JPS6369819A - High temperature resistant rapid solderable wire enamel - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention provides high temperature resistance and rapid soldering to magnet wires when coated (insulated) with the enamel of the present invention. Concerning insulated wire enamel giving ability.

BACKGROUND OF THE INVENTION Magnet wire is a small diameter copper or aluminum wire coated with an insulating material known as wire emerl. Wire enamels usually consist of a base resin and various additives that improve the properties and performance of the overall composition.

In today's electrical and electronic industries, large quantities of red wire are used to produce motors, transformers, television yoke coils, and many other products. Electrical equipment and mechanical device designs have increasingly required smaller motors, coils, transformers, and other products that use magnet wire and have required operation at higher temperatures than larger components. Therefore, the demand for high temperature resistant magnetic screws 1 to wires used in these electric motors and transformers is increasing. For this purpose, the temperature resistance is
and/or defined based on the temperature index measured by the NEMA (National Electrical Manufacturers Association) classification.

A further requirement of these products for various applications is the possibility that the ends of the magnet wires used in these products can be brazed. It is important that the wire can be brazed quickly.

In many areas of industry, there is an increasing requirement for strict quality control of products. This demand makes industry
leading to a shift to automated production. In the electrical and electronic industry, automated production systems have an important role in any product. In fields where magnet wire is used in these products, the temperature required for soldering the magnetic screw 1 to the wire or the speed required for soldering the magnet wire will depend on how well the automated production line is run. It determines whether or not you get it.

Many types of wire enamel are known.

Examples include conventional heat-resistant enamels in which the base resin is polyimide, polyamideimide, polyesterimide (or polyesteramideimide), or polyester. 2 on polyester imide wire enamel
There are two main types, and these have different heat resistance classifications. One type is polyesterimide, which has polyester units derived from polyfunctional aliphatic alcohols such as glycerin and trimethylolpropane, and dihydric alcohols such as ethylene glycol. The polyester units further contain an aromatic carboxylic acid, usually terephthalic acid.

In the second type, instead of the polyfunctional aliphatic alcohol, it contains an isocyanurate group, usually a group derived from tris-(2-hydroxyethyl)isocyanurate (THEIC>). , polyester imides contain the imide m-position, which is usually derived from an aromatic diamine such as methylene dianiline and a polyfunctional carboxylic acid or acid anhydride (usually l-limellit-t-anhydride).

Types of polyesterimide containing aliphatic polyhydric alcohols are typically classified as having a heat resistance of less than Class 18 board according to the NEMA standard -1,1-. The type of polyesterimide containing isocyanuride-I ring in the molecule is class 18 according to NEMA standards.
Classified as 0\ or more. The latter type of polyester imide wire enamel is described in U.S. Pat. No. 3,426,0
It is described in No. 98.

In addition, it is also known that there are two different types of polyester wire emels. One type is based on polyesters with polyfunctional aliphatic alcohols but without isocyanurate rings. This type of wire enamel is classified as class ]-5 according to NEMA standards.
Rated as 5. The other type is based on polyesters with polyhydric alcohol units containing isocyanurate rings. These wire enamels are usually NE
According to MA standards, it is rated as exceeding class 180. This type of polyester is described in U.S. Patent No. 3.34
．． No. 2,780.

Polyester wire enamels, whether or not they contain isocyanurate rings in the molecule, typically require a nylon or polyamideimide finish for most of their applications.

Of the base resins listed above, the only one that can provide a reasonably brazeable high temperature resistant magnet wire enamel is
It is a polyesterimide that does not contain incyanure in its molecule. However, in order to make the material brazable, a substantial reduction in molecular weight is required in this type of polyesterimide. Unfortunately, a decrease in the molecular weight of the base resin leads to a deterioration of the wire enamel's high temperature resistance. Furthermore, even if the molecular weight of polyesterimide is reduced, the speed at which it can be brazed and its ability to braze at a low temperature are still insufficient.

The only base resin that provides wire that meets the fast speed and low temperature brazing requirements is conventional polyurethane. Polyurethanes are polymers made by the reaction of polyfunctional isocyanates and prepolymers containing free hydroxyl groups. Free drosyl groups can be provided, for example, by polyesters or polyethers. Such polyurethane resin is methylene bis-
U.S. Pat. No. 3.1.74-., in which phenyl isocyanate was reacted with tris(2-hydroxyethyl)isocyanurate (THEIC). No. 950.

However, wire enamels based on this type of polymer cannot provide sufficient high temperature resistance as required by the Class F and Class H standards set by NEMA.

U.S. Pat. No. 3,869,428 is a reaction product of an aromatic hydroxyl group-containing compound and an aromatic isocyanate whose composition contains imide and urethane groups, and one of these reactants contains an imide group. A polyurethane enamel composition is disclosed. U.S. Patent No. 3,86
The compositions according to No. 9,428 are said to produce brazing properties comparable to polyurethane enamels and heat resistance comparable to polyesterimide enamels.

The polyester wire enamel according to the invention is magnetic [
- Provide a wire that can provide good heat resistance and quick brazing properties. These wires are NEM
It is possible to provide electrical insulation for magnet wires that meets all requirements for Class F insulation according to A standards.

Magnet wires made from these wire enamels also pass heat shock tests at 200-220°C versus 175°C heat shock tests obtained from commonly known class F brazeable polyester imides. NE of crust or higher category
Provide wires according to MA requests. The heat shock test is carried out by prestretching the material by 20%, wrapping it around a mandrel and holding it at the corresponding temperature for 30 minutes.

To pass this test, the coating on the wire must not crack.

What was further discovered was that when the polyesterimide of the present invention, which contains an incyanure-I ring in its molecule and is made of an aromatic carboxylic acid, is used in polyurethane enamels, it The object of the present invention is to provide a sufficient heat resistance index to replace the polyesterimide wire enamel of F. When isocyanurate-free polyesterimide-type resins utilized in Classes F through H are formulated with blocked isocyanates to make polyurethane enamels, the resulting enamels have certain desired electrical properties, but generally The temperature index of the class F brazeable polyesterimides used cannot be matched.

The polyurethane enamel of the present invention provides magnet wire manufacturers with the advantage of faster magnet wire manufacturing processes and lower baking temperatures than Class F brazeable polyimide-based enamels. In addition, users of these wire enamel coated wires will enjoy faster and lower temperature brazes compared to those of current Class F brazeable polyesterimides. Additionally, the polyurethane wire enamel of the present invention provides better heat shock than commonly used Class F brazeable polyesterimides.

L (a>consists of a mixture of blocked isocyanate and (b) polyesterimide resin (b), wherein the polyesterimide resin (b) comprises (i>units of polyester of alcohols and at least one carboxylic acid and ( i
i) comprises at least one alcohol consisting of diimidodicarboxylic acid units, the alcohols containing an isocyanurate group, and the blocked isocyanate (a)
is prepared from an isocyanate selected from the group consisting of diphenylmethane diisocyanate-1, diphenylsulfone diisocyanate, and 'diphenyl ether diisocyanate, or from a urethane polymer derived from the reaction of said diisocyanate with an alcohol. Composition.

2. The polyurethane wire enamel composition of item 1 above, wherein the alcohol containing isocyanate groups comprises at least 16 and up to 60 equivalent % of the alcohol in the polyesterimide units.

3. The proportion of the isocyanurate group-containing alcohol is 40
% or more, the imide group is at least 16 equivalent % of the total number of imide groups and ester groups, or when the proportion of the isocyanurate group-containing alcohol is less than 40 equivalent %, the imide group is an imide group. The polyurethane wire enamel composition of item 2 above, wherein the polyesterimide is at least 35 equivalent percent of the total number of ester groups.

4. The polyurethane wire enamel composition according to item 1 above, wherein the proportion of imide bonds in the total imide and ester bonds is at least 16% by weight and up to 50% by weight.

5. The polyurethane wire enamel composition according to item 4 above, wherein the proportion of the imide bond is up to 45 equivalent %.

6. The polyesterimide resin has a ratio of hydroxyl groups to carboxyl groups of 1-. 4:1 to 2.5;
The polyurethane wire enamel composition described in .

7. The polyurethane wire enamel composition according to item 1 above, wherein the ratio of isocyanate groups to hydroxyl groups in the reaction ranges from 0.82:1 to 1.50:]-.

8. The polyester imide resin contains an imide containing a compound produced by a reaction between an acid anhydride and a polyamine, and an ester containing a compound produced by a reaction between an alcoholic component and a carboxylic acid or its ester-forming derivative. It is produced by the reaction of The polyurethane wire enamel composition according to item 1 above.

9. A mono- to polycyclic acid anhydride in which the acid anhydride contains 1 to 3 non-adjacent carboxyl groups, or a monocyclic acid anhydride containing 1 to 3 non-adjacent carboxyl groups and having 5 or more carbon atoms in the alicyclic ring. 9. The polyurethane wire enamel composition according to item 8 above, which is a polycyclic monoanhydride.

10. The polyurethane wire enamel composition according to item 9 above, wherein the acid anhydride is Trimeric I acid anhydride.

1-1. 9. The polyurethane wire enamel composition according to item 8 above, wherein the polyamine component is an aromatic diamine.

12, the diamine is methylene dianiline, benzidine,
3,3'-diaminodiphenyl, 1,4-diaminonaphthalene, p-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4-dimethylheptamethylenediamine-1,7, diaminodiphenyl ketone,
m-phenylenediamine, xylenediamine, hexamethylenediamine, ethylene diamine, 4,4'-
The polyurethane wire enamel composition according to item 11 above, which is dicyclohexylmethanediamine, diaminodiphenylsulfone or oxydianiline.

13. The polyurethane wire enamel composition It according to item 8 above, wherein the polyamine is methylene dianiline or oxydianiline.

]-4, the alcoholic component heli-(2-hydroxyethyl) isocyanurate and ethylene glycol, butanediol 1,4.1 to rimethylene glycol, propylene glycol, benzidineol-1,5,
Neopentyl glycol, butene 2-diol-1,4
14. The polyurethane wire enamel composition according to item 13 above, containing a glycol component selected from the group consisting of , and mixtures of these glycols.

15. The alcoholic component further contains glycerin, pentaerythritol, i, 1. i-trimethylolethane,
15. The polyurethane wire enamel composition according to item 14, which also contains a polyhydric alcohol selected from the group consisting of 1,1.1-trimethylolpropane, dipentaerythritol, and mixtures thereof.

16. The polyurethane wire enamel according to item 8 above, wherein the alcoholic component consists of 16 to 60 equivalent % I.lis-(2-hydroxyethyl)incyanure-I., and the remainder of the component is a dihydric alcohol. Composition.

]7. The polyurethane wire enamel composition according to item 8, wherein the carboxylic acid or its ester-forming derivative is terephthalic acid or isophthalic acid or its ester-forming derivative.

], 8. A carboxylic acid component containing 80 to 100 equivalents of terephthalic acid or isophthalic acid or its ester-forming derivative, the remainder of which is adipic acid, orthophthalic anhydride, hemimellitic acid, trimellitic anhydride, succinic acid, and tetrahydrophthalic acid. Polyurethane wire enamel composition according to item 17 above, which is acid, maleic acid or sebacic acid.

1.91A) A polyesterimide resin produced by a reaction between a compound containing an imide bond and a compound containing an ester bond, wherein the imide bond-containing compound is produced by a reaction between trimellitic anhydride and methylene dianiline. and the ester bond-containing compound is tris-
(2-Hydroxyethyl)isocyanuride [·, polyesterimide resin produced by reaction with other dihydric alcohols and terephthalic acid or isophthalic acid,
and (F'3) A polyurethane wire enamel composition comprising a reaction product of a blocked isocyanate compound produced by reacting diphenylmethane diisocyanate with trimethylolpropane and cresylic acid.

20. The blocking agent for the blocked isocyanate is selected from the group consisting of phenol, cresylic acid, and alkylated phenols in which the alkyl group contains up to 9 carbon atoms. The polyurethane wire enamel composition described in .

21, ``Electrical conductor coated with a cured polyurethane wire enamel obtained by applying a double term 1 polyurethane wire enamel to an electric conductor and heating the coated conductor.

(Function) According to the invention 1. Polyurethane wire enamels are formulated by mixing polyesterimide polymers with blocked isocyanates.

The polyesterimide resins used to make the polyurethanes of this invention are made by the reaction of a polyester-forming component and an imide-forming component. The principal portions of the technology required to synthesize such polyesterimide resins are described in US Pat. No. 3,426,098.

The polyester-forming components described in more detail below are:
Contains alcohols and aromatic carbons.

This will also be explained in more detail below2, but the imide-forming component is aromatic carboxylic acid monoanhydride (...omo anhydride).
rides) and aromatic diamines.

In the polyesterimide resin according to the present invention, 1-6 to 60 equivalent % of hydroxyl functionality in the raw material is provided by bonding hydroxyl groups to isocyanurate rings, such as the hydroxyl functionality of THEIC. If the (equivalent) % of said hydroxyl functional groups is less than 40%, at least 35% imide bonds are required in the total amount of imide and ester bonds, otherwise sufficient heat shock value and temperature resistance as class F are required. and proper soldering properties. If the percent (equivalent) T of hydroxyl functional groups attached to the incyanure-1 ring is greater than 40 equivalent %, a minimum of 16 equivalent % of imide bonds (of the total amount of imide and ester bonds) is sufficient. This is sufficient to maintain a good heat shock value and adequate solderability.

THE on the other hand in the component providing the hydroxyl functionality
The highest percentage of IC is the one that provides about 60 equivalent % of hydroxyl groups as noted in 1, and the highest equivalent percentage of imide (of the total amount of imide and 'ester groups) is 50% and preferably 45%. %.

The OH/C001-1 ratio of the raw materials used to make polyesterimides is about 1-. 4:1-2.5;
Should be 1. If this ratio is less than 1.4, the solderability will decrease, and if this ratio exceeds 2.5, the molecular weight of polyesterimide is class F, and soldering is possible.It is used in place of polyesterimide. The molecular weight will be reduced below that required for class F upper polyurethane enamels. The following can be used as the imide generating component. (a) trimellitic anhydride or ]-
Other mono- or polycyclic monoanhydrides containing ~3 non-adjacent carboxyl groups, or mono- or polyalicyclic rings containing ~3 non-adjacent carboxyl groups and having 5 or more carbon atoms in the alicyclic ring anhydrides such as the formula mono and (b) e.g. methylene dianiline, benzidine, 3,3'-diaminodiphenyl, 1,4-diaminonaphthalene, p-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,
Polyamines, preferably aromatic, such as 4-dimethylheptamethylenediamine-1,7,diaminocyferketone, m-phenylenediamine, xylenediamine, hexamethylenediamine, ethylenediamine, 4,4"-dicyclohexylmethanediamine, diaminodiphenylsulfone Trimelib 1 is a preferred acid anhydride.
~An acid anhydride, and preferred diamines are methylene dianiline and oxydianiline.

Reactants (a) and (b) are usually required in an amount of 2 moles (a>) per mole of (b) to form the monoacid diimide. The acid anhydride may be used in excess. However, generally 1.92 to 2.08 moles of acid anhydride are used per mole of diamine.
The reaction product of moles of aromatic diamine has the formula % (f, -DashiR is 0 for oxydianiline or CH2 for methylene dianiline).

) is shown. Furthermore, for example 4,4'-diisocyanene-todiphenyl ether instead of 4,4°-diaminodiphenyl ether or 4
．． Similar structures, which can be produced by pre-reacting 1-1 mole of the corresponding diisoane, such as 4°-diisocyanate diphenylmethane, with 2 moles of trimellitic anhydride, are also well suited for use in the polyesterimides of the present invention. You should be careful about what you get.

As mentioned above, the polyester-forming components include alcohols and carboxylic acids. Alcohols that can be used in the polyester-forming component of the polyesterimide include polyhydric alcohols or dihydric alcohols containing three or more hydroxyl groups. Trihydric or trihydric or higher polyhydric alcohols include THE T C and other trihydric or polyhydric alcohols having two or more times as many incyanuryl rings, or saturated aliphatic alcohols, e.g. Contains glycerin, pentaerythriol, 1,1,11-limethylolethane, 1,1,14-limethylolpropane and dipentaerythritol. As the dihydric alcohol component, ethylene glycol is preferred, butanediol-1,4,
)-rimethylene chloride, propylene glycol, pentanediol-1,5, neopentyl glycol and butene-2-diol-1,4 may also be used. T)(
If E I C is used, at least 20 equivalent percent of the total alcohol content is used from this source. Preferably, THE IC is the only polyfunctional alcohol and the only other alcohol present is a dihydric alcohol, preferably ethylene glycol.

Preferred carboxylic acids for use in the polyester forming component are dicarboxylic acids, particularly the aromatic carboxylic acids terephthalic acid and isophthalic acid. These acids can generally be replaced by their ester-forming derivatives, such as their dimethyl esters or acid anhydrides. Other carboxylic acids or derivatives thereof that may be used are adipic acid, orthophthalic anhydride, hemimellitic acid, trimellitic anhydride,
Contains succinic acid, tetrahydrophthalate, maleic acid or sebacic acid. The carboxylic acids used are preferably all aromatic carboxylic acids, and it is preferred that at least 80 equivalent % of the carboxylic acids are terephthalic acid or inphthalic acid (or ester-forming derivatives thereof).

When using acids containing three or more carboxyl groups, it may be necessary to make adjustments to the composition of the alcohol component. It should be noted that the degree of crosslinking of the final product is controlled to some extent by the proportion of the trifunctional to polyfunctional acid composition used in the polyesterimide. Therefore, if there are many polyfunctional acids in the acid, it may be necessary to increase the proportion of dihydric alcohol in the alcohol component.

The blocked polyisocyanates used according to the invention are polyisocyanate derivatives that are not reactive at room temperature but liberate isocyanate groups at elevated temperatures. This is induced by the reaction of the polyisocyanate with a blocking agent such as phenol or other alcohols as mentioned above.

Preferred isocyanates which can be used to obtain blocked isocyanates are diphenylmethane diisocyanate, diphenylsulfone diisocyanate, diphenyl ether diisocyanate and urethane compounds thereof with polyhydric alcohols such as trimethylolpropane. 1-ruene diisocyanates may also be used. However, toluene diisocyanate can generate harmful fumes during brazing operations. Therefore, less volatile isocyanates are preferred. A preferred diisocyanate is diphenylmethane diisocyanate.

Diphenylmethane diisocyanate (or similar diisocyanate) is preferable to toluene diisocyanate for the additional reason that the resulting polyurethane product provides better heat shock performance and is more likely to produce hole-free magnet wire. is preferable to the use of

As a blocking agent to provide a blocked isocyanate polymer, cresylic acid is preferred, but the phenol itself or one or more alkyl groups in a total amount of 9
Similar raw materials such as alkylated phenols containing up to carbon atoms can be used.

For example, ethylene glycol, propylene glycol, diethylene glycol, glycerin, and pentaerythritol. 1,1.1-1~ Alcohol type blocking agents such as rimethylolpropane, neopentyl glycol, hydantoin glycol, butanediol-1,4, t-rimethylene glycol, 1,3~cyclobutanediol as a phenol type blocking agent May be used with. Monohydric alcohols such as benzyl alcohol may also be used. However, the use of alcohols should be limited to the extent that suitable polymer-blocked isocyanates can be formed. THEIC itself may also be used as an alcoholic blocking agent as described in U.S. Pat. However, polyurethanes made using THEIC as a blocking agent were found to have acceptable shock and braze properties as shown in the examples below.

The ratio of isocyanate groups provided by blocked incyane-1 to free hydroxyl groups in the polyesterimide is sufficient in the polyurethane enamel to be used to replace the Class F brazeable polyesterimide in the final polyurethane formulation. In order to maintain balanced properties, it should be up to 0°82; ], , 50:i.

Furthermore, the weight of the hydroxyl functional group groups provided by THEIC should be at least 45% as the total weight of these groups in the polyesterimide resin in the final polyurethane enamel, otherwise the thermal resistance of the enamel will be disadvantageous. It acts on

EXAMPLES The following examples are given for illustrative purposes only and should not be construed as limiting the invention to these embodiments.

Examples] - Preparation of blocked isocyanate The following raw materials were used.

A xylene, 156 parts by weight B
Tsurpets #100 [5olvesso 111001 15
6 parts by weight C4,4--diphenylmethane-diisocyanate F-486 parts by weight D Trimethylolpropane 78 parts by weight E Cresylic acid 323 parts by weight F Cresylic acid 423 parts by weight G Phenol
In a 3p flask equipped with a 436-weight condenser, stirrer, thermometer and addition funnel, feedstock fA was first added.
'' and ``B'' and then the raw material ``CJ'' into the reaction vessel. The batch was heated until it reached a temperature of 48°C. When this temperature was reached, the raw material ``DJ'' was slowly added and the raw material ``DJ'' was added to the batch. The temperature was maintained at 85°C.

After adding all ingredients "D" to the batch, feed rE.

was added slowly through the addition funnel and the batch temperature was maintained at 87°C. After adding all ingredients [EJ to the batch, the vessel was kept at 85°-90°C for 1 hour. Batch temperature to 11
Gradually raise to 0°C and keep at this temperature for 2 hours, then dilute by adding raw material "F" and rQJ. The final raw material obtained was determined by Gardner-Holdt viscosity measurement to have a viscosity of
Solids content was 42% determined by charging 2 g of sample for 1 hour at 50°C.

Example 2 - Preparation of polyesterimide resin The following raw materials were used.

A Ethylene glycol 129 parts by weight B
[-Lis- (2-hydroxyethyl) isocyanurate 243 parts by weight C trimellitic anhydride 233 parts by weight D Methylene dianiline 120 parts by weight E Terephthalic acid
290 parts by weight of the above mixture was added to a Dean-Stark tube connected to a thermometer, a stirrer and a condenser.
5 tark) Do not put into a reaction vessel equipped with a trap.

The batch temperature was increased to 460°F over 15 hours. The reaction was carried out at a blackness of 'rV-Vl/2J with a viscosity of 1~(Cbeck cut) (according to the Gardner-Hol method as 30% isomorphic content in cresylic acid).
I continued until I got it. The batch was then recovered as 100% solids.

Example 3 - Preparation of polyurethane wire enamel The following raw materials were used.

A xylene ]-40 parts by weight B
Cresylic acid parts by weight C Phenol 61 parts by weight D Polyesterimide resin of Example 2 100 parts by weight E Example 1
Blocked isocyanate 455 parts by weight F Triethylenediamine 0.35 parts by weight G Dibutyltin dilaurate 0.35 parts by weight Raw materials "A", "B" and "C" were mixed, and then raw material "D" was added. The batch was heated to 180°F with stirring. Do not maintain batch temperature at 180'F until all of ingredient "D" is dissolved.

-36 to reduce batch temperature to 140°F and feedstock [E
The final viscosity of the enamel is ``K'' according to the Gardner-Holdt method, and the solid The minute content was 30.6% determined by testing a 2g sample at 200°C for 2 hours.

(All solids measurements mentioned above were determined by the same method unless otherwise specified).

EXAMPLE Preparation of 4-Polyesterimide Resin The following raw materials were used.

A Cresylic acid 90 parts by weight B Ethylene glycol 86 parts by weight C Neopentyl glycol 37 parts by weight D 'I'HEIC
75 parts by weight E Terephthalic acid 71 parts by weight F
) - Lithlic acid anhydride 192 parts by weight Methylene dianiline 99 parts by weight The reaction was allowed to proceed until 33% of the sample resin was obtained. The only difference in the reaction is the use of cresylic acid to minimize clumping during the process due to the amic acid formulation. The batch is then recovered as solid resin.

Example 5 - Preparation of polyurethane enamel The following raw materials were used.

A Cresylic acid 53 parts by weight B Phenol 42 parts by weight C Xylene
1-40 parts by weight D Polyesterimide resin of Example 4]] 7-layer plate part E Example]
Blocked isocyanate 453 parts by weight F Triethylenediamine 0.35 parts by weight G Dibutyltin dilaurate 0.35 parts by weight This enamel was prepared according to Example 3.
It was prepared in a manner similar to that described in . The final viscosity of the enamel according to the Gardner-Holdt method was [L-], while the solids content was 33.37%.

Example 6 - Preparation of polyesterimide resin The following raw materials were used.

A Cresylic acid 1075 parts by weight B Ethylene glycol 1433 parts by weight CTHEIC
1,438 parts by weight D Terephthalic acid 861 parts by weight E Trimellitic acid 2794 parts by weight F Methylene dianiline 1442 parts by weight Don't react in a similar way. The only difference in the reaction is the use of cresylic acid to minimize clumping during the process due to the amic acid formulation.

-39 = Do not react this batch until a check cut viscosity of ``U'' (33% sample resin in cresylic acid) is obtained using the Gardner-Hol method.

Example 7 - Preparation of polyurethane enamel The following raw materials were used.

A Cresylic acid 56 parts by weight I3
Xylene 140 parts by weight C Phenol 42 parts by weight D Polyesterimide resin of Example 6 114 parts by weight E Example 1
．． Blocked isocyanate 453 parts by weight F Triethylenediamine 0.35 parts by weight G Dibutyltin dilaurate 0.53 parts by weight The above raw materials were converted into wire enamel in a manner as described in Example 3. The final viscosity obtained was rl=J according to the Gardner-Holdt method, while the solids content was 30.4%.

40 Example 8 - Preparation of Polyesterimide Resin The following raw materials were used.

A Cresylic acid 142 parts by weight B Neopentyl glycol 111 parts by weight CTHEIC
70 parts by weight D Trimellitic anhydride 384 parts by weight E Methylene dianiline 1-98 parts by weight The above raw materials were reacted in the same manner as described in Examples 2 and 6. Check cut viscosity as 33% solids in cresylic acid was "■".

Example 9 - A modified raw material of polyurethane enamel was used.

A Cresylic acid 53 parts by weight B Xylene 140 parts by weight C Phenol 42 parts by weight D Example 8 = 41 = Polyesterimide resin 117 parts by weight E Example 1
Blocked isocyanate 453 parts by weight F Triethylenediamine 0.35 parts by weight G Dibutyltin dilaurate 0.35 parts by weight The above raw materials were converted into wire enamel in the manner described in Example 3. The final viscosity obtained was determined by the Gardner-Holdt method to be rM1/2.
On the other hand, the solid content was 32.0%.

Example 10 - Preparation of polyurethane enamel The following raw materials were used.

A Cresylic acid 35 parts by weight B Phenol 72 parts by weight C Xylene
135 parts by weight D Polyesterimide resin of Example 2 86 parts by weight E Example 1
Blocked isocyanate 487 parts F Dibutyltin dilaurate 0.53 parts by weight Triethylenediamine 0.35 parts by weight The above raw materials were mixed in the manner described in Example 3. The final viscosity obtained was determined by the Gardner-Holdt method to be rL1/2. , while the solids content was 30.5%.

Example 11 - Preparation of polyesterimide resin The following raw materials were used.

A Cresylic acid 1-52 parts by weight B
Ethylene glycol 144 parts by weight CTHEI
C135 parts by weight D trimellitic acid anhydride 454 parts by weight E
Methylene dianiline 2] 7 parts by weight The above raw materials were reacted in the same manner as described in Examples 2 and 6. The viscosity was determined as 33% solids in cresylic acid.

43 Example] 2- Preparation of polyurethane enamel The following raw materials were used.

A Cresylic acid 52 parts by weight B Phenol 42 parts by weight C Example 11
Polyesterimide resin 1.1. s weight i part D xylene 140 weight parts E Example 1
Blocked incyane 1-4.53 parts by weight F Triethylenediamine 0.35 parts by weight G Dibutyltin dilaurate 0.53 parts by weight The above raw materials were mixed in a process similar to that described in Example 3 to form wire enamel. It was converted to The final viscosity obtained is Gardner-Hol I~
3/4", while the solids content is 30.
It was 5%.

Example 13 - Preparation of polyesterimide resin The following raw materials were used.

A Cresylic acid 81 parts by weight B Ethylene glycol 128 parts by weight CTHEIC
179 parts by weight D r-limellitic anhydride 240 parts by weight E
Methylene dianiline 117 parts by weight F Terephthalic acid 83 parts by weight The above raw materials were reacted in a manner similar to that described in Examples 2 and 6. The batch was stopped when a total distillation volume of 68 ml was collected.

Example 14 - Preparation of polyurethane enamel The following raw materials were used.

A Cresylic acid 52 parts by weight B Phenol 42 parts by weight C Xylene
1-40 parts by weight D Polyesterimide resin of Example 13 1-18 parts by weight E -45 of Example 1 Blocked isocyanate 453 parts by weight F l-lyethylenediamine 0.35 parts by weight G Dibutyltin dilaurate 0.53 parts by weight Example 3 Using the above raw materials
The mixture was mixed as described in . The final viscosity is rN
1/4. , while the solids content was 30.2%.

The wire enamels prepared in Example 3.5.7.9.1-0.1.2 and]-4 were heated at a General Electric
Electric) Type M By using a two-head experimental furnace (conventional class F brazeable polyester imide wire enamels can be fabricated at 45 feet/min in similar equipment to obtain favorable results in electrical properties). (as applicable), 8006F for the radiator plate, 400°F for the bottom region ■ and 70°F for the top region II.
By using a temperature of 0°F (traditional class F
The brazeable polyesterimide requires operating at 900° F. for the radiant plate temperature, 500° F. for the bottom region and 800° F. for the top region temperature. >1.024mrJI”l wire.

A class F brazeable polyesterimide wire enamel was prepared to compare the performance of a class F polyurethane wire enamel according to the present invention.

Comparative example Comparative Example 1 Class F brazeable polyester imide enamel The following raw materials were used.

A Cresylic acid 750 parts by weight B Ethylene glycol 194 parts C Methylene dianiline 1-37 parts by weight D Trimellitic anhydride 312 parts by weight E Tetrabutyl titanate 37 parts by weight (TBT) The above raw materials were gradually heated to 380°. The batch was kept at 370-380°F and the Gardner-Holdt method was used to obtain a viscosity of Y to Z (no check marks and no check marks, i.e. 43-45% solids). ).

Add 157 parts by weight of phenol to the batch and
Cooled to -40°F. Then 160 parts by weight of xylene and 3 parts by weight of TBT were added and mixed thoroughly for 30 minutes. The final viscosity according to Gardner-Holt is rR1/
2. On the other hand, the solid content is rR1/2. Met.

Comparative Example 2 Class F brazeable polyester imide enamel Do not use the following ingredients.

A Ethylene glycol 294 parts by weight B Terephthalic acid 268 parts by weight C Zinc acetate
0.4 parts by weight D Trimellitic anhydride 294 parts by weight E Methylene dianiline
129 parts by weight "T" by Cartner-Hol I method
Check cuttle viscosity of ~U'' (30 in cresylic acid)
% solids) in the same manner as described in Example 2. Then dilute the batch with the next ingredient.

F Cresylic acid 660 parts by weight G Tsurpetz 8100 381 parts by weight H Phenol 660 parts by weight ■ Xylene
374 parts by weight J m-/p-cresol-based phenolic resin (40% solids) 33 parts by weight K Tetrabutyl titanate 16.5 parts by weight Final viscosity is "C" by Gardner-Holdt method, while its solids content The content was 30.5%.

Comparative example 3 Class F brazing possible polyesterimide resin Do not use the following ingredients.

A Ethylene glycol 528 parts by weight B Glycerin (96% purity) 125 parts by weight C Dimethyl terephthalate 620 parts by weight D Trimeric anhydride 592 parts by weight E Methylene dianiline 262 parts by weight F Xylene
1-20 parts by weight G zinc acetate
All 4 parts by weight of the raw materials were placed into the flask described in Example 1. The batch was gradually heated to 195° C. while the system was distilled under atmospheric pressure to remove methanol and water produced as by-products. The acid value of the batch is 10.8
When reaching rQ3/4. .

Excess ethylene glycol and xylene in the batch was distilled off until a check cut viscosity of . Then recover the batch as 100% solids.

Comparative Example 4 Class F brazeable polyester = 5
0- Imide enamel A Cresylic acid 1-55 parts by weight B
Phenol 327 parts by weight C Turpetz #1-00], 77 parts by weight D Mondenir S (Mobay Chemical 11 28
Weight part [Mondur S (Mobay C
chemical)]E Polyester of Comparative Example 3
275 parts by weight Imide resin F Propylene gel blade coal 35 parts G octanoic acid) 1 15 parts by weight (8% zinc as naphthenate) Raw materials rD and "E" are used as raw materials "A, rB" and "
C'' and heated to 200'F while stirring. When all ingredients "D" and "E" were dissolved, the batch was cooled to 140°F and ingredients "F" and "G" were added. The final viscosity of the batch is r by the Gardner-Holdt method.
E1/2. , while the solids content was 28.7%.

In addition to the batches made according to Comparative Examples 1-4, the following raw materials were made to compare their ability to impart electrical properties when used as insulation coatings on copper wire.

Comparative Example 5 Class ■1 polyester resin The following raw materials were not used.

A ethylene glycol 250 parts by weight B
THEIC 804 parts by weight C Terephthalic acid 395 parts by weight D Terephthalic acid 395 parts by weight Raw materials 'AJ, r
B' and 'C-1 were placed in the flask described in Example 2 and the batch was gradually heated to 420°F while the distillate (water) was removed from the batch and collected.
Cool to 60°F and add ingredient "D". The batch temperature was increased to 360°F and held there until a check cut viscosity of rWJ (as 30% solids in cresylic acid) was obtained. The batch was then collected at 100% solids = 52 minutes.

Comparative Example 6 Polyurethane wire enamel The following raw materials were mixed into 1
Don't use it.

A Cresylic acid 100 parts by weight B Phenol 21 parts by weight C Xylene
143 parts by weight D Polyester of Comparative Example 5 100 parts by weight Resin E Blocked isoester of Example 1 441 parts by weight Anate Ft - lyethylenediamine 0.35 parts by weight G Dibutyltin silica 0.35 parts by weight Urate raw material "D" was added to a flask Inside, the raw materials rA, rB" and "
C'' and heated to 250°F.

This batch temperature was maintained until all raw materials [Dj were dissolved. The batch temperature was then lowered to 140°F and the raw material
E', 'F' and 'G' were added to Batch-53= and mixed thoroughly for another 11 hours. The final viscosity according to the Gardner-Holt method was "M", while the solids content was 29.6%.

Comparative Example 7 Blocked Incyanate-1 - Do not use the following raw materials.

A xylene 158 parts by weight B Tsurpetz #], OO 158 parts by weight C diphenylmethane 486 parts by weight Socyanate D THEIC 17 parts by weight E Trimethylolpropane 78 parts by weight F Cresylic acid 300 parts by weight G Cresylic acid 431 parts by weight ■'' Phenol
442 parts by weight In a 3 g flask equipped with a condenser, stirrer, thermometer and addition funnel, raw material rAJ
, FB, and "C" were rapidly added and heated to 48°C. A mixture of ingredients "D" and "E" was then slowly added to the batch. The temperature of the batch was kept below 85°C. After the addition of feed "D" and rEJ, feed "F" was added very slowly while maintaining the batch temperature not to exceed 87°C. After adding all raw materials “FJ” to the batch,
Maintain batch temperature at 87°C to 90°C for 1 hour. The temperature of the batch was then gradually increased to 110°C and held at this temperature for 2 hours.

After 2 hours at 11-0°C, the batch was mixed with raw material "G" and r
Diluted with HJ. The check viscosity obtained by the Gardner-Holt method was "2 minus" while its solids content was 42.6% (1 at 150°C).
time 2g of sample).

Comparative Example 8 Polyurethane enamel The following raw materials were used.

A Curzonic acid 100 parts by weight B Phenol 67 parts by weight C Xylene
]-40 parts by weight D Polyester of Example 2 100 parts by weight Imide resin E Blocking of Comparative Example 7 444 parts by weight Isocyanate F Triethylenediamine 0.35 parts by weight G Dibutyltin dilaurate 0.35 parts by weight The above raw materials were used in Example 3 Converted to wire enamel using the method described in .

The final viscosity according to the Gardner-Holdt method is "M and 1/
2'' while its solids content was 29.92%.

The test results for all examples of enamel are shown in the following table.

C) 00 0 00 0
C) Fh-018)
μ C) 6r 0ΦΦ’s ω■ −(su u〕 co co co v−】■size←
0] (0 dimension - to ω dimension - to Cθ dimension - O to σ] -〇〇O lfl ''' Comparative example number 1-2750°F (
Braze 60/40 Tin/Lead at 850°F (Sec) 60/40 Tin/Lead Heat Durability at 5-66 (hours) 220°C 200°C 180°C 20,000 hours estimated? C(-12Uζ (continued) 3 3~4 5.5 4.5 (undetermined) 60 - (Effect of the invention) The explanations in Table 1 and Table 2 are based on the improved heat of the present invention. In particular, Example 3 represents the first developed wire enamel of the present invention, while Example 5, Example 7, Example 9, Example 1
0, Examples 12 and 14 are improvements on the enamel of Example 3.

Comparative Examples 1-5 Comparative Examples 2 and 4 are all brazeable polyesterimide coated wires and radiant plates used to process Class F polyurethane enamels of the present invention. 11,1-% higher temperature at the radiant plate compared to the temperature at 20
% higher temperature and 12.5% higher temperature in region 11.

Furthermore, the interest rate operation speed I shown in the embodiment of the present invention is
At least as fast as that of brazeable polyesterimide, but mostly faster.

The improved brazing speed is clearly demonstrated by comparing the inventive enamel examples with the comparative examples.

-61 = The majority of embodiments consistent with the present invention braze at 750°F in 3 seconds (actual range is 2.0 to 4.0 seconds), whereas conventional brazeable polyesterimide brazes The speed is 5-8 at 850°F. This conventional brazeable polyester imide coated wire wire has a
High temperatures are required, while brazing speeds are 1 to 6 seconds slower. Therefore, the brazing speed of conventional brazeable polyesterimides is on average 100% slower than that of the present invention.

The improved thermal durability of the coating of the present invention will be demonstrated by comparing Example 3 with Comparative Example 4.

Overall, therefore, the production of polyurethanes according to the method of the invention results in waxed wire coatings of clearly superior properties.

Although only specific embodiments of the invention have been described in detail, it will be understood that modifications and variations may be made in the details of the composition and modes of operation while still retaining the novel features and advantages of the invention. Accordingly, all such changes and modifications are hereby characterized as falling within the scope of the appended claims.
Schenectaden Chemicals, Inc.

Claims (1)

[Claims] 1. Consists of a mixture of (a) blocked isocyanate and (b) polyesterimide resin (b), wherein the polyesterimide resin (b) contains (i) alcohol and at least one carboxylic acid. polyester units with and (ii
) consisting of diimidodicarboxylic acid units, the alcohols comprising at least one alcohol containing an isocyanurate group, and the blocked isocyanate (a) is selected from the group consisting of diphenylmethane diisocyanate, diphenylsulfone diisocyanate, and diphenyl ether diisocyanate. A polyurethane wire enamel composition prepared from a urethane polymer derived from the reaction of diisocyanates or diisocyanates with alcohols. 2. The polyurethane wire enamel composition of claim 1, wherein the alcohol containing isocyanurate groups comprises at least 16 and up to 60 equivalent % of the alcohol in the polyesterimide units. 3. The proportion of the isocyanurate group-containing alcohol is 40
% or more, the imide group is at least 16 equivalent % of the total number of imide groups and ester groups, or when the proportion of the isocyanurate group-containing alcohol is less than 40 equivalent %, the imide group is an imide group. 3. The polyurethane wire enamel composition of claim 2, wherein the polyesterimide is at least 35 equivalent percent of the total number of ester groups. 4. The polyurethane wire enamel composition according to claim 1, wherein the proportion of imide bonds in the total imide and ester bonds is at least 16% by weight and up to 50% by weight. 5. The polyurethane wire enamel composition according to claim 4, wherein the proportion of imide bonds is up to 45 equivalent %. 6. Claim 1, wherein the polyesterimide resin is derived from the reaction of an alcohol with an acid in which the ratio of hydroxyl groups to carboxyl groups is in the range of 1.4:1 to 2.5:1. The polyurethane wire enamel composition described. 7. The polyurethane wire enamel composition according to claim 1, wherein the ratio of isocyanate groups to hydroxyl groups in the reaction ranges from 0.82:1 to 1.50:1. 8. The polyester imide resin contains an imide containing a compound produced by a reaction between an acid anhydride and a polyamine, and an ester containing a compound produced by a reaction between an alcoholic component and a carboxylic acid or its ester-forming derivative. A polyurethane wire enamel composition according to claim 1 produced by the reaction of 9. A mono- to polycyclic acid anhydride in which the acid anhydride contains 1 to 3 non-adjacent carboxyl groups, or a monocyclic acid anhydride containing 1 to 3 non-adjacent carboxyl groups and having 5 or more carbon atoms in the alicyclic ring. or polyalicyclic monoanhydride, Claim 8
The polyurethane wire enamel composition described in . 10. The polyurethane wire enamel composition according to claim 9, wherein the acid anhydride is trimellitic anhydride. 11. The polyurethane wire enamel composition according to claim 8, wherein the polyamine component is an aromatic diamine. 12, the diamine is methylene dianiline, benzidine,
3,3'-diaminodiphenyl, 1,4-diaminonaphthalene, p-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4-dimethylheptamethylenediamine-1,7, diaminodiphenylketone, m-phenylenediamine, 12. The polyurethane wire enamel composition according to claim 11, which is xylene diamine, hexamethylene diamine, ethylene diamine, 4,4'-dicyclohexylmethane diamine, diaminodiphenylsulfone or oxydianiline. 13. The polyurethane wire enamel composition according to claim 8, wherein the polyamine is methylene dianiline or oxydianiline. 14, the alcoholic component is tris-(2-hydroxyethyl)isocyanurate and ethylene glycol;
A glycol component selected from the group consisting of butanediol-1, 4, trimethylene glycol, propylene glycol, pentanediol-1, 5, neopentyl glycol, butene-2-diol-1, 4, and mixtures of these glycols. A polyurethane wire enamel composition according to claim 13 containing. 15. The alcoholic component further includes glycerin, pentaerythritol, 1,1,1-trimethylolethane,
15. The polyurethane wire enamel composition of claim 14 which also includes a polyhydric alcohol selected from the group consisting of 1,1,1-trimethylolpropane, dipentaerythritol and mixtures thereof. 16, the alcoholic component is 16 to 60 equivalent% Tris-
(2-hydroxyethyl)isocyanurate,
9. The polyurethane wire enamel composition according to claim 8, wherein the remainder of the components are dihydric alcohols. 17. The polyurethane wire enamel composition according to claim 8, wherein the carboxylic acid or its ester-forming derivative is terephthalic acid or isophthalic acid or its ester-forming derivative. 18. A carboxylic acid component containing 80 to 100 equivalents of terephthalic acid or isophthalic acid or an ester-forming derivative thereof, the remainder of which is adipic acid, orthophthalic anhydride, hemimellitic acid, trimellitic anhydride, succinic acid, The polyurethane wire enamel composition according to claim 17, which is tetrahydrophthalic acid, maleic acid or sebacic acid. 19, (A) A polyester imide resin produced by a reaction between a compound containing an imide bond and a compound containing an ester bond, wherein the imide bond-containing compound is a reaction between trimellitic acid anhydride and methylene dianiline. and the ester bond-containing compound is produced by tris-
(2-Hydroxyethyl)isocyanurate, other dihydric alcohols, and a polyesterimide resin produced by reaction with terephthalic acid or isophthalic acid, and (B) diphenylmethane diisocyanate, which is produced by reacting with trimethylolpropane and cresylic acid. A polyurethane wire enamel composition comprising a reaction product with a blocked isocyanate compound produced by. 20. Claim 1, wherein the blocking agent for the blocked isocyanate is selected from the group consisting of phenol, cresylic acid, and alkylated phenols in which the alkyl group(s) contain up to 9 carbon atoms. The polyurethane wire enamel composition described. 21, consisting of a mixture of (a) a blocked isocyanate and (b) a polyesterimide resin, the polyesterimide resin (b) containing (i) units of a polyester of alcohols and at least one carboxylic acid; and (ii) The blocked isocyanate (a) is an isocyanate selected from the group consisting of diphenylmethane diisocyanate, diphenyl sulfone diisocyanate, and diphenyl ether diisocyanate, which is composed of diimide dicarboxylic acid units, the alcohols containing at least one alcohol containing an isocyanurate group. or a conductor coated with a cured polyurethane wire enamel obtained by applying to a conductor a polyurethane wire enamel prepared from a urethane polymer derived by reaction of said diisocyanate with an alcohol and heating said coated conductor. .