Block copolymer, method for producing block copolymer, insulating material, polyimide, and printed substrate

Abstract

The present disclosure pertains to a block copolymer containing a polyimide block (BI) and a polyamic acid block (BA), and containing a structural unit (X) having a group (X) containing at least one non-aromatic hydrocarbon group, the total number of carbon atoms of the at least one non-aromatic hydrocarbon group being 9 or more.

Description

Technical Field

[0001] The present disclosure relates to a block copolymer, a method for producing the block copolymer, an insulating material, a heat-resistant insulating material, a composition, a composition for an insulator, a composition for a heat-resistant insulator, a composition for a printed circuit board, a polyimide, a molded body, an insulator, a heat-resistant insulator, and a printed circuit board. Background Art

[0002] With the popularization of automobile driving safety support system (DSSS), the demand for vehicle-mounted millimeter-wave radar is increasing. The insulating material of the substrate for vehicle-mounted millimeter-wave radar requires a resin with low transmission signal loss and high heat resistance that can withstand the high temperature near the engine. Polyimide is known to be an insulating material with excellent heat resistance (for example, Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2010 / 113412 Summary of the invention

[0006] Technical problem to be solved by the invention

[0007] The present disclosure provides a block copolymer capable of obtaining a polyimide having a low dielectric constant, a low dielectric loss tangent, and a low thermal expansion coefficient, and a method for producing the same. In addition, the present disclosure also provides a polyimide, a molded body, an insulator, a heat-resistant insulator, and a printed circuit board exhibiting excellent insulation, excellent heat resistance, or both, and an insulating material, a heat-resistant insulating material, a composition, a composition for an insulator, a composition for a heat-resistant insulator, and a composition for a printed circuit board capable of obtaining any of the above.

[0008] Means for solving technical problems

[0009] The present invention includes the following embodiments. The present invention is not limited to the following embodiments.

[0010] One embodiment relates to a block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and comprising a structural unit (X) having a group (X), wherein the group (X) contains at least one non-aromatic hydrocarbon group and the total carbon number of the at least one non-aromatic hydrocarbon group is 9 or more.

[0011] Another embodiment relates to a block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and comprising at least one selected from the group consisting of a structural unit represented by the following formula (XI) and a structural unit represented by the following formula (XA).

[0012] [Chemical formula 1]

[0013]

[0014] (Where R 1 and R 2 Each independently represents an organic group, R 1 and R 2 At least one of the groups is a group (X) containing at least one non-aromatic hydrocarbon group and the total carbon number of the at least one non-aromatic hydrocarbon group is 9 or more.

[0015] [Chemical formula 2]

[0016]

[0017] (Where R 3 and R 4 Each independently represents an organic group, R 3 and R 4 At least one of the groups is a group (X) containing at least one non-aromatic hydrocarbon group and the total carbon number of the at least one non-aromatic hydrocarbon group is 9 or more.

[0018] Another embodiment relates to a block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and having a structure derived from a diamine or a diisocyanate and a structure derived from a tetracarboxylic dianhydride, wherein at least one of the structure derived from a diamine or a diisocyanate and the structure derived from a tetracarboxylic dianhydride contains a structure having a group (X), wherein the group (X) contains at least one non-aromatic hydrocarbon group and the total number of carbon atoms of the at least one non-aromatic hydrocarbon group is 9 or more.

[0019] Another embodiment relates to a method for producing a block copolymer, comprising the steps of: obtaining a polyimide (PI) using a diamine or a diisocyanate and a tetracarboxylic dianhydride; obtaining a polyamic acid (PA) using a diamine and a tetracarboxylic dianhydride; and obtaining a block copolymer using the polyimide (PI) and the polyamic acid (PA), wherein at least one selected from the diamine or a diisocyanate and a tetracarboxylic dianhydride used to obtain the polyimide, and the diamine and the tetracarboxylic dianhydride used to obtain the polyamic acid has a group (X) containing at least one non-aromatic hydrocarbon group and the total carbon number of the at least one non-aromatic hydrocarbon group is 9 or more.

[0020] Another embodiment relates to an insulating material and a heat-resistant insulating material, which contain any one of the above block copolymers.

[0021] Another embodiment relates to a composition, a composition for an insulator, a composition for a heat-resistant insulator, and a composition for a printed circuit board, which contain any of the above block copolymers or any of the above materials.

[0022] Another embodiment relates to a polyimide obtained using any of the above block copolymers, any of the above materials, or any of the above compositions.

[0023] Another embodiment relates to a molded article, an insulator, and a heat-resistant insulator obtained by using any of the above block copolymers, any of the above materials, or any of the above compositions, or containing the above polyimide.

[0024] Another embodiment relates to a printed circuit board obtained by using any of the above block copolymers, any of the above materials, or any of the above compositions, or containing the above polyimide, the above molded article, the above insulator, or the above heat-resistant insulator.

[0025] Effects of the Invention

[0026] According to the present disclosure, a block copolymer capable of obtaining a polyimide having a low dielectric constant, a low dielectric loss tangent, and a low thermal expansion coefficient and a method for producing the same can be obtained. In addition, according to the present disclosure, a polyimide, a molded body, an insulator, a heat-resistant insulator, and a printed circuit board showing excellent insulation, excellent heat resistance, or both can be obtained, as well as an insulating material, a heat-resistant insulating material, a composition, a composition for an insulator, a composition for a heat-resistant insulator, and a composition for a printed circuit board that can obtain any of these. DETAILED DESCRIPTION

[0027] The embodiments of the present invention are described. The present invention is not limited by the following embodiments. In addition, the following embodiments can be implemented individually or in combination. The combination of multiple embodiments is also included in the present invention.

[0028] In the numerical range recorded hierarchically in the disclosure, the upper limit or lower limit that a certain numerical range is recorded can be replaced by the upper limit or lower limit of other numerical ranges. In addition, the upper limit or lower limit of the numerical range recorded in the disclosure can be replaced by the value shown in the embodiment. Also can select a certain numerical value as the numerical range of hierarchy from the numerical value of the upper limit recorded hierarchically in the disclosure and the numerical value of the lower limit. In addition, the numerical value of the upper limit recorded in the disclosure and the numerical value of the lower limit can also be replaced by the value shown in the embodiment.

[0029] In the present disclosure, each component may contain multiple substances belonging to the component. When multiple substances belonging to each component exist in the composition, unless otherwise specified, the content rate or content of each component refers to the total content rate or content of the multiple substances present in the composition.

[0030] In the present disclosure, each structure in a polymer may contain multiple structures belonging to the structure. When there are multiple structures belonging to each structure in a polymer, unless otherwise specified, the content or content of each structure refers to the total content or content of the multiple structures present in the polymer.

[0031] The term "layer" in the present disclosure includes a layer formed over the entire region when the region where the layer exists is observed, and a layer formed only over a portion of the region. The same applies to the "film".

[0032] <Block copolymer>

[0033] In some embodiments of the present invention, the block copolymer contains a polyimide block (BI) and a polyamic acid block (BA). The block copolymer contains: a group (X) containing at least one non-aromatic hydrocarbon group and the total carbon number of the at least one non-aromatic hydrocarbon group is 9 or more. In the present disclosure, sometimes "a group (X) containing at least one non-aromatic hydrocarbon group and the total carbon number of the at least one non-aromatic hydrocarbon group is 9 or more" is simplified to "group (X)" or "hydrocarbon group (X)".

[0034] The polyamic acid block (BA) may also be a block of a polyimide block (BI-A) different from the polyimide block (BI) by amic acid bond ring closure. The block copolymer may further contain any block different from the polyimide block (BI) and the polyamic acid block (BA). The block copolymer may contain one or more any blocks.

[0035] In the present disclosure, whether the blocks are the same or not can be distinguished by the structural units contained in the blocks. For example, in the case where there is a structural unit contained in one block but not in another block, the two are different blocks. As an example of a combination of 2 different blocks, it can be cited that: block 1 contains structural unit 1, block 2 contains structural unit 2; block 1 contains structural unit 1, block 2 contains structural unit 1 and structural unit 2; block 1 contains structural unit 1 and structural unit 2, block 2 contains structural unit 1 and structural unit 3, etc. The structural unit 1, structural unit 2, and structural unit 3 used in the description here are structural units that are different from each other. In the present disclosure, the number of types of structural units contained in each block is not limited to 1 or 2, and may be 3 or more. In the present disclosure, the number of types of blocks contained in the block copolymer is not limited to 2, and may be 3 or more.

[0036] The block copolymer containing the polyimide block (BI) and the polyamic acid block (BA) contains an imide bond (also referred to as an "imide group") and an amic acid bond (also referred to as an "amic acid structure" or "amic acid group") in the polymer chain. The hydrocarbon group (X) may be a group located between an imide group and an imide group, between an amic acid group and an amic acid group, or between an imide group and an amic acid group. The block copolymer may contain one or more hydrocarbon groups (X).

[0037] The copolymer can obtain a polyimide with a low thermal expansion coefficient by having a block structure. The block copolymer can obtain a polyimide with a low dielectric constant and a low dielectric loss tangent by having a hydrocarbon group (X). Furthermore, the block copolymer can easily obtain a polyimide with a low water absorption by having a hydrocarbon group (X).

[0038] [Block copolymer containing structural unit (X)]

[0039] In some embodiments of the present invention, the block copolymer contains a polyimide block (BI) and a polyamic acid block (BA), and contains a structural unit (X) having a group (X). In the present disclosure, "a structural unit (X) having a group (X) containing at least one non-aromatic hydrocarbon group and the total carbon number of the at least one non-aromatic hydrocarbon group is 9 or more" is sometimes simplified to "structural unit (X)".

[0040] The block copolymer may contain a structural unit other than the structural unit (X). As the structural unit other than the structural unit (X), for example, the structural unit (Y) described below can be cited. The structural unit (Y) is a structural unit that does not have a hydrocarbon group (X).

[0041] In block copolymer, only any one of polyimide block (BI) and polyamic acid block (BA) contains structural unit (X), or both polyimide block (BI) and polyamic acid block (BA) contain structural unit (X). Polyimide block (BI) and polyamic acid block (BA) can each independently contain one or more structural units (X). In the case where block copolymer contains structural unit (Y), only any one of polyimide block (BI) and polyamic acid block (BA) can contain structural unit (Y), or both polyimide block (BI) and polyamic acid block (BA) contain structural unit (Y). Polyimide block (BI) and polyamic acid block (BA) can each independently contain one or more structural units (Y).

[0042] (Structural unit (X))

[0043] The structural unit (X) contains at least a hydrocarbon group (X). The structural unit (X) may further contain at least one of an imide group and an amic acid group. The number of carbons contained in the imide group and the amic acid group is not included in the total carbon number of at least one non-aromatic hydrocarbon group in the hydrocarbon group (X). For example, the structural unit (X) is a structural unit containing a hydrocarbon group (X), and an imide group or an amic acid group. The block copolymer may contain a hydrocarbon group (X), an imide group or an amic acid group contained in the structural unit (X) in the polymer chain. The structural unit (X) may contain one or more hydrocarbon groups (X). The structural unit (X) may further contain any group other than the hydrocarbon group (X), the imide group and the amic acid group. As any group, an organic group that does not belong to the hydrocarbon group (X) may be cited, for example. In the present disclosure, an organic group is a group containing at least one carbon atom. In the present disclosure, an organic group other than the hydrocarbon group (X) that does not belong to the hydrocarbon group (X) is sometimes referred to as an "organic group (Y)". The organic group (Y) may be a group located between imide groups, between amic acid groups, or between imide groups and amic acid groups. The block copolymer may contain the organic group (Y) in the polymer chain.

[0044] (Hydrocarbon group (X))

[0045] The hydrocarbon group (X) contains at least one non-aromatic hydrocarbon group. In the hydrocarbon group (X), the total carbon number of at least one non-aromatic hydrocarbon group is 9 or more. When the hydrocarbon group (X) contains one non-aromatic hydrocarbon group, the total carbon number is the total carbon number contained in the one non-aromatic hydrocarbon group. When the hydrocarbon group (X) contains two or more non-aromatic hydrocarbon groups, the total carbon number is the total carbon number contained in the two or more non-aromatic hydrocarbon groups. When the hydrocarbon group (X) contains two or more non-aromatic hydrocarbon groups, the non-aromatic hydrocarbon groups may be the same or different from each other. The hydrocarbon group (X) may also contain any group other than a non-aromatic hydrocarbon group. The hydrocarbon group (X) is, for example, a 1- to 4-valent group. The structural unit (X) preferably contains a 2- to 4-valent hydrocarbon group (X), more preferably contains a 2- or 4-valent hydrocarbon group (X), and further preferably contains a 2-valent hydrocarbon group (X).

[0046] The non-aromatic hydrocarbon group is a non-aromatic hydrocarbon group that does not contain an aromatic ring. The non-aromatic hydrocarbon group is, for example, a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group, an unsaturated alicyclic hydrocarbon group, or a group formed by two or more selected from them. The saturated aliphatic hydrocarbon group may be straight-chain or branched. The unsaturated aliphatic hydrocarbon group may be straight-chain or branched. When the 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.

[0047] The following lists examples of the total carbon number of a hydrocarbon group (X) and at least one non-aromatic hydrocarbon group contained in the hydrocarbon group (X). In addition, as a reference example, an example of the total carbon number of an organic group (Y) and at least one non-aromatic hydrocarbon group contained in the organic group (Y) is listed. As described later, the carbon number contained in the -C(O)- group is not included in the total carbon number. In the present disclosure, the "*" in the formula represents the position bonded to other atoms.

[0048] Table 1

[0049]

[0050] The total carbon number of at least one non-aromatic hydrocarbon group contained in the hydrocarbon group (X) may be 9 to 50. The carbon number is, 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 carbon number is, for example, 48 or less, 44 or less, 40 or less, or 36 or less. The carbon number is, for example, 12 to 48, 20 to 44, or 28 to 40. It can be considered that when the total carbon number of the non-aromatic hydrocarbon group is 9 or more, a polyimide with a low dielectric constant and a low dielectric loss tangent can be obtained due to the increase in free volume, the decrease in polarity, etc. When the total carbon number of the non-aromatic hydrocarbon group is 50 or less, good solubility in the solvent can be maintained. Even if the block copolymer has a group with a total carbon number of 9 or more of an aromatic hydrocarbon group and a heteroaromatic ring compound group instead of the hydrocarbon group (X), a polyimide with a low dielectric constant and a low dielectric loss tangent cannot be obtained due to the small free volume.

[0051] The following lists examples of saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, unsaturated alicyclic hydrocarbon groups, and groups formed by two or more selected from them that the hydrocarbon group (X) may contain. The following examples can be applied to the saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, unsaturated alicyclic hydrocarbon groups, and groups formed by two or more selected from them disclosed herein.

[0052] The carbon number of the saturated aliphatic hydrocarbon group is, for example, 1 to 50, 2 to 40, 3 to 30, 4 to 20, or 5 to 10. The saturated aliphatic hydrocarbon group is, for example, an atomic group obtained by removing 1 to 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, triacontan, tetracontan and pentacontan.

[0053] The carbon number of 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 number of carbon-carbon unsaturated bonds contained in the unsaturated aliphatic hydrocarbon group is 1 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 olefin containing 1 carbon-carbon double bond, or an alkyne containing 1 carbon-carbon triple bond. The unsaturated aliphatic hydrocarbon group is, for example, an atomic group obtained by removing 1 to 4 hydrogen atoms from a straight-chain or branched olefin, or an atomic group obtained by removing 1 to 4 hydrogen atoms from a straight-chain or branched alkyne. Examples of olefins include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, hexienecene, docosene, tricosene, tetracosene, pentacosene, hexacosene, heptacosene, octacosene, nonacosene, triaconta ...

[0054] The carbon number of 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, an atomic 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, quadricyclane, and adamantane.

[0055] The carbon number of the unsaturated alicyclic hydrocarbon group is, for example, 4 to 20, 5 to 10, or 6 to 8. The number of carbon-carbon unsaturated bonds contained in the unsaturated aliphatic hydrocarbon group is 1 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 cycloolefin containing 1 carbon-carbon double bond, or a cycloalkyne containing 1 carbon-carbon triple bond. The unsaturated alicyclic hydrocarbon group is, for example, an atomic group obtained by removing 1 to 4 hydrogen atoms from a cycloolefin, or an atomic group obtained by removing 1 to 4 hydrogen atoms from a cycloalkyne. Examples of unsaturated alicyclic hydrocarbons include cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, norbornene, norbornadiene, and bicyclooctadiene.

[0056] The carbon number of the group formed by two or more selected from them is, for example, 4 to 50, 9 to 50, 16 to 48, 24 to 44, or 32 to 40. The group formed by two or more selected from them is a group formed by two or more selected from saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, and unsaturated alicyclic hydrocarbon groups, and the above two or more groups are bonded to each other. The group having two or more selected from them, for example, contains at least one selected from the following groups: a group formed by a saturated aliphatic hydrocarbon group and a saturated alicyclic hydrocarbon group, a group formed by a saturated aliphatic hydrocarbon group and an unsaturated alicyclic hydrocarbon group, a group formed by an unsaturated aliphatic hydrocarbon group and a saturated alicyclic hydrocarbon group, and a group formed by an unsaturated aliphatic hydrocarbon group and an unsaturated alicyclic hydrocarbon group.

[0057] As the arbitrary group that the hydrocarbon group (X) may contain, for example, an aromatic hydrocarbon group, an aromatic heterocyclic compound group, and a heteroatom-containing group can be cited. The following examples can be applied to the aromatic hydrocarbon group, aromatic heterocyclic compound group, and heteroatom-containing group disclosed in the present invention.

[0058] 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, 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. The number of carbon atoms in the aromatic heterocyclic compound group is 2 to 30, 4 to 20, or 5 to 10. The aromatic heterocyclic compound group is, for example, an atomic group obtained by removing 1 to 4 hydrogen atoms from an aromatic heterocyclic compound. Examples of aromatic heterocyclic compounds include pyridine, furan, benzofuran, thiophene, and benzothiophene.

[0059] As the group containing heteroatoms, for example, heteroatom-containing connecting groups (except imido groups and amic acid groups) and heteroatom-containing substituents can be listed. As examples of heteroatom-containing connecting groups, oxy groups, sulfenyl groups, sulfonyl groups, sulfinyl groups, carbonyl groups, carbonyloxy groups, imino groups, etc. can be listed. As examples of heteroatom-containing substituents, hydroxyl groups, thiol groups, sulfonyl groups, sulfinyl groups, carboxyl groups, fluoro groups, chloro groups, etc. can be listed. In the present disclosure, the carbon number of the -C(O)- group contained in the heteroatom-containing group is not included in the total carbon number of at least one non-aromatic hydrocarbon group.

[0060] The hydrocarbon group (X) is, for example, composed of a non-aromatic hydrocarbon group having a carbon number of 9 or more. When the hydrocarbon group (X) is composed of a non-aromatic hydrocarbon group, the hydrocarbon group (X) does not contain an aromatic hydrocarbon group, an aromatic heterocyclic compound group, and a group containing a heteroatom. The hydrocarbon group (X) is, for example, a saturated aliphatic hydrocarbon group having a carbon number of 9 or more, an unsaturated aliphatic hydrocarbon group having a carbon number of 9 or more, a saturated alicyclic hydrocarbon group having a carbon number of 9 or more, an unsaturated alicyclic hydrocarbon group having a carbon number of 9 or more, or a group having a carbon number of 9 or more formed by two or more groups selected from saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, and unsaturated alicyclic hydrocarbon groups. The saturated aliphatic hydrocarbon group may be linear or branched. The unsaturated aliphatic hydrocarbon group may be linear or branched. When the hydrocarbon group (X) is composed of a non-aromatic hydrocarbon group having a carbon number of 9 or more, it is easy to reduce the concentration of polar groups contained in the block copolymer.

[0061] The hydrocarbon group (X) preferably contains at least one group selected from a saturated alicyclic hydrocarbon group and an unsaturated alicyclic hydrocarbon group, and more preferably contains a saturated alicyclic hydrocarbon group. When the block copolymer contains at least one of a saturated alicyclic hydrocarbon group and an unsaturated alicyclic hydrocarbon group, there is a tendency to easily obtain a polyimide with a lower dielectric constant. It is speculated that the reason is that the free volume of the polyimide increases due to the alicyclic structure. However, the present invention is not limited by the above speculation.

[0062] The hydrocarbon group (X) preferably contains at least one group selected from a linear saturated aliphatic hydrocarbon group having a carbon number of 6 or more and a linear unsaturated aliphatic hydrocarbon group having a carbon number of 6 or more, and more preferably contains a linear saturated aliphatic hydrocarbon group having a carbon number of 6 or more. When the block copolymer contains at least one of a linear saturated aliphatic hydrocarbon group having a carbon number of 6 or more and a linear unsaturated aliphatic hydrocarbon group having a carbon number of 6 or more, there is a tendency to easily obtain a polyimide having a lower dielectric loss tangent. It is speculated that the reason is that the concentration of the imide group in the polyimide is reduced due to the long chain structure of the polyimide, that is, the number of polar groups in the polyimide is relatively reduced. However, the present invention is not limited by the above speculation.

[0063] In some embodiments, the total number of carbon atoms of the saturated aliphatic hydrocarbon group and the unsaturated aliphatic hydrocarbon group contained in the hydrocarbon group (X) may be greater than the total number of carbon atoms of the saturated alicyclic hydrocarbon group and the unsaturated alicyclic hydrocarbon group contained in the hydrocarbon group (X).

[0064] In some embodiments, the hydrocarbon group (X) may not contain an aromatic hydrocarbon group or an aromatic heterocyclic compound group.

[0065] The hydrocarbon group (X) preferably contains a group represented by the following formula (G1).

[0066] [Chemical formula 3]

[0067] *-Rx -* (G1)

[0068] In the formula, R x It represents a group (X) containing at least one non-aromatic hydrocarbon group, wherein the total carbon number of the at least one non-aromatic hydrocarbon group is 9 or more.

[0069] The hydrocarbon group (X) more preferably contains at least one selected from the group represented by the following formula (G2) to the group represented by the following formula (G6).

[0070] [Chemical formula 4]

[0071] *-R a -* (G2)

[0072] *-R b -R a -R b -* (G3)

[0073] *-R a -R b -R a -* (G4)

[0074] *-R b -LR b -* (G5)

[0075]

[0076] In the formula, R a Each independently represents a straight-chain or branched saturated aliphatic hydrocarbon group (carbon number is, for example, 1 or more, 6 or more, or 8 or more) or a straight-chain or branched unsaturated aliphatic hydrocarbon group (carbon number is, for example, 1 or more, 6 or more, or 8 or more), preferably a straight-chain saturated aliphatic hydrocarbon group (carbon number is, for example, 1 or more, 6 or more, or 8 or more) or a straight-chain unsaturated aliphatic hydrocarbon group (carbon number is, for example, 1 or more, 6 or more, or 8 or more). b Each independently represents a saturated alicyclic hydrocarbon group or an unsaturated alicyclic hydrocarbon group, preferably a saturated alicyclic hydrocarbon group (for example, a carbon number of 6 (cyclohexyl) or 7 (norbornyl)). L represents a single bond or a heteroatom-containing linking group (except for an imide group and an amic acid group). a and R b Each independently may have a substituent or may not have a substituent. a and R b The upper limit of the carbon number is, for example, 48 or less, 44 or less, 40 or less, or 36 or less.

[0077] The hydrocarbon group (X) further preferably contains at least one selected from the group shown in the following formula (G7), the group shown in the following formula (G8) and the group shown in the following formula (G9). These groups can be introduced into the block copolymer by using as a monomer for obtaining a block copolymer, such as dimer diamine. The hydrocarbon group (X) particularly preferably contains the group shown in the formula (G8). When the structural unit (X) contains at least one selected from the group shown in the formula (G7), the group shown in the formula (G8) and the group shown in the formula (G9), there is a tendency to easily obtain sufficient low dielectric constant, low dielectric loss tangent, and low thermal expansion coefficient.

[0078] [Chemical formula 5]

[0079]

[0080] In the formula, R c Each independently represents a linear alkylene group or a linear alkenylene group (having, for example, 6 or more, 8 or more, or 9 or more carbon atoms), R d Each independently represents a linear alkyl group or a linear alkenyl group (having, for example, 6 or more, 8 or more, or 9 or more carbon atoms). c and R d Each independently may have a substituent or may not have a substituent. c and R d The upper limit of the carbon number is, for example, 48 or less, 44 or less, 40 or less, or 36 or less.

[0081] (Organic group (Y))

[0082] The structural unit (X) may contain an organic group (Y). The organic group (Y) is a group containing at least one selected from, for example, the following groups: a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group, an unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group, an aromatic heterocyclic compound group, and a group formed by two or more selected from them. When the organic group (Y) contains at least one non-aromatic hydrocarbon group, the total number of carbon atoms contained in the at least one non-aromatic hydrocarbon group is 8 or less. The organic group (Y) preferably contains an aromatic hydrocarbon group. The organic group (Y) may further contain a heteroatom-containing connecting group, a heteroatom-containing substituent, etc. The organic group (Y) is, for example, a 1- to 4-valent group. The structural unit (X) preferably contains a 2- to 4-valent organic group (Y), more preferably contains a 2- or 4-valent organic group (Y), and further preferably contains a 4-valent organic group (Y).

[0083] The organic group (Y) preferably includes a group represented by the following formula (G11).

[0084] [Chemical formula 6]

[0085]

[0086] In the formula, R y represents an organic group (Y).

[0087] It is more preferable that the organic group (Y) contains at least one selected from the group represented by the following formula (G12) to the group represented by the following formula (G14).

[0088] [Chemical formula 7]

[0089]

[0090] In the formula, R e Each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic compound group, preferably represents an aromatic hydrocarbon group, and more preferably represents a phenyl group. f represents a linear or branched saturated aliphatic hydrocarbon group, or a linear or branched unsaturated aliphatic hydrocarbon group. f The carbon number of is 8 or less. L represents a single bond or a heteroatom-containing linking group (except for an imide group and an amic acid group). e and R f Each independently may or may not have a substituent.

[0091] According to some embodiments, the organic group (Y) contains at least one selected from the group represented by formula (G12) and the group represented by formula (G14), preferably contains a group represented by formula (12) and R e A group is a phenyl group, and a group represented by formula (14) and R e is at least one of a phenyl group, a single bond or a heteroatom-containing linking group (e.g., a carbonyl group). For example, the organic group (Y) contains a group represented by formula (12) and R e For example, the organic group (Y) contains the group represented by formula (14) and R e is a phenyl group, and L is a single bond. For example, the organic group (Y) contains a group represented by formula (14) and R e is a phenyl group, and L is a linking group containing a heteroatom (such as a carbonyl group).

[0092] As an example of a structural unit (X), a structural unit shown in formula (XI) described later and a structural unit shown in formula (XA) can be listed. In a preferred embodiment, the structural unit (X) contains at least one selected from the structural unit shown in formula (XI) and the structural unit shown in formula (XA). As an example of a structural unit (X), a structural unit (Xd) described later can be listed. In a preferred embodiment, the structural unit (X) contains a structural unit (Xd).

[0093] (Structural unit (Y))

[0094] The block copolymer may contain a structural unit (Y). The structural unit (Y) is a structural unit without a hydrocarbon group (X). The structural unit (Y) may have, for example, the above-mentioned organic group (Y). The structural unit (Y) may further contain at least one of an imide group and an amic acid group. For example, the structural unit (Y) is a structural unit containing an organic group (Y) and an imide group or an amic acid group. The block copolymer may contain an organic group (Y) and an imide group or an amic acid group contained in the structural unit (Y) in the polymer chain. The structural unit (Y) may contain one or more organic groups (Y).

[0095] According to some embodiments, in the structural unit (Y), the organic group (Y) preferably contains a group represented by the above formula (G11) and a group represented by the following formula (G15), and more preferably contains at least one selected from the group represented by the above formula (G12) to the group represented by the following formula (G14), and at least one selected from the group represented by the following formula (G16) to the group represented by the following formula (G18).

[0096] [Chemical formula 8a]

[0097] *-R y -* (G15)

[0098] *-R e -* (G16)

[0099] *-R e -R f -R e -* (G17)

[0100] *-R e -LR e -* (G18)

[0101] In the formula, R y represents an organic group (Y). e Each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic compound group, preferably represents an aromatic hydrocarbon group, and more preferably represents a phenyl group. f represents a linear or branched saturated aliphatic hydrocarbon group, or a linear or branched unsaturated aliphatic hydrocarbon group. f The carbon number of is 8 or less. L represents a single bond or a linking group containing a hetero atom (except for an imide group and an amic acid group). e and R f Each independently may or may not have a substituent.

[0102] According to some embodiments, in the structural unit (Y), the organic group (Y) contains, for example, at least one selected from the group represented by the above formula (G12) to the group represented by the above formula (G14), and at least one selected from the group represented by the above formula (G16) to the group represented by the above formula (G18), the group represented by the following formula (G18a) and the group represented by the following formula (G18b), preferably contains at least one selected from the group represented by the above formula (G12) and the group represented by the above formula (G14), and at least one selected from the group represented by the above formula (G16), the group represented by the above formula (G18) and the group represented by the following formula (G18b).

[0103] [Chemical formula 8b]

[0104] *-R e -LR e -LR e -* (G18a)

[0105] *-R e -LR e -LR e -LR e -* (G18b)

[0106] In the formula, R e Each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic compound group, preferably an aromatic hydrocarbon group, and more preferably a phenyl group. L represents a single bond or a heteroatom-containing linking group (except for an imide group and an amic acid group). e Each independently may or may not have a substituent.

[0107] As an example of a structural unit (Y), a structural unit represented by formula (YI) described later and a structural unit represented by formula (YA) can be cited. In a preferred embodiment, the structural unit (Y) comprises at least one selected from the structural unit represented by formula (YI) and the structural unit represented by formula (YA). As an example of a structural unit (Y), a structural unit (Yd) described later can be cited. In a preferred embodiment, the structural unit (Y) comprises a structural unit (Yd).

[0108] [Block copolymer comprising a structural unit represented by formula (XI) and / or a structural unit represented by formula (XA)]

[0109] In some embodiments of the present invention, the block copolymer contains a polyimide block (BI) and a polyamic acid block (BA), and contains at least one structural unit selected from the structural unit represented by the following formula (XI) and the structural unit represented by the following formula (XA). As examples of block copolymers, there can be cited a block copolymer in which the polyimide block (BI) contains the structural unit represented by the formula (XI); a block copolymer in which the polyamic acid block (BA) contains the structural unit represented by the formula (XA); a block copolymer in which the polyimide block (BI) contains the structural unit represented by the formula (XI) and the polyamic acid block (BA) contains the structural unit represented by the formula (XA), etc.

[0110] The block copolymer may also contain structural units other than the structural units shown in the following formula (XI) and the structural units shown in the following formula (XA). As structural units other than the structural units shown in the following formula (XI) and the structural units shown in the following formula (XA), for example, the structural units shown in the formula (YI) described later and the structural units shown in the formula (YA) can be listed. The block copolymer may contain at least one structural unit selected from the structural units shown in the formula (YI) and the structural units shown in the formula (YA). The structural units shown in the formula (YI) and the structural units shown in the formula (YA) do not have a hydrocarbon group (X).

[0111] The structural unit represented by formula (XI) and the structural unit represented by formula (XA) are structural units equivalent to the structural unit (X), and examples of the structural unit represented by formula (XI) and the structural unit represented by formula (XA) include the structural unit (Xd) described below. The structural unit represented by formula (YI) and the structural unit represented by formula (YA) are structural units equivalent to the structural unit (Y), and examples of the structural unit represented by formula (YI) and the structural unit represented by formula (YA) include the structural unit (Yd) described below.

[0112] (Structural unit represented by formula (XI))

[0113] [Chemical formula 9]

[0114]

[0115] In the formula, R 1 and R 2 Each independently represents an organic group, R 1 and R 2 At least one of them is a hydrocarbon group (X).

[0116] Examples of the organic group include a hydrocarbon group (X) and an organic group (Y).

[0117] According to some embodiments, in the structural unit represented by formula (XI), for example, R1 is a hydrocarbon group (X), R 2 is an organic group (Y); preferably, R 1 is a group selected from the group represented by formula (G2) to the group represented by formula (G6), R 2 is a group selected from the group represented by formula (G12) to the group represented by formula (G14); more preferably, R 1 is a group selected from the group represented by (G4) and the group represented by the formula (G7) to the group represented by the formula (G9), and R 2 is a group represented by formula (G12); further preferably, R 1 is a group represented by formula (G8), R 2 is shown in formula (G12) and R e It is phenyl.

[0118] According to some embodiments, in the structural unit represented by formula (XI), for example, R 1 is a group selected from the group represented by formula (G2) to the group represented by formula (G6), R 2 is a group selected from the group represented by formula (G12) to the group represented by formula (G14); preferably, R 1 is a group selected from the group represented by (G4) and the group represented by the formula (G7) to the group represented by the formula (G9), R 2 is a group selected from the group represented by formula (G12) and the group represented by formula (G14). For example, the structural unit represented by formula (XI) contains R 1 is a group represented by formula (G8), R 2 is a group represented by formula (G12) (R e For example, the structural unit represented by formula (XI) comprises R 1 is a group represented by formula (G8), R 2 is a group represented by formula (G14) (R e is a structural unit in which L is a phenyl group and L is a heteroatom-containing linking group (eg, a carbonyl group).

[0119] (Structural unit represented by formula (XA))

[0120] [Chemical formula 10]

[0121]

[0122] In the formula, R 3 and R 4 Each independently represents an organic group, R 3 and R 4 At least one of them is a hydrocarbon group (X).

[0123] Examples of the organic group include a hydrocarbon group (X) and an organic group (Y).

[0124] According to some embodiments, in the structural unit represented by formula (XA), for example, R 3 is a hydrocarbon group (X), R 4 is an organic group (Y), preferably, R 3 is a group selected from the group represented by formula (G2) to the group represented by formula (G6), R 4 is a group selected from the group represented by formula (G12) to the group represented by formula (G14); more preferably, R 3 is a group selected from the group represented by (G4) and the group represented by the formula (G7) to the group represented by the formula (G9), and R 4 is a group represented by formula (G14); further preferably, R 3 is a group represented by formula (G8), R 4 is shown in formula (G14) and R e It is phenyl.

[0125] According to some embodiments, in the structural unit represented by formula (XA), for example, R 3 is a group selected from the group represented by formula (G2) to the group represented by formula (G6), R 4 is a group selected from the group represented by formula (G12) to the group represented by formula (G14); preferably, R 3 is a group selected from the group represented by (G4) and the group represented by the formula (G7) to the group represented by the formula (G9), and R 4 is a group selected from the group represented by formula (G12) and the group represented by formula (G14). For example, the structural unit represented by formula (XA) contains R 3 is a group represented by formula (G8), R 4 is a group represented by formula (G12) (R e For example, the structural unit represented by formula (XA) comprises R 3 is a group represented by formula (G8), R 4 is a group represented by formula (G14) (R e is a phenyl group, and L is a single bond).

[0126] (Structural unit represented by formula (YI))

[0127] [Chemical formula 11]

[0128]

[0129] In the formula, R 5 and R 6Each independently represents an organic group (Y).

[0130] According to some embodiments, in the structural unit represented by formula (YI), for example, R 5 is a group selected from the group represented by the formula (G16) to the group represented by the formula (G18), R 6 is a group selected from the group represented by formula (G12) to the group represented by formula (G14); preferably, R 5 is a group represented by formula (G16) or a group represented by formula (G18), R 6 is a group represented by formula (G12) or a group represented by formula (G14); more preferably, R 5 is shown in formula (G16) and R e is phenyl or is represented by formula (18) and R e is phenyl, R 6 is shown in formula (G12) and R e is phenyl or is represented by formula (14) and R e It is phenyl.

[0131] According to some embodiments, in the structural unit represented by formula (YI), for example, R 5 is a group selected from the group represented by the formula (G16) to the group represented by the formula (G18b), R 6 is a group selected from the group represented by formula (G12) to the group represented by formula (G14); preferably, R 5 is a group selected from the group represented by formula (G16), the group represented by formula (G18) and the group represented by formula (G18b), R 6 is a group represented by formula (G12) or a group represented by formula (G14); more preferably, R 5 is a group represented by formula (G18), R 6 is a group represented by formula (12). For example, the structural unit represented by formula (YI) comprises R 5 is a group represented by formula (G18) (R e is phenyl, L is a group containing a heteroatom (such as an oxy group), R 6 is a group represented by formula (12) (R e is a phenyl) structural unit.

[0132] (Structural unit represented by formula (YA))

[0133] [Chemical formula 12]

[0134]

[0135] In the formula, R 7 and R 8Each independently represents an organic group (Y).

[0136] According to some embodiments, in the structural unit represented by formula (YA), for example, R 7 is a group selected from the group represented by the formula (G16) to the group represented by the formula (G18), R 8 is a group selected from the group represented by formula (G12) to the group represented by formula (G14); preferably, R 7 is a group represented by formula (G16) or a group represented by formula (G18), R 8 is a group represented by formula (G12) or a group represented by formula (G14); more preferably, R 7 is shown in formula (G16) and R e is phenyl or is represented by formula (18) and R e is phenyl, R 8 is shown in formula (G12) and R e is phenyl or is represented by formula (14) and R e It is phenyl.

[0137] According to some embodiments, in the structural unit represented by formula (YA), for example, R 7 is a group selected from the group represented by the formula (G16) to the group represented by the formula (G18b), R 8 is a group selected from the group represented by formula (G12) to the group represented by formula (G14); preferably, R 7 is a group selected from the group represented by formula (G16), the group represented by formula (G18) and the group represented by formula (G18b), R 6 is a group represented by formula (G12) or a group represented by formula (G14); more preferably, R 7 is a group represented by formula (16) or a group represented by formula (18b), R 8 is a group represented by formula (14). For example, the structural unit represented by formula (YA) comprises R 7 is a group represented by formula (16) (R e is phenyl), R 8 is a group represented by formula (G14) (R e For example, the structural unit represented by formula (YA) comprises R 7 is a group represented by formula (18b) (R e is phenyl, L is each independently a single bond or a heteroatom-containing group (such as an oxy group)), R 8 is a group represented by formula (G14) (R e is a phenyl group, and L is a single bond).

[0138] (Content ratio, etc.)

[0139] The polyimide block (BI) preferably contains a structural unit represented by the formula (XI), and more preferably contains a structural unit represented by the formula (XI) in which the hydrocarbon group (X) includes a saturated alicyclic hydrocarbon group.

[0140] In the polyimide block (BI), R 1 ~R 8 The content of the hydrocarbon group (X) is preferably 0 to 70 mass %, 10 to 60 mass %, or 20 to 50 mass %. In particular, when the content of the hydrocarbon group (X) is 20 mass % or more, a polyimide having a low dielectric constant and a low dielectric loss tangent is easily obtained. 1 ~R 8 The content of the organic group (Y) is preferably 0 to 60% by mass, 2 to 50% by mass, or 4 to 40% by mass, based on the total mass of the organic group (Y). In particular, when the content of the organic group (Y) containing at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group is 4% by mass or more, a polyimide having good mechanical strength and heat resistance is easily obtained. In the present disclosure, according to the structure contained in the block or polymer, “R 1 ~R 8 Total mass" R 1 ~R 8 Any one or more masses of can also be 0.

[0141] The polyamic acid block (BA) preferably contains a structural unit represented by the formula (YA), and more preferably contains a structural unit represented by the formula (YA) in which the organic group (Y) contains an aromatic hydrocarbon group.

[0142] In the polyamic acid block (BA), R 1 ~R 8 The content of the hydrocarbon group (X) is preferably 0 to 80% by mass, 0 to 50% by mass, or 0 to 30% by mass based on the total mass of 1 ~R 8 The content of the organic group (Y) is preferably 20 to 100 mass %, 30 to 80 mass %, or 40 to 60 mass %, based on the total mass of the organic group (Y). In particular, when the content of the organic group (Y) containing at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group is 40 mass % or more, a polyimide having good mechanical strength and heat resistance is easily obtained.

[0143] In block copolymers, R 1 ~R 8The total mass of is taken as the reference, and the content of hydrocarbon group (X) is preferably 5-70 mass %, 10-60 mass %, or 20-50 mass %. From the viewpoint of reducing the dielectric constant and the dielectric loss tangent, it is preferred that the content of hydrocarbon group (X) is large. In particular, when the content of hydrocarbon group (X) is 10 mass % or more, it is easy to obtain a polyimide with a low dielectric constant and a low dielectric loss tangent.

[0144] In block copolymers, R 1 ~R 8 The total mass of is taken as a reference, and the content of the organic group (Y) is preferably 30 to 95 mass %, 40 to 90 mass %, or 50 to 80 mass %. From the viewpoint of obtaining good mechanical strength and heat resistance, it is preferred that the organic group (Y) contains at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group, and it is preferred that the content of such an organic group (Y) is large. In particular, when the content of the organic group (Y) containing at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group is 50 mass % or more, it is easy to obtain a polyimide with good mechanical strength and heat resistance.

[0145] (arbitrary structural unit)

[0146] Block copolymers can further contain other arbitrary structural units in addition to the structural units shown in formula (YI) and the structural units shown in formula (YA). In block copolymers, based on the total mass of all structural units contained in block copolymers, the content of other arbitrary structural units is, for example, 0 to 10% by mass or 0 to 5% by mass. As other arbitrary structural units, for example, structural units containing structures derived from trifunctional or more polyamines or structures derived from trifunctional or more polyisocyanates, structural units with amide bonds (also referred to as amide groups), structural units with imide groups and amide groups, structural units with amic acid groups and amide groups, and other arbitrary structural units. These arbitrary structural units may contain or not contain hydrocarbon groups (X).

[0147] [Block copolymer containing a structure derived from a diamine or a diisocyanate and a structure derived from a tetracarboxylic dianhydride]

[0148] In some embodiments of the present invention, the block copolymer contains a polyimide block (BI) and a polyamic acid block (BA), and has a structure derived from a diamine or a diisocyanate and a structure derived from a tetracarboxylic dianhydride, and at least one of the structure derived from a diamine or a diisocyanate and the structure derived from a tetracarboxylic dianhydride contains a structure having a hydrocarbon group (X). As an example of a structure having a hydrocarbon group (X), a structure derived from a diamine or a diisocyanate having a hydrocarbon group (X) and a structure derived from a tetracarboxylic dianhydride having a hydrocarbon group (X) can be cited. In the present disclosure, "diamine or diisocyanate" refers to "at least one compound selected from diamines and diisocyanates".

[0149] In a preferred embodiment, at least the structure derived from diamine or diisocyanate includes a structure derived from diamine or diisocyanate having a hydrocarbon group (X). The structure derived from tetracarboxylic dianhydride may include a structure derived from tetracarboxylic dianhydride having a hydrocarbon group (X).

[0150] In a preferred embodiment, at least the structure derived from tetracarboxylic dianhydride includes a structure derived from tetracarboxylic dianhydride having an organic group (Y). The structure derived from diamine or diisocyanate may include a structure derived from diamine or diisocyanate having an organic group (Y).

[0151] In the present disclosure, a structural unit including the following structure is sometimes referred to as a "structural unit (Xd)": a structure having a structure derived from a diamine or a diisocyanate and a structure derived from a tetracarboxylic dianhydride, and at least one of the structure derived from a diamine or a diisocyanate and the structure derived from a tetracarboxylic dianhydride has a hydrocarbon group (X).

[0152] (Diamine having a hydrocarbon group (X))

[0153] The diamine having a hydrocarbon group (X) can be represented by, for example, the following formula (Ax).

[0154] [Chemical formula 13]

[0155] H2N-R x -NH2 (Ax)

[0156] In the formula, R x represents a hydrocarbon group (X). x Examples of the group include the group represented by the above formula (G2) to the group represented by the formula (G9).

[0157] Specific examples of the diamine having a hydrocarbon group (X) are listed below.

[0158] Diamines having a saturated aliphatic hydrocarbon group and having 9 or more carbon atoms, such as 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,14-diaminotetradecane, and 1,16-diaminohexadecane;

[0159] Diamines having an unsaturated aliphatic hydrocarbon group and having 9 or more carbon atoms, such as 1,9-diaminononene, 1,10-diaminodecene, 1,11-diaminoundecene, 1,12-diaminododecene, 1,14-diaminotetradecene, and 1,16-diaminohexadecene;

[0160] Diamines having a saturated alicyclic hydrocarbon group and having 9 or more carbon atoms, such as isophoronediamine, bis(aminomethyl)norbornane, 1,3-diaminoadamantane, and 4,4'-diaminodicyclohexylmethane;

[0161] Diamines having an unsaturated alicyclic hydrocarbon group and having 9 or more carbon atoms, such as bis(aminomethyl)norbornene and 4,4'-diaminodicyclohexenylmethane;

[0162] Diamines derived from monounsaturated fatty acids such as crotonic acid, myristic 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; dimers (also called dimer acids) of unsaturated fatty acids such as triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, and eicosatrienoic acid; and dimer diamines having 9 or more carbon atoms, such as diamines in which the carbon-carbon double bonds contained in the molecules of these diamines are hydrogenated

[0163] Examples of commercially available products of the dimerized diamine having 9 or more carbon atoms include "PRIAMINE 1075" and "PRIAMINE 1074" manufactured by Croda Japan KK.

[0164] (Diamine having an organic group (Y))

[0165] The diamine having an organic group (Y) can be represented by, for example, the following formula (Ay).

[0166] [Chemical formula 14]

[0167] H2N-Ry -NH2 (Ay)

[0168] In the formula, R y represents an organic group (Y). y Examples of include the group represented by the above formula (G16) to the group represented by the formula (G18b).

[0169] Specific examples of the diamine having an organic group (Y) are listed below.

[0170] Diamines having a saturated aliphatic hydrocarbon group and having a carbon number of 8 or less, such as 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane;

[0171] Diamines having 8 or less carbon atoms and having a saturated aliphatic hydrocarbon group, such as 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, and 1,4-bis(aminomethyl)cyclohexane;

[0172] Diamines having an aromatic hydrocarbon group and a non-aromatic hydrocarbon group with a carbon number of 8 or less, such as 1,4-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diamino-3,3'-dimethyldiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, and 4,4'-bis(4-aminophenoxy)biphenyl

[0173] (Diisocyanate having a hydrocarbon group (X))

[0174] The diisocyanate having a hydrocarbon group (X) can be represented by, for example, the following formula (Ix).

[0175] [Chemical formula 15]

[0176] OCN-R x -NCO (Ix)

[0177] In the formula, R x represents a hydrocarbon group (X). x Examples of the group include the group represented by the above formula (G2) to the group represented by the formula (G9).

[0178] Specific examples of the diisocyanate having a hydrocarbon group (X) include compounds having the same structure as the compounds listed above as specific examples of the diamine except that the amino group is replaced by an isocyanate group.

[0179] (Diisocyanate having an organic group (Y))

[0180] The diisocyanate having an organic group (Y) can be represented by, for example, the following formula (Iy).

[0181] [Chemical formula 16]

[0182] OCN-R y -NCO (Iy)

[0183] In the formula, R y represents an organic group (Y). y Examples of the group include the group represented by the above-mentioned formula (G16) to the group represented by the formula (G18b).

[0184] Specific examples of the diisocyanate having an organic group (Y) include compounds having the same structure as the compounds described above as specific examples of the diamine, except that the amino group is replaced by an isocyanate group.

[0185] (Tetracarboxylic dianhydride having a hydrocarbon group (X))

[0186] The tetracarboxylic dianhydride having a hydrocarbon group (X) can be represented by, for example, the following formula (Cx).

[0187] [Chemical formula 17]

[0188]

[0189] In the formula, R x represents a hydrocarbon group (X). Preferred examples of the hydrocarbon group (X) are as described above.

[0190] Specific examples of tetracarboxylic dianhydride having a hydrocarbon group (X) are listed below. The "carbon number" below refers to the carbon number of the hydrocarbon group (X), and the number of carbon atoms contained in the carboxylic anhydride group is not included in the "carbon number" below.

[0191] Tetracarboxylic dianhydrides having 9 or more carbon atoms and having an alicyclic hydrocarbon group, such as 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride and 2,2-bis(3,4-dicarboxycyclohexyl)propane dianhydride

[0192] (Tetracarboxylic dianhydride having an organic group (Y))

[0193] The tetracarboxylic dianhydride having an organic group (Y) can be represented by, for example, the following formula (Cy).

[0194] [Chemical formula 18]

[0195]

[0196] In the formula, R y represents an organic group (Y). yExamples of the group include the group represented by the above formula (G12) to the group represented by the formula (G14).

[0197] Specific examples of tetracarboxylic dianhydrides having an organic group (Y) are listed below. The "carbon number" below refers to the carbon number of the non-aromatic hydrocarbon group contained in the organic group (Y), and the "carbon number" below does not include the number of carbons contained in the aromatic ring and the carboxylic anhydride group.

[0198] Tetracarboxylic dianhydrides having a carbon number of 8 or less and having a saturated aliphatic hydrocarbon group, such as 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,5,6-hexanetetracarboxylic dianhydride;

[0199] Tetracarboxylic dianhydrides having 8 or less carbon atoms and having a saturated alicyclic hydrocarbon group, such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride;

[0200] Tetracarboxylic dianhydrides having an aromatic hydrocarbon group and having a carbon number of 8 or less, such as pyromellitic dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, and 3,4'-oxydiphthalic anhydride;

[0201] Tetracarboxylic dianhydrides having an aromatic heterocyclic compound group and having a carbon number of 8 or less, such as pyridinetetracarboxylic dianhydride and thiophenetetracarboxylic dianhydride

[0202] The structure derived from a diamine or a diisocyanate preferably contains a structure derived from a diamine or a diisocyanate having a hydrocarbon group (X); more preferably contains at least one structure selected from the following structures: a structure derived from a diamine having 9 or more carbon atoms and having a saturated aliphatic hydrocarbon group, a structure derived from a diamine having 9 or more carbon atoms and having an unsaturated aliphatic hydrocarbon group, a structure derived from a diamine having 9 or more carbon atoms and having a saturated alicyclic hydrocarbon group, a structure derived from a diamine having 9 or more carbon atoms and having an unsaturated alicyclic hydrocarbon group, and a structure derived from a diamine having 9 or more carbon atoms; and further preferably contains a structure derived from a diamine having 9 or more carbon atoms and having a diamine having 9 or more carbon atoms.

[0203] The structure derived from a diamine or a diisocyanate preferably contains a structure derived from a diamine or a diisocyanate having a hydrocarbon group (X), and more preferably contains a structure derived from a diamine or a diisocyanate having a hydrocarbon group (X) and a structure derived from a diamine or a diisocyanate having an aromatic hydrocarbon group.

[0204] In the block copolymer, for example, the structure derived from diamine or diisocyanate contained in the polyamic acid block (BA) includes a structure derived from diamine or diisocyanate having an aromatic hydrocarbon group.

[0205] The structure derived from tetracarboxylic dianhydride preferably contains a structure derived from tetracarboxylic dianhydride having an organic group (Y), more preferably contains a structure derived from tetracarboxylic dianhydride having an aromatic hydrocarbon group, and further preferably contains at least one selected from a structure derived from pyromellitic dianhydride and a structure derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0206] (Content ratio, etc.)

[0207] In the polyimide block (BI), the content of the structure having the hydrocarbon group (X) is, for example, 0 to 95% by mass, preferably 40 to 95% by mass, 50 to 95% by mass, or 70 to 90% by mass, based on the total mass of the structure derived from diamine or diisocyanate and the structure derived from tetracarboxylic dianhydride. In particular, when the content of the structure having the hydrocarbon group (X) is 70% by mass or more, a polyimide having a low dielectric constant and a low dielectric loss tangent is easily obtained. In the polyimide block (BI), the content of the structure having the organic group (Y) is, for example, 5 to 100% by mass, preferably 5 to 60% by mass, 5 to 50% by mass, or 10 to 30% by mass, based on the total mass of the structure derived from diamine or diisocyanate and the structure derived from tetracarboxylic dianhydride. In particular, when the content of the structure having the organic group (Y) containing at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group is 10 mass % or more, a polyimide having good mechanical strength and heat resistance is easily obtained.

[0208] In the polyamic acid block (BA), the content of the structure having a hydrocarbon group (X) is preferably 0 to 60 mass%, 10 to 50 mass%, or 20 to 40 mass%, based on the total mass of the structure derived from diamine or diisocyanate and the structure derived from tetracarboxylic dianhydride. In particular, when the content of the structure having a hydrocarbon group (X) is 10 mass% or more, it is easy to obtain a polyimide with a low dielectric constant and a low dielectric loss tangent. In the polyamic acid block (BA), the content of the structure having an organic group (Y) is preferably 30 to 100 mass%, 50 to 95 mass%, or 70 to 90 mass%, based on the total mass of the structure derived from diamine or diisocyanate and the structure derived from tetracarboxylic dianhydride. In particular, when the content of the structure having an organic group (Y) containing at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group is 70 mass% or more, it is easy to obtain a polyimide with good mechanical strength and heat resistance.

[0209] In the block copolymer, the total mass of the structure derived from diamine or diisocyanate and the structure derived from tetracarboxylic dianhydride is used as a reference, and the content of the structure having a hydrocarbon group (X) is preferably 3 to 60 mass%, 5 to 50 mass%, or 10 to 40 mass%. From the viewpoint of reducing the dielectric constant and the dielectric loss tangent, it is preferred that the content of the structure having a hydrocarbon group (X) is large. In particular, when the content of the structure having a hydrocarbon group (X) is 5 mass% or more, it is easy to obtain a polyimide with a low dielectric constant and a low dielectric loss tangent.

[0210] In the block copolymer, the total mass of the structure derived from diamine or diisocyanate and the structure derived from tetracarboxylic dianhydride is used as a benchmark, and the content of the structure with the organic group (Y) is preferably 40 to 97 mass%, 50 to 95 mass%, or 60 to 90 mass%. From the viewpoint of obtaining good mechanical strength and heat resistance, the organic group (Y) preferably contains at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group, and the content of the structure with such an organic group (Y) is large and is preferred. In particular, when the content of the structure with the organic group (Y) containing at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group is 50 mass% or more, it is easy to obtain a polyimide with good mechanical strength and heat resistance.

[0211] (arbitrary structure)

[0212] In addition to containing a structure derived from diamine or diisocyanate and a structure derived from tetracarboxylic dianhydride, the block copolymer may further contain other arbitrary structures. In the block copolymer, the total mass of all structures contained in the block copolymer is used as a benchmark, and the content of other arbitrary structural units is, for example, 0 to 10% by mass or 0 to 5% by mass. As other arbitrary structures, it is possible to contain arbitrary structures such as a structure derived from a polyamine or polyisocyanate having more than three functions, a structure derived from a dicarboxylic acid compound, and a structure derived from a tricarboxylic acid compound. These arbitrary structures may contain or not contain a hydrocarbon group (X).

[0213] [Block copolymer obtained using diamine or diisocyanate and tetracarboxylic dianhydride]

[0214] In some embodiments of the present invention, the block copolymer is a block copolymer obtained using polyimide (PI) and polyamic acid (PA), wherein the polyimide (PI) is obtained using diamine or diisocyanate and tetracarboxylic dianhydride, and the polyamic acid (PA) is obtained using diamine and tetracarboxylic dianhydride, and at least one selected from the diamine or diisocyanate and tetracarboxylic dianhydride used to obtain the polyimide (PI), and the diamine and tetracarboxylic dianhydride used to obtain the polyamic acid (PA) has a hydrocarbon group (X). The method for obtaining polyimide (PI), polyamic acid (PA) and block copolymer will be described later.

[0215] [Polyimide block (BI)]

[0216] The block copolymer having the polyimide block (BI) can prevent an exchange reaction or crosslinking from occurring when the block copolymer is obtained or when the amic acid group is ring-closed.

[0217] In the present disclosure, the content of the imide group in the polyimide block (BI) relative to the total of the imide group and the amic acid group is, for example, more than 50 mol%, 80 mol% or more, or 90 mol% or more. The upper limit of the content of the imide group can be 100 mol%. In the present disclosure, the content can be measured by Fourier Transform Infrared Spectroscopy (FITR).

[0218] The polyimide block (BI) may contain the structural unit (X) or may not contain the structural unit (X). In the case where the polyimide block (BI) does not contain the structural unit (X) in the block copolymer, the polyimide block (BI) contains the structural unit (Y). In the case where the polyimide block (BI) does not contain the structural unit (X) in the block copolymer, the polyamic acid block (BA) contains the structural unit (X).

[0219] The number average molecular weight of the polyimide block (BI) is, for example, 500 or more, 1000 or more, 2000 or more, or 3000 or more. The number average molecular weight of the polyimide block (BI) is, for example, 10000 or less, 8000 or less, 7000 or less, or 5000 or less. When the number average molecular weight is 500 or more, it tends to be easy to obtain a polyimide with a low coefficient of expansion. When the number average molecular weight is 10000 or less, it tends to be easy to ensure the solubility of the block copolymer in a solvent. The number average molecular weight of the polyimide block (BI) is, for example, 500 to 10000, 1000 to 8000, 2000 to 7000, or 3000 to 5000. In the present disclosure, the number average molecular weight can be measured by gel permeation chromatography (GPC) using a standard curve of standard polystyrene. Specifically, it can be obtained by the method described in the examples.

[0220] The polyimide block (BI) may be a linear block or a branched block, and is preferably a linear block.

[0221] [Polyamic acid block (BA)]

[0222] The block copolymer tends to easily obtain good solubility in a solvent by containing a polyamic acid block.

[0223] In the present disclosure, the content of the amic acid group in the polyamic acid block (BA) relative to the total of the imide group and the amic acid group is, for example, more than 50 mol%, 80 mol% or more, or 90 mol% or more. The upper limit of the content of the amic acid group may be 100 mol%. The content can be measured by FTIR.

[0224] The polyamic acid block (BA) may contain the structural unit (X) or may not contain the structural unit (X). In the block copolymer, when the polyamic acid block (BA) does not contain the structural unit (X), the polyamic acid block (BA) contains the structural unit (Y). In the block copolymer, when the polyamic acid block (BA) does not contain the structural unit (X), the polyimide block (BI) contains the structural unit (X).

[0225] The number average molecular weight of the polyamic acid block (BA) is, for example, 500 or more, 1000 or more, 3000 or more, or 6000 or more. The number average molecular weight of the polyamic acid block (BA) is, for example, 30,000 or less, 25,000 or less, 20,000 or less, or 10,000 or less. A number average molecular weight of 500 or more tends to easily obtain good film-forming properties. A number average molecular weight of 30,000 or less tends to easily adjust the composition containing the block copolymer and the solvent to a viscosity suitable for coating. The number average molecular weight of the polyamic acid block (BA) is, for example, 500 to 30,000, 1,000 to 25,000, 3,000 to 20,000, or 6,000 to 10,000.

[0226] The polyamic acid block (BA) may be a linear block or a branched block, and is preferably a linear block.

[0227] [Molecular weight of block copolymer, content of structural unit (X), etc.]

[0228] The block copolymer contains a polyimide block (BI) and a polyamic acid block (BA), and tends to easily obtain a polyimide having a low coefficient of thermal expansion. This is presumably because the polyimide molecules are easily oriented due to the block structure.

[0229] In the block copolymer, only one of the polyimide block (BI) and the polyamic acid block (BA) contains a hydrocarbon group (X), or both the polyimide block (BI) and the polyamic acid block (BA) contain a hydrocarbon group (X). The polyimide block (BI) and the polyamic acid block (BA) may each independently contain one or more hydrocarbon groups (X).

[0230] The number average molecular weight of the block copolymer is, for example, more than 5000, more than 10000, more than 20000, or more than 30000. The number average molecular weight of the block copolymer is, for example, less than 100000, less than 80000, less than 70000, or less than 60000. A number average molecular weight of more than 5000 has a tendency to easily obtain good film-forming properties. A number average molecular weight of less than 100000 has a tendency to easily adjust the composition containing the block copolymer and the solvent to a viscosity suitable for coating. The number average molecular weight of the block copolymer is, for example, 5000 to 100000, 10000 to 80000, 20000 to 70000, or 30000 to 60000.

[0231] Based on the mass of the block copolymer, the content of the polyimide block (BI) in the block copolymer is more than 0 mass % and less than 100 mass %. The content of the polyimide block (BI) is, for example, more than 0 mass %, more than 30 mass %, more than 60 mass %, or more than 90 mass %. The content of the polyimide block (BI) is, for example, less than 100 mass %, less than 70 mass %, less than 40 mass %, or less than 10 mass %. The content of the polyimide block (BI) is, for example, more than 0 mass % and less than 70 mass %, more than 0 mass % and less than 40 mass %, more than 30 mass % and less than 100 mass %, or more than 60 mass % and less than 100 mass %. The content of the polyimide block (BI) can also be, for example, 10 to 60 mass % or 20 to 50 mass %.

[0232] Based on the mass of the block copolymer, the content of the polyamic acid block (BA) in the block copolymer is more than 0 mass % and less than 100 mass %. The content of the polyamic acid block (BA) is, for example, more than 0 mass %, more than 30 mass %, more than 60 mass %, or more than 90 mass %. The content of the polyamic acid block (BA) is, for example, less than 100 mass %, less than 70 mass %, less than 40 mass %, or less than 10 mass %. The content of the polyamic acid block (BA) is, for example, more than 0 mass % and less than 70 mass %, more than 0 mass % and less than 40 mass %, more than 30 mass % and less than 100 mass %, or more than 60 mass % and less than 100 mass %. The content of the polyimide block (BI) can also be, for example, 40 to 90 mass % or 50 to 80 mass %.

[0233] The higher the content of the polyimide block (BI), the more it is possible to prevent exchange reactions or crosslinking when obtaining the block copolymer or when the amic acid group is ring-closed. On the other hand, the higher the content of the polyamic acid block (BA), the easier it is for the block copolymer to dissolve in an organic solvent.

[0234] In block copolymer, for example, the number average molecular weight of polyimide block (BI) is smaller than the number average molecular weight of polyamic acid block (BA). Preferably, block copolymer contains polyimide block (BI) and polyamic acid block (BA) having a number average molecular weight greater than polyimide block (BI). In the case where the number average molecular weight of polyimide block (BI) is less than the number average molecular weight of polyamic acid block (BA), there is a tendency to easily synthesize block copolymer and to ensure the solubility of block copolymer. By containing polyamic acid block (BA) having a number average molecular weight greater than polyimide block (BI), there is a tendency to easily synthesize block copolymers with sufficient number average molecular weight.

[0235] The polyimide obtained by using the block copolymer satisfies any one or more of the relative dielectric constant, dielectric loss tangent, thermal expansion coefficient and water absorption rate described later. In particular, the polyimide obtained by using the block copolymer satisfies any one or more of the relative dielectric constant, dielectric loss tangent and thermal expansion coefficient described later.

[0236] [use]

[0237] In some embodiments of the present invention, a block copolymer can be used to obtain a polyimide with a low dielectric constant, a low dielectric loss tangent and a low thermal expansion coefficient. The obtained polyimide can be used for various electronic components and mechanical parts, and can be used for, for example, displays, solar cells, touch panels, organic EL lighting, millimeter wave radars, high-frequency antennas, substrates for high-speed transmission, etc. Among them, instruments that can be preferably used in high-frequency fields can be listed, such as millimeter wave radars, high-frequency antennas, substrates for high-speed transmission, etc. Millimeter wave radars are radars that send millimeter waves to a target and receive reflected waves from a target to detect the target. The vehicle-mounted millimeter wave radars carried in vehicles, etc. can be applied to anti-collision systems, automatic driving systems, etc. For high-frequency antennas, high frequency and high-speed transmission are required in communication instruments, etc., and when the high-frequency antenna is stored in a housing in a small communication instrument, etc., it is desired to have a lower dielectric constant and a lower dielectric loss tangent material. As a substrate for high-speed transmission, high-speed transmission cables and high-speed transmission connectors, etc. can be listed.

[0238] <Method for producing block copolymer>

[0239] In some embodiments of the present invention, the method for producing a block copolymer comprises the following steps: obtaining a polyimide (PI) using a diamine or a diisocyanate and a tetracarboxylic dianhydride; obtaining a polyamic acid (PA) using a diamine and a tetracarboxylic dianhydride; and obtaining a block copolymer using the polyimide (PI) and the polyamic acid (PA), wherein at least one selected from the diamine or a diisocyanate and a tetracarboxylic dianhydride used to obtain the polyimide (PI), and the diamine and the tetracarboxylic dianhydride used to obtain the polyamic acid (PA) has a hydrocarbon group (X). According to this production method, the block copolymer of the above embodiment can be easily produced.

[0240] In the synthesis of polyimide (PI) and polyamic acid (PA), monomers such as the above-mentioned diamine, diisocyanate, tetracarboxylic dianhydride, polyamine, polyisocyanate, dicarboxylic acid compound, and tricarboxylic acid compound can be used.

[0241] The reaction of the monomers can be carried out by solution polymerization. As the solvent for the reaction, for example, polar solvents such as N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), 3-methoxy-N,N-dimethylpropionamide (MPA), N,N'-dimethylformamide, N,N'-dimethylpropyleneurea [1,3-dimethyl-3,4,5,6-tetrahydropyrimidin-2(1H)-one], dimethyl sulfoxide, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and cyclopentane; aromatic hydrocarbon solvents such as xylene and toluene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, etc. can be used. The solvent preferably contains at least one selected from N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and 3-methoxy-N,N-dimethylpropionamide (MPA), and more preferably contains at least one selected from N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), and 3-methoxy-N,N-dimethylpropionamide (MPA).

[0242] Relative to the total amount of 100 parts by mass of monomers, the amount of solvent used is preferably 100 to 600 parts by mass, more preferably 200 to 400 parts by mass. By making the amount of solvent used 100 parts by mass or more, each monomer can be reacted homogeneously. By making the amount of solvent used 600 parts by mass or less, the polymerization reaction can be promoted. In addition, by making the amount of solvent used less, a polyimide (PI) or polyamic acid (PA) solution containing polyimide (PI) or polyamic acid (PA) at a high concentration can be obtained.

[0243] The reaction temperature when using the monomer to synthesize polyamic acid is not particularly limited. The reaction temperature can be, for example, 10 to 50° C., or 20 to 40° C. The reaction time is, for example, 30 minutes to 24 hours, 1 to 12 hours, or 3 to 6 hours. The reaction product can be sampled to measure the number average molecular weight, the concentration of the residual amino group or isocyanate group, etc., and the reaction time can be adjusted in a manner to obtain the desired reaction product.

[0244] The temperature for obtaining polyimide using polyamic acid (i.e., imidization) is not particularly limited. The imidization temperature may be, for example, 120 to 200° C., or 160 to 180° C. The reaction time may be, for example, 30 minutes to 24 hours, 1 to 12 hours, or 3 to 6 hours. The reaction product may be sampled to measure the number average molecular weight, the concentration of the residual amic acid group, etc., and the reaction time may be adjusted in a manner to obtain the desired reaction product.

[0245] From the aspect of easy synthesis, it is preferred that the end of the polymer chain of polyimide (PI) is a carboxylic acid anhydride group and the end of the polymer chain of polyamic acid (PA) is an amino group. The ratio of diamine or diisocyanate used to obtain polyimide (PI) and tetracarboxylic dianhydride is, based on diamine or diisocyanate, tetracarboxylic dianhydride is, for example, more than 1.00 mol%, 1.05 mol% or more, or 1.10 mol% or more. The ratio of diamine and tetracarboxylic dianhydride used to obtain polyamic acid (PA) is, based on diamine, tetracarboxylic dianhydride is, for example, less than 1.00 mol%, less than 0.98 mol%, or less than 0.97 mol%.

[0246] The block copolymer is synthesized using polyimide (PI) and polyamic acid (PA). Any polymer may be further used in the synthesis.

[0247] The reaction of polyimide (PI) and polyamic acid (PA) can be carried out by solution polymerization. As a solvent during the reaction, the above-mentioned solvents can be used.

[0248] The reaction temperature is not particularly limited. From the viewpoint of allowing the reaction to proceed sufficiently, the reaction temperature may be, for example, 20 to 100° C., 30 to 80° C., or 40 to 70° C. The reaction time may be, for example, 30 minutes to 24 hours, 1 to 12 hours, or 3 to 6 hours. The reaction product may be sampled to measure the number average molecular weight, the concentration of the residual amino group or isocyanate group, etc., and the reaction time may be adjusted in a manner to obtain the desired reaction product.

[0249] <Insulating materials, heat-resistant insulating materials>

[0250] In some embodiments of the present invention, the insulating material and the heat-resistant insulating material contain the block copolymer of any of the above embodiments. Since the polyimide obtained using the block copolymer has excellent insulation and heat-resistant insulation, the block copolymer can be preferably used as the insulating material or the heat-resistant insulating material.

[0251] <Composition>

[0252] In some embodiments of the present invention, the composition contains the block copolymer of any of the above embodiments and a solvent. As the solvent contained in the composition, the solvent during the above reaction that can be used in the synthesis of the block copolymer can be listed. It is preferred that the solvent contains at least one selected from N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and 3-methoxy-N, N-dimethylpropionamide (MPA), and it is more preferred that it contains at least one selected from N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and 3-methoxy-N, N-dimethylpropionamide (MPA). The composition can be preferably used as an insulator composition, a heat-resistant insulator composition, or a printed circuit board composition.

[0253] The composition may further contain any component such as polyamide, polyethersulfone, acrylic polymer, epoxy compound, isocyanate compound, melamine compound, filler, defoamer, preservative, surfactant, etc. The composition can be produced by, for example, mixing and stirring the block copolymer and the solvent and any component used as needed.

[0254] The content of the block copolymer can be set to a range suitable for the use of the composition. The content of the block copolymer is, for example, 5 to 50% by mass, 8 to 40% by mass, or 10 to 30% by mass based on the mass of the composition.

[0255] The viscosity of the composition is preferably 2 to 30 Pa·s, more preferably 5 to 20 Pa·s, and even more preferably 10 to 15 Pa·s at 30° C. In the present disclosure, the viscosity can be measured using a rotary B-type viscometer at 30° C. using a No. 3 rotor.

[0256] <Polyimide>

[0257] In some embodiments of the present invention, polyimide can be obtained using the block copolymer of any of the above embodiments or the composition of any of the above embodiments. For example, since the block copolymer contains a polyamic acid block (BA), a polyimide can be obtained by converting the amic acid group into an imide group (this conversion is sometimes referred to as "imidization" in this disclosure). The method of imidization is not particularly limited. The method of heating the block copolymer is preferably used because it is simple. The heating temperature is, for example, 250 to 400°C.

[0258] The polyimide obtained by the block copolymer contains a polyimide block (BI) and a polyamic acid block (BA) that is imidized, i.e., a polyimide block (BI-A). The polyimide block (BI) and the polyimide block (BI-A) are different blocks. The polyimide has a block structure and shows a low thermal expansion coefficient. The polyimide has a low dielectric constant and a low dielectric loss tangent by having a hydrocarbon group (X). Furthermore, the polyimide has a tendency to show a low water absorption rate by having a hydrocarbon group (X).

[0259] From the viewpoint of obtaining excellent insulation, for example, the relative dielectric constant of polyimide is less than 3.5, less than 3.0, or less than 2.5. The relative dielectric constant of polyimide is not particularly limited, for example, it is greater than 2.0. The relative dielectric constant (Dk) can be measured using a polyimide film (for example, a thickness of 25 μm) by a resonant cavity method (TE mode) at a frequency of 10 GHz and a measurement temperature of 25°C. The relative dielectric constant (Dk) can be a value obtained by measuring the polyimide film after it is fully dried and left to stand for 24 hours in an atmosphere at a temperature of 23°C and a relative humidity of 50%.

[0260] From the viewpoint of suppressing transmission loss, for example, the dielectric loss tangent of polyimide is less than 0.0100, less than 0.0050, or less than 0.0020. The dielectric loss tangent of polyimide is not particularly limited, for example, it is greater than 0.0005. The dielectric loss tangent (Df) can be measured using a polyimide film (for example, a thickness of 25 μm) by a resonant cavity method (TE mode) at a frequency of 10 GHz and a measurement temperature of 25°C. The dielectric loss tangent (Df) can be a value obtained by measuring the polyimide film after it is fully dried and left to stand for 24 hours in an atmosphere at a temperature of 23°C and a relative humidity of 50%.

[0261] From the viewpoint of obtaining excellent heat resistance, for example, the coefficient of thermal expansion (CTE) of polyimide is 80 ppm / K or less, 50 ppm / K or less, or 20 ppm / K or less. Considering the situation that the polyimide film is attached to other materials, for example, the coefficient of thermal expansion of the polyimide is -5 ppm / K or more, 0 ppm / K or more, 10 ppm / K or more, or 15 ppm / K or more. The coefficient of thermal expansion (ppm / K) can be obtained by converting the average linear thermal expansion coefficient (ppm / °C) of 30 to 200°C measured at a heating rate of 10°C / min using a polyimide film (for example, 25 μm thick) in a thermomechanical analysis device. The coefficient of thermal expansion can be, for example, 70 ppm / K or less, 60 ppm / K or less, 40 ppm / K or less, or 30 ppm / K or less.

[0262] For example, from the viewpoint of heat resistance of the molded body, the glass transition temperature (Tg) of the polyimide is 200°C or more, 250°C or more, or 300°C or more. The glass transition temperature (Tg) of the polyimide is not particularly limited, and is, for example, 600°C or less. The glass transition temperature can be obtained as follows: a linear thermal expansion coefficient curve of 30 to 200°C is measured using a polyimide film (for example, 25 μm thick) in a thermomechanical analysis device at a heating rate of 10°C / min, and the temperature (°C) corresponding to the inflection point in the curve is obtained as the glass transition temperature.

[0263] For example, from the viewpoint of preventing the dielectric properties from changing due to moisture absorption, the water absorption of polyimide is 1.0% or less, 0.5% or less, or 0.3% or less. The water absorption of polyimide is not particularly limited, for example, it is 0.0% or more. The water absorption (%) can be calculated based on the weight of a polyimide film (e.g., 25 μm thick, 70 mm wide, 70 mm long) before and after being immersed in 23° C. water for 24 hours after drying, using the following calculation formula.

[0264] Water absorption rate (%) = (weight of polyimide film after water absorption - weight of polyimide film before water absorption) / weight of polyimide film before water absorption × 100

[0265] More specifically, a polyimide film was prepared according to the method described in the examples, and the relative dielectric constant, dielectric loss tangent, thermal expansion coefficient, glass transition temperature and water absorption of the polyimide were measured using the prepared polyimide film according to the method described in the examples.

[0266] <Moldings, insulators, heat-resistant insulators>

[0267] In some embodiments of the present invention, the molded body, insulator, and heat-resistant insulator are obtained using the block copolymer, material or composition of any of the above embodiments, or contain the polyimide of the above embodiments. The relative dielectric constant of the insulator is preferably 3.5 or less, and the dielectric loss tangent is preferably 0.0100 or less. The relative dielectric constant of the heat-resistant insulator is preferably 3.5 or less, the dielectric loss tangent is preferably 0.0100 or less, and the thermal expansion coefficient is preferably 80 ppm / K or less.

[0268] The shape of the molded body, insulator, and heat-resistant insulator is not particularly limited, and is preferably a shape suitable for the application. For example, it can be in the shape of a film, a plate, a thin film, a layer, etc. The molded body, insulator, and heat-resistant insulator can be used in various electronic components and mechanical components.

[0269] <Printed circuit board>

[0270] In some embodiments of the present invention, the printed circuit board is obtained using the block copolymer, material, or composition of any of the above embodiments, or contains the polyimide, molded article, insulator, or heat-resistant insulator of the above embodiments. The printed circuit board of the embodiments of the present invention has low transmission loss and excellent heat resistance.

[0271] Examples of printed substrates include printed wiring boards and printed circuit boards. Examples of printed substrates include flexible substrates and rigid substrates. Examples of printed substrates include single-sided substrates, double-sided substrates, and multilayer substrates. For example, the materials, protective films, insulating layers, etc. of these substrates are obtained using block copolymers, or contain polyimide, etc.

[0272] Examples of flexible substrates include substrates having a base film, wherein the base film is obtained using a block copolymer or contains polyimide, etc. Other examples of flexible substrates include substrates having 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 a block copolymer or contains polyimide, etc.

[0273] <Example of embodiment>

[0274] Examples of embodiments of the present invention are listed below, but the present invention is not limited to the following embodiments.

[0275] [1] A block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and comprising a structural unit (X) having a group (X), wherein the group (X) contains at least one non-aromatic hydrocarbon group and the total carbon number of the at least one non-aromatic hydrocarbon group is 9 or more.

[0276] [2] A block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and comprising at least one of a structural unit represented by the following formula (XI) and a structural unit represented by the following formula (XA).

[0277] Or a block copolymer that satisfies the above [1] and [2].

[0278] [Chemical formula 19]

[0279]

[0280] (Where R 1 and R 2 Each independently represents an organic group, R 1 and R 2 At least one of the groups is a group (X) containing at least one non-aromatic hydrocarbon group and the total carbon number of the at least one non-aromatic hydrocarbon group is 9 or more.

[0281] [Chemical formula 20]

[0282]

[0283] (Where R 3 and R 4 Each independently represents an organic group, R 3 and R 4 At least one of the groups is a group (X) containing at least one non-aromatic hydrocarbon group and the total carbon number of the at least one non-aromatic hydrocarbon group is 9 or more.

[0284] [3] The block copolymer according to [2], further comprising at least one of a structural unit represented by the following formula (YI) and a structural unit represented by the following formula (YA).

[0285] [Chemical formula 21]

[0286]

[0287] (Where R 5 and R 6 Each independently represents an organic group (Y), and the organic group (Y) is an organic group that does not belong to the above group (X).

[0288] [Chemical formula 22]

[0289]

[0290] (Where R 7 and R 8 Each independently represents an organic group (Y), and the organic group (Y) is an organic group that does not belong to the above group (X).

[0291] [4] The block copolymer according to [3] above, wherein R 1 ~R 8 The content of the group (X) is 5 to 70% by mass based on the total mass of .

[0292] [5] The block copolymer according to [3] or [4], wherein in the formula (YI) and the formula (YA), the organic group (Y) contains an aromatic hydrocarbon group.

[0293] [6] The block copolymer according to any one of [3] to [5], wherein the polyamic acid block (BA) contains a structural unit represented by the formula (YA).

[0294] [7] A block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and having a structure derived from a diamine or a diisocyanate and a structure derived from a tetracarboxylic dianhydride,

[0295] At least one of the structure derived from diamine or diisocyanate and the structure derived from tetracarboxylic dianhydride contains a structure having a group (X) containing at least one non-aromatic hydrocarbon group having a total carbon number of 9 or more.

[0296] Or a block copolymer satisfying the above [1] and [7], the above [2] and [7], or the above [1], [2] and [7].

[0297] [8] The block copolymer according to [7], wherein the content of the structure having the group (X) is 3 to 60% by mass based on the total mass of the structure derived from the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride.

[0298] [9] The block copolymer according to [7] or [8] above, wherein the structure derived from a diamine or diisocyanate includes a structure derived from a diamine or diisocyanate having the group (X) and a structure derived from a diamine or diisocyanate having an aromatic hydrocarbon group.

[0299]

[10] The block copolymer according to [9] above, wherein the structure derived from a diamine or a diisocyanate contained in the polyamic acid block (BA) includes a structure derived from a diamine or a diisocyanate having an aromatic hydrocarbon group.

[0300]

[11] The block copolymer according to any one of [1] to

[10] above, wherein the at least one non-aromatic hydrocarbon group is a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group, an unsaturated alicyclic hydrocarbon group, or a group consisting of two or more selected from these.

[0301]

[12] The block copolymer according to any one of [1] to

[11] , wherein the group (X) is a saturated aliphatic hydrocarbon group having 9 or more carbon atoms, an unsaturated aliphatic hydrocarbon group having 9 or more carbon atoms, a saturated alicyclic hydrocarbon group having 9 or more carbon atoms, an unsaturated alicyclic hydrocarbon group having 9 or more carbon atoms, or a group having 9 or more carbon atoms formed from two or more selected from a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group, and an unsaturated alicyclic hydrocarbon group.

[0302]

[13] The block copolymer according to any one of [1] to

[12] above, wherein the group (X) contains a saturated alicyclic hydrocarbon group.

[0303]

[14] The block copolymer according to any one of [1] to

[13] above, wherein the group (X) contains a linear saturated aliphatic hydrocarbon group having 6 or more carbon atoms.

[0304]

[15] The block copolymer according to any one of [1] to

[14] above, wherein the carbon number is 12 or more.

[0305]

[16] The block copolymer according to any one of [1] to

[15] above, wherein the carbon number is 28 or more.

[0306]

[17] The block copolymer according to any one of [1] to

[16] above, wherein only one of the polyimide block (BI) and the polyamic acid block (BA) contains the group (X).

[0307]

[18] The block copolymer according to any one of [1] to

[16] above, wherein both the polyimide block (BI) and the polyamic acid block (BA) contain the group (X).

[0308]

[19] The block copolymer according to any one of [1] to

[18] above, wherein the number average molecular weight of the polyimide block (BI) is 500 to 10,000.

[0309]

[20] The block copolymer according to any one of [1] to

[19] above, wherein the number average molecular weight of the polyamic acid block (BA) is 500 to 30,000.

[0310]

[21] A method for producing a block copolymer, comprising the following steps:

[0311] Polyimide (PI) is obtained using diamine or diisocyanate and tetracarboxylic dianhydride;

[0312] Using diamine and tetracarboxylic dianhydride to obtain polyamic acid (PA); and

[0313] A block copolymer is obtained by using the above polyimide (PI) and the above polyamic acid (PA),

[0314] Among them, at least one selected from the diamine or diisocyanate and tetracarboxylic dianhydride used to obtain the above-mentioned polyimide (PI), and the diamine and tetracarboxylic dianhydride used to obtain the above-mentioned polyamic acid (PA) contains a compound having a group (X), wherein the group (X) contains at least one non-aromatic hydrocarbon group and the total number of carbon atoms of the at least one non-aromatic hydrocarbon group is 9 or more.

[0315] Or a method for producing a block copolymer, which satisfies any one or more of the above [1], [2], and [7], and the above

[21] .

[0316]

[22] An insulating material comprising the block copolymer according to any one of [1] to

[20] above.

[0317]

[23] A heat-resistant insulating material comprising the block copolymer described in any one of [1] to

[20] above.

[0318]

[24] A composition comprising the block copolymer according to any one of [1] to

[20] above, and a solvent.

[0319]

[25] An insulator composition comprising the block copolymer according to any one of [1] to

[20] or the insulating material according to

[22] , and a solvent.

[0320]

[26] A heat-resistant insulator composition comprising the block copolymer described in any one of [1] to

[20] or the heat-resistant insulating material described in

[23] , and a solvent.

[0321]

[27] A composition for a printed circuit board, comprising the block copolymer described in any one of [1] to

[20] , the insulating material described in

[22] or the heat-resistant insulating material described in

[23] , and a solvent.

[0322]

[28] A polyimide obtained using the block copolymer described in any one of [1] to

[20] or the composition described in

[24] .

[0323]

[29] A molded article obtained using the block copolymer described in any one of [1] to

[20] , the insulating material described in

[22] , the heat-resistant insulating material described in

[23] , or the composition described in any one of

[24] to

[27] , or containing the polyimide described in

[28] .

[0324]

[30] An insulator obtained using the block copolymer described in any one of [1] to

[20] , the insulating material described in

[22] , the heat-resistant insulating material described in

[23] , or the composition described in any one of

[24] to

[27] , or containing the polyimide described in

[28] .

[0325]

[31] The insulator according to

[30] above, having a relative dielectric constant of 3.5 or less and a dielectric loss tangent of 0.0100 or less.

[0326]

[32] A heat-resistant insulator obtained using the block copolymer described in any one of [1] to

[20] , the insulating material described in

[22] , the heat-resistant insulating material described in

[23] , or the composition described in any one of

[24] to

[27] , or containing the polyimide described in

[28] .

[0327]

[33] The heat-resistant insulator according to

[32] above, which has a relative dielectric constant of 3.5 or less, a dielectric loss tangent of 0.0100 or less, and a thermal expansion coefficient of 80 ppm / K or less.

[0328]

[34] A printed circuit board obtained using the block copolymer described in any one of [1] to

[20] , the insulating material described in

[22] , the heat-resistant insulating material described in

[23] , or the composition described in any one of

[24] to

[27] , or containing the polyimide described in

[28] , the molded article described in

[29] , the insulator described in

[30] or

[31] , or the heat-resistant insulator described in

[32] or

[33] .

[0329]

[35] In any of the above embodiments [1] to

[34] , the block copolymer contains at least one selected from the following structural units: 1 A structural unit of a group (X) containing at least one non-aromatic hydrocarbon group and the total carbon number of the at least one non-aromatic hydrocarbon group is 12 or more; and a structural unit of a group (X) represented by the above formula (XA) and R 3 It is a structural unit of a group (X) containing at least one non-aromatic hydrocarbon group, wherein the total carbon number of the at least one non-aromatic hydrocarbon group is 12 or more.

[0330]

[36] In any one of the above-mentioned embodiments [1] to

[35] , the structure derived from a diamine or a diisocyanate includes a structure having a group (X) having 12 or more carbon atoms.

[0331]

[37] In any of the above embodiments [1] to

[36] , the total number of carbon atoms of the saturated aliphatic hydrocarbon group and the unsaturated aliphatic hydrocarbon group contained in the above group (X) is greater than the total number of carbon atoms of the saturated alicyclic hydrocarbon group and the unsaturated alicyclic hydrocarbon group contained in the above group (X).

[0332]

[38] In any one of the embodiments [1] to

[37] above, the group (X) does not contain an aromatic hydrocarbon group or an aromatic heterocyclic compound group.

[0333]

[39] In any one of the above-mentioned embodiments [1] to

[38] , the carbon number is 16 or more.

[0334] The present disclosure is related to the subject matter described in PCT / JP2023 / 017047 filed on May 1, 2023, and all disclosed contents thereof are incorporated herein by reference.

[0335] Example

[0336] The embodiments of the present invention are described in more detail by way of examples. The embodiments of the present invention are not limited to the following examples.

[0337] <Synthesis of polyimide (PI) and polyamic acid (PA)>

[0338] [Polyimide (PI-1)]

[0339] 62.3 g (0.12 mol) of dimer diamine ("PRIAMINE1075", Croda Japan KK, containing dimer diamine represented by the following formula) (hereinafter referred to as "DDA") was dissolved in 400.0 g of dimethylacetamide and 20.0 g of toluene to obtain a diamine solution. 29.0 g (0.13 mol) of pyromellitic dianhydride (hereinafter referred to as "PMDA") was added to the diamine solution and reacted until a uniform transparent solution was obtained. The solution was stirred at below 50°C for more than 1 hour to react. Thereafter, the transparent solution was subjected to a dehydration thermal imidization reaction at 180°C for more than 4 hours while stirring to obtain a solution (varnish) of a polyimide (PI-1) having an acid anhydride structure derived from PMDA at the end. The number average molecular weight of the polyimide (PI-1) is 6100.

[0340] [Chemical formula 23]

[0341]

[0342] [Polyimide (PI-2) to (PI-9)]

[0343] Solutions of polyimides (PI-2) to (PI-9) were obtained in the same manner as in polyimide (PI-1) except that the diamine and tetracarboxylic dianhydride shown in Table 2 were used.

[0344] [Polyamic acid (PA-1)]

[0345] 32.6 g (0.30 mole) of p-phenylenediamine (hereinafter referred to as "PPD") was dissolved in 485.6 g of dimethylacetamide to obtain a diamine solution. 84.9 g (0.29 mole) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter referred to as "BPDA") was added to the diamine solution to react to obtain a solution of polyamic acid (polyimide precursor) (PA-1) having an amine structure derived from PPD at the end. The solution was stirred at 50°C or less for more than 8 hours to react. The number average molecular weight of the polyamic acid (PA-1) was 9100.

[0346] [Polyamic acid (PA-2) to (PA-9)]

[0347] Solutions of polyamic acids (PA-2) to (PA-9) were obtained in the same manner as in polyamic acid (PA-1) except that diamines and tetracarboxylic dianhydride shown in Table 2 and dimethylacetamide and N-methyl-2-pyrrolidone were used as solvents.

[0348] <Synthesis of block copolymer (block polyamic acid imide)>

[0349] [Example 1]

[0350] 506.5 g of a solution of polyimide (PI-1) and 603.1 g of a solution of polyamic acid (PA-1) were mixed and reacted to obtain a varnish of block polyamic acid imide 1. The solution was stirred at 100° C. or less for more than 1 hour to react. The number average molecular weight of block polyamic acid imide 1 was 25240. The concentration of block polyamic acid imide 1 was 19.5% by mass based on the mass of the varnish. The varnish is a composition containing a block copolymer and a solvent.

[0351] [Examples 2 to 9]

[0352] Varnishes of block polyamic acid imides 2 to 9 were obtained in the same manner as in Example 1 except that the polyimide and polyamic acid solutions shown in Table 2 were used.

[0353] <Synthesis of polyamic acid>

[0354] [Comparative Example 1]

[0355] 76.6 g (0.38 mol) of 4,4'-diaminodiphenyl ether (hereinafter referred to as "ODA") was dissolved in 640.0 g of dimethylacetamide to obtain a diamine solution. 81.8 g (0.38 mol) of pyromellitic dianhydride (hereinafter referred to as "PMDA") was added to the diamine solution to react and obtain a solution of polyamic acid (polyimide precursor). The solution was stirred at 50°C or less for 8 hours or more to react.

[0356] [Comparative Examples 2 to 6]

[0357] Varnishes of polyamic acids 2 to 6 were obtained in the same manner as in Comparative Example 1 except that the diamine and tetracarboxylic dianhydride shown in Table 3 were used.

[0358] Tables 2 and 3 show the types and quantities of diamines and tetracarboxylic dianhydrides used in the synthesis of polyimide and polyamic acid, and polyimide and polyamic acid used in the synthesis of block polyamic acid imide. In addition, Tables 2 and 3 show the number average molecular weights of polyimide and polyamic acid. The number average molecular weight is measured by the following method.

[0359] The meanings of the abbreviations in Table 2 and Table 3 are as follows.

[0360] PMDA: Pyromellitic Dianhydride

[0361] BTDA: 3,3',4,4'-Benzophenonetetracarboxylic dianhydride

[0362] BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

[0363] DDA: Dimer diamine

[0364] NBDA: Bis(aminomethyl)norbornane

[0365] ODA: 4,4'-diaminodiphenyl ether

[0366] PPD: p-phenylenediamine

[0367] BODA: 4,4'-bis(4-aminophenoxy)biphenyl

[0368]

[0369]

[0370] (Number average molecular weight)

[0371] The number average molecular weight (Mn) was measured by gel permeation chromatography (GPC) and converted using a calibration curve of standard polystyrene. The calibration curve was approximated by a cubic equation using a set of 5 samples of standard polystyrene ("TSK standard POLYSTYRENE", manufactured by Tosoh Corporation). The GPC conditions are as follows.

[0372] GPC device: High-speed GPC device HLC-8320GPC (manufactured by Tosoh Corporation)

[0373] Detector: UV-8320 ultraviolet absorption detector (manufactured by Tosoh Corporation)

[0374] Chromatographic column: Gelpack GL-S300MDT-5 (2 in total) (manufactured by Resonac Corporation)

[0375] Eluent: THF / DMF=1 / 1 (volume ratio)+LiBr(0.06mol / L)+H3PO4(0.06mol / L)

[0376] Flow rate: 1mL / min

[0377] Column size: 8mm ID×300mm

[0378] Sample concentration: 5mg / 1mL

[0379] Injection volume: 5μL

[0380] Measurement temperature: 40℃

[0381] <Film production>

[0382] [Example 1]

[0383] Using the obtained varnish (composition), a film was produced by the following procedure.

[0384] The surface of a commercially available glass substrate was degreased with acetone, and a varnish of block polyamic acid imide 1 was applied using a film applicator with a film thickness adjustment function so that the film thickness after imidization was 25 μm. The applied varnish was pre-dried at 80°C for 60 minutes using a hot plate to form a layer of block polyamic acid imide 1. Next, an inert gas oven was used to heat the layer of block polyamic acid imide 1 at 350°C in a nitrogen atmosphere for 1 hour to obtain a film of block polyimide 1. After the glass substrate with the film formed was soaked in warm water for about 15 minutes, the film was peeled off from the glass substrate.

[0385] [Examples 2 to 9 and Comparative Examples 1 to 6]

[0386] Films were obtained by the same method as above except that the varnish of block polyamic acid imide 1 was changed to the varnish of Examples 2 to 9 and Comparative Examples 1 to 6.

[0387] <Evaluation of film>

[0388] The properties of the films produced using the varnishes of Examples 1 to 9 and Comparative Examples 1 to 6 were evaluated by the following methods. The evaluation results are shown in Tables 2 and 3. Examples 1 to 9 showed good results in terms of tensile strength, tensile elastic modulus, and elongation at break.

[0389] (Relative dielectric constant and dielectric loss tangent)

[0390] The film was cut into 60 mm × 60 mm size, dried at 125°C for 1 hour, and then placed at 23°C and 50% relative humidity for 24 hours. Immediately after placement, the dielectric properties (relative dielectric constant Dk and dielectric loss tangent Df) of the film were measured by the cavity resonance method (TE mode). The measurement was performed using "MS46122B" manufactured by Anritsu Corporation. The conditions were a frequency of 10 GHz and a measurement temperature of 25°C.

[0391] (Linear thermal expansion coefficient (thermal expansion rate) and glass transition temperature)

[0392] The film was cut into a test piece with a width of 4 mm and a length of 25 mm. The test piece was measured using a thermomechanical analyzer ("TMA7100", manufactured by Hitachi High-Tech Corporation). The test piece was heated from room temperature to 350°C at a rate of 10°C / min by a tensile method with a distance between chucks of 10 mm and a load of 10 g, and then cooled to 30°C at a rate of 10°C / min. The temperature was raised again at a rate of 10°C / min, and the average linear thermal expansion coefficient (ppm / °C) from 30°C to 200°C was calculated, and the obtained value was used as the linear thermal expansion coefficient (ppm / K). In addition, the temperature corresponding to the inflection point of the linear thermal expansion coefficient curve was used as the glass transition temperature (°C).

[0393] (Water absorption)

[0394] Cut the film into a size of 70 mm in width and 70 mm in length to make a test piece. After drying the test piece at 125°C for 1 hour, measure the weight of the test piece. Then, soak the test piece in 23°C water for 24 hours, take it out of the water, and completely remove the water on the surface. Measure the weight of the test piece 1 minute after taking it out, and calculate the increase in weight before and after the test. Calculate the water absorption rate based on the following formula.

[0395] Water absorption (%) = (weight of test piece after water absorption - weight of test piece before water absorption) / weight of test piece before water absorption × 100

[0396] (Tensile strength, tensile elastic modulus, and elongation at break)

[0397] Film is cut into the size of 10mm in width and 60mm in length to make test piece. Under the following determination conditions, tensile test is carried out, and the maximum tensile stress applied in the tensile test is used as tensile strength (MPA). Elongation at break (%) is calculated by dividing the elongation of the test piece until fracture by the distance 20mm between chucks. In addition, Young's modulus (MPA) is calculated by the slope of the elastic deformation zone in the initial stage of stress rise, and the value obtained is used as tensile elastic modulus (MPA). Other detailed conditions and calculation methods are carried out according to international standard ISO 5271 (1993).

[0398] Device name: "Autograph AGS-100NG" (trade name) manufactured by Shimadzu Corporation

[0399] Test speed: 5mm / min

[0400] Distance between chucks: 20mm

[0401] Test piece size: width 10mm, length 60mm

[0402] Set temperature: room temperature (25°C)

Claims

1. A block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and comprising a structural unit (X) having a group (X), wherein the group (X) contains at least one non-aromatic hydrocarbon group and the total carbon number of the at least one non-aromatic hydrocarbon group is 9 or more.

2. A block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and comprising at least one selected from the group consisting of a structural unit represented by the following formula (XI) and a structural unit represented by the following formula (XA), [Chemical formula 1] In formula (XI), R 1 and R 2 Each independently represents an organic group, R 1 and R 2 At least one of the groups (X) is a group containing at least one non-aromatic hydrocarbon group and the total carbon number of the at least one non-aromatic hydrocarbon group is 9 or more, [Chemical formula 2] In formula (XA), R 3 and R 4 Each independently represents an organic group, R 3 and R 4 At least one of the groups (X) is a group containing at least one non-aromatic hydrocarbon group, and the total carbon number of the at least one non-aromatic hydrocarbon group is 9 or more.

3. The block copolymer according to claim 2, further comprising at least one selected from the group consisting of a structural unit represented by the following formula (YI) and a structural unit represented by the following formula (YA), [Chemical formula 3] In formula (YI), R 5 and R 6 Each independently represents an organic group (Y), the organic group (Y) is an organic group that does not belong to the group (X), [Chemical formula 4] In formula (YA), R 7 and R 8 Each independently represents an organic group (Y), and the organic group (Y) is an organic group that does not belong to the above group (X).

4. The block copolymer according to claim 3, wherein R 1 ~R 8 The content of the group (X) is 5 to 70% by mass based on the total mass of 5. The block copolymer according to claim 3 or 4, wherein In the formula (YI) and the formula (YA), the organic group (Y) contains an aromatic hydrocarbon group.

6. The block copolymer according to claim 5, wherein The polyamic acid block (BA) contains a structural unit represented by the formula (YA).

7. A block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and having a structure derived from a diamine or a diisocyanate and a structure derived from a tetracarboxylic dianhydride, At least one of the structure derived from diamine or diisocyanate and the structure derived from tetracarboxylic dianhydride contains a structure having a group (X), wherein the group (X) contains at least one non-aromatic hydrocarbon group and the total number of carbon atoms of the at least one non-aromatic hydrocarbon group is 9 or more.

8. The block copolymer according to claim 7, wherein The content of the structure having the group (X) is 3 to 60% by mass based on the total mass of the structure derived from the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride.

9. The block copolymer according to claim 7 or 8, wherein The structure derived from a diamine or a diisocyanate includes a structure derived from a diamine or a diisocyanate having the group (X) and a structure derived from a diamine or a diisocyanate having an aromatic hydrocarbon group.

10. The block copolymer according to claim 9, wherein The structure derived from diamine or diisocyanate contained in the polyamic acid block (BA) includes a structure derived from diamine or diisocyanate having an aromatic hydrocarbon group.

11. The block copolymer according to any one of claims 1 to 10, wherein The at least one non-aromatic hydrocarbon group is a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group, an unsaturated alicyclic hydrocarbon group, or a group consisting of two or more selected from these groups.

12. The block copolymer according to any one of claims 1 to 11, wherein The group (X) is a saturated aliphatic hydrocarbon group having 9 or more carbon atoms, an unsaturated aliphatic hydrocarbon group having 9 or more carbon atoms, a saturated alicyclic hydrocarbon group having 9 or more carbon atoms, an unsaturated alicyclic hydrocarbon group having 9 or more carbon atoms, or a group having 9 or more carbon atoms formed by two or more selected from a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group, and an unsaturated alicyclic hydrocarbon group.

13. The block copolymer according to any one of claims 1 to 12, wherein The group (X) contains a saturated alicyclic hydrocarbon group.

14. The block copolymer according to any one of claims 1 to 13, wherein The group (X) contains a linear saturated aliphatic hydrocarbon group having 6 or more carbon atoms.

15. The block copolymer according to any one of claims 1 to 14, wherein The carbon number is 12 or more.

16. The block copolymer according to any one of claims 1 to 15, wherein The carbon number is 28 or more.

17. The block copolymer according to any one of claims 1 to 16, wherein Only one of the polyimide block (BI) and the polyamic acid block (BA) contains the group (X).

18. The block copolymer according to any one of claims 1 to 16, wherein Both the polyimide block (BI) and the polyamic acid block (BA) contain the group (X).

19. The block copolymer according to any one of claims 1 to 18, wherein The number average molecular weight of the polyimide block (BI) is 500 to 10,000.

20. The block copolymer according to any one of claims 1 to 19, wherein The number average molecular weight of the polyamic acid block (BA) is 500 to 30,000.

21. A method for producing a block copolymer, comprising the steps of: Polyimide (PI) is obtained using diamine or diisocyanate and tetracarboxylic dianhydride; Using diamine and tetracarboxylic dianhydride to obtain polyamic acid (PA); and Using the polyimide (PI) and the polyamic acid (PA) to obtain a block copolymer, in, At least one selected from the diamine or diisocyanate and tetracarboxylic dianhydride used to obtain the polyimide (PI), and the diamine and tetracarboxylic dianhydride used to obtain the polyamic acid (PA) contains a compound having a group (X), wherein the group (X) contains at least one non-aromatic hydrocarbon group and the total number of carbon atoms of the at least one non-aromatic hydrocarbon group is 9 or more.

22. An insulating material comprising the block copolymer according to any one of claims 1 to 20.

23. A heat-resistant insulating material comprising the block copolymer according to any one of claims 1 to 20. 24 . A composition comprising the block copolymer according to claim 1 , and a solvent. 25 . An insulator composition comprising the block copolymer according to claim 1 or the insulating material according to claim 22 , and a solvent. 26 . A heat-resistant insulator composition comprising the block copolymer according to claim 1 or the heat-resistant insulating material according to claim 23 , and a solvent.

27. A composition for a printed circuit board, comprising the block copolymer according to any one of claims 1 to 20, the insulating material according to claim 22 or the heat-resistant insulating material according to claim 23, and a solvent.

28. A polyimide obtained using the block copolymer according to any one of claims 1 to 20 or the composition according to claim 24.

29. A molded article obtained using the block copolymer according to any one of claims 1 to 20, the insulating material according to claim 22, the heat-resistant insulating material according to claim 23, or the composition according to any one of claims 24 to 27, or containing the polyimide according to claim 28.

30. An insulator obtained by using the block copolymer according to any one of claims 1 to 20, the insulating material according to claim 22, the heat-resistant insulating material according to claim 23, or the composition according to any one of claims 24 to 27, or containing the polyimide according to claim 28.

31. The insulator according to claim 30, which has a relative dielectric constant of 3.5 or less and a dielectric loss tangent of 0.0100 or less.

32. A heat-resistant insulator obtained by using the block copolymer according to any one of claims 1 to 20, the insulating material according to claim 22, the heat-resistant insulating material according to claim 23, or the composition according to any one of claims 24 to 27, or containing the polyimide according to claim 28.

33. The heat-resistant insulator according to claim 32, which has a relative dielectric constant of 3.5 or less, a dielectric loss tangent of 0.0100 or less, and a thermal expansion coefficient of 80 ppm / K or less.

34. A printed circuit board obtained by using the block copolymer according to any one of claims 1 to 20, the insulating material according to claim 22, the heat-resistant insulating material according to claim 23, or the composition according to any one of claims 24 to 27, or containing the polyimide according to claim 28, the molded article according to claim 29, the insulator according to claim 30 or 31, or the heat-resistant insulator according to claim 32 or 33.

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