KR100983761B1 - Highly heat-resistant electrical wire - Google Patents

Abstract

The present invention provides a high heat resistant insulated wire comprising an insulating layer formed of a poly (diphenylamide benzobisimidazole) polymer, a poly (diphenylamide benzobisimidazole) resin composition for the same, and a varnish for wire coating using the composition. It is about. The high heat resistant insulated wire of the present invention can be used more stably than the heat resistant wire according to the prior art at a temperature of 250 ° C. or higher without containing a halogen element, and has excellent abrasion resistance, so that it can be used for magnetic coils and motors used in electric devices. It is suitable for high heat resistance windings, especially for electric vehicle (HEV) motor wires, for aviation equipment, for naval equipment and for military communication equipment.

Poly (diphenylamide benzobisimidazole), high heat resistance

Description

High heat-resistant insulated wire {HIGHLY HEAT-RESISTANT ELECTRICAL WIRE}

The present invention relates to a resin composition constituting an insulating layer of a high heat resistant insulated wire and a high heat resistant wire using the composition. More specifically, the present invention relates to wires usable at temperatures above 250 ° C.

As electrical and electronic devices become smaller and higher in density, the heat resistance requirements of electric wires used in parts of electric equipment are becoming more demanding. Heat-resistant electric wires, which are traditionally used for high heat generation electric products, are also more heat-resistant according to the trend of increased capacity and safety of products. You are in a situation where you need to raise. For example, magnetic coils used in electrical equipment, high heat-resistant windings for motors, especially wires for hybrid electric vehicle (HEV) motors, aviation equipment, naval equipment, military communications equipment and electrical / electronic harnesses Electric wires for harness should be excellent in electrical, mechanical and chemical performance, such as being able to be used even in very harsh conditions such as high temperature and high temperature while reducing the thickness of the insulation coating for ultra-light weight.

In the prior art, in order to support such high heat resistance and chemical stability, an insulating layer composed mainly of fluorine resin or polyesterimide, polyimide, and polyamideimide paper resin have been used.

However, fluorine resins such as tetrafluoroethylene contain fluorine, which is a halogen element, and thus are not preferable in the current situation where the allowable field of use is gradually reduced in the situation where environmental regulations and safety requirements are reinforced, and polyesterimide, polyamideimide, In the case of the polyimide, the usable temperatures are about 180 ° C., 200 ° C. and 220 ° C., respectively.

For this reason, the field has continued to study the high heat-resistant insulated wire that can be used stably at a temperature of 250 ℃ or more, and the present situation has not been satisfactory.

The technical problem of this invention can be used at the temperature of 250 degreeC or more, without containing a halogen element, and is providing the resin composition for coating insulation layers, the coating varnish of a high heat resistant electric wire excellent in abrasion resistance, and the insulated wire using the same.

In order to achieve this technical problem, the present inventors provide a heat resistant composition for insulated wire comprising a poly (diphenylamide benzobisimidazole) polymer. In this invention, the varnish for electric wire coating using such a heat resistant composition is also provided together. The varnish according to the present invention comprises a solid comprising a poly (diphenylamide benzobisimidazole) polymer and a solvent, wherein the solid concentration is 5 to 40% by weight.

The present invention also provides a heat-resistant insulated wire comprising a conductor and an insulating layer surrounding the conductor, the insulating layer formed of a poly (diphenylamide benzobisimidazole) polymer.

Since the poly (diphenylamide benzobisimidazole) insulated wire according to the present invention has high heat resistance and excellent wear resistance higher than 250 ° C, it is suitable as an insulating layer for wires requiring high heat resistance such as windings for motors and alternator wires. .

The insulating layer of the high heat resistance insulated wire according to the present invention is characterized by including a poly (diphenylamide benzobisimidazole) polymer (hereinafter abbreviated as PDPABI). The PDPABI resin according to the present invention comprises a benzobisimidazole ring in the repeating unit followed by two para -phenylene units, which are interposed with an amide functional group. The amide group can be linked to the benzobisimidazole ring in one repeating unit in two directions, on the carbonyl side and on the amide nitrogen side, with no particular restriction on this orientation in the PDPABI resin according to the invention. One example of the PDPABI resin according to the present invention is shown in the formula (1).

Although Formula 1 inevitably indicates that the amide functional groups in all repeating units are linked to the benzobisimidazole ring through the carbonyl group carbon, the PDPABI polymer according to the present invention actually has the benzobisimime in the opposite direction, ie in one repeating unit. It is to be understood that the azole functional group may be linked to the amide group via the nitrogen atom, and the polymer represented by the formula (1) also includes such repeating units. This point also applies to other chemical formulas below.

The method for preparing the PDPABI resin according to the present invention is not particularly limited to any one method, but the following formula 2 may be a preferred synthesis example. In this manner, a PDPABI polymer according to the present invention can be obtained by condensation polymerization of a substituted or unsubstituted tetraaminobenzene monomer with a substituted or unsubstituted dicarboxydiphenylamide monomer.

In the above formula, R ₁ , R _{2 ,} R _m , R _n is a functional group selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, a vinyl group, an acryl group, a methacryl group and a hydroxyl group, each of R ₁ , R _{2 ,} R _m , R _n may be the same or different. In the dicarboxylic diphenylamide molecule, R _m and R _n may be substituted at either ortho or both meta positions of the benzene ring based on the amide group. However, R and R ^* _m ^* _n is thus the two-directional possible to create a multi-carboxyl-diphenyl-amide and tetra-aminobenzene the amide bond in the reaction product, R _m and R _n each , Or alternatively, R _n and R _m , which can be varied for each repeating unit.

PDPABI polymer according to the present invention preferably has a molecular weight of 10,000 ~ 100,000. When the molecular weight of the PDPABI polymer is within the above range, the viscosity property is good and preferable.However, if the molecular weight is less than 10,000, the viscosity is so low that smooth coating becomes difficult due to flow down during the coating operation, and when the molecular weight exceeds 100,000, the viscosity becomes too high It's not good because you get too much work.

In the synthesis example represented by the formula (2) it is necessary to remove the water generated by the addition of a dehydrating agent for the condensation polymerization reaction, the dehydrating agent is phosphorus pentoxide (P ₂ O ₅ ) and substituted methyl sulfonate CX ₃ SO ₃ H (where X is preferably a dehydrating agent containing hydrogen or fluorine), a polyphosphoric acid (PPA) dehydrating agent, or a mixed dehydrating agent of phosphoric acid and phosphorus pentoxide.

The PDPABI resin of the present invention thus obtained is coated and baked on a conductor for electric wire in the form of varnish to form an insulating layer of a high heat resistant insulated wire. PDPABI is dissolved in a suitable solvent for coating and baking to form varnishes. At this time, varnish solvents include basic solvents such as dimethylacetamide (DMA), dimethylformamide (DMF) and N -methylpyrrolidone (NMP). Is preferred. The concentration of PDPABI solids in the varnish may be 1 to 80% by weight, more preferably 5 to 40% by weight. When the concentration of PDPABI solids in the varnish is less than 5% by weight, the amount of PDPABI constituting the insulating resin layer is insufficient to satisfy heat and abrasion resistance, or when an excess solvent is used, and the concentration of solids exceeds 40% by weight. The viscosity of the varnish becomes excessive, and smooth coating and baking become difficult.

The PDPABI varnish according to the present invention may further include, in addition to the PDPABI polymer and the solvent, additional ingredients suitably selected according to the use. Examples of such additive components include radical polymerization initiators, copper antioxidants, thickeners, surfactants, etc., which are added when the degree of polymerization of the PDPABI polymer is low. The amount of these additives is suitably 0.5 to 10 parts by weight based on 100 parts by weight of the PDPABI resin in the solid.

The PDPABI insulated wire according to the present invention comprises a conductor layer made of a conductive material such as copper and a PDPABI insulated layer surrounding the same. In addition to the conductor layer and the insulating layer, other conventional components (other coating layers, sheath layers, braids, etc.) constituting the insulated wire may be included. In the case of cables for special fields such as aviation, military, etc., there may be additional configuration appropriate for the application.

The present invention will be described in more detail with reference to the following Examples. The average person skilled in the art to which the present invention pertains may change the present invention in various other forms in addition to the embodiments described in the following examples, and the following examples merely illustrate the present invention, and the scope of the technical spirit of the present invention is given below. It is not to be construed as limiting the scope of the examples.

In order to evaluate the performance of the insulated wire having a PDPABI insulating layer according to the present invention, an Example and Comparative Example insulating resin composition was prepared, and coated with copper wire to prepare an insulated wire specimen having a PDPABI insulating layer.

Example  One

EXAMPLES To synthesize PDPABI of the insulating layer, 50 g of polyphosphoric acid was added to 10 mmol of tetraaminobenzene and heated at 120 ° C. for 25 minutes. Thereafter, 10 mmol of dicarboxydiphenylamide was added thereto, followed by polymerization at 170 ° C. for 6 hours to prepare PDPABI represented by Chemical Formula 1. The PDPABI was dissolved in NMP solvent to have a concentration of 15% by weight to prepare an insulating layer forming varnish. A varnish was coated on a bare copper wire having a diameter of 1.000 mm using a conventional method and baked to prepare an insulated wire.

Example  2

70-30 parts by weight of N -methylpyrrolidone and xylene were used as a solvent in a reactor equipped with a reflux device, and 4,4'-diphenylmethane diisocyanate (MDI) and trimellitic anhydride (TMA) were used at a ratio of 1 to 1.04. The reaction yielded a polyamideimide varnish.

A polyamideimide varnish made of the first insulating layer was applied to have a thickness of 5 micrometers, and PDPABI was applied to the second insulating layer on the first insulating layer as in Example 1.

Example  3

The polyamideimide varnish prepared in Experimental Example 2 was applied to the first insulating layer to 15 micrometers, and PDPABI was applied to the second insulating layer on the first insulating layer, as in Example 1.

Comparative example  One

A bare wire having a diameter of 1.4 mm was used to coat and bake in an ordinary manner using the polyamideimide varnish prepared in Example 2 as the insulating layer to prepare an insulated wire.

Comparative example  2

Using a copper wire having a diameter of 1.4 mm, a polyester imide (DuPont THEIC E 3533) varnish was used as the first insulating layer, and the polyamideimide varnish prepared in Example 2 was used as the second insulating layer, and then coated in a conventional manner. And baked to prepare an insulated wire.

Comparative example  3

A bare wire having a diameter of 1.5 mm was used to coat and bake an insulated wire by a conventional method using a polyester (Altana DEATHERM T 810) varnish as an insulating layer.

Physical properties such as insulation breakdown voltage, high temperature insulation breakdown voltage, flame retardant temperature, thermal shock resistance and external appearance were evaluated for the Examples and Comparative Examples insulated wires obtained as described above.

Appearance : The appearance of the electric wire was evaluated by visual inspection.

Pinhole was measured according to regulations of KS C 3006 Standards.

Film flaw : measured according to the provisions of KS C 3006

Insulation breakdown voltage : The insulation breakdown voltage of the electric wire was measured according to the JIS C 3005 standard.

High Temperature Breakdown Voltage : 250 ° C x 168h heat treatment followed by breakdown voltage test.

Flame retardant temperature : measured according to the standard of KS C 3006.

Heat shock : The heat shock of the wire was measured according to the standard of KS C 3006.

The physical property evaluation results of the insulated wire manufactured according to the Example and the comparative example are summarized in Table 1 below.

unit Example number Comparative example number One 2 3 One 2 3 Exterior ━ Good Good Good Good Good Good Outer diameter mm 1.474 1.471 1.472 1.467 1.583 1.604 Conductor mm 1.399 1.401 1.401 1.400 1.499 1.502 Film thickness mm 0.038 0.036 0.036 0.034 0.042 0.051 Pinhole amount 0 0 0 0 0 0 Film defect - Good Good Good Good Good Good Wear resistance gf 1231 1344 1226 1057 1664 1131 Breakdown Voltage kV 13.1 12.2 12.1 8.20 9.00 8.40 Breakdown voltage (high temperature) kV 9.00 9.50 10.8 5.70 4.10 ━ Flame retardant temperature ℃ 452 454 447 399 382 318 Heat-resistant shock ━ Good Good Good Good Good Bad

Example insulated wires with a PDPABI insulator layer according to the present invention were comparable in appearance and thermal shock resistance as compared with the comparative wires according to the prior art. However, the embodiment wire according to the present invention showed a significantly improved performance compared to the prior art in terms of heat resistance, which can be defined as the softening temperature and the high temperature breakdown voltage.

As described above, an embodiment according to the present invention has been disclosed. The terminology used in the description and examples herein is for the purpose of describing the invention in detail to those skilled in the art, and is intended to limit the scope of the invention in any particular sense or in the claims. It was not intended.

Claims (15)

Heat-resistant composition for insulated wire containing poly (diphenylamide benzobisimidazole) polymer. The heat resistant composition for an insulated wire according to claim 1, wherein the repeating unit constituting the poly (diphenylamide benzobisimidazole) polymer has a structure of Formula 3 or Formula 4 below.

Wherein in the above formula R ₁ , R _{2 ,} R _m And R _n is a functional group selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, a vinyl group, an acryl group, a methacryl group, and a hydroxyl group, wherein each of R ₁ , R _{2 ,} R _m , and R _n is the same R _m may be placed in the ortho or meta site on the basis of the carbonyl group in formula (3) or on the amide nitrogen of formula (4), wherein R _n is ortho and meta based on the amide nitrogen of formula (3) or the carbonyl group of formula (4) Can be set in place. The method of claim 2, R ₁ , R _{2 , and} R _m And R _n is a hydrogen atom. The method of claim 1, The poly (diphenylamide benzobisimidazole) polymer has a molecular weight of 10,000 to 100,000, wherein the heat-resistant composition for insulated wire. A solid coating comprising a poly (diphenylamide benzobisimidazole) polymer and a solvent, wherein the solid content concentration is 5 to 40% by weight. The varnish for electric wire coating according to claim 5, wherein the repeating unit constituting the poly (diphenylamide benzobisimidazole) polymer has a structure of Formula 5 or Formula 6 below.

Wherein in the above formula R ₁ , R _{2 ,} R _m And R _n is a functional group selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, a vinyl group, an acryl group, a methacryl group, and a hydroxyl group, wherein each of R ₁ , R _{2 ,} R _m , and R _n is the same R _m may be placed in the ortho or meta site based on the carbonyl group in the formula (5) or on the amide nitrogen of the formula (6), wherein R _n is ortho and meta based on the amide nitrogen of the formula (5) or the carbonyl group of the formula (6) Can be set in place. The method of claim 6, R ₁ , R _{2 , and} R _m And R _n is a hydrogen atom, the varnish for wire coating. The method of claim 5, The poly (diphenylamide benzobisimidazole) polymer has a molecular weight of 10,000 to 100,000, the varnish for electric wire coating. The method of claim 5, The varnish is 0.5 to 10 with respect to 100 parts by weight of poly (diphenylamide benzobisimidazole) at least one additive selected from the group consisting of a radical polymerization initiator, an antioxidation agent, a thickener, an antifoaming agent, a surface tension lowering agent and a surfactant. An electric wire coating varnish further comprising a weight part. The method of claim 5, And the solvent is selected from the group consisting of dimethylacetamide (DMA), dimethylformamide (DMF) and N -methylpyrrolidone (NMP). Conductor and An insulated wire comprising an insulating layer surrounding the conductor, The insulating layer is a heat-resistant insulated wire, characterized in that formed of a poly (diphenylamide benzobisimidazole) polymer. The heat-resistant insulated wire according to claim 11, wherein the repeating unit constituting the poly (diphenylamide benzobisimidazole) polymer has a structure of Formula 7 or Formula 8 below.

Wherein in the above formula R ₁ , R _{2 ,} R _m And R _n is a functional group selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, a vinyl group, an acryl group, a methacryl group, and a hydroxyl group, wherein each of R ₁ , R _{2 ,} R _m , and R _n is the same R _m may be placed in the ortho or meta site based on the carbonyl group in formula (7) or on the amide nitrogen of formula (8), wherein R _n is ortho and meta based on the amide nitrogen of formula (5) or the carbonyl group of formula (6) Can be set in place. The method of claim 12, R ₁ , R _{2 , and} R _m And R _n is a hydrogen atom. The method of claim 11, The poly (diphenylamide benzobisimidazole) polymer has a molecular weight of 10,000 to 100,000. The method of claim 11, The insulating layer may include at least one additive selected from the group consisting of a radical polymerization initiator, an antioxidant, a thickener, an antifoaming agent, a surface tension reducing agent, and a surfactant based on 100 parts by weight of a poly (diphenylamide benzobisimidazole) polymer. A heat resistant insulated wire, further comprising 0.5 to 10 parts by weight based on 100 parts by weight of poly (diphenylamide benzobisimidazole).