Polyamic acid composition with excellent adhesive strength and polyimide cured product containing the same

Abstract

The present invention provides a polyamic acid composition for conductor coating that simultaneously satisfies heat resistance, insulation, and mechanical properties, and has excellent adhesion to conductors, and a polyimide cured product produced by curing the polyamic acid composition. [Solution] The present invention provides a polyamic acid composition comprising a dianhydride monomer and a diamine monomer as polymerization units, wherein the diamine monomer comprises a first diamine monomer, a second diamine monomer, and a third diamine monomer, the second diamine monomer being a flexible diamine monomer having three or more benzene rings, and the third diamine monomer being represented by the following chemical formula. JPEG2026047326000006.jpg37170

Description

Technical Field

[0001] The present invention relates to a polyamic acid composition and a polyimide cured product containing the same, and more particularly, to a polyamic acid composition for winding coating having excellent wire adhesion and a polyimide cured product (film) containing the same.

Background Art

[0002] Generally, a polyimide (PI) resin means a high heat-resistant resin produced by solution polymerization of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to produce a polyamic acid derivative, followed by ring-closing dehydration and imidization at a high temperature. The polyimide resin, as an insoluble and infusible ultra-high heat-resistant resin, has excellent properties such as heat oxidation resistance, heat resistance, radiation resistance, low-temperature properties, and chemical resistance, and is widely used in heat-resistant advanced materials such as automotive materials, aerospace materials, and cosmic ray materials, and electronic materials such as insulating coating agents, insulating films, semiconductors, and electrode protection films for TFT-LCDs. Recently, it is also used in display materials such as optical fibers and liquid crystal alignment films, and transparent electrode films by containing conductive fillers in the film or coating the surface.

[0003] Particularly, in an insulated wire used as a winding for a coil such as a motor, the insulating layer (insulating film) covering the conductor is required to have excellent insulation, adhesion to the conductor, heat resistance, mechanical strength, etc. Polyimide is used as the resin for forming the insulating layer. Generally, the polyimide insulating layer is formed by applying a polyamic acid composition to the conductor and then curing it.

[0004] However, despite their excellent physical properties, general polyamic acid compositions and the polyimide resins produced therefrom do not have good adhesion to conductors, which can lead to problems with appearance defects when forming insulating coatings. Thus, there are many drawbacks to improving the properties required for polyamic acid compositions and the polyimide resins produced therefrom. In particular, improving one property generally leads to a decrease in other properties, so simultaneously satisfying various properties is a challenge that has been continuously researched in related technological fields.

[0005] Therefore, there is a high demand for polyamic acid compositions for conductor coatings that simultaneously satisfy the heat resistance, insulation, and mechanical properties of polyimide, while also exhibiting excellent adhesion to conductors. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a polyamic acid composition for conductor coating that simultaneously satisfies heat resistance, insulation, and mechanical properties, and has excellent adhesion to conductors.

[0007] Furthermore, the present invention aims to provide a polyimide cured product (or film) produced by curing the polyamic acid composition.

[0008] Furthermore, the present invention aims to provide a polyimide coated material containing a cured product of the polyamic acid composition. [Means for solving the problem]

[0009] Because the present invention can be modified in various ways and has various embodiments, specific embodiments will be illustrated and described in detail. However, this should not be understood as limiting the present invention to specific embodiments, but rather as including all modifications, equivalents, or substitutions that fall within the spirit and technical scope of the present invention.

[0010] The terms used in this application are used solely to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, terms such as “includes” or “having” specify the presence of features, figures, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood not to preclude the presence or possibility of adding one or more other features, figures, steps, actions, components, parts, or combinations thereof.

[0011] Wherever a quantity, concentration, or other value or parameter is given in this specification by enumeration of ranges, preferred ranges, preferred upper limits, and preferred lower limits, it should be understood that this specifically discloses all ranges formed by any pair of limits or preferred values ​​of any upper range and any limits or preferred values ​​of any lower range, regardless of whether the ranges are disclosed separately.

[0012] Where a range of numerical values ​​is referred to herein, unless otherwise specified, that range is intended not to be limited to the specific values ​​referred to when defining the range, including its endpoints and the models within that range.

[0013] In this specification, “dianhydride” is intended to include its precursors or derivatives, but it may also be referred to as “dianhydric acid,” “dianhydride,” or “acidic dianhydride.” These may not be technically dianhydrides, but nevertheless react with diamines to form polyamic acids, which can also be converted to polyimides.

[0014] In this specification, “diamine” is intended to include its precursors or derivatives, which may not be technically diamines, but nevertheless react with dianhydride acids to form polyamic acids, which can also be converted to polyimides.

[0015] In the present invention, the term "halogen" means a substituted product selected from fluoro(F), chloro(Cl), bromo(Br), and iod(I).

[0016] In this invention, the term "unsubstituted" means not substituted with any substituent, either absent or in a hydrogen state.

[0017] In this invention, the term "substituted" refers to a portion having substituents used in place of hydrogen atoms on one or more carbon atoms in the main chain. "Substituting" or "substituted with ~" is defined as including the implicit condition that such substitution leads to a stable compound, such as a compound that does not spontaneously deform through rearrangement, cyclization, removal, etc., depending on the acceptability of the substituted atom and the substituted product.

[0018] In the present invention, "C x-y " means having a number of carbon atoms between x and y.

[0019] In the present invention, the term "C1-C6 alkyl" means a C1-C6 linear or branched saturated hydrocarbon such as methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, and 2-ethylbutyl. Preferred alkyl groups contain about 1, 2, 3, 4, 5, or 6 carbon atoms in the chain.

[0020] In the present invention, the term "C1-C6 alkylene" may be linear or branched, and specifically refers to saturated aliphatic hydrocarbons such as methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, t-butylene, n-pentylene, or n-hexylene groups. "Alkylene" may be unsubstituted or may be optionally substituted with one or more substituted products that may be identical or different.

[0021] In the present invention, the term "C1-C3 haloalkyl" means a C1-C3 straight-chain or branched-chain saturated hydrocarbon in which at least one hydrogen atom of the C1-C3 straight-chain or branched-chain saturated hydrocarbon is substituted with a halogen atom (i.e., F, Cl, Br, or I). For example, "C1-C3 haloalkyl" may be CH2F, CHF2, CF3, etc.

[0022] In the present invention, the term "C3-C5 heteroaryl" refers to a selectively substituted aromatic ring containing 3 to 5 carbon atoms, in which at least one of the ring carbon atoms is replaced by a heteroatom selected from oxygen (O), nitrogen (N), and sulfur (S), or an aromatic ring fused to one or more rings (e.g., a bicyclic or tricyclic system), such as a heteroaryl ring, aryl ring, heterocyclic ring, or carbocycle ring, each of which may have selective substituents. For example, heteroaryls may include, but are not limited to, pyrrole, pyrazole, imidazole, furan, isoxazole, oxazole, thiophene, isothiazole, thiazole, pyridine, pyridazine, pyrimidine, pyrazine, or triazine (e.g., 1,2,4-triazine, 1,3,5-triazine). Furthermore, the heteroaryl may be substituted or unsubstituted.

[0023] Unless otherwise defined, all terms used herein, including technical or scientific terms, shall have the same meaning as commonly understood by those of ordinary skill in the art to which this invention pertains. Terms such as those defined in commonly used dictionaries shall be interpreted as having a meaning consistent with the meaning in the context of the related art, and shall not be interpreted in an ideal or overly formal sense unless explicitly defined in this application. The specific content for realizing the invention is described as follows.

[0024] Polyamic acid composition The present invention relates to a polyamic acid composition having improved wire adhesion and adhesion, and being usable for applications of conductor coating.

[0025] The polyamic acid composition of the present invention may be a polyimide varnish.

[0026] In one aspect of the present invention, there is provided a polyamic acid composition containing dianhydride monomer and diamine monomer as polymerization units, wherein the diamine monomer includes a first diamine monomer, a second diamine monomer, and a third diamine monomer, the second diamine monomer is a flexible diamine monomer having three or more benzene rings, and the third diamine monomer is represented by the following Chemical Formula 1. [Chemical Formula]

[0027] In Chemical Formula 1, A may be unsubstituted or substituted, and is hydrogen, halogen, C1-C6 alkyl, phenyl, (C1-C6 alkylene)-(C3-C5 heteroaryl), (C1-C6 alkylene)-COOH, or -OH, where the substitution is substitution with halogen, C1-C3 alkyl, C1-C3 haloalkyl, or oxo (=O).

[0028] Here, the first diamine monomer may be a diamine having two or less benzene rings.

[0029] Specifically, the first diamine monomer is 1,4-diaminobenzene (or paraphenylenediamine, PDA, PPD), 1,3-diaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobenzoic acid (DABA), 4,4'-diaminodiphenyl ether (or oxydianiline, ODA), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane (methylenediamine), 3,3'-diaminodiphenyl Nylmethane, 3,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 4,4'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine (or o-tolidine), 2,2'-dimethylbenzidine (or m -Toridine), 3,3'-Dimethoxybenzidine, 2,2'-Dimethoxybenzidine, 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 It may contain one or more selected from the group consisting of '-dimethoxybenzophenone, 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, and 4,4'-diaminodiphenyl sulfoxide.

[0030] More specifically, the first diamine monomer may contain one or more selected from the group consisting of 1,4-diaminobenzene, 1,3-diaminobenzene, and 4,4'-diaminodiphenyl ether, and more preferably, it may contain 4,4'-diaminodiphenyl ether.

[0031] Furthermore, the second diamine monomer is 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 2,2-bisaminophenoxyphenylpropane (BAPP), 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-phenyl)phenoxybenzophenone, 3,3'-diamino-4,4'-di(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenyl sulfide)benzene, 1 ,3-bis(4-aminophenylsulfide)benzene, 1,4-bis(4-aminophenylsulfide)benzene, 1,3-bis(3-aminophenylsulfone)benzene, 1,3-bis(4-aminophenylsulfone)benzene, 1,4-bis(4-aminophenylsulfone)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)phenyl] ether, bis[3-(3-aminophenoxy)phenyl] ketone, bis[3-(4-aminophenoxy)phenyl] ketone, bis[4-(4-aminophenoxy)phenyl] ketone, bis[4-(4-aminophenoxy) [Phenoxy)phenyl]ketone, bis[3-(3-aminophenoxy)phenyl]sulfide, bis[3-(4-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[3-(3-aminophenoxy)phenyl]sulfone, bis[3-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy 2,2-bis[3-(3-aminophenoxy)phenyl]sulfone, bis[3-(3-aminophenoxy)phenyl]methane, bis[3-(4-aminophenoxy)phenyl]methane, bis[4-(4-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[3-(3-A It may contain one or more selected from the group consisting of minophenoxy)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 (BDAF).

[0032] More specifically, the second diamine monomer may include one or more selected from the group consisting of 2,2-bisaminophenoxyphenylpropane (BAPP), 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,4-bis(3-aminophenoxy)benzene (TPE-Q), and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane (BDAF).

[0033] Furthermore, in the above chemical formula 1, A is hydrogen, fluoro(F), chloro(Cl), bromo(Br), methyl, ethyl, propyl, phenyl, (C1-C6 alkylene)-imidazolyl, (C1-C6 alkylene)-COOH, or -OH, and A may be unsubstituted or substituted with at least one methyl, ethyl, trifluoromethyl, or oxo(=O).

[0034] More specifically, A is hydrogen, fluoro(F), chloro(Cl), methyl, ethyl, propyl, phenyl, methylene-imidazolyl, ethylene-imidazolyl, propylene-imidazolyl, methylene-COOH, ethylene-COOH, propylene-COOH, butylene-COOH, or -OH, wherein A is unsubstituted or substituted with at least one methyl, ethyl, trifluoromethyl, or oxo(=O).

[0035] More specifically, A may be a methylene-imidazolyl substituted with hydrogen, fluoro(F), chloro(Cl), methyl, ethyl, propyl, phenyl, or methyl; a methyl-substituted ethylene-imidazolyl; a methyl-substituted propylene-imidazolyl; an oxo(=O)-substituted methylene-COOH; an oxo(=O)-substituted ethylene-COOH; an oxo(=O)-substituted propylene-COOH; an oxo(=O)-substituted butylene-COOH; or an -OH group.

[0036] In the chemical formula 1, the ratio of carbon to nitrogen (C / N) may be 0.5 to 2.5, preferably 0.6 to 2.1, and more preferably 0.7 to 1.9.

[0037] The third diamine monomer may also contain a triazine-based diamine, specifically 1,3,5-triazine-2,4-diamine, 6-chloro-1,3,5-triazine-2,4-diamine, 4,6-diamino-1,3,5-triazin-2-ol, and 6-methyl-1,3,5-triazine-2,4-diamine. e) It may contain one or more selected from the group consisting of 6-phenyl-1,3,5-triazine-2,4-diamine, 6-[2-(2-methylimidazol-1-yl)ethyl]-1,3,5-triazine-2,4-diamine, and 4-(4,6-diamino-1,3,5-triazin-2-yl)-4-oxobutanoic acid.

[0038] In one embodiment, the third diamine monomer may be 6-chloro-1,3,5-triazine-2,4-diamine alone, 4,6-diamino-1,3,5-triazine-2-ol alone, 6-methyl-1,3,5-triazine-2,4-diamine alone, 2,6-diamino-4-phenyl-1,3,5-triazine alone, 6-[2-(2-methylimidazolyl-1-yl)ethyl]-1,3,5-triazine-2,4-diamine alone, or 4-(4,6-diamino-1,3,5-triazine-2-yl)-4-oxobutanoic acid alone.

[0039] The third diamine monomer, which contains a functional group capable of coordinating with Cu, is incorporated into the polyimide chain, improving adhesion and thereby preventing the peeling of the coating layer caused by low adhesion between the conductor and the polyimide insulator. Furthermore, after curing the polyamic acid composition, the physical properties of the polyimide film can be adjusted to suit the purpose.

[0040] In the present invention, the diamine monomer may contain 50 to 98 mol% of the first diamine monomer, preferably 60 to 95 mol%, 70 to 90 mol%, and more preferably 78 to 88 mol%, based on 100 mol% of the total content of the diamine monomer. By including 50 to 98 mol% of the first diamine monomer, it is possible to provide a polyamic acid composition having the desired thermal, mechanical, and electrical properties after curing.

[0041] Furthermore, the diamine monomer may contain 1 to 25 mol% of the second diamine monomer, preferably 1.5 to 15 mol%, 1.8 to 8 mol%, and more preferably 2 to 5 mol%, based on 100 mol% of the total content of the diamine monomer. By including 1 to 25 mol% of the second diamine monomer, a polyamic acid composition having the desired thermal, mechanical, and electrical properties and adhesive strength after curing can be provided.

[0042] In detail, the second diamine monomer contained in the present invention (polyamic acid composition) has the effect of making polymer chains flexible, improving the appearance of the film produced thereafter, and broadening the range of content of the third diamine monomer (triazine-based diamine) for improving adhesive strength. Therefore, if the second diamine monomer is contained in an amount of less than 1 mol%, the above effect cannot be expected and is therefore undesirable, and if it is contained in an amount of more than 25 mol%, the cost incurred from using the second diamine monomer is economically inefficient compared to the above effect and is therefore undesirable.

[0043] Furthermore, the diamine monomer may contain 1 to 25 mol% of the third diamine monomer, preferably 5 to 23 mol%, 8 to 21 mol%, and more preferably 10 to 20 mol%, based on 100 mol% of the total content of the diamine monomer. Including 1 to 25 mol% of the third diamine monomer has the effect of providing a polyamic acid composition that does not crack after curing and has excellent adhesion to conductors.

[0044] In detail, the third diamine monomer contained in the present invention (polyamic acid composition) forms a coordination bond with Cu, thereby enhancing the adhesion between the polyimide insulator and the conductor. Therefore, by including 1 to 25 mol% of the third diamine monomer, it is possible to provide a polyamic acid composition that has improved adhesion and does not crack after curing.

[0045] In the present invention, the dianhydride monomer is pyromeretic dianehydride (PMDA), biphenyltetracarboxylic dianehydride (BPDA), 3,3',4,4'-benzophenone tetracarboxylic dianehydride (BTDA), oxydiphthalic dianehydride (ODPA), diphenylsulfone-3,4,3',4'-tetracarboxylic dianehydride (DSDA), bis(3,4-dicarboxyphenyl ) Sulfide diane hydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane diane hydride, 2,3,3',4'-benzophenone tetracarboxylic diane hydride, bis(3,4-dicarboxyphenyl)methane diane hydride, 2,2-bis(3,4-dicarboxyphenyl)propane diane hydride, p-phenylene bis(trimeltic monoester acid anhydride 1,3-bis(3,4-dicarboxyphenoxy)benzenedianehydride, 1,4-bis(3,4-dicarboxyphenoxy)benzenedianehydride, 1,4-bis(3,4-dicarboxyphenoxy)benzenedianehydride, 1,4-bis(3,4-dicarboxyphenoxy)benzenedianehydride It may contain one or more selected from the group consisting of -dicarboxyphenoxy)biphenyl dianehydride, 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propanedianehydride (BPADA), 2,3,6,7-naphthalenetetracarboxylic acid dianehydride, 1,4,5,8-naphthalenetetracarboxylic dianehydride, and 4,4'-(2,2-hexafluoroisopropylidene)diphthalic acid dianehydride.

[0046] Specifically, the dianhydride monomer may contain one or more selected from the group consisting of pyromeretic dianehydride (PMDA), biphenyltetracarboxylic dianehydride (BPDA), and benzophenone tetracarboxylic dianehydride (BTDA), and preferably contains pyromeretic dianehydride (PMDA).

[0047] In one embodiment, the polyamic acid composition may contain pyromeretic dianehydride (PMDA), 4,4'-diaminodiphenyl ether (ODA), 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), and 6-methyl-1,3,5-triazine-2,4-diamine as polymerization units.

[0048] In one embodiment, the polyamic acid composition may contain pyromeretic dianehydride (PMDA), 4,4'-diaminodiphenyl ether (ODA), 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), and 6-phenyl-1,3,5-triazine-2,4-diamine as polymerization units.

[0049] In one embodiment, the polyamic acid composition may contain pyromeretic dianehydride (PMDA), 4,4'-diaminodiphenyl ether (ODA), 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), and 6-[2-(2-methylimidazolyl-1-yl)ethyl]-1,3,5-triazine-2,4-diamine as polymerization units.

[0050] In one embodiment, the polyamic acid composition may contain pyromeretic dianehydride (PMDA), 4,4'-diaminodiphenyl ether (ODA), 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), and 4-(4,6-diamino-1,3,5-triazine-2-yl)-4-oxobutanoic acid as polymerization units.

[0051] In one embodiment, the polyamic acid composition may contain pyromeretic dianehydride (PMDA), 4,4'-diaminodiphenyl ether (ODA), 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), and 6-chloro-1,3,5-triazine-2,4-diamine as polymerization units.

[0052] In one embodiment, the polyamic acid composition may contain pyromeretic dianehydride (PMDA), 4,4'-diaminodiphenyl ether (ODA), 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), and 4,6-diamino-1,3,5-triazine-2-ol as polymerization units.

[0053] Furthermore, the molar ratio of the dianhydride monomer to the diamine monomer may be 6:4 to 4:6, preferably 5.5:4.5 to 4.5:6.5, and more preferably 5:5.

[0054] Furthermore, the polyamic acid composition may have a polyimide solids content of 10 to 50% by weight. The lower limit of the polyimide solids content may be, for example, 11% or more by weight, 12% or more by weight, 13% or more by weight, 14% or more by weight, or 15% or more by weight, and the upper limit may be, for example, 48% or less by weight, 45% or less by weight, 43% or less by weight, 40% or less by weight, 38% or less by weight, 35% or less by weight, 33% or less by weight, or 30% or less by weight. By adjusting the polyimide solids content of the polyamic acid composition, the increase in viscosity can be controlled and the process time during the curing process can be shortened.

[0055] Furthermore, the polyamic acid composition of the present invention further comprises an organic solvent, and the organic solvent is not particularly limited as long as it is an organic solvent in which the polyamic acid can dissolve, but one example is an aprotic polar solvent.

[0056] Specifically, the organic solvent may include one or more selected from the group consisting of N-methylpyrrolidone (NMP), N,N'-dimethylformamide (DMF), N,N'-diethylformamide (DEF), N,N'-dimethylacetamide (DMAc), dimethylpropanamide (DMPA), N,N-diethylacetamide (DEAc), dimethyl sulfoxide (DMSO), 3-methoxy-N,N-dimethylpropanamide (KJCMPA), p-chlorophenol, o-chlorophenol, γ-butyrolactone (GBL), diglyme, and naphthalene. Preferably, N-methylpyrrolidone (NMP), N,N'-dimethylformamide (DMF), N,N'-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), etc.

[0057] Furthermore, the organic solvent may further contain a modifier containing a hydroxyl group (OH) or an amine group (NH). Examples of modifiers containing a hydroxyl group (OH) or an amine group (NH) include ethylamine, triethanolamine, dimethylamine, trimethylamine, diethylenetriamine, ethylenediamine, tributylamine, pyridine, pyrrolidine, methanol, ethanol, propanol, isopropanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, hexanol, octanol, caprylic alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, allyl alcohol, clotyl alcohol, propargyl alcohol, ethylene glycol, propylene glycol, benzyl alcohol, and phenol. The modifier can react with a dianhydride monomer to control its reactivity.

[0058] Furthermore, the polyamic acid composition of the present invention may further contain nanosilica surface-modified with an organic silane. The nanosilica surface-modified with an organic silane prevents aggregation of inorganic particles within the polyamic acid composition, and the functional groups of the compound enhance the interaction with the solid content (polyamic acid), thereby improving dispersibility and miscibility.

[0059] The average particle size of the nanosilica surface-modified with the aforementioned organic silane may be 1 to 200 nm, specifically 5 to 150 nm, 5 to 100 nm, 5 to 70 nm, 10 to 50 nm, or 10 to 30 nm. The average particle size can be measured using equipment such as BET, SEM, or zeta potential.

[0060] The organic silanes used to modify the surface of nanosilica with the aforementioned organic silanes are methyltrimethoxysilane, hexamethyldisiloxane, n-octyltrimethoxysilane, n-octyltriethoxysilane, isooctyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-(methacryloxy)propyltriethoxysilane, 3-(methacryloxy)propylmethyldimethoxysilane, 3-(acryloxypropyl)methyldimethoxysilane, and 3-(methacryloxy)propyl Dimethylethoxysilane, Styrylethyltrimethoxysilane, Phenyltriethoxysilane, p-Tolyltriethoxysilane, Vinylmethyldiacetoxysilane, Vinyldimethylethoxysilane, Vinylmethyldiethoxysilane, Vinyltriethoxysilane, Vinyltriacetoxysilane, Vinyltriisopropoxysilane, Vinyltrimethoxysilane, Vinyltriphenoxysilane, Vinyltri-t-butoxysilane, Vinyltris(isobutoxy)silane, Vinyltriisopropenoxysilane, Vinyltris(2-methoxyethoxy)silane, Diisopropylethylaminephenyltrimethoxysilane (N,N-Diisopropylethylamine It may also contain one or more selected from the group consisting of phenyltrimethoxysilane, glycidoxypropyl trimethoxysilane (GPTMS), aminopropyltrimethoxysilane ((3-Aminopropyl)trimethoxy-silane:APTMS), phenyltrimethoxysilane (Phenyltrimethoxysilane:PTMS), and phenylaminopropyltrimethoxysilane (N-Phenyl-3-aminopropyltrimethoxysilane:PAPTES).

[0061] The nanosilica surface-modified with the aforementioned organic silane may have compounds containing at least one phenyl group at its terminal and compounds containing at least one amine group, hydroxyl group, thiol group, or epoxide group bonded to its surface. Specifically, the compound containing at least one phenyl group at its terminal may be phenyltrimethoxysilane (PTMS) or phenylaminopropyltrimethoxysilane (N-Phenyl-3-aminopropyltrimethoxysilane:PAPTES). The compound containing at least one amine group, hydroxyl group, thiol group, or epoxide group at its terminal may be glycidoxypropyl trimethoxysilane (GPTMS) or aminopropyltrimethoxysilane ((3-Aminopropyl)trimethoxy-silane:APTMS).

[0062] The nanosilica surface-modified with the aforementioned organic silane can be produced by surface-treating nanosilica with the organic silane. For example, nanosilica can be obtained by heating the organic silane under acidic or basic conditions for approximately 1 to 24 hours. Surface modification can also be achieved by other known methods; for example, surface-modified nanosilica can be obtained by mixing the organic silane with a solvent and then reacting it at a temperature of 10 to 100°C or 20 to 60°C for 1 to 10 hours or 1 to 5 hours. The above methods can be used to bond two or more compounds to the surface of the nanosilica.

[0063] Furthermore, the nanosilica surface-modified with the organic silane may be included in an amount of 0.1 to 12.0 parts by weight per 100 parts by weight of the polyamic acid composition. For example, the lower limit of the content of nanosilica surface-modified with the organic silane may be 0.2 parts by weight or more, 0.3 parts by weight or more, 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, or 0.55 parts by weight or more. Furthermore, for example, the upper limit may be 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, 1.5 parts by weight or less, 1.25 parts by weight or less, 1.20 parts by weight or less, 1.15 parts by weight or less, 1.10 parts by weight or less, 1.05 parts by weight or less, 1.0 part by weight or less, 0.95 parts by weight or less, 0.9 parts by weight or less, 0.85 parts by weight or less, 0.8 parts by weight or less, 0.79 parts by weight or less, 0.78 parts by weight or less, 0.77 parts by weight or less, or 0.76 parts by weight or less. Containing the nanosilica within the above range is effective in improving properties and is preferable because it prevents a decrease in physical properties due to aggregation and reduced usability.

[0064] Polyamic acid composition and its cured product In this invention, the adhesive strength was confirmed by peel strength and the crosscut test, which are mainly used as criteria for determining the adhesiveness of the polyimide.

[0065] After curing, the peel strength of the polyamic acid composition according to the present invention may be at a level where peeling is not possible. Here, the peel strength was measured using a UTM (Instron, model 5564) equipped with a 90° peel strength while peeling at 50 mm / sec under conditions of 23°C and 50% RH.

[0066] After curing, the polyamic acid composition according to the present invention may have an adhesion strength of 5B or higher according to ASTM D 3359. Here, the adhesion strength was measured by the method presented in ASTM D 3359.

[0067] In this invention, tensile strength, modulus, and elongation, which are mainly used as criteria for determining the mechanical properties of the polyimide, were confirmed.

[0068] After curing, the tensile strength of the polyamic acid composition according to the present invention may be 95 MPa or higher. The lower limit of the tensile strength may be, for example, 98 MPa, 100 MPa, 102 MPa, 104 MPa, 105 MPa, 106 MPa, 107 MPa, 108 MPa, 109 MPa, or 110 MPa or higher. The upper limit is not particularly limited, but may be 400 MPa or lower. The tensile strength was measured using an Instron 5564 UTM equipped with an INSTRON instrument, with samples measuring 220 mm in length and 10 mm in width, at a grip spacing of 50 mm and a speed of 50 mm / min, in accordance with the ASTM D-882 standard, and the average of 10 samples was calculated.

[0069] After curing, the modulus of the polyamic acid composition according to the present invention may be 2.0 GPa or higher. The lower limit of the modulus may be, for example, 2.1 GPa or higher, 2.2 GPa or higher, 2.3 GPa or higher, 2.4 GPa or higher, or 2.5 GPa or higher, and the upper limit is not particularly limited, but may be 10 GPa or lower. The modulus was measured using an Instron 5564 UTM from INSTRON, Inc., with samples measuring 220 mm in length and 10 mm in width, at a speed of 50 mm / min in accordance with the ASTM D-882 standard, and the average of 10 samples was calculated.

[0070] After curing, the elongation of the polyamic acid composition according to the present invention may be 3% or more, and the lower limit of the elongation may be, for example, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, or 12% or more. The upper limit is not particularly limited, but may be 80% or less. In one embodiment, the elongation can be measured in accordance with the ASTM D-882 standard by preparing a sample with a length of 220 mm and a width of 10 mm using an Instron 5564 UTM manufactured by INSTRON, and measuring the elongation at a speed (50 mm / min).

[0071] In this invention, the thermal decomposition temperature (Td), glass transition temperature (Tg), and coefficient of thermal expansion (CTE), which are mainly used as criteria for determining the thermal properties of the polyimide, were confirmed.

[0072] After curing, the glass transition temperature (Tg) of the polyamic acid composition according to the present invention may be 300°C or higher. The lower limit of the glass transition temperature may be, for example, 310°C±5°C, 320°C±5°C, 330°C±5°C, 340°C±5°C, or 350°C±5°C or higher. The upper limit is not particularly limited, but may be 600°C or lower. The glass transition temperature can be measured with respect to polyimide using DMA at a rate of 5°C / min.

[0073] The temperature at which a 1% weight loss occurs after curing of the polyamic acid composition according to the present invention, i.e., the 1% by weight thermal decomposition temperature (Td), may be 340°C or higher, and the lower limit of the 1% by weight thermal decomposition temperature (Td) may be, for example, 342°C±2°C, 345°C±2°C, 350°C±2°C, 355°C±2°C, 360°C±2°C, 365°C±2°C, 370°C±2°C, 375°C±2°C, or 380°C±2°C or higher. Here, the upper limit is not particularly limited, but may be 600°C or lower. Furthermore, the temperature at which a 5% weight loss occurs, i.e., the 5% by weight thermal decomposition temperature (Td), may be 500°C or higher. The lower limit of the 5% by weight thermal decomposition temperature (Td) may be, for example, 510°C±2°C, 515°C±2°C, 520°C±2°C, 525°C±2°C, 530°C±2°C, 533°C±2°C, or 535°C±2°C or higher. The upper limit is not particularly limited, but may be 750°C or lower. The thermal decomposition temperature can be measured using a TA-Q50 thermogravimetric analysis model. As a specific example, polyimide is heated to 150°C at a rate of 10°C / min under a nitrogen atmosphere, and then the water is removed by maintaining an isotherm for 30 minutes. Next, the temperature is raised to 600°C at a rate of 10°C / min, and the temperature at which a 1% or 5% weight loss occurs can be measured.

[0074] After curing, the thermal expansion coefficient of the polyamic acid composition according to the present invention may be 30 ppm / °C or more in the range of 100°C to 350°C, and the lower limit of the thermal expansion coefficient may be, for example, 31 ppm / °C, 32 ppm / °C, 33 ppm / °C, 34 ppm / °C, or 35 ppm / °C or more. Here, the upper limit is not particularly limited, but may be 70 ppm / °C or less. In one embodiment, the thermal expansion coefficient was measured by measuring the gradient in the range of 100 to 250°C when the temperature was raised from room temperature to 350°C at a heating rate of 10°C / min using TMA equipment.

[0075] In this invention, the dielectric constant and dielectric breakdown strength, which are mainly used as criteria for determining the electrical properties of the polyimide, were confirmed.

[0076] After curing, the dielectric constant of the polyamic acid composition according to the present invention may be 4 or less. The upper limit of the dielectric constant may be, for example, 3.9 or less, 3.85 or less, 3.8 or less, 3.75 or less, or 3.7 or less. The lower limit is not particularly limited, but may be 2.0 or more. Here, the dielectric constant was measured at 10 GHz using a Keysight SPDR (split post dielectric resonator) measuring instrument.

[0077] After curing, the dielectric breakdown voltage (BDV) of the polyamic acid composition according to the present invention may be 100kV / mm or higher as measured by the ASTM D149 standard. The lower limit of the dielectric breakdown voltage may be, for example, 150kV / mm or higher, 160kV / mm or higher, 170kV / mm or higher, 180kV / mm or higher, 190kV / mm or higher, 195kV / mm or higher, 200kV / mm or higher, 205kV / mm or higher, 208kV / mm or higher, or 210kV / mm or higher. The upper limit is not particularly limited, but may be 500kV / mm or lower. Specifically, the dielectric breakdown voltage (BDV) was measured by pre-treating the sample in a 100°C oven to remove moisture, then fixing it in a measurement device (PHENIX TECHNOLOGIES 6CCE50-5) set to a room temperature atmosphere, applying a voltage of 10 kVAc to the electrodes, and increasing the AC voltage from 0 at a constant rate.

[0078] Furthermore, the polyamic acid composition of the present invention is prepared at a temperature of 23°C and 1s -1The viscosity measured under the shear rate conditions may be in the range of 200 to 50,000 cP. Specifically, the lower limit of the viscosity of the polyimide solution may be 300 cP or higher, 400 cP or higher, 500 cP or higher, 600 cP or higher, 700 cP or higher, 800 cP or higher, 900 cP or higher, or 1,000 cP or higher, and the upper limit may be 45,000 cP or lower, 40,000 cP or lower, 35,000 cP or lower, 30,000 cP or lower, 25,000 cP or lower, 20,000 cP or lower, 18,000 cP or lower, 16,000 cP or lower, 15,000 cP or lower, 14,000 cP or lower, 13,000 cP or lower, 12,000 cP or lower, 11,000 cP or lower, or 10,000 cP or lower. By adjusting the viscosity range of the polyamic acid composition, it is possible to produce polyimide cured products with excellent processability and desired physical properties.

[0079] In another aspect of the present invention, a polyimide cured product obtained by curing the polyamic acid composition is provided, wherein the polyimide cured product may be a polyimide film.

[0080] In another aspect of the present invention, a polyimide is provided which is produced by imidizing the polyamic acid composition, and the polyimide may be in the form of a film.

[0081] In another aspect of the present invention, a polyimide coating containing the polyimide cured product is provided.

[0082] In one embodiment, the method for producing the polyimide coating may include the steps of coating the surface of a conductor with a polyamic acid composition and imidizing the polyamic acid composition coated on the surface of the conductor.

[0083] The conductor may be a copper wire made of copper or a copper alloy, but it may also be a conductor made of other metallic materials such as silver wire, or various metal-plated wires such as aluminum or tin-plated wire. The thickness of the conductor and the sheath may conform to the KS C 3107 standard. The diameter of the conductor may be in the range of 0.3 to 3.2 mm, and the standard thickness of the sheath (average value of the maximum and minimum thicknesses) may be 21 to 194 μm for type 0, 14 to 169 μm for type 1, and 10 to 31 μm for type 2. Furthermore, the cross-sectional shape of the conductor may be annular, rectangular, or hexagonal, but is not limited to these.

[0084] In another aspect of the present invention, a wire containing the polyimide coating is provided.

[0085] Specifically, the insulated wire may include a polyimide coating produced by coating the surface of the electric wire with the polyamic acid composition and imidizing it. In one specific example, the insulated wire may include an electric wire and a coating in which the above-mentioned polyimide is coated and imidized on the surface of the electric wire.

[0086] Furthermore, this application can provide an electronic device including the aforementioned insulated wire. An example of such an electronic device is an electric motor.

[0087] In another aspect of the present invention, a component is provided which includes a molded article formed from a polyamic acid composition.

[0088] Specifically, the components may include electronic circuit board components, semiconductor devices, lithium-ion battery components, solar cell components, fuel cell components, motor windings, engine peripheral components, paints, optical components, heat dissipation materials, electromagnetic shielding materials, surge components, dental materials, slide coatings, and electrostatic chucks. [Effects of the Invention]

[0089] The polyamic acid composition of the present invention exhibits excellent adhesive strength and adhesion to conductive wires such as copper, which makes it highly suitable for use as an insulating coating material for electric wires and the like.

[0090] Furthermore, the polyamic acid composition of the present invention contains a high content of nucleophilic functional group monomers (triazine monomers), resulting in excellent adhesion and bonding to conductive wires such as copper, and enabling the stable formation of films.

[0091] More specifically, recently, as an alternative to improve the adhesion between conductors and polyimide insulators, nucleophilic (triazine-based) monomers capable of coordinating with Cu have been used. However, increasing the content of nucleophilic (triazine-based) monomers to improve adhesion has resulted in the inability to form a film. On the other hand, the polyamic acid composition of the present invention contains a flexible diamine having three or more benzene rings, which makes the polymer chain flexible, improves the appearance of the film, and has the effect of stably forming a film even when containing a high content of triazine-based monomers. [Modes for carrying out the invention]

[0092] To aid in understanding the present invention, examples are provided below. The following examples are provided to facilitate understanding of the present invention and do not limit the scope of the invention.

[0093] <Example 1. Polyamic acid composition> Example 1-1 Dimethylacetamide (DMAc) solvent was added to a reaction vessel purged with nitrogen gas, and nanosilica surface-treated with organosilane (0.5-0.75 mol% relative to the content of diamine and dianhydride), 4,4'-diaminodiphenyl ether (ODA), triazine-based diamine, and 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) were added. Next, pyromeretic dianehydride (PMDA) was added, and the mixture was stirred and polymerized for about 1 hour to produce a polyamic acid composition (solids content 15-30%, viscosity at 30°C 1,000-10,000 cP).

[0094] Examples 1-2 to 1-18, Comparative Examples 1-1 to 1-11, and Comparative Examples A-1 to A-6 A polyamic acid composition was prepared using the same method as in Example 1-1, except that the content of each component or the type of triazine diamine was changed as shown in Table 1. [Table 1]

[0095] The abbreviations in Table 1 above are as follows: PMDA: Pyromeretic dianhydride PPD: Paraphenylenediamine ODA: 4,4'-diaminodiphenyl ether BAPP: 2,2'-Bis[4-(4-aminophenoxy)phenyl]propane

[0096] <Example 2: Polyimide film (cured polyimide product)> Example 2-1 The polyamic acid composition produced in Example 1-1 was subjected to high-speed rotation at 2,000 rpm to remove air bubbles. Next, the polyamic acid composition was coated onto a soda-limeglass substrate to a thickness of 20-26 μm using a spin coater. Then, under a nitrogen atmosphere, it was cured at 110°C (20 min) → 150°C (20 min) → 200°C (20 min) → 300°C (20 min) to obtain a polyimide film.

[0097] Examples 2-2 to 2-18, Comparative Examples 2-1 to 2-11, and Comparative Examples B-1 to B-7 A polyimide film was produced using the same method as in Example 2-1, except that the polyamic acid composition was modified as shown in Table 2. [Table 2]

[0098] According to Table 2, Comparative Examples B-1 to B-7, which contained 10 mol% or more of a triazine diamine, specifically 6-Methyl-1,3,5-triazine-2,4-diamine, 6-Phenyl-1,3,5-triazine-2,4-diamine, 6-[2-(2-methylimidazol-1-yl)ethyl]-1,3,5-triazine-2,4-diamine, 4-(4,6-diamino-1,3,5-triazin-2-yl)-4-oxobutanoic acid, 6-chloro-1,3,5-triazine-2,4-diamine, or 4,6-Diamino-1,3,5-triazin-2-ol, were confirmed to have cracked during the curing step and no film was formed.

[0099] On the other hand, even when containing 10 mol% or more of triazine-based diamine, it was confirmed that films were formed after curing in Examples 1-1 to 1-18, which contained flexible diamine (BAPP) (Examples 2-1 to 2-18).

[0100] <Examples> Experimental Example 1: Evaluation of Adhesion The physical properties of the cured polyamic acid compositions produced in Examples 1-1 to 1-18 and Comparative Examples 1-1 to 1-11, as well as the cured products of Examples 2-1 to 2-18 and Comparative Examples 2-1 to 2-11, were confirmed using the following method, and the results are shown in Table 3 below.

[0101] (1) Peel Strength The polyamic acid compositions prepared in the examples and comparative examples were applied to copper foil (Cu foil), spin-coated, and cured to coat the copper foil (Cu foil) with a polyimide cured product (film). The peel strength was measured while peeling the copper foil (Cu foil) layer and the polyimide cured product layer using a UTM (Instron model 5564) system.

[0102] A polyimide cured layer (film layer) was fixed to the upper grip, and a copper foil (Cu foil) layer was fixed to the lower grip. The strength was then measured by applying force at a peeling angle of 90° and a peeling speed of 50 mm / min under conditions of 23°C and 50% RH. The results are shown in Table 3 below.

[0103] (2) Adhesion (Crosscut Test) The adhesion strength of the polyimide films produced according to the examples and comparative examples was measured using the method described in ASTM D 3359, and the results are shown in Table 3 below. Specifically, the polyimide films produced according to the examples and comparative examples were engraved in a grid pattern at 1 mm intervals with a cutter, and then a peel test was performed using a special tape, and the degree of peeling was recorded. A smaller degree of peeling is preferable because it increases the reliability as an insulator (5B: 0% of the total area removed, 4B: greater than 0% to less than 5% of the total area removed, 3B: 5% or more to less than 15%, 2B: 15% or more to less than 35%, 1B: 35% or more to less than 65%, 0B: 65% or more of the area removed).

[0104] [Table 3]

[0105] Table 3 confirms that Comparative Examples 2-1 and 2-2, which do not contain triazine-based diamines, exhibited low peel strength and low adhesion (Crosscut Test) evaluation results.

[0106] Furthermore, it was confirmed that the examples containing triazine-based diamines and flexible diamines (BAPP) showed improved copper (Cu) adhesion compared to comparative examples containing only triazine-based diamines (Comparative Examples 2-3 to 2-11). This indicates that the examples could increase the triazine-based diamine content by further including flexible diamines, resulting in further improved copper (Cu) adhesion.

[0107] Experimental Example 2: Evaluation of Mechanical and Thermal Properties The physical properties of the cured polyamic acid compositions produced according to all embodiments of the present invention were confirmed by the following method.

[0108] (1) Tensile strength, Young's modulus, and elongation For the polyimide films produced according to all embodiments of the present invention, samples measuring 50 mm in length and 10 mm in width were prepared using an Instron 5564 UTM from INSTRON, Inc., and measured at a speed of 50 mm / min in accordance with ASTM D-882-91. The average of 10 samples was calculated.

[0109] As a result, it was confirmed that the polyimide films produced by all embodiments of the present invention had a tensile strength of 95 MPa or higher, a modulus of 2.0 GPa or higher, and an elongation of 3% or higher.

[0110] (2) Temperature of 1% by weight decrease and temperature of 5% by weight decrease (Td) Using a TA-manufactured Q50 thermogravimetric analysis system, the polyimide films produced in the examples and comparative examples were heated to 150°C at a rate of 10°C / min under a nitrogen atmosphere, and then kept isothermal for 30 minutes to remove moisture. Next, the temperature was increased to 600°C at a rate of 10°C / min, and the temperature at which a 1% or 5% weight loss occurred was measured.

[0111] As a result, it was confirmed that the temperature (Td) at which a 1% weight loss occurs in the polyimide film produced by all embodiments of the present invention is 340°C or higher, and the temperature (Td) at which a 5% weight loss occurs is 500°C or higher.

[0112] (3) Glass transition temperature (Tg) The glass transition temperature of polyimide films produced according to all examples and comparative examples of the present invention was measured using DMA at a rate of 5°C / min up to 350°C.

[0113] As a result, it was confirmed that the glass transition temperature of the polyimide films produced by all embodiments of the present invention was 300°C or higher.

[0114] (4) Coefficient of thermal expansion (CTE) For polyimide films produced according to the examples and comparative examples of the present invention, the gradient in the 100-250°C range was measured when the temperature was increased from room temperature to 350°C at a heating rate of 10°C / min using a TMA-equipped (Q400) manufactured by TA Corporation.

[0115] As a result, it was confirmed that the coefficient of thermal expansion (CTE) of the polyimide films produced by all embodiments of the present invention was 30 ppm / °C or higher.

[0116] Experimental Example 3: Evaluation of Electrical Characteristics The physical properties of the cured polyamic acid composition produced according to the examples of the present invention were confirmed using the following method.

[0117] (1) Dielectric constant The dielectric constant at 10 GHz was measured for the polyimide films produced according to the examples and comparative examples of the present invention using a Keysight SPDR (Split post dielectric resonator) under conditions of 23°C and 50% RH, and the average of 2 to 3 samples was calculated.

[0118] As a result, it was confirmed that the dielectric constant of the polyimide films produced by all embodiments of the present invention after curing was 4 or less.

[0119] (2) Dielectric breakdown strength The dielectric breakdown voltage (BDV) of polyimide films produced according to the examples and comparative examples of the present invention was measured according to the ASTM D149 standard, and the average of eight samples was calculated. Specifically, the polyimide films were pre-treated in a 100°C oven to remove moisture, then fixed in a measuring device (TECHNOLOGIES 6CCE50-5, manufactured by PHENIX) set to a room temperature atmosphere, and a voltage of 10 kVAc was applied to the electrodes, and the BDV was measured by increasing the AC voltage from 0 at a constant rate.

[0120] As a result, it was confirmed that the dielectric breakdown strength (BDV) of the polyimide films produced by all embodiments of the present invention, as measured in accordance with the ASTM D149 standard, was 100 kV / mm or higher.

[0121] Summarizing the results of Experimental Examples 1-3, it was confirmed that the polyamic acid composition and its cured product (film) of the present invention, by containing a specific triazine-based diamine and a flexible diamine having three or more benzene rings, exhibits stable mechanical, thermal, and electrical properties, and significantly improved adhesion to Cu. In particular, when obtaining a polyamic acid composition that satisfies such effects, improving one property generally leads to a decrease in other properties, and simultaneously satisfying various properties is considerably limiting and complex. Therefore, the present invention has technical significance in that it has found optimal monomer components and component ratios that are excellent in various properties.

[0122] Recently, as an alternative to improving the adhesion between conductors and polyimide insulators, nucleophilic (triazine-based) monomers capable of coordinating with Cu have been used. However, increasing the content of nucleophilic (triazine-based) monomers to improve adhesion presented a problem: film formation was impossible. To improve this, the present invention further includes a flexible diamine having three or more benzene rings, and has confirmed that even when the content of nucleophilic (triazine-based) monomers capable of coordinating with Cu is increased to improve adhesion to Cu, a film can be stably formed. Furthermore, the present invention includes a flexible diamine having three or more benzene rings, and by designing the content of triazine-based monomers so that the film does not crack and the polymer chains remain flexible, it has been confirmed that the adhesion between conductors and polyimide insulators is excellently improved, and that various physical properties are also superior.

[0123] This specification omits detailed descriptions of matters that can be fully understood and inferred by a person with ordinary skill in the art of the present invention, and various modifications are possible without changing the technical idea or essential configuration of the present invention, other than the specific examples given herein. Therefore, the present invention can be implemented in ways different from those specifically described and illustrated herein, and this is something that can be understood by a person with ordinary skill in the art of the present invention.

Claims

1. It contains dianhydride monomers and diamine monomers as polymerization units, The diamine monomer comprises a first diamine monomer, a second diamine monomer, and a third diamine monomer. The second diamine monomer is a soft diamine monomer having three or more benzene rings. The third diamine monomer is a polyamic acid composition represented by the following chemical formula 1. 【Chemistry 1】 In the aforementioned chemical formula 1, A may be unsubstituted or substituted and is hydrogen, halogen, C １ -C ６ alkyl, phenyl, (C １ -C ６ alkylene)-(C ３ -C ５ heteroaryl), (C １ -C ６ alkylene)-COOH, or -OH, where the substitution is substitution with halogen, C １ -C ３ alkyl, C １ -C ３ haloalkyl or oxo(=O).

2. The polyamic acid composition according to claim 1, wherein the first diamine monomer is a diamine having two or fewer benzene rings.

3. The first diamine monomer is 1,4-diaminobenzene (or paraphenylenediamine, PDA, PPD), 1,3-diaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobenzoic acid (DABA), 4,4'-diaminodiphenyl ether (or oxydianiline, ODA), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane (methylenediamine), 3,3'-diaminodiphenylmethane, 3, 4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 4,4'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine (or o-tolidine), 2,2'-dimethylbenzidine (or m-tolidine), 3,3' -Dimethoxybenzidine, 2,2'-Dimethoxybenzidine, 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 The polyamic acid composition according to claim 2, comprising one or more selected from the group consisting of n, 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, and 4,4'-diaminodiphenyl sulfoxide.

4. The aforementioned second diamine monomer is 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 2,2-bisaminophenoxyphenylpropane (BAPP), 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-phenyl)phenoxybenzophenone, 3,3'-diamino-4,4'-di(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenyl sulfide)benzene, 1, 3-bis(4-aminophenylsulfide)benzene, 1,4-bis(4-aminophenylsulfide)benzene, 1,3-bis(3-aminophenylsulfone)benzene, 1,3-bis(4-aminophenylsulfone)benzene, 1,4-bis(4-aminophenylsulfone)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)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]sulfide, bis[3-(4-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[3-(3-aminophenoxy)phenyl]sulfone, bis[3-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone Lufon, 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 The polyamic acid composition according to claim 1, comprising one or more selected from the group consisting of 2,1,1,3,3,3-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 (BDAF).

5. A is hydrogen, fluoro(F), chloro(Cl), bromo(Br), methyl, ethyl, propyl, phenyl, (C １ -C ６ Alkilen)-Imidazolyl, (C １ -C ６ Alkylene)-COOH or -OH, The polyamic acid composition according to claim 1, wherein A is unsubstituted or substituted with at least one methyl, ethyl, trifluoromethyl, or oxo (=O).

6. The third diamine monomer is 1,3,5-triazine-2,4-diamine, 6-chloro-1,3,5-triazine-2,4-diamine, 4,6-diamino-1,3,5-triazine-2-ol, 6-methyl-1,3,5-triazine-2,4-diamine, 6-phenyl-1, The polyamic acid composition according to claim 1, comprising one or more selected from the group consisting of 3,5-triazine-2,4-diamine (6-Phenyl-1,3,5-triazine-2,4-diamine), 6-[2-(2-methylimidazolyl-1-yl)ethyl]-1,3,5-triazine-2,4-diamine (6-[2-(2-methylimidazol-1-yl)ethyl]-1,3,5-triazine-2,4-diamine), and 4-(4,6-diamino-1,3,5-triazin-2-yl)-4-oxobutanoic acid (4-(4,6-diamino-1,3,5-triazin-2-yl)-4-oxobutanoic acid).

7. The polyamic acid composition according to claim 1, wherein the diamine monomer contains 50 to 98 mol% of the first diamine monomer based on 100 mol% of the total content of the diamine monomer.

8. The polyamic acid composition according to claim 1, wherein the diamine monomer contains 1 to 25 mol% of the second diamine monomer based on 100 mol% of the total content of the diamine monomer.

9. The polyamic acid composition according to claim 1, wherein the diamine monomer contains 1 to 25 mol% of the third diamine monomer based on 100 mol% of the total content of the diamine monomer.

10. The aforementioned dianhydride monomers include pyromeretic dianehydride (PMDA), biphenyltetracarboxylic dianehydride (BPDA), 3,3',4,4'-benzophenone tetracarboxylic dianehydride (BTDA), oxydiphthalic dianehydride (ODPA), diphenylsulfone-3,4,3',4'-tetracarboxylic dianehydride (DSDA), and bis(3,4-dicarboxyphenyl) sulfide dianehydride. Hydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropanedianehydride, 2,3,3',4'-benzophenonetetracarboxylic dianehydride, bis(3,4-dicarboxyphenyl)methanedianehydride, 2,2-bis(3,4-dicarboxyphenyl)propanedianehydride, p-phenylenebis(trimeltic monoester acid anhydride), p-biphenyl Lenbis (trimeltic monoester acid anhydride), m-terphenyl-3,4,3',4'-tetracarboxylic dianehydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianehydride, 1,3-bis(3,4-dicarboxyphenoxy)benzenedianehydride, 1,4-bis(3,4-dicarboxyphenoxy)benzenedianehydride, 1,4-bis(3,4-dicarboxyphenoxy) The polyamic acid composition according to claim 1, comprising one or more selected from the group consisting of biphenyl dianehydride, 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propanedianehydride (BPADA), 2,3,6,7-naphthalenetetracarboxylic acid dianehydride, 1,4,5,8-naphthalenetetracarboxylic dianehydride, and 4,4'-(2,2-hexafluoroisopropylidene)diphthalic acid dianehydride.

11. The polyamic acid composition according to claim 1, wherein, after curing, the polyamic acid composition has an adhesion strength of 5B or higher in accordance with the ASTM D 3359 standard.

12. After curing, the tensile strength of the polyamic acid composition is 95 MPa or higher. The modulus is 2.0 GPa or higher. The polyamic acid composition according to claim 1, wherein the elongation rate is 3% or more.

13. After curing, the glass transition temperature of the polyamic acid composition is 300°C or higher. The temperature (Td) at which a 1% weight loss occurs is 340°C or higher. The temperature (Td) at which a 5% weight loss occurs is 500°C or higher. The polyamic acid composition according to claim 1, wherein the coefficient of thermal expansion (CTE) is 30 ppm / °C or more in the range of 100°C to 350°C.

14. After curing, the dielectric constant of the polyamic acid composition is 4 or less. The polyamic acid composition according to claim 1, wherein the dielectric breakdown strength (BDV) measured in accordance with the ASTM D149 standard is 100 kV / mm or more.

15. A polyimide cured product produced by curing a polyamic acid composition according to any one of claims 1 to 14.

16. A polyimide coated material comprising the polyimide cured product described in claim 15.

17. An electric wire comprising the polyimide coating described in claim 16.

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