JPH03102709A - Polyamide-imide ester resin and insulated wire - Google Patents

Abstract

PURPOSE:To improve a lubrication property, a sliding property, anti-deterioration and refrigerant fluid resistant property by applying specific polyamide imide resin, aromatic polyisocyanate masked by a phenol kind and specific polyamide ester resin on a conductor followed by baking. CONSTITUTION:Polyamide imide ester resin having polyamide imide resin, wherein multivalent carboxylic acid, which contains at least 5 mole% of dibasic acid or its delivative, is made to react on polyisocyanate or its delivative at an equivalent weight ratio of 1 to 1 in phenol solvent under coexistence of polyamide resin, aromatic polyisocyanate being masked by a kind of phenol, and lybricant denatured polyester imide resin, as essential components, is applied, based for being made an insulated wire. An insulated wire being excellent in a lubrication property, a sliding property, an anti-deterioration property and in refrigerant oiliness resistance is thereby obtained while being good for a refrigerant fluid resistant motor.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Def) The present invention relates to a polyamide-imide ester resin having excellent lubricity and suitable for refrigerant-resistant motors, and an insulated wire.

<Conventional technology> In recent years, it has been desired to further increase the efficiency of various motors and various transformers by 1r due to energy saving. There is a strong demand for increasing the efficiency of various motors such as motors. In order to improve the efficiency of these various motors, measures have been taken to insert more enamelled wires into a narrow slot to further increase the space factor. Traditionally, refrigerator motors have mainly used polyester-imide wires and polyamide-imide overcoated wires, which have excellent mechanical strength, wear resistance, and resistance to refrigerants. (Problem to be Solved by the Invention) However, as described above, in order to increase the space factor of the enameled wire inserted into the slot, using a liquid lubricant such as refrigerating machine oil does not improve the lubricity. The lack of slip properties made it difficult to increase the space factor. On the other hand, attempts have also been made to apply solid lubricants such as solid paraffin and carbanal wax to enamelled wire. However, when enameled wire coated with a solid lubricant is applied to a refrigerator motor, the solid lubricant extracted by the refrigerant may clog the compressor valve or refrigerant blowout nozzle in the expander, reducing the refrigerating capacity. was there. In order to eliminate these drawbacks, we added 2 carbon atoms to polyamide-imide resin.
There have also been proposals for insulated wires that are made to have lubricating properties by reacting with one or more IS carboxylic acids or derivatives thereof (for example, Japanese Patent Publication No. 51193/1983, Japanese Patent Application Laid-Open No. 209967/1982). ．． The polyamideimide resin used in these products is basically N-methyl-2
-Uses an aprotic polar solvent such as pyrrolidone, which has the drawback of making the varnish expensive and lacking in industrial utility. Insulated wires have also been proposed in which polyester resins or polyesterimide resins are reacted with linear carboxylic acids having 21 or more carbon atoms or derivatives thereof to impart lubricity to the wire itself. However, when this is used as a refrigerant-resistant insulated wire, it is essentially a double coat of polyesterimide resin/polyamideimide resin, which has the disadvantage that the process is complicated and the cost of the insulated wire is high. The present invention has been made in view of the above circumstances, and aims to provide a polyamide-imide ester resin having excellent lubricity, slipperiness, deterioration resistance, and refrigerant oil resistance, and an insulated wire made by coating and baking the same. It is. [Structure 1 of the Invention (Means for Solving the Problems) The present inventors have achieved lubricity, slip resistance, and resistance by blending a lubricant-modified polyesterimide resin with a polyamideimide resin that is soluble in phenols. It was discovered that a resin with excellent deterioration resistance and refrigerant extraction resistance could be obtained, and the present invention was completed. That is, the present invention provides (A) a polyhydric carboxylic acid consisting of a tribasic acid or a derivative thereof containing at least 5 mol % of a dibasic acid or a derivative thereof based on the total acid component; and (b) a polyisocyanate i. - or a derivative thereof at an equivalent ratio of 1:1 in a phenolic solvent in the coexistence of polyamide a fat, (B) aromatic polyisocyanate masked with phenols , and (C) a lubricant-modified polyesterimide resin, a polyamideimide ester resin characterized in that it has as an essential component,
It is also an insulated wire made by coating and baking it. The present invention will be explained in detail below. (A) Polyamideimide resin used in the present invention is <a>
It is obtained by reacting a polyhydric carboxylic acid and (b) polyisocyanate or its 2A IQ form at an equivalent ratio of 1=1 in a phenolic solvent in the coexistence of a polyamide resin. (a) The polyhydric carboxylic acid consists of a 21M base acid or a Mitsanawa base acid or its conductor containing at least 5 mol % of the total acid component. As the dibasic acid or its derivative, for example, an aromatic dicarboxylic acid or an aromatic dicarboxylic acid ester represented by the formula <I) can be used. R'OOC-几'-COOR'...<I
) Here, R1 is a hydrogen atom, an alkyl group, or a phenyl group, and R2 is R"(COOR')3...(n) (However, X is -CH2+, -co, -so2-C (
C H3) 2. 0-). Generally, it is desirable to use isophthalic acid and terephthalic acid as these compounds due to reactivity, economical efficiency, etc. The proportion of the dibasic acid or its derivative is preferably at least 5 mol % of the total acid components. If it is less than 5 mol%, it has no effect on the visibility of the insulating coating and is not preferred. In order to improve flexibility, adhesion to mida bodies, and crazing resistance, the content is preferably 20 mol% or more. Examples of tribasic acids or derivatives thereof include aromatic tricarboxylic acids, aromatic tricarboxylic acid esters, aromatic tricarboxylic acid anhydrides, and the like represented by formulas (n) and (In). may be used alone or in combination of two or more. Here, RI R' is a hydrogen atom, an alkyl group, or a phenyl group, and R' and R' are (however, Y is -CH2+, -co+, -3021C
(C H3 ) 2-. 10). Trimellitic anhydride is generally used as this compound due to its heat resistance, high reactivity, and economic efficiency. A small amount of a dibasic acid or a derivative thereof, or a part of a tribasic acid or a derivative thereof, such as less than 5 mol% of the total acid component, such as pyromellitic anhydride, 3,3'4,4'-benzophenonetetracarboxylic acid, etc. Acid anhydride, 3.3', 4.4'-diphenyltetracarboxylic acid anhydride, ? Substitution with tetrabasic acids or derivatives thereof such as tantetracarboxylic anhydride, aliphatic dibasic acids or derivatives thereof such as oxalic acid, malonic acid, succinic acid, glutaric acid, adivic acid, pimelic acid, suberic acid, azelaic acid, etc. Children can do it.

As the polyisocyanate or its conductor (b), which is the other component of the <A> polyamideimide resin used in the present invention, aliphatic, alicyclic, and aromatic diisocyanates are used. Suitable diisocyanates include, for example, ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, bentamethylene diisocyanate, hexamethylene diisocyanate, peptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, trimethylhexamethylene diisocyanate, morphol. Lin diisocyanate 1., hexane diisocyanate 1., 3,9-bis(3-probyl isocyanate)-2■4.8.10-tel.laoxaspiro[5,5]undecane, 4. 4'-diphenylmethane diisocyanate, 4.4'-diphenyl ether diisocyanate, 4.4'-diphenylpropane diisocyanate, 4.4'-diphenylsulfone diisocyanate-1-, 3.3'-diphenylsulfone diisocyanate, 4 .4'-diphenyl sulfide diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dichloro. 4.4'
-diphenylmethane diisocyanate, 3.3'-dimethyl-4,4'-bisphenyl diisocyanate, 3.
3'-dimethoxy 4.4'-bisphenyl diisocyanate 1-, 4.4'-bisphenyl diisocyanate 1-
, phenylene diisocyanate, ρ-7 phenylene diisocyanate, 2.4-tolylene diisocyanate, incyane 1.
, 2,6-tolylene diisocyanate, n4-silylene diisocyanate, p-xylylene diisocyanate, etc., and these can be used alone or in combination of two or more. Polyisocyanates other than diisocyanates include:
For example, polymethylene polyphenyl polyisocyanate, 4.4', 4"-triisocyanate triphenylmethane, 2.2', 5.5"-tetraisocyanate-4.4'-dimethyldiphenylmethane, 2,4.4'
-diphenyl ether triisocyanate, tris(4
-Methyl-4-isocyanate phenyl)in cyanurate and the like. Polyisocyanate derivatives in which the isocyanate groups of polyisocyanate are masked with phenols such as phenol, cresol, and xylenol can also be used. These polyisocyanates are appropriately selected depending on the required properties such as heat resistance and mechanical properties of the polyamideimide resin obtained.
Aromatic diisocyanates are preferred from the viewpoint of heat resistance, mechanical properties, and economic efficiency of the insulating film, which are particularly required for electrical insulating varnishes. Among them, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, i-I silylene diisocyanate, p-xylylene diisocyanate, and 4,4'-diphenyl ether diisocyanate. Preferably, these diisocyanates are particularly preferably one or a mixture of phenol-masked dirods in order to provide the above-mentioned properties. The blending ratio of the polyisocyanate or its derivative is 2 equivalents and 3 equivalents of the dibasic acid or its derivative and the tribasic acid or its derivative, respectively, and the incyanate component of the polyisocyanate or its derivative in an equivalent ratio of 1. :1
It is preferable that (a) polyhydric carboxylic acid and (b)
) A polyamide-imide resin is obtained by reacting a polyisocyanate or a derivative thereof in a phenolic solvent in the presence of a polyamide resin at a temperature of 150 to 250°C for 2 to 20 hours. The phenolic solvent used here is
Phenol, 0-cresol, 0-cresol, p-cresol, xylenol, and chlorophenol are used. Polyamide resins used in this reaction include nylon 6, nylon 12, nylon 6.6, and nylon 6.
- Examples include l2, nylon 11, etc. Among these, when using nylon 6 and nylon 6.6, the reaction time is shorter than when using other nylons, and the enamelled wire has the advantage of excellent wear resistance, but it can be selected as appropriate depending on the required characteristics. The polyamide resin may be charged at the same time as starting the reaction of (a) polyvalent carbon and (b) polyisocyanate or its conductor, or one component may be dissolved in a solvent and the other component may be added. At one time,
Alternatively, it can be prepared in several batches, and there are no particular restrictions on the preparation method. However, in order to obtain a high molecular weight polyamide-imide resin, it is preferable to charge the polyamide resin from the beginning of the reaction. On the other hand, when used as an insulating varnish, the reaction proceeds during the baking process to form the enamel film, so the polyamide resin can be added relatively late in the varnish synthesis stage. The function of polyamide resin in the reaction of polyamide-imide resin is not clear, but it is known that it significantly accelerates the reaction between polycarboxylic acid and polyisocyanate or its derivatives. It is inferred that the polyamide-imide resin and the polyamide resin react and integrate with each other from the results of molecular weight distribution measurements using infrared charts, thermogravimetric analysis, and gel permeation chromatography. In the reaction between a tribasic acid or its derivative and a polyisocyanate or its derivative, it is thought that the polyamide resin exhibits a matrix effect and, at the same time, a polymerization reaction occurs mainly in the amide groups of the polyamide resin. The blending ratio of the polyamide resin can be changed depending on the amount sufficient to express the matrix effect, the purpose of use of the obtained polyamide-imide resin, and the required characteristics.

For example, in the case of electrical insulating varnish, it is desirable to mix the polyamide-imide resin with a proportion of 3 to 40% by weight. Exceeding the weight percentage is undesirable because the heat resistance of the enameled wire obtained from the evergreen varnish decreases. The phenol-masked aromatic polyisocyanate (B) used in the present invention is obtained by replacing the isocyanate group of the aromatic diisocyanate or aromatic polyisocyanate used in (b) with a phenol such as phenol, cresol, or xylenol. Masked products are used. Specific examples include MS-50 (manufactured by Nippon Polyurethane Co., Ltd., trade name), Coronate AP Stable (
manufactured by Nippon Polyurethane Co., Ltd. (trade name), etc., and these can be used alone or in a mixture of two or more.
Although it is possible to use the above-mentioned (A) polyamideimide m#1 alone as an electrically insulating varnish,
When manufacturing enamelled wire using a high-efficiency baking machine,
The disadvantage is that it tends to foam. By incorporating aromatic polyisocyanate masked with phenols, this foaming can be significantly reduced. As the lubricant-modified polyesterimide resin (C) used in this invention, a part of the alcohol component in the usual polyesterimide consisting of dimethyl terephthalate, trimellitic anhydride, 4,4'-diaminodiphenylmethane, and ethylene glycol is added to tris( 2-hydroxyethyl)
It is a polyesterimide resin substituted with isocyanurate and modified with a detergent. The lubricant used here is a linear carboxylic acid having 18 or more carbon atoms, specifically,
Stearic acid, nonadecanoic acid, eicosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid, octacosanoic acid and derivatives thereof can also be used. By blending this lubricant-modified polyesterimide resin, the lubricity and abrasion resistance of the wire coating can be improved. This blending ratio is desirably 0.5 to 5 mol% based on the total acid component. Polyisocyanate, (C
) It can be easily produced by combining lubricant-modified polyesterimide resin with a1. The blending ratio of each of these ingredients is
Based on the total polyamide-imide ester resin (A>60-99% by weight of polyamide-imide resin, (B) 5-40% of aromatic polyisocyanate masked with phenol)
gLjt%, and (C) lubricant-modified polyesterimide resin is preferably blended in an amount of 1 to 30% by weight. Preferably, the content of (A) is 70 to 90% by weight, the content of (B) is 5 to 20% by weight, and the content of (C) is 3 to 15% by weight. The polyamide-imide ester resin of the present invention has the above-mentioned (A) to (C) as essential components, but other components and additives may be added to the extent that it does not contradict the purpose of the present invention. If the aromatic polyisocyanate masked with phenols (B) is less than 3% by weight,
Foaming tends to occur, and if it exceeds 40% by weight, the flexibility and abrasion resistance of the enamelled wire decreases, which is not preferable.
(C) lubricant-modified polyesterimide resin is 1% by weight
If it is ungrooved, it has no effect on lubricity, deterioration resistance, or refrigerant oil resistance, and if it exceeds 30% by weight, the blister properties of the enamelled wire improve, but winding pinholes tend to occur, which is not desirable6. Insulated wires can be manufactured by coating and baking polyamide-imide ester resin over copper wire or an insulating layer. Among these, particularly favorable results can be obtained using polyesterimide resin for the undercoat and polyamideimide ester resin for the topcoat. (Example) Next, the present invention will be explained using an example. [Production of lubricant-modified polyesterimide resin ◎-1 to 3 7 ■-1 Thermometer, 1゛1! 2 with a machine, cooling pipe, and nitrogen gas pipe attached.
A4 [300g dimethyl derephthalate in 1 flask《1
, 5 monole), trimellitic acid anhydride 1 270Q (
1.4 mol), 4.4'-diaminodiphenylmethane 1
40 g (0.7 mol), ethylene glycol 50a (
0.8 mol), 30 g (1.1 mol) of tris(2-hydroxyethyl)isocyanurate, 0.8 mol of 6K sodium, and 30 g of Hoechst Wax S (manufactured by Hoechst, trade name) in a nitrogen stream. IQ 4'
The temperature was gradually raised to 240° C. over 8 hours.

The reaction was continued for an additional 30 minutes under reduced pressure, and after fS, the reaction was stopped by adding 1040 liters of Moroccan cresol to obtain a resin solution with a viscosity of 380 boads (at 30°C) and a non-volatile content of 50%. ■-2 ■- In 1, the reaction was carried out in the same manner as in ◎-1 except that Hoechst Wax E {manufactured by Hoechst Co., Ltd., trade name} was used instead of Hoechst Wax S. It was made into a resin solution.

■-3 In ■-1, all cases were 0 except for using methyl stearate 40 (J) instead of Hoechstwax S3Qg.
The reaction was carried out in the same manner as -1, and the viscosity was 345 boads (30°C).
) and a resin solution with a nonvolatile content of 51%. ■-4 ■-1 All 0 except for Hoechst Wax S
A resin solution with a viscosity of 370 boads (30°C) and a non-volatile content of 50% was prepared in the same manner as in -1. Then Hoechst E30i
;1 was added and thoroughly stirred and mixed. [Manufacture of polyesterimide resin Y for undercoat] In a 21 four-necked flask equipped with a thermometer, stirrer, cooling tube, and nitrogen introduction tube, 300 g (1.5 mol) of dimethyl terephthalate and 2 trimellitic anhydride were added.
70 (J (1.4 mol), 4.4'-diaminodiphenylmethane 140 g (0.7 mol), ethylene glycol sog (o.a mol), tris(2-hydroxyethyl)in cyanurate 300 g (i.
i mol) and 0.8 g of sodium acetate, the temperature was gradually raised while stirring in a nitrogen stream, and the temperature was increased over 8 hours.
The temperature rose to 40℃. Next, the reaction was continued for another 30 minutes under reduced pressure, and then 10401 J of 11-cresol was added to stop the reaction. Furthermore, 20g of tetrabutyl rapeseed 1- was added and mixed to this resin to give a viscosity of 40 Boaz (30
℃) with cresol and naphtha No. 2 to make a resin solution with a nonvolatile content of 42%. Actual travel example 1 Temperature word 1, stirring {1! 2 with a machine, cooling pipe, and nitrogen introduction pipe attached.
In a four-ring flask, add 130 g of l.limellitic anhydride.
0.7 mol], isophthalic acid 8bLJ (0.5 mol), 4,4'-diphenylmethane diisocyanate 3
00g (1.2mol}, amilan CM as nylon 6
1007 (manufactured by Toray Industries, Inc., trade name) and 470 g of cresylic acid were charged, and the temperature was raised from room temperature to 200° C. in about 1 hour in a nitrogen stream. A lot of decarbonation gas foaming occurs from 80 to 130℃, and even more at 200℃.
It was observed to continue up to around °C. Set the reaction temperature to 200~
The temperature was set at 205°C, and the reaction was carried out at normal pressure while refluxing the cresol. The contents were a little opaque at first, but2
After 3 hours at 05°C, a clear solution was obtained. After that, the reaction continued for 7 hours while refluxing the cresol! After a total of 10 hours, 176 g of fresh cresol was added to stop the reaction. After cooling to 100°C, 100 (l) of lubricant-modified polyesterimide resin (manufacturing example ◎-1) was added, and aromatic polyisocyanate MS-50 (manufactured by Nippon Polyurethane Co., Ltd., trade name) was further masked with phenol.
ioog was added and thoroughly stirred and mixed to produce a uniform resin solution. This resin solution was reddish-brown and transparent, and when the viscosity was adjusted to 40 boads (at 30°C) using cresol and naphtha No. 2, the nonvolatile content was 31%. Example 2
~5 Using the same equipment as in Example 1, a resin solution was produced according to the composition shown in Table 1. This v! 1 fat solution was adjusted to a viscosity of 39 to 75 boads (at 30°C) using cresol and naphtha No. 21, and the nonvolatile content was 30 to 75 Boaz.
It was 32%. Comparative Example 1 A comparative example was prepared using a commercially available polyamide-imide paint (non-volatile content: 25%). Using a furnace with a furnace length of 6I1, the furnace temperature (upper, middle, lower) is 430-
At 380-270°C and a line speed of 11 Il/llin, the resin solution obtained in Production Example Y was coated once on a copper wire with a diameter of 1 lIl as an undercoat and baked, and then Examples 1 to 5 were applied as an overcoat. Insulated wires were manufactured by applying and baking the VA fat solution of Comparative Example twice. Regarding this insulated wire, J I
Various properties were tested according to S-C-3003 to obtain mucilage, which are shown in Tables 1 and 2.

The insulated wire of the present invention has excellent lubricity, wear resistance, slipperiness, deterioration resistance, and refrigerant oil resistance, and the remarkable effects of the present invention were confirmed. [Effects of the Invention] As is clear from the above explanation and Table 2, the polyamide-imide ester resin and insulated wire of the present invention have excellent lubricity, slipperiness, deterioration resistance, and refrigerant oil resistance. It is suitable for refrigerant motors, etc.

Claims (1)

[Scope of Claims] 1(A) (a) a polyhydric carboxylic acid consisting of a tribasic acid or a derivative thereof containing at least 5 mol % of a dibasic acid or its derivative based on the total acid component; and (b) a polyisocyanate or (B) Aromatic polyisocyanate masked with phenols; (C) An insulated wire characterized in that it is made by applying and baking a polyamide-imide ester resin containing a lubricant-modified polyester-imide resin as an essential component onto a conductor directly or through another insulating layer. 2(A) (a) A polycarboxylic acid consisting of a tribasic acid or a derivative thereof containing at least 5 mol % of a dibasic acid or a derivative thereof based on the total acid component, and (b) a polyisocyanate or a derivative thereof, in an equivalent amount. A polyamide-imide resin obtained by reacting in a phenolic solvent in the coexistence of a polyamide resin at a ratio of 1:1, (B) an aromatic polyisocyanate masked with phenols, and (C) a lubricant-modified polyesterimide resin. Polyamideimide ester resin is an essential component.