polymer

Abstract

A polymer wherein the repeating unit comprises only the repeating unit represented by the following formula (1). [In formula (1), -N(R')-RN(R')- is a structure derived from an unsubstituted or substituent-substituted dimer diamine, and R', R1 and R2 are independently hydrogen atoms, halogen atoms, unsubstituted or substituent-substituted hydrocarbon groups having 1 to 20 carbon atoms, or unsubstituted or substituent-substituted heterocyclic aromatic groups having 3 to 20 carbon atoms.]

Description

polymer One embodiment of the present invention relates to a novel polymer. In recent years, to cope with the increasing speed and volume of data processing in high-performance mobile terminals such as smartphones and tablets, the frequency of digital signals is developing. To achieve high performance in such high-frequency electronic components, the design of the printed wiring for transmission is crucial, requiring the signal propagation speed to be increased without compromising the quality of high-speed digital signals containing high-order frequencies. For example, when placing various electronic component materials on a substrate such as a printed wiring board, a polymer is used to bond the various electronic component materials to the substrate. There are various types of polymers used to bond the various electronic component materials, but for such polymers, in addition to requiring low dielectric loss tangent and dielectric constant, high adhesion to the substrate or performance suitable for manufacturing processes is also required. As the polymer, Patent Document 1 discloses a polymer containing pyrimidine units, and Patent Document 2 discloses a polyarylene ester. [Prior Art Documents] [Patent Documents] [Patent Document 1] Japanese Patent Application Publication No. 2017-197725 [Patent Document 2] International Publication No. 2016 / 152295 However, the polymers described in the patent documents and other prior polymers have room for improvement in terms of solubility in solvents. When using the polymer, it is easy to obtain a solution with excellent coatability (hereinafter also referred to as "coatability"), or the adhesion of the layer obtained from the polymer to the substrate (hereinafter also referred to as "adhesion to the substrate") can be further improved. One embodiment of the present invention provides a polymer that is soluble in common solvents and exhibits excellent balanced properties in terms of heat resistance, mechanical properties, coatability, and adhesion to substrates. [Means for Solving the Problem] The inventors have discovered that the aforementioned problem can be solved by using polymers with specific structures. Examples of the present invention can be shown in [1] to [2] below. [1] A polymer wherein the repeating units comprise only the repeating units represented by the following formula (1). [Chemistry 1] In formula (1), -N(R')-RN(R')- is the structure derived from unsubstituted or substituent-substituted dimer diamines. R', R 1 and R 2 Each of the following is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms (unsubstituted or substituted), or a heterocyclic aromatic group having 3 to 20 carbon atoms (unsubstituted or substituted). [2] The polymer as described in [1], wherein the weight-average molecular weight (Mw) of polystyrene is 1,000 to 400,000. [Effects of the Invention] According to one embodiment of the present invention, a polymer that is soluble in common solvents and has excellent heat resistance, mechanical properties (especially tensile elastic modulus, tensile elongation and tensile strength), coatability and adhesion to substrates can be provided. In one embodiment of the present invention, the polymer (hereinafter also referred to as "the polymer") comprises only repeating units represented by the following formula (1). Furthermore, the polymer refers to a polymer whose repeating units comprise only repeating units represented by the following formula (1), and its ends are not particularly limited. For example, when the polymer is synthesized by reacting the compound represented by the following formula (A) with the compound represented by the following formula (B), it is preferred to be derived from the ends of the compound represented by the following formula (A) or the compound represented by the following formula (B). [Chemistry 2] In formula (1), -N(R')-RN(R')- is the structure derived from unsubstituted or substituent-substituted dimer diamines. R', R 1 and R 2 Each of the following is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms (unsubstituted or substituted), or a heterocyclic aromatic group having 3 to 20 carbon atoms (unsubstituted or substituted). Structures that are sources of unsubstituted or substituented dimeric diamines include, for example, divalent dimeric acid diamine residues derived from dimeric acid diamines or at least a portion of such divalent dimeric acid diamine residues that are substituented. The so-called dimeric acid type diamine refers to a dimeric acid (obtained as a dimer of unsaturated fatty acids (18 carbons) in cyclic and acyclic forms (mainly composed of 36 carbons)) whose two terminal carboxylic acid groups (-COOH) are separated by a primary amino methyl group (-CH). 2-NH 2) or amino group (-NH 2) Diamines formed by substitution. The dimeric acid type diamine is a compound derived from dimeric acids, which are dimers of unsaturated fatty acids such as oleic acid (see Japanese Patent Application Publication No. 9-12712, etc.), and various known dimeric diamines can be used without particular restriction. Dimeric acids are known dicarboxylic acids obtained through intermolecular polymerization of unsaturated fatty acids. Their industrial manufacturing process is largely standardized, typically using clay catalysts or similar methods to dimerize unsaturated fatty acids with 11 to 22 carbon atoms. Industrially obtained dimer acids usually have a 36-carbon dicarboxylic acid as the main component, obtained by dimerizing 18-carbon unsaturated fatty acids such as oleic acid or linoleic acid. However, depending on the degree of refining, they may contain arbitrary amounts of monomeric acids (18 carbon atoms), trimeric acids (54 carbon atoms), and other polymeric fatty acids with 20 to 54 carbon atoms. In one embodiment of the present invention, the dimer acid is preferably one whose content has been increased to 90% by weight or more through molecular distillation. Furthermore, in one embodiment of the present invention, if double bonds remain after the dimerization reaction, hydrogenation is further performed to reduce the degree of unsaturation, and this is also included in the dimer acid. By possessing a structure derived from dimeric acid-type diamines, this polymer can be endowed with properties derived from the dimeric acid backbone. Specifically, the following properties can be imparted: Since dimeric acid-type diamines are aliphatic compounds containing multiple isomers of a large molecule with a molecular weight of approximately 500-620, the molar volume of this polymer can be increased, relatively reducing the amount of polar groups in the polymer. This characteristic of dimeric acid-type diamines is believed to help suppress the decrease in the polymer's heat resistance while improving its dielectric properties. Furthermore, when the dimeric acid-type diamine contains two freely moving hydrophobic chains with 4-9 carbon atoms and two chain-like aliphatic amine groups with a length close to 8-10 carbon atoms, the structure derived from this dimeric acid-type diamine not only imparts flexibility to the polymer but also allows the polymer to be configured with a non-target chemical structure or a non-planar chemical structure. Therefore, it is believed that the solubility of this polymer can be improved. The following are non-limiting structural formulas of dimer diamines. In the following formulas, m+n=6~17, p+q=8~19, and the wavy part refers to carbon-carbon single bonds or carbon-carbon double bonds. [Chemistry 3] [Chemistry 4] [Chemistry 5] [Chemistry 6] [Chemistry 7] [Chemistry 8] [Chemistry 9] [Chemistry 10] The preferred diamine dimer is a compound with an active hydrogen equivalent of 130-140 and an amine valence of 180-220. Commercially available products of dimer acidic diamines include, for example, versamine 551 (manufactured by BASF Japan), versamine 552 (manufactured by Cognis Japan; a hydride of versamine 551), Priamine 1075, and Priamine 1074 (all manufactured by Croda Japan). As R', R 1 and R 2 Halogen atoms in the atom can be, for example, fluorine, chlorine, bromine, and iodine. As R', R 1 and R 2 Hydrocarbon groups with 1 to 20 carbon atoms, such as monovalent chain hydrocarbon groups, monovalent alicyclic hydrocarbon groups, monovalent aromatic hydrocarbon groups, or groups formed by combining these groups, are used as R', ...""""""""'s ''''''''' 1 and R 2 Heterocyclic aromatic groups with 3 to 20 carbon atoms, including monovalent heterocyclic aromatic groups, are also included. These hydrocarbon groups and heterocyclic aromatic groups can also be substituted by substituents. Examples of monovalent chain hydrocarbon groups include: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, and n-pentyl; alkenyl groups such as vinyl, propenyl, butenyl, and pentenyl; and alkynyl groups such as ethynyl, propynyl, butynyl, and pentynyl. Examples of monovalent alicyclic hydrocarbon groups include: monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; polycyclic cycloalkyl groups such as norbornyl and adamantyl; monocyclic cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl; and polycyclic cycloalkenyl groups such as norbornyl. Examples of monovalent aromatic hydrocarbon groups include aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthracene. Examples of aryl groups that can be formed by combining these groups include: benzyl, phenethyl, phenylpropyl, naphthylmethyl, and other aryl groups. Examples of monovalent heterocyclic aromatic groups include those derived from heterocycles such as thiophene, benzothiophene, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, indole, isoindole, benzimidazole, purine, indazole, quinoline, isoquinoline, quinoxoline, quinazoline, clopyralid, furan, benzofuran (1-benzofuran), isobenzofuran (2-benzofuran), oxazole, isoxazole, thiazole, benzoxazole, benzoisoxazole, benzothiazole, etc. As substituents derived from the structure of the dimer diamine, and R', R 1 and R 2 There are no particular restrictions on the substituents in hydrocarbon groups with 1 to 20 carbon atoms and heterocyclic aromatic groups with 3 to 20 carbon atoms. Examples include: allyl, halogen atom, monovalent hydrocarbon group with 1 to 20 carbon atoms, monovalent haloalkyl hydrocarbon group with 1 to 20 carbon atoms, alkoxy group with 1 to 20 carbon atoms, alkoxycarbonyl group with 1 to 20 carbon atoms, alkylthio group with 1 to 20 carbon atoms, nitro group, cyano group, carboxyl group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxyl group, primary amino group to tertiary amino group, salt of carboxyl group, salt of sulfonic acid group, salt of phosphonic acid group, salt of phosphoric acid group, salt of hydroxyl group, and salt of primary amino group to tertiary amino group. R' is preferably a hydrogen atom. At R 1 Or R 2 In the case of hydrogen atoms, the interaction caused by hydrogen bonding between the hydrogen atom and the heteroatom site other than the nitrogen atom or the triazine ring site bonded to the hydrogen atom is more likely to result in a polymer with relatively excellent adhesion to the substrate, and is therefore preferred. The number of repeating units represented by the formula (1) is not particularly limited, for example, 2 to 10,000, preferably 3 to 8,000, and even more preferably 3 to 5,000. When the polymer has structural units derived from the compound represented by formula (A) and structural units derived from the compound represented by formula (B), regarding the proportion of these, when the total of the structural units derived from the compound represented by formula (A) and the structural units derived from the compound represented by formula (B) is set to 100 mol%, the structural units derived from the compound represented by formula (A) are preferably 40 mol% or more and 60 mol% or less, more preferably 43 mol% or more and 57 mol% or less, and even more preferably 45 mol% or more and 55 mol% or less, and the structural units derived from the compound represented by formula (B) are preferably 40 mol% or more and 60 mol% or less, more preferably 43 mol% or more and 57 mol% or less, and even more preferably 45 mol% or more and 55 mol% or less. When the polymer has structural units derived from the compound represented by formula (A) and structural units derived from the compound represented by formula (B), the structural units derived from the compound represented by formula (A) in the polymer may be one or more. Furthermore, the structural units derived from the compound represented by formula (B) in the polymer may also be one or more. <Physical Properties of the Polymer> In terms of being a polymer that has good solubility in common organic solvents, excellent coatability to substrates, and excellent heat resistance, the weight average molecular weight (Mw) of the polystyrene-based polymer of the present polymer is preferably 1,000 to 200,000, more preferably 3,000 to 100,000, and even more preferably 3,000 to 70,000. The glass transition temperature (Tg) of this polymer, as determined by differential scanning calorimetry (DSC), is preferably -50°C to 200°C, and more preferably -0°C to 150°C. Specifically, this Tg can be determined by the method described in the following examples. The 5% weight loss temperature (Td5) of this polymer, determined by thermogravimetric analysis (TGA), is preferably 300°C to 600°C, more preferably 350°C to 600°C, and even more preferably 400°C to 500°C. Polymers with a Td5 within this range are considered to have excellent heat resistance. Specifically, the Td5 can be determined by the method described in the following examples. The elongation at break of this polymer is preferably 30% to 700%, more preferably 160% to 500%, and even more preferably 170% to 500%. Polymers with elongation at break within this range are considered to have excellent mechanical properties. Specifically, this elongation at break can be measured by the method described in the examples below. In terms of reducing transmission losses when using this polymer, the dielectric loss tangent of this polymer is preferably 0.0060 or less, more preferably 0.0050 or less, and there is no particular limitation on the lower limit, but it is preferably 0.0005 or more. Specifically, the dielectric loss tangent can be measured by the method described in the following examples. This polymer is soluble in common solvents, exhibiting excellent solubility in such solvents. Examples of common solvents include those with a boiling point below 180°C at atmospheric pressure; specific examples include cyclohexanone and cyclopentanone. Furthermore, if at 25°C, more than 1 g of this polymer dissolves relative to 100 g of solvent, this polymer can be considered soluble in the solvent. Dissolution can be determined by the presence or absence of precipitate. If this polymer is soluble in the solvent, a solution in which the polymer is dissolved can be prepared, exhibiting excellent coatability and drying properties, thus being preferable. This polymer (the layer obtained from this polymer) exhibits excellent adhesion to the substrate. There are no particular limitations on the substrate, but preferably include: metal substrates such as gold, silver, copper, stainless steel, iron, nickel, beryllium, aluminum, zinc, indium, tin, zirconium, tantalum, titanium, lead, magnesium, manganese, and alloys thereof; and substrates such as polyester resin films (e.g., polyethylene terephthalate films and polybutylene terephthalate films), olefin resin films (e.g., polyethylene films and polypropylene films), cyclic olefin resin films, and polyimide resin films, etc., on which layers of these metals and / or alloys are disposed (e.g., wiring). <Synthesis Method of This Polymer> This polymer can be manufactured, for example, by the condensation reaction of a previously known trihalomethane compound with a dimer diamine. Specifically, as described in the examples, one example is shown. This polymer can be synthesized, for example, by heating and polymerizing the compound represented by formula (A) and the dimer diamine represented by formula (B) in a suitable organic solvent such as N-methyl-2-pyrrolidone (NMP) or N,N-dimethylacetamide (DMAc) in the presence of an alkali metal compound such as potassium carbonate. [Chemistry 11] In formula (A), R 1 and R 2 respectively with R in equation (1) 1 and R 2 [For the same meaning, X represents a halogen atom] [Chemistry 12] [In formula (B), -N(R')-RN(R')- is the structure derived from unsubstituted or substituent-substituted dimer diamines, and R' independently has the same meaning as R' in formula (1).] As for the heating conditions, there are no particular limitations as long as the polymerization reaction is carried out, but in terms of suppressing side reactions, the heating temperature is preferably 0°C to 150°C, more preferably 10°C to 130°C, and the heating time is preferably 0.5 hours to 100 hours, more preferably 1 hour to 24 hours. In particular, for obtaining polymers with less coloring, the heating temperature is preferably about 40°C to 110°C and the heating time is 4 hours to 24 hours. Furthermore, for obtaining polymers with less low molecular weight components and high molecular weight components, the heating temperature is more preferably about 50°C to 100°C. Regarding the ratio of the compound represented by formula (A) to the compound represented by formula (B), when the total percentage of the compound represented by formula (A) and the compound represented by formula (B) is set to 100 mol%, the compound represented by formula (A) is preferably 40 mol% or more and 60 mol% or less, more preferably 43 mol% or more and 57 mol% or less, and even more preferably 45 mol% or more and 55 mol% or less; the compound represented by formula (B) is preferably 40 mol% or more and 60 mol% or less, more preferably 43 mol% or more and 57 mol% or less, and even more preferably 45 mol% or more and 55 mol% or less. One or more compounds represented by formula (A) may be used. Similarly, one or more compounds represented by formula (B) may also be used. Examples of alkali metal compounds include: alkali metals such as lithium, potassium, and sodium; alkali metal hydrides such as lithium hydride, potassium hydride, and sodium hydride; alkali metal hydroxides such as lithium hydroxide, potassium hydroxide, and sodium hydroxide; alkali metal carbonates such as lithium carbonate, potassium carbonate, and sodium carbonate; alkali metal bicarbonates such as lithium bicarbonate, potassium bicarbonate, and sodium bicarbonate; alkali metal alkoxides such as sodium ethoxide; alkali metal acetates such as sodium acetate and potassium acetate; alkali metal oxides such as lithium oxide; alkali metal phosphates such as trilithium phosphate, trisodium phosphate, and tripotassium phosphate; and alkali metal fluorides such as cesium fluoride. Among these, potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium bicarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, trilithium phosphate, trisodium phosphate, tripotassium phosphate, and cesium fluoride are preferred. One or more of the alkali metal compounds may be used. In addition, organic bases may also be used in the aforementioned reaction. Specifically, examples include: ammonia, trimethylamine, triethylamine, diisopropylmethylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine, etc. One or more organic bases may be used. The amount of alkali metal compound used is typically 1.0 to 3.0 equivalents, more preferably 1.0 to 2.5 equivalents, and even more preferably 1.0 to 2.0 equivalents, relative to one -NH-R' in the compound represented by formula (B). [Example] The following describes one embodiment of the present invention in detail based on examples, but the present invention is not limited to the following embodiments. Furthermore, unless otherwise specified, the percentages below are based on weight. < 1 H-NMR spectrum > polymer 1 H-NMR spectra were obtained using a nuclear magnetic resonance apparatus (ECX400P manufactured by NEC Corporation) with deuterated chloroform as the measuring solvent. [Example 1] 4,6-Dichloro-N,N-diphenyl-1,3,5-triazine-2-amine (PDCT) (16.3 g), dimer diamine (Priamine 1075, manufactured by Croda Japan) (27.5 g), and potassium carbonate (7.8 g) were weighed into a four-necked separable flask including a stirrer. N-methyl-2-pyrrolidone (71.4 g) and water (30.6 g) were added, and the mixture was reacted at 100°C under nitrogen for 20 hours. After the reaction, methanol coagulation, filtration, and methanol washing were performed to obtain 32 g (80% yield) of the target polymer containing repeating units represented by the following formula. Furthermore, as described, the dimer diamine is not a single substance; therefore, the structure of the dimer diamine source shown in the following formula represents its representative structure. The formulas described in the following examples are also the same. The obtained polymer was... 1 The H-NMR spectrum is shown in Figure 1. [Chemistry 13] [Example 2] 11.8 g of 4,6-dichloro-N,N-dimethyl-1,3,5-triazine-2-amine (MDCT), 32.7 g of dimerized diamine (Priamine 1075), and 9.3 g of potassium carbonate were measured into a four-necked separable flask including a stirrer. 72.6 g of N-methyl-2-pyrrolidone and 31.1 g of water were added, and the mixture was reacted at 100°C under nitrogen for 20 hours. After the reaction, methanol coagulation, filtration, and methanol washing were performed to obtain 35 g (88% yield) of the target polymer containing repeating units represented by the following formula. The obtained polymer was... 1 The H-NMR spectrum is shown in Figure 2. [Chemistry 14] [Example 3] 10.5 g of 4,6-dichloro-1,3,5-triazine-2-amine (ADCT), 34.1 g of diamine dimer (Priamine 1075), and 9.7 g of potassium carbonate were measured into a four-necked separable flask including a stirrer. 72.9 g of N-methyl-2-pyrrolidone and 31.3 g of water were added, and the mixture was reacted at 100°C under nitrogen for 20 hours. After the reaction, methanol coagulation, filtration, and methanol washing were performed to obtain 30 g (75% yield) of the target polymer containing repeating units represented by the following formula. The obtained polymer was... 1 The H-NMR spectrum is shown in Figure 3. [Chemistry 15] [Example 4] 13.2 g of 2-phenylamino-4,6-dichloro-triazine (AnDCT), 30.8 g of dimeric diamine (Priamine 1075), and 8.7 g of potassium carbonate were measured into a four-necked separable flask including a stirrer. 71.9 g of N-methyl-2-pyrrolidone and 30.8 g of water were added, and the mixture was reacted at 100°C under nitrogen for 20 hours. After the reaction, methanol coagulation, filtration, and methanol washing were performed to obtain 31 g (76% yield) of the target polymer containing repeating units represented by the following formula. The obtained polymer was... 1 The H-NMR spectrum is shown in Figure 4. [Chemistry 16] [Example 5] The contents were changed to 2-phenylamino-4,6-dichlorotriazine (AnDCT) (13.5 g), dimer diamine (Priamine 1075) (30.6 g), potassium carbonate (8.7 g), N-methyl-2-pyrrolidone (72.0 g), and water (30.9 g), and the same operation as in Example 4 was performed to obtain 35 g of the target polymer (yield 88%). [Example 6] The contents were changed to 2-phenylamino-4,6-dichlorotriazine (AnDCT) (13.6 g), dimer diamine (Priamine 1075) (30.5 g), potassium carbonate (8.7 g), N-methyl-2-pyrrolidone (72.0 g), and water (30.9 g), and the same operation as in Example 4 was performed to obtain 37 g of the target polymer (yield 93%). [Example 7] The contents were changed to 2-phenylamino-4,6-dichlorotriazine (AnDCT) (13.7 g), dimer diamine (Priamine 1075) (30.4 g), potassium carbonate (8.6 g), N-methyl-2-pyrrolidone (72.1 g), and water (30.9 g), and the same operation as in Example 4 was performed to obtain 38 g of the target polymer (95% yield). [Example 8] The contents were changed to 2-phenylamino-4,6-dichlorotriazine (AnDCT) (11.9 g), dimer diamine (Priamine 1075) (31.7 g), potassium carbonate (9.0 g), N-methyl-2-pyrrolidone (71.2 g), and water (30.5 g), and the same operation as in Example 4 was performed to obtain 29 g of the target polymer (73% yield). [Comparative Example 1] A flexible bismaleimide oligomer, namely the commercially available ULTIMID3000A (manufactured by ABC Nanotech., LTD.), was designated as Comparative Example 1. [Comparative Example 2] A flexible bisphenol A type epoxy resin, namely commercially available jER872 (manufactured by Mitsubishi Chemical Co., Ltd.), was designated as Comparative Example 2. [Comparative Example 3] 2,4-Dichloro-6-phenoxy-1,3,5-triazine (24.3 g), 2,2-bis(4-hydroxyphenyl)propane (23.0 g), and potassium carbonate (15.3 g) were measured into a four-necked separable flask including a stirrer. N-methyl-2-pyrrolidone (77.3 g) and water (33.1 g) were then added, and the mixture was reacted at 100°C under nitrogen for 20 hours. After the reaction was completed, the mixture was subjected to methanol coagulation, filtration, and methanol washing to obtain 31 g (78% yield) of the target polymer containing repeating units represented by the following formula. [Chemistry 17] [Comparative Example 4] 2,4-Dichloro-6-phenoxy-1,3,5-triazine (26.1 g), bis(4-hydroxyphenyl) ether (21.8 g), and potassium carbonate (16.4 g) were measured into a four-necked separable flask including a stirrer. N-methyl-2-pyrrolidone (78.1 g) and water (33.5 g) were then added, and the mixture was reacted at 100°C under nitrogen for 20 hours. After the reaction was completed, methanol coagulation, filtration, and methanol washing were performed to obtain 30 g of the target polymer (yield 75%). [Chemistry 18] [Comparative Example 5] 2-Phenylamino-4,6-dichloro-triazine (AnDCT) (24.4 g), 4,4'-diaminobenzylaniline (23.0 g), and potassium carbonate (15.4 g) were weighed into a four-necked separable flask including a stirrer. N-methyl-2-pyrrolidone (77.4 g) and water (33.2 g) were added, and the mixture was reacted at 100°C under nitrogen for 20 hours. After the reaction was completed, methanol coagulation, filtration, and methanol washing were performed to obtain 30 g (75% yield) of the target polymer containing repeating units represented by the following formula. [Chemistry 19] [Comparative Example 6] 2-phenylamino-4,6-dichloro-triazine (AnDCT) (29.9 g), bis(aminomethyl)norbornene (19.1 g), and potassium carbonate (18.9 g) were measured into a four-necked separable flask including a stirrer. N-methyl-2-pyrrolidone (80.1 g) and water (34.3 g) were then added, and the mixture was reacted at 100°C under nitrogen for 20 hours. After the reaction was completed, the mixture was subjected to methanol coagulation, filtration, and methanol washing to obtain 29 g (73% yield) of the target polymer containing repeating units represented by the following formula. [Chemistry 20] [Comparative Example 7] 2-Phenylamino-4,6-dichloro-triazine (AnDCT) (26.2 g), 1,12-diaminododecane (21.7 g), and potassium carbonate (16.5 g) were measured into a four-necked separable flask including a stirrer. N-methyl-2-pyrrolidone (78.3 g) and water (33.5 g) were then added, and the mixture was reacted at 100°C under nitrogen for 20 hours. After the reaction was completed, the mixture was subjected to methanol coagulation, filtration, and methanol washing to obtain 31 g (78% yield) of the target polymer containing repeating units represented by the following formula. [Chemistry 21] [Comparative Example 8] 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (15.5 g), 4,4'-dichlorodiphenyl sulfonate (14.4 g), and potassium carbonate (9.3 g) were measured into a four-necked separable flask including a stirrer. N-methylpyrrolidone (128 g) and toluene (50 g) were added and stirred. After refluxing the toluene under nitrogen for several hours, the toluene was removed by distillation, and the reaction was carried out at 190°C for 6 hours. After the reaction was completed, N-methylpyrrolidone (398 g) was added and diluted. The salt was filtered through filter paper, and the filtrate was solidified with methanol (10.5 kg). The solidified powder was separated by filtration, washed again with a small amount of methanol, filtered again, and dried under reduced pressure at 120°C for 12 hours using a vacuum dryer to obtain 23 g (yield 89%) of the target polymer containing repeating units represented by the following formula. [Chemistry 22] [Comparative Example 9] A target polymer containing repeating units represented by the following formula was obtained according to the method described in "Macromolecules", 3, 533-535 (1970). [Chemistry 23] [Polymer Property Evaluation] Using the polymers obtained as described, the following methods were used to evaluate the weight-average molecular weight (Mw), glass transition temperature (Tg), 5% weight loss temperature (Td5), solubility in common organic solvents, coatability, mechanical properties (tensile elastic modulus, elongation at break, tensile strength), adhesion to substrates, and dielectric loss tangent. The evaluation results are shown in Table 1. Furthermore, "-" in Table 1 indicates that the corresponding evaluation item was not measured. <Weight Average Molecular Weight (Mw)> The weight average molecular weight (Mw) of each polymer was determined using a GPC apparatus (HLC-8320 and 8420 models manufactured by Tosoh Corporation) under the following THF conditions when the obtained polymers were dissolved in tetrahydrofuran (THF) (Examples 1 to 8), and under the following N-methyl-2-pyrrolidone conditions when the obtained polymers were insoluble in THF (Comparative Examples 3 to 9). Furthermore, regarding Comparative Example 7, although a portion was insoluble in N-methyl-2-pyrrolidone, the soluble portion was used for Mw determination. • THF Conditioning Column: A combination of "TSKgel α-M" and "TSKgel guardc0lumn α" manufactured by Tosoh Corporation. Development Solvent: THF. Column Temperature: 40℃. Flow Rate: 1.0 mL / min. Sample Concentration: 0.75 wt%. Sample Injection Volume: 50 μL. Detector: Differential Refractometer. Standard Material: Monodisperse Polystyrene. • N-Methyl-2-pyrrolidone conditional column: A combination of TSKgel α-M and TSKgel guardc0lumn α manufactured by Tosoh Corporation. Development solvent: N-methyl-2-pyrrolidone (with 10 mM LiBr added). Column temperature: 40℃. Flow rate: 1.0 mL / min. Sample concentration: 0.75 wt%. Sample injection volume: 50 μL. Detector: Differential refractometer. Standard material: Monodisperse polystyrene. <Glass Transition Temperature (Tg)> The glass transition temperature (Tg) of each polymer is defined as the temperature corresponding to the intersection of the baseline and the tangent at the inflection point of the DSC heating curve obtained using a differential scanning calorimetry (DSC device "Thermo Plus DSC8230" manufactured by Rigaku Corporation) under nitrogen atmosphere at a heating rate of 20°C / min. The inflection point is defined as the temperature corresponding to the peak value in the DDSC curve, which is the differential curve of the DSC heating curve. In addition, the DDSC curve is appropriately referenced in confirming the baseline of the DSC. The DSC curves of the polymers obtained in Examples 1 to 4 are shown in Figure 5. <Softening Point: TMA Inflection Point> For polymers where the glass transition temperature (Tg) is difficult to determine or is unclear, the softening point is determined based on the TMA inflection point. The softening point is defined as the temperature at which the tangent to the neutral baseline of the thermal displacement curve obtained using a thermomechanical analysis apparatus (TMA7100 manufactured by Hitachi High-Tech Science, Inc.) at a heating rate of 5°C / min intersects with the tangent to the line shown in the graph after the polymer has undergone significant deformation at a certain temperature (the line after the inflection point). <5% Weight Reduction Temperature (Td5)> The 5% weight reduction temperature (Td5) for each polymer is set as follows: The temperature at which the polymer's weight cumulatively decreases by 5% is obtained using a differential thermometric balance (NETZSCH TG209F1 Libra) under nitrogen atmosphere and a heating rate of 10°C / min. Furthermore, Td5 is one of the indicators of heat resistance; a higher value indicates better heat resistance. <Solubility in general organic solvents> Regarding the solubility of each polymer in organic solvents, each polymer was added to cyclohexanone (CHN) or cyclopentanone (CPN) at a concentration of 1% by weight and stirred. The case where no precipitate could be visually identified was rated as "○", and the case where precipitate could be visually identified or where the polymer swelled but did not dissolve was rated as "×". <Membrane Preparation Method> An evaluation membrane is prepared as follows and used for the determination of tensile elastic modulus, tensile elongation, tensile strength, and dielectric loss tangent. A solution prepared by dissolving 2 g of each polymer in 8 g of N-methyl-2-pyrrolidone is coated onto a copper foil. The solution is then pre-dried at 70°C for 3 minutes, followed by pre-drying at 130°C for 3 minutes, then evaporating the solvent at 150°C for 30 minutes, and finally evaporating the solvent at 250°C under nitrogen atmosphere for 3 hours, thereby forming a copper foil-coated film. The copper foil-coated film is then immersed in a 40% ferric chloride (III) solution to remove the copper foil, washed with pure water, and dried at 80°C, thus preparing the evaluation membrane. <Copyability> Regarding coatingability, in the method for manufacturing the film, the appearance of the coating film formed on the copper foil is visually observed and evaluated according to the following criteria: "○": A uniform film without repulsion or thickness unevenness is formed on the copper foil; a coating film that does not peel off from the copper foil is formed. "×": A coating film that exhibits repulsion, peels off from the copper foil, and / or has uneven thickness is formed on the copper foil. <Tension elastic modulus, elongation and tensile strength> Regarding the tensile elastic modulus, elongation and tensile strength, the evaluation film was cut into dumbbell shape No. 7 as described in JIS K 6251:2017, and tensile tests were performed at room temperature and 5.0 mm / min using a small benchtop testing machine (manufactured by Shimadzu Corporation, "EZ-LX"). <Copper Foil Adhesion> A solution prepared by dissolving 2 g of each polymer in 8 g of N-methyl-2-pyrrolidone was coated onto copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.]), pre-dried at 70°C for 3 minutes, then pre-dried at 130°C for 3 minutes, then evaporated the solvent at 150°C for 30 minutes, and finally evaporated the solvent at 250°C under nitrogen atmosphere for 3 hours, thereby obtaining a laminate containing a polymer layer and a copper foil. The obtained laminate was cut into pieces with a width of 5 mm and a length of 10 cm, and stretched at 500 mm / min in a 90-degree direction using an Instron 5567 stretcher. The adhesion strength between the polymer layer and the copper foil was evaluated according to IPC-TM-650 2.4.9. Cases with a tightness of 0.3 N / mm or higher are rated as "○", and cases with a tightness of less than 0.3 N / mm are rated as "×". <Adhesion to Gold Substrate> A solution of 2 g of each polymer dissolved in 8 g of N-methyl-2-pyrrolidone was spin-coated onto a gold sputtering wafer to form a film. The film was pre-dried at 70°C for 5 minutes, then pre-dried at 150°C for 5 minutes, and subsequently evaporated at 250°C under nitrogen for 1 hour to form a coating. A post bolt pin with epoxy resin attached was fixed to the surface of this coating by bonding the coating to the epoxy resin. The film was cured at 160°C for 1 hour. The adhesion between the gold sputtering wafer and the formed coating was evaluated using a film adhesion strength tester (manufactured by QuadGroup) under a test condition of 20 N / s. Deterioration of the epoxy resin in the anti-slip stud was rated as "○", and peeling of the coating at the interface with the gold sputtering wafer was rated as "×". <Dielectric Loss Tangent> A test piece (width: 6 cm × length: 6 cm) was cut from the evaluation film and the dielectric loss tangent of the test piece at 10 GHz was measured using the cavity resonator method (manufactured by Aet (stock), dielectric constant measurement system TE mode resonator). [Table 1] As clearly shown in Table 1, the polymers obtained in the examples exhibit excellent heat resistance and mechanical properties, as well as excellent solubility in common organic solvents and excellent coating properties to substrates. Specifically, the polymers obtained in Examples 1 and 3 through 7 show a Td5 of 403°C to 480°C, exhibiting an elongation of 170% to 450%, are soluble in cyclohexanone (○ evaluation), and demonstrate excellent coating properties and adhesion to substrates such as gold or copper substrates. These results confirm that this polymer possesses a high thermal decomposition temperature, excellent mechanical properties (especially tensile elongation), excellent solubility in organic solvents, and excellent adhesion to substrates such as gold or copper substrates. This polymer is suitable for various electronic component applications. On the other hand, although the polymer obtained in Comparative Example 1 had a Td5 of 410°C, its elongation at break was as low as 150%, and it exhibited poor coatability and poor adhesion to substrates. The polymer obtained in Comparative Example 2 had an elongation at break as low as 60%, poor coatability, excellent adhesion to gold substrates, but poor adhesion to copper substrates. The polymers obtained in Comparative Examples 3 through 9 exhibited poor solubility in common organic solvents such as cyclohexanone or cyclopentanone. none Figure 1 shows the polymer obtained in Example 1. 1 ¹H-NMR spectra. Figure 2 shows the ¹H-NMR spectra of the polymer obtained in Example 2. 1 ¹H-NMR spectra. Figure 3 shows the ¹H-NMR spectra of the polymer obtained in Example 3. 1 ¹H-NMR spectra. Figure 4 shows the ¹H-NMR spectra of the polymer obtained in Example 4. 1 H-NMR spectra. Figure 5 shows the DSC curves of the polymers obtained in Examples 1 to 4.

Claims

1. A polymer, wherein the repeating unit comprises only the repeating unit represented by the following formula (1): In formula (1), -N(R')-RN(R')- represents a divalent dimeric acid-type diamine residue derived from a dimeric acid-type diamine or at least a portion of the divalent dimeric acid-type diamine residue being substituted by a substituent, wherein the dimeric acid-type diamine is a diamine obtained by substituting two terminal carboxylic acid groups (-COOH) of a cyclic or acyclic dimeric acid obtained as a dimer of an unsaturated fatty acid having 11 to 22 carbon atoms with a primary amino methyl group (-CH2-NH2), and has a hydrophobic chain having 4 to 9 carbon atoms and a chain-like aliphatic amino group having 8 to 10 carbon atoms, wherein the dimeric acid is mainly composed of a 36-carbon diacid obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms, but contains any amount of monomeric acid (18 carbon atoms), trimeric acid (54 carbon atoms), and other polymeric fatty acids having 20 to 54 carbon atoms. R1 and R2 are, independently, a hydrogen atom, a halogen atom, a hydrocarbon group with 1 to 20 carbon atoms that is unsubstituted or substituted, or a heterocyclic aromatic group with 3 to 20 carbon atoms that is unsubstituted or substituted.

2. A polymer wherein the repeating unit comprises only the repeating unit represented by the following formula (1): In formula (1), -N(R')-RN(R')- represents a structure derived from any of the diamines represented by the following formula, R1 and R2 are independently hydrogen atoms, halogen atoms, unsubstituted or substituted hydrocarbon groups having 1 to 20 carbon atoms, or unsubstituted or substituted heterocyclic aromatic groups having 3 to 20 carbon atoms, respectively, and in the following formula, m+n=6 to 17, p+q=8 to 19, and the wavy part refers to a carbon-carbon single bond or a carbon-carbon double bond.

3. A polymer wherein the repeating unit comprises only the repeating unit represented by the following formula (1): In formula (1), -N(R')-RN(R')- represents a structure derived from versamine 551 (manufactured by BASF Japan), versamine 552 (manufactured by Cognis Japan; hydride of versamine 551), Priamine 1075 (manufactured by Croda Japan), or Priamine 1074 (manufactured by Croda Japan), and R1 and R2 are independently hydrogen atoms, halogen atoms, unsubstituted or substituted hydrocarbon groups having 1 to 20 carbon atoms, or unsubstituted or substituted heterocyclic aromatic groups having 3 to 20 carbon atoms.

4. The polymer as claimed in any one of claims 1 to 3, wherein the weight-average molecular weight (Mw) of polystyrene is 1,000 to 400,000.

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