Polyamide-imide and polyamide-imide films

Abstract

To provide a polyamide-imide having a low dielectric constant and a dielectric tangent.SOLUTION: Provided is a polyamide-imide: including a structure derived from a compound containing at least one type selected from a group consisting of a diamine and a diisocyanate and a structure derived from a carboxylic acid compound containing at least a tricarboxylic acid anhydride; containing a compound in which at least one type selected from the compound and the carboxylic acid compound contains at least one non-aromatic hydrocarbon group, and which has a group in which the total carbon number of the at least one non-aromatic hydrocarbon group is 8 or more; and containing a compound in which at least one type selected from the compound and the carboxylic acid compound has an aromatic hydrocarbon group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to polyamideimide, a polyamideimide-containing liquid, a polyamideimide film, and a printed circuit board.

Background Art

[0002] Polyamideimide is widely used in various applications because of its excellent electrical insulation, heat resistance, chemical resistance, and solvent resistance. For example, polyamideimide is used as a material for enamel wire varnish, protective films for electronic components, optical or display films, etc. (for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In recent years, higher integration and higher frequencies of electronic components have been demanded, and it has been desired to further improve the dielectric properties of insulating materials in a wide frequency range including high frequencies. Therefore, the present disclosure provides a polyamideimide having a low dielectric constant and a low dielectric tangent, and a polyamideimide-containing liquid containing the polyamideimide. Further, the present disclosure provides a polyamideimide film and a printed circuit board that exhibit excellent insulation properties.

Means for Solving the Problems

[0005] Examples of embodiments are listed below. The present invention is not limited to the following embodiments.

[0006] (1) It includes a structure derived from a compound containing at least one selected from the group consisting of diamine and diisocyanate, and a structure derived from a carboxylic acid compound containing at least a tricarboxylic anhydride. At least one selected from the above compound and the above carboxylic acid compound includes a compound having a group comprising at least one non-aromatic hydrocarbon group, wherein the total number of carbon atoms of the at least one non-aromatic hydrocarbon group is 8 or more. At least one selected from the above compound and the above carboxylic acid compound includes a compound having an aromatic hydrocarbon group. Polyamide-imide. (2) The polyamide-imide according to (1) above, wherein the carboxylic acid compound further comprises a dicarboxylic acid. (3) The polyamide imide according to (1) or (2) above, comprising at least one non-aromatic hydrocarbon group, wherein the group comprising the at least one non-aromatic hydrocarbon group having a total of 8 or more carbon atoms comprises a saturated aliphatic hydrocarbon group having 8 or more carbon atoms. (4) The polyamide imide according to any one of (1) to (3) above, wherein the number of carbon atoms is 28 or more. (5) A polyamide-imide according to any of (1) to (4) above, having a tensile strength of 80 MPa or more. (6) A polyamide-imide according to any of (1) to (5) above, wherein the elongation at break is 8% or more. (7) A polyamide-imide according to any of (1) to (6) above, wherein the tensile modulus is 1.5 GPa or more. (8) at 10GHz ratio A polyamide-imide according to any of (1) to (7) above, wherein the dielectric constant is 3.6 or less. (9) A polyamide-imide according to any of (1) to (8) above, wherein the dielectric loss tangent at 10 GHz is 0.015 or less. (10) A polyamide-imide-containing liquid comprising the polyamide-imide described in any of (1) to (9) above and a solvent. (11) A polyamide-imide film obtained using any of the polyamide-imide described in (1) to (9) above or the polyamide-imide-containing liquid described in (10) above. (12) A printed circuit board obtained using the polyamide-imide described in any of (1) to (9) above or the polyamide-imide-containing liquid described in (10) above. [Effects of the Invention]

[0007] This disclosure provides a polyamide-imide having a low dielectric constant and dielectric loss tangent, as well as a polyamide-imide-containing liquid containing the polyamide-imide. Furthermore, this disclosure provides a polyamide-imide film and substrate exhibiting excellent insulating properties. [Modes for carrying out the invention]

[0008] Embodiments of the present invention will now be described. The present invention is not limited to the following embodiments. Furthermore, the following embodiments can be implemented individually or in combination. Combinations of multiple embodiments are also included in the present invention.

[0009] In numerical ranges described stepwise within this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range. Furthermore, the upper or lower limits of numerical ranges described within this disclosure may be replaced with the values ​​shown in the examples. A numerical value may be selected from the upper and lower limits described stepwise within this disclosure to form a stepped numerical range. Also, the upper and lower limits described within this disclosure may be replaced with the values ​​shown in the examples. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. In this disclosure, each structure in the polymer may contain multiple types of that structure. When multiple types of structures exist in the polymer, the content or amount of each structure means the total content or amount of those multiple types of structures present in the polymer, unless otherwise specified. In this disclosure, “layers” include continuous and discontinuous layers. The thickness of a “layer” may be uniform or non-uniform. The outer edges of a “layer” in the planar direction and the outer edges in the thickness direction may be defined or indefinite, respectively. The same applies to “films.”

[0010] <Polyamide-imide> In embodiments of the present invention, the polyamide-imide comprises a structure derived from a compound comprising at least one selected from the group consisting of diamines and diisocyanates, and a structure derived from a carboxylic acid compound comprising at least a tricarboxylic acid anhydride. The compound and the at least one selected from the carboxylic acid compound comprises a compound having a group comprising at least one non-aromatic hydrocarbon group, wherein the total number of carbon atoms of the at least one non-aromatic hydrocarbon group is 8 or more. Furthermore, the compound and the at least one selected from the carboxylic acid compound comprises a compound having an aromatic hydrocarbon group. In this disclosure, "a compound comprising at least one selected from the group consisting of diamines and diisocyanates" may be referred to as "a diamine or diisocyanate compound." The carboxylic acid compound may further contain a dicarboxylic acid. In this disclosure, "a group comprising at least one non-aromatic hydrocarbon group, wherein the total number of carbon atoms of the at least one non-aromatic hydrocarbon group is 8 or more" may be referred to as "hydrocarbon group (X)."

[0011] In a polyamide-imide, for example, it includes a compound in which at least one diamine or diisocyanate compound has a hydrocarbon group (X), and at least one carboxylic acid compound has an aromatic hydrocarbon group. Or, in a polyamide-imide, for example, it includes a compound in which at least one diamine or diisocyanate compound has an aromatic hydrocarbon group, and at least one carboxylic acid compound has a hydrocarbon group (X). Note that when the carboxylic acid compound has a hydrocarbon group (X), the number of carbon atoms in the carboxyl group is not included in the number of carbon atoms of the hydrocarbon group (X).

[0012] In a preferred embodiment, the polyamide-imide comprises a diamine or diisocyanate compound having a hydrocarbon group (X) and a diamine or diisocyanate compound having an aromatic hydrocarbon group, and the carboxylic acid compound comprises a carboxylic acid compound having an aromatic hydrocarbon group. In another preferred embodiment, the polyamide-imide comprises a diamine or diisocyanate compound having an aromatic hydrocarbon group, and the carboxylic acid compound comprises a carboxylic acid compound having a hydrocarbon group (X) and a carboxylic acid compound having an aromatic hydrocarbon group.

[0013] (Hydrogen group (X)) The hydrocarbon group (X) that a diamine or diisocyanate compound and a carboxylic acid compound may have includes at least one non-aromatic hydrocarbon group. In the hydrocarbon group (X), the total number of carbon atoms of the at least one non-aromatic hydrocarbon group is 8 or more. If the hydrocarbon group (X) includes one non-aromatic hydrocarbon group, the total number of carbon atoms means the total number of carbon atoms contained in that one non-aromatic hydrocarbon group. If the hydrocarbon group (X) includes two or more non-aromatic hydrocarbon groups, the total number of carbon atoms means the total number of carbon atoms contained in those two or more non-aromatic hydrocarbon groups. The hydrocarbon group (X) may further include any group other than a non-aromatic hydrocarbon group. The hydrocarbon group (X) is, for example, a 1- to 4-valent group, preferably 2- to 4-valent, and more preferably 2-valent.

[0014] Non-aromatic hydrocarbon groups are, for example, saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, unsaturated alicyclic hydrocarbon groups, or groups consisting of two or more selected from these. Saturated aliphatic hydrocarbon groups may be linear or branched. Unsaturated aliphatic hydrocarbon groups may be linear or branched. If hydrocarbon group (X) contains two or more non-aromatic hydrocarbon groups, the two or more non-aromatic hydrocarbon groups may be the same or different from each other.

[0015] The number of carbon atoms in a saturated aliphatic hydrocarbon group is, for example, 1-50, 2-40, 3-30, 4-20, or 5-10. A saturated aliphatic hydrocarbon group is, for example, an atomic group obtained by removing 1-4 hydrogen atoms from a linear or branched alkane. Examples of alkanes include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, hexacosane, octacosane, triacontane, tetracontane, and pentacontane.

[0016] The number of carbon atoms in the unsaturated aliphatic hydrocarbon group is, for example, 2 to 50, 2 to 40, 3 to 30, 4 to 20, or 5 to 10. The carbon-carbon unsaturated bonds contained in the unsaturated aliphatic hydrocarbon group are one or more, and may be, for example, 5 or less, 4 or less, 3 or less, or 2 or less. The unsaturated aliphatic hydrocarbon may be an alkene containing one carbon-carbon double bond or an alkyne containing one carbon-carbon triple bond. The unsaturated aliphatic hydrocarbon group is, for example, a group obtained by removing 1 to 4 hydrogen atoms from a linear or branched alkene, or a group obtained by removing 1 to 4 hydrogen atoms from a linear or branched alkyne. Examples of alkenes include ethene, propene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, heneicosene, docosene, tricosene, tetracosene, pentacosene, hexacosene, heptacosene, octacosene, nonacosene, triacontene, tetracontene, and pentacontene. Examples of alkynes include ethyne, propyne, butyne, pentyne, hexyne, heptyne, octyne, nonyne, decyne, undecyne, dodecyne, tridecyne, tetradecyne, pentadecyne, hexadecyne, heptadecyne, octadecyne, nonadecyne, eicosyne, heneicosyne, docosyne, tricosyne, tetracosyne, pentacosyne, hexacosyne, heptacosyne, octacosyne, nonacosyne, triacontyne, tetracontyne, and pentacontyne.

[0017] The number of carbon atoms in the saturated alicyclic hydrocarbon group is, for example, 3 to 20, 4 to 16, 5 to 10, or 6 to 8. The saturated alicyclic hydrocarbon group is, for example, a group obtained by removing 1 to 4 hydrogen atoms from a cycloalkane. Examples of cycloalkanes include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, decalin, bicyclobutane, bicyclohexane, bicyclooctane, spiropentane, spiroheptane, guadricyclane, and adamantane.

[0018] The number of carbon atoms in the unsaturated alicyclic hydrocarbon group is, for example, 4 to 20, 5 to 10, or 6 to 8. Unsaturated alicyclic The carbon-carbon unsaturated bonds contained in the hydrocarbon group are one or more, and may be, for example, 5 or less, 4 or less, 3 or less, or 2 or less. The unsaturated aliphatic hydrocarbon may be a cycloalkene containing one carbon-carbon double bond, or a cycloalkyne containing one carbon-carbon triple bond. The unsaturated alicyclic hydrocarbon group is, for example, a group obtained by removing 1 to 4 hydrogen atoms from a cycloalkene, or a group obtained by removing 1 to 4 hydrogen atoms from a cycloalkyne. Examples of the unsaturated alicyclic hydrocarbon include cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, norbornene, norbornadiene, and bicyclooctadiene.

[0019] Examples of any group that the hydrocarbon group (X) can contain include an aromatic hydrocarbon group and a group containing a heteroatom.

[0020] The number of carbon atoms in the aromatic hydrocarbon group is, for example, 6 to 30, 6 to 20, or 6 to 10. The aromatic hydrocarbon group is, for example, a group obtained by removing 1 to 4 hydrogen atoms from an aromatic hydrocarbon. Examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, pyrene, and pentane.

[0021] Examples of heteroatom-containing groups include heterocyclic compound groups, heteroatom-containing linking groups, and heteroatom-containing substituents. Heterocyclic compound groups are atomic groups obtained by removing 1 to 4 hydrogen atoms from a non-aromatic heterocyclic compound, or from an aromatic heterocyclic compound. Examples of non-aromatic heterocyclic compounds include tetrahydrofuran, tetrahydrothiophene, and dioxane. Examples of aromatic heterocyclic compounds include pyridine, benzofuran, and benzothiophene. Examples of heteroatom-containing linking groups include oxy groups, thio groups, sulfonyl groups, sulfinyl groups, carbonyl groups, carbonyloxy groups, and imino groups. Examples of heteroatom-containing substituents include hydroxyl groups, mercapto groups, sulfo groups, sulfino groups, carboxyl groups, fluoro groups, and chloro groups.

[0022] The total number of carbon atoms in at least one non-aromatic hydrocarbon group contained within the hydrocarbon group (X) is 8 or more. Examples of hydrocarbon groups (X) and the total number of carbon atoms in at least one non-aromatic hydrocarbon group contained within them are given below. Additionally, examples of groups that do not qualify as hydrocarbon groups (X) are given for reference.

[0023] [Table 1]

[0024] The total number of carbon atoms in at least one non-aromatic hydrocarbon group contained in hydrocarbon group (X) is 8 or more. The number of carbon atoms may be, for example, 12 or more, 16 or more, 20 or more, 24 or more, 28 or more, 32 or more, or 36 or more. The total number of carbon atoms in at least one non-aromatic hydrocarbon group contained in hydrocarbon group (X) is, for example, 50 or less. The number of carbon atoms may be, for example, 48 or less, 44 or less, 40 or less, or 36 or less. When the total number of carbon atoms in the non-aromatic hydrocarbon group is 8 or more, a polyamide-imide with a low dielectric constant and a low dielectric loss tangent can be obtained. When the total number of carbon atoms in the non-aromatic hydrocarbon group is 50 or less, the starting monomers are readily available, and the polyamide-imide can be easily synthesized. Even if the polyamide-imide has a group in which the total number of carbon atoms in the aromatic hydrocarbon group is 8 or more, it is not possible to obtain a polyamide-imide with a low dielectric constant and a low dielectric loss tangent.

[0025] The hydrocarbon group (X) preferably includes a saturated aliphatic hydrocarbon group, and more preferably a linear saturated aliphatic hydrocarbon group having 6 or more carbon atoms (preferably 8 or more carbon atoms). When the polyamide-imide contains a structure that includes a linear saturated aliphatic hydrocarbon group having 6 or more carbon atoms, the dielectric constant tends to be lower and the dielectric loss tangent tends to be lower. It is thought that the presence of a linear saturated aliphatic hydrocarbon group having 6 or more carbon atoms reduces the polarity (dipole moment) within the polyamide-imide molecule, thus lowering the dielectric constant.

[0026] The hydrocarbon group (X) preferably includes at least one selected from the group consisting of a group represented by the following formula (G1) to a group represented by the following formula (G5).

[0027] [ka]

[0028] In the formula, Ra independently represents a linear or branched saturated aliphatic hydrocarbon group, or a linear or branched unsaturated aliphatic hydrocarbon group. Rb independently represents a saturated alicyclic hydrocarbon group or an unsaturated alicyclic hydrocarbon group. L represents a linking group containing a single bond or a heteroatom. Ra and Rb independently may or may not have substituents.

[0029] In preferred embodiments, the polyamide-imide includes a structure derived from a compound having a group represented by formula (G1) (for example, Ra has 8 or more carbon atoms). Examples of such compounds include polymethylenediamine, polymethylenediisocyanate, and polymethylenedicarboxylic acid. In other preferred embodiments, the polyamide-imide includes at least one structure selected from the group consisting of structures derived from compounds having a group represented by formula (G2) (for example, each Rb independently has 6 or more carbon atoms, preferably 8 or more), structures derived from compounds having a group represented by formula (G3) (for example, each Ra independently has 6 or more carbon atoms, preferably 8 or more), and structures derived from compounds having a group represented by formula (G5) (for example, Rb has 6 carbon atoms, each Ra independently has 6 or more carbon atoms, preferably Rb has 6 carbon atoms, and each Ra independently has 6 or more carbon atoms). Examples of these compounds include dimer acids, hydrogenated dimer acids, dimer amines, hydrogenated dimer amines, dimer isocyanates, and hydrogenated dimer isocyanates.

[0030] (Aromatic hydrocarbon group) The number of carbon atoms in the aromatic hydrocarbon group that diamine or diisocyanate compounds and carboxylic acid compounds may have is, for example, 6 to 30, 6 to 20, or 6 to 10. An aromatic hydrocarbon group is, for example, an atomic group obtained by removing 1 to 4 hydrogen atoms from an aromatic hydrocarbon. Examples of aromatic hydrocarbons include benzene, naphthalene, anthracene, pyrene, and pentane. When polyamide-imides contain aromatic hydrocarbon groups, good heat resistance and mechanical properties are easily obtained.

[0031] (Diamine or diisocyanate compounds having a hydrocarbon group (X)) Examples of diamine or diisocyanate compounds having a hydrocarbon group (X) include a diamine having the aforementioned hydrocarbon group (X) and two amino groups bonded to the hydrocarbon group (X), or a diisocyanate having the aforementioned hydrocarbon group (X) and two isocyanate groups bonded to the hydrocarbon group (X).

[0032] Furthermore, the following are specific examples of diamines having a hydrocarbon group (X): Diamines having 8 or more carbon atoms and containing saturated aliphatic hydrocarbon groups, such as 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,14-diaminotetradecane, and 1,16-diaminohexadecane; Diamines having 9 or more carbon atoms and possessing an unsaturated aliphatic hydrocarbon group, such as 1,9-diaminooctene, 1,9-diaminononene, 1,10-diaminodecene, 1,11-diaminoundecene, 1,12-diaminododecene, 1,14-diaminotetradecene, and 1,16-diaminohexadecene; Isophorone diamine, bis(aminomethyl)norbornane, 1,3-diaminoadamantane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-teto Lamethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexylmethane, 3,5-diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, 3,3'-dimethyl-4,4'-diaminodicyclohexyl ether, 3,3'-diethyl-4,4'-diaminodicyclohexyl Diamines with 8 or more carbon atoms having saturated alicyclic hydrocarbon groups, such as tetrahexyl ether, 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexyl ether, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexyl ether, 3,5-diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexyl ether, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(3-methyl-4-aminocyclohexyl)propane, 2,2-bis(3-ethyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-dimethyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-diethyl-4-aminocyclohexyl)propane, and 2,2-(3,5-diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexyl)propane; Diamines with 8 or more carbon atoms having an unsaturated alicyclic hydrocarbon group, such as bis(aminomethyl)norbornene and 4,4'-diaminodicyclohexenylmethane; Dimer amines with 8 or more carbon atoms derived from dimers (also called dimer acids) of unsaturated fatty acids such as crotonic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, and nervonic acid; diunsaturated fatty acids such as linoleic acid, eicosadienoic acid, and docosadienoic acid; and triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, meadic acid, dihomo-γ-linolenic acid, and eicosatrienoic acid. The dimer amines mentioned above are hydrogenated dimer amines having 8 or more carbon atoms, in which the carbon-carbon double bond contained in the molecule is hydrogenated.

[0033] Specific examples of diisocyanates having a hydrocarbon group (X) include compounds that have the same structure as the compounds shown as specific examples of diamines, except that the amino group is replaced with an isocyanate group.

[0034] (Carboxylic acid compounds having a hydrocarbon group (X)) Examples of carboxylic acid compounds having a hydrocarbon group (X) include a tricarboxylic acid anhydride having the above-mentioned hydrocarbon group (X) and one carboxyl group and one acid anhydride group bonded to the hydrocarbon group (X), or a dicarboxylic acid having the above-mentioned hydrocarbon group (X) and two carboxyl groups bonded to the hydrocarbon group (X). Furthermore, the following are specific examples of carboxylic acid compounds having a hydrocarbon group (X): Aliphatic tricarboxylic acid anhydrides such as decahydronaphthalentricarboxylic acid anhydride, 3,4,4'-bicyclohexanetricarboxylic acid anhydride, 2,3,2'-bicyclohexanetricarboxylic acid anhydride, and 3,4,4'-bicyclohexanemethanetricarboxylic acid anhydride; A dicarboxylic acid having the same structure as the compound shown as a specific example of a diamine having the above hydrocarbon group (X), except that the amino group is replaced with a carboxyl group.

[0035] (Diamine or diisocyanate compounds having aromatic hydrocarbon groups) Examples of diamines or diisocyanate compounds having aromatic hydrocarbon groups include diamines having one or more of the above-mentioned aromatic hydrocarbon groups and two amino groups, or diisocyanates having one or more of the above-mentioned aromatic hydrocarbon groups and two isocyanate groups.

[0036] Furthermore, the following are specific examples of diamines having aromatic hydrocarbon groups. 1,4-Phenylenediamine, 1,2-Phenylenediamine, 1,3-Phenylenediamine, 4,4'-(Biphenyl-2,5-Diylbisoxy)bisaniline, 4,4'-Diaminodiphenylmethane, 4,4'-Diaminodiphenyl ether, 3,4'-Diaminodiphenyl ether, 1,4-Bis(4-aminophenoxy)benzene, 1,3-Bis(4-aminophenoxy)benzene, 2,2-Bis(4-(4-aminophenoxy)phenyl)propane, Bis(4-(4-aminophenoxy)phenyl)sulfone, Bis(4 -(3-aminophenoxy)phenyl)sulfone, 1,3-bis(4-aminophenoxy)neopentane, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(4-amino-3-carboxyphenyl)methane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, N-(4- Aminophenoxy)-4-aminobenzamine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, bis(3-aminophenyl)sulfone, norbornanediamine, 4,4'-diamino-2-(trifluoromethyl)diphenyl ether, 5-trifluoromethyl-1,3-benzenediamine, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2-bis[4-{4-amino-2-(triflu Diamines having aromatic hydrocarbon groups, such as oromethyl)phenoxy}phenyl]hexafluoropropane, 2-trifluoromethyl-p-phenylenediamine, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 4,4'-(9-fluorenylidene)dianiline, 2,7-diaminofluorene, 1,5-diaminonaphthalene, and 3,7-diamino-2,8-dimethyldibenzothiophene 5,5-dioxide (however, the total number of carbon atoms in the non-aromatic hydrocarbon groups contained in the diamine is between 0 and 7).

[0037] Specific examples of diisocyanates having aromatic hydrocarbon groups include compounds that have the same structure as the compounds shown as specific examples of diamines, except that the amino group is replaced with an isocyanate group.

[0038] (Carboxylic acid compounds containing aromatic hydrocarbon groups) Aromatic hydrocarbon groups As a carboxylic acid compound having the above-mentioned One or more aromatic hydrocarbon groups and 、 A dicarboxylic acid having two carboxyl groups, or the above-mentioned One or more aromatic hydrocarbon groups and 、 Examples include tricarboxylic acid anhydrides having one carboxyl group and one acid anhydride group. Furthermore, the following are specific examples of carboxylic acid compounds having aromatic hydrocarbon groups. Aromatic tricarboxylic acids such as trimellitic anhydride, naphthalenetricarboxylic acid anhydride, 3,4,4'-biphenyltricarboxylic acid anhydride, 2,3,2'-biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, 3,4,4'-biphenylethertricarboxylic acid anhydride, 3,4,4'-benzophenonetricarboxylic acid anhydride, or 3,4,4'-biphenylsulfonetricarboxylic acid anhydride; Dicarbon has the same structure as the compound shown above as a specific example of a diamine having an aromatic hydrocarbon group, except that the amino group is replaced with a carboxyl group. acid

[0039] (Any structure) Polyamide-imides may include structures derived from compounds containing at least one selected from the group consisting of diamines and diisocyanates, and structures derived from carboxylic acid compounds containing at least a tricarboxylic acid anhydride, as well as any other arbitrary structures. Examples of arbitrary structures include structures derived from trifunctional or more amines or isocyanates, and structures derived from monofunctional amines or isocyanates. Carboxylic acid compounds may include any compounds other than tricarboxylic acid anhydrides. Examples of arbitrary compounds include dicarboxylic acids, dicarboxylic acid anhydrides, tricarboxylic acids, tetracarboxylic acids, and tetracarboxylic acid anhydrides.

[0040] (Manufacturing method) Polyamide-imides are obtained by reacting at least a diamine or diisocyanate compound with a carboxylic acid compound. These compounds may be used individually, in combination of two or more, or with any other compound.

[0041] The synthesis conditions for polyamide-imide vary and cannot be generalized, but for example, it can be carried out at a temperature of 80 to 180°C. Synthesis is preferably carried out under a nitrogen atmosphere to reduce the influence of moisture in the air. The synthesized polyamide-imide can be obtained, for example, as a polyamide-imide-containing solution dissolved in the solvent used in the reaction.

[0042] There are no particular restrictions on the solvent, but for example, polar solvents such as N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), 3-methoxy-N,N-dimethylpropanamide (MPA), N,N'-dimethylformamide, N,N'-dimethylpropylene urea [1,3-dimethyl-3,4,5,6-tetrahydropyridimine-2(1H)-one], dimethyl sulfoxide, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and sulfolane can be used; aromatic hydrocarbon solvents such as xylene and toluene; and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be used. The solvent preferably contains at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and 3-methoxy-N,N-dimethylpropanamide (MPA), and more preferably contains at least one selected from the group consisting of N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and 3-methoxy-N,N-dimethylpropanamide (MPA).

[0043] The amount of solvent used during the reaction is preferably 100 to 300 parts by mass, and more preferably 150 to 250 parts by mass, per 100 parts by mass of the total amount of the carboxylic acid compound and the diamine or diisocyanate compound. Using 100 parts by mass or more of solvent tends to prevent reactions accompanied by foaming. Using 300 parts by mass or less of solvent tends to prevent the synthesis time from becoming too long, and also tends to result in a sufficient concentration of polyamideimide in the solution obtained after synthesis.

[0044] When a carboxylic acid compound is reacted with a diamine or diisocyanate compound, if carboxyl groups, acid anhydride groups, and reactive hydroxyl groups are present, it is preferable that the ratio of the number of moles of amino groups and isocyanate groups to the number of moles of these functional groups is preferably 0.6 to 1.4, more preferably 0.7 to 1.3, and even more preferably 0.8 to 1.2. A ratio of 0.6 or higher tends to facilitate increasing the molecular weight of the polyamideimide. A ratio of 1.4 or lower tends to prevent vigorous foaming reactions and the accumulation of large amounts of unreacted material, thus making it easier to obtain good stability for the polyamideimide.

[0045] (Content of structures derived from compounds having a hydrocarbon group (X), etc.) The content of structures derived from compounds having hydrocarbon groups (X) in polyamide-imide is, for example, 5-50 mol%, 7-30 mol%, or 8-20 mol%, based on the content of structures derived from diamine or diisocyanate compounds and structures derived from carboxylic acid compounds. The content of structures derived from compounds having aromatic hydrocarbon groups in polyamide-imide is, for example, 50-95 mol%, 70-93 mol%, or 80-92 mol%, based on the content of structures derived from diamine or diisocyanate compounds and structures derived from carboxylic acid compounds.

[0046] In polyamide-imide, if the diamine or diisocyanate compound includes a diamine or diisocyanate compound having a hydrocarbon group (X) and a diamine or diisocyanate compound having an aromatic hydrocarbon group, and the carboxylic acid compound includes a carboxylic acid compound having an aromatic hydrocarbon group, the content of the structure derived from the diamine or diisocyanate compound having a hydrocarbon group (X) is, for example, 5-50 mol%, 8-40 mol%, or 10-30 mol%, based on the content of the structure derived from the diamine or diisocyanate compound. The content of the structure derived from the diamine or diisocyanate compound having an aromatic hydrocarbon group is, for example, 50-95 mol%, 60-92 mol%, or 70-90 mol%, based on the content of the structure derived from the diamine or diisocyanate compound. In polyamide-imide, if the diamine or diisocyanate compound includes a diamine or diisocyanate compound having an aromatic hydrocarbon group, and the carboxylic acid compound includes a carboxylic acid compound having a hydrocarbon group (X) and a carboxylic acid compound having an aromatic hydrocarbon group, the content of the structure derived from the carboxylic acid compound having a hydrocarbon group (X) is, for example, 10-60 mol%, 15-50 mol%, or 20-40 mol%, based on the content of the structure derived from the carboxylic acid compound. The content of the structure derived from the carboxylic acid compound having an aromatic hydrocarbon group is, for example, 40-90 mol%, 50-85 mol%, or 60-80 mol%, based on the content of the structure derived from the carboxylic acid compound.

[0047] In polyamide-imides, the content of structures derived from tricarboxylic acid anhydrides is, for example, greater than 50 mol%, 60 mol% or more, or 65 mol% or more, based on the content of structures derived from carboxylic acid compounds. The upper limit may be 100 mol%, but if structures derived from other carboxylic acids such as dicarboxylic acids are included, the upper limit is, for example, 90 mol% or less, 80 mol% or less, or 75 mol% or less. In polyamide-imides, if structures derived from dicarboxylic acids are included, the content of structures derived from dicarboxylic acids is, for example, less than 50 mol%, 40 mol% or less, or 35 mol% or less.

[0048] (number average molecular weight) The number-average molecular weight of polyamideimide is preferably 3,000 to 100,000. When the number-average molecular weight is 3,000 or higher, various properties such as strength tend to improve. The number-average molecular weight of polyamideimide may be 5,000 or higher, 8,000 or higher, 15,000 or higher, or 20,000 or higher. When the number-average molecular weight is 100,000 or lower, good coating properties tend to be easily obtained. The number-average molecular weight of polyamideimide may be 80,000 or lower, 50,000 or lower, 35,000 or lower, 30,000 or lower, or 27,000 or lower.

[0049] The relative permittivity (10 GHz) of polyamide-imide is, for example, 4.0 or less, 3.6 or less, 3.3 or less, or 3.1 or less, from the viewpoint of obtaining excellent insulation properties. The relative permittivity of polyamide-imide is not particularly limited, but from the viewpoint of preventing a decrease in heat resistance, tensile strength, and tensile modulus, it is, for example, 2.0 or more.

[0050] The dielectric loss tangent (10 GHz) of polyamide-imide is, for example, 0.020 or less, 0.015 or less, or 0.010 or less, from the viewpoint of suppressing transmission loss. The dielectric loss tangent of polyamide-imide is not particularly limited, but may be 0.0001 or more, or 0.0005 or more.

[0051] The tensile strength of polyamide-imide is, for example, 30 MPa or more, 50 MPa or more, or 80 MPa or more, from the viewpoint of the strength of the molded article. The tensile strength of polyamide-imide is not particularly limited, but for example, from the viewpoint of stretchability during processing, it is 400 MPa or less, 300 MPa or less, or 250 MPa or less.

[0052] The elongation at break of polyamide-imide is, for example, 3% or more, 5% or more, or 8% or more, from the viewpoint of the flexibility of the molded article. It may also be 20% or more, 30% or more, or 50% or more. The elongation at break of polyamide-imide is not particularly limited, but for example, it may be 300% or less, 200% or less, or 100% or less.

[0053] The tensile modulus of polyamide-imide is, for example, 0.5 GPa or higher, 0.7 GPa or higher, 1.0 GPa or higher, or 1.5 GPa or higher, from the viewpoint of the strength of the molded article. The tensile modulus of polyamide-imide is, for example, 7 GPa or less, 6 GPa or less, or 5 GPa or less, from the viewpoint of the flexibility of the molded article.

[0054] The glass transition temperature (Tg) of polyamide-imide is, for example, 120°C or higher, 140°C or higher, or 160°C or higher, from the viewpoint of the heat resistance of the molded article. There is no particular upper limit, but for example, it is 350°C or lower, or 300°C or lower.

[0055] In this disclosure, the dielectric constant, dielectric loss tangent, tensile strength, elongation at break, tensile modulus, and glass transition temperature (Tg) of polyamide-imide can be measured, respectively, by preparing a polyamide-imide film according to the method described in the Examples and using the prepared polyamide-imide film according to the method described in the Examples.

[0056] [Application] Polyamide-imide can be used in various electronic and mechanical components, such as displays, solar cells, touch panels, organic EL lighting, and printed circuit boards.

[0057] <Polyamide-imide-containing liquid> An embodiment of the present invention, a polyamide-imide-containing liquid, contains polyamide-imide and a solvent. The solvent can be any of the reaction solvents described above that can be used in the synthesis of polyamide-imide. The solvent preferably contains at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and 3-methoxy-N,N-dimethylpropanamide (MPA), and more preferably contains at least one selected from the group consisting of N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and 3-methoxy-N,N-dimethylpropanamide (MPA).

[0058] The polyamideimide content in the polyamideimide-containing solution can be set to a range suitable for the application of the polyamideimide-containing solution. The polyamideimide content is, for example, 5-60% by mass, 10-50% by mass, or 20-45% by mass, based on the mass of the polyamideimide-containing solution.

[0059] Polyamide-imide-containing liquids can be preferably used as insulating compositions, heat-resistant insulating compositions, or printed circuit board compositions, or for the preparation of these compositions. The compositions may further contain any components such as polyamide, polyethersulfone, acrylic polymer, epoxy compound, isocyanate compound, melamine compound, filler, defoamer, preservative, and surfactant. The compositions can be produced, for example, by mixing the polyamide-imide-containing liquid with any components used as needed and stirring the mixture.

[0060] <Polyamide-imide film> The polyamide-imide film according to an embodiment of the present invention is obtained using the polyamide-imide or polyamide-imide-containing liquid according to the above embodiment, or includes the polyamide-imide film according to the above embodiment. The polyamide-imide film according to an embodiment of the present invention has excellent insulating properties.

[0061] Polyamide-imide films can be obtained, for example, by coating a polyamide-imide-containing liquid onto a substrate such as a glass plate, drying it, and then heating it. The drying temperature can be, for example, 50 to 100°C. The heating temperature can be, for example, 230 to 350°C. The film thickness of the polyamide-imide film can be set appropriately according to the application, for example, 5 to 1,000 μm, 10 to 100 μm, or 20 to 50 μm.

[0062] <Printed circuit board> A printed circuit board according to an embodiment of the present invention is obtained using the polyamide-imide or polyamide-imide-containing liquid of the above embodiment, or comprises the polyamide-imide film of the above embodiment. The printed circuit board according to an embodiment of the present invention has low transmission loss and excellent heat resistance.

[0063] Examples of printed circuit boards include printed wiring boards and printed circuit boards. Examples of printed circuit boards include flexible boards and rigid boards. Examples of printed circuit boards include single-sided boards, double-sided boards, and multilayer boards. For example, the materials, protective films, insulating layers, etc., of these boards are obtained using polyamide-imide or a polyamide-imide-containing liquid, or include a polyamide-imide film.

[0064] Examples of flexible substrates include substrates comprising a base film, wherein the base film is obtained using polyamide-imide or a polyamide-imide-containing liquid, or substrates containing a polyamide-imide film. Other examples of flexible substrates include substrates comprising a base film and a heat-resistant insulating layer formed on the base film, wherein at least the heat-resistant insulating layer is obtained using polyamide-imide or a polyamide-imide-containing liquid, or substrates containing a polyamide-imide film. [Examples]

[0065] Embodiments of the present invention will be specifically described by reference to examples. Embodiments of the present invention are not limited to the following examples.

[0066] [Example 1] (Preparation of polyamide-imide) 19.2 g of trimellitic anhydride (TMAC), 20.0 g of 4,4'-diphenylmethane diisocyanate (MDI), 10.7 g of diamine dimer acid (DDA) (having a 36-carbon hydrocarbon group (X), "PRIAMINE1075", Croda Japan Co., Ltd.), and 60.0 g of N-methyl-2-pyrrolidone (NMP) were placed in a flask equipped with a thermometer, stirrer, and condenser, and the temperature was gradually raised to 130°C over 2 hours while stirring in a dry nitrogen stream. While paying attention to the rapid effervescence of carbon dioxide gas produced by the reaction, the temperature was maintained at 130°C and heating continued for 6 hours, after which the reaction was stopped to obtain a polyamideimide solution. The number-average molecular weight of the obtained polyamideimide was 32,000. The number-average molecular weight was determined by the following method. The structural formula of the diamine dimer acid used is shown below.

[0067] [ka]

[0068] (number average molecular weight) The number-average molecular weight (Mn) was measured by gel permeation chromatography (GPC) and converted using a calibration curve for standard polystyrene. The calibration curve was approximated by a cubic equation using a set of five standard polystyrene samples ("TSK standard POLYSTYRENE," manufactured by Tosoh Corporation). The GPC conditions are shown below. GPC equipment: High-speed GPC system HLC-8320GPC (manufactured by Tosoh Corporation) Detector: UV-8320 ultraviolet absorption detector (manufactured by Tosoh Corporation) Columns: Gelpack GL-S300MDT-5 (2 pieces total) (Manufactured by Showa Denko Materials Co., Ltd.) Eluent: THF / DMF=1 / 1 (volume ratio) + LiBr (0.06mol / L) + H3PO4 (0.06mol / L) Flow rate: 1mL / min Column size: 8mm I.D. × 300mm Sample concentration: 5 mg / 1 mL Injection volume: 5μL Measurement temperature: 40℃

[0069] (Preparation of polyamide-imide film) The obtained polyamide-imide solution was applied to a glass substrate to form a coating. After drying the coating by heating at 80°C for 30 minutes, a polyamide-imide film with a thickness of 20 μm was prepared by heating at 270°C for 30 minutes. The polyamide-imide film was peeled from the glass substrate and used for various evaluations.

[0070] [Example 2 and Comparative Examples 1 and 2] A polyamide-imide solution was obtained in the same manner as in Example 1, except that the diamine compound and / or diisocyanate compound and the acid component were changed as shown in Table 2. The number-average molecular weight of the polyamide-imide is shown in Table 2. A polyamide-imide film was prepared using the obtained polyamide-imide solution in the same manner as in Example 1 and used for various evaluations. In Table 2, SEBAC means sebacic acid (having a hydrocarbon group (X) with 8 carbon atoms), and TODI means 3,3'-dimethylbiphenyl-4,4'-diyldiisocyanate.

[0071] <Film Evaluation> The properties of films prepared using the varnishes of Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated according to the following method. The evaluation results are shown in Table 2.

[0072] (Tensile strength, tensile modulus, and elongation at break) Test specimens were prepared by cutting polyamide-imide film to a size of 10 mm in width and 60 mm in length. Tensile tests were performed under the following measurement conditions, and the maximum tensile stress applied during the tensile test was defined as the tensile strength (MPa). The elongation at break (%) was calculated by dividing the elongation of the test specimen until break by the chuck distance of 20 mm. In addition, the Young's modulus (MPa) was calculated from the slope of the elastic deformation region in the initial stages of stress rise, and the obtained value was defined as the tensile modulus of elasticity (MPa). Other detailed conditions and calculation methods were carried out in accordance with the international standard ISO 5271 (1993). Device name: Shimadzu Corporation "Autograph AGS-100NG" Test speed: 5 mm / min Chuck spacing: 20mm Test specimen size: 10mm wide, 60mm long Setting temperature: Room temperature (25℃)

[0073] (Glass transition temperature) A polyamide-imide film was cut into strips 4 mm wide and 25 mm long to prepare the sample pieces. A thermomechanical analyzer (TMA7100, Hitachi High-Tech Science Corporation) was used for the measurements. The test pieces were heated from room temperature to 350°C at a rate of 10°C / min using the tensile method with a chuck distance of 10 mm and a load of 10 g. The temperature corresponding to the inflection point of the linear thermal expansion coefficient curve was defined as the glass transition temperature (°C).

[0074] (Relative permittivity and dielectric loss tangent) Polyamide-imide film was cut to a size of 60 mm x 60 mm, dried at 125°C for 1 hour, and then measured. The dielectric properties of the film (relative permittivity Dk and dielectric loss tangent Df) were measured using the cavity resonator method (TE mode). Anritsu Corporation's "MS46122B" was used for the measurements. The conditions were a frequency of 10 GHz and a measurement temperature of 25°C.

[0075] [Table 2]

Claims

1. The structure includes a structure derived from a compound containing at least one selected from the group consisting of diamines and diisocyanates, and a structure derived from a carboxylic acid compound containing at least a tricarboxylic acid anhydride. At least one selected from the above compound and the above carboxylic acid compound includes a compound having a group comprising at least one non-aromatic hydrocarbon group, wherein the total number of carbon atoms of the at least one non-aromatic hydrocarbon group is 8 or more. At least one selected from the above compound and the above carboxylic acid compound includes a compound having an aromatic hydrocarbon group, The content of the structure derived from the compound having the aromatic hydrocarbon group is 50 to 95 mol%, based on the content of the structure derived from the compound and the structure derived from the carboxylic acid compound. The compound comprises a dimer amine having 8 or more carbon atoms or a hydrogenated dimer amine having 8 or more carbon atoms. The carboxylic acid compound includes a tricarboxylic acid anhydride having an aromatic hydrocarbon group, The number-average molecular weight is between 8,000 and 100,000. Polyamide-imide.

2. The polyamide imide according to claim 1, wherein the content of the structure derived from the tricarboxylic acid anhydride is more than 50 mol%, based on the content of the structure derived from the carboxylic acid compound.

3. The polyamide imide according to claim 1, comprising at least one non-aromatic hydrocarbon group, wherein the group having a total of 8 or more carbon atoms in the at least one non-aromatic hydrocarbon group comprises a saturated aliphatic hydrocarbon group having 8 or more carbon atoms.

4. The polyamide imide according to claim 1, wherein the number of carbon atoms is 28 or more.

5. The polyamide-imide according to claim 1, wherein the tensile strength is 80 MPa or more.

6. The polyamide-imide according to claim 1, wherein the elongation at break is 8% or more.

7. The polyamide-imide according to claim 1, wherein the tensile modulus is 1.5 GPa or more.

8. The polyamide-imide according to claim 1, wherein the relative permittivity at 10 GHz is 3.6 or less.

9. The polyamide-imide according to claim 1, wherein the dielectric loss tangent at 10 GHz is 0.015 or less.

10. A polyamide-imide-containing liquid comprising the polyamide-imide described in claim 1 and a solvent.

11. A polyamide-imide film obtained using the polyamide-imide described in claim 1.

12. A printed circuit board obtained using the polyamide-imide described in claim 1.

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