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

Abstract

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

Description

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

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

[0002] With the widespread adoption of driving safety support systems (DSSS), demand for in-vehicle millimeter-wave radar is increasing. Insulating materials for substrates for in-vehicle millimeter-wave radar require resins with low transmission signal loss and high heat resistance that can withstand high temperatures near the engine. Polyimide is known as an insulating material with excellent heat resistance (see, for example, Patent Document 1).

[0003] International Publication No. 2010 / 113412

[0004] The present disclosure provides a block copolymer capable of producing a polyimide having a low dielectric constant, a low dielectric loss tangent, and a low coefficient of thermal expansion, and a method for producing the same. The present disclosure also provides a polyimide, a molded article, an insulator, a heat-resistant insulator, and a printed circuit board that exhibit excellent insulating properties, excellent heat resistance, or both, as well as an insulating material, a heat-resistant insulating material, a composition, a composition for an insulator, a composition for a heat-resistant insulator, and a composition for a printed circuit board that can produce any of these.

[0005] The present invention includes the following embodiments, but is not limited to the following embodiments.

[0006] One embodiment relates to a block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and comprising a structural unit (X) having a group (X) containing at least one non-aromatic hydrocarbon group, the at least one non-aromatic hydrocarbon group having a total carbon number of 9 or more.

[0007] Another embodiment relates to a block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and including at least one structural unit selected from the group consisting of a structural unit represented by the following formula (XI) and a structural unit represented by the following formula (XA): (In the formula, R １ and R ２ each independently represents an organic group; R １ and R ２ At least one of the groups (X) contains at least one non-aromatic hydrocarbon group, and the total number of carbon atoms in the at least one non-aromatic hydrocarbon group is 9 or more. (In the formula, R ３ and R ４ each independently represents an organic group; R ３ and R ４ At least one of the groups (X) contains at least one non-aromatic hydrocarbon group, and the total number of carbon atoms in the at least one non-aromatic hydrocarbon group is 9 or more.

[0008] Another embodiment relates to a block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and having a structure derived from a diamine or a diisocyanate and a structure derived from a tetracarboxylic dianhydride, wherein at least one of the structure derived from the diamine or the diisocyanate and the structure derived from the tetracarboxylic dianhydride contains at least one non-aromatic hydrocarbon group and has a group (X) having a total carbon number of 9 or more in the at least one non-aromatic hydrocarbon group.

[0009] Another embodiment relates to a method for producing a block copolymer, comprising: obtaining a polyimide (PI) using a diamine or a diisocyanate and a tetracarboxylic dianhydride; obtaining a polyamic acid (PA) using a diamine and a tetracarboxylic dianhydride; and obtaining a block copolymer using the polyimide (PI) and the polyamic acid (PA); wherein at least one selected from the group consisting of a diamine or a diisocyanate and a tetracarboxylic dianhydride used to obtain the polyimide, and a diamine and a tetracarboxylic dianhydride used to obtain the polyamic acid, contains at least one non-aromatic hydrocarbon group and has a group (X) in which the total number of carbon atoms in the at least one non-aromatic hydrocarbon group is 9 or more.

[0010] Another embodiment relates to an insulating material and a heat-resistant insulating material containing any of the above block copolymers.

[0011] Other embodiments relate to a composition, a composition for an insulator, a composition for a heat-resistant insulator, and a composition for a printed circuit board, each containing any of the above block copolymers or any of the above materials.

[0012] Another embodiment relates to a polyimide obtained using any of the above block copolymers, any of the above materials, or any of the above compositions.

[0013] Other embodiments relate to molded articles, insulators, and heat-resistant insulators obtained using any of the above block copolymers, any of the above materials, or any of the above compositions, or including the above polyimides.

[0014] Another embodiment relates to a printed circuit board obtained using any of the above block copolymers, any of the above materials, or any of the above compositions, or including any of the above polyimides, the above molded articles, the above insulators, or the above heat-resistant insulators.

[0015] According to the present disclosure, it is possible to obtain a block copolymer capable of producing a polyimide having a low dielectric constant, a low dielectric loss tangent, and a low coefficient of thermal expansion, and a method for producing the same. Furthermore, according to the present disclosure, it is possible to obtain a polyimide, a molded article, an insulator, a heat-resistant insulator, and a printed circuit board that exhibit excellent insulating properties, excellent heat resistance, or both, as well as an insulating material, a heat-resistant insulating material, a composition, a composition for an insulator, a composition for a heat-resistant insulator, and a composition for a printed circuit board that can produce any of these.

[0016] The following describes embodiments of the present invention. The present invention is not limited to the following embodiments. The following embodiments can be implemented alone or in combination. Combinations of multiple embodiments are also included in the present invention.

[0017] In the numerical ranges described in stages in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range. Furthermore, the upper or lower limit value of a numerical range described in the present disclosure may be replaced with a value shown in the Examples. A numerical value may be selected from the upper and lower limit values ​​described in stages in the present disclosure to form a stepped numerical range. Furthermore, the upper and lower limit values ​​described in the present disclosure may be replaced with values ​​shown in the Examples. In the present disclosure, each component may contain multiple corresponding substances. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, each structure in the polymer may contain multiple corresponding structures. When multiple structures corresponding to each structure are present in the polymer, the content or amount of each structure means the total content or amount of the multiple structures present in the polymer, unless otherwise specified. In the present disclosure, the term "layer" includes not only a layer that is formed over the entire area when the area where the layer exists is observed, but also a layer that is formed only over a portion of the area. The same applies to "film."

[0018] <Block Copolymer> In some embodiments of the present invention, the block copolymer comprises a polyimide block (BI) and a polyamic acid block (BA). The block copolymer comprises a group (X) containing at least one non-aromatic hydrocarbon group, the at least one non-aromatic hydrocarbon group having a total carbon number of 9 or more. In the present disclosure, the "group (X) containing at least one non-aromatic hydrocarbon group, the at least one non-aromatic hydrocarbon group having a total carbon number of 9 or more" may be simply referred to as the "group (X)" or the "hydrocarbon group (X)."

[0019] The polyamic acid block (BA) may be a block that becomes a polyimide block (BI-A) different from the polyimide block (BI) by ring closure of the amic acid bond. The block copolymer may further contain an optional block different from the polyimide block (BI) and the polyamic acid block (BA). The block copolymer may contain one or more types of optional blocks.

[0020] In the present disclosure, whether blocks are the same or different can be distinguished by the structural units contained in the blocks. For example, if one block contains a structural unit that is not contained in the other block, the two blocks are different blocks. Examples of combinations of two different types of blocks include when block 1 contains structural unit 1 and block 2 contains structural unit 2; when block 1 contains structural unit 1 and block 2 contains structural unit 1 and structural unit 2; when block 1 contains structural unit 1 and structural unit 2 and block 2 contains structural unit 1 and structural unit 3; etc. The structural units 1, 2, and 3 used in the description here are different structural units. In the present disclosure, the number of types of structural units contained in each block is not limited to one or two, and may be three or more. In the present disclosure, the number of types of blocks contained in a block copolymer is not limited to two, and may be three or more.

[0021] A block copolymer containing a polyimide block (BI) and a polyamic acid block (BA) contains imide bonds (also referred to as "imide groups") and amic acid bonds (also referred to as "amidic acid structures" or "amidic acid groups") in the polymer chain. The hydrocarbon group (X) may be a group located between an imide group and an imide group, an amic acid group and an amic acid group, or a group located between an imide group and an amic acid group. The block copolymer may contain one or more types of hydrocarbon groups (X).

[0022] The copolymer has a block structure, which allows the production of polyimides with a low thermal expansion coefficient. The block copolymer has a hydrocarbon group (X), which allows the production of polyimides with a low dielectric constant and a low dielectric loss tangent. Furthermore, the block copolymer has a hydrocarbon group (X), which allows the production of polyimides with a low water absorption coefficient.

[0023] [Block Copolymer Comprising Structural Unit (X)] In some embodiments of the present invention, the block copolymer comprises a polyimide block (BI) and a polyamic acid block (BA), and comprises a structural unit (X) having a group (X). In the present disclosure, a "structural unit (X) having a group (X) that contains at least one non-aromatic hydrocarbon group, the at least one non-aromatic hydrocarbon group having a total carbon number of 9 or more" may be simply referred to as a "structural unit (X)."

[0024] The block copolymer may contain a structural unit other than the structural unit (X). An example of the structural unit other than the structural unit (X) is the structural unit (Y) described below. The structural unit (Y) is a structural unit that does not have a hydrocarbon group (X).

[0025] In the block copolymer, only one of the polyimide block (BI) and the polyamic acid block (BA) contains the structural unit (X), or both the polyimide block (BI) and the polyamic acid block (BA) contain the structural unit (X). The polyimide block (BI) and the polyamic acid block (BA) may each independently contain one or more structural units (X). When the block copolymer contains the structural unit (Y), only one of the polyimide block (BI) and the polyamic acid block (BA) may contain the structural unit (Y), or both the polyimide block (BI) and the polyamic acid block (BA) may contain the structural unit (Y). The polyimide block (BI) and the polyamic acid block (BA) may each independently contain one or more structural units (Y).

[0026] (Structural Unit (X)) The structural unit (X) contains at least a hydrocarbon group (X). The structural unit (X) may further contain at least one of an imide group and an amic acid group. The number of carbon atoms contained in the imide group and the amic acid group is not included in the total number of carbon atoms of the at least one non-aromatic hydrocarbon group in the hydrocarbon group (X). For example, the structural unit (X) is a structural unit containing a hydrocarbon group (X) and an imide group or an amic acid group. The block copolymer may contain the hydrocarbon group (X) contained in the structural unit (X) and the imide group or the amic acid group in the polymer chain. The structural unit (X) may contain one or more types of hydrocarbon groups (X). The structural unit (X) may further contain an optional group other than the hydrocarbon group (X), the imide group, and the amic acid group. Examples of the optional group include organic groups that do not fall under the category of hydrocarbon groups (X). In the present disclosure, an organic group is a group containing at least one carbon atom. In the present disclosure, an organic group other than the hydrocarbon group (X) that does not fall under the category of the hydrocarbon group (X) may be referred to as an "organic group (Y)." The organic group (Y) may be a pair of imide groups, an amic acid group, or a group located between an imide group and an amic acid group. The block copolymer may contain the organic group (Y) in the polymer chain.

[0027] (Hydrocarbon Group (X)) The hydrocarbon group (X) contains at least one non-aromatic hydrocarbon group. In the hydrocarbon group (X), the total number of carbon atoms in the at least one non-aromatic hydrocarbon group is 9 or more. When the hydrocarbon group (X) contains one non-aromatic hydrocarbon group, the total number of carbon atoms means the total number of carbon atoms contained in the one non-aromatic hydrocarbon group. When the hydrocarbon group (X) contains two or more non-aromatic hydrocarbon groups, the total number of carbon atoms means the total number of carbon atoms contained in the two or more non-aromatic hydrocarbon groups. When the hydrocarbon group (X) contains two or more non-aromatic hydrocarbon groups, the non-aromatic hydrocarbon groups may be the same or different. The hydrocarbon group (X) may further contain any group other than a non-aromatic hydrocarbon group. The hydrocarbon group (X) is, for example, a monovalent to tetravalent group. The structural unit (X) preferably contains a divalent to tetravalent hydrocarbon group (X), more preferably a divalent or tetravalent hydrocarbon group (X), and even more preferably a divalent hydrocarbon group (X).

[0028] The non-aromatic hydrocarbon group is a non-aromatic hydrocarbon group that does not contain an aromatic ring. The non-aromatic hydrocarbon group is, for example, a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group, an unsaturated alicyclic hydrocarbon group, or a group consisting of two or more selected from these. The saturated aliphatic hydrocarbon group may be linear or branched. The unsaturated aliphatic hydrocarbon group may be linear or branched. When the hydrocarbon group (X) contains two or more non-aromatic hydrocarbon groups, the two or more non-aromatic hydrocarbon groups may be the same or different.

[0029] Examples of hydrocarbon groups (X) and the total number of carbon atoms in at least one non-aromatic hydrocarbon group contained in the hydrocarbon group (X) are given below. Furthermore, as a reference example, examples of organic groups (Y) and the total number of carbon atoms in at least one non-aromatic hydrocarbon group contained in the organic group (Y) are given below. As will be described later, the number of carbon atoms contained in —C(O)— groups is not included in the total number of carbon atoms. In the present disclosure, "*" in a formula indicates the bonding position to another atom.

[0030]

[0031] The total carbon number of the at least one non-aromatic hydrocarbon group contained in the hydrocarbon group (X) may be 9 to 50. The carbon number is, for example, 12 or more, 16 or more, 20 or more, 24 or more, 28 or more, 32 or more, or 36 or more. The carbon number is, for example, 48 or less, 44 or less, 40 or less, or 36 or less. The carbon number is, for example, 12 to 48, 20 to 44, or 28 to 40. When the total carbon number of the non-aromatic hydrocarbon group is 9 or more, it is believed that a polyimide having a low dielectric constant and a low dielectric dissipation factor can be obtained due to reasons such as an increase in free volume and a decrease in polarity. When the total carbon number of the non-aromatic hydrocarbon group is 50 or less, good solubility in solvents can be maintained. Even if the block copolymer has a group in which the total carbon number of an aromatic hydrocarbon group and a heteroaromatic ring compound group is 9 or more instead of the hydrocarbon group (X), a polyimide having a low dielectric constant and a low dielectric dissipation factor cannot be obtained due to a small free volume.

[0032] Examples of saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, unsaturated alicyclic hydrocarbon groups, and groups consisting of two or more selected from these that the hydrocarbon group (X) may contain are given below. The following examples can be applied to saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, unsaturated alicyclic hydrocarbon groups, and groups consisting of two or more selected from these in the present disclosure.

[0033] The number of carbon atoms in the saturated aliphatic hydrocarbon group is, for example, 1 to 50, 2 to 40, 3 to 30, 4 to 20, or 5 to 10. The saturated aliphatic hydrocarbon group is, for example, an atomic group formed by removing 1 to 4 hydrogen atoms from a linear or branched alkane. Examples of the alkane include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, hexacosane, octacosane, triacontane, tetracontane, and pentacontane.

[0034] The number of carbon atoms in the unsaturated aliphatic hydrocarbon group is, for example, 2 to 50, 2 to 40, 3 to 30, 4 to 20, or 5 to 10. The unsaturated aliphatic hydrocarbon group may contain one or more carbon-carbon unsaturated bonds, and may have, for example, 5 or less, 4 or less, 3 or less, or 2 or less. The unsaturated aliphatic hydrocarbon may be an alkene containing one carbon-carbon double bond or an alkyne containing one carbon-carbon triple bond. The unsaturated aliphatic hydrocarbon group is, for example, an atomic group obtained by removing 1 to 4 hydrogen atoms from a linear or branched alkene, or an atomic group obtained by removing 1 to 4 hydrogen atoms from a linear or branched alkyne. Examples of alkenes include ethene, propene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, heneicosene, docosene, tricosene, tetracosene, pentacosene, hexacosene, heptacosene, octacosene, nonacosene, triacontene, tetracontene, and pentacontene. Examples of alkynes include ethyne, propyne, butyne, pentyne, hexyne, heptyne, octyne, nonyne, decyne, undecyne, dodecyne, tridecyne, tetradecyne, pentadecyne, hexadecyne, heptadecyne, octadecyne, nonadecyne, eicosine, heneicosine, docosine, tricosine, tetracosine, pentacosine, hexacosine, heptacosine, octacosine, nonacosine, triacontine, tetracontine, and pentacontine.

[0035] The saturated alicyclic hydrocarbon group has, for example, 3 to 20, 4 to 16, 5 to 10, or 6 to 8 carbon atoms. The saturated alicyclic hydrocarbon group is, for example, an atomic group obtained by removing 1 to 4 hydrogen atoms from a cycloalkane. Examples of cycloalkanes include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, decalin, bicyclobutane, bicyclohexane, bicyclooctane, spiropentane, spiroheptane, guadricyclane, and adamantane.

[0036] The number of carbon atoms in the unsaturated alicyclic hydrocarbon group is, for example, 4 to 20, 5 to 10, or 6 to 8. The unsaturated aliphatic hydrocarbon group may contain one or more carbon-carbon unsaturated bonds, and may have, for example, 5 or less, 4 or less, 3 or less, or 2 or less. The unsaturated aliphatic hydrocarbon may be a cycloalkene containing one carbon-carbon double bond or a cycloalkyne containing one carbon-carbon triple bond. The unsaturated alicyclic hydrocarbon group is, for example, an atomic group obtained by removing 1 to 4 hydrogen atoms from a cycloalkene, or an atomic group obtained by removing 1 to 4 hydrogen atoms from a cycloalkyne. Examples of unsaturated alicyclic hydrocarbons include cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, norbornene, norbornadiene, and bicyclooctadiene.

[0037] The number of carbon atoms in the group consisting of two or more selected from these 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 selected from these is a group consisting of two or more groups selected from the group consisting of saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, and unsaturated alicyclic hydrocarbon groups, in which the two or more groups are bonded to each other. The group having two or more selected from these includes, for example, at least one selected from the group consisting 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.

[0038] The hydrocarbon group (X) may optionally contain, for example, an aromatic hydrocarbon group, an aromatic heterocyclic group, and a group containing a heteroatom. The following examples are applicable to the aromatic hydrocarbon group, aromatic heterocyclic group, and group containing a heteroatom in the present disclosure.

[0039] The number of carbon atoms in the aromatic hydrocarbon group is, for example, 6 to 30, 6 to 20, or 6 to 10. The aromatic hydrocarbon group is, for example, an atomic group obtained by removing 1 to 4 hydrogen atoms from an aromatic hydrocarbon. Examples of aromatic hydrocarbons include benzene, naphthalene, anthracene, pyrene, and pentane. The number of carbon atoms in the aromatic heterocyclic compound group is, for example, 2 to 30, 4 to 20, or 5 to 10. The aromatic heterocyclic compound group is, for example, an atomic group obtained by removing 1 to 4 hydrogen atoms from an aromatic heterocyclic compound. Examples of aromatic heterocyclic compounds include pyridine, furan, benzofuran, thiophene, and benzothiophene.

[0040] Examples of groups containing a heteroatom include linking groups containing a heteroatom (excluding imide groups and amic acid groups) and substituents containing a heteroatom. Examples of linking groups containing a heteroatom include an oxy group, a thio group, a sulfonyl group, a sulfinyl group, a carbonyl group, a carbonyloxy group, and an imino group. Examples of substituents containing a heteroatom include a hydroxy group, a mercapto group, a sulfo group, a sulfino group, a carboxy group, a fluoro group, and a chloro group. In the present disclosure, the number of carbon atoms in the —C(O)— group contained in the group containing a heteroatom is not included in the total number of carbon atoms in the at least one non-aromatic hydrocarbon group.

[0041] The hydrocarbon group (X) is, for example, a non-aromatic hydrocarbon group having 9 or more carbon atoms. When the hydrocarbon group (X) is a non-aromatic hydrocarbon group, the hydrocarbon group (X) does not contain an aromatic hydrocarbon group, an aromatic heterocyclic compound group, or a group containing a heteroatom. 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 having 9 or more carbon atoms and consisting of two or more selected from saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, and unsaturated alicyclic hydrocarbon groups. The saturated aliphatic hydrocarbon group may be linear or branched. The unsaturated aliphatic hydrocarbon group may be linear or branched. When the hydrocarbon group (X) is a non-aromatic hydrocarbon group having 9 or more carbon atoms, the concentration of polar groups contained in the block copolymer is easily reduced.

[0042] The hydrocarbon group (X) preferably contains at least one group selected from the group consisting of saturated alicyclic hydrocarbon groups and unsaturated alicyclic hydrocarbon groups, and more preferably contains a saturated alicyclic hydrocarbon group. When the block copolymer contains at least one of a saturated alicyclic hydrocarbon group and an unsaturated alicyclic hydrocarbon group, a polyimide with a lower dielectric constant tends to be obtained. This is presumably because the polyimide has an alicyclic structure, which increases the free volume. However, the present invention is not limited by this presumption.

[0043] The hydrocarbon group (X) preferably contains at least one group selected from the group consisting of linear saturated aliphatic hydrocarbon groups having 6 or more carbon atoms and linear unsaturated aliphatic hydrocarbon groups having 6 or more carbon atoms, and more preferably contains a linear saturated aliphatic hydrocarbon group having 6 or more carbon atoms. When the block copolymer contains at least one of a linear saturated aliphatic hydrocarbon group having 6 or more carbon atoms and a linear unsaturated aliphatic hydrocarbon group having 6 or more carbon atoms, a polyimide with a lower dielectric loss tangent tends to be obtained. This is presumably because the polyimide has a long chain structure, which reduces the concentration of imide groups in the polyimide, i.e., relatively reduces the number of polar groups in the polyimide. However, the present invention is not limited by this presumption.

[0044] In some embodiments, the total number of carbon atoms in the saturated aliphatic hydrocarbon group and the unsaturated aliphatic hydrocarbon group contained in the hydrocarbon group (X) may be greater than the total number of carbon atoms in the saturated alicyclic hydrocarbon group and the unsaturated alicyclic hydrocarbon group contained in the hydrocarbon group (X).

[0045] In some embodiments, the hydrocarbon group (X) may be free of aromatic hydrocarbon groups and aromatic heterocyclic groups.

[0046] The hydrocarbon group (X) preferably contains a group represented by the following formula (G1).

[0047]

[0048] In the formula, R ｘrepresents a group (X) containing at least one non-aromatic hydrocarbon group, the total number of carbon atoms of which is 9 or more.

[0049] The hydrocarbon group (X) more preferably contains at least one selected from the group consisting of groups represented by the following formulae (G2) to (G6):

[0050]

[0051] In the formula, R ａ R each independently represents a linear or branched saturated aliphatic hydrocarbon group (having, for example, 1 or more, 6 or more, or 8 or more carbon atoms) or a linear or branched unsaturated aliphatic hydrocarbon group (having, for example, 1 or more, 6 or more, or 8 or more carbon atoms), and preferably represents a linear saturated aliphatic hydrocarbon group (having, for example, 1 or more, 6 or more, or 8 or more carbon atoms) or a linear unsaturated aliphatic hydrocarbon group (having, for example, 1 or more, 6 or more, or 8 or more carbon atoms). ｂ each independently represents a saturated alicyclic hydrocarbon group or an unsaturated alicyclic hydrocarbon group, preferably a saturated alicyclic hydrocarbon group (having, for example, 6 carbon atoms (cyclohexane group) or 7 carbon atoms (norbornane group)). L represents a single bond or a linking group containing a hetero atom (excluding imide groups and amic acid groups). R ａ and R ｂ may each independently have a substituent or may not have a substituent. ａ and R ｂ The upper limit of the number of carbon atoms is, for example, 48 or less, 44 or less, 40 or less, or 36 or less.

[0052] The hydrocarbon group (X) more preferably 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, dimer diamine as a monomer for obtaining the block copolymer. The hydrocarbon group (X) particularly preferably contains a group represented by formula (G8). When the structural unit (X) contains at least one selected from the group consisting of a group represented by formula (G7), a group represented by formula (G8), and a group represented by formula (G9), sufficient effects of low dielectric constant, low dielectric loss tangent, and low thermal expansion coefficient tend to be easily obtained.

[0053]

[0054] In the formula, R ｃ each independently represents a linear alkylene group or a linear alkenylene group (having, for example, 6 or more, 8 or more, or 9 or more carbon atoms); R ｄ R each independently represents a linear alkyl group or a linear alkenyl group (having, for example, 6 or more, 8 or more, or 9 or more carbon atoms). ｃ and R ｄ may each independently have a substituent or may not have a substituent. ｃ and R ｄ The upper limit of the number of carbon atoms is, for example, 48 or less, 44 or less, 40 or less, or 36 or less.

[0055] (Organic Group (Y)) The structural unit (X) can contain an organic group (Y). The organic group (Y) is, for example, a group containing at least one selected from the group consisting of saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups, aromatic heterocyclic compound groups, and groups consisting of two or more selected from these. When the organic group (Y) contains at least one non-aromatic hydrocarbon group, the total number of carbon atoms contained in the at least one non-aromatic hydrocarbon group is 8 or less. The organic group (Y) preferably contains an aromatic hydrocarbon group. The organic group (Y) may further contain a linking group containing a heteroatom, a substituent containing a heteroatom, or the like. The organic group (Y) is, for example, a monovalent to tetravalent group. The structural unit (X) preferably contains a divalent to tetravalent organic group (Y), more preferably contains a divalent or tetravalent organic group (Y), and even more preferably contains a tetravalent organic group (Y).

[0056] The organic group (Y) preferably contains a group represented by the following formula (G11).

[0057]

[0058] In the formula, R ｙ represents an organic group (Y).

[0059] The organic group (Y) more preferably includes at least one selected from the group consisting of groups represented by the following formulae (G12) to (G14):

[0060]

[0061] In the formula, R ｅ R each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic compound group, preferably an aromatic hydrocarbon group, more preferably a benzene group. ｆ represents a linear or branched saturated aliphatic hydrocarbon group, or a linear or branched unsaturated aliphatic hydrocarbon group. ｆ has 8 or less carbon atoms. L represents a single bond or a linking group containing a hetero atom (excluding imide groups and amic acid groups). ｅ and R ｆ may each independently have a substituent or may not have a substituent.

[0062] According to some embodiments, the organic group (Y) comprises at least one selected from the group consisting of a group represented by formula (G12) and a group represented by formula (G14), and preferably is represented by formula (12), and R ｅ is a benzene group, and a group represented by formula (14), ｅ is a benzene group, and L is a single bond or a linking group containing a hetero atom (for example, a carbonyl group). For example, the organic group (Y) is represented by formula (12), and R ｅ For example, the organic group (Y) is represented by the formula (14), and R ｅ For example, the organic group (Y) is represented by the formula (14), and R ｅ is a benzene group and L is a linking group containing a heteroatom (for example, a carbonyl group).

[0063] Examples of the structural unit (X) include a structural unit represented by formula (XI) and a structural unit represented by formula (XA) described below. In a preferred embodiment, the structural unit (X) includes at least one selected from the group consisting of a structural unit represented by formula (XI) and a structural unit represented by formula (XA). Examples of the structural unit (X) include a structural unit (Xd) described below. In a preferred embodiment, the structural unit (X) includes the structural unit (Xd).

[0064] (Structural Unit (Y)) The block copolymer may contain a structural unit (Y). The structural unit (Y) is a structural unit that does not have a hydrocarbon group (X). The structural unit (Y) may have, for example, the above-mentioned organic group (Y). The structural unit (Y) may further contain at least one of an imide group and an amic acid group. For example, the structural unit (Y) is a structural unit that contains an organic group (Y) and an imide group or an amic acid group. The block copolymer may contain the organic group (Y) contained in the structural unit (Y) and the imide group or the amic acid group in the polymer chain. The structural unit (Y) may contain one or more types of organic groups (Y).

[0065] According to some embodiments, in the structural unit (Y), the organic group (Y) preferably includes a group represented by the above formula (G11) and a group represented by the following formula (G15), and more preferably includes at least one selected from the group consisting of groups represented by the above formulas (G12) to (G14) and at least one selected from the group consisting of groups represented by the following formulas (G16) to (G18):

[0066]

[0067] In the formula, R ｙ represents an organic group (Y). ｅ R each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic compound group, preferably an aromatic hydrocarbon group, more preferably a benzene group. ｆ represents a linear or branched saturated aliphatic hydrocarbon group, or a linear or branched unsaturated aliphatic hydrocarbon group. ｆ has 8 or less carbon atoms. L represents a single bond or a linking group containing a hetero atom (excluding imide groups and amic acid groups). ｅ and R ｆ may each independently have a substituent or may not have a substituent.

[0068] According to some embodiments, in the structural unit (Y), the organic group (Y) includes, for example, at least one selected from the group consisting of groups represented by the above formulas (G12) to (G14), and at least one selected from the group consisting of groups represented by the above formulas (G16) to (G18), a group represented by the following formula (G18a), and a group represented by the following formula (G18b); preferably, it includes at least one selected from the group consisting of groups represented by the above formula (G12) and groups represented by the above formula (G14), and at least one selected from the group consisting of groups represented by the above formula (G16), groups represented by the above formula (G18), and groups represented by the following formula (G18b).

[0069]

[0070] In the formula, R ｅeach independently represents an aromatic hydrocarbon group or an aromatic heterocyclic compound group, preferably an aromatic hydrocarbon group, more preferably a benzene group. L represents a single bond or a linking group containing a hetero atom (excluding imide groups and amic acid groups). R ｅ may each independently have a substituent or may not have a substituent.

[0071] Examples of the structural unit (Y) include a structural unit represented by the formula (YI) and a structural unit represented by the formula (YA) described below. In a preferred embodiment, the structural unit (Y) includes at least one selected from the group consisting of a structural unit represented by the formula (YI) and a structural unit represented by the formula (YA). Examples of the structural unit (Y) include a structural unit (Yd) described below. In a preferred embodiment, the structural unit (Y) includes the structural unit (Yd).

[0072] [Block Copolymer Comprising a Structural Unit Represented by Formula (XI) and / or a Structural Unit Represented by Formula (XA)] In some embodiments of the present invention, the block copolymer comprises a polyimide block (BI) and a polyamic acid block (BA), and comprises at least one structural unit selected from the group consisting of a structural unit represented by the following formula (XI) and a structural unit represented by the following formula (XA). Examples of the block copolymer include a block copolymer in which the polyimide block (BI) comprises a structural unit represented by formula (XI); a block copolymer in which the polyamic acid block (BA) comprises a structural unit represented by formula (XA); and a block copolymer in which the polyimide block (BI) comprises a structural unit represented by formula (XI) and the polyamic acid block (BA) comprises a structural unit represented by formula (XA).

[0073] The block copolymer may 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). Examples of structural units other than the structural unit represented by the following formula (XI) and the structural unit represented by the following formula (XA) include a structural unit represented by the formula (YI) and a structural unit represented by the formula (YA) described below. The block copolymer may contain at least one structural unit selected from the group consisting of the structural unit represented by the formula (YI) and the structural unit represented by the formula (YA). The structural unit represented by the formula (YI) and the structural unit represented by the formula (YA) do not have a hydrocarbon group (X).

[0074] The structural unit represented by formula (XI) and the structural unit represented by formula (XA) are structural units corresponding to the structural unit (X), and examples of the structural unit represented by formula (XI) and the structural unit represented by formula (XA) include the structural unit (Xd) described below. The structural unit represented by formula (YI) and the structural unit represented by formula (YA) are structural units corresponding to the structural unit (Y), and examples of the structural unit represented by formula (YI) and the structural unit represented by formula (YA) include the structural unit (Yd) described below.

[0075] (Structural unit represented by formula (XI))

[0076]

[0077] In the formula, R １ and R ２ each independently represents an organic group; R １ and R ２ At least one of the groups is a hydrocarbon group (X).

[0078] Examples of the organic group include a hydrocarbon group (X) and an organic group (Y).

[0079] According to some embodiments, 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 consisting of groups represented by formula (G2) to groups represented by formula (G6), and R ２is a group selected from the group consisting of groups represented by formula (G12) to (G14); more preferably, R １ is a group selected from the group consisting of a group represented by (G4) and a group represented by formula (G7) to a group represented by formula (G9), and R ２ is a group represented by formula (G12); more preferably, R １ is a group represented by formula (G8), and R ２ is represented by formula (G12), and R ｅ is a benzene group.

[0080] According to some embodiments, in the structural unit represented by formula (XI), for example, R １ is a group selected from the group consisting of groups represented by formula (G2) to groups represented by formula (G6), and R ２ is a group selected from the group consisting of groups represented by formula (G12) to groups represented by formula (G14); preferably, R １ is a group selected from the group consisting of a group represented by (G4) and a group represented by formula (G7) to a group represented by formula (G9), and R ２ is a group selected from the group consisting of groups represented by formula (G12) and groups represented by formula (G14). For example, the structural unit represented by formula (XI) is １ is a group represented by formula (G8), and R ２ is a group represented by formula (G12) (R ｅ is a benzene group). For example, the structural unit represented by formula (XI) includes a structural unit represented by formula (XI) １ is a group represented by formula (G8), and R ２ is a group represented by formula (G14) (R ｅ is a benzene group and L is a linking group containing a heteroatom (for example, a carbonyl group).

[0081] (Structural unit represented by formula (XA))

[0082]

[0083] In the formula, R ３ and R ４ each independently represents an organic group; R ３ and R ４At least one of the groups is a hydrocarbon group (X).

[0084] Examples of the organic group include a hydrocarbon group (X) and an organic group (Y).

[0085] According to some embodiments, in the structural unit represented by formula (XA), for example, R ３ is a hydrocarbon group (X), and R ４ is an organic group (Y), preferably R ３ is a group selected from the group consisting of groups represented by formula (G2) to groups represented by formula (G6), and R ４ is a group selected from the group consisting of groups represented by formula (G12) to (G14); more preferably, R ３ is a group selected from the group consisting of a group represented by (G4) and a group represented by formula (G7) to a group represented by formula (G9), and R ４ is a group represented by formula (G14); more preferably, R ３ is a group represented by formula (G8), and R ４ is represented by formula (G14), and R ｅ is a benzene group.

[0086] According to some embodiments, in the structural unit represented by formula (XA), for example, R ３ is a group selected from the group consisting of groups represented by formula (G2) to groups represented by formula (G6), and R ４ is a group selected from the group consisting of groups represented by formula (G12) to groups represented by formula (G14); preferably, R ３ is a group selected from the group consisting of a group represented by (G4) and a group represented by formula (G7) to a group represented by formula (G9), and R ４ is a group selected from the group consisting of groups represented by formula (G12) and groups represented by formula (G14). For example, the structural unit represented by formula (XA) is ３ is a group represented by formula (G8), and R ４ is a group represented by formula (G12) (R ｅ is a benzene group). For example, the structural unit represented by formula (XA) includes a structural unit represented by formula (XB) ３ is a group represented by formula (G8), and R ４is a group represented by formula (G14) (R ｅ is a benzene group and L is a single bond.

[0087] (Structural unit represented by formula (YI))

[0088]

[0089] In the formula, R ５ and R ６ each independently represents an organic group (Y).

[0090] According to some embodiments, in the structural unit represented by formula (YI), for example, R ５ is a group selected from the group consisting of groups represented by formula (G16) to groups represented by formula (G18), and R ６ is a group selected from the group consisting of groups represented by formula (G12) to groups represented by formula (G14); preferably, R ５ is a group represented by formula (G16) or a group represented by formula (G18), and R ６ is a group represented by formula (G12) or a group represented by formula (G14); more preferably, R ５ is expressed by formula (G16) and R ｅ is a benzene group or a group represented by formula (18), ｅ is a benzene group, and R ６ is expressed by formula (G12) and R ｅ is a benzene group or a group represented by formula (14), ｅ is a benzene group.

[0091] According to some embodiments, in the structural unit represented by formula (YI), for example, R ５ is a group selected from the group consisting of groups represented by formula (G16) to groups represented by formula (G18b), and R ６ is a group selected from the group consisting of groups represented by formula (G12) to groups represented by formula (G14); preferably, R ５ is a group selected from the group consisting of a group represented by formula (G16), a group represented by formula (G18), and a group represented by formula (G18b), and R ６ is a group represented by formula (G12) or a group represented by formula (G14); more preferably, R ５is a group represented by formula (G18), and R ６ is a group represented by formula (12). For example, the structural unit represented by formula (YI) is ５ is a group represented by formula (G18) (R ｅ is a benzene group, L is a group containing a heteroatom (e.g., an oxy group), and R ６ is a group represented by formula (12) (R ｅ is a benzene group).

[0092] (Structural unit represented by formula (YA))

[0093]

[0094] In the formula, R ７ and R ８ each independently represents an organic group (Y).

[0095] According to some embodiments, in the structural unit represented by formula (YA), for example, R ７ is a group selected from the group consisting of groups represented by formula (G16) to groups represented by formula (G18), and R ８ is a group selected from the group consisting of groups represented by formula (G12) to groups represented by formula (G14); preferably, R ７ is a group represented by formula (G16) or a group represented by formula (G18), and R ８ is a group represented by formula (G12) or a group represented by formula (G14); more preferably, R ７ is expressed by formula (G16) and R ｅ is a benzene group or a group represented by formula (18), ｅ is a benzene group, and R ８ is expressed by formula (G12) and R ｅ is a benzene group or a group represented by formula (14), ｅ is a benzene group.

[0096] According to some embodiments, in the structural unit represented by formula (YA), for example, R ７ is a group selected from the group consisting of groups represented by formula (G16) to groups represented by formula (G18b), and R ８is a group selected from the group consisting of groups represented by formula (G12) to groups represented by formula (G14); preferably, R ７ is a group selected from the group consisting of a group represented by formula (G16), a group represented by formula (G18), and a group represented by formula (G18b), and R ６ is a group represented by formula (G12) or a group represented by formula (G14); more preferably, R ７ is a group represented by formula (16) or a group represented by formula (18b), and R ８ is a group represented by formula (14). For example, the structural unit represented by formula (YA) is ７ is a group represented by formula (16) (R ｅ is a benzene group, and R ８ is a group represented by formula (G14) (R ｅ is a benzene group, and L is a single bond). For example, the structural unit represented by formula (YA) includes a structural unit represented by formula (YA) ７ is a group represented by formula (18b) (R ｅ is a benzene group, each L is independently a single bond or a group containing a heteroatom (e.g., an oxy group), and R ８ is a group represented by formula (G14) (R ｅ is a benzene group and L is a single bond.

[0097] (Content, etc.) The polyimide block (BI) preferably contains a structural unit represented by formula (XI), and more preferably contains a structural unit represented by formula (XI) in which the hydrocarbon group (X) contains a saturated alicyclic hydrocarbon group.

[0098] In the polyimide block (BI), the content of the hydrocarbon group (X) is R １ ~R ８ The content of the hydrocarbon group (X) is preferably 0 to 70 mass %, 10 to 60 mass %, or 20 to 50 mass % based on the total mass of the above. In particular, when the content of the hydrocarbon group (X) is 20 mass % or more, a polyimide having a low dielectric constant and a low dielectric loss tangent is likely to be obtained. In the polyimide block (BI), the content of the organic group (Y) is preferably 0 to 70 mass %, 10 to 60 mass %, or 20 to 50 mass % based on the total mass of the above. １ ~R ８The content of the organic group (Y) containing at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group is preferably 0 to 60 mass %, 2 to 50 mass %, or 4 to 40 mass % based on the total mass of the blocks and the polymers. In particular, when the content of the organic group (Y) containing at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group is 4 mass % or more, a polyimide having good mechanical strength and heat resistance is likely to be obtained. In the present disclosure, depending on the structure contained in the block or polymer, the content of "R １ ~R ８ R in "total mass" １ ~R ８ The mass of any one or more of the above may be zero.

[0099] The polyamic acid block (BA) preferably contains a structural unit represented by formula (YA), and more preferably contains a structural unit represented by formula (YA) in which the organic group (Y) contains an aromatic hydrocarbon group.

[0100] In the polyamic acid block (BA), the content of the hydrocarbon group (X) is R １ ~R ８ In the polyamic acid block (BA), the content 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 ８ In particular, when the content of the organic group (Y) containing at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group is 40 mass % or more, a polyimide having good mechanical strength and heat resistance is likely to be obtained.

[0101] In the block copolymer, the content of the hydrocarbon group (X) is R １ ~R ８ 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 components (a) and (b). From the viewpoint of reducing the dielectric constant and the dielectric loss tangent, it is preferable that the content of the hydrocarbon group (X) is large. In particular, when the content of the hydrocarbon group (X) is 10 mass % or more, a polyimide having a low dielectric constant and a low dielectric loss tangent is likely to be obtained.

[0102] In the block copolymer, the content of the organic group (Y) is 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 components. From the viewpoint of obtaining good mechanical strength and heat resistance, it is preferable that the organic group (Y) contains at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group, and it is preferable that the content of such organic group (Y) is high. In particular, when the content of the organic group (Y) containing at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group is 50 mass % or more, a polyimide having good mechanical strength and heat resistance is likely to be obtained.

[0103] (Optional Structural Unit) The block copolymer may further contain other optional structural units in addition to the structural units represented by formula (YI) and formula (YA). The content of the other optional structural units 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 structural units contained in the block copolymer. Examples of the other optional structural units include structural units containing a structure derived from a trifunctional or higher polyamine or a structure derived from a trifunctional or higher polyisocyanate, 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, and a structural unit having an amic acid group and an amide group. These optional structural units may or may not contain a hydrocarbon group (X).

[0104] [Block Copolymer Comprising a Structure Derived from a Diamine or Diisocyanate and a Structure Derived from a Tetracarboxylic Dianhydride] In some embodiments of the present invention, the block copolymer comprises a polyimide block (BI) and a polyamic acid block (BA), and has a structure derived from a diamine or diisocyanate and a structure derived from a tetracarboxylic dianhydride, wherein at least one of the structure derived from the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride comprises a structure having a hydrocarbon group (X). Examples of the structure having a hydrocarbon group (X) include a structure derived from a diamine or diisocyanate having a hydrocarbon group (X) and a structure derived from a tetracarboxylic dianhydride having a hydrocarbon group (X). In the present disclosure, "diamine or diisocyanate" means "at least one compound selected from the group consisting of diamines and diisocyanates."

[0105] In a preferred embodiment, the structure derived from at least a diamine or a diisocyanate includes a structure derived from a diamine or a diisocyanate having a hydrocarbon group (X). The structure derived from a tetracarboxylic dianhydride may include a structure derived from a tetracarboxylic dianhydride having a hydrocarbon group (X).

[0106] In a preferred embodiment, the structure derived from at least a tetracarboxylic dianhydride includes a structure derived from a tetracarboxylic dianhydride having an organic group (Y). The structure derived from a diamine or a diisocyanate may include a structure derived from a diamine or a diisocyanate having an organic group (Y).

[0107] In the present disclosure, a structural unit having a structure derived from a diamine or diisocyanate and a structure derived from a tetracarboxylic dianhydride, in which 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 hydrocarbon group (X), may be referred to as a "structural unit (Xd)".

[0108] (Diamine Having Hydrocarbon Group (X)) The diamine having a hydrocarbon group (X) can be represented by, for example, the following formula (Ax).

[0109]

[0110] In the formula, R ｘ represents a hydrocarbon group (X). ｘ Examples of the group include the groups represented by the above formulae (G2) to (G9).

[0111] Specific examples of diamines having a hydrocarbon group (X) include the following: diamines having 9 or more carbon atoms and having a saturated aliphatic hydrocarbon group, such as 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,14-diaminotetradecane, and 1,16-diaminohexadecane; diamines having 9 or more carbon atoms and having an unsaturated aliphatic hydrocarbon group, such as 1,9-diaminononene, 1,10-diaminodecene, 1,11-diaminoundecene, 1,12-diaminododecene, 1,14-diaminotetradecene, and 1,16-diaminohexadecene; diamines having 9 or more carbon atoms and having a saturated alicyclic hydrocarbon group, such as isophoronediamine, bis(aminomethyl)norbornane, 1,3-diaminoadamantane, and 4,4'-diaminodicyclohexylmethane; Diamines having 9 or more carbon atoms and having an unsaturated alicyclic hydrocarbon group, such as bis(aminomethyl)norbornene and 4,4'-diaminodicyclohexenylmethane; monounsaturated fatty acids, such as crotonic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, and nervonic acid; diunsaturated fatty acids, such as linoleic acid, eicosadienoic acid, and docosadienoic acid; and diamines derived from dimers (also called dimer acids) of unsaturated fatty acids, such as linolenic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, and triunsaturated fatty acids, such as eicosatrienoic acid; and dimer diamines having 9 or more carbon atoms, such as diamines in which the carbon-carbon double bonds contained in the molecule of these diamines have been hydrogenated.

[0112] Commercially available dimer diamines having 9 or more carbon atoms include, for example, "PRIAMINE 1075" and "PRIAMINE 1074" manufactured by Croda Japan Co., Ltd.

[0113] (Diamine Having Organic Group (Y)) The diamine having the organic group (Y) can be represented by, for example, the following formula (Ay).

[0114]

[0115] In the formula, R ｙ represents an organic group (Y). ｙ Examples of the group include the groups represented by the above formulae (G16) to (G18b).

[0116] Specific examples of the diamine having an organic group (Y) include the following. Diamines having a saturated aliphatic hydrocarbon group and a carbon number of 8 or less, such as 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane; diamines having a saturated aliphatic hydrocarbon group and a carbon number of 8 or less, such as 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, and 1,4-bis(aminomethyl)cyclohexane; diamines having a non-aromatic hydrocarbon group and a carbon number of 8 or less, such as 1,4-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diamino-3,3'-dimethyldiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, and 4,4'-bis(4-aminophenoxy)biphenyl.

[0117] (Diisocyanate Having Hydrocarbon Group (X)) The diisocyanate having a hydrocarbon group (X) can be represented, for example, by the following formula (Ix).

[0118]

[0119] In the formula, R ｘ represents a hydrocarbon group (X). ｘ Examples of the group include the groups represented by the above formulae (G2) to (G9).

[0120] Specific examples of diisocyanates having a hydrocarbon group (X) include compounds having the same structure as the compounds shown as specific examples of the diamines above, except that the amino group is replaced with an isocyanate group.

[0121] (Diisocyanate Having Organic Group (Y)) The diisocyanate having the organic group (Y) can be represented by, for example, the following formula (Iy).

[0122]

[0123] In the formula, R ｙ represents an organic group (Y). ｙ Examples of the group include the groups represented by the above formulae (G16) to (G18b).

[0124] Specific examples of diisocyanates having an organic group (Y) include compounds having the same structure as the compounds shown as specific examples of diamines above, except that the amino group is replaced with an isocyanate group.

[0125] (Tetracarboxylic acid dianhydride having hydrocarbon group (X)) The tetracarboxylic acid dianhydride having hydrocarbon group (X) can be represented by, for example, the following formula (Cx).

[0126]

[0127] In the formula, R ｘ represents a hydrocarbon group (X). Preferred examples of the hydrocarbon group (X) are as described above.

[0128] Specific examples of tetracarboxylic dianhydrides having a hydrocarbon group (X) include the following. The "carbon number" below refers to the number of carbon atoms in the hydrocarbon group (X), and does not include the number of carbon atoms contained in the carboxylic acid anhydride group. Tetracarboxylic dianhydrides having 9 or more carbon atoms and an alicyclic hydrocarbon group, such as 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride and 2,2-bis(3,4-dicarboxycyclohexyl)propane dianhydride.

[0129] (Tetracarboxylic acid dianhydride having organic group (Y)) The tetracarboxylic acid dianhydride having organic group (Y) can be represented by, for example, the following formula (Cy).

[0130]

[0131] In the formula, R ｙ represents an organic group (Y). ｙ Examples of the group include the groups represented by the above formulae (G12) to (G14).

[0132] Specific examples of tetracarboxylic dianhydrides having an organic group (Y) include the following: The "number of carbon atoms" below refers to the number of carbon atoms in the non-aromatic hydrocarbon group contained in the organic group (Y), and does not include the number of carbon atoms contained in the aromatic ring and the carboxylic acid anhydride group. Tetracarboxylic acid dianhydrides having 8 or less carbon atoms and containing a saturated aliphatic hydrocarbon group, such as 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,5,6-hexanetetracarboxylic acid dianhydride; Tetracarboxylic acid dianhydrides having 8 or less carbon atoms and containing a saturated alicyclic hydrocarbon group, such as 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride; Tetracarboxylic acid dianhydrides having 8 or less carbon atoms and containing an aromatic hydrocarbon group, such as pyromellitic acid dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic anhydride, 3,4'-oxydiphthalic anhydride; Tetracarboxylic acid dianhydrides having an aromatic heterocyclic group and having 8 or less carbon atoms, such as pyridinetetracarboxylic acid dianhydride and thiophenetetracarboxylic acid dianhydride

[0133] The structure derived from a 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 having 9 or more carbon atoms and having a saturated aliphatic hydrocarbon group, a structure derived from a diamine having 9 or more carbon atoms and having an unsaturated aliphatic hydrocarbon group, a structure derived from a diamine having 9 or more carbon atoms and having a saturated alicyclic hydrocarbon group, a structure derived from a diamine having 9 or more carbon atoms and having an unsaturated alicyclic hydrocarbon group, and a structure derived from a diamine having 9 or more carbon atoms; and even more preferably includes a structure derived from a diamine having 9 or more carbon atoms.

[0134] The structure derived from a diamine or diisocyanate preferably includes a structure derived from a diamine or diisocyanate having a hydrocarbon group (X), and more preferably includes a structure derived from a diamine or diisocyanate having a hydrocarbon group (X) and a structure derived from a diamine or diisocyanate having an aromatic hydrocarbon group.

[0135] In the block copolymer, for example, the structure derived from a diamine or diisocyanate contained in the polyamic acid block (BA) includes a structure derived from a diamine or diisocyanate having an aromatic hydrocarbon group.

[0136] The structure derived from a tetracarboxylic dianhydride preferably includes a structure derived from a tetracarboxylic dianhydride having an organic group (Y); more preferably includes a structure derived from a tetracarboxylic dianhydride having an aromatic hydrocarbon group; and even more preferably includes at least one selected from the group consisting of a structure derived from pyromellitic dianhydride and a structure derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0137] (Content, etc.) In the polyimide block (BI), the content 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. In particular, when the content 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 dissipation factor is likely to be obtained. In the polyimide block (BI), the content 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. In particular, when the content of the structure having the organic group (Y) containing at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group is 10 mass % or more, a polyimide having good mechanical strength and heat resistance is likely to be obtained.

[0138] In the polyamic acid block (BA), the content of the structure having a hydrocarbon group (X) is preferably 0 to 60 mass%, 10 to 50 mass%, or 20 to 40 mass%, based on the total mass of the structure derived from a diamine or diisocyanate and the structure derived from a tetracarboxylic dianhydride. In particular, when the content of the structure having a hydrocarbon group (X) is 10 mass% or more, a polyimide having a low dielectric constant and a low dielectric dissipation factor is likely to be obtained. In the polyamic acid block (BA), the content of the structure having an organic group (Y) is preferably 30 to 100 mass%, 50 to 95 mass%, or 70 to 90 mass%, based on the total mass of the structure derived from a diamine or diisocyanate and the structure derived from a tetracarboxylic dianhydride. In particular, when the content of the structure having an organic group (Y) containing at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group is 70 mass% or more, a polyimide having good mechanical strength and heat resistance is likely to be obtained.

[0139] In the block copolymer, the content of the structure having a hydrocarbon group (X) is preferably 3 to 60 mass%, 5 to 50 mass%, or 10 to 40 mass%, 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 reducing the dielectric constant and the dielectric loss tangent, a large content of the structure having a hydrocarbon group (X) is preferred. In particular, when the content of the structure having a hydrocarbon group (X) is 5 mass% or more, a polyimide having a low dielectric constant and a low dielectric loss tangent is likely to be obtained.

[0140] In the block copolymer, the content of the structure having an organic group (Y) is preferably 40 to 97% by mass, 50 to 95% by mass, or 60 to 90% by 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 good mechanical strength and heat resistance, the organic group (Y) preferably contains at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group, and the content of such a structure having an organic group (Y) is preferably high. In particular, when the content of the structure having an organic group (Y) containing at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group is 50% by mass or more, a polyimide having good mechanical strength and heat resistance is likely to be obtained.

[0141] (Optional Structure) The block copolymer may further contain another optional structure in addition to the structure derived from a diamine or diisocyanate and the structure derived from a tetracarboxylic dianhydride. In the block copolymer, the content of the other optional structural unit is, for example, 0 to 10% by mass or 0 to 5% by mass based on the total mass of all structures contained in the block copolymer. The other optional structure may include an optional structure derived from a tri- or higher functional polyamine or polyisocyanate, a structure derived from a dicarboxylic acid compound, or a structure derived from a tricarboxylic acid compound. These optional structures may or may not contain a hydrocarbon group (X).

[0142] [Block Copolymer Obtained Using Diamine or Diisocyanate and Tetracarboxylic Acid Dianhydride] In some embodiments of the present invention, the block copolymer is obtained using a polyimide (PI) obtained using a diamine or diisocyanate and a tetracarboxylic acid dianhydride, and a polyamic acid (PA) obtained using a diamine and a tetracarboxylic acid dianhydride, wherein at least one selected from the group consisting of the diamine or diisocyanate and the tetracarboxylic acid dianhydride used to obtain the polyimide (PI) and the diamine and the tetracarboxylic acid dianhydride used to obtain the polyamic acid (PA) has a hydrocarbon group (X). Methods for obtaining the polyimide (PI), the polyamic acid (PA), and the block copolymer will be described later.

[0143] [Polyimide Block (BI)] When the block copolymer has the polyimide block (BI), it is possible to prevent an exchange reaction or crosslinking from occurring when the block copolymer is obtained or when the amide acid group is ring-closed.

[0144] In the present disclosure, the polyimide block (BI) has an imide group content relative to the total of imide groups and amic acid groups of, for example, more than 50 mol%, 80 mol% or more, or 90 mol% or more. The upper limit of the imide group content may be 100 mol%. In the present disclosure, the content can be measured by Fourier Transform Infrared Spectroscopy (FTIR).

[0145] The polyimide block (BI) may or may not contain the structural unit (X). In the block copolymer, when the polyimide block (BI) does not contain the structural unit (X), the polyimide block (BI) contains the structural unit (Y). In the block copolymer, when the polyimide block (BI) does not contain the structural unit (X), the polyamic acid block (BA) contains the structural unit (X).

[0146] 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. A number average molecular weight of 500 or more tends to make it easier to obtain a polyimide with a low expansion coefficient. A number average molecular weight of 10,000 or less tends to make it easier to ensure the solubility of the block copolymer in a solvent. The number average molecular weight of the polyimide block (BI) is, for example, 500 to 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 measured by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. Specifically, it can be determined by the method described in the Examples.

[0147] The polyimide block (BI) may be a linear block or a branched block, and is preferably a linear block.

[0148] [Polyamic Acid Block (BA)] When the block copolymer contains a polyamic acid block, it tends to have good solubility in a solvent.

[0149] In the present disclosure, the polyamic acid block (BA) has a content of amic acid groups relative to the total of imide groups and amic acid groups of, for example, more than 50 mol%, 80 mol% or more, or 90 mol% or more. The upper limit of the content of amic acid groups may be 100 mol%. The content can be measured by FTIR.

[0150] The polyamic acid block (BA) may or may not contain the structural unit (X). In the block copolymer, when the polyamic acid block (BA) does not contain the structural unit (X), the polyamic acid block (BA) contains the structural unit (Y). In the block copolymer, when the polyamic acid block (BA) does not contain the structural unit (X), the polyimide block (BI) contains the structural unit (X).

[0151] 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 6,000 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. A number average molecular weight of 500 or more tends to make it easier to obtain good film-forming properties. A number average molecular weight of 30,000 or less tends to make it easier to adjust the viscosity of a composition containing a block copolymer and a solvent to a level suitable for application. The number average molecular weight of the polyamic acid block (BA) is, for example, 500 to 30,000, 1,000 to 25,000, 3,000 to 20,000, or 6,000 to 10,000.

[0152] The polyamic acid block (BA) may be a linear block or a branched block, and is preferably a linear block.

[0153] [Molecular Weight of Block Copolymer, Content of Structural Unit (X), etc.] When a block copolymer contains a polyimide block (BI) and a polyamic acid block (BA), a polyimide having a low thermal expansion coefficient tends to be obtained. This is thought to be because the block structure facilitates orientation of polyimide molecules.

[0154] In the block copolymer, 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) may each independently contain one or more types of hydrocarbon groups (X).

[0155] 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. A number average molecular weight of 5,000 or more tends to make it easier to obtain good film-forming properties. A number average molecular weight of 100,000 or less tends to make it easier to adjust the viscosity of a composition containing the block copolymer and a solvent to a level suitable for application. 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.

[0156] The content of the polyimide block (BI) in the block copolymer is more than 0% by mass and less than 100% by mass, based on the mass of the block copolymer. The content of the polyimide block (BI) is, for example, more than 0% by mass, 30% by mass or more, 60% by mass or more, or 90% by mass or more. The content of the polyimide block (BI) is, for example, less than 100% by mass, 70% by mass or less, 40% by mass or less, or 10% by mass or less. The content of the polyimide block (BI) is, for example, more than 0% by mass and 70% by mass or less, more than 0% by mass and 40% by mass or less, 30% by mass or more and less than 100% by mass, or 60% by mass or more and less than 100% by mass. The content of the polyimide block (BI) may be, for example, 10 to 60% by mass or 20 to 50% by mass.

[0157] The content of the polyamic acid block (BA) in the block copolymer is greater than 0% by mass and less than 100% by mass, based on the mass of the block copolymer. The content of the polyamic acid block (BA) is, for example, greater than 0% by mass, 30% by mass or more, 60% by mass or more, or 90% by mass or more. The content of the polyamic acid block (BA) is, for example, less than 100% by mass, 70% by mass or less, 40% by mass or less, or 10% by mass or less. The content of the polyamic acid block (BA) is, for example, greater than 0% by mass and 70% by mass or less, greater than 0% by mass and 40% by mass or less, 30% by mass or more and less than 100% by mass, or 60% by mass or more and less than 100% by mass. The content of the polyimide block (BI) may be, for example, 40 to 90% by mass or 50 to 80% by mass.

[0158] The higher the content of the polyimide block (BI), the more effectively it is possible to prevent exchange reactions and crosslinking when obtaining a block copolymer or when ring-closing an amic acid group.On the other hand, the higher the content of the polyamic acid block (BA), the more easily the block copolymer dissolves in an organic solvent.

[0159] In the block copolymer, for example, the number average molecular weight of the polyimide block (BI) is smaller than that of the polyamic acid block (BA). Preferably, the block copolymer contains a polyimide block (BI) and a polyamic acid block (BA) having a number average molecular weight larger than that of the polyimide block (BI). When the number average molecular weight of the polyimide block (BI) is smaller than that of the polyamic acid block (BA), the block copolymer is easy to synthesize and the solubility of the block copolymer tends to be ensured. By including a polyamic acid block (BA) having a number average molecular weight larger than that of the polyimide block (BI), a block copolymer having a sufficient number average molecular weight tends to be easy to synthesize.

[0160] The block copolymer is preferably such that a polyimide obtained by using the block copolymer satisfies one or more of the dielectric constant, dielectric loss tangent, thermal expansion coefficient, and water absorption described below. Particularly preferably, the block copolymer is such that a polyimide obtained by using the block copolymer satisfies one or more of the dielectric constant, dielectric loss tangent, and thermal expansion coefficient described below.

[0161] [Applications] In some embodiments of the present invention, a polyimide having a low dielectric constant, low dielectric loss tangent, and low thermal expansion coefficient can be obtained using a block copolymer. The resulting polyimide can be used in various electronic and mechanical components, such as displays, solar cells, touch panels, organic electroluminescence (EL) lighting, millimeter-wave radar, high-frequency antennas, and high-speed transmission substrates. Among these, the polyimide is preferably used in devices used in high-frequency ranges, such as millimeter-wave radar, high-frequency antennas, and high-speed transmission substrates. Millimeter-wave radar detects objects by transmitting millimeter waves toward them and receiving reflected waves from them. Automotive millimeter-wave radars installed in vehicles are used in collision prevention systems, autonomous driving systems, and the like. High-frequency antennas require high frequencies and high-speed transmission for high-speed communication in communication devices and the like. Therefore, materials with lower dielectric constants and lower dielectric loss tangents are desirable when high-frequency antennas are housed in the housings of compact communication devices and the like. Examples of high-speed transmission substrates include high-speed transmission cables and high-speed transmission connectors.

[0162] <Method for Producing Block Copolymer> In some embodiments of the present invention, a method for producing a block copolymer includes obtaining a polyimide (PI) using a diamine or diisocyanate and a tetracarboxylic dianhydride; obtaining a polyamic acid (PA) using a diamine and a tetracarboxylic dianhydride; and obtaining a block copolymer using the polyimide (PI) and the polyamic acid (PA), wherein at least one selected from the group consisting of the diamine or 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) has a hydrocarbon group (X). This production method makes it possible to easily produce the block copolymer of the above-mentioned embodiment.

[0163] For the synthesis of polyimide (PI) and polyamic acid (PA), monomers such as the above-mentioned diamines, diisocyanates, tetracarboxylic dianhydrides, polyamines, polyisocyanates, dicarboxylic acid compounds, and tricarboxylic acid compounds can be used.

[0164] The reaction of the monomers can be carried out by solution polymerization. Examples of solvents that can be used during the reaction include polar solvents such as N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), 3-methoxy-N,N-dimethylpropanamide (MPA), N,N'-dimethylformamide, N,N'-dimethylpropyleneurea [1,3-dimethyl-3,4,5,6-tetrahydropyridimine-2(1H)-one], dimethyl sulfoxide, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and sulfolane; aromatic hydrocarbon solvents such as xylene and toluene; and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. The solvent preferably contains at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and 3-methoxy-N,N-dimethylpropanamide (MPA), and more preferably contains at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), and 3-methoxy-N,N-dimethylpropanamide (MPA).

[0165] The amount of solvent used is preferably 100 to 600 parts by mass, and more preferably 200 to 400 parts by mass, per 100 parts by mass of the total amount of monomers. When the amount of solvent used is 100 parts by mass or more, the respective monomers can be reacted homogeneously. When the amount of solvent used is 600 parts by mass or less, the polymerization reaction can be promoted. Furthermore, when the amount of solvent used is small, a polyimide (PI) or polyamic acid (PA)-containing liquid containing polyimide (PI) or polyamic acid (PA) at a high concentration can be obtained.

[0166] The reaction temperature when synthesizing polyamic acid using monomers is not particularly limited. The reaction temperature may be, for example, 10 to 50°C, or 20 to 40°C. The reaction time may be, for example, 30 minutes to 24 hours, 1 to 12 hours, or 3 to 6 hours. The reaction product may be sampled to measure the number average molecular weight, the concentration of residual amino groups or isocyanate groups, etc., and the reaction time may be adjusted so as to obtain the desired reaction product.

[0167] The temperature when obtaining a polyimide using a polyamic acid (i.e., when imidizing) is not particularly limited. The imidization temperature may be, for example, 120 to 200°C, or 160 to 180°C. The reaction time may be, for example, 30 minutes to 24 hours, 1 to 12 hours, or 3 to 6 hours. The reaction product may be sampled to measure the number average molecular weight, the concentration of remaining amic acid groups, etc., and the reaction time may be adjusted so as to obtain the desired reaction product.

[0168] In view of ease of synthesis, it is preferred that the polymer chain of the polyimide (PI) be terminated with a carboxylic acid anhydride group, and the polymer chain of the polyamic acid (PA) be terminated with an amino group. The ratio of the diamine or diisocyanate to the tetracarboxylic acid dianhydride used to obtain the 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 the diamine to the tetracarboxylic acid dianhydride used to obtain the 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.

[0169] A block copolymer is synthesized using polyimide (PI) and polyamic acid (PA). Any other polymer may also be used in the synthesis.

[0170] The reaction between the polyimide (PI) and the polyamic acid (PA) can be carried out by solution polymerization. As the solvent for the reaction, the above-mentioned solvents can be used.

[0171] The reaction temperature is not particularly limited. From the viewpoint of allowing the reaction to proceed sufficiently, the reaction temperature may be, for example, 20 to 100°C, 30 to 80°C, or 40 to 70°C. The reaction time is, for example, 30 minutes to 24 hours, 1 to 12 hours, or 3 to 6 hours. The reaction product is sampled to measure the number average molecular weight, the concentration of remaining amino groups or isocyanate groups, and the like, and the reaction time can be adjusted so that the desired reaction product is obtained.

[0172] In some embodiments of the present invention, the insulating material and the heat-resistant insulating material contain the block copolymer according to any one of the above-described embodiments. The block copolymer is preferably used as the insulating material or the heat-resistant insulating material because the polyimide obtained using the block copolymer has excellent insulating properties and heat-resistant insulating properties.

[0173] <Composition> In some embodiments of the present invention, a composition contains the block copolymer of any of the above-described embodiments and a solvent. Examples of solvents contained in the composition include the above-described reaction solvents that can be used in synthesizing the block copolymer. The solvent preferably contains at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and 3-methoxy-N,N-dimethylpropanamide (MPA), and more preferably contains at least one solvent selected from the group consisting of N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and 3-methoxy-N,N-dimethylpropanamide (MPA). The composition can be preferably used as a composition for an insulator, a composition for a heat-resistant insulator, or a composition for a printed circuit board.

[0174] The composition may further contain optional components such as polyamide, polyethersulfone, acrylic polymer, epoxy compound, isocyanate compound, melamine compound, filler, antifoaming agent, preservative, surfactant, etc. The composition can be produced, for example, by a method in which the block copolymer, a solvent, and optional components used as needed are mixed and stirred.

[0175] The content of the block copolymer can be within a range suitable for the intended use of the composition, for example, 5 to 50 mass %, 8 to 40 mass %, or 10 to 30 mass %, based on the mass of the composition.

[0176] The viscosity of the composition is preferably 2 to 30 Pa s, more preferably 5 to 20 Pa s, and even more preferably 10 to 15 Pa s at 30° C. In the present disclosure, the viscosity can be measured using a rotational B-type viscometer with a No. 3 rotor at 30° C.

[0177] <Polyimide> In some embodiments of the present invention, a polyimide can be obtained using the block copolymer of any of the above-described embodiments or the composition of any of the above-described embodiments. For example, since the block copolymer contains a polyamic acid block (BA), the polyimide can be obtained by converting the amic acid group into an imide group through ring closure (this conversion may be referred to as "imidization" in the present disclosure). The imidization method is not particularly limited. A method of heating the block copolymer is preferably used because it is simple. The heating temperature is, for example, 250 to 400°C.

[0178] Polyimides obtained from block copolymers contain polyimide blocks (BI) and polyimide blocks (BI-A) which are blocks formed by imidizing polyamic acid blocks (BA). The polyimide blocks (BI) and (BI-A) are different blocks. Due to their block structure, polyimides exhibit a low coefficient of thermal expansion. Due to the presence of hydrocarbon groups (X), polyimides exhibit a low dielectric constant and a low dielectric loss tangent. Furthermore, due to the presence of hydrocarbon groups (X), polyimides tend to exhibit low water absorption.

[0179] The dielectric constant of the polyimide is, for example, 3.5 or less, 3.0 or less, or 2.5 or less from the viewpoint of obtaining excellent insulating properties. The dielectric constant of the polyimide is not particularly limited, but is, for example, 2.0 or more. The dielectric constant (Dk) can be measured using a polyimide film (e.g., 25 μm thick) by a cavity resonator method (TE mode) under conditions of a frequency of 10 GHz and a measurement temperature of 25°C. The dielectric constant (Dk) may be a value obtained by measuring the polyimide film immediately after thoroughly drying it and leaving it to stand in an atmosphere at a temperature of 23°C and a relative humidity of 50% for 24 hours.

[0180] The dielectric dissipation factor of the polyimide is, for example, 0.0100 or less, 0.0050 or less, or 0.0020 or less from the viewpoint of suppressing transmission loss. The dielectric dissipation factor of the polyimide is not particularly limited, but is, for example, 0.0005 or more. The dielectric dissipation factor (Df) can be measured using a polyimide film (e.g., 25 μm thick) by a cavity resonator method (TE mode) under conditions of a frequency of 10 GHz and a measurement temperature of 25°C. The dielectric dissipation factor (Df) may be a value obtained by measuring the polyimide film immediately after thoroughly drying it and leaving it to stand for 24 hours in an atmosphere at a temperature of 23°C and a relative humidity of 50%.

[0181] The coefficient of thermal expansion (CTE) of polyimide 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 polyimide 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 consideration that the polyimide film will be used by being attached to another material. The coefficient of thermal expansion (ppm / K) can be determined by converting the average linear thermal expansion coefficient (ppm / °C) from 30 to 200°C measured using a polyimide film (e.g., 25 μm thick) at a heating rate of 10°C / min using a thermomechanical analyzer. The coefficient of thermal expansion may be, for example, 70 ppm / K or less, 60 ppm / K or less, 40 ppm / K or less, or 30 ppm / K or less.

[0182] The glass transition temperature (Tg) of the polyimide is, for example, 200°C or higher, 250°C or higher, or 300°C or higher from the viewpoint of the heat resistance of the molded article. The glass transition temperature (Tg) of the polyimide is not particularly limited, but is, for example, 600°C or lower. The glass transition temperature can be determined as the temperature (°C) corresponding to the inflection point in a linear thermal expansion coefficient curve from 30 to 200°C measured using a polyimide film (for example, a thickness of 25 μm) at a heating rate of 10°C / min using a thermomechanical analyzer.

[0183] The water absorption rate of polyimide is, for example, 1.0% or less, 0.5% or less, or 0.3% or less from the viewpoint of preventing changes in dielectric properties due to moisture absorption. The water absorption rate of polyimide is not particularly limited, but is, for example, 0.0% or more. The water absorption rate (%) can be calculated using the following formula from the weights before and after immersion of a polyimide film (e.g., thickness 25 μm, width 70 mm, length 70 mm) in water at 23° C. for 24 hours after drying: Water absorption rate (%) = (weight of polyimide film after water absorption - weight of polyimide film before water absorption) / weight of polyimide film before water absorption × 100

[0184] More specifically, the relative dielectric constant, dielectric loss tangent, coefficient of thermal expansion, glass transition temperature, and water absorption of a polyimide can be measured by preparing a polyimide film according to the method described in the Examples and using the prepared polyimide film according to the method described in the Examples.

[0185] <Molded body, insulator, heat-resistant insulator> In some embodiments of the present invention, a molded body, an insulator, and a heat-resistant insulator are obtained using the block copolymer, material, or composition of any of the above-described embodiments, or include the polyimide of any of the above-described embodiments. The insulator preferably has a relative dielectric constant of 3.5 or less and a dielectric dissipation factor of 0.0100 or less. The heat-resistant insulator preferably has a relative dielectric constant of 3.5 or less, a dielectric dissipation factor of 0.0100 or less, and a thermal expansion coefficient of 80 ppm / K or less.

[0186] The shapes of the molded body, insulator, and heat-resistant insulator are not particularly limited and may be any shape suitable for the application. For example, they may be in the form of a film, plate, membrane, layer, etc. The molded body, insulator, and heat-resistant insulator can be used in various electronic and mechanical parts.

[0187] In some embodiments of the present invention, a printed circuit board is obtained using the block copolymer, material, or composition of any of the above-described embodiments, or includes the polyimide, molded article, insulator, or heat-resistant insulator of any of the above-described embodiments. The printed circuit board of the present invention has low transmission loss and excellent heat resistance.

[0188] Examples of printed circuit boards include printed wiring boards and printed circuit boards. Examples of printed circuit boards include flexible boards and rigid boards. Examples of printed circuit boards include single-sided boards, double-sided boards, and multilayer boards. For example, the materials, protective films, insulating layers, etc. of these boards are obtained using block copolymers or include polyimides, etc.

[0189] An example of a flexible substrate is a substrate that includes a base film, and the base film is obtained using a block copolymer or contains polyimide, etc. Another example of a flexible substrate is a substrate that includes a base film and a heat-resistant insulating layer formed on the base film, and at least the heat-resistant insulating layer is obtained using a block copolymer or contains polyimide, etc.

[0190] <Examples of Embodiments> Examples of embodiments of the present invention are listed below. The present invention is not limited to the following embodiments. [1] A block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and comprising a structural unit (X) having a group (X) which contains at least one non-aromatic hydrocarbon group and in which the total number of carbon atoms in the at least one non-aromatic hydrocarbon group is 9 or more. [2] A block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and comprising at least one structural unit selected from the group consisting of a structural unit represented by the following formula (XI) and a structural unit represented by the following formula (XA): Or a block copolymer which satisfies the above [1] and [2]. (In the formula, R １ and R ２ each independently represents an organic group; R １ and R ２ At least one of the groups (X) contains at least one non-aromatic hydrocarbon group, and the total number of carbon atoms in the at least one non-aromatic hydrocarbon group is 9 or more. (In the formula, R ３ and R ４ each independently represents an organic group; R ３ and R ４ at least one of which is a group (X) containing at least one non-aromatic hydrocarbon group, the at least one non-aromatic hydrocarbon group having a total carbon number of 9 or more. [3] The block copolymer according to the above [2], further containing at least one selected from the group consisting of a structural unit represented by the following formula (YI) and a structural unit represented by the following formula (YA): (In the formula, R ５ and R ６ each independently represents an organic group (Y), and the organic group (Y) is an organic group that does not fall under the group (X). (In the formula, R ７ and R ８ each independently represents an organic group (Y), and the organic group (Y) is an organic group that does not fall under the group (X). [4] The content of the group (X) is １ ~R ８[5] The block copolymer according to [3] above, wherein the organic group (Y) in formula (YI) and formula (YA) contains an aromatic hydrocarbon group. [6] The block copolymer according to any of [3] to [5] above, wherein the polyamic acid block (BA) contains a structural unit represented by formula (YA). [7] A block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and having a structure derived from a diamine or diisocyanate and a structure derived from a tetracarboxylic dianhydride, wherein at least one of the structure derived from the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride contains at least one non-aromatic hydrocarbon group, and the at least one non-aromatic hydrocarbon group has a total carbon number of 9 or more and has a group (X). Or a block copolymer satisfying the above [1] and [7], the above [2] and [7], or the above [1], [2] and [7]. [8] The block copolymer according to the above [7], wherein the content of the structure having the group (X) is 3 to 60 mass% based on the total mass of the structure derived from the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride. [9] The block copolymer according to the above [7] or [8], wherein the structure derived from the diamine or diisocyanate includes a structure derived from a diamine or diisocyanate having the group (X) and a structure derived from a diamine or diisocyanate having an aromatic hydrocarbon group.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[21] A method for producing a block copolymer, comprising: obtaining a polyimide (PI) using a diamine or diisocyanate and a tetracarboxylic dianhydride; obtaining a polyamic acid (PA) using a diamine and a tetracarboxylic dianhydride; and obtaining a block copolymer using the polyimide (PI) and the polyamic acid (PA), wherein at least one selected from the group consisting of a diamine or diisocyanate and a tetracarboxylic dianhydride used to obtain the polyimide (PI) and a diamine and a tetracarboxylic dianhydride used to obtain the polyamic acid (PA) contains a compound having a group (X) containing at least one non-aromatic hydrocarbon group, the at least one non-aromatic hydrocarbon group having a total carbon number of 9 or more. Or, a method for producing a block copolymer, satisfying one or more of [1], [2], and [7] above, as well as

[21] .

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

[20] above.

[23] A heat-resistant insulating material containing the block copolymer according to any one of [1] to

[20] above.

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

[20] above and a solvent.

[25] A composition for an insulator containing the block copolymer according to any one of [1] to

[20] above or the insulating material according to

[22] above and a solvent.

[26] A composition for a heat-resistant insulator containing the block copolymer according to any one of [1] to

[20] above or the heat-resistant insulating material according to

[23] above and a solvent.

[27] A composition for a printed circuit board containing the block copolymer according to any one of [1] to

[20] above, the insulating material according to

[22] above, or the heat-resistant insulating material according to

[23] above and a solvent.

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

[20] above or the composition according to

[24] above.

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

[20] above, the insulating material according to

[22] above, the heat-resistant insulating material according to

[23] above, or the composition according to any one of

[24] to

[27] above, or comprising the polyimide according to

[28] above.

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

[20] above, the insulating material according to

[22] above, the heat-resistant insulating material according to

[23] above, or the composition according to any one of

[24] to

[27] above, or comprising the polyimide according to

[28] above.

[31] The insulator according to

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

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

[20] above, the insulating material according to

[22] above, the heat-resistant insulating material according to

[23] above, or the composition according to any one of

[24] to

[27] above, or comprising the polyimide according to

[28] above.

[33] The heat-resistant insulator according to

[32] above, having a relative dielectric constant of 3.5 or less, a dielectric dissipation factor of 0.0100 or less, and a thermal expansion coefficient of 80 ppm / K or less.

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

[20] above, the insulating material according to

[22] above, the heat-resistant insulating material according to

[23] above, or the composition according to any one of

[24] to

[27] above, or comprising the polyimide according to

[28] above, the molded product according to

[29] above, the insulator according to

[30] or

[31] above, or the heat-resistant insulator according to

[32] or

[33] above.

[0191]

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

[34] , the block copolymer is represented by the above-mentioned formula (XI), and R １ a structural unit which is a group (X) containing at least one non-aromatic hydrocarbon group, the at least one non-aromatic hydrocarbon group having a total carbon number of 12 or more, and a structural unit which is represented by the formula (XA), ３The compound includes at least one structural unit selected from the group consisting of structural units which are groups (X) containing at least one non-aromatic hydrocarbon group, and the at least one non-aromatic hydrocarbon group has a total carbon number of 12 or more.

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

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

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

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

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

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

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

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

[0192] The disclosure of this application is related to the subject matter described in PCT / JP2023 / 017047, filed on May 1, 2023, the entire disclosure of which is incorporated herein by reference.

[0193] The embodiments of the present invention will be described in more detail with reference to examples, but the embodiments of the present invention are not limited to the following examples.

[0194] <Synthesis of Polyimide (PI) and Polyamic Acid (PA)> [Polyimide (PI-1)] 62.3 g (0.12 mol) of dimer diamine ("PRIAMINE 1075", Croda Japan Co., Ltd., containing a dimer diamine represented by the following formula) (hereinafter referred to as "DDA") was dissolved in 400.0 g of dimethylacetamide and 20.0 g of toluene to obtain a diamine solution. 29.0 g (0.13 mol) of pyromellitic dianhydride (hereinafter referred to as "PMDA") was added to the diamine solution, and the reaction was carried out until a uniform, transparent solution was obtained. The reaction was carried out by stirring the solution at 50°C or less for one hour or more. The transparent solution was then subjected to a dehydrothermal imidization reaction while stirring at 180°C for four hours or more, to obtain a solution (varnish) of polyimide (PI-1) having an acid anhydride structure derived from PMDA at the terminal. The number average molecular weight of polyimide (PI-1) was 6,100.

[0195]

[0196] [Polyimides (PI-2) to (PI-9)] Solutions of polyimides (PI-2) to (PI-9) were obtained in the same manner as for polyimide (PI-1), except that the diamines and tetracarboxylic dianhydrides shown in Table 2 were used.

[0197] [Polyamic Acid (PA-1)] 32.6 g (0.30 mol) of p-phenylenediamine (hereinafter referred to as "PPD") was dissolved in 485.6 g of dimethylacetamide to obtain a diamine solution. 84.9 g (0.29 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter referred to as "BPDA") was added to the diamine solution and reacted to obtain a solution of polyamic acid (polyimide precursor) (PA-1) having a PPD-derived amine structure at the end. The reaction was carried out by stirring the solution at 50°C or below for at least 8 hours. The number average molecular weight of polyamic acid (PA-1) was 9,100.

[0198] [Polyamic Acids (PA-2) to (PA-9)] Solutions of polyamic acids (PA-2) to (PA-9) were obtained in the same manner as for polyamic acid (PA-1), except that the diamines and tetracarboxylic dianhydrides shown in Table 2 and dimethylacetamide and N-methyl-2-pyrrolidone were used as the solvents.

[0199] <Synthesis of Block Copolymer (Block Polyamic Acid Imide)> [Example 1] 506.5 g of a solution of polyimide (PI-1) and 603.1 g of a solution of polyamic acid (PA-1) were mixed and reacted to obtain a varnish of block polyamic acid imide 1. The reaction was carried out by stirring the solution at 100°C or less for 1 hour or more. The number average molecular weight of block polyamic acid imide 1 was 25,240. The concentration of block polyamic acid imide 1 was 19.5% by mass based on the mass of the varnish. The varnish was a composition containing a block copolymer and a solvent.

[0200] Examples 2 to 9 Varnishes of block polyamic acid imides 2 to 9 were obtained in the same manner as in Example 1, except that the polyimide and polyamic acid solutions shown in Table 2 were used.

[0201] <Synthesis of Polyamic Acid> [Comparative Example 1] 76.6 g (0.38 mol) of 4,4'-diaminodiphenyl ether (hereinafter referred to as "ODA") was dissolved in 640.0 g of dimethylacetamide to obtain a diamine solution. 81.8 g (0.38 mol) of pyromellitic dianhydride (hereinafter referred to as "PMDA") was added to the diamine solution and reacted to obtain a solution of polyamic acid (polyimide precursor). The reaction was carried out by stirring the solution at 50°C or less for 8 hours or more.

[0202] Comparative Examples 2 to 6 Varnishes of polyamic acids 2 to 6 were obtained in the same manner as in Comparative Example 1, except that the diamines and tetracarboxylic dianhydrides shown in Table 3 were used.

[0203] Tables 2 and 3 show the diamines and tetracarboxylic dianhydrides used in the synthesis of the polyimides and polyamic acids, and the types and amounts of the polyimides and polyamic acids used in the synthesis of the block polyamic acid imides. Tables 2 and 3 also show the number average molecular weights of the polyimides and polyamic acids. The number average molecular weights were measured according to the following method.

[0204] The meanings of the abbreviations in Tables 2 and 3 are as follows: PMDA: Pyromellitic dianhydride BTDA: 3,3',4,4'-benzophenonetetracarboxylic dianhydride BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride DDA: Dimer diamine NBDA: Bis(aminomethyl)norbornane ODA: 4,4'-diaminodiphenyl ether PPD: p-phenylenediamine BODA: 4,4'-bis(4-aminophenoxy)biphenyl

[0205]

[0206]

[0207] (Number Average Molecular Weight) The number average molecular weight (Mn) was measured by gel permeation chromatography (GPC) and converted using a calibration curve of standard polystyrene. The calibration curve was approximated by a cubic equation using a set of five standard polystyrene samples ("TSK Standard POLYSTYRENE", manufactured by Tosoh Corporation). The GPC conditions are as follows: GPC apparatus: High-speed GPC apparatus HLC-8320GPC (manufactured by Tosoh Corporation) Detector: Ultraviolet absorption detector UV-8320 (manufactured by Tosoh Corporation) Column: Gelpack GL-S300MDT-5 (total of 2 columns) (manufactured by Resonac Corporation) Eluent: THF / DMF = 1 / 1 (volume ratio) + LiBr (0.06 mol / L) + H ３ P.O. ４ (0.06 mol / L) Flow rate: 1 mL / min Column size: 8 mm ID x 300 mm Sample concentration: 5 mg / 1 mL Injection volume: 5 μL Measurement temperature: 40°C

[0208] <Film Production> [Example 1] A film was produced using the obtained varnish (composition) according to the following procedure. The surface of a commercially available glass substrate was degreased with acetone, and a varnish of block polyamic acid imide 1 was applied using a film applicator with a film thickness adjustment function so that the film thickness after imidization would be 25 μm. The applied varnish was pre-dried using a hot plate at 80°C for 60 minutes to form a layer of block polyamic acid imide 1. Next, the layer of block polyamic acid imide 1 was heated in an inert gas oven in a nitrogen atmosphere at 350°C for 1 hour to obtain a film of block polyimide 1. The glass substrate on which the film was formed was immersed in warm water for about 15 minutes, and then the film was peeled off from the glass substrate.

[0209] [Examples 2 to 9 and Comparative Examples 1 to 6] Films were obtained in the same manner as above, except that the varnish of block polyamic acid imide 1 was changed to the varnishes of Examples 2 to 9 and Comparative Examples 1 to 6.

[0210] <Film Evaluation> The properties of the films produced using the varnishes of Examples 1 to 9 and Comparative Examples 1 to 6 were evaluated according to the following methods. The evaluation results are shown in Tables 2 and 3. All of Examples 1 to 9 showed good results in terms of tensile strength, tensile modulus, and elongation at break.

[0211] (Dielectric Constant and Dielectric Loss Tangent) The film was cut into a size of 60 mm x 60 mm, dried at 125°C for 1 hour, and then left for 24 hours under conditions of a temperature of 23°C and a relative humidity of 50%. Immediately after leaving, the dielectric properties (dielectric constant Dk and dielectric loss tangent Df) of the film were measured using a cavity resonator method (TE mode). Anritsu Corporation's "MS46122B" was used for the measurement. The conditions were a frequency of 10 GHz and a measurement temperature of 25°C.

[0212] (Linear thermal expansion coefficient (thermal expansion coefficient) and glass transition temperature) The film was cut into a width of 4 mm and a length of 25 mm to prepare a test piece. For the measurement, a thermomechanical analyzer ("TMA7100", manufactured by Hitachi High-Tech Science Corporation) was used. The test piece was heated from room temperature to 350 ° C. at a rate of 10 ° C. / min using a tensile method with a chuck distance of 10 mm and a load of 10 g, and then cooled to 30 ° C. at a rate of 10 ° C. / min. The temperature was again raised at a rate of 10 ° C. / min, and the average linear thermal expansion coefficient (ppm / ° C.) from 30 ° C. to 200 ° C. was calculated, and the obtained value was taken as the linear thermal expansion coefficient (ppm / K). The temperature corresponding to the inflection point of the linear thermal expansion coefficient curve was taken as the glass transition temperature (° C.).

[0213] (Water absorption rate) The film was cut into a size of 70 mm wide and 70 mm long to prepare a test piece. The test piece was dried at 125°C for 1 hour, and then the weight of the test piece was measured. Next, the test piece was immersed in water at 23°C for 24 hours, and then the test piece was removed from the water, and the water on the surface was completely removed. The weight of the test piece was measured 1 minute after removal, and the increase in weight before and after the test was determined. The water absorption rate was calculated based on the following formula: Water absorption rate (%) = (weight of test piece after water absorption - weight of test piece before water absorption) / weight of test piece before water absorption x 100

[0214] (Tensile strength, tensile modulus, and elongation at break) A film was cut into a size of 10 mm wide and 60 mm long to prepare a test specimen. A tensile test was conducted under the following measurement conditions, and the maximum tensile stress applied during the tensile test was defined as the tensile strength (MPa). The elongation at break (%) was calculated by dividing the amount of elongation of the test specimen until breakage by the chuck distance of 20 mm. In addition, Young's modulus (MPa) was calculated from the slope of the elastic deformation region at the beginning of the stress rise, and the obtained value was defined as the tensile modulus (MPa). Other detailed conditions and calculation methods were performed in accordance with the international standard ISO 5271 (1993). Apparatus name: "Autograph AGS-100NG" (product name) manufactured by Shimadzu Corporation Test speed: 5 mm / min Chuck distance: 20 mm Test specimen size: Width 10 mm, length 60 mm Set temperature: Room temperature (25°C)

Claims

1. It contains a polyimide block (BI) and a polyamic acid block (BA), The polymerizable compound includes a structural unit (X) having a group (X) which contains at least one non-aromatic hydrocarbon group, and the total number of carbon atoms in the at least one non-aromatic hydrocarbon group is 9 or more. Block copolymer.

2. It contains a polyimide block (BI) and a polyamic acid block (BA), The structural unit includes at least one selected from the group consisting of a structural unit represented by the following formula (XI) and a structural unit represented by the following formula (XA): Block copolymer. 【Chemical 1】 (In the formula, R １ and R ２ each independently represents an organic group; R １ and R ２ At least one of the groups (X) contains at least one non-aromatic hydrocarbon group, and the total number of carbon atoms in the at least one non-aromatic hydrocarbon group is 9 or more. 【Chemistry 2】 (In the formula, R ３ and R ４ each independently represents an organic group; R ３ and R ４ At least one of the groups (X) contains at least one non-aromatic hydrocarbon group, and the total number of carbon atoms in the at least one non-aromatic hydrocarbon group is 9 or more.

3. The block copolymer according to claim 2 , further comprising at least one selected from the group consisting of a structural unit represented by the following formula (YI) and a structural unit represented by the following formula (YA): 【Chemistry 3】 (In the formula, R ５ and R ６ each independently represents an organic group (Y), and the organic group (Y) is an organic group that does not fall under the group (X). 【Chemistry 4】 (In the formula, R ７ and R ８ each independently represents an organic group (Y), and the organic group (Y) is an organic group that does not fall under the group (X).

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

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

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

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

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

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

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

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

12. The block copolymer according to any one of claims 1 to 10, wherein the group (X) is a saturated aliphatic hydrocarbon group having 9 or more carbon atoms, an unsaturated aliphatic hydrocarbon group having 9 or more carbon atoms, a saturated alicyclic hydrocarbon group having 9 or more carbon atoms, an unsaturated alicyclic hydrocarbon group having 9 or more carbon atoms, or a group having 9 or more carbon atoms and consisting of two or more types selected from saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, and unsaturated alicyclic hydrocarbon groups.

13. The block copolymer according to any one of claims 1 to 10, wherein the group (X) contains a saturated alicyclic hydrocarbon group.

14. The block copolymer according to any one of claims 1 to 10, wherein the group (X) contains a linear saturated aliphatic hydrocarbon group having 6 or more carbon atoms.

15. The block copolymer according to any one of claims 1 to 10, wherein the number of carbon atoms is 12 or more.

16. The block copolymer according to any one of claims 1 to 10, wherein the number of carbon atoms is 28 or more.

17. The block copolymer according to any one of claims 1 to 10, wherein only one of the polyimide block (BI) and the polyamic acid block (BA) contains the group (X).

18. The block copolymer according to any one of claims 1 to 10, wherein both the polyimide block (BI) and the polyamic acid block (BA) contain the group (X).

19. 11. The block copolymer according to claim 1, wherein the polyimide block (BI) has a number average molecular weight of 500 to 10,000.

20. 11. The block copolymer according to claim 1, wherein the polyamic acid block (BA) has a number average molecular weight of 500 to 30,000.

21. Obtaining polyimide (PI) using diamine or diisocyanate and tetracarboxylic dianhydride; Obtaining polyamic acid (PA) using a diamine and a tetracarboxylic dianhydride; and obtaining a block copolymer using the polyimide (PI) and the polyamic acid (PA), at least one selected from the group consisting of a diamine or diisocyanate and a tetracarboxylic dianhydride used to obtain the polyimide (PI), and a diamine and a tetracarboxylic dianhydride used to obtain the polyamic acid (PA) contains at least one non-aromatic hydrocarbon group, and the at least one non-aromatic hydrocarbon group contains a compound having a group (X) in which the total number of carbon atoms in the non-aromatic hydrocarbon group is 9 or more; Method for producing block copolymers.

22. An insulating material comprising the block copolymer according to any one of claims 1 to 10.

23. A heat-resistant insulating material comprising the block copolymer according to any one of claims 1 to 10.

24. A composition comprising the block copolymer according to any one of claims 1 to 10 and a solvent.

25. An insulating composition comprising the block copolymer according to any one of claims 1 to 10.

26. A heat-resistant insulating composition comprising the block copolymer according to any one of claims 1 to 10.

27. A composition for printed circuit boards, comprising the block copolymer according to any one of claims 1 to 10.

28. A polyimide obtained by using the block copolymer according to any one of claims 1 to 10.

29. A molded article obtained by using the block copolymer according to any one of claims 1 to 10, or comprising a polyimide obtained by using said block copolymer.

30. An insulator obtained by using the block copolymer according to any one of claims 1 to 10, or comprising a polyimide obtained by using said block copolymer.

31. 31. The insulator of claim 30, having a dielectric constant of 3.5 or less and a dissipation factor of 0.0100 or less.

32. A heat-resistant insulator obtained by using the block copolymer according to any one of claims 1 to 10, or comprising a polyimide obtained by using said block copolymer.

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

34. A printed circuit board obtained by using the block copolymer according to any one of claims 1 to 10, or comprising a polyimide, a molded product, an insulator, or a heat-resistant insulator obtained by using said block copolymer.

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