CN111675964B - Polyamide-imide varnish, insulating film, insulated wire, coil, and motor - Google Patents
Polyamide-imide varnish, insulating film, insulated wire, coil, and motor Download PDFInfo
- Publication number
- CN111675964B CN111675964B CN202010587126.9A CN202010587126A CN111675964B CN 111675964 B CN111675964 B CN 111675964B CN 202010587126 A CN202010587126 A CN 202010587126A CN 111675964 B CN111675964 B CN 111675964B
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- Prior art keywords
- polyamide
- varnish
- imide
- insulated wire
- imide varnish
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
- H01B3/306—Polyimides or polyesterimides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/308—Wires with resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/02—Disposition of insulation
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02K—DYNAMO-ELECTRIC MACHINES
- H02K3/00—Details of windings
Abstract
The invention provides a polyamide-imide varnish, an insulating film, an insulated wire, a coil and a motor. The acid in the raw materials of the polyamide-imide varnish comprises tricarboxylic anhydride and acid dianhydride, wherein the mole percentage of the acid dianhydride in the acid is 5-50%.
Description
Technical Field
The present invention relates to a polyamide-imide varnish, an insulating film, an insulated wire, a coil, and a motor.
Background
In order to achieve a reduction in size and an increase in output of motors, very severe processing of winding wires has been started, and high flexibility is required as winding wire characteristics. Polyimide is a typical material having excellent flexibility, but in reality, it is an extremely expensive material and has poor storage stability, so that it has to be stored in a frozen state and is not widely used. On the other hand, polyamideimide is an inexpensive material having good heat resistance, but has a problem that it is poor in flexibility and cannot withstand the severe processing described above.
Disclosure of Invention
Technical problem to be solved by the invention
The purpose of the present invention is to provide a polyamide-imide varnish which can maintain solubility, has excellent flexibility, and can withstand severe processing, an insulated wire obtained using the varnish, a method for producing the insulated wire, a coil obtained using the insulated wire, and a motor having the coil.
Means for solving the problems
In a first aspect, the invention provides a polyamide imide varnish, wherein the acid in the raw materials of the polyamide imide varnish comprises tricarboxylic anhydride and acid dianhydride, and the molar percentage of the acid dianhydride in the acid is 5-50%.
According to the present invention, the polyamideimide is denatured by an acid dianhydride in the skeleton to increase the number of imide groups while maintaining solubility, thereby improving the flexibility of the polyamideimide and allowing it to withstand severe processing.
Preferably, the weight average molecular weight of the polyamideimide resin in the polyamideimide varnish is 3000 to 100000.
Preferably, the acid dianhydride is at least one selected from ethylene glycol bis (trimellitic anhydride) ester and 1,2,3, 4-butane tetracarboxylic dianhydride.
Preferably, the tricarboxylic acid anhydride is trimellitic anhydride.
In a second aspect, the present invention provides an insulated wire comprising a conductor and an insulating film obtained using any of the above polyamideimide varnishes.
In a third aspect, the present invention provides a coil obtained using the above insulated wire.
In a fourth aspect, the present invention provides an electric motor comprising the above-described coil.
Effects of the invention
According to the present invention, there can be provided a polyamideimide varnish which can maintain solubility and is excellent in performance, and an insulated wire formed using the polyamideimide varnish has excellent flexibility and puncture resistance, and a method for producing the same.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
Disclosed herein is a polyamideimide varnish, wherein acids in raw materials of the polyamideimide varnish include a tricarboxylic acid anhydride and an acid dianhydride. The mol percentage of the acid dianhydride in the acid is 5 to 50 percent. If the molar ratio is less than 5%, the effect of high flexibility is difficult to obtain; if the molar ratio is more than 50%, the cost is too high, and therefore it is not preferable. In addition, in the range of 5% to 50%, the larger the molar percentage of acid dianhydride in the acid, the more the elongation of the insulating film obtained from the polyamideimide varnish becomes, and the more advantageous the processing becomes. In one embodiment, the molar percentage of acid dianhydride in the acid is greater than 40% and less than 50%.
In some embodiments, the acid consists of a tricarboxylic anhydride and an acid dianhydride.
In some embodiments, the molar ratio of acid dianhydride to the sum of the tricarboxylic anhydride and acid dianhydride is from 5% to 50%.
The weight average molecular weight of the resin in the polyamide-imide varnish is 3000-100000. The weight average molecular weight is a value measured by Gel Permeation Chromatography (GPC). If the weight average molecular weight is less than 3000, the toughness of the coating film decreases, and if the weight average molecular weight is more than 100000, the viscosity of the varnish becomes too high, and the handling property deteriorates.
The acid dianhydride may be at least one selected from ethylene glycol bis (trimellitic anhydride) ester (TMEG) and 1,2,3, 4-butanetetracarboxylic dianhydride (BT). TMEG and BT have a lower proportion of aromatic structures or do not contain aromatic structures than other acid dianhydrides such as BTDA, and therefore are highly soluble in an imidizing solvent, and can form a varnish without clouding even when used in a large amount. More preferably, the acid dianhydride is BT. Because BT is cheaper and less costly than TMEG and the like.
As the tricarboxylic acid anhydride, trimellitic anhydride (TMA) or the like can be used.
The raw material of the polyamide-imide varnish further comprises isocyanate, preferably diisocyanate. Examples thereof include aromatic diisocyanates such as diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), diphenyl Ether Diisocyanate (EDI), Naphthalene Diisocyanate (NDI), Phenylene Diisocyanate (PDI), Xylylene Diisocyanate (XDI), diphenyl Sulfone Diisocyanate (SDI), dimethylbiphenyl diisocyanate (TODI) and dimethoxyaniline diisocyanate (DADI), isocyanates having a biphenyl structure, isomers thereof, polyfunctional isocyanates and polymeric isocyanates such as aliphatic diisocyanates such as Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H-MDI) and hydrogenated XDI, triphenylmethane triisocyanate, and polymers such as TDI. These isocyanates may be used singly or in combination of two or more.
The polyamide-imide varnish contains a solvent in addition to the resin. The solvent is not particularly limited, and is generally an organic solvent. For example, at least one selected from the group consisting of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), and xylene.
The following is an example of the preparation of the polyamideimide varnish.
Dissolving raw materials of the polyamide-imide varnish into a reaction solvent, and heating to 50-150 ℃ until the reaction is continued to a specified viscosity. The predetermined viscosity is, for example, 2000cps or more. The feed ratio of acid to isocyanate may be stoichiometric. The reaction solvent is selected from, for example, N-methyl-2-pyrrolidone (NMP), γ -butyrolactone, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), Dimethylimidazolidinone (DMI), cyclohexanone, methylcyclohexanone, and the like. When the viscosity reaches the specified value, the resin can be diluted by a solvent until the resin concentration is 20-40 wt%.
The polyamide-imide varnish of the present invention has excellent solubility and can be transparent.
In one embodiment, the insulating film is obtained by coating and baking a polyamide-imide varnish. The insulating film has excellent flexibility.
When the coated substrate is a conductor, an insulated wire can be obtained.
The insulated wire according to the embodiment of the present invention may be wound into a coil. For example, the coil may be formed by winding the core (e.g., a core made of a magnetic material) on the outside thereof.
The coil can be used for manufacturing motors, such as EV and HEV motors.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
In the following examples, TMEG was New Japanese physicochemical TMEG-100; BT uses リカシッド BT-100 of new Japan physicochemical; BTDA (benzophenone tetracarboxylic dianhydride) is available from Tokyo chemical Co., Ltd, and PMDA (1,2,4, 5-pyromellitic dianhydride) is available from Tokyo chemical industry Co., Ltd.
Preparation of polyamide-imide varnish.
Example 1.
Adding dehydrated NMP into a three-neck flask with a stainless steel stirring wing, adding TMA, TMEG and MDI into the three-neck flask, stirring and dissolving, heating the mixture to 120 ℃, reacting for a period of time, and diluting the mixture with xylene until the resin concentration reaches 30 wt% to obtain the polyamide-imide varnish with the viscosity of 2000 cps. The amounts of the raw materials are shown in Table 1.
In the same manner as in the other examples and comparative examples, the components of the polyamideimide varnish were adjusted by changing the kind and amount of the raw material acid dianhydride. The amounts of the raw materials are shown in Table 1.
TABLE 1 tables of raw materials recipes for examples 1 to 13 and comparative examples 1 to 4 (in the tables, the units of numerical values are g)
A method for manufacturing an insulated wire.
An enameled wire was produced using the above polyamideimide varnish, specifically, copper was cast, drawn, and softened to obtain a conductor having a circular cross section and an average diameter of 1mm, and the varnish for forming an insulation layer produced by the above method was applied to the outer peripheral surface of the conductor and fired under conditions that the inlet temperature of a heating furnace was 350 ℃ and the outlet temperature of the heating furnace was 450 ℃, so that the insulation layers were laminated to obtain an insulated wire. The insulating layer was a single layer and had an average thickness of 35 μm.
A method for measuring flexibility.
The flexibility is an index indicating the toughness of the coating film, and the flexibility test is evaluated in accordance with JIS C3216-320115.1.1. In the column of "flexibility" in table 2, 1d represents the diameter of the wire itself. For example, if the wire is a wire having a diameter of 1.0mm, it is marked as 1d when it is wound around a rod having a diameter of 1.0mm without being cracked. 2d is 2.0 mm. If the cracking at 1d is not occurred at 2d, it is designated as 2 d. If the crack is 2d and the crack is not 3d, it is designated as 3 d.
Film elongation measuring method.
The varnish was cast on glass with a bar coater (bar coater), and after heat curing at 180 ℃ for 1 hour and at 200 ℃ for 1 hour, the film was peeled off from the glass to give a film of 40 μm. The film was subjected to a tensile test, and the elongation at break was defined as the film elongation.
2 twist breakdown voltage (BDV): measured according to the test method described in JIS C3003, item 10. That is, a 12cm long portion of the test piece was twisted at a predetermined twist number, an alternating voltage was applied between the wires, and the voltage at the time of breakage was obtained by increasing the voltage at 500V/sec.
TABLE 2 Performance test Table for Polyamide-imide varnish and insulated wire
In comparative example 2, only 5% of PMDA was added to lower the solubility, and the film was not formed continuously because turbidity was generated by precipitation during the production of the varnish. From comparative examples 3 and 4, it is clear that when BTDA is used as the acid dianhydride, only 15 mol% of BTDA can be added at most from the viewpoint of solubility, and when 20 mol% is added, the solubility is lowered, and turbidity is generated by precipitation during the production of varnish, and continuous film formation cannot be performed. Examples 1 to 13 are superior in flexibility, and the insulation property after heat deterioration is maintained, compared with comparative examples 1 and 3, and the flexibility is improved while the heat resistance as the polyamideimide is maintained, and the film elongation is large and the processability is good.
Claims (4)
1. The polyamide-imide varnish is characterized in that acids in raw materials of the polyamide-imide varnish are tricarboxylic anhydride and acid dianhydride, and the mole percentage of the acid dianhydride in the acids is 10-50%; the acid dianhydride is at least one selected from ethylene glycol bis (trimellitic anhydride) ester and 1,2,3, 4-butane tetracarboxylic dianhydride; the tricarboxylic anhydride is trimellitic anhydride; the raw materials of the polyamide-imide varnish also comprise isocyanate, wherein the isocyanate is selected from at least one of aromatic diisocyanate or isocyanate with a biphenyl structure and isomers thereof, aliphatic diisocyanate, polyfunctional isocyanate and polymeric isocyanate; the raw material of the polyamide-imide varnish also comprises a solvent, wherein the solvent is selected from at least one of N-methyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylacetamide, N-dimethylformamide, dimethyl imidazolidinone, cyclohexanone, methylcyclohexanone and xylene; the weight average molecular weight of the polyamide-imide resin in the polyamide-imide varnish is 3000-100000.
2. An insulated wire comprising a conductor and an insulating film obtained by using the polyamideimide varnish according to claim 1.
3. A coil obtained using the insulated wire according to claim 2.
4. An electric motor comprising the coil of claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010587126.9A CN111675964B (en) | 2020-06-24 | 2020-06-24 | Polyamide-imide varnish, insulating film, insulated wire, coil, and motor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010587126.9A CN111675964B (en) | 2020-06-24 | 2020-06-24 | Polyamide-imide varnish, insulating film, insulated wire, coil, and motor |
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| Publication Number | Publication Date |
|---|---|
| CN111675964A CN111675964A (en) | 2020-09-18 |
| CN111675964B true CN111675964B (en) | 2021-10-12 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1855316A (en) * | 2005-04-25 | 2006-11-01 | 日立卷线株式会社 | Polyamide-imide resin insulating coating material, insulated wire and method of making the same |
| CN101597462A (en) * | 2008-06-04 | 2009-12-09 | 日立卷线株式会社 | Polyamide-imide resin insulating coating material and the insulated line that has used this coating |
| CN101636432A (en) * | 2007-02-09 | 2010-01-27 | Lg化学株式会社 | The polyimide for preparing the method for polyimide and use this method to make |
| CN102206464A (en) * | 2010-03-30 | 2011-10-05 | 日立卷线株式会社 | Insulating varnish and insulated wire formed by using the same |
| CN103370371A (en) * | 2011-02-01 | 2013-10-23 | Dic株式会社 | Thermosetting resin composition, cured product thereof, and interlayer adhesive film for printed wiring board |
| CN109293920A (en) * | 2018-09-25 | 2019-02-01 | 住井工业（湖南）有限公司 | Resin combination and the insulated electric conductor for using it |
| CN109935392A (en) * | 2019-03-14 | 2019-06-25 | 住井工业（湖南）有限公司 | Insulated electric conductor varnish, insulated electric conductor and motor |
-
2020
- 2020-06-24 CN CN202010587126.9A patent/CN111675964B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1855316A (en) * | 2005-04-25 | 2006-11-01 | 日立卷线株式会社 | Polyamide-imide resin insulating coating material, insulated wire and method of making the same |
| CN101636432A (en) * | 2007-02-09 | 2010-01-27 | Lg化学株式会社 | The polyimide for preparing the method for polyimide and use this method to make |
| CN101597462A (en) * | 2008-06-04 | 2009-12-09 | 日立卷线株式会社 | Polyamide-imide resin insulating coating material and the insulated line that has used this coating |
| CN102206464A (en) * | 2010-03-30 | 2011-10-05 | 日立卷线株式会社 | Insulating varnish and insulated wire formed by using the same |
| CN103370371A (en) * | 2011-02-01 | 2013-10-23 | Dic株式会社 | Thermosetting resin composition, cured product thereof, and interlayer adhesive film for printed wiring board |
| CN109293920A (en) * | 2018-09-25 | 2019-02-01 | 住井工业（湖南）有限公司 | Resin combination and the insulated electric conductor for using it |
| CN109935392A (en) * | 2019-03-14 | 2019-06-25 | 住井工业（湖南）有限公司 | Insulated electric conductor varnish, insulated electric conductor and motor |
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| CN111675964A (en) | 2020-09-18 |
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Denomination of invention: Polyamide Imide varnish, insulating film, insulated wire, coil and motor Effective date of registration: 20230607 Granted publication date: 20211012 Pledgee: Shenzhen small and medium sized small loan Co.,Ltd. Pledgor: Zhujing Technology (Shenzhen) Co.,Ltd. Registration number: Y2023980043158 |
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