Disclosure of Invention
Technical problem to be solved by the invention
In view of the above problems, an object of the present invention is to provide a polyamideimide varnish in which nanosilica is uniformly dispersed, and a film obtained using the polyamideimide varnish has high toughness, better V-t characteristics than commercially available surge-resistant polyamideimide varnish, and can withstand severe motor processing, and a method for preparing the same and use thereof.
Means for solving the problems
The first invention provides a polyamideimide varnish obtained by dispersing nano silica surface-modified with a silane coupling agent in a polyamideimide precursor solution, wherein the silane coupling agent contains two or more silane coupling agents, at least one of which is an amino silane coupling agent.
According to the invention, the nano-silica surface-modified by the silane coupling agent containing the amino silane coupling agent has excellent compatibility with the polyamide imide precursor solution, and can be uniformly dispersed in the polyamide imide precursor solution.
Preferably, the silane coupling agent contains at least one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and a non-amino silane coupling agent.
Preferably, the weight average molecular weight of the polyamide-imide precursor is 3000-200000.
Preferably, the particle size of the nano silica is 100nm or less.
Preferably, the polyamide imide varnish is obtained by mixing and stirring a polyamide imide precursor solution and a colloidal nano silica solution treated by a silane coupling agent.
Preferably, the mass of the silane coupling agent is 1-20% of the mass of the silica in the colloidal nano silica solution.
Preferably, the method of stirring is mechanical stirring, for example stirring with a helical stirrer.
Preferably, the amount of the nanosilica added to the polyamideimide precursor is 5 to 50% by weight.
The second invention provides a film obtained using any one of the above polyamideimide varnishes.
The third invention provides a coil provided with the film.
Effects of the invention
According to the present invention, there can be provided a polyamideimide varnish in which nanosilica is uniformly dispersed, and a polyamideimide coating film which has high toughness, better V-t characteristics than commercially available surge-resistant polyamideimide varnish, and can withstand severe motor processing.
Detailed Description
The present invention is further described below in conjunction with the following embodiments, which are to be understood as merely illustrative, and not restrictive, of the invention.
The polyamide-imide varnish according to an embodiment of the present invention is obtained by dispersing nano silica surface-modified with a silane coupling agent in a polyamide-imide precursor solution, wherein the silane coupling agent contains two or more silane coupling agents, and at least one of the silane coupling agents is an amino silane coupling agent.
The amino silane coupling agent is a silane coupling agent having an amino group in the molecule, wherein the amino group may be-NH2Or may be-NH2And at least one hydrogen on the above group is substituted with a substituent selected from, for example, alkyl, alkenyl, phenyl, and the like.
Examples of the amino silane coupling agent include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane.
In some embodiments, the silane coupling agent comprises an amino silane coupling agent and a non-amino silane coupling agent. The non-amino silane coupling agent refers to a silane coupling agent having no amino group in the molecule.
Examples of the non-amino silane coupling agent include silane coupling agents containing at least one of an epoxy group, an acryloxy group, a methacryloxy group, a vinyl group, a styryl group, and an acid anhydride in a molecule; alkoxysilanes, and the like.
The polyamideimide precursor solution contains a polyamideimide precursor and a solvent. The solvent is not particularly limited, and may be an organic solvent, and may be at least one selected from the group consisting of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, and xylene.
Polyamideimide precursors include any polyamideimide precursor material derived from a diisocyanate and/or diamine and a triacid anhydride monomer and capable of being converted to a polyamideimide.
The polyamideimide precursor may have a weight average molecular weight of 3000 to 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 particle size of the nano-silica dispersed in the polyamide-imide varnish may be 100nm or less, and preferably 10 to 100 nm. The toughness of the coating can be improved by adjusting the particle size of the dispersed nano-silica to 100nm or less.
In some embodiments, the polyamideimide varnish is obtained by mixing and stirring a polyamideimide precursor solution (also referred to as a base varnish) with a colloidal nanosilica solution treated with a silane coupling agent, wherein the silane coupling agent contains two or more silane coupling agents, at least one of which is an amino silane coupling agent.
The polyamideimide precursor solution may be used as it is in commercial products, or may be prepared by methods known in the art.
The colloidal nano-silica solution treated by the silane coupling agent is obtained by treating the colloidal nano-silica with the silane coupling agent.
Colloidal nanosilica (or called colloidal silica, silica sol) refers to a colloid in which nano-sized silica (or called nano-silica) has been dispersed in a solvent.
In the present embodiment, colloidal nanosilica is used, and the affinity between the nanosilica and the polyamideimide precursor can be improved by surface-treating the nanosilica with a silane coupling agent, and the silica particles can maintain the original particle diameter after the colloidal nanosilica and the polyamideimide precursor are mixed and after the polyamideimide varnish is formed into a film as described below. That is, the silica in the resulting polyamideimide varnish was dispersed in a nano size. Thus, the light was not scattered, and the polyamideimide varnish was transparent. Moreover, the polyamideimide varnish has good storage stability. The coating film of the polyamide-imide varnish has good toughness. If the nano silica powder is used as it is, it is agglomerated into secondary, tertiary, and quaternary particles, and it is difficult to break the particles by means of ultrasound or the like. The polyamide-imide varnish thus obtained is very cloudy and the toughness and electrical characteristics of the coating film are poor. In the present embodiment, a plurality of silane coupling agents are used, at least one of which is an amino silane coupling agent, and if only the amino silane coupling agent is used, the affinity with the resin increases, but the affinity with the varnish decreases, and aggregation occurs, resulting in turbidity. Further, if only the amino silane coupling agent is used, the colloidal silica itself is gelled with time.
The nano-sized silica in the colloidal nanosilica has a size of the order of nanometers in at least one dimension, and preferably has a size of the order of nanometers in each dimension. In a preferred embodiment, the nanosilica has a size in at least one dimension of 5 to 100 nm. This makes it possible to impart surge resistance without impairing the toughness of the obtained coating film.
The solvent in the colloidal nanosilica is an organic solvent, and may be, for example, at least one selected from the group consisting of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, and xylene.
The concentration of silica in the colloidal nano-silica can be 5 to 40 wt%. Colloidal silica can be prepared on its own or purchased.
The amount of the silane coupling agent used may be 1 to 20%, preferably 5 to 20% by mass of the silica in the colloidal nano silica, whereby the affinity with the polyamideimide varnish can be improved. The amount of the amino silane coupling agent used in the silane coupling agent may be 1 to 5% by mass of the silica in the colloidal nanosilica, and in this range, gelation of the colloidal silica can be prevented.
In one example, the colloidal nanosilica is mixed with a silane coupling agent and stirred to obtain a colloidal nanosilica solution treated with the silane coupling agent. The stirring method may be a usual stirring method, for example, a usual mechanical stirring method. The stirring temperature can be 20-70 ℃, and the stirring time can be 1-24 hours.
The mixing ratio of the polyamide imide precursor solution to the colloidal nano-silica solution treated by the silane coupling agent is preferably as follows: the amount of the nanosilica added is 5 to 50 wt% relative to the polyamideimide precursor. The amount of the nanosilica added is more preferably 10 to 30% by weight from the viewpoint of achieving both surge resistance and processing resistance.
The method of mixing and stirring the polyamideimide precursor solution and the colloidal nanosilica solution treated with the silane coupling agent may be a general stirring method, for example, a general mechanical stirring method. The stirring temperature can be 20-70 ℃, and the stirring time can be 1-24 hours. In the present embodiment, the nano-silica can be uniformly dispersed in the polyamideimide precursor solution by a general stirring method without a special mixing method such as 3-roll or planetary stirring.
Also provided are films (or "films" and "skins") obtained using the above-described polyamideimide varnish. The film contains polyamideimide and nano-silica filler.
The film has a flexibility of 1d as measured in JIS C3216-320115.1.1, and a breaking time (V-t breaking time) of 55 hours or more, preferably 79 hours or more, under the measurement conditions of 1500Vp, 155 ℃ and 50 kHz. The failure time is the time from the start of the test to the time when the skin burns out and becomes short-circuited.
In one embodiment, a polyamideimide varnish is coated and heated to form an imide ring, resulting in a film.
There is also provided a coil having the above membrane. More specifically, in the coil, a film is coated on the surface of the lead.
The film of the present embodiment has excellent toughness and V-t characteristics, and can withstand severe motor processing, and the coil having the film can be widely applied to motors for EVs and HEVs.
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.
Preparation of a silica solution.
DMAC-ST (20 wt% silica concentration, silica particle size: 10 to 15nm, manufactured by Nissan chemical Co., Ltd.) and a silane coupling agent (both available from shin-Etsu chemical Co., Ltd.) were mixed according to the weight described in Table 1, and the mixture was stirred at 70 ℃ for 5 hours by a conventional helical stirrer to prepare silica solutions 1 to 67, 71 to 78.
According to the weight described in table 2, fumed silica was added to DMAC and stirred, and a silane coupling agent was added thereto and stirred at 70 ℃ for 5 hours to prepare silica solutions 68 to 70.
Preparation of polyamide-imide varnish.
Examples 76 to 79: the silicon dioxide solution 7 in the weight as described in Table 3 was mixed with 1000g of a base varnish (Ulmide-AI, manufactured by the well industry, having a solid content of 30%) and stirred at 30 ℃ for 2 hours by a conventional helical stirrer to prepare a polyamideimide varnish.
Comparative examples 1 and 2: the lacquer Voltatex8534 (ALTAA) and the lacquer Tongmid595CR (ELANTA) were used, respectively.
Comparative examples 3 to 5: 60g of fumed silica (A), (B), (C) and (C) were each separately added
R972CF、
RA200H、
R711) was mixed with 1000g of the base varnish (same as in example 1) and stirred for 2 hours by means of a helical stirrer, to obtain a polyamideimide varnish.
Comparative examples 6 and 7: 300g of silica solution 77 and 78 were mixed with 1000g of a base varnish (Ulmide-AI, manufactured by the well industry, having a solid content of 30%) respectively, and stirred at 30 ℃ for 2 hours by a conventional helical stirrer to prepare a polyamideimide varnish.
Production of enameled wire
An enameled wire was produced using the above polyamideimide varnish. The specific method comprises the following steps: copper was cast, drawn and softened to obtain a conductor having a circular cross section and an average diameter of 1mm, and the polyamide-imide varnish was applied to the outer peripheral surface of the conductor and fired at a furnace inlet temperature of 350 ℃ and a furnace outlet temperature of 450 ℃ to laminate the insulating layers to obtain an insulated wire. The insulating layer was a single layer having an average thickness of 45 μm.
The obtained enameled wire was subjected to various characteristic evaluations. The test methods for each property are as follows:
and (3) flexibility test: a sample having an elongation of 10% was wound in different diameters and observed for the occurrence of cracks in the evaluation in accordance with JIS C3216-320115.1.1. for example, in the case of an electric wire having a diameter of 1.0mm, the result was recorded as 1d when the wire was not cracked when wound on a rod having a diameter of 1.0 mm. 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 not generated when the crack is generated in 2d and when the crack is generated in 3d, the crack is recorded as 3 d;
v-t destruction time: 1500Vp voltage is applied to the coating at the frequency of 50Hz under the environment temperature of 155 ℃, and the time of the coating burning loss and short circuit is V-t failure time.
TABLE 1
TABLE 2
TABLE 3
As is apparent from table 3, the surge-resistant polyamideimide winding wire using colloidal silica having a surface treated with a plurality of silane coupling agents has characteristics that (i) flexibility is excellent and (ii) the wire is not broken for a long time even in a severe V-t test because the silica is uniformly dispersed.