Antenna substrate material and method of manufacturing the same

Abstract

The present disclosure relates to a substrate material for antennas, which is a substrate material for antennas containing a block copolymer including a polyimide block (BI) and a polyamide acid block (BA).

Description

TECHNICAL FIELD

[0001] The present disclosure relates to an antenna substrate material, a method for manufacturing an antenna substrate material, and an antenna substrate material composition. BACKGROUND

[0002] 5G (5th Generation Mobile Communication System) that can connect large-capacity data simultaneously without delay is expanding. In order to keep up with post 5G and promote further high frequency of action frequency, an increase in the number of wireless substations and high functionality are required. A wireless unit (RU) included in a wireless substation employs an antenna such as a patch antenna in order to transmit and receive electric waves. The patch antenna has, for example, a multilayer substrate including an insulating substrate and an antenna element mounted on the multilayer substrate (see Patent Literature 1).

[0003] PRIOR ART DOCUMENT PATENT LITERATURE Patent Literature 1: Japanese Patent Application Laid-Open No. 2020-174114 SUMMARY

[0004] PROBLEMS TO BE SOLVED BY THE INVENTION In order to obtain good transmission characteristics, an organic material included in a multilayer substrate is preferably low in dielectricity and low in thermal expansion rate. The present disclosure provides an antenna substrate material, an antenna substrate material composition, and a method for manufacturing an antenna substrate material, each of which exhibits low dielectric constant, low dielectric loss tangent, and low thermal expansion rate.

[0005] MEANS FOR SOLVING THE PROBLEMS The present invention includes the following embodiments. The present invention is not limited to the following embodiments.

[0006] One embodiment relates to an antenna substrate material that is an antenna substrate material containing a block copolymer, the block copolymer containing a polyimide block (BI) and a polyamide acid block (BA).

[0007] Another embodiment relates to an antenna substrate material containing a block copolymer, the block copolymer containing a polyimide block (BI) and a polyamide acid block (BA), and containing a structural unit represented by the following formula (I) and a structural unit represented by the following formula (A), at least the following R A is different from the following R C , or at least the following R B is different from the following R D .

[0008] [Chemical Formula 1] (in the formula, R A and R B each independently represents an organic group.) [Chemical Formula 2] (in the formula, R C and R D each independently represents an organic group.) Another embodiment relates to a substrate material for an antenna, which is a substrate material for an antenna containing a block copolymer, the block copolymer containing a polyimide block (BI) and a polyamide acid block (BA), and having a structure derived from a diamine or a diisocyanate and a structure derived from a tetracarboxylic dianhydride.

[0009] Another embodiment relates to a method for manufacturing a substrate material for an antenna, which is a method for manufacturing a substrate material for an antenna containing a block copolymer, the method including: a step of obtaining a polyimide (PI) using a diamine or a diisocyanate and a tetracarboxylic dianhydride; a step of obtaining a polyamide acid (PA) using a diamine and a tetracarboxylic dianhydride; and a step of obtaining a block copolymer using the polyimide (PI) and the polyamide acid (PA).

[0010] Another embodiment relates to a substrate material for an antenna composition containing the substrate material for an antenna described in any one of the above and a solvent.

[0011] Effects of Invention According to the present disclosure, it is possible to provide a substrate material for an antenna, a substrate material for an antenna composition, and a method for manufacturing a substrate material for an antenna, which exhibit low dielectric constant, low dielectric loss tangent, and low thermal expansion rate. BRIEF DESCRIPTION OF DRAWINGS

[0012] Figure 1 is a schematic view showing an example of a substrate for an antenna.

[0013] Figure 2 is a schematic view showing an example of a substrate for an antenna. DETAILED DESCRIPTION

[0014] Embodiments of the present application are described. The present application is not limited to the following embodiments. In addition, the following embodiments can be implemented alone or in combination. Combinations of a plurality of embodiments are also included in the present application.

[0015] In the numerical ranges described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range can be replaced with the upper limit value or the lower limit value of another numerical range. In addition, the upper limit value or the lower limit value of the numerical range described in the present disclosure can be replaced with the value shown in the examples. A certain numerical range can also be formed by selecting each of the upper limit value and the lower limit value described in the present disclosure. In addition, the upper limit value and the lower limit value described in the present disclosure can be replaced with the value shown in the examples.

[0016] In the present disclosure, each component can include a plurality of substances belonging thereto. In the case where a plurality of substances belonging to each component is present in the composition, unless otherwise specified, the content ratio or the content of each component refers to the total content ratio or the total content of the plurality of substances present in the composition.

[0017] In the present disclosure, each structure in the polymer can include a plurality of structures belonging thereto. In the case where a plurality of structures belonging to each structure is present in the polymer, unless otherwise specified, the content ratio or the content of each structure refers to the total content ratio or the total content of the plurality of structures present in the polymer.

[0018] In the present disclosure, the term "layer" includes, in addition to the layer formed on the entire region of the region where the layer exists when the region is observed, the layer formed only on a part of the region. The same applies to "film".

[0019] <Antenna substrate material> In some embodiments, the antenna substrate material contains a block copolymer containing a polyimide block (BI) and a polyamic acid block (BA). The antenna substrate material can further contain any component. The antenna substrate material is a material for forming a substrate for an antenna. The substrate for an antenna is, for example, a substrate for mounting an antenna element such as a patch antenna, or a substrate for mounting an antenna device containing an antenna element.

[0020] <Block copolymer> The block copolymer contains a polyimide block (BI) and a polyamic acid block (BA). The block copolymer containing a polyimide block (BI) and a polyamic acid block (BA) contains an imide bond (also referred to as "imide group") and a polyamic acid bond (also referred to as "polyamic acid structure" or "polyamic acid group") in the polymer chain. The polyamic acid block (BA) can be a block that becomes a polyimide block (BI-A) different from the polyimide block (BI) by ring-closing the polyamic acid bond. The block copolymer can further contain any block different from the polyimide block (BI) and the polyamic acid block (BA). The block copolymer can contain one or two or more arbitrary blocks.

[0021] In the present disclosure, the blocks being the same or different can be distinguished by the structural units contained in the blocks. For example, where there are structural units contained in one block but not contained in another block, the two are different blocks. As examples of combinations of two different blocks, there are cases where block 1 contains structural unit 1 and block 2 contains structural unit 2; block 1 contains structural unit 1 and block 2 contains structural unit 1 and structural unit 2; block 1 contains structural unit 1 and structural unit 2 and block 2 contains structural unit 1 and structural unit 3; and the like. Structural unit 1, structural unit 2, and structural unit 3 used in the description herein are mutually different structural units. In the present disclosure, the number of types of structural units contained in each block is not limited to 1 or 2, and can 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 can be 3 or more.

[0022] It is generally considered that the greater the increase in the free volume within the molecule of a polyimide, the greater the tendency to exhibit a low dielectric constant and a low dielectric loss tangent. The free volume can be increased by introducing bulky groups into the polyimide, having substituents at appropriate positions in order to introduce a twisting structure in the backbone, having ether bonds (oxy groups), carbonyl bonds (carbonyl groups), sulfonyl bonds (sulfonyl groups), and the like linking groups in the backbone in order to introduce a bending structure in the backbone, and the like. On the other hand, it is considered that the more rigid the molecule of a polyimide, the greater the tendency to exhibit a low thermal expansion rate. Where a polyimide has a benzene ring structure, a biphenyl structure, and the like without the above-described groups, the molecule becomes more rigid. Therefore, it is generally difficult to balance low dielectric constant and low dielectric loss tangent with low thermal expansion rate. In contrast, the present disclosure provides a material containing a block copolymer that can balance them. Furthermore, in the present disclosure, the recitations of investigation, speculation, and the like do not limit the present invention.

[0023] In some embodiments, the block copolymer contains a block having a large free volume and a block being rigid. For example, the polyimide block (BI) and the polyamic acid block (BA) can be a combination of a block containing a structural unit that increases the free volume of the polyimide and a block containing a structural unit that increases the rigidity of the polyimide. For example, the polyimide block (BI) and the polyamic acid block (BA) can be a combination of a block containing a structural unit containing a non-aromatic hydrocarbon group, a structural unit containing an oxy group, a carbonyl group, or the like as a linking group in the backbone, and the like, and a block not containing or containing a structural unit containing a non-aromatic hydrocarbon group, a structural unit containing an oxy group, a carbonyl group, or the like as a linking group in the backbone in an amount less than the above block. For example, the polyimide block (BI) and the polyamic acid block (BA) can be a combination of a block showing a dielectric constant A, a dielectric loss tangent B, and a thermal expansion rate C, and a block showing a dielectric constant a smaller than the A, a dielectric loss tangent b smaller than the B, and a thermal expansion rate c larger than the C. In the present disclosure, the polyimide obtained from the material containing the block copolymer is low in dielectric constant and low in dielectric loss tangent, and is low in thermal expansion rate.

[0024] [Block copolymer containing structural unit (X)] In some embodiments, the block copolymer contains a polyimide block (BI) and a polyamic acid block (BA), and contains a structural unit (X) having a group (X) containing at least one non-aromatic hydrocarbon group. In the present disclosure, the "group (X) containing at least one non-aromatic hydrocarbon group" is sometimes referred to simply as "group (X)" or "hydrocarbon group (X)". In the present disclosure, the "structural unit (X) having a group (X) containing at least one non-aromatic hydrocarbon group" is sometimes referred to simply as "structural unit (X)". The hydrocarbon group (X) can be a group located between an imide group and an imide group, an amic acid group and an amic acid group, or an imide group and an amic acid group. The block copolymer can contain one or more than two hydrocarbon groups (X). By the block copolymer having the hydrocarbon group (X), the polyimide has a tendency to be low in dielectric constant and low in dielectric loss tangent.

[0025] The block copolymer can 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 later can be given. The structural unit (Y) can be a structural unit having a group (Y) containing at least one aromatic ring group. In the present disclosure, the "group (Y) containing at least one aromatic ring group" is sometimes referred to simply as "group (Y)" or "organic group (Y)". In the present disclosure, the "structural unit (Y) having a group (Y) containing at least one aromatic ring group" is sometimes referred to simply as "structural unit (Y)".

[0026] In the case where the block copolymer contains the structural unit (X), only either one of the polyimide block (BI) and the polyamic acid block (BA) can contain the structural unit (X), or both the polyimide block (BI) and the polyamic acid block (BA) can contain the structural unit (X). The polyimide block (BI) and the polyamic acid block (BA) can each independently contain one or two or more kinds of the structural unit (X). For example, the block copolymer can be a block copolymer containing the polyimide block (BI) containing the structural unit (X) and the polyamic acid block (BA) containing a structural unit (X) different from the structural unit (X).

[0027] In the case where the block copolymer contains the structural unit (Y), only either one of the polyimide block (BI) and the polyamic acid block (BA) can contain the structural unit (Y), or both the polyimide block (BI) and the polyamic acid block (BA) can contain the structural unit (Y). The polyimide block (BI) and the polyamic acid block (BA) can each independently contain one or two or more kinds of the structural unit (Y). For example, the block copolymer can be a block copolymer containing the polyimide block (BI) containing the structural unit (X) and the polyamic acid block (BA) containing the structural unit (Y), or a block copolymer containing the polyimide block (BI) containing the structural unit (Y) and the polyamic acid block (BA) containing the structural unit (X).

[0028] (structural unit (X)) The structural unit (X) contains at least a hydrocarbon group (X). The structural unit (X) can further contain at least one of an imide group and an amic acid group. The total number of carbons of "at least 1 non-aromatic hydrocarbon group" contained in the hydrocarbon group (X) is 1 or more. The number of carbons contained in the imide group and the amic acid group is not included in the total number of carbons of at least 1 non-aromatic hydrocarbon group in the hydrocarbon group (X). For example, the structural unit (X) is a structural unit containing the hydrocarbon group (X), and the imide group or the amic acid group. The block copolymer can contain the hydrocarbon group (X) and the imide group or the amic acid group contained in the structural unit (X) in the polymer chain. The structural unit (X) can contain one or two or more kinds of the hydrocarbon group (X). The structural unit (X) can further contain an arbitrary group other than the hydrocarbon group (X), the imide group, and the amic acid group. As the arbitrary group, for example, an organic group (Y) or the like can be mentioned. In the present disclosure, the "organic group" is a group containing at least 1 carbon atom. The organic group (Y) can be a group located between the imide group and the imide group, the amic acid group and the amic acid group, or the imide group and the amic acid group. The block copolymer can contain the organic group (Y) in the polymer chain.

[0029] (hydrocarbon group (X)) The hydrocarbon group (X) contains at least one non-aromatic hydrocarbon group. In the hydrocarbon group (X), the total number of carbons of the at least one non-aromatic hydrocarbon group is 1 or more. In the case where the hydrocarbon group (X) contains one non-aromatic hydrocarbon group, the total number of carbons refers to the total number of carbons contained in the one non-aromatic hydrocarbon group. In the case where the hydrocarbon group (X) contains two or more non-aromatic hydrocarbon groups, the total number of carbons refers to the total number of carbons contained in the two or more non-aromatic hydrocarbon groups. In the case where the hydrocarbon group (X) contains two or more non-aromatic hydrocarbon groups, the two or more non-aromatic hydrocarbon groups can be the same as or different from each other. The hydrocarbon group (X) can further contain any group other than the 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 a 2-valent or 4-valent hydrocarbon group (X), further preferably a 2-valent hydrocarbon group (X).

[0030] The non-aromatic hydrocarbon group is a non-aromatic hydrocarbon group not containing an aromatic ring. The at least one 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 composed of two or more selected from among them. The saturated aliphatic hydrocarbon group can be linear or branched. The unsaturated aliphatic hydrocarbon group can be linear or branched.

[0031] Examples of the hydrocarbon group (X) and the total number of carbons of the at least one non-aromatic hydrocarbon group contained in the hydrocarbon group (X) are listed below. In addition, as reference examples, examples of the organic group (Y) and the total number of carbons of the at least one non-aromatic hydrocarbon group contained in the organic group (Y) are listed. The number of carbons contained in the -C(O)- group is not included in the total number of carbons. The number of carbons contained in the non-aromatic hydrocarbon group in which a hydrogen atom is substituted with a halogen atom is included in the total number of carbons. In the present disclosure, "*" in the formula indicates the bonding position to other atoms. Groups 7 to 14 are examples of the hydrocarbon group (X), and groups 1 to 3 are examples of the organic group (Y). Groups 4 to 6 are examples of the hydrocarbon group (X) and also examples of the organic group (Y).

[0032] The total number of carbons of the at least one non-aromatic hydrocarbon group included in the hydrocarbon group (X) can be 1 to 50. The number of carbons is, for example, 2 or more, 3 or more, 6 or more, 9 or more, 12 or more, 16 or more, 20 or more, 24 or more, 28 or more, 32 or more, or 36 or more. The number of carbons is, for example, 48 or less, 44 or less, 40 or less, or 36 or less. The number of carbons is, for example, 6 to 50, 9 to 50, 12 to 48, 20 to 44, or 28 to 40. It is considered that, in the case where the block copolymer has a non-aromatic hydrocarbon group, a polyimide having a low dielectric constant and a low dielectric loss tangent can be obtained for the reason of an increase in free volume, a decrease in polarity, or the like. In the case where the total number of carbons of the non-aromatic hydrocarbon group is 9 or more, there is a tendency that these effects are easily obtained. In the case where the total number of carbons of the non-aromatic hydrocarbon group is 50 or less, it is possible to maintain good solubility to a solvent.

[0033] Examples of the saturated aliphatic hydrocarbon group, the unsaturated aliphatic hydrocarbon group, the saturated alicyclic hydrocarbon group, the unsaturated alicyclic hydrocarbon group, and the group composed of two or more selected from among them, which the hydrocarbon group (X) can include, are listed below. The examples below can be applied to the saturated aliphatic hydrocarbon group, the unsaturated aliphatic hydrocarbon group, the saturated alicyclic hydrocarbon group, the unsaturated alicyclic hydrocarbon group, and the group composed of two or more selected from among them in the present disclosure.

[0034] The number of carbons 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, a group obtained by removing 1 to 4 hydrogen atoms from an alkane which is linear or branched. As examples of the alkane, there can be mentioned methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, hexacosane, octacosane, triacontane, tetracontane, and pentacontane. In the case where the hydrocarbon group (X) includes, for example, a saturated aliphatic hydrocarbon group having a small number of carbons such as 1, 2, 3, or the like, the number of such saturated aliphatic hydrocarbon groups in the hydrocarbon group (X) can be 2 or more.

[0035] The number of carbons 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 one or more, and can be, for example, five or less, four or less, three or less, or two or less. The unsaturated aliphatic hydrocarbon can be an olefin containing one carbon-carbon double bond or an alkyne containing one carbon-carbon triple bond. The unsaturated aliphatic hydrocarbon group is, for example, a group obtained by removing one to four hydrogen atoms from a straight-chain or branched-chain olefin, or a group obtained by removing one to four hydrogen atoms from a straight-chain or branched-chain alkyne. As examples of the olefin, there are mentioned ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, eicosylene, heneicosylene, docosylene, tricosylene, tetracosylene, pentacosylene, hexacosylene, heptacosylene, octacosylene, nonacosylene, triacontylene, tetracontylene, and pentacontylene. As examples of the alkyne, there are mentioned ethyne, propyne, butyne, pentyne, hexyne, heptyne, octyne, nonyne, decyne, undecyne, dodecyne, tridecyne, tetradecyne, pentadecyne, hexadecyne, heptadecyne, octadecyne, nonadecyne, eicosyne, heneicosyne, docosyne, tricosyne, tetracosyne, pentacosyne, hexacosyne, heptacosyne, octacosyne, nonacosyne, triacontyne, tetracontyne, and pentacontyne. In the case where the hydrocarbon group (X) contains, for example, an unsaturated aliphatic hydrocarbon group having a small number of carbons, such as one, two, or three carbons, the number of such unsaturated aliphatic hydrocarbon groups in the hydrocarbon group (X) can be two or more.

[0036] The number of carbons 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, a group obtained by removing one to four hydrogen atoms from a cycloalkane. As examples of the cycloalkane, there are mentioned cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, decalin, bicyclobutane, bicyclohexane, bicyclooctane, spiropentane, spiroheptane, tetracycloheptane, and adamantane.

[0037] The number of carbons 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 one or more, and can be, for example, five or less, four or less, three or less, or two or less. The unsaturated aliphatic hydrocarbon can be a cycloalkene containing one carbon-carbon double bond or a cycloalkyne containing one carbon-carbon triple bond. The unsaturated alicyclic hydrocarbon group is, for example, a group obtained by removing one to four hydrogen atoms from a cycloalkene, or a group obtained by removing one to four hydrogen atoms from a cycloalkyne. As examples of the unsaturated alicyclic hydrocarbon, there are mentioned cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, norbornene, norbornadiene, and bicyclooctadiene.

[0038] The carbon number of the "group consisting of two or more groups selected from among them" is, for example, 4 to 50, 9 to 50, 16 to 48, 24 to 44, or 32 to 40. The "group consisting of two or more groups selected from among them" consists of two or more groups selected from among a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group, and an unsaturated alicyclic hydrocarbon group, and is a group in which the two or more groups described above are bonded to each other. The "group consisting of two or more groups selected from among them" includes, for example, at least one of a group consisting of a saturated aliphatic hydrocarbon group and a saturated alicyclic hydrocarbon group, a group consisting of a saturated aliphatic hydrocarbon group and an unsaturated alicyclic hydrocarbon group, a group consisting of an unsaturated aliphatic hydrocarbon group and a saturated alicyclic hydrocarbon group, and a group consisting of an unsaturated aliphatic hydrocarbon group and an unsaturated alicyclic hydrocarbon group.

[0039] As an arbitrary group that the hydrocarbon group (X) can include, for example, an aromatic hydrocarbon group, an aromatic heterocyclic compound group, and a group containing a hetero atom can be mentioned. Examples of the aromatic hydrocarbon group, the aromatic heterocyclic compound group, and the group containing a hetero atom that the hydrocarbon group (X) can include are listed. The following examples can be applied to the aromatic hydrocarbon group, the aromatic heterocyclic compound group, and the group containing a hetero atom in the present disclosure. From the viewpoint of reducing polarity, the hydrocarbon group (X) can not include an oxygen atom, and further can not include a hetero atom.

[0040] The carbon number of the aromatic hydrocarbon group is, for example, 6 to 30, 6 to 20, or 6 to 10. The aromatic hydrocarbon group is, for example, a group of atoms obtained by removing 1 to 4 hydrogen atoms from an aromatic hydrocarbon. As examples of the aromatic hydrocarbon, benzene, naphthalene, anthracene, pyrene, and perylene can be mentioned. The carbon number of the aromatic heterocyclic compound group is 2 to 30, 4 to 20, or 5 to 10. The aromatic heterocyclic compound group is, for example, a group of atoms obtained by removing 1 to 4 hydrogen atoms from an aromatic heterocyclic compound. As examples of the aromatic heterocyclic compound, pyridine, furan, benzofuran, thiophene, and benzothiophene can be mentioned.

[0041] As the group containing a hetero atom, for example, a linking group containing a hetero atom (excluding an imide group and an amide acid group) and a substituent containing a hetero atom can be mentioned. As examples of the linking group containing a hetero atom, an oxy group, a thio group, a sulfonyl group, a sulfinyl group, a carbonyl group, a carbonyloxy group, an imino group, and the like can be mentioned. As examples of the substituent containing a hetero atom, a hydroxyl group, a mercapto group, a sulfo group, a sulfinyl group, a carboxyl group, a fluorine group, a chlorine group, and the like can be mentioned. In the present disclosure, the carbon number of the -C(O)- group contained in the group containing a hetero atom is not included in the total carbon number of the at least one non-aromatic hydrocarbon group.

[0042] The hydrocarbon group (X) is composed of a non-aromatic hydrocarbon group having 1 or more carbon atoms, for example. In the case where the hydrocarbon group (X) is composed of a non-aromatic hydrocarbon group having 1 or more carbon atoms, the hydrocarbon group (X) does not include an aromatic hydrocarbon group, an aromatic heterocyclic compound group, and a group containing a hetero atom. The hydrocarbon group (X) 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 composed of two or more kinds selected from a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group, and an unsaturated alicyclic hydrocarbon group. The saturated aliphatic hydrocarbon group can be linear or branched. The unsaturated aliphatic hydrocarbon group can be linear or branched. In the case where the hydrocarbon group (X) is composed of a non-aromatic hydrocarbon group, it is easy to reduce the concentration of a polar group contained in the block copolymer.

[0043] The hydrocarbon group (X) is composed of a non-aromatic hydrocarbon group having 9 or more carbon atoms, for example. In the case where the hydrocarbon group (X) is composed of a non-aromatic hydrocarbon group, the hydrocarbon group (X) does not include an aromatic hydrocarbon group, an aromatic heterocyclic compound group, and a group containing a hetero atom. The hydrocarbon group (X) is, for example, 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 composed of two or more kinds selected from a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group, and an unsaturated alicyclic hydrocarbon group, having 9 or more carbon atoms. The saturated aliphatic hydrocarbon group can be linear or branched. The unsaturated aliphatic hydrocarbon group can be linear or branched. In the case where the hydrocarbon group (X) is composed of a non-aromatic hydrocarbon group having 9 or more carbon atoms, it is easy to reduce the concentration of a polar group contained in the block copolymer.

[0044] The hydrocarbon group (X) preferably includes at least one group selected from a saturated alicyclic hydrocarbon group and an unsaturated alicyclic hydrocarbon group, and more preferably includes a saturated alicyclic hydrocarbon group. The number of carbon atoms of the saturated alicyclic hydrocarbon group and the unsaturated alicyclic hydrocarbon group can be 3 or more, 5 or more, or 6 or more. The number of carbon atoms of the saturated alicyclic hydrocarbon group and the unsaturated alicyclic hydrocarbon group can be 20 or less, 10 or less, or 8 or less. In the case where the block copolymer includes at least one of a saturated alicyclic hydrocarbon group and an unsaturated alicyclic hydrocarbon group, there is a tendency that a polyimide having a lower dielectric constant is easily obtained. The reason is presumably because the free volume of the polyimide increases by having an alicyclic structure.

[0045] The hydrocarbon group (X) preferably contains at least one group selected from a linear saturated aliphatic hydrocarbon group having 6 or more carbons and a linear unsaturated aliphatic hydrocarbon group having 6 or more carbons, and more preferably contains a linear saturated aliphatic hydrocarbon group having 6 or more carbons. The linear saturated aliphatic hydrocarbon group and the linear unsaturated aliphatic hydrocarbon group can have 8 or more, 10 or more, or 12 or more carbons. The linear saturated aliphatic hydrocarbon group and the linear unsaturated aliphatic hydrocarbon group can have 30 or less, 20 or less, or 16 or less carbons. When the block copolymer contains at least one of a linear saturated aliphatic hydrocarbon group having 6 or more carbons and a linear unsaturated aliphatic hydrocarbon group having 6 or more carbons, there is a tendency that a polyimide having a lower dielectric loss tangent is easily obtained. It is presumed that the reason is that the concentration of imide groups in the polyimide becomes low, i.e., the number of polar groups in the polyimide relatively decreases, because the polyimide has a long chain structure.

[0046] The hydrocarbon group (X) preferably contains at least one group selected from a saturated alicyclic hydrocarbon group and an unsaturated alicyclic hydrocarbon group, and at least one group selected from a linear saturated aliphatic hydrocarbon group having 6 or more carbons and a linear unsaturated aliphatic hydrocarbon group having 6 or more carbons, and more preferably contains a saturated alicyclic hydrocarbon group and a linear saturated aliphatic hydrocarbon group having 6 or more carbons.

[0047] In some embodiments, the total number of carbons of the saturated aliphatic hydrocarbon group and the unsaturated aliphatic hydrocarbon group contained in the hydrocarbon group (X) is greater than the total number of carbons of the saturated alicyclic hydrocarbon group and the unsaturated alicyclic hydrocarbon group contained in the hydrocarbon group (X), from the viewpoint of the balance between the dielectric constant and the dielectric loss tangent of the polyimide. In some embodiments, the hydrocarbon group (X) does not contain an aromatic hydrocarbon group and an aromatic heterocyclic compound group, from the viewpoint of obtaining a low dielectric constant and a low dielectric loss tangent.

[0048] The hydrocarbon group (X) preferably contains a group represented by the following formula (G1).

[0049] [Chemical Formula 3] In the formula, R x represents a group (X) containing at least one non-aromatic hydrocarbon group.

[0050] The hydrocarbon group (X) more preferably contains at least one selected from the group consisting of a group represented by the following formula (G2), a group represented by the following formula (G6), a group represented by the following formula (GA1), and a group represented by the following formula (GA3b). The hydrocarbon group (X) further preferably contains at least one selected from the group consisting of a group represented by the following formula (G2) and a group represented by the following formula (G6). The hydrocarbon group (X) can contain at least one selected from the group consisting of a group represented by the following formula (GA1) and a group represented by the following formula (GA3b) without containing at least one selected from the group consisting of a group represented by the following formula (G2) and a group represented by the following formula (G6), or contain at least one selected from the group consisting of a group represented by the following formula (GA1) and a group represented by the following formula (GA3b) and contain at least one selected from the group consisting of a group represented by the following formula (G2) and a group represented by the following formula (G6).

[0051] [Chemical Formula 4] In the formula, R a Each independently represents a linear or branched saturated aliphatic hydrocarbon group (the number of carbons is, for example, 1 or more, 6 or more, or 8 or more) or a linear or branched unsaturated aliphatic hydrocarbon group (the number of carbons is, for example, 1 or more, 6 or more, or 8 or more), preferably represents a linear saturated aliphatic hydrocarbon group (the number of carbons is, for example, 1 or more, 6 or more, or 8 or more) or a linear unsaturated aliphatic hydrocarbon group (the number of carbons is, for example, 1 or more, 6 or more, or 8 or more). R b Each independently represents a saturated alicyclic hydrocarbon group (the number of carbons is, for example, 4 or more, 6 or more, or 7 or more) or an unsaturated alicyclic hydrocarbon group (the number of carbons is, for example, 4 or more, 6 or more, or 7 or more), preferably represents a saturated alicyclic hydrocarbon group (the number of carbons is, for example, 6 (cyclohexane group) or 7 (norbornane group)). R a and R b Each independently can have a substituent, or can not have a substituent. As examples of the substituent, a substituent containing a heteroatom can be given, and examples of the substituent containing a heteroatom in the present disclosure are as described above. R a and R b The upper limit of the number of carbons is, for example, 48 or less, 44 or less, 40 or less, or 36 or less.

[0052] L represents a single bond or a linking group containing a heteroatom (except for an imide group and an amide acid group). Examples of the linking group containing a heteroatom represented by L in the present disclosure are as described above.

[0053] 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. R e Each independently can have a substituent, or can not have a substituent. As examples of the substituent, a substituent containing a heteroatom can be given, and examples of the substituent containing a heteroatom in the present disclosure are as described above. R eExamples of substituents that can be present include non-aromatic hydrocarbon groups and heteroatom-containing substituents. Non-aromatic hydrocarbon groups are, for example, alkyl groups having a carbon number of 1 to 3.

[0054] R f represents a linear or branched saturated aliphatic hydrocarbon group, or a linear or branched unsaturated aliphatic hydrocarbon group. R f The carbon number of R, for example, is 1 to 12, 2 to 8, or 3 to 6.

[0055] wherein the groups represented by formulae (GA1) to (GA3b) each contain at least one non-aromatic hydrocarbon group (the total carbon number of which is, for example, 1 to 12, 2 to 8, or 3 to 6) as a substituent and R f one or both of R and R e one or both of R and R

[0056] In some embodiments, in the case where the hydrocarbon group (X) contains an aromatic ring group, the total carbon number of the non-aromatic hydrocarbon group can be greater than the total carbon number of the aromatic ring group from the viewpoint of low dielectric constant and low dielectric loss tangent. The total carbon number of the aromatic ring group, for example, is 12 or less, or 6 or less.

[0057] In some embodiments, in the case where the hydrocarbon group (X) contains a small-number-carbon unsaturated aliphatic hydrocarbon group having a carbon number of 1, 2, 3, etc., and an aromatic ring group, the number of the small-number-carbon unsaturated aliphatic hydrocarbon groups can be 2 or more. In this case, the total carbon number of the non-aromatic hydrocarbon group can be less than the total carbon number of the aromatic ring group.

[0058] In some embodiments, the hydrocarbon group (X) contains at least one selected from the group consisting of a group represented by the following formula (G7), a group represented by the following formula (G8), and a group represented by the following formula (G9). These groups can be introduced into the block copolymer by using, for example, a dimer diamine or a dimer diisocyanate as a monomer for obtaining the block copolymer. The hydrocarbon group (X) preferably contains the group represented by formula (G8). In the case where the structural unit (X) contains at least one selected from the group consisting of the group represented by formula (G7), the group represented by formula (G8), and the group represented by formula (G9), there is a tendency to have a sufficient effect of easily obtaining a low dielectric constant and a low dielectric loss tangent.

[0059] [Chemical Formula 5] In the formula, R c each independently represents a linear alkylene group (the carbon number of which is, for example, 6 or more, 8 or more, or 9 or more) or a linear alkenylene group (the carbon number of which is, for example, 6 or more, 8 or more, or 9 or more), Rd Each can independently represent a straight-chain alkyl group (with, for example, 6 or more, 8 or more, or 9 or more carbon atoms) or a straight-chain alkenyl group (with, for example, 6 or more, 8 or more, or 9 or more carbon atoms). R c and R d Each can independently have substituents, or it can be without substituents. R c and R d The upper limit for the number of carbon atoms is, for example, below 48, below 44, below 40, or below 36.

[0060] In some embodiments, the hydrocarbon group (X) comprises at least one group selected from the groups shown in formula (GA4) and formula (GA5). The hydrocarbon group (X) preferably comprises the group shown in formula (GA4). When the structural unit (X) comprises at least one group selected from the groups shown in formula (GA4) and formula (GA5), it tends to readily achieve the effects of a low dielectric constant, a low dielectric loss tangent, and a low coefficient of thermal expansion.

[0061] [Chemical Formula 6] In the formula, R d Each can independently represent a straight-chain alkyl group (with, for example, 1 or more, 2 or more, or 3 or more carbon atoms) or a straight-chain alkenyl group (with, for example, 2 or more, 3 or more, or 4 or more carbon atoms). R d Each can independently have substituents, or it can be without substituents. R d The upper limit for the number of carbon atoms is, for example, below 12, below 8, or below 6.

[0062] (Organic group (Y)) The structural unit (X) may contain an organic group (Y). The organic group (Y) is a group containing at least one aromatic ring group. Examples of aromatic ring groups include aromatic hydrocarbon groups and aromatic heterocyclic compound groups. The organic group (Y) may, for example, contain at least one group selected from aromatic hydrocarbon groups, aromatic heterocyclic compound groups, and groups composed of two or more of these. The organic group (Y) preferably contains an aromatic hydrocarbon group. The organic group (Y) may be an organic group that does not contain a non-aromatic hydrocarbon group. The organic group (Y) may further contain a non-aromatic hydrocarbon group, a linking group containing a heteroatom, a substituent containing a heteroatom, etc. The organic group (Y) may, for example, be a group with a 1 to 4 valence. The structural unit (X) preferably contains an organic group (Y) with a 2 to 4 valence, more preferably contains an organic group (Y) with a 2 or 4 valence, and even more preferably contains an organic group (Y) with a 4 valence.

[0063] The organic group (Y) preferably contains the group shown in the following formula (G11).

[0064] [Chemical Formula 7] in the formula, R y represents an organic group (Y).

[0065] The organic group (Y) more preferably contains at least one selected from a group represented by the following formula (G12) and a group represented by the following formula (G14b).

[0066] [Chemical Formula 8] 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. L represents a single bond or a linking group containing a hetero atom (except for imide group and amide acid group). R e Each independently can have a substituent, or can not have a substituent.

[0067] In the case where the block copolymer has a group represented by the formula (G12), there is a tendency that the glass transition temperature of the polyimide is increased. In the case where the block copolymer has at least one selected from a group represented by the formula (G13) (L is a single bond) and a group represented by the formula (G14b) (L is a single bond), it is possible to introduce a rigid structure in the polyimide. In the case where the block copolymer has at least one selected from a group represented by the formula (G13) (L is a linking group containing a hetero atom) and a group represented by the formula (G14b) (L is a linking group containing a hetero atom), there is a tendency that it is possible to maintain good solubility to a solvent. In the case where the block copolymer has at least one selected from a group represented by the formula (G13) (L is an oxygen group or a carbonyl group) and a group represented by the formula (G14b) (L is an oxygen group or a carbonyl group), there is a tendency that it is possible to introduce an ether bond or a carbonyl bond in the block chain, and the dielectric constant and the dielectric loss tangent are easily small. The block copolymer can contain a group represented by the formula (G14a) (L is an oxo carbonyl group) without containing at least one selected from a group represented by the formula (G13) (L is an oxygen group or a carbonyl group) and a group represented by the formula (G14b) (L is an oxygen group or a carbonyl group), or can contain a group represented by the formula (G14a) (L is an oxo carbonyl group) in addition to containing at least one selected from a group represented by the formula (G13) (L is an oxygen group or a carbonyl group) and a group represented by the formula (G14b) (L is an oxygen group or a carbonyl group).

[0068] As examples of the structural unit (X), there are mentioned the structural unit represented by the formula (XI) and the structural unit represented by the formula (XA) described later. In a preferred embodiment, the structural unit (X) contains at least one selected from the group consisting of the structural unit represented by the formula (XI) and the structural unit represented by the formula (XA). As examples of the structural unit (X), there are mentioned the structural unit (Xd) described later. In a preferred embodiment, the structural unit (X) contains the structural unit (Xd).

[0069] (structural unit (Y)) The block copolymer can contain a structural unit (Y). The structural unit (Y) is a structural unit different from the structural unit (X) contained in the block copolymer. The structural unit (Y) can have, for example, the organic group (Y) described above. The structural unit (Y) can further contain at least one of an imide group and an amide acid group. For example, the structural unit (Y) is a structural unit containing the organic group (Y) and either an imide group or an amide acid group. The block copolymer can contain, in the polymer chain, the organic group (Y) and either an imide group or an amide acid group contained in the structural unit (Y). The structural unit (Y) can contain one or two or more kinds of the organic group (Y).

[0070] Among the structural unit (Y), the organic group (Y) preferably contains the group represented by the formula (G11) and the group represented by the formula (G15) described above, more preferably at least one selected from the group consisting of the group represented by the formula (G12) to the group represented by the formula (G14b) and at least one selected from the group consisting of the group represented by the formula (G16) to the group represented by the formula (G19).

[0071] [Chemical Formula 9] In the formula, R y represents an organic group (Y). R e Each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic compound group, preferably an aromatic hydrocarbon group, more preferably a phenyl group. R e Each independently can have a substituent, or can not have a substituent. As R e Examples of the substituent that can be present include a non-aromatic hydrocarbon group and a heteroatom-containing substituent. R f represents a linear or branched saturated aliphatic hydrocarbon group, or a linear or branched unsaturated aliphatic hydrocarbon group. R f The carbon number of R

[0072] L represents a single bond or a linking group containing a heteroatom (excluding an imide group and an amide acid group).

[0073] In some embodiments, in the case where the organic group (Y) contains a non-aromatic hydrocarbon group, the total number of carbons of the non-aromatic hydrocarbon group can be less than the total number of carbons of the aromatic ring group from the viewpoint of low thermal expansion rate. The total number of carbons of the non-aromatic hydrocarbon group is, for example, 8 or less, 6 or less, 4 or less, or 2 or less.

[0074] In the case where the block copolymer has a group represented by Formula (G16), there is a tendency that the thermal expansion rate of the polyimide can be suppressed to be low. In the case where the block copolymer has at least one selected from a group represented by Formula (G17) (L is a single bond) to a group represented by Formula (G18b) (L is a single bond), there is a tendency that the polyimide can be introduced with a rigid structure, and the thermal expansion rate easily becomes small. In the case where the block copolymer has at least one selected from a group represented by Formula (G17) (L is a linking group containing a hetero atom) to a group represented by Formula (G18b) (L is a linking group containing a hetero atom), there is a tendency that good solubility to a solvent can be maintained. In the case where the block copolymer has at least one selected from a group represented by Formula (G17) (L is an oxy group or a carbonyl group) to a group represented by Formula (G18b) (L is an oxy group or a carbonyl group), an ether bond or a carbonyl bond can be introduced in the block chain. In the case where the block copolymer has a group represented by Formula (G17) (L is a single bond, R e In the case where one or both of the group represented by Formula (G17) and the group represented by Formula (G18b) have a non-aromatic hydrocarbon group as a substituent, a rigid structure can be introduced in the polyimide, and the free volume can be increased.

[0075] As examples of the structural unit (Y), a structural unit represented by Formula (YI) and a structural unit represented by Formula (YA) described later can be given. In a preferred embodiment, the structural unit (Y) contains at least one selected from a structural unit represented by Formula (YI) and a structural unit represented by Formula (YA). As examples of the structural unit (Y), a structural unit (Yd) described later can be given. In a preferred embodiment, the structural unit (Y) contains the structural unit (Yd).

[0076] [Block copolymer containing a structural unit represented by Formula (I) and / or a structural unit represented by Formula (A)] In some embodiments, the block copolymer contains a polyimide block (BI) and a polyamide acid block (BA), and contains a structural unit represented by the following Formula (I) and a structural unit represented by the following Formula (A). A and different from the following R C and different from the following R B and different from the following R D .

[0077] (structural unit represented by Formula (I)) [Chemical Formula 10] in the formula, R A and R B each independently represents an organic group.

[0078] (structural unit represented by formula (A)) [Chemical Formula 11] in the formula, R C and R D each independently represents an organic group.

[0079] As examples of the organic group, a hydrocarbon group (X) and an organic group (Y) can be given.

[0080] As examples of the structural unit represented by formula (I), a structural unit represented by the following formula (XI) and a structural unit represented by the following formula (YI) can be given. As examples of the structural unit represented by formula (A), a structural unit represented by the following formula (XA) and a structural unit represented by the following formula (YA) can be given. The polyimide block (BI) contains the structural unit represented by formula (I), and the polyamic acid block (BA) contains the structural unit represented by formula (A).

[0081] In some embodiments, the block copolymer contains a polyimide block (BI) and a polyamic acid block (BA), and contains at least one structural unit selected from a structural unit represented by the following formula (XI) and a structural unit represented by the following formula (XA). As examples of the block copolymer, a block copolymer in which the polyimide block (BI) contains a structural unit represented by formula (XI) can be given; a block copolymer in which the polyamic acid block (BA) contains a structural unit represented by formula (XA) can be given; a block copolymer in which the polyimide block (BI) contains a structural unit represented by formula (XI) and the polyamic acid block (BA) contains a structural unit represented by formula (XA) can be given; and the like.

[0082] The block copolymer can contain a structural unit other than the structural unit represented by the following formula (XI) and the structural unit represented by the following formula (XA). As examples of the structural unit other than the structural unit represented by formula (XI) and the structural unit represented by formula (XA), a structural unit represented by the following formula (YI) and a structural unit represented by the following formula (YA) can be given. The block copolymer can contain at least one structural unit selected from a structural unit represented by formula (YI) and a structural unit represented by formula (YA). The structural unit represented by formula (YI) and the structural unit represented by formula (YA) can be a structural unit having no hydrocarbon group (X).

[0083] The structural unit represented by formula (XI) and the structural unit represented by formula (XA) are structural units belonging to structural unit (X), and as examples of the structural unit represented by formula (XI) and the structural unit represented by formula (XA), the structural unit (Xd) described later can be given. The structural unit represented by formula (YI) and the structural unit represented by formula (YA) are structural units belonging to structural unit (Y), and as examples of the structural unit represented by formula (YI) and the structural unit represented by formula (YA), the structural unit (Yd) described later can be given.

[0084] (The structural unit represented by formula (XI)) [Chemical Formula 12] In the formula, R 1 and R 2 each independently represent an organic group, R 1 and R 2 at least one of R 1 is a hydrocarbon group (X).

[0085] As examples of the organic group, a hydrocarbon group (X) and an organic group (Y) can be given.

[0086] In the structural unit represented by formula (XI), for example, R 1 is a hydrocarbon group (X), and 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), and R 2 is a group selected from the group represented by formula (G12) to the group represented by formula (G14b); more preferably R 1 is a group selected from the group represented by formula (G4) and the group represented by formula (G7) to the group represented by formula (G9), and R 2 is a group selected from the group represented by formula (G12) and the group represented by formula (G13); further preferably R 1 is the group represented by formula (G8), and R 2 is the group represented by formula (G13); particularly preferably R 1 is the group represented by formula (G8), and R 2 is the group represented by formula (G13) (for example, in the formula, R e is a phenyl group, and L is a carbonyl group).

[0087] (The structural unit represented by formula (XA)) [Chemical Formula 13] In the formula, R 3 and R 4 each independently represent an organic group, R 3 and R4 At least one of them is a hydrocarbon group (X).

[0088] Examples of organic groups include hydrocarbon groups (X) and organic groups (Y).

[0089] In the structural unit shown in equation (XA), for example R 3 For hydrocarbon group (X), R 4 It is an organic group (Y); preferably R 3 R is a group selected from the groups shown in formula (G2) to the groups shown in formula (G6). 4 The group is selected from the group shown in formula (G12) to the group shown in formula (G14b); more preferably, R 3 R is a group selected from the groups shown in (G4) and (G7) to (G9). 4 The group is selected from the groups shown in formula (G12) and formula (G13); R is further preferred. 3 For the group represented by formula (G8), R 4 The group is represented by formula (G13); R is particularly preferred. 3 For the group represented by formula (G8), R 4 The group represented by formula (G13) (e.g., R in the formula) e (where L is phenyl and L is carbonyl).

[0090] In the structural unit shown in equation (XA), for example R 3 For hydrocarbon group (X), R 4 It is an organic group (Y); preferably R 3 R is a group selected from the groups shown in formulas (GA1) to (GA3b). 4 The group is selected from the group shown in formula (G12) to the group shown in formula (G14b); more preferably, R 3 For the group shown as (GA3a), R 4 The group is selected from the group shown in formula (G13) and the group shown in formula (G14a); R is further preferred. 3 R is a group selected from the groups shown in formula (GA4) and formula (GA5). 4 The group is selected from the group shown in formula (G13) and the group shown in formula (G14a); R is particularly preferred. 3 R is the group represented by formula (GA4). 4 For groups selected from those shown in formula (G13) (e.g., R in the formula) e (where L is a single bond) and groups represented by formula (G14a) (e.g., R in the formula) e (where L is a phenyl group and L is a carbonyl group)

[0091] (structural unit represented by formula (YI)) [Chemical Formula 14] in the formula, R 5 and R 6 each independently represents an organic group (Y).

[0092] In the structural unit represented by formula (YI), for example, R 5 is a group selected from the group represented by formula (G16) to the group represented by formula (G19), R 6 is a group selected from the group represented by formula (G12) to the group represented by formula (G14b); preferably R 5 is the group represented by formula (G16), the group represented by formula (G17), or the group represented by formula (G18), R 6 is the group represented by formula (G12) or the group represented by formula (G13); more preferably R 5 is the group represented by formula (G16) (for example, the group in the formula where R e is a phenyl group), the group represented by formula (G17) (for example, the group in the formula where R e is a phenyl group), or the group represented by formula (G18b) (for example, the group in the formula where R e is a phenyl group, and L is an oxygen group), R 6 is the group represented by formula (G12) (for example, the group in the formula where R e is a phenyl group), or the group represented by formula (G13) (for example, the group in the formula where R e is a phenyl group, and L is a single bond).

[0093] (structural unit represented by formula (YA)) [Chemical Formula 15] in the formula, R 7 and R 8 each independently represents an organic group (Y).

[0094] In the structural unit represented by formula (YA), for example, R 7 is a group selected from the group represented by formula (G16) to the group represented by formula (G19), R 8 is a group selected from the group represented by formula (G12) to the group represented by formula (G14b); preferably R 7 is the group represented by formula (G16), the group represented by formula (G17), or the group represented by formula (G18a), R 8 is the group represented by formula (G12) or the group represented by formula (G13); more preferably R 7 is the group represented by formula (G16) (for example, the group in the formula where R ea group represented by formula (G17) (e.g., a group in which R e a group represented by formula (G18b) (e.g., a group in which R e a group represented by formula (G18b) (e.g., a group in which R 8 a group represented by formula (G12) (e.g., a group in which R e a group represented by formula (G13) (e.g., a group in which R e a group represented by formula (G13) (e.g., a group in which R

[0095] (Examples of block copolymer) In a preferred embodiment, the block copolymer satisfies any one or two or more of the following.

[0096] • The block copolymer contains at least one of a structural unit selected from formula (XI) (in which R 1 and at least one of R 2 is the group (X) and is a group having a total carbon number of 9 or more of the at least one non-aromatic hydrocarbon group.) and a structural unit represented by formula (XA) (in which R 3 and at least one of R 4 is the group (X) and is a group having a total carbon number of 9 or more of the at least one non-aromatic hydrocarbon group).

[0097] • The block copolymer contains at least one of a structural unit selected from formula (YI) (in which R 5 and R 6 each independently is a group containing an aromatic hydrocarbon group) and a structural unit represented by formula (YA) (in which R 7 and R 8 each independently is a group containing an aromatic hydrocarbon group).

[0098] • The block copolymer contains at least one of a structural unit selected from formula (XI) (in which R 1 is the above group (X)) and a structural unit represented by formula (XA) (in which R 3 is the group (X).

[0099] • The block copolymer contains at least one of a structural unit selected from formula (YI) (in which R 5 is a group containing an aromatic hydrocarbon group) and a structural unit represented by formula (YA) (in which R 7 is a group containing an aromatic hydrocarbon group).

[0100] • The block copolymer contains a structural unit represented by formula (XI) (in which R 1 is the above group (X)), and a structural unit represented by formula (YA) (in which R 7 is a group containing an aromatic hydrocarbon group).

[0101] • the block copolymer contains structural units represented by formula (XI) (wherein R 5 is a group containing an aromatic hydrocarbon group) and structural units represented by formula (XA) (wherein R 3 is the above group (X)).

[0102] • the block copolymer contains structural units represented by formula (XI) (wherein R 1 is the above group (X)) and structural units represented by formula (XA) (wherein R 3 is the above group (X)).

[0103] • the polyimide block (BI) preferably contains structural units represented by formula (XI), more preferably structural units represented by formula (XI) in which the hydrocarbon group (X) contains a saturated alicyclic hydrocarbon group.

[0104] • the polyamic acid block (BA) preferably contains structural units represented by formula (YA), more preferably structural units represented by formula (YA) in which the organic group (Y) contains an aromatic hydrocarbon group.

[0105] (Content ratio, etc.) In the polyimide block (BI), the content ratio of the hydrocarbon group (X) is preferably 0 to 70 mass%, 10 to 60 mass%, or 20 to 50 mass%, based on the total mass of R 1 ~R 8 . In particular, in the case where the content ratio 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. In the polyimide block (BI), the content ratio of the organic group (Y) is preferably 0 to 60 mass%, 2 to 50 mass%, or 4 to 40 mass%, based on the total mass of R 1 ~R 8 . In particular, in the case where the content ratio of the organic group (Y) containing an aromatic hydrocarbon group is 4 mass% or more, a polyimide having a low thermal expansion rate is easily obtained. In the present disclosure, according to the structure contained in the block or polymer, any one or more of R 1 ~R 8 in the "total mass of R 1 ~R 8 " can be 0.

[0106] In the polyamic acid block (BA), the content ratio of the hydrocarbon group (X) is preferably 0 to 80 mass%, 0 to 50 mass%, or 0 to 30 mass%, based on the total mass of R 1 ~R 8 . In the polyamic acid block (BA), the content ratio of the organic group (Y) is preferably 0 to 80 mass%, 0 to 50 mass%, or 0 to 30 mass%, based on the total mass of R 1 ~R 8The 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 block copolymer. Particularly in the case where the content of the organic group (Y) containing an aromatic hydrocarbon group is 40 mass% or more, it is easy to obtain a polyimide having a low thermal expansion rate.

[0107] In the block copolymer, the content of the hydrocarbon group (X) is preferably 5 to 70 mass%, 10 to 60 mass%, or 20 to 50 mass% based on the total mass of the block copolymer. The content of the hydrocarbon group (X) is preferably large from the viewpoint of reducing the dielectric constant and the dielectric loss tangent. Particularly in the case where the content of the hydrocarbon group (X) is 10 mass% or more, it is easy to obtain a polyimide having a low dielectric constant and a low dielectric loss tangent. 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 block copolymer. Particularly in the case where the content of the organic group (Y) containing an aromatic hydrocarbon group is 40 mass% or more, it is easy to obtain a polyimide having a low thermal expansion rate.

[0108] In the block copolymer, the content of the hydrocarbon group (X) is preferably 5 to 70 mass%, 10 to 60 mass%, or 20 to 50 mass% based on the total mass of the block copolymer. The content of the hydrocarbon group (X) is preferably large from the viewpoint of reducing the dielectric constant and the dielectric loss tangent. Particularly in the case where the content of the hydrocarbon group (X) is 10 mass% or more, it is easy to obtain a polyimide having a low dielectric constant and a low dielectric loss tangent. 1 ~R 8 The content of the organic group (Y) is preferably 30 to 95 mass%, 40 to 90 mass%, or 50 to 80 mass% based on the total mass of the block copolymer. The organic group (Y) preferably contains an aromatic hydrocarbon group from the viewpoint of obtaining a low thermal expansion rate, and the content of such an organic group (Y) is preferably large. Particularly in the case where the content of the organic group (Y) containing an aromatic hydrocarbon group is 50 mass% or more, it is easy to obtain a polyimide having a low thermal expansion rate.

[0109] For example, in the case where R 1 ~R 8 contains a group (for example, group 14 of Table 1) belonging only to the hydrocarbon group (X), and a group (for example, group 5 of Table 1) belonging to both the hydrocarbon group (X) and the organic group (Y), the content of the above-described hydrocarbon group (X) can be set to the content of the "group belonging only to the hydrocarbon group (X)", and the content of the above-described organic group (Y) can be set to the content of the "group belonging to both the hydrocarbon group (X) and the organic group (Y)". In the case where R 1 ~R 8In the case of a group that belongs to both the hydrocarbon group (X) and the organic group (Y) (for example, Group 5 of Table 1) and a group that belongs only to the organic group (Y) (for example, Group 1 of Table 1), the content of the above hydrocarbon group (X) can be applied as the content of the "group that belongs to both the hydrocarbon group (X) and the organic group (Y)", and the content of the above organic group (Y) can be applied as the content of the "group that belongs only to the organic group (Y)". Alternatively, for example, the content of the above hydrocarbon group (X) can be applied as the content of the "hydrocarbon group (X) having a total carbon number of n or more (for example, 9 or more) of non-aromatic hydrocarbon groups", and the content of the above organic group (Y) can be applied as the content of the "organic group (Y) having a total carbon number of n-1 or less (for example, 0 to 8) of non-aromatic hydrocarbon groups".

[0110] (Any structural unit) The block copolymer can further include any other structural unit in addition to the structural unit represented by Formula (I) and the structural unit represented by Formula (A). The content of the other any structural unit in the block copolymer is, for example, 0 to 10% by mass or 0 to 5% by mass, based on the total mass of all the structural units included in the block copolymer. As the other any structural unit, for example, a structural unit derived from a polyamine having a functionality of 3 or more, a structural unit derived from a polyisocyanate having a functionality of 3 or more, a structural unit having an amide bond (also referred to as an amide group), a structural unit having an imide group and an amide group, a structural unit having an amic acid group and an amide group, and the like can be included. These any structural units can include the hydrocarbon group (X), or can not include the hydrocarbon group (X).

[0111] [Block copolymer including a structure derived from a diamine or a diisocyanate and a structure derived from a tetracarboxylic dianhydride] In some embodiments, the block copolymer includes a polyimide block (BI) and a polyamide acid block (BA), and has a structure derived from a diamine or a diisocyanate and a structure derived from a tetracarboxylic dianhydride.

[0112] In some embodiments, at least one of the structure derived from a diamine or a diisocyanate and the structure derived from a tetracarboxylic dianhydride includes a structure having a hydrocarbon group (X). As examples of the 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 given. In the present disclosure, "diamine or diisocyanate" means "at least one compound selected from a diamine and a diisocyanate".

[0113] In some embodiments, the structure derived from a diamine or diisocyanate and the structure derived from a tetracarboxylic dianhydride include a structure having an organic group (Y). As examples of the structure having an organic group (Y), there can be mentioned structures derived from a diamine or diisocyanate having an organic group (Y) and structures derived from a tetracarboxylic dianhydride having an organic group (Y).

[0114] In the present disclosure, a structural unit having a structure derived from a diamine or diisocyanate and a structure derived from a tetracarboxylic dianhydride, and at least one of the structure derived from a diamine or diisocyanate and the structure derived from a tetracarboxylic dianhydride including a structure having a hydrocarbon group (X) is sometimes referred to as "structural unit (Xd)".

[0115] (Diamine having a hydrocarbon group (X)) The diamine having a hydrocarbon group (X) can be represented by the following formula (Ax), for example.

[0116] [Chemical Formula 16] In the formula, R x represents a hydrocarbon group (X). As examples of R x , there can be mentioned the group represented by formula (G2) to the group represented by formula (G9) and the group represented by formula (GAl) to the group represented by formula (GA3b) described above.

[0117] As specific examples of the diamine having a hydrocarbon group (X), there can be mentioned the following.

[0118] 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,14-diaminotetradecane, 1,16-diaminohexadecane and the like diamines having a saturated aliphatic hydrocarbon group; 1,9-diaminononene, 1,10-diaminodecene, 1,11-diaminoundecene, 1,12-diaminododecene, 1,14-diaminotetradecene, 1,16-diaminohexadecene and the like diamines having an unsaturated aliphatic hydrocarbon group; 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophorone diamine, bis(aminomethyl)norbornane, 1,3-diaminoadamantane, 4,4'-diaminodicyclohexylmethane and the like diamines having a saturated alicyclic hydrocarbon group; bis(aminomethyl)norbornene, 4,4'-diaminodicyclohexenylmethane and the like diamines having an unsaturated alicyclic hydrocarbon group; diamines derived from dimers (also referred to as dimer acids) of monounsaturated fatty acids such as phytanic acid, myristoleic acid, palmitoleic acid, cis-6-hexadecenoic acid, oleic acid, elaidic acid, frans-vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid; diunsaturated fatty acids such as linoleic acid, eicosadienoic acid, docosadienoic acid; triunsaturated fatty acids such as linolenic acid, pinoic acid, eleostearic acid, midellic acid, dihomo-γ-linolenic acid, parinaric acid; and diamines and dimer diamines as compounds in which carbon-carbon double bonds contained in these diamines are hydrogenated; 4,4'-diamino-2,2'-dimethylbiphenyl (m-tolidine), 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethyldiphenyl ether, 4,4'-diaminodiphenyl methane, 4,4'-diamino-3,3'-dimethyldiphenyl methane, 4,4'-diaminodiphenyl propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, and the like, diamines having both non-aromatic hydrocarbon groups and aromatic hydrocarbon groups As commercially available products of dimer diamines, for example, "PRIAMINE 1075", "PRIAMINE 1074", and the like manufactured by Croda Japan K.K. can be given.

[0119] (Diamines having an organic group (Y)) The diamine having an organic group (Y) can be represented by the following formula (Ay), for example.

[0120] [Chemical Formula 17] In the formula, R y represents an organic group (Y). As examples of R y , the groups represented by the formula (G16) to the group represented by the formula (G19) described above can be given.

[0121] As specific examples of the diamine having an organic group (Y), the following can be given.

[0122] 1,4-diaminobenzene, 4,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, and the like, diamines having an aromatic hydrocarbon group and not having a non-aromatic hydrocarbon group; the above-described examples of diamines having both a non-aromatic hydrocarbon group and an aromatic hydrocarbon group (Diisocyanates having a hydrocarbon group (X)) The diisocyanate having a hydrocarbon group (X) can be represented by the following formula (Ix), for example.

[0123] [Chemical Formula 18] wherein R x represents a hydrocarbon group (X). As examples of R x , the above-mentioned group represented by formula (G2) to the group represented by formula (G9), and the group represented by formula (GA1) to the group represented by formula (GA3b) can be given.

[0124] As specific examples of the diisocyanate having the hydrocarbon group (X), compounds having the same structure as the compounds represented by the above-mentioned specific examples of the diamine except that the amino group is replaced by the isocyanate group can be given.

[0125] (Diisocyanate having organic group (Y)) The diisocyanate having the organic group (Y) can be represented by, for example, the following formula (Iy).

[0126] [Chemical Formula 19] wherein R y represents an organic group (Y). As examples of R y , the above-mentioned group represented by formula (G16) to the group represented by formula (G19) can be given.

[0127] As specific examples of the diisocyanate having the organic group (Y), compounds having the same structure as the compounds represented by the above-mentioned specific examples of the diamine except that the amino group is replaced by the isocyanate group can be given.

[0128] (Tetracarboxylic dianhydride having hydrocarbon group (X)) The tetracarboxylic dianhydride having the hydrocarbon group (X) can be represented by, for example, the following formula (Cx).

[0129] [Chemical Formula 20] wherein R x represents a hydrocarbon group (X). The hydrocarbon group (X) is preferably, for example, as described above.

[0130] As specific examples of the tetracarboxylic dianhydride having the hydrocarbon group (X), the following can be given. In the tetracarboxylic dianhydride, the "carbon number" does not include the carbon number contained in the carboxylic anhydride group in the case where the carbon number of the hydrocarbon group (X) is counted.

[0131] 1,2,3,4-Butanetetracarboxylic dianhydride, 1,2,5,6-hexanetetracarboxylic dianhydride, and the like tetracarboxylic dianhydride having a saturated aliphatic hydrocarbon group; 1,2,3,4-Cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxylatocyclohexyl)propanedionic anhydride, and the like tetracarboxylic dianhydride having an alicyclic hydrocarbon group; bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, and the like (tetracarboxylic dianhydride having an organic group (Y)) The tetracarboxylic dianhydride having an organic group (Y) can be represented by the following formula (Cy), for example.

[0132] [Chemical Formula 21] In the formula, R y represents an organic group (Y). As examples of R y , the groups represented by the formulae (G12) to (G14b) described above can be given.

[0133] As specific examples of the tetracarboxylic dianhydride having an organic group (Y), the following can be given.

[0134] phthalic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,4'-oxydiphthalic dianhydride, bis(l,3-dioxo-l,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene ester, and the like, which have an aromatic hydrocarbon group and do not have a non-aromatic hydrocarbon group; pyridine tetracarboxylic dianhydride, thiophene tetracarboxylic dianhydride, and the like, which have an aromatic heterocyclic compound group and do not have a non-aromatic hydrocarbon group; the above-described examples of the tetracarboxylic dianhydride having an aromatic hydrocarbon group and a non-aromatic hydrocarbon group (examples of block copolymers) In the preferred embodiments, the block copolymer satisfies any one or two or more of the following.

[0135] • In the block copolymer, the structure derived from the diamine or diisocyanate preferably includes a structure derived from a diamine or diisocyanate having a hydrocarbon group (X); more preferably includes at least one selected from the group consisting of a structure derived from a diamine or diisocyanate having a saturated aliphatic hydrocarbon group, a structure derived from a diamine or diisocyanate having an unsaturated aliphatic hydrocarbon group, a structure derived from a diamine or diisocyanate having a saturated alicyclic hydrocarbon group, a structure derived from a diamine or diisocyanate having an unsaturated alicyclic hydrocarbon group, and a structure derived from a dimer diamine or dimer diisocyanate; further preferably includes a structure derived from a dimer diamine or dimer diisocyanate.

[0136] • In the block copolymer, the structure derived from the diamine or diisocyanate preferably contains a structure derived from a diamine or diisocyanate having a hydrocarbon group (X) having a total carbon number of 9 or more having at least one non-aromatic hydrocarbon group; more preferably contains at least one selected from a structure derived from a diamine or diisocyanate having a saturated aliphatic hydrocarbon group having a carbon number of 9 or more, a structure derived from a diamine or diisocyanate having an unsaturated aliphatic hydrocarbon group having a carbon number of 9 or more, a structure derived from a diamine or diisocyanate having a saturated alicyclic hydrocarbon group having a carbon number of 9 or more, a structure derived from a diamine or diisocyanate having an unsaturated alicyclic hydrocarbon group having a carbon number of 9 or more, and a structure derived from a dimer diamine or dimer diisocyanate having a carbon number of 9 or more; further preferably contains a structure derived from a dimer diamine or dimer diisocyanate having a carbon number of 9 or more. The structure derived from the diamine or diisocyanate can contain a structure derived from m-tolidine.

[0137] • In the block copolymer, the structure derived from the diamine or diisocyanate preferably contains a structure derived from a dimer diamine or dimer diisocyanate, and a structure derived from a diamine or diisocyanate having a saturated aliphatic hydrocarbon group (excluding the dimer diamine or dimer diisocyanate); more preferably contains a structure derived from a dimer diamine or dimer diisocyanate having a carbon number of 9 or more, and a structure derived from m-tolidine.

[0138] • In the block copolymer, the structure derived from the tetracarboxylic dianhydride preferably contains a structure derived from a tetracarboxylic dianhydride having an organic group (Y), more preferably contains a structure derived from a tetracarboxylic dianhydride having an aromatic hydrocarbon group, further preferably contains at least one selected from a structure derived from pyromellitic dianhydride, a structure derived from 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and a structure derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0139] • In the block copolymer, at least one of the structure derived from the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride contains a structure having a group (X) containing at least one non-aromatic hydrocarbon group and having a total carbon number of 9 or more.

[0140] • In the block copolymer, the structure derived from the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride contain a structure having a group (Y) which is an organic group and an aromatic ring group which is an aromatic hydrocarbon group.

[0141] • In the block copolymer, the structure derived from the diamine or diisocyanate contained in, for example, the polyimide block (BI) contains a structure having a group (X) containing at least one non-aromatic hydrocarbon group.

[0142] • In the block copolymer, the structure derived from a diamine or diisocyanate included in the polyimide block (BI) and the structure derived from a diamine or diisocyanate included in the polyamide acid block (BA) both include a structure having a group (X) including at least one non-aromatic hydrocarbon group.

[0143] • In the block copolymer, the structure derived from a diamine or diisocyanate included in the polyimide block (BI) and the structure derived from a diamine or diisocyanate included in the polyamide acid block (BA) both include a structure having a group (X) including at least one non-aromatic hydrocarbon group.

[0144] • In the block copolymer, at least the structure derived from a diamine or diisocyanate includes: a structure derived from a diamine or diisocyanate having a hydrocarbon group (X); and a structure having an organic group (Y) in which an aromatic ring group is an aromatic hydrocarbon group.

[0145] • The block copolymer includes a structure derived from a dimer diamine or a dimer diisocyanate.

[0146] • The block copolymer includes a structure derived from m-tolidine.

[0147] • The block copolymer includes a structure derived from at least one selected from the group consisting of 4,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diisocyanatodiphenyl ether, 1,4-bis(4-isocyanatophenoxy)benzene, and 4,4'-bis(4-isocyanatophenoxy)biphenyl.

[0148] (Content rate, etc.) In the polyimide block (BI), the content rate of the structure having a 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 a diamine or diisocyanate and the structure derived from a tetracarboxylic dianhydride. Particularly in the case where the content rate of the structure having a 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 rate of the structure having an 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 a diamine or diisocyanate and the structure derived from a tetracarboxylic dianhydride. Particularly in the case where the content rate of the structure having an organic group (Y) including an aromatic hydrocarbon group is 10% by mass or more, a polyimide having a low thermal expansion rate is easily obtained.

[0149] In the polyamic acid block (BA), the content ratio of the structure having the hydrocarbon group (X) is preferably 3 to 60 mass%, 5 to 50 mass%, or 10 to 40 mass%, based on the total mass of the structure derived from the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride. From the viewpoint of lowering the dielectric constant and the dielectric loss tangent, the content ratio of the structure having the hydrocarbon group (X) is preferably large. Particularly, in the case where the content ratio of the structure having the hydrocarbon group (X) is 5 mass% or more, it is easy to obtain a polyimide having a low dielectric constant and a low dielectric loss tangent.

[0150] In the block copolymer, the content ratio of the structure having the organic group (Y) is preferably 40 to 97 mass%, 50 to 95 mass%, or 60 to 90 mass%, based on the total mass of the structure derived from the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride. From the viewpoint of obtaining a low thermal expansion rate, the organic group (Y) preferably contains an aromatic hydrocarbon group, and the content ratio of the structure having such an organic group (Y) is preferably large. Particularly, in the case where the content ratio of the structure having the organic group (Y) containing an aromatic hydrocarbon group is 50 mass% or more, it is easy to obtain a polyimide having a low thermal expansion rate.

[0151] In the block copolymer, the content ratio of the structure having the organic group (Y) is preferably 40 to 97 mass%, 50 to 95 mass%, or 60 to 90 mass%, based on the total mass of the structure derived from the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride. From the viewpoint of obtaining a low thermal expansion rate, the organic group (Y) preferably contains an aromatic hydrocarbon group, and the content ratio of the structure having such an organic group (Y) is preferably large. Particularly, in the case where the content ratio of the structure having the organic group (Y) containing an aromatic hydrocarbon group is 50 mass% or more, it is easy to obtain a polyimide having a low thermal expansion rate.

[0152] As for the content ratio of the structure having the hydrocarbon group (X) and the content ratio of the structure having the organic group (Y), the same applies to the block copolymer as R 1 ~R 8 Likewise, it is classified as "a group belonging only to the hydrocarbon group (X)", "a group belonging to the hydrocarbon group (X) and the organic group (Y)", or "a group belonging only to the organic group (Y)", and the like, or is distinguished by the number of carbons of the non-aromatic hydrocarbon group and is applied to the block copolymer.

[0153] (Structure) The block copolymer can further include another arbitrary structure in addition to the structure derived from the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride. The content of the other arbitrary structure unit in the block copolymer is, for example, 0 to 10% by mass or 0 to 5% by mass, based on the total mass of all structures included in the block copolymer. As the other arbitrary structure, a structure derived from a polyamine or polyisocyanate having a functionality of 3 or more, a structure derived from a dicarboxylic acid compound, a structure derived from a tricarboxylic acid compound, or the like can be included. These arbitrary structures can include the hydrocarbon group (X) or can not include the hydrocarbon group (X).

[0154] [Block copolymer obtained using diamine or diisocyanate and tetracarboxylic dianhydride] In some embodiments, the block copolymer is a block copolymer obtained using a polyimide (PI) obtained using a diamine or diisocyanate and a tetracarboxylic dianhydride and a polyamic acid (PA) obtained using a diamine and a tetracarboxylic dianhydride. In some embodiments, at least one selected from the diamine or diisocyanate and the tetracarboxylic dianhydride used to obtain the above-described polyimide (PI) and the diamine and the tetracarboxylic dianhydride used to obtain the above-described polyamic acid (PA) can have a hydrocarbon group (X). The method of obtaining the polyimide (PI), the polyamic acid (PA), and the block copolymer is described later.

[0155] [Polyimide block (BI)] By the block copolymer having the polyimide block (BI), it is possible to prevent the occurrence of a cross-linking reaction or the formation of cross-linking at the time of obtaining the block copolymer or at the time of closing the ring of the amic acid group.

[0156] In the present disclosure, the content of the imide group in the polyimide block (BI) with respect 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 (FTIR).

[0157] The polyimide block (BI) can include the structural unit (X) or can not include the structural unit (X). For example, in the block copolymer, in the case where the polyimide block (BI) does not include the structural unit (X), the polyimide block (BI) includes the structural unit (Y). For example, in the block copolymer, in the case where the polyimide block (BI) does not include the structural unit (X), the polyamic acid block (BA) includes the structural unit (X).

[0158] The number average molecular weight of the polyimide block (BI) is, for example, 500 or more, 1,000 or more, 2,000 or more, or 3,000 or more. The number average molecular weight of the polyimide block (BI) is, for example, 10,000 or less, 8,000 or less, 7,000 or less, or 5,000 or less. When the number average molecular weight is 500 or more, there is a tendency that a polyimide having a small thermal expansion rate is easily obtained. When the number average molecular weight is 10,000 or less, there is a tendency that the solubility of the block copolymer in a solvent is easily ensured. The number average molecular weight of the polyimide block (BI) is, for example, 500 to 10,000, 1,000 to 8,000, 2,000 to 7,000, or 3,000 to 5,000. In the present disclosure, the number average molecular weight can be determined by gel permeation chromatography (GPC) using a standard curve of standard polystyrene. Specifically, it can be obtained by the method described in the examples.

[0159] The polyimide block (BI) can be a linear polymer block, or can also be a branched polymer block, and is preferably a linear polymer block.

[0160] [Polyamide acid block (BA)] By including the polyamide acid block in the block copolymer, there is a tendency that good solubility in a solvent is easily obtained.

[0161] In the present disclosure, the content ratio of the amic acid group with respect to the total of the imide group and the amic acid group in the polyamide acid block (BA) is, for example, more than 50 mol%, 80 mol% or more, or 90 mol% or more. The upper limit of the content ratio of the amic acid group can be 100 mol%. The content ratio can be determined by FTIR.

[0162] The polyamide acid block (BA) can include the structural unit (X), or can also not include the structural unit (X). For example, in the block copolymer, in the case where the polyamide acid block (BA) does not include the structural unit (X), the polyamide acid block (BA) includes the structural unit (Y). For example, in the block copolymer, in the case where the polyamide acid block (BA) does not include the structural unit (X), the polyimide block (BI) includes the structural unit (X).

[0163] The number average molecular weight of the polyamic acid block (BA) is, for example, 500 or more, 1,000 or more, 3,000 or more, or 4,000 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. When the number average molecular weight is 500 or more, there is a tendency that good film formability is easily obtained. When the number average molecular weight is 30,000 or less, there is a tendency that the composition containing the block copolymer and a solvent is easily adjusted 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 4,000 to 10,000.

[0164] The polyamic acid block (BA) can be a linear polymer block, or can be a branched polymer block, and is preferably a linear polymer block.

[0165] [Molecular weight of block copolymer, content of structural unit (X), etc.] By the block copolymer containing the polyimide block (BI) and the polyamic acid block (BA), a polyimide that gives low dielectric constant and low dielectric loss tangent and low thermal expansion rate is easily obtained. It is considered that this is because the polyimide molecules are easily oriented by having a block structure.

[0166] In the block copolymer, only either one of the polyimide block (BI) and the polyamic acid block (BA) contains the hydrocarbon group (X), or both the polyimide block (BI) and the polyamic acid block (BA) contain the hydrocarbon group (X). The polyimide block (BI) and the polyamic acid block (BA) can each independently contain one or two or more kinds of the hydrocarbon group (X). In the block copolymer, only either one of the polyimide block (BI) and the polyamic acid block (BA) contains the organic group (Y), or both the polyimide block (BI) and the polyamic acid block (BA) contain the organic group (Y). The polyimide block (BI) and the polyamic acid block (BA) can each independently contain one or two or more kinds of the organic group (Y).

[0167] In the block copolymer, the organic group (Y) can be a group different from the hydrocarbon group (X) contained in the block copolymer. When exemplified using the groups of Table 1, a block copolymer having any one of the groups selected from groups 7 to 14 and any one of the groups selected from groups 1 to 3 is a block copolymer having a hydrocarbon group (X) and an organic group (Y). A block copolymer having any one of the groups selected from groups 7 to 14 and any one of the groups selected from groups 4 to 6 is a block copolymer having a hydrocarbon group (X) and an organic group (Y). A block copolymer having any one of the groups selected from groups 4 to 6 and any one of the groups selected from groups 1 to 3 is a block copolymer having a hydrocarbon group (X) and an organic group (Y). A block copolymer having group 6 and group 4 is a block copolymer having a hydrocarbon group (X) and an organic group (Y).

[0168] The number average molecular weight of the block copolymer is, for example, 5,000 or more, 10,000 or more, 20,000 or more, or 30,000 or more. The number average molecular weight of the block copolymer is, for example, 100,000 or less, 80,000 or less, 70,000 or less, or 60,000 or less. When the number average molecular weight is 5,000 or more, there is a tendency that a good film formability is easily obtained. When the number average molecular weight is 100,000 or less, there is a tendency that the composition containing the block copolymer and the solvent is easily adjusted to a viscosity suitable for coating. The number average molecular weight of the block copolymer is, for example, 5,000 to 100,000, 10,000 to 80,000, 20,000 to 70,000, or 30,000 to 60,000.

[0169] The content ratio of the polyimide block (BI) in the block copolymer is more than 0 mass% and less than 100 mass% based on the mass of the block copolymer. The content ratio of the polyimide block (BI) is, for example, more than 0 mass%, 30 mass% or more, 60 mass% or more, or 90 mass% or more. The content ratio of the polyimide block (BI) is, for example, less than 100 mass%, 70 mass% or less, 40 mass% or less, or 10 mass% or less. The content ratio of the polyimide block (BI) is, for example, more than 0 mass% and 70 mass% or less, more than 0 mass% and 40 mass% or less, 30 mass% or more and less than 100 mass%, or 60 mass% or more and less than 100 mass%. The content ratio of the polyimide block (BI) is, for example, 30 to 70 mass% or 35 to 65 mass%.

[0170] The content of the polyamic acid block (BA) in the block copolymer is more than 0 mass% and less than 100 mass% based on the mass of the block copolymer. 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 polyamic acid block (BA) is, for example, 30 to 70 mass% or 35 to 65 mass%.

[0171] The greater the content of the polyimide block (BI), the more the occurrence of exchange reactions or the formation of crosslinks can be prevented when the block copolymer is obtained or when the amic acid group is subjected to ring closure. On the other hand, the greater the content of the polyamic acid block (BA), the more easily the block copolymer is dissolved in an organic solvent.

[0172] In the block copolymer, the number average molecular weight of the polyimide block (BI) is, for example, less than the number average molecular weight of the polyamic acid block (BA). It is preferable that the block copolymer contain the polyimide block (BI) and the polyamic acid block (BA) having a number average molecular weight greater than the polyimide block (BI). In the case where the number average molecular weight of the polyimide block (BI) is less than the number average molecular weight of the polyamic acid block (BA), there is a tendency that the block copolymer is easily synthesized and the solubility of the block copolymer can be ensured. By containing the polyamic acid block (BA) having a number average molecular weight greater than the polyimide block (BI), there is a tendency that the block copolymer having a sufficient number average molecular weight is easily synthesized.

[0173] For the block copolymer, it is preferable that the polyimide film obtained using the block copolymer satisfy any one or more of the relative dielectric constant, the dielectric loss tangent, and the thermal expansion rate described later. It is particularly preferable that, for the block copolymer, the polyimide film obtained using the block copolymer satisfy the relative dielectric constant and the dielectric loss tangent described later, or satisfy the relative dielectric constant, the dielectric loss tangent, and the thermal expansion rate described later.

[0174] [Optional Components] In some embodiments, the antenna substrate material can further contain any of a thermoplastic resin, an organic filler, a flame retardant, a flame retardant aid, an ultraviolet absorber, a peroxide, an antioxidant, a photopolymerization initiator, an optical brightener, an adhesion improver, and the like.

[0175] [Properties, Uses, and the Like] In some embodiments, a polyimide material having a low dielectric constant, a low dielectric loss tangent, and a low thermal expansion rate can be obtained using the antenna substrate material. For the antenna substrate material, it is preferable that the polyimide film obtained using the antenna substrate material satisfy any one or more of the relative dielectric constant, the dielectric loss tangent, and the thermal expansion rate described below. It is particularly preferable that, for the antenna substrate material, the polyimide film obtained using the antenna substrate material satisfy the relative dielectric constant and the dielectric loss tangent described below, or satisfy the relative dielectric constant, the dielectric loss tangent, and the thermal expansion rate described below.

[0176] <Method for manufacturing antenna substrate material> In some embodiments, a method for manufacturing an antenna substrate material containing a block copolymer includes a step of obtaining a polyimide (PI) using a diamine or a diisocyanate, and a tetracarboxylic dianhydride; a step of obtaining a polyamic acid (PA) using a diamine and a tetracarboxylic dianhydride; and a step of obtaining a block copolymer using the polyimide (PI) and the polyamic acid (PA). In some embodiments, at least one selected from the diamine or the diisocyanate and the tetracarboxylic dianhydride used to obtain the polyimide (PI), and the diamine and the tetracarboxylic dianhydride used to obtain the polyamic acid (PA) can have a hydrocarbon group (X). According to this method for manufacturing, the antenna substrate material of the above-described embodiments can be easily manufactured.

[0177] The synthesis of the polyimide (PI) and the polyamic acid (PA) can use the above-described monomers such as diamines, diisocyanates, tetracarboxylic dianhydrides, polyamines, polyisocyanates, dicarboxylic acid compounds, and tricarboxylic acid compounds.

[0178] The reaction of the monomers can be performed by solution polymerization. As a solvent at the time of the reaction, for example, polar solvents such as N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), N,N'-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide (MPA), N,N'-dimethylformamide, N,N'-dimethylpropyleneurea [1,3-dimethyl-3,4,5,6-tetrahydro- pyrimidine-2(1H)-one], dimethyl sulfoxide, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and sulfolane; aromatic hydrocarbon solvents such as cyclohexanone, xylene, and toluene; ketone-based solvents such as methyl ethyl ketone and methyl isobutyl ketone; and the like 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).

[0179] The amount of solvent used is preferably 100 to 600 parts by mass, more preferably 200 to 500 parts by mass, relative to 100 parts by mass of the total amount of monomers. By using 100 parts by mass or more of solvent, the monomers can be uniformly reacted. By using 600 parts by mass or less of solvent, the polymerization reaction can be promoted. In addition, by using a small amount of solvent, a polyimide (PI) or polyamic acid (PA)-containing solution containing polyimide (PI) or polyamic acid (PA) at a high concentration can be obtained.

[0180] The reaction temperature when synthesizing polyamic acid using monomers is not particularly limited. The reaction temperature can be, for example, 10 to 50°C, or 20 to 40°C. The reaction time can be, for example, 30 minutes to 24 hours, 1 to 12 hours, or 3 to 6 hours. The reaction product can be sampled, and the number average molecular weight, the concentration of residual amino groups or isocyanate groups, and the like can be measured, to adjust the reaction time in a manner to obtain a desired reaction product.

[0181] The temperature when obtaining polyimide using polyamic acid (i.e., when performing imidization) is not particularly limited. The imidization temperature can be, for example, 120 to 200°C, or 160 to 180°C. The reaction time can be, for example, 30 minutes to 24 hours, 1 to 12 hours, or 3 to 6 hours. The reaction product can be sampled, and the number average molecular weight, the concentration of residual amic acid groups, and the like can be measured, to adjust the reaction time in a manner to obtain a desired reaction product.

[0182] For the reason of easy synthesis, it is preferable that the terminal of the polymer chain of polyimide (PI) is a carboxylic anhydride group, and the terminal of the polymer chain of polyamic acid (PA) is an amino group. The ratio of diamine or diisocyanate to tetracarboxylic dianhydride for obtaining polyimide (PI) is, for example, more than 1.00 mol%, 1.05 mol% or more, or 1.10 mol% or more, based on the diamine or diisocyanate. The ratio of diamine to tetracarboxylic dianhydride for obtaining polyamic acid (PA) is, for example, less than 1.00 mol%, 0.98 mol% or less, or 0.97 mol% or less, based on the diamine.

[0183] A block copolymer is synthesized using polyimide (PI) and polyamic acid (PA). Any polymer can be further used in the synthesis.

[0184] The reaction of polyimide (PI) and polyamic acid (PA) can be performed by solution polymerization. As the solvent at the time of reaction, the above-described solvent can be used.

[0185] The reaction temperature is not particularly limited. From the viewpoint of sufficiently proceeding the reaction, the reaction temperature can be, for example, 20 to 100°C, 30 to 80°C, or 40 to 70°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, and the number average molecular weight, the concentration of the residual amino group or isocyanate group, and the like can be measured, and the reaction time can be adjusted in such a manner that the desired reaction product is obtained.

[0186] <Antenna substrate material composition> In some embodiments, the antenna substrate material composition contains the antenna substrate material of any of the above embodiments and a solvent. As the solvent contained in the composition, the solvent at the time of the above reaction that can be used for the synthesis of the block copolymer can be cited. The solvent preferably contains at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and 3-methoxy-N,N-dimethylpropionamide (MPA), and more preferably contains at least one selected from the group consisting of N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and 3-methoxy-N,N-dimethylpropionamide (MPA).

[0187] The composition can further contain any of a polyamide, a polyether sulfone, an acrylic polymer, an epoxy compound, an isocyanate compound, a melamine compound, a filler, an antifoaming agent, a preservative, a surfactant, and the like. The composition can be produced, for example, by a method in which the block copolymer and the solvent and any of the components used as necessary are mixed and stirred. The composition can be, for example, a composition not containing a photoacid generator, a composition not containing a crosslinking agent, a composition not containing a photosensitizer, a composition not containing a photopolymerization initiator, and the like. The composition can be a thermosetting composition or a photosensitive composition. From the viewpoint of an excellent storage stability and the ability to form a polyimide material in the shape of a thin film, a layer, a film, or the like in a simple method, the composition can be a composition not having photosensitivity. According to some embodiments, the composition can be a composition except for a case where at least one selected from the group consisting of a photoacid generator, a crosslinking agent, a photosensitizer, and a photopolymerization initiator is contained.

[0188] 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.

[0189] <Polyimide material> In some embodiments, the polyimide material can be obtained using the antenna substrate material of any of the embodiments described above or the composition of any of the embodiments described above. For example, the block copolymer, because it contains a polyamide acid block (BA), is converted to an imide group by ring-closing the amide acid group (in this disclosure, this conversion is sometimes referred to as "imidization"), and thus a polyimide can be obtained. The method of imidization is not particularly limited. For the sake of convenience, a method of heating the block copolymer can be preferred. The heating temperature is, for example, 250 to 400°C. The polyimide material contains a polyimide and can further contain any of the components. The any of the components can be, for example, any of the components described above that can be contained in the antenna substrate material or the composition.

[0190] The polyimide obtained from the block copolymer contains a polyimide block (BI) and a block formed by imidization of the polyamide acid block (BA), i.e., a polyimide block (BI-A). The polyimide block (BI) and the polyimide block (BI-A) are different blocks. The polyimide exhibits a low thermal expansion rate by having a block structure. In the case where the polyimide has a hydrocarbon group (X), there is a tendency to exhibit a low dielectric constant and a low dielectric loss tangent. Furthermore, in the case where the polyimide has a hydrocarbon group (X), there is a tendency to exhibit a low water absorption rate.

[0191] The relative dielectric constant of the polyimide material is, for example, 3.50 or less, 3.00 or less, 2.95 or less, 2.90 or less, 2.85 or less, or 2.80 or less at a frequency of 10 to 100 GHz or a frequency of 10 to 300 GHz, from the viewpoint of obtaining excellent insulating properties over a wide frequency band. The relative dielectric constant of the polyimide material is not particularly limited and is, for example, 2.0 or more. The relative dielectric constant (Dk) of the polyimide material can be measured using a polyimide film (for example, 100 μm in thickness) formed using the antenna substrate material or the composition, by the balanced disk resonator method at a measurement temperature of 25°C. The relative dielectric constant (Dk) can be a value obtained by measuring immediately after the polyimide film is sufficiently dried and left to stand for 24 hours in an environment gas at a temperature of 23°C and a relative humidity of 50%. The relative dielectric constant of the polyimide material preferably satisfies the above range at a frequency of 10 GHz, more preferably satisfies the above range at frequencies of 10 GHz and 100 GHz, further preferably satisfies the above range at frequencies of 10 GHz, 30 GHz, 50 GHz, and 100 GHz, and particularly preferably satisfies the above range at frequencies of 10 GHz, 30 GHz, 50 GHz, 100 GHz, and 300 GHz.

[0192] The dielectric loss tangent of the polyimide material is, for example, 0.0100 or less, 0.0070 or less, 0.0050 or less, 0.0040 or less, 0.0030 or less, or 0.0020 or less at a frequency of 10 to 100 GHz or a frequency of 10 to 300 GHz from the viewpoint of suppressing transmission loss in a wide frequency band. The dielectric loss tangent of the polyimide material is not particularly limited, and is, for example, 0.0005 or more. The dielectric loss tangent (Df) can be measured using a polyimide film (for example, 100 μm in thickness) by a balanced disk resonator method at a measurement temperature of 25°C. The dielectric loss tangent (Df) can be a value measured immediately after the polyimide film is sufficiently dried and left to stand in an environment gas at a temperature of 23°C and a relative humidity of 50% for 24 hours. The dielectric loss tangent of the polyimide material preferably satisfies the above range at a frequency of 10 GHz, more preferably satisfies the above range at frequencies of 10 GHz and 100 GHz, further preferably satisfies the above range at frequencies of 10 GHz, 30 GHz, 50 GHz, and 100 GHz, particularly preferably satisfies the above range at frequencies of 10 GHz, 30 GHz, 50 GHz, 100 GHz, and 300 GHz.

[0193] The coefficient of thermal expansion (CTE) of the polyimide material is, for example, 80 ppm / K or less, 50 ppm / K or less, or 20 ppm / K or less from the viewpoint of obtaining excellent heat resistance. The coefficient of thermal expansion of the polyimide material is, for example, -5 ppm / K or more, 0 ppm / K or more, 10 ppm / K or more, or 15 ppm / K or more, taking into account, for example, use of the polyimide film adhered to another material. The coefficient of thermal expansion (ppm / K) can be calculated using the average linear thermal expansion coefficient (ppm / °C) measured at 30 to 200°C at a temperature increase rate of 10°C / min using a thermal mechanical analysis device, with respect to a polyimide film (for example, 25 μm in thickness).

[0194] The glass transition temperature (Tg) of the polyimide material is, for example, 200°C or more, 250°C or more, or 300°C or more from the viewpoint of heat resistance. The glass transition temperature (Tg) of the polyimide material is not particularly limited, and is, for example, 600°C or less. The glass transition temperature can be calculated as a temperature (°C) corresponding to an inflection point in the linear thermal expansion coefficient curve measured at 30 to 200°C at a temperature increase rate of 10°C / min using a thermal mechanical analysis device, with respect to a polyimide film (for example, 25 μm in thickness).

[0195] More specifically, the relative dielectric constant, the dielectric loss tangent, the thermal expansion rate, and the glass transition temperature of the polyimide material can be measured using the polyimide film produced according to the method described in the examples.

[0196] <metal-clad laminate> In some embodiments, a metal-clad laminate is obtained using the antenna substrate material or the composition according to any of the above embodiments. The metal-clad laminate is used to obtain an antenna substrate. The metal-clad laminate can be a flexible substrate or a rigid substrate. The metal-clad laminate has a polyimide material layer and a metal layer in contact with the polyimide material layer. The antenna substrate can have a metal layer on only one surface of the polyimide material layer, or on both surfaces of the polyimide material layer. The polyimide material layer can consist of one polyimide material layer, or can include multiple polyimide material layers. In the case where the insulating substrate includes multiple polyimide material layers, the insulating substrate can have an adhesive layer between the polyimide material layers.

[0197] The material of the metal layer can be, for example, copper, aluminum, gold, silver, alloys thereof, or the like. The metal layer is preferably a copper foil. The polyimide layer has high adhesion to copper foils having a small surface roughness, such as a non-roughened copper foil, a low-roughness copper foil, or the like. With a copper foil having a small surface roughness, transmission loss can be suppressed. The surface roughness (ten-point average roughness: Rz JIS ) of the copper foil is, for example, 3.0 μm or less, 2.0 μm or less, or 1.0 μm or less, based on JIS B 0601:2001. The lower limit of the surface roughness is not particularly limited, and is, for example, 0.5 μm or more. As an example of the metal-clad laminate, a flexible copper-clad laminate (FCCL) can be given.

[0198] <antenna substrate> In some embodiments, an antenna substrate is obtained using the antenna substrate material, the composition, or the metal-clad laminate according to any of the above embodiments. The antenna substrate can be a printed substrate. As examples of the printed substrate, a flexible substrate and a rigid substrate can be given. As examples of the printed substrate, a single-sided substrate, a double-sided substrate, and a multilayer substrate can be given. For example, the organic material contained in the insulating substrate material, the protective film, the insulating layer, or the like of the printed substrate is obtained using the antenna substrate material or the composition. The organic material contained in the insulating substrate material, the protective film, the insulating layer, or the like of the printed substrate can include the polyimide material according to the above embodiments.

[0199] For the antenna substrate, since the polyimide material has a small change in dielectric properties in a wide frequency band (e.g., millimeter waves to terahertz waves), the antenna substrate can be used in various frequency bands. In addition, it can also be used as an antenna substrate that allows the antenna substrate to operate in multiple frequency bands. For the antenna substrate, since the polyimide material exhibits good adhesion to the conductive layer, the design margin is high, and the antenna substrate can be efficiently manufactured with ease of handling. For the antenna substrate, since the polyimide material has a small thermal expansion rate and excellent dimensional stability, an antenna with good antenna gain can be obtained, and it is also suitable for use in multiple frequency bands.

[0200] In some embodiments, the antenna substrate has an insulating substrate and a conductive layer in contact with the insulating substrate. The antenna substrate can have the conductive layer only on one surface of the insulating substrate, or can also have the conductive layer on both surfaces of the insulating substrate. The insulating substrate contains one layer of a polyimide material layer or multiple layers of a polyimide material layer. The insulating substrate can have an insulating layer other than the polyimide material layer. The insulating layer can be, for example, an insulating film, an insulating sheet, a prepreg, or the like. In the case where the insulating substrate contains multiple layers selected from the insulating layer other than the polyimide material layer and the polyimide material layer, the insulating substrate can have a conductive layer, an adhesive layer, or the like between the layers. The antenna substrate can further have an interlayer conductive portion. The conductive layer has, for example, a pattern for power supply, a pattern for grounding, a pattern for wiring, or the like. The material of the conductive layer and the interlayer conductive portion can be, for example, copper, aluminum, gold, silver, an alloy thereof, or the like.

[0201] The antenna substrate can be, for example, a printed wiring board formed with a transmission line (a microstrip line, a slot line, a coplanar line, or the like), a power supply circuit, a via hole, a through-hole, or the like.

[0202] In some embodiments, the antenna substrate is used to mount multiple antenna elements on the substrate. In some embodiments, the antenna substrate is used to mount an antenna device on the substrate.

[0203] Figure 1 An example of an antenna substrate is shown. The antenna substrate 110 is a composite printed substrate having a printed wiring substrate 120 and a printed wiring substrate 130.

[0204] The printed wiring board 120 is a multilayer printed wiring board having a plurality of polyimide material layers. The polyimide material layers 120a, 120b, 120c, 120d, 120e, and 120f can be layers having the same composition as each other, or can be layers having different compositions from each other. The printed wiring board 120 can have an adhesive layer between the polyimide material layers. The printed wiring board 120 has a conductive layer 121 and an interlayer conductive portion 122. An antenna element is mounted on the surface of the polyimide material layer 120a side of the printed wiring board 120. The printed wiring board 120 can have a conductive layer (not shown) on the surface of the polyimide material layer 120a, the conductive layer including a conductive layer having a shape of a wiring pattern and a conductive layer having a shape of a pattern for a connection portion connected to the antenna element. The printed wiring board 120 can have a conductive layer on the surface of the polyimide material layer 120f as well.

[0205] The printed wiring board 130 is a multilayer printed wiring board having a plurality of insulating layers. The insulating layers 130a, 130b, 130c, 130d, 130e, and 130f can be layers having the same composition as each other, or can be layers having different compositions from each other. The insulating layers can be polyimide material layers, or can be insulating layers other than polyimide material layers. The printed wiring board 130 can have an adhesive layer between the insulating layers. The printed wiring board 130 has an interlayer conductive portion 132 and a conductive layer 131. A semiconductor element is mounted on the surface of the insulating layer 130f side of the printed wiring board 130. The printed wiring board 130 can have a conductive layer on the surface of the insulating layer 130f, the conductive layer including a conductive layer (not shown) having a shape of a wiring pattern and a conductive layer 133 having a shape of a pattern for a connection portion connected to the semiconductor element. The printed wiring board 130 can have a conductive layer on the surface of the insulating layer 130a as well.

[0206] In the printed wiring board 120, at least a portion of the plurality of polyimide material layers can be insulating layers other than polyimide material layers. In this case, at least the layer (polyimide material layer 120a) closest to the mounting portion of the antenna element can be a polyimide material layer. In this case, the printed wiring board 120 can have a conductive layer on the surface of the insulating layer 120a, the conductive layer including a conductive layer (not shown) having a shape of a wiring pattern and a conductive layer having a shape of a pattern for a connection portion connected to the antenna element. Figure 1 An example in which the printed wiring board 120 has a plurality of polyimide material layers is shown in FIG. 12, but as another example of the printed wiring board 120, a printed wiring board having one polyimide material layer can be given. In this case, the printed wiring board 120 can have a conductive layer on the surface of the polyimide material layer 120a, the conductive layer including a conductive layer (not shown) having a shape of a wiring pattern and a conductive layer having a shape of a pattern for a connection portion connected to the antenna element. Figure 1 An example in which the printed wiring board 130 has a plurality of insulating layers is shown in FIG. 13, but as another example of the printed wiring board 130, a printed wiring board having one insulating layer can be given. In this case, the printed wiring board 130 can have a conductive layer on the surface of the insulating layer 130f, the conductive layer including a conductive layer (not shown) having a shape of a wiring pattern and a conductive layer 133 having a shape of a pattern for a connection portion connected to the semiconductor element.

[0207] Figure 2 An example of an antenna substrate is shown in FIG. 21. The antenna substrate 210 has one printed wiring board.

[0208] The antenna substrate 210 includes the insulating layer 220, the insulating layer 230, the conductive layers 221, 241, and 233, and the via 232. The power amplifier is mounted on the surface of the conductive layer 221, and the antenna element is mounted on the side surface of the antenna substrate 210.

[0209] <Antenna device> The antenna device has the antenna substrate of the above-described embodiment and the antenna element on one surface of the substrate. The antenna element can be a patch antenna (also referred to as a "microstrip antenna"). The antenna device can also be an array antenna device having antenna elements present in an array shape. The array antenna device can be a phased array antenna device and can be used for beamforming technology.

[0210] In some embodiments, the antenna device is an antenna module including the antenna substrate of the above-described embodiment, the antenna on one surface of the substrate, and a radio frequency integrated circuit (RF-IC) on the other surface of the substrate. The antenna device can also include parts that are included in a general antenna device. As examples of the parts, a switch, a power amplifier, a low-noise amplifier, an attenuator, a phase shifter, a signal combining / dividing device, a mixer, an amplification circuit, and the like can be given.

[0211] The antenna module includes one or two or more antennas. For example, the antenna module can be a module of a type including only one set of array antennas, or can also be a module of a multiple array antenna type including multiple sets of array antennas. The antenna module can be a module of a multi-band antenna type used under multiple frequency bands. In a case where the antenna is caused to act under multiple frequency bands, it is preferable that the organic material be a material having small changes in dielectric properties and excellent dimensional stability in a wide frequency band range. For example, according to the multi-band antenna module including only one set of array antennas, miniaturization of the module can be achieved.

[0212] As the shape of the antenna device, for example, an AiB (Antenna in Board), an AiP (Antenna in Package), and the like can be given. In any of the shapes, from the viewpoint of suppressing transmission loss to be lower, it is preferable that the polyimide material included in the antenna substrate have a small dielectric constant and a small dielectric loss tangent and have a small thermal expansion rate.

[0213] <Wireless unit, wireless substation> The antenna device can be used, for example, in a Radio Unit (RU), a radio substation, a base station, a user terminal, a communication device, a communication system, etc. According to some embodiments, an RU, a radio substation, a smartphone, an Advanced driver-assistance system (ADAS), etc. comprising the antenna device of the above embodiments are provided.

[0214] <Examples of Embodiments> Examples of embodiments of the present application are listed below. The present application is not limited to the following embodiments.

[0215] [1] An antenna substrate material containing a block copolymer, the block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA).

[0216] [2] The antenna substrate material according to the above [1], wherein the block copolymer contains a structural unit (X) having a group (X) containing at least one non-aromatic hydrocarbon group.

[0217] [3] The antenna substrate material according to the above [1] or [2], wherein the block copolymer contains a structural unit (Y) having a group (Y) containing at least one aromatic ring group.

[0218] [4] An antenna substrate material containing a block copolymer, the block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and containing a structural unit represented by the above formula (I) and a structural unit represented by the above formula (A), at least the R A being different from the R C , or at least the R B being different from the R D .

[0219] [5] The antenna substrate material according to the above [4], wherein the block copolymer contains at least one selected from a structural unit represented by the above formula (XI) and a structural unit represented by the above formula (XA).

[0220] [6] The antenna substrate material according to the above [4] or [5], wherein the block copolymer contains at least one selected from a structural unit represented by the above formula (YI) and a structural unit represented by the above formula (YA).

[0221] [7] The antenna substrate material according to any one of the above [4] to [6], wherein the block copolymer contains a structural unit represented by the above formula (XI) (wherein R 1 and R 2at least one of R 3 and R 4 is the group (X) having a total carbon number of 9 or more for the at least 1 non-aromatic hydrocarbon group.

[0222] [8] The antenna substrate material according to any one of the above [4] to [7], wherein the block copolymer contains at least one of a structural unit represented by the above formula (YI) (wherein R 5 and R 6 are each independently a group containing an aromatic hydrocarbon group) and a structural unit represented by the above formula (YA) (wherein R 7 and R 8 are each independently a group containing an aromatic hydrocarbon group).

[0223] [9] The antenna substrate material according to any one of the above [4] to [8], wherein the polyimide block (BI) contains a structural unit represented by the above formula (XI).

[0224]

[10] The antenna substrate material according to any one of the above [4] to [9], wherein the polyamic acid block (BA) contains a structural unit represented by the above formula (YA).

[0225]

[11] The antenna substrate material according to any one of the above [4] to

[10] , wherein the block copolymer contains a structural unit represented by the above formula (XI) (wherein R 1 is the above group (X)) and a structural unit represented by the above formula (YA) (wherein R 7 is a group containing an aromatic hydrocarbon group).

[0226]

[12] The antenna substrate material according to any one of the above [4] to

[11] , wherein the block copolymer contains a structural unit represented by the above formula (YI) (wherein R 5 is a group containing an aromatic hydrocarbon group) and a structural unit represented by the above formula (XA) (wherein R 3 is the above group (X)).

[0227]

[13] An antenna substrate material containing a block copolymer, the block copolymer containing 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.

[0228]

[14] The antenna substrate material according to the above

[13] , wherein at least one of the structure derived from a diamine or diisocyanate and the structure derived from a tetracarboxylic dianhydride contains a structure having a group (X) containing at least one non-aromatic hydrocarbon group.

[0229]

[15] The antenna substrate material according to the above

[13] or

[14] , wherein the structure derived from a diamine or diisocyanate and the structure derived from a tetracarboxylic dianhydride contain a structure having a group (Y) containing at least one aromatic ring group.

[0230]

[16] The antenna substrate material according to any one of the above

[13] to

[15] , wherein at least one of the structure derived from a diamine or diisocyanate and the structure derived from a tetracarboxylic dianhydride contains a structure having a group which is a group (X) containing at least one non-aromatic hydrocarbon group, and the total number of carbons of the at least one non-aromatic hydrocarbon group is 9 or more.

[0231]

[17] The antenna substrate material according to any one of the above

[13] to

[16] , wherein the structure derived from a diamine or diisocyanate and the structure derived from a tetracarboxylic dianhydride contain a structure having a group which is a group (Y) containing at least one aromatic ring group, and the aromatic ring group is an aromatic hydrocarbon group.

[0232]

[18] The antenna substrate material according to any one of the above

[13] to

[17] , wherein the structure derived from a diamine or diisocyanate contained in the polyimide block (BI) contains a structure derived from a diamine or diisocyanate having a group (X) containing at least one non-aromatic hydrocarbon group.

[0233]

[19] The antenna substrate material according to any one of the above

[13] to

[18] , wherein the structure derived from a diamine or diisocyanate contained in the polyamic acid block (BA) contains a structure derived from a diamine or diisocyanate having a group (Y) containing at least one aromatic ring group.

[0234]

[20] The antenna substrate material according to any one of the above

[13] to

[19] , wherein the structure derived from a diamine or diisocyanate contains: a structure derived from a diamine or diisocyanate having a group (X) containing at least one non-aromatic hydrocarbon group, and the total number of carbons of the at least one non-aromatic hydrocarbon group is 9 or more; and a structure derived from a diamine or diisocyanate having a group (Y) containing at least one aromatic ring group, and the aromatic ring group is an aromatic hydrocarbon group.

[0235]

[21] The antenna substrate material according to any one of the above

[13] to

[20] , wherein the block copolymer contains a structure derived from a dimer diamine or a dimer diisocyanate.

[0236]

[22] The antenna substrate material according to any one of the above [1] to

[21] , 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 composed of two or more selected from among them.

[0237]

[23] The antenna substrate material according to any one of the above [1] to

[22] , wherein the group (X) is a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group, an unsaturated alicyclic hydrocarbon group, or a group composed of two or more selected from among a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group, and an unsaturated alicyclic hydrocarbon group.

[0238]

[24] The antenna substrate material according to any one of the above [1] to

[23] , wherein the total number of carbons of the saturated aliphatic hydrocarbon group and the unsaturated aliphatic hydrocarbon group contained in the group (X) is greater than the total number of carbons of the saturated alicyclic hydrocarbon group and the unsaturated alicyclic hydrocarbon group contained in the group (X).

[0239]

[25] The antenna substrate material according to any one of the above [1] to

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

[0240]

[26] The antenna substrate material according to any one of the above [1] to

[25] , wherein the group (X) does not contain an aromatic ring group.

[0241]

[27] The antenna substrate material according to any one of the above [1] to

[26] , wherein the group (X) contains a linear saturated aliphatic hydrocarbon group having a number of carbons of 6 or more.

[0242]

[28] The antenna substrate material according to any one of the above [1] to

[27] , wherein the total number of carbons of the at least one non-aromatic hydrocarbon group is 16 or more.

[0243]

[29] The antenna substrate material according to any one of the above [1] to

[28] , wherein the total number of carbons of the at least one non-aromatic hydrocarbon group is 28 or more.

[0244]

[30] The antenna substrate material according to any one of the above [1] to

[29] , which is used for a multi-band antenna.

[0245]

[31] The antenna substrate material according to any one of the above [1] to

[30] , which is used for a patch antenna.

[0246]

[32] The antenna substrate material according to any one of the above [1] to

[31] , wherein a film is produced using the above antenna substrate material, and when the relative dielectric constant and the dielectric loss tangent at a frequency of 10 GHz, and the thermal expansion rate of the film are measured, the relative dielectric constant is 3.5 or less, the dielectric loss tangent is 0.0100 or less, and the thermal expansion rate is 80 ppm / K or less.

[0247]

[33] The antenna substrate material according to any one of the above [1] to

[32] , wherein a film is produced using the above antenna substrate material, and when the relative dielectric constant and the dielectric loss tangent at a frequency of 10 GHz and 100 GHz of the film are measured, the relative dielectric constant is 3.5 or less, and the dielectric loss tangent is 0.0100 or less.

[0248]

[34] A method for producing an antenna substrate material, which is a method for producing the antenna substrate material according to any one of the above [1] to

[33] , comprising: a step of obtaining a polyimide (PI) using a diamine or a diisocyanate, and a tetracarboxylic dianhydride; a step of obtaining a polyamic acid (PA) using a diamine and a tetracarboxylic dianhydride; and a step of obtaining a block copolymer using the polyimide (PI) and the polyamic acid (PA).

[0249]

[35] An antenna substrate material composition containing the antenna substrate material according to any one of the above [1] to

[33] , and a solvent.

[0250] The disclosure of the present application is associated with the subject matter described in PCT / JP2024 / 003168 filed on January 31, 2024, the entire disclosure of which is hereby incorporated by reference.

[0251] Examples The embodiments of the present application are not limited to the following examples.

[0252] <Synthesis of polyimide (PI) and polyamic acid (PA)> [Polyimide (PI-1)] A dimer diamine ("PRIAMINE 1075", Croda Japan K.K., containing a dimer diamine represented by the following formula) (hereinafter referred to as "DDA") 35.5 g (0.066 mol) was dissolved in N-methylpyrrolidone 205.6 g and xylene 30.8 g to obtain a diamine solution. To the diamine solution was added 3,3',4,4'-benzophenonetetracarboxylic dianhydride (hereinafter referred to as "BTDA") 28.5 g (0.088 mol) and allowed to react until a uniform transparent solution was obtained. The reaction was carried out by stirring the solution at 50°C or lower for 1 hour or more. Then, dehydration imidization reaction was carried out by stirring the transparent solution at 180°C for 4 hours or more to obtain a solution (varnish) of a polyimide (PI-1) having an anhydride structure derived from BTDA at the terminal. The number average molecular weight of the polyimide (PI-1) was 3,000.

[0253] [Chemical Formula 22] [Polyimides (PI-2) to (PI-6)] A solution of a polyimide (PI-2) to (PI-6) was obtained by the same procedure as in the polyimide (PI-1) except that the diamine and the tetracarboxylic dianhydride shown in Table 2 were used.

[0254] [Polyamic acid (PA-1)] A diamine solution was obtained by dissolving 57.3 g (0.155 mol) of 4,4'-bis(4-aminophenoxy)biphenyl (hereinafter referred to as "BODA") in 235.6 g of N,N'-dimethylacetamide and 167.9 g of N-methylpyrrolidone. To the diamine solution was added 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter referred to as "BPDA") 38.7 g (0.132 mol) and allowed to react to obtain a solution of a polyamic acid (polyimide precursor) (PA-1) having an amine structure derived from BODA at the terminal. The reaction was carried out by stirring the solution at 50°C or lower for 8 hours or more. The number average molecular weight of the polyamic acid (PA-1) was 4,000.

[0255] [Polyamic acids (PA-2) to (PA-6)] A solution of a polyamic acid (PA-2) to (PA-6) was obtained by the same procedure as in the polyamic acid (PA-1) except that the diamine and the tetracarboxylic dianhydride shown in Table 2 were used.

[0256] <Synthesis of block copolymer (block polyamic acid imide)> [Example 1] A solution 300.4 g of polyimide (PI-1) was mixed with a solution 499.6 g of polyamic acid (PA-1) and allowed to react, to obtain a varnish of block polyamic acid imide 1. The reaction was performed by stirring the solutions at 100°C or lower for 1 hour or more. The number average molecular weight of the block polyamic acid imide 1 was 30,000. The concentration of the block polyamic acid imide 1 was 20 mass% based on the mass of the varnish. The block copolymer (block polyamic acid imide) was an antenna substrate material, and the varnish was a composition containing the block copolymer and a solvent.

[0257] [Examples 2 to 9] A varnish of block polyamic acid imides 2 to 9 was obtained in the same manner as in Example 1, except that the solutions of polyimide and polyamic acid shown in Table 2 were used.

[0258] <Synthesis of polyamic acid> [Comparative Example 1] A diamine solution was obtained by dissolving 76.6 g (0.38 mol) of 4,4'-diaminodiphenyl ether (hereinafter referred to as "ODA") in 640.0 g of N,N'-dimethylacetamide. To the diamine solution was added pyromellitic dianhydride (hereinafter referred to as "PMDA") 81.8 g (0.38 mol) and allowed to react, to obtain a varnish of polyamic acid 1 (polyimide precursor). The reaction was performed by stirring the solutions at 50°C or lower for 8 hours or more.

[0259] [Comparative Example 2] A varnish of polyamic acid 2 was obtained in the same manner as in Comparative Example 1, except that the diamine and tetracarboxylic dianhydride shown in Table 3 were used.

[0260] The kinds and amounts of diamines and tetracarboxylic dianhydrides used in the synthesis of polyimides and polyamic acids, and polyimides and polyamic acids used in the synthesis of block polyamic acid imides are shown in Table 2 and Table 3. In addition, the number average molecular weights of the polyimides and polyamic acids are shown in Table 2 and 3. The number average molecular weights were measured according to the following method.

[0261] The meanings of the abbreviations in Table 2 and 3 are as follows.

[0262] BTDA: 3,3',4,4'-benzophenonetetracarboxylic dianhydride BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride PMDA: pyromellitic dianhydride TAHQ: bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene ester DDA: dimer diamine BODA: 4,4'-bis(4-aminophenoxy) biphenyl PPD: p-phenylenediamine ODA: 4,4'-diaminodiphenyl ether m-TB: m-tolidine (4,4'-diamino-2,2'-dimethylbiphenyl) (number average molecular weight) The number average molecular weight (Mn) was measured by gel permeation chromatography (GPC) and converted using a standard curve of polystyrene. The standard curve was approximated by a cubic equation using five samples of standard polystyrene ("TSK standard POLYSTYRENE", manufactured by Tosoh Corporation). The conditions for GPC are shown below.

[0263] GPC device: High-speed GPC device HLC-8320GPC (manufactured by Tosoh Corporation) Detector: Ultraviolet absorbance detector UV-8320 (manufactured by Tosoh Corporation) Chromatography column: Gelpack GL-S300MDT-5 (total of 2) (manufactured by Resonac Corporation) Eluent: THF / DMF = 1 / 1 (volume ratio) + LiBr (0.06 mol / L) + H3PO4 (0.06 mol / L) Flow rate: 1 mL / minute Chromatography column size: 8 mm I.D. x 300 mm Sample concentration: 5 mg / 1 mL Injection amount: 5 μL Measurement temperature: 40°C <Manufacture of film> [Example 1] A film was manufactured using the obtained varnish (composition) in the following manner.

[0264] The surface of a commercially available glass substrate was degreased with acetone, and the varnish of the block polyamic acid imide 1 was applied using a film applicator with a film thickness adjustment function in such a manner that the film thickness after imidization would be 100 μm. The applied varnish was pre-dried at 80°C for 30 minutes using a hot plate (heating plate), and a layer of the block polyamic acid imide 1 was formed. Next, the layer of the block polyamic acid imide 1 was heated at 350°C for 30 minutes under a nitrogen environment gas using an inert gas oven, and a film of the block polyamic acid imide 1 was obtained. The glass substrate on which the film was formed was immersed in warm water for about 15 minutes, and the film was peeled off from the glass substrate, and a film having a film thickness of 100 μm was manufactured.

[0265] A film having a thickness of 25 μm was produced in the same manner as described above, except that the varnish of the block polyamic acid imide 1 was applied so as to have a thickness of 25 μm after imidization.

[0266] [Examples 2 to 9 and Comparative Examples 1 to 2] A film was obtained in the same manner as described above, except that the varnish of the block polyamic acid imide 1 was changed to the varnish of Examples 2 to 9 and Comparative Examples 1 to 2.

[0267] <Evaluation of the film> The properties of the film produced using the varnish of Examples 1 to 9 and Comparative Examples 1 to 2 were evaluated in the following manner. The results of the evaluation are shown in Tables 2 and 3.

[0268] (Relative dielectric constant and dielectric loss tangent) The film (thickness: 100 μm) was cut into a size of 48 mm in diameter, and after drying treatment at 125°C for 1 hour, it was left to stand under conditions of temperature: 23°C, relative humidity: 50% for 24 hours. Then, the dielectric properties (relative dielectric constant Dk and dielectric loss tangent Df) of the film were measured using a balanced circular disk resonator (BCDR). In the measurement, "PS-XSN-100" manufactured by Keysight Technologies was used. The conditions were set to a frequency of 10 to 100 GHz, and a measurement temperature of 25°C.

[0269] (Linearity thermal expansion coefficient (thermal expansion rate) and glass transition temperature) The film (thickness: 25 μm) was cut into a width of 4 mm and a length of 25 mm to produce a test piece. In the measurement, a thermal mechanical analysis device ("TMA7100" manufactured by Hitachi High-Tech Corporation) was used. The test piece was heated from room temperature to 350°C at a rate of 10°C / minute using a chuck distance of 10 mm, a load of 10 g, and a tensile method, and then cooled to 30°C at a rate of 10°C / minute. The average linearity thermal expansion coefficient (ppm / °C) from 30°C to 200°C was calculated by again heating at a rate of 10°C / minute, and the obtained value was taken as the linearity thermal expansion coefficient (ppm / K). In addition, the temperature corresponding to the inflection point of the linearity thermal expansion coefficient curve was taken as the glass transition temperature (°C).

[0270] <Production of flexible copper-clad laminate (FCCL)> [Example 1] A flexible copper-clad laminate (FCCL) was produced using the obtained varnish (composition) in the following manner.

[0271] The surface roughness (Rz JIS) On a matte surface of a low-roughened copper foil having a roughness of 1.2 μm, a varnish of the block polyamic acid imide 1 was applied using a film applicator with a film thickness adjustment function in a manner such that the film thickness after imidization became 25 μm. The applied varnish was pre-dried at 80°C for 30 minutes using a hot plate (heating plate) to form a layer of the block polyamic acid imide 1. Next, the copper foil on which the layer of the block polyamic acid imide 1 was formed was heated at 350°C for 30 minutes under a nitrogen environment gas using an inert gas oven to obtain an FCCL having a layer of the block polyamic acid imide 1.

[0272] [Examples 2 to 9 and Comparative Examples 1 to 2] The varnish of the block polyamic acid imide 1 was changed to the varnish of Examples 2 to 9 and Comparative Examples 1 to 2, and otherwise, an FCCL was obtained by the same method as described above.

[0273] [Examples 2 to 9 and Comparative Examples 1 to 2] Using the FCCLs produced using the varnishes of Examples 1 to 9 and Comparative Examples 1 to 2, the adhesion of the block polyimide was evaluated according to the following method. The evaluation results are shown in Tables 2 and 3.

[0274] (90° Peeling Strength) The copper foil of the FCCL was processed into a straight line pattern having a width of 5 mm by etching. Using a material testing machine ("Small Table Type Tester EZ-S50N" manufactured by Shimadzu Corporation), the peeling strength when the copper foil processed into the straight line pattern was peeled in the 90° direction with respect to the face direction of the layer of the block polyimide was measured. The tensile speed was 50 mm / minute.

[0275] Explanation of Reference Numerals 110 antenna substrate; 120 printed wiring substrate; 120a to 120f polyimide material layer; 121 conductive layer; 122 interlayer conductive portion; 130 printed wiring substrate; 130a to 130f insulating layer; 131 conductive layer; 132 interlayer conductive portion; 133 conductive layer; 140 connection portion; 141 insulating layer; 142 conductive portion; 210 antenna substrate; 220 insulating layer; 221 conductive layer; 222 conductive portion; 230 insulating layer; 232 conductive portion; 233 conductive layer; 241 conductive layer.

Claims

1. An antenna substrate material comprising a block copolymer, said block copolymer comprising polyimide blocks (BI) and polyamic acid blocks (BA).

2. The antenna substrate material according to claim 1, wherein, The block copolymer comprises a structural unit (X) having a group (X) containing at least one non-aromatic hydrocarbon group.

3. The antenna substrate material according to claim 2, wherein, The block copolymer comprises a structural unit (Y) having a group (Y) containing at least one aromatic ring group.

4. An antenna substrate material comprising a block copolymer, said block copolymer comprising polyimide blocks (BI) and polyamic acid blocks (BA), and comprising structural units shown in formula (I) and formula (A), wherein at least the following R A With the following R C Different, or at least the following R B With the following R D different, In the formula, R A and R B Each can independently represent an organic group; In the formula, R C and R D Each can independently represent an organic group.

5. The antenna substrate material according to claim 4, wherein, The block copolymer comprises at least one structural unit selected from the structural units shown in formula (XI) and formula (XA). 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 group (X) containing at least one non-aromatic hydrocarbon group; 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 group (X) containing at least one non-aromatic hydrocarbon group.

6. The antenna substrate material according to claim 5, wherein, The block copolymer comprises at least one structural unit selected from the structural units shown in formula (YI) and formula (YA). In the formula, R 5 and R 6 Each of the above represents a group (Y) containing at least one aromatic ring group. In the formula, R 7 and R 8 Each of the above represents a group (Y) containing at least one aromatic ring group.

7. The antenna substrate material according to claim 5 or 6, wherein, The block copolymer comprises at least one structural unit selected from the structural units shown in formula (XI) and formula (XA), wherein R in formula (XI) 1 and R 2 At least one of the groups (X) is a group whose total number of carbon atoms is 9 or more of the at least one non-aromatic hydrocarbon group, wherein R in the formula (XA) 3 and R 4 At least one of the groups (X) is the group whose total number of carbon atoms is 9 or more of the at least one non-aromatic hydrocarbon group.

8. The antenna substrate material according to claim 6, wherein, The block copolymer comprises at least one structural unit selected from the structural units shown in formula (YI) and formula (YA), wherein R in formula (YI) 5 and R 6 Each is an independent group containing an aromatic hydrocarbon group, and R in the formula (YA) 7 and R 8 Each is an independent group containing an aromatic hydrocarbon group.

9. The antenna substrate material according to any one of claims 5 to 8, wherein, The polyimide block (BI) comprises the structural unit shown in formula (XI).

10. The antenna substrate material according to claim 6 or 8, wherein, The polyamic acid block (BA) comprises the structural unit shown in formula (YA).

11. The antenna substrate material according to any one of claims 6 to 10, wherein, The block copolymer comprises the structural unit shown in formula (XI) and the structural unit shown in formula (YA), wherein R in formula (XI) 1 For the group (X), R in the formula (YA) 7 It is a group containing an aromatic hydrocarbon group.

12. The antenna substrate material according to any one of claims 6 to 8, wherein, The block copolymer comprises structural units represented by formula (YI) and structural units represented by formula (XA), wherein R in formula (YI) 5 For a group containing an aromatic hydrocarbon group, R in formula (XA) 3 The group (X) is mentioned above.

13. An antenna substrate material comprising a block copolymer, said block copolymer comprising polyimide blocks (BI) and polyamic acid blocks (BA), and having a structure derived from a diamine or diisocyanate and a structure derived from a tetracarboxylic dianhydride.

14. The antenna substrate material according to claim 13, wherein, The structure derived from diamine or diisocyanate and the structure derived from tetracarboxylic dianhydride at least one of them comprises a structure having a group (X) containing at least one non-aromatic hydrocarbon group.

15. The antenna substrate material according to claim 14, wherein, The structures derived from diamines or diisocyanates and the structures derived from tetracarboxylic dianhydrides comprise structures having a group (Y) containing at least one aromatic ring group.

16. The antenna substrate material according to any one of claims 13 to 15, wherein, The structure derived from diamine or diisocyanate and the structure derived from tetracarboxylic dianhydride at least one of them comprises a structure having a group (X) that comprises 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.

17. The antenna substrate material according to claim 16, wherein, The structures derived from diamines or diisocyanates and the structures derived from tetracarboxylic dianhydrides comprise structures having a group (Y) comprising at least one aromatic ring group, wherein the aromatic ring group is an aromatic hydrocarbon group.

18. The antenna substrate material according to any one of claims 13 to 17, wherein, The polyimide block (BI) contains a structure derived from a diamine or diisocyanate, including a structure derived from a diamine or diisocyanate having a group (X) containing at least one non-aromatic hydrocarbon group.

19. The antenna substrate material according to claim 18, wherein, The polyamic acid block (BA) contains a structure derived from a diamine or diisocyanate, including a structure derived from a diamine or diisocyanate having a group (Y) containing at least one aromatic ring group.

20. The antenna substrate material according to any one of claims 13 to 19, wherein, The structure derived from diamine or diisocyanate comprises: The structure is derived from a diamine or diisocyanate having a group comprising at least one non-aromatic hydrocarbon group (X), wherein the total number of carbon atoms in the at least one non-aromatic hydrocarbon group is 9 or more; and The structure is derived from a diamine or diisocyanate having a group (Y) comprising at least one aromatic ring group, wherein the aromatic ring group is an aromatic hydrocarbon group.

21. The antenna substrate material according to any one of claims 13 to 20, wherein, The block copolymer contains a structure derived from dimer diamine or dimer diisocyanate.

22. The antenna substrate material according to any one of claims 2, 3, 5-12 and 14-20, 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 composed of two or more of them.

23. The antenna substrate material according to any one of claims 2, 3, 5-12 and 14-20, wherein, The group (X) is a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group, an unsaturated alicyclic hydrocarbon group, or a group composed of two or more selected from saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, and unsaturated alicyclic hydrocarbon groups.

24. The antenna substrate material according to any one of claims 2, 3, 5-12 and 14-20, wherein, The total number of carbon atoms in the saturated and unsaturated aliphatic hydrocarbon groups contained in the group (X) is greater than the total number of carbon atoms in the saturated and unsaturated alicyclic hydrocarbon groups contained in the group (X).

25. The antenna substrate material according to any one of claims 2, 3, 5-12, 14-20, and 22-24, wherein, The group (X) comprises a saturated alicyclic hydrocarbon group.

26. The antenna substrate material according to any one of claims 2, 3, 5-12, 14-20, and 22-25, wherein, The group (X) does not contain aromatic ring groups.

27. The antenna substrate material according to any one of claims 2, 3, 5-12, 14-20 and 22-26, wherein, The group (X) comprises a straight-chain saturated aliphatic hydrocarbon group having 6 or more carbon atoms.

28. The antenna substrate material according to any one of claims 2, 3, 5-12, 14-20 and 22-26, wherein, The total number of carbon atoms in at least one non-aromatic hydrocarbon group is 16 or more.

29. The antenna substrate material according to any one of claims 2, 3, 5-12, 14-20, and 22-26, wherein, The total number of carbon atoms in at least one non-aromatic hydrocarbon group is 28 or more.

30. The antenna substrate material according to any one of claims 1 to 29, used in a multi-band antenna.

31. The antenna substrate material according to any one of claims 1 to 30, used in patch antennas.

32. The antenna substrate material according to any one of claims 1 to 31, wherein, When a film is fabricated using the aforementioned antenna substrate material, and the relative permittivity, dielectric loss tangent, and thermal expansion coefficient of the film are measured at a frequency of 10 GHz, the relative permittivity is 3.5 or less, the dielectric loss tangent is 0.0100 or less, and the thermal expansion coefficient is 80 ppm / K or less.

33. The antenna substrate material according to any one of claims 1 to 32, wherein, A film was fabricated using the aforementioned antenna substrate material. When the relative permittivity and dielectric loss tangent of the film were measured at frequencies of 10 GHz and 100 GHz, the relative permittivity was 3.5 or less and the dielectric loss tangent was 0.0100 or less.

34. A method for manufacturing an antenna substrate material, comprising the method for manufacturing the antenna substrate material according to any one of claims 1 to 33, and comprising: The steps of obtaining polyimide (PI) using diamine or diisocyanate and tetracarboxylic dianhydride; The steps for obtaining polyamic acid (PA) using diamine and tetracarboxylic dianhydride; and The step of obtaining a block copolymer using the polyimide (PI) and the polyamic acid (PA).

35. An antenna substrate material composition comprising the antenna substrate material according to any one of claims 1 to 33 and a solvent.

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