Self-lubricating polyimide paint and polyimide coating prepared from same

Abstract

The present invention provides a polyimide paint comprising: a polyamic acid containing at least one dianhydride monomer and at least one diamine monomer as polymerized units; the surface of the nano silicon dioxide is modified by organosilane; a silicone-based additive represented by Chemical Formula 1; and an organic solvent.

Description

Technical Field

[0001] The invention relates to self-lubricating polyimide varnish and polyimide, polyimide coating material, polyimide molded body and parts prepared from the same. Background Art

[0002] Polyimide resin refers to a highly heat-resistant resin obtained by: solution polymerization of aromatic dianhydride and aromatic diamine or aromatic diisocyanate to prepare a polyamic acid derivative, followed by closed-loop dehydration and imidization at high temperature. Polyimide resin is an insoluble, infusible, ultra-high heat-resistant resin, and has excellent properties such as thermal oxidation resistance, heat resistance, radiation resistance, low temperature properties, chemical resistance, etc., and therefore it is used in a wide range of fields, including heat-resistant advanced materials, such as automotive materials, aviation materials and spacecraft materials, etc.; and electronic materials, such as insulating coatings, insulating films, semiconductors and electrode protective films for TFT-LCDs. Recently, polyimide resins are also used in display materials, such as optical fibers and liquid crystal alignment films, transparent electrode films by including conductive fillers in the film or surface coating, etc.

[0003] In particular, use as an insulated wire for coil (e.g., motor) windings requires a conductor-coated insulating layer (insulating film) that provides excellent insulation, adhesion to the conductor, heat resistance, mechanical strength, etc. Therefore, polyimide is used as a resin forming the insulating layer.

[0004] Specifically, polyimide varnish is applied as an insulating coating for electric vehicle (EV) windings, processed into a hairpin shape, and inserted into a motor core. However, this process has a problem that when friction is high, workability is reduced due to shape deformation of the winding.

[0005] Therefore, there is a need for a polyimide lacquer for winding / wire coating that has excellent adhesion to the conductor while satisfying the heat resistance, insulation and mechanical properties of polyimide, with excellent process efficiency due to reduced friction. Summary of the invention

[0006] Technical issues

[0007] An object of the present invention is to provide a self-lubricating polyimide varnish having a low coefficient of friction.

[0008] Another object of the present invention is to provide a polyimide prepared by imidizing a polyimide lacquer.

[0009] Still another object of the present invention is to provide a polyimide coating material comprising a cured product of the polyimide varnish.

[0010] It is a further object of the present invention to provide a component comprising a molded body formed from a polyimide lacquer.

[0011] Still another object of the present invention is to provide a method for preparing the polyimide varnish.

[0012] Technical Solution

[0013] Various modifications can be made in the present disclosure and multiple embodiments can be realized, and specific embodiments are shown and described in detail in the accompanying drawings. However, it should be understood that this is not intended to limit the present disclosure to specific embodiments, but to include all modifications, equivalents and alternatives included in the spirit and scope of the present disclosure.

[0014] The terms used in this application are only used to describe specific embodiments and are not intended to limit the present disclosure. Unless the context clearly indicates otherwise, singular expressions should include plural expressions. In this specification, terms such as "including" or "having" are intended to specify the presence of features, quantities, steps, operations, elements, components or combinations thereof described in the specification, and should not be understood as excluding the possibility of existing or adding one or more other features, quantities, steps, operations, components, parts or combinations thereof.

[0015] When amounts, concentrations or other values ​​or parameters are given herein as ranges, preferred ranges or lists of upper desired values ​​and lower desired values, it should be understood that all ranges formed by any pair of any upper range or preferred value and any lower range or preferred value are specifically disclosed, whether or not such ranges are disclosed individually.

[0016]

[0013] When a range of values ​​is stated herein, unless otherwise indicated, it is intended that the endpoints of the range and the scope of the invention within that range are not limited to the specific values ​​stated when defining the range.

[0017] As used herein, "dianhydride" is intended to include its precursors or derivatives, which are also referred to as "dianhydrides" or "acid dianhydrides." These products may not technically be dianhydrides, but will still react with diamines to form polyamic acids, and polyamic acids can be converted back to polyimides.

[0018] As used herein, "diamine" is intended to include precursors or derivatives thereof, which may not technically be diamines, but will still react with the dianhydride to form a polyamic acid, and the polyamic acid can be converted back to a polyimide.

[0019] In the present invention, “C x-y ” means that the carbon number is x or more and y or less.

[0020] As used herein, the term “C 1-20 "Alkyl" means C 1-20Straight or branched saturated hydrocarbons, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl or hexyl. Preferred alkyl groups contain about 1 to 20 carbon atoms in the chain. Side chain means that at least one lower alkyl group (such as methyl, ethyl or propyl) is connected to a linear alkyl chain. "Lower alkyl" means a group having about 1 to about 20 carbon atoms in the chain that can be straight or branched. "Alkyl" can be unsubstituted, or optionally substituted with one or more substituents that can be the same or different, each of which is a halogen, alkyl, aryl, cycloalkyl, cyano, hydroxyl, alkoxy, alkylthio, amino, carboxyl, etc. Preferably, the alkyl group can be methyl or ethyl. As used herein, "methyl (methyl group)" is the smallest alkyl group having a structure in which three hydrogen atoms are bonded to one carbon atom. The methyl group can exist in three forms: anion, cation and free radical.

[0021] As used herein, the term "C 6-20 "Aryl" refers to an aromatic hydrocarbon containing 6 to 20 carbon atoms. For example, aryl can refer to a monocyclic (e.g., phenyl) or a bicyclic (e.g., indenyl, naphthyl, tetrahydronaphthyl, tetrahydroindenyl) ring system. Preferably, aryl can be a ring having the formula C wherein the six carbon atoms are arranged in a cyclic ring structure. 6 H 5 of phenyl.

[0022] Unless otherwise defined, all terms (including technical terms or scientific terms) used herein have the same meanings as those generally understood by those of ordinary skill in the art to which the present invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having meanings consistent with those in the context of the relevant technology, and unless clearly defined in this application, are not interpreted in an idealized or overly formal sense. Specific details for implementing the present invention will be described below.

[0023] Self-lubricating polyimide paint of the present invention

[0024] The present invention relates to a self-lubricating polyimide varnish having a low coefficient of friction and useful in conductor coating applications.

[0025] In one general aspect, a polyimide lacquer is provided, comprising: a polyamic acid containing at least one dianhydride monomer and at least one diamine monomer as polymerized units;

[0026] Nano-silica surface modified with organosilane;

[0027] a silicone-based additive represented by the following Chemical Formula 1; and

[0028] Organic solvents:

[0029] [Chemical formula 1]

[0030]

[0031] In the above chemical formula 1,

[0032] R 1 To R 10 Each independently is C 1-20 Alkyl or C 6-20 Aryl; and

[0033] X 1 To X 3 are independently a hydrogen atom, C 1-3 Alkyl, C 6-10 aromatic group, hydroxyl group, amino group, epoxy group, acrylic group, anhydride group, carboxyl group, methacryloyl group, mercapto group, alkoxy group, silanol group or polyether group,

[0034] Where X 1 To X 3 At least one of the following is a hydroxyl group, an amino group, an epoxy group, an acrylic group, an acid anhydride group, a carboxyl group, a methacryloyl group, a mercapto group, an alkoxy group, a silanol group or a polyether group, and

[0035] m and n are each independently an integer from 0 to 50, wherein m+n is 1 or greater.

[0036] Polyamic acid

[0037] In the present disclosure, the dianhydride monomer may include at least one selected from the group consisting of pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), benzophenonetetracarboxylic dianhydride (BTDA), oxydiphthalic dianhydride (ODPA), diphenylsulfone-3,4,3',4'-tetracarboxylic dianhydride (DSDA), bis(3,4-dicarboxyphenyl)sulfide dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, Phenylenebis(trimellitic acid monoester anhydride), p-biphenylenebis(trimellitic acid monoester anhydride), m-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride and 4,4'-(2,2-hexafluoroisopropylidene)diphthalic dianhydride.

[0038] Specifically, the dianhydride monomer may include at least one selected from the group consisting of pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), and benzophenonetetracarboxylic dianhydride (BTDA), and preferably pyromellitic dianhydride (PMDA).

[0039] In addition, the diamine monomer may include at least one selected from the following: 1,4-diaminobenzene (PPD), 4,4'-diaminodiphenyl ether (ODA), 2,2-bisaminophenoxyphenylpropane (BAPP), metaphenylenediamine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobenzoic acid (DABA), 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane (MDA), 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (meta-tolidine), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (DABA), 3,3'-dimethyl-4,4'-diaminobiphenyl (DABA), 2,2 ...3,3'-dimethyl-4,4'-diaminobiphenyl (DABA), 3,3'-dimethyl-4,4'-diaminobiphenyl (DABA), 3,3'-dimethyl-4,4'-diaminobiphenyl (DABA), 3,3' aminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis(4-aminophenyl)sulfide, 4,4'-diaminobenzanilide, 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diamino 4,4'-dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4 -aminophenyl)benzene, 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,4-bis(3-aminophenoxy)benzene (TPE-Q), 1,3-bis(3-aminophenoxy)-4-trifluoromethylbenzene, 3,3'-diamino-4-(4-phenylphenoxy)benzophenone, 3,3'-diamino-4,4'-bis(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenyl sulfide)benzene, 1,3-bis(4-aminophenyl sulfide)benzene, 1,4-bis(4-aminophenyl sulfide)benzene, 1,3-bis(3-aminophenyl sulfone)benzene, 1,3-bis(4-aminophenyl sulfone)benzene, 1,4-bis(4-aminophenyl sulfone)benzene, 1,3-bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis[2-(4-aminophenyl)isopropyl]benzene, 3,3'-bis(3-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[3-(3-aminophenoxy)phenyl]ether, bis[3-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)biphenyl]ether, bis[3-(3-aminophenoxy)phenyl]ether, bis[3-(4-aminophenoxy)phenyl]ketone, bis[3-(4-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone, bis[3-(3-aminophenoxy)phenyl]thioether, bis[3-(4-aminophenoxy)phenyl]thioether, bis[4-(3-aminophenoxy)phenyl]thioether, bis[4-(4-aminophenoxy)phenyl]thioether, bis[3-(3-aminophenoxy)phenyl]sulfone , bis[3-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[3-(3-aminophenoxy)phenyl]methane, bis[3-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]methane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4-aminophenoxy)phenyl]propane , 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane.

[0040] Specifically, the diamine monomer may include at least one selected from the group consisting of 1,4-diaminobenzene (PPD), 4,4′-diaminodiphenyl ether (ODA), and 2,2-bisaminophenoxyphenylpropane (BAPP), and may preferably be 4,4′-diaminodiphenyl ether (ODA).

[0041] In the present invention, in the total dianhydride monomers, pyromellitic dianhydride (PMDA) may be included in a ratio of 50 mol % or more, specifically, 60 mol % or more, 70 mol % or more, 75 mol % or more, 80 mol % or more, 85 mol % or more, 90 mol % or more, 95 mol % or more, 99 mol % or more, or 100 mol % or more.

[0042] In addition, in the total diamine monomers, 4,4'-diaminodiphenyl ether (ODA) may be included in a ratio of 50 mol% or more, specifically, 60 mol% or more, 70 mol% or more, 75 mol% or more, 80 mol% or more, 85 mol% or more, 90 mol% or more, 95 mol% or more, 99 mol% or more, or 100 mol% or more.

[0043] Based on the diamine monomer of 100mol%, polyamic acid can include the dianhydride monomer of 95mol% to 105mol%.For example, the lower limit of dianhydride monomer can be 95.5mol% or more, 96mol% or more, 96.5mol% or more, 97mol% or more, 97.5mol% or more, 98mol% or more, 98.5mol% or more, 99mol% or more, or 99.5mol% or more, and its upper limit can be 105mol% or less, 104.5mol% or less, or 104mol% or less.

[0044] In addition, the molar ratio of dianhydride monomer (mol%) / diamine monomer (mol%) can be 95 to 105, specifically 97.5 to 102.5, more specifically 99 to 101, and even more specifically 99.4 to 99.9. In one embodiment, the molar ratio of dianhydride monomer (mol%) / diamine monomer (mol%) is 99.6, 99.7 and 103.8.

[0045] In addition, the polyimide varnish of the present invention may further contain an aromatic carboxylic acid. The aromatic carboxylic acid may be further added to form an optimal molar ratio.

[0046] The aromatic carboxylic acid may include at least one selected from the group consisting of pyromellitic acid (PMA), 3,3',4,4'-biphenyltetracarboxylic acid (BPTA), 1,2,3,4-benzenetetracarboxylic acid, benzophenone-3,3',4,4'-tetracarboxylic acid, pyrazinetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, and naphthalene-1,4,5,8-tetracarboxylic acid. In one embodiment, pyromellitic acid (PMA) is used.

[0047] In addition, an aromatic carboxylic acid may be further included in an amount of 0 mol% to 1.0 mol%, specifically, 0 mol% to 0.8 mol%, and more preferably 0.1 mol% to 0.6 mol%. Here, 0 mol% may mean that the aromatic carboxylic acid is not included in the polyimide varnish.

[0048] Nano-silica surface modified by organosilane

[0049] The polyimide paint of the present invention may contain inorganic particles to improve physical properties, such as pulse resistance, etc., wherein the inorganic particles are nano-silicon dioxide, that is, nano-sized silicon dioxide (SiO2) with an average particle size of 1000 nm or less. 2 ) fine particles, and their form and shape are not particularly limited.

[0050] The organosilane of the nano-silica surface modified by organosilane in the present invention may include at least one selected from the following: methyltrimethoxysilane, hexamethyldisiloxane, n-octyltrimethoxysilane, n-octyltriethoxysilane, isooctyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-(methacryloxy)propyltriethoxysilane, 3-(methacryloxy)propylmethyldimethoxysilane, 3-(acryloxypropyl)methyldimethoxysilane, 3-(methacryloxy)propyldimethylethoxysilane, styrylethyltrimethoxysilane, phenyltrimethoxysilane, Methoxysilane, phenyltriethoxysilane, p-tolyltriethoxysilane, vinylmethyldiacetoxysilane, vinyldimethylethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriphenoxysilane, vinyltri-tert-butoxysilane, vinyltri(isobutoxy)silane, vinyltriisopropenoxysilane, vinyltri(2-methoxyethoxy)silane, glycidoxypropyltrimethoxysilane (GPTMS), 3-aminopropyltrimethoxy-silane (APTMS), phenyltrimethoxysilane (PTMS) and N-phenyl-3-aminopropyltrimethoxysilane (PAPTES). Specifically, the organosilane of the nano-silica surface modified by organosilane may include at least one selected from the following: methyltrimethoxysilane, hexamethyldisiloxane, phenyltrimethoxysilane, hexyltrimethoxysilane, aminopropyltrimethoxysilane and phenylaminopropyltrimethoxysilane. In one embodiment, the organosilane may include methyltrimethoxysilane or hexamethyldisiloxane.

[0051] In addition, the nano-silica surface modified by organosilane can be obtained by the following: on the surface of nano-silica, the compound containing at least one phenyl at the terminal and the compound combination containing at least one amine group, hydroxyl group, thiol group or epoxy group at the terminal. Specifically, the compound containing at least one phenyl at the terminal can be phenyltrimethoxysilane (PTMS) or N-phenyl-3-aminopropyltrimethoxysilane (PAPTES). In addition, the compound containing at least one amine group, hydroxyl group, thiol group or epoxy group at the terminal can be glycidyloxypropyltrimethoxysilane (GPTMS) or 3-aminopropyltrimethoxy-silane (APTMS).

[0052] Nano-silica surface-modified by organosilane can be prepared by surface-treating nano-silica with organosilane. For example, nano-silica can be obtained by heating organosilane under acidic or alkaline conditions for surface treatment for about 1 hour to 24 hours. In addition, surface modification can be achieved by other known methods, for example, by mixing organosilane in a solvent and reacting at a temperature of 10°C to 100°C or 20°C to 60°C for 1 hour to 10 hours or 1 hour to 5 hours to obtain surface-modified nano-silica. In order to combine two or more compounds on the surface of nano-silica, each of the above methods can be performed.

[0053] The nano-silica surface-modified with organosilane of the present invention can prevent the aggregation of inorganic particles in the polyimide paint, and can enhance the interaction with the solid content (polyamic acid) due to the functional groups of the compound, thereby improving the organic-inorganic hybrid.

[0054] In addition, the nano-silica surface-modified with organic silane may have an average particle size of 10 nm to 200 nm, for example, an average particle size of 10 nm to 190 nm, 20 nm to 180 nm, 30 nm to 170 nm, 40 nm to 160 nm, or 50 nm to 150 nm.

[0055] Based on 100 parts by weight of total polyimide paint, the nano silicon dioxide surface modified by organosilane can also be included in an amount of 0.3 to 7.0 parts by weight. For example, the lower limit of the amount of the nano silicon dioxide surface modified by organosilane can be, for example, 0.35 parts by weight or more, 0.40 parts by weight or more, 0.45 parts by weight or more, 0.50 parts by weight or more, 0.55 parts by weight or more, or 0.35 parts by weight or more. In addition, for example, its upper limit can be for example 6 weight parts or less, 5 weight parts or less, 3 weight parts or less, 2 weight parts or less, 1.5 weight parts or less, 1.25 weight parts or less, 1.20 weight parts or less, 1.15 weight parts or less, 1.10 weight parts or less, 1.05 weight parts or less, 1.0 weight parts or less, 0.95 weight parts or less, 0.9 weight parts or less, 0.85 weight parts or less, 0.8 weight parts or less, 0.79 weight parts or less, 0.78 weight parts or less, 0.77 weight parts or less or 0.76 weight parts or less.When the amount of nano silicon dioxide modified through organosilane surface was less than 0.3 weight part, it was not effective in improving characteristics, and when its amount exceeded 7 weight parts, due to the availability of reunion and reduction, the deterioration of mistiness and physical properties may occur.

[0056] Silicone-based additives

[0057] The polyimide paint of the present invention reduces the friction coefficient by comprising an organic silicon-based additive. The organic silicon-based additive of the present invention refers to a modified silicone oil having a linear siloxane skeleton and a functional group other than hydrogen or hydrocarbon group in the molecular structure.

[0058] Specifically, the silicone-based additive represented by the above Chemical Formula 1 may be a silicone-based additive represented by the following Chemical Formula 2:

[0059] [Chemical formula 2]

[0060]

[0061] In the above chemical formula 2,

[0062] R 1 , R 7 and R 10 Each independently is C 1-20 Alkyl; and

[0063] X 1 To X 3 are independently a hydrogen atom, C 1-3 Alkyl, C 6-10aromatic group, hydroxyl group, amino group, epoxy group, acrylic group, anhydride group, carboxyl group, methacryloyl group, mercapto group, alkoxy group, silanol group or polyether group,

[0064] Where X 1 To X 3 At least one of the following is a hydroxyl group, an amino group, an epoxy group, an acrylic group, an acid anhydride group, a carboxyl group, a methacryloyl group, a mercapto group, an alkoxy group, a silanol group or a polyether group, and

[0065] m and n are each independently an integer from 0 to 50, wherein m+n is 1 or greater.

[0066] In addition, the silicone-based additive represented by the above Chemical Formula 1 may be a silicone-based additive represented by the following Chemical Formula 3:

[0067] [Chemical formula 3]

[0068]

[0069] In the above chemical formula 3,

[0070] R 7 C 1-20 alkyl,

[0071] X 2 is a hydroxyl group, an amino group, an epoxy group, an acrylic group, an anhydride group, a carboxyl group, a methacryloyl group, a mercapto group, an alkoxy group, a silanol group or a polyether group, and

[0072] m and n are each independently an integer from 0 to 50, wherein m+n is 1 or greater.

[0073] Preferably, in the above chemical formula 3, X 2 It may be an amino group.

[0074] In addition, the silicone-based additive represented by the above Chemical Formula 1 may be a silicone-based additive represented by the following Chemical Formula 4:

[0075] [Chemical formula 4]

[0076]

[0077] In the above chemical formula 4, R 1 , R 10 , X 1 , X 3 , m and n are as defined above.

[0078] R 1 and R 10 Each independently is C 1-20 Alkyl, and

[0079] X 1 and X 3 Each is independently a hydroxyl group, an amino group, an epoxy group, an acrylic group, an anhydride group, a carboxyl group, a methacryloyl group, a mercapto group, an alkoxy group, a silanol group or a polyether group, and m and n are each independently an integer from 0 to 50, wherein m+n is 1 or greater.

[0080] Preferably, in Chemical Formula 4, X 1 and X 3 Each may independently be an amino group.

[0081] In addition, the silicone-based additive can have a refractive index of 1.40 to 1.50 (based on 25°C), a functional group equivalent of 100 g / mol to 10,000 g / mol, and a viscosity of 10 cP to 20,000 cP (based on 25°C), wherein the functional group can be a hydroxyl group, an amino group, an epoxy group, an acrylic group, an anhydride group, a carboxyl group, a methacryloyl group, a mercapto group, an alkoxy group, a silanol group or a polyether group.

[0082] As used herein, the functional group equivalent refers to the mass of the main skeleton bonded with one functional group, and is a value obtained by dividing the weight average molecular weight of the silicone-based additive by the number of functional groups per molecule. In other words, the functional group equivalent of the present invention means a value represented by the following formula:

[0083] [Mode]

[0084] Functional group equivalent (g / mol) = total weight average molecular weight (g / mol) / number of functional groups

[0085] For example, when a silicone-based additive having a total molecular weight of 1,000 g / mol contains two functional groups in the molecule, the functional group equivalent weight is 500 g / mol.

[0086] Preferably, the silicone-based additive may have a refractive index of 1.40 to 1.45 (based on 25°C), a functional group equivalent of 200 g / mol to 9,000 g / mol, and a viscosity of 10 cP to 1,000 cP (based on 25°C), wherein the functional group may be a hydroxyl group, an amino group, an epoxy group, an acrylic group, an anhydride group, a carboxyl group, a methacryloyl group, a mercapto group, an alkoxy group, a silanol group or a polyether group.

[0087] More preferably, the silicone-based additive may have a refractive index of 1.40 to 1.42 (based on 25°C), a functional group equivalent of 300 g / mol to 8,000 g / mol, and a viscosity of 10 cP to 800 cP (based on 25°C), wherein the functional group may be a hydroxyl group, an amino group, an epoxy group, an acrylic group, an anhydride group, a carboxyl group, a methacryloyl group, a mercapto group, an alkoxy group, a silanol group or a polyether group.

[0088] Even more preferably, the refractive index may be 1.40 to 1.42 (based on 25° C.), the functional group equivalent weight may be 400 to 6,000 g / mol, the viscosity may be 10 to 500 cP (based on 25° C.), and the functional group may be an amino group.

[0089] In one embodiment, as the side chain amino-modified silicone, a silicone-based additive having a refractive index of 1.405 (based on 25° C.), an amino equivalent of 5,000 g / mol, and a viscosity of 110 cP (based on 25° C.) may be used.

[0090] In one embodiment, as the side chain amino-modified silicone, a silicone-based additive having a refractive index of 1.408 (based on 25° C.), an amino equivalent of 1,600 g / mol, and a viscosity of 1,000 cP (based on 25° C.) may be used.

[0091] In one embodiment, as the silicone modified with amino groups at both ends, a silicone-based additive having a refractive index of 1.418 (based on 25° C.), an amino equivalent of 400 g / mol, and a viscosity of 12 cP (based on 25° C.) may be used.

[0092] In the present invention, the silicone-based additive may be contained in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the total polyimide paint. Specifically, for example, the lower limit thereof may be 0.2 parts by weight or more, 0.06 parts by weight or more, 0.07 parts by weight or more, 0.08 parts by weight or more, 0.09 parts by weight or more, 0.1 parts by weight or more, 0.2 parts by weight or more, 0.3 parts by weight or more, 0.4 parts by weight or more, or 0.5 parts by weight or more, and the upper limit thereof may be 4 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, 1.8 parts by weight or less, 1.6 parts by weight or less, 1.4 parts by weight or less, 1.2 parts by weight or less, 1.0 parts by weight or less, 0.8 parts by weight or less, or 0.6 parts by weight or less.

[0093] When the amount of the silicone-based additive exceeds 5 parts by weight, it is not preferred because the mechanical properties of the polyimide coating material to be prepared may be deteriorated, and the silicone-based additive may be decomposed at a high temperature during heat treatment for imidization, which may cause a decrease in adhesion between the polyimide coating material and the conductor or an increase in haze. On the other hand, when the amount of the silicone-based additive is less than 0.05 parts by weight, it is not preferred because there is no effect of improving the friction coefficient.

[0094] Organic solvents

[0095] In the present invention, the organic solvent may include at least one selected from the group consisting of N-methyl-pyrrolidone (NMP), N,N'-dimethylformamide (DMF), N,N'-diethylformamide (DEF), N,N'-dimethylacetamide (DMAc), dimethylpropionamide (DMPA), N,N-diethylacetamide (DEAc), dimethyl sulfoxide (DMSO), 3-methoxy-N,N-dimethylpropionamide (KJCMPA), p-chlorophenol, o-chlorophenol, γ-butyrolactone (GBL), diethylene glycol dimethyl ether and naphthalene. Preferably, N-methyl-pyrrolidone (NMP), N,N'-dimethylformamide (DMF), N,N'-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) and the like may be used.

[0096] The organic solvent can also include a modifier containing a hydroxyl group (OH) or an amine group (NH). The example of the modifier containing a hydroxyl group (OH) or an amine group (NH) can include ethylamine, triethanolamine, dimethylamine, trimethylamine, diethylenetriamine, ethylenediamine, tributylamine, pyridine, pyrrolidine, methanol, ethanol, propanol, isopropanol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isopentanol, hexanol, octanol, octyl alcohol, nonanol, decanol, undecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, ethylene glycol, propylene glycol, benzyl alcohol, phenol, etc. The modifier can control reactivity by reacting with the dianhydride monomer.

[0097] The organic solvent may be used to synthesize polyamic acid by polymerizing dianhydride monomers and diamine monomers, and may be included in an amount of 50 to 80 parts by weight, and preferably 60 to 75 parts by weight, based on 100 parts by weight of the total polyimide varnish.

[0098] In addition, based on 100 parts by weight of total polyimide varnish, the polyimide solid content can be included in an amount of 10 parts by weight to 30 parts by weight, and specifically, for example, its lower limit can be 12 parts by weight, 15 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, or 25 parts by weight or more, and its upper limit can be 30 parts by weight, 29 parts by weight, 28 parts by weight, or 27 parts by weight or less. By adjusting the solid content of the polyimide varnish, the increase in viscosity can be controlled and the processing time during the curing process can be shortened.

[0099] Polyimide paint and its cured products

[0100] Polyimide paint at 30°C and 1 second -1The viscosity measured at a shear rate of 500 cP to 20,000 cP can be. For example, the upper limit of the viscosity can be 20,000 cP, 15,000 cP, 10,000 cP or less. The lower limit of the viscosity is not particularly limited, but can be 1,000 cP, 1,500 cP, 2,000 cP, or 2,500 cP or more. The viscosity can be measured using, for example, Haake's Rheostress 600, and can be measured under the conditions of a shear rate of 1 / sec, a temperature of 30 ° C, and a plate gap of 1 mm. The present invention can provide a polyimide paint with excellent processability by adjusting the viscosity range.

[0101] The coefficient of thermal expansion (CTE) of the polyimide paint according to the present invention after curing can be 60ppm / ℃ or less. For example, the upper limit of CTE can be 55ppm / ℃ or less, 50ppm / ℃ or less, 45ppm / ℃ or less, 40ppm / ℃ or less, 38ppm / ℃ or less, 36ppm / ℃ or less, 35ppm / ℃ or less, or 30ppm / ℃ or less, and its lower limit can be, for example, 0.1ppm / ℃, 1ppm / ℃, 2.0ppm / ℃, 2.6ppm / ℃, 2.8ppm / ℃, 3.5ppm / ℃, or 4ppm / ℃ or more. In one embodiment, the coefficient of thermal expansion can be measured at 100℃ to 350℃. In one embodiment, the CTE can be determined using TA's Thermomechanical Analyzer Q400, specifically, by forming a polyimide as a film, cutting the formed polyimide film into a width of 2 mm and a length of 10 mm, while applying a tensile force of 0.02 N in a nitrogen atmosphere, increasing the temperature from room temperature to 350°C at a rate of 10°C / min, and measuring the slope of the 100°C to 250°C section.

[0102] For example, the glass transition temperature (Tg) of the polyimide varnish according to the present invention after curing can be in the range of 250°C to 450°C. For example, the lower limit of the glass transition temperature can be 250°C or higher, 255°C or higher, 260°C or higher, 270°C or higher, or 300°C or higher. The upper limit thereof can be 445°C or lower, 440°C or lower, 435°C or lower, 430°C or lower, 425°C or lower, 420°C or lower, 415°C or lower, 410°C or lower, or 400°C or lower. In one embodiment, the glass transition temperature of the polyimide prepared by curing the polyimide varnish can be measured at 10°C / min using TMA.

[0103] The thermal decomposition temperature (Td) of the polyimide varnish according to the present invention at 5% weight loss after curing can be 450°C or higher. The thermal decomposition temperature can be measured using the thermogravimetric analyzer Q50 of TA. In a specific example, the polyimide cured with the polyimide varnish is heated to 150°C at a rate of 10°C / minute in a nitrogen atmosphere, and then isothermal for 30 minutes to remove moisture. Then, the temperature can be raised to 600°C at a rate of 10°C / minute, and the temperature at which 1% weight loss occurs can be measured. The lower limit of the thermal decomposition temperature can be, for example, 450°C or higher, 460°C or higher, 470°C or higher, or 480°C or higher. The upper limit can be, for example, 800°C or lower, or 600°C or lower.

[0104] In addition, the elongation of the polyimide cured with polyimide varnish can be 60% or more, for example 60%, 62%, 64% and 66% or more. Its upper limit is not particularly limited, but can be 80% or less. In one embodiment, the elongation can be determined by: the polyimide varnish is cured into a polyimide film, the film is cut into a width of 10mm and a length of 40mm, and the elongation is measured using an Instron 5564 UTM instrument according to ASTM D-882 standard.

[0105] In addition, the dielectric constant (Dk) of the polyimide cured with the polyimide varnish may be 4 or less, specifically, 3.8 or less, 3.6 or less, or 3.5 or less, and the lower limit of the dielectric constant is not particularly limited, but may be 2.0 or more.

[0106] In another aspect of the present invention, there is provided a polyimide prepared by imidizing the polyimide lacquer as described above, wherein the polyimide may be in the form of a film.

[0107] In yet another aspect of the present invention, a polyimide coating material comprising a cured product of a polyimide varnish is provided.

[0108] The friction coefficient of the polyimide coating material (PI-SUS) can be 0.4 or less. The friction coefficient can specifically be 0.39 or less, 0.38 or less, 0.36 or less, 0.34 or less, 0.32 or less, 0.30 or less, 0.29 or less, or 0.28 or less. When the friction coefficient exceeds 0.4, there is a problem that when the polyimide paint is applied as an insulating coating for an electric vehicle (EV) winding, processed into a hairpin shape and inserted into a motor core, the processability is reduced due to the shape deformation of the winding.

[0109] In one embodiment, a method for preparing a polyimide coating material may include coating a polyimide varnish on a surface of a conductor; and imidizing the polyimide varnish coated on the surface of the conductor.

[0110] The conductor may be a copper wire made of copper or a copper alloy, but may also include a conductor made of other metal materials (e.g., silver wire, etc.) or various metal-plated wires (e.g., aluminum-plated or tin-plated wires, etc.). The conductor and the coating material may have a thickness according to the KS C3107 standard. The diameter of the conductor may be in the range of 0.3 mm to 3.2 mm, and the standard film thickness of the coating material (the average value of the maximum film thickness and the minimum film thickness) may be 21 μm to 194 μm for type 0, 14 μm to 169 μm for type 1, and 10 μm to 31 μm for type 2. Depending on the cross-sectional shape of the conductor, the conductor may be a circular wire, a rectangular wire, a hexagonal wire, etc., but is not limited thereto.

[0111] The polyimide coating material according to the present invention can have a pulse resistance of 170 minutes or longer, where the pulse resistance is the time that the insulating material withstands a specific voltage according to IEC-60851-5, wherein the pulse resistance can be, for example, 180 minutes or longer, 200 minutes or longer, 220 minutes or longer, or 230 minutes or longer.

[0112] In another aspect of the present invention, an electrical wire comprising a polyimide coating material is provided.

[0113] Specifically, the wire may be a coated wire comprising a polyimide coating material prepared by coating a polyamic acid solution on the surface of the wire and then imidizing it. In one embodiment, the coated wire may include an electric wire; and a coating material in which the above-mentioned polyimide is coated on the surface of the electric wire and imidized.

[0114] Furthermore, the present invention may provide an electronic device comprising the coated wire. The electronic device may be, for example, an electric motor.

[0115] Furthermore, in yet another aspect, a component including a molded body formed of a polyimide lacquer is provided.

[0116] Specifically, the components can be electronic circuit board components, semiconductor devices, lithium ion battery components, solar cell components, fuel cell components, motor windings, engine peripheral components, coatings, optical components, thermal insulators, electromagnetic shielding materials, surge components, dental materials, slide coatings, and electrostatic chucks.

[0117] Method for preparing polyimide paint

[0118] The method for preparing a polyimide paint according to the present invention comprises mixing and heating a dianhydride monomer, a diamine monomer, nano-silica surface-modified with organosilane, an organosilicon-based additive and an organic solvent.

[0119] Specifically, the method may include (a) mixing and heating the surface-modified nano-silica surface-modified by organosilane and a dianhydride monomer in an organic solvent;

[0120] (b) adding a diamine monomer to react; and

[0121] (c) preparing a polyimide varnish by adding an organic silicon-based additive; and may further include adding an aromatic carboxylic acid after step (b) and before step (c).

[0122] Organic solvents, dianhydride monomers, diamine monomers, nano-silica surface-modified with organosilane, silicone-based additives, etc. are applied in the same manner as the contents of the above-mentioned polyimide varnish.

[0123] Beneficial Effects

[0124] The polyimide varnish of the present invention can have self-lubricating properties by reducing the friction coefficient, thereby producing excellent process efficiency, while satisfying the heat resistance, insulation and mechanical properties of polyimide and having excellent adhesion to the conductor, thereby achieving excellent usability for wire coating. DETAILED DESCRIPTION

[0125] The following exemplary embodiments are presented to help understand the present invention. The following examples are provided only to make it easier to understand the present invention, but the content of the present invention is not limited to these examples.

[0126] <Example>

[0127] Preparation Example 1. Silicone-based Additive 1

[0128] Side chain amino-modified silicone oil (refractive index 1.405 (based on 25° C.), amino equivalent 5,000 g / mol, viscosity 110 cP (based on 25° C.), and specific gravity 0.97 g / mL (based on 25° C.)).

[0129] Preparation Example 2. Silicone-based Additive 2

[0130] Side chain amino-modified silicone oil (refractive index 1.408 (based on 25° C.), amino equivalent 1,600 g / mol, viscosity 1,000 cP (based on 25° C.), and specific gravity 0.98 g / mL (based on 25° C.)).

[0131] Preparation Example 3. Silicone-based Additive 3

[0132] Both-terminal amino-modified silicone oil (refractive index 1.418 (based on 25° C.), amino equivalent 430 g / mol, viscosity 12 cP (based on 25° C.), and specific gravity 1.00 g / mL (based on 25° C.)).

[0133] Example 1. Polyimide paint

[0134] An organic solvent containing dimethylacetamide and a modifier is introduced into a reaction vessel replaced with nitrogen, and pyromellitic dianhydride (PMDA) (99.6 mol% to 103.8 mol%) as a dianhydride monomer and nanosilica surface-modified by organosilane (ethylene glycol-dispersed silica sol, having a silica solid content of 20 wt%, an average silica particle size of 70 nm to 100 nm, a viscosity of 20 mPa·s to 100 mPa·s, and an organic silica sol of 2% or less in moisture content) (0.75 wt%) are mixed and stirred at 40°C for 30 minutes. Then, 4,4'-diaminodiphenyl ether (ODA) (100 mol%) as a diamine monomer is added, pyromellitic acid (0 mol% to 0.5 mol%) is added, and an organic silicon-based additive (0.53 wt%) is added. Then, the resulting mixture was stirred at 40° C. for about 1 hour to be polymerized, thereby preparing a polyamic acid solution having a solid content of 15 to 25 wt %.

[0135] Comparative Examples 1 to 7. Polyimide Paint

[0136] A polyimide precursor was prepared in the same manner as in Example 1, except that the components and amount ratios of the dianhydride monomer, the diamine monomer, the organosilane surface-modified nanosilica, and the organosilicon-based additive were adjusted as shown in Table 1 below.

[0137] [Table 1]

[0138]

[0139]

[0140] <Experimental example>

[0141] Polyimide Preparation for Measurement of Physical Properties

[0142] Each of the polyimide varnishes prepared in the examples and comparative examples was subjected to high-speed spinning at 1,500 rpm or more to remove bubbles. Then, each of the defoamed polyimide varnishes was applied to a glass substrate using a spin coater.

[0143] Under a nitrogen atmosphere, the obtained product was heated from room temperature to 400°C at a rate of 4°C / min, heat treated at 400°C for 60 minutes, and then cooled to 30°C at a rate of 4°C / min to obtain polyimide films each having a thickness of 20±1.0 μm.

[0144] Experimental Example 1. Friction coefficient

[0145] The friction coefficient was measured by ASTM D1894, D4918 method using QMESYS's QM110CF model at a speed of 150 mm / min, a load of 200 g, a displacement of 65 mm and an atmosphere of 23° C., and the results are shown in Table 2 below.

[0146] [Table 2]

[0147]

[0148] The polyimide varnish of the present invention was found to have a low friction coefficient (PI-SUS) of 0.4 or less.

[0149] In this specification, detailed descriptions of contents that can be fully recognized and inferred by those skilled in the art in the field of the present disclosure are omitted, and in addition to the specific exemplary embodiments described in this specification, various changes and modifications can be made within the scope of not changing the technical spirit or basic configuration of the present disclosure. Therefore, the present disclosure can also be practiced in a manner different from that specifically described and illustrated herein, which is understandable to those skilled in the art.

Claims

1. A polyimide paint comprising: A polyamic acid containing at least one dianhydride monomer and at least one diamine monomer as polymerized units; Nano-silica surface modified with organosilane; a silicone-based additive represented by the following Chemical Formula 1; and Organic solvents: [Chemical formula 1] In the above chemical formula 1, R1 to R 10 Each independently is C 1-20 Alkyl or C 6-20 Aryl; and X1 to X3 are each independently a hydrogen atom, C 1-3 Alkyl, C 6-10 aromatic group, hydroxyl group, amino group, epoxy group, acrylic group, anhydride group, carboxyl group, methacryloyl group, mercapto group or polyether group, wherein at least one of X1 to X3 is a hydroxyl group, an amino group, an epoxy group, an acrylic group, an anhydride group, a carboxyl group, a methacryloyl group, a mercapto group, an alkoxy group, a silanol group or a polyether group, and m and n are each independently an integer from 0 to 50, wherein m+n is 1 or greater.

2. The polyimide paint according to claim 1, wherein the dianhydride monomer comprises at least one selected from the group consisting of pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), benzophenonetetracarboxylic dianhydride (BTDA), oxydiphthalic dianhydride (ODPA), diphenyl sulfone-3,4,3',4'-tetracarboxylic dianhydride (DSDA), bis(3,4-dicarboxyphenyl)sulfide dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Propane dianhydride, p-phenylenebis(trimellitic acid monoester anhydride), p-biphenylenebis(trimellitic acid monoester anhydride), m-terphenyl-3,4,3',4'-tetracarboxylic acid dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic acid dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride and 4,4'-(2,2-hexafluoroisopropylidene)diphthalic dianhydride.

3. The polyimide paint according to claim 1, wherein the diamine monomer comprises at least one selected from the group consisting of 1,4-diaminobenzene (PPD), 4,4'-diaminodiphenyl ether (ODA), 2,2-bisaminophenoxyphenylpropane (BAPP), m-phenylenediamine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobenzoic acid (DABA), 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-methylenedianiline (MDA), 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), and 2 ,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis(4-aminophenyl) sulfide, 4,4'-diaminobenzanilide, 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 4 ,4'-diaminobenzophenone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1 ,4-bis(3-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,4-bis(3-aminophenoxy)benzene (TPE-Q), 1,3-bis(3-aminophenoxy)-4-trifluoromethylbenzene, 3,3'-diamino-4-(4-phenylphenoxy)benzophenone, 3,3'-diamino-4,4'-bis(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenyl sulfide)benzene, 1,3-bis(4-aminophenyl sulfide)benzene, 1,4-bis(4-aminophenyl sulfide)benzene, 1,3-bis(3-aminophenyl sulfone)benzene, 1,3-bis(4-aminophenyl sulfone)benzene, 1,4-bis(4-aminophenyl sulfone)benzene, 1,3-Bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis[2-(4-aminophenyl)isopropyl]benzene, 3,3'-bis(3-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[3-(3-aminophenoxy)phenyl]ether, bis[3-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy) phenoxy) phenyl] ether, bis[4-(4-aminophenoxy) phenyl] ether, bis[3-(3-aminophenoxy) phenyl] ketone, bis[3-(4-aminophenoxy) phenyl] ketone, bis[4-(3-aminophenoxy) phenyl] ketone, bis[4-(4-aminophenoxy) phenyl] ketone, bis[3-(3-aminophenoxy) phenyl] thioether, bis[3-(4-aminophenoxy) phenyl] thioether, bis[4-(3-aminophenoxy) phenyl] thioether, bis[4-(4-aminophenoxy) phenyl] thioether, bis[3-(3-aminophenoxy) phenyl] thioether, bis[4-(4-aminophenoxy) phenyl] thioether, bis[3-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[3-(3-aminophenoxy)phenyl]methane, bis[3-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]methane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4-aminophenoxy)phenyl]propane )phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane.

4. The polyimide paint according to claim 1, wherein the organosilane of the nano-silica surface modified by organosilane comprises at least one selected from the group consisting of methyltrimethoxysilane, hexamethyldisiloxane, n-octyltrimethoxysilane, n-octyltriethoxysilane, isooctyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-(methacryloxy)propyltriethoxysilane, 3-(methacryloxy)propylmethyldimethoxysilane, 3-(acryloxypropyl)methyldimethoxysilane, 3-(methacryloxy)propyldimethylethoxysilane, styrylethyltrimethoxysilane, Methoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-tolyltriethoxysilane, vinylmethyldiacetoxysilane, vinyldimethylethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriphenoxysilane, vinyltri-tert-butoxysilane, vinyltri(isobutoxy)silane, vinyltriisopropenoxysilane, vinyltri(2-methoxyethoxy)silane, glycidoxypropyltrimethoxysilane (GPTMS), 3-aminopropyltrimethoxy-silane (APTMS), phenyltrimethoxysilane (PTMS) and N-phenyl-3-aminopropyltrimethoxysilane (PAPTES).

5. The polyimide paint according to claim 1, wherein the average particle size of the nano-silicon dioxide surface-modified by organosilane is 10 nm to 200 nm.

6. The polyimide varnish according to claim 1, wherein the silicone-based additive represented by Chemical Formula 1 is an silicone-based additive represented by the following Chemical Formula 2: [Chemical formula 2] In the above chemical formula 2, R1, R7 and R 10 Each independently is C 1-20 Alkyl; and X1 to X3 are each independently a hydrogen atom, C 1-3 Alkyl, C 6-10 aromatic group, hydroxyl group, amino group, epoxy group, acrylic group, anhydride group, carboxyl group, methacryloyl group, mercapto group, alkoxy group, silanol group or polyether group, wherein at least one of X1 to X3 is a hydroxyl group, an amino group, an epoxy group, an acrylic group, an anhydride group, a carboxyl group, a methacryloyl group, a mercapto group or a polyether group, and m and n are each independently an integer from 0 to 50, wherein m+n is 1 or greater.

7. The polyimide lacquer according to claim 1, wherein the silicone-based additive has a refractive index of 1.40 to 1.50 (based on 25°C), 100 g / mol to 10,000 g / mol of functional group equivalents, and 10cP to 20,000cP viscosity (based on 25°C), The functional group is a hydroxyl group, an amino group, an epoxy group, an acrylic group, an anhydride group, a carboxyl group, a methacryloyl group, a mercapto group, an alkoxy group, a silanol group or a polyether group.

8. The polyimide paint according to claim 1, wherein the organic solvent is at least one selected from the group consisting of N-methyl-pyrrolidone (NMP), N,N'-dimethylformamide (DMF), N,N'-diethylformamide (DEF), N,N'-dimethylacetamide (DMAc), dimethylpropionamide (DMPA), N,N-diethylacetamide (DEAc), dimethyl sulfoxide (DMSO), 3-methoxy-N,N-dimethylpropionamide (KJCMPA), p-chlorophenol, o-chlorophenol, γ-butyrolactone (GBL), diethylene glycol dimethyl ether and naphthalene. 9 . The polyimide paint according to claim 8 , wherein the organic solvent further comprises a modifier containing a hydroxyl group (OH) or an amine group (NH).

10. The polyimide paint according to claim 9, wherein the modifier containing a hydroxyl group (OH) or an amine group (NH) is at least one selected from the group consisting of ethylamine, triethanolamine, dimethylamine, trimethylamine, diethylenetriamine, ethylenediamine, tributylamine, pyridine, pyrrolidine, methanol, ethanol, propanol, isopropanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, hexanol, octanol, octyl alcohol, nonanol, decanol, undecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, ethylene glycol, propylene glycol, benzyl alcohol, and phenol. 11 . The polyimide varnish according to claim 1 , wherein the polyimide solid content is contained in an amount of 10 to 30 parts by weight based on 100 parts by weight of the total polyimide varnish. 12 . The polyimide paint according to claim 1 , wherein the nano-silica surface-modified with organosilane is contained in an amount of 0.3 to 7 parts by weight based on 100 parts by weight of the total polyimide paint. 13 . The polyimide varnish according to claim 1 , wherein the silicone-based additive is included in an amount of 0.05 parts by weight to 5 parts by weight based on 100 parts by weight of the total polyimide varnish.

14. The polyimide varnish according to claim 1, wherein pyromellitic dianhydride (PMDA) is contained in a ratio of 50 mol% or more in the total dianhydride monomers. 15 . The polyimide varnish according to claim 1 , wherein 4,4′-diaminodiphenyl ether (ODA) is contained in a ratio of 50 mol % or more in the total diamine monomers.

16. The polyimide varnish according to claim 1, further comprising an aromatic carboxylic acid.

17. The polyimide paint according to claim 16, wherein the aromatic carboxylic acid comprises at least one selected from the group consisting of pyromellitic acid (PMA), 3,3',4,4'-biphenyltetracarboxylic acid (BPTA), 1,2,3,4-benzenetetracarboxylic acid, benzophenone-3,3',4,4'-tetracarboxylic acid, pyrazinetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, and naphthalene-1,4,5,8-tetracarboxylic acid. 18 . The polyimide varnish according to claim 1 , wherein the dianhydride monomer is included in an amount of 95 mol % to 105 mol % based on 100 mol % of the diamine monomer.

19. The polyimide varnish according to claim 18, further comprising 0 mol% to 1.0 mol% of an aromatic carboxylic acid.

20. The polyimide paint according to claim 1, wherein the polyimide paint is resistant to aging at a temperature of 30°C and a temperature of 1 second. -1 The viscosity measured at a shear rate of 500 cP to 20,000 cP.

21. A polyimide coating material comprising a cured product of the polyimide varnish according to any one of claims 1 to 20.

22. The polyimide coating material according to claim 21, wherein the friction coefficient (PI-SUS) of the polyimide coating material is 0.4 or less.

23. An electric wire comprising the polyimide coating material according to claim 21.

24. A component comprising a shaped body formed from the polyimide varnish according to any one of claims 1 to 20.

25. The component of claim 24, wherein the component is any one of the following: an electronic circuit board component, a semiconductor device, a lithium ion battery component, a solar cell component, a fuel cell component, a motor winding, an engine peripheral component, a coating, an optical component, a thermal insulator, an electromagnetic shielding material, a surge component, a dental material, a sliding coating, and an electrostatic chuck.

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