JPS58179277A - Heat-resistant insulating paint - Google Patents

Abstract

PURPOSE:To prepare an insulating paint having excellent heat resistance and high-speed workability, by compounding a specific polyester resin with a polyisocyanate stabilized with a phenolic compound and a reaction product of tetraalkyl titanate and phenol. CONSTITUTION:The objective paint is prepared by mixing (A) 100pts.wt. of a polyester resin wherein >=20mol% of the polyhydric alcohol component is tris (2-hydroxyethyl)isocyanate and preferably >=80mol% of the acid component is aromatic dicarboxylic acid with (B) 1-10pts.wt. of a polyisocyanate stabilized with a phenolic compound and (C) a compound obtained by reacting 1mol of a tetraalkyl titanate with >=5mol of a phenolic compound and distilling out >=3mol of lower alkyl alcohol from the reaction product, and dissolving the mixture in an organic solvent. The amount of the component (C) is 0.1-2.0pts.wt. in terms of titanium. A polyester resin having amide bond or amide-imide bond is also preferable as the component (A).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel heat-resistant insulating paint that has excellent high-speed workability.

Conventionally, as heat-resistant insulating paints used for enamel In, paints in which polyimide, polyamideimide, polyesterimide, polyester indium, I-lyester resin, etc. are dissolved in organic solvents have been used.

These medium polyimides and polyamideimides are generally soluble only in nitrogen-containing solvents such as N-methyl-2-hyrolidone, dimethylformamide, and dimethylacetamide. This solvent is expensive and removes moisture from the air.
Since it is difficult to handle as it absorbs and reduces its dissolving power, it has been difficult to make it widely available. On the other hand, polyester resin coatings such as polyester amide imide, polyester imide, and polyester are soluble in phenolic solvents and are therefore relatively inexpensive and easy to handle.

Additionally, in order to improve the heat resistance of this poly't-stellate resin, tris(2-hydroxyethyl)in cyanurate (hereinafter referred to as THEIC) is added to the polyhydric alcohol component.
is used.

In order to reduce the cost of a machine that uses this pigment to produce enameled wire, a high-temperature, high-speed hot-air oven is used to improve the production phase per unit time.

However, polyester resin paints containing THEIC as a polyhydric alcohol component are inferior in productivity to monoester resin paints that do not contain THEIC as a polyhydric alcohol component, and the manufacturing cost increases due to the twisting process. rises.

It is known that 7-enol bro-, di-, or tetraano-kyltitanate of bolyinone f-nate is used as a modified material for polyester resin paints, and this tetraalkyl nathanate is added to the solution and added to the polyester resin during coating and curing. It is made to react with resin. On the other hand, since the solvent is not sufficiently recovered, and since the solvent is expensive, there is a tendency to make the paint highly concentrated in order to save resources. However, since a highly concentrated resin solution inevitably has a high viscosity, it is difficult to properly mix the above-mentioned tetraalkyl titanate and it is necessary to raise the temperature. It has a high concentration, ie, a high probability of reaction with the resin, and when the temperature rises, it reacts with the resin and causes crosslinking, resulting in an increase in viscosity or a gluing state.

Historically, it reacts with tetraalkyl titanate Fi/lyester resin to produce lower alcohol as a by-product. In other words, the alkyl alcohol generated when this paint is baked to harden the paint film rapidly evaporates from the paint film, and when it is heated and hardened rapidly at high temperatures, it forms uneven parts on the eardrum surface and deteriorates the appearance. It was something to encourage.

The present invention was developed based on the results of extensive research into the power and energy congratulations.
By adding a reaction product of alkyl titanate and phenol in combination, an insulating paint with excellent heat resistance and good productivity was discovered.In other words, the polyhydric alcohol component of the unexploded Elti polyester resin The polyester resin toO111i containing tris(2-hydroxyethyl) isocyanurate is burnt as 20 molar or more to prepare phenol-stabilized polyisocyanate 1-1.
A compound obtained by extracting at least 3 moles of lower alkyl alcohol from a reaction product of 0 parts and 1 mole of tetraalkyl titanate and at least 5 moles of phenols is used to prepare a compound containing titanium from 0.1 to 0.1 moles of lower alkyl alcohol. The image is obtained by adding 201 L parts to each and dissolving it in a single solvent.

In the present invention, the polyester resin containing THE I C as a polyhydric alcohol component refers to a polyester resin containing THE I
In addition to C, ethylene glycol, flobylene glycol,
A product obtained by reacting glycerin, trimethylol, aliphatic polyhydric alcohol as an alcohol component, and (
Preferably, 80 moles or more of the nocaronic acid is an aromatic dicarboxylic acid). .5
Bis(3,4-cartoxyphenyl) 1.3.4-oxadiazole, cyclobencunetetracarmenic acid (its anhydride), trivalent or higher polycargenic acid of cicada, and the following (1)
Formula or formula (11) (/(ta l X r, i -0-, -CH2-, -8-
, -8o2-, iuJf)l), J r R
2+ R3 is H, -CH, -.

-C2H5-(/-+inner ⅅ"), A is -NC
O, -NH2. ) 7], G t + noamine or noisocyanate and reaction 1, the broken imide bond is a mixture of a compound having an amide-imide bond, or the above polyester side force 'rr
At the time of production, the above compounds are copolymerized and l-lyesterimide and polyesteramide-1mide are also impregnated.

In the present invention, tetraalkyl titanates and pheno-nfp
The reason why the reaction compound was limited to one in which 3 or more moles of lower alcohol produced by reacting 1 mole of tetraalkyl nathanate with at least 5 moles of phenols is that when baked at madder temperature, It does not deteriorate the appearance of the coating, and the compound becomes liquid and becomes muddy when handled. Also, reaction nyokko distribution Il
lt/! :I have at least 37 γ-L calls.
However, if the amount is less than 3 moles, the effect will be as high as 10.

In addition, the amount of the compound in titanium equivalent is 1 ester thread 1 fat 1
0.0 Ikii part to 1. -r O, 1-2. O11
The reason why the amount is limited to m5 is that if o and tlk are less than 11 m, the above-mentioned effect of -F cannot be obtained, and if it exceeds 260 parts by weight, the thermal properties of the insulating film will decrease.

The tetraalkyl titanates include tetrapropyl titanate and tetrabutyl titanate, and the phenols include phenol, cresol, and xylenol.

The reason why the amount of the phenol stabilized polyisocyanate was set at 1 to 10 parts per 100 parts of the resin is that when used in combination with the reaction product of tetraalkyl titanate and phenol, the effect of the combined use is less than 1 part by weight. This is because the amount is too thin, and if 1011 parts or more is added, the thermal and physical properties of the resulting film are reduced. As an example of a phenol stabilized polyisocyanate, three moles of tolylene diisocyanate and trithi 11--9)+1-? After reaction, phenol is added to the free incyanate group to stabilize it (for example, Nippon Polyurethane's Coro 4, -) AP Sutaple) and tolylene diisocyanate. There is a product with the following structural formula (91J, Desmosier CT Stable, manufactured by De1zbainil), which is stabilized by adding phenol to the free incyanate group in the body.

Hisashi (I will talk about the examples of contamination of this heather invention).

Proverb: Inferior f-Sili (11) Heat a cell of mahebutyl titanate (containing titanium -111) and 6 moles of cresol at 1130°C. Heat 1 and bring out 357 ln of normalzotyl-fA-col and make a solution ( P) was obtained (Titanium content: 41%) #Example (2) German Bayer u&IcT staple (51 7-enol adducts of tolylene diisocyanate) was melted in cresol to obtain a 3o chronic solution (Q).

1] 8 cases (:3) Tetraisonoropyrticunate (titanium content 16.91
) 1 mole and 6 moles of cresol,! : =i After heating at 120°C and distilling 3.7 moles of isofloglobil alcohol, it was diluted with cresol to obtain liquid #2 (R) containing titanium and 29 ml.

Example (]) 1 mol of terental sheet methyl, 0.84 mol of THEIC,
Add 03 moles of ethylene glycol into the reaction volume t1.1
A condensation reaction was carried out at 20° C. for 5 hours at 200" C1 to obtain a polyester. This resin was bath dissolved in cresol to obtain 40 ml of yarn Hoh & (A). Resin solution (A) 1 kl and bath solution (R) 20?
and Solution (Q): 3θ were added to obtain the braided cord and paint of the present invention.

The thus obtained insulating paint of the present invention was coated on a 1.0 m-thick copper wire and baked in a furnace at 500°C at a speed of 20 m/min 6 times. As a result, the surface appearance was good. An insulated wire with a &8 edge coating was obtained.

Comparative Example (1) When 3.4 N of tetraisofurovir tetanate and 30 N of Solution 1 (Q) were added to 1 ki of the solution (A) obtained by Paris at room temperature, a partially glue-like substance appeared. When this was heated to 80°C and stirred, a transparent paint was obtained.

This production system is the same as the example 1. When the tube was wrapped around a copper wire of Owmφ and baked at a speed of 20 m/min in a furnace at 500°C, many wavy spots appeared on the surface.
(So, set the furnace f11 degree to 400 degrees Celsius and set the speed to 10 m.
/ minute, we caught a whale with a good surface condition.

Example 1 (2) To 1 kg of the solution (A) obtained in Example (1), 34 g of tetraisofuropyrnathanate was added at 80°C to obtain a transparent paint. As in Example 1, this paint was applied to a 1.0 mm diameter copper wire and baked at a speed of 20 m/min in a 500°C oven, which was repeated. Example (2) 1 mol of trimellitic anhydride, 0.5 mol of cyanodiphenylmethane, and 10.4 mol of ethele carbonate were reacted, and the terminal Does it have a carboxyl group? I used lyester imidosol polymer.

To this, 1 mol of trimethyl prephthalate, 1 mol of T)IEIC, and 0.2 mol of ethylene glycol were added, and the resulting poly(L) sterimide resin was dissolved in cresol to obtain a solution <m> of 40-valent nonvolatile components.

To this solution (B) 625N, add bath & (P) 25 and the number of baths (
Q) An insulating coating of the present invention was obtained by adding 20P.

Comparative Example (3) Tetrabutyl titanate 731 and solution (Q) 209 were gradually added to solution (D) 625P obtained in Example (2) to obtain comparative soft sample 4I2.

Example (3) 0.8 mol of trimellitic anhydride, 02 mol of inphthalic acid, and 07 mol of diphenylmethane diisoleanate were reacted in cresol to obtain a polyamide-imide prepolymer in which the terminal terminal group is a xyphenyl group. .

Separately, 1.0 mol of terephthal, 1 mol of THEIC, and 0.5 mol of ethylene glycol were reacted to obtain a polyester tree Th.

So the above polyamide imidosol? The reamer and polyester side holes were mixed to form a polyester amide-imide resin, which was then dissolved in cresol and xylene to form a 301
#solution (C) was obtained.

The number of baths (C) is 1000ft and the solution (R) is 150? and ll'1k (Q) 1009 were mixed to obtain the insulating paint of the present invention.

Comparative Example (4) A comparative insulating paint was obtained by adding 26 grams of tetraisopropyl netanate and Solution (Q) 100F to Solution Q(C) 100054.

The insulating paint of the present invention and the comparative insulating paint obtained in this way were the first in the copper wire of 1.0 ws-! ! The drum cloth was baked on the row crop shown in Figure 2, and its performance was measured. The conclusion Jj1.
Fi as shown in Table 1.

As mentioned in Table 1 above, the insulating vibration material of the present invention can cause burnout.
It is extremely unnecessary in the industry because it uses an insulated WL wire with excellent appearance, electric properties, and heat resistance, while reducing the speed of the stray wire.

Claims (3)

[Claims] (1) Phenol stabilized polyincyanate 1 to 101 to polyester thread resin 100 heavy duty containing tris(2-hydroxyethyl) incyanurate as a polyhydric alcohol component of 20 moles or more of polyester thread tree Mh Quantity, and detraalkyl titanade＼
A compound obtained by distilling 3 moles or more of a lower alkyl alcohol from a reaction product of 1 mole and at least 5 moles of phenols has a titanium content of 0.1 to 2, Omxit.
1. A heat-resistant insulating paint characterized in that it is made by adding each of these parts to an organic solvent. (2) A highly heat-resistant paint according to item 1 of the patent application, wherein the polyester resin is a polyester resin having an amide or amide-imide bond. (3) The heat resistance according to item 1 of the scope of the patent application, wherein the polyester thread resin is a polyester resin in which the aromatic radical is phosphoric acid, in which 80 moles or more of the acid component constituting the ester bonds thereof Insulating paint.