hours. During this time 1
At 40°C, five-membered diimide dicarboxylic acid is produced and precipitated, resulting in a cloudy and highly viscous solution. 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 taken over time. The end point of the reaction is when the viscosity of the resin sample is 4
When z2+ (Gardner viscometer) is reached in 0% cresol, cresol is added to make the non-volatile content 40%, and to this, Nisseki Kagaku Hysol #100 mentioned above is added to make the non-volatile content 35.
% resin solution.

The thus 1:I resin solution was processed as in Example 1 to form an insulating coating.

Example 5 105g of 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 (1.11"! convex 1).

Example 6 105g of ethylene glycol in the formulation example of Example 3
(3,4 equivalents) instead of 1,6-hexanediol 2
00 g (3,4"5Q), 26 g of glycerin (0
An insulating coating material was obtained in the same manner as in Example 3 using 3Bg (0.85 equivalents) of 1.1.1-trimethylolpropane instead of 1.1.1-trimethylolpropane (0.85 equivalents).

Example 7 Trimellitic anhydride 58 g (0, g equivalent), ethylene glycol 93 g (3,0 equivalent), glycerin qzg (
3,0 equivalent), xylene 20g, cresol 900g,
384 g (2.0 mol) of trimellitic anhydride and 4.
198 g (1.0 mol) of 4'-diaminodiphenylmethane (i.e., 2.0 equivalents of diimidodicarboxylic acid)] was reacted in the same manner as in Example 3, and an insulating paint was obtained in the same manner as in Example 8. 250 g of acid anhydride (3,0 eq., 1), 310 g of ethylene glycol (10,0 eq. Ii°C), 92 g of glycerin (3,0 eq.), 20 g of xylene, 1,100 g of cresol, 192 g of trimellitic anhydride ( 1
,0 mol) and 99 g (0.5 mol) of 4,4'-cyaminocyphenylenemethane [i.e.
．． 0 equivalent)] was reacted in the same manner as in Example 3, and an insulating paint was obtained in the same manner.

Examples 9 to 13 Trimellitic anhydride 192 in the formulation example of Example 2
The following procedure was carried out in the same manner as in Example 2, using the five-membered diimidodicarboxylic acids of Reference Examples 2 to 6 instead of g (1.0 mol) and 4,4'-diaminodiphenylmethane 99H (0.5 mol). I got the absolute &j paint.

Example 14 Trimellitic anhydride 192 in the formulation example of Example 3
Insulation was carried out in the same manner as in Example 3 using the Li-membered ring diimide dicarboxylic acid of Reference Example 8 instead of g (1.0 mol) and 99 g (0.5 mol) of 4,4'-diaminodiphenylmethane. Got the paint.

Comparative Example 1 2 equipped with a stirrer, nitrogen gas introduction pipe, thermometer and cooling pipe
, 0OOcc in a four-bottle flask, 340 g of dimethyl terephthalate (1.5 equivalents), 155 g of ethylene glycol (5,0 equivalents), 4 g of glycerin (s, o
4), 0.4 g of Lissage, and 300 g of xylene were added, mixed and stirred, and the temperature was raised to 180°C.
Allowed time to react. 410 g (1.5 equivalents) of the five-membered ring diimidodicarboxylic acid obtained in Reference Example 7 was gradually added to this, and the reaction temperature was raised to 200°C! , F warm. This open one-ring diimide dicarboxylic acid reacts with the polyester component to obtain a transparent resin solution. Then the reaction temperature was increased to 24
After raising the temperature to 0°C and keeping it warm for 1 to 2 hours, vacuum distillation is performed and when it becomes sufficiently viscous, cresol is added to make the non-volatile content 40%, and Shiraishi Kagaku Hysol #10 is added to this.
0 to make a resin solution with a nonvolatile content of 35%.

Furthermore, 3% of the resin content of tetrabutyl titanate was added to form an insulating paint.

Comparative Example 2 In a 2,000 cc four rJ flask equipped with a stirrer, a nitrogen gas introduction 7'ζ, a thermometer, and a cooling tube, 340 g (3,5 equivalents) of dimethyl terephthalate and 155 g (5,0 Add 1 s of glycerin
Add 4 g (5.0 equivalents (t), 0.4 g of Resurge and 300 g of xylene, mix and stir, and raise the temperature to 180 ° C.
The reaction was allowed to proceed at this temperature for 5 hours. After cooling the stiffness to 80°C, 288 g (1.5 mol) of trimeltic acid anhydride and 149 g (0
, 75 mol) and the reaction temperature is raised to 200°C. During this time, rL (
IQ's diimide dicarboxylic acid reacts with the polyester component to yield a transparent resin solution. Then the reaction temperature was increased to 240
The temperature rises to ℃! ! ■ After keeping each conger warm for 2 hours,
Distillation was carried out under reduced pressure, and when the mixture became viscous, cresol was added to make the non-volatile content 40%. This was subjected to the same treatment as in Comparative Example 1 to obtain an insulating paint.

Comparative Example 3 155 g of ethylene glycol of Comparative Example 2 (5,0 units!1
Instead of 1), 295 g of 1.6-hexanediol (
An insulating paint was obtained in the same manner as in Comparative Example 2 using 5.0 equivalents).

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: 0.32 m/m Baking furnace; (horizontal baking furnace with f-effect furnace length of 2.5 m Baking temperature: 5
00°C (maximum temperature) Squeezing method: Die method Number of applications: 6 times for lower layer, 10 times for upper layer, 3 times for upper layer. 025 to 0.030 m/m test method was conducted according to JISC3003-1984 enameled copper wire and enameled aluminum wire test method. The test results are shown in Table 1.

As is clear from the above test results, when the polyesterimide insulation 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 insulation paint. It is clear that there has been a significant improvement.

Furthermore, T I (Temperature Index)
IEc 251-1978 Methods
of Lest for winding w
ires Partl:Hnamelled rou
nd wires.

Chi 1 Koni Example 1 330 9.5 5.5 3.5 -
2: +38 9.0 5.5 3.5 -3
338 9.0 5.0 3.0 202-20
64 :l:11 9.5 5.0 3.
0 200-2025 320 7.0 3.5
2.0 -6 :]2:1 7.5
4.5 3.5 -7 :'114 1
0.0 7.0 5.0 2058 34
2 7.5 5.0 2.5 2079
337 8.5 5.5 : ], 0
-103:16 8.5 5.0
3.5 -11:]:+6 8.0 5
．． 5 3.5 -12321 7.5
3.5 2.0 -+3336 9
．． 0 5.5 3.0 -14338
9.5 6.0 3.5 - Comparative Example 1 301 2 (1,07,55,018123071
9,57,55,5182-18532389,56,
53,5162-164 engineering: Softening temperature °C, load ffl:
400g, 2℃/min.

■: Soldering properties (seconds/temperature) ■・Limit temperature

Claims (1)

[Claims] (A) a divalent carboxylic acid containing a five-membered imide group, a derivative thereof, or a mixture thereof; (B) a trivalent carboxylic acid, a derivative thereof, or a mixture thereof; (C
) A dihydric alcohol and (D) a trivalent aliphatic alcohol are reacted in the presence of an organic solvent to coat and bake an insulating paint containing a polyesterimide resin on the conductor, and then cresol is applied on top of the insulating paint. A heat-resistant insulated wire that can be soldered and is characterized by being coated and baked with an insulating paint containing a soluble linear polyesteramide-imide resin.