Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present disclosure relates to block copolymers, methods for producing block copolymers, insulating materials, heat-resistant insulating materials, compositions, compositions for insulators, compositions for heat-resistant insulators, compositions for printed circuit boards, polyimides, molded bodies, insulators, heat-resistant insulators, and printed circuit boards.
• Insulating materials for in-vehicle millimeter wave radar circuit boards require resins with low transmission signal loss and high heat resistance that can withstand the high temperatures near the engine.
• Polyimide is known as an insulating material with excellent heat resistance (for example, Patent Document 1).
• the present disclosure provides a block copolymer capable of producing a polyimide having a low dielectric constant, a low dielectric tangent, and a low coefficient of thermal expansion, and a method for producing the same.
• the present disclosure also provides polyimides, molded bodies, insulators, heat-resistant insulators, and printed circuit boards that exhibit excellent insulating properties, excellent heat resistance, or both, as well as insulating materials, heat-resistant insulating materials, compositions, compositions for insulators, compositions for heat-resistant insulators, and compositions for printed circuit boards that can produce any of these.
• the present invention includes the following embodiments.
• the present invention is not limited to the following embodiments.
• 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.
• a block copolymer comprising a polyimide block (BI) and a polyamic acid block (BA), and comprising at least one selected from the group consisting of a structural unit represented by the following formula (XI) and a structural unit represented by the following formula (XA):
• R1 and R2 each independently represent an organic group, and at least one of R1 and R2 is a group (X) containing at least one non-aromatic hydrocarbon group, the total number of carbon atoms of the at least one non-aromatic hydrocarbon group being 9 or more.
• R3 and R4 each independently represent an organic group, and at least one of R3 and R4 is a group (X) containing at least one non-aromatic hydrocarbon group, the total number of carbon atoms of the at least one non-aromatic hydrocarbon group being 9 or more.
• Another embodiment relates to a block copolymer that includes a polyimide block (BI) and a polyamic acid block (BA), has a structure derived from a diamine or diisocyanate and a structure derived from a tetracarboxylic dianhydride, and at least one of the structure derived from the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride includes at least one non-aromatic hydrocarbon group, and includes a group (X) having a total carbon number of 9 or more in the at least one non-aromatic hydrocarbon group.
• BI polyimide block
• BA polyamic acid block
• Another embodiment relates to 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 the diamine or diisocyanate and the tetracarboxylic dianhydride used to obtain the polyimide, and the diamine and the 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.
• compositions 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 of which contains any of the above block copolymers or any of the above materials.
• 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.
• inventions 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.
• Another embodiment relates to a printed circuit board obtained by using any of the block copolymers, any of the materials, or any of the compositions, or including the polyimide, the molded body, the insulator, or the heat-resistant insulator.
• a block copolymer capable of obtaining a polyimide having a low dielectric constant, a low dielectric tangent, and a low coefficient of thermal expansion, and a method for producing the same.
• polyimides, molded bodies, insulators, heat-resistant insulators, and printed circuit boards that exhibit excellent insulating properties, excellent heat resistance, or both, as well as insulating materials, heat-resistant insulating materials, compositions, compositions for insulators, compositions for heat-resistant insulators, and compositions for printed circuit boards that can obtain any of these.
• the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range.
• the upper limit or lower limit of the numerical range described in the present disclosure may be replaced with a value shown in the examples.
• a certain numerical value may be selected from the upper limit numerical value and the lower limit numerical value described in the present disclosure in stages to form a stepped numerical range.
• the upper limit numerical value and the lower limit numerical value described in the present disclosure may be replaced with a value shown in the examples.
• each component may contain multiple types of corresponding substances.
• each structure in the polymer may contain multiple types of corresponding structures.
• the content or amount of each structure means the total content or amount of the multiple types of structures present in the polymer, unless otherwise specified.
• the term "layer” includes a layer that is formed over the entire area when the area is observed, as well as a layer that is formed only in a part of the area. The same applies to "film.”
• the block copolymer includes a polyimide block (BI) and a polyamic acid block (BA).
• the block copolymer includes a group (X) that includes 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.
• group (X) that includes 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 may be simply referred to as “group (X)” or "hydrocarbon group (X)".
• 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.
• whether blocks are the same or different can be distinguished by the structural units contained in the blocks.
• the two blocks are different blocks.
• Examples of combinations of two different types of blocks include a case where block 1 contains structural unit 1 and block 2 contains structural unit 2; a case where block 1 contains structural unit 1 and block 2 contains structural unit 1 and structural unit 2; a case where 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 explanation here are different structural units.
• the number of types of structural units contained in each block is not limited to 1 or 2, and may be 3 or more.
• the number of types of blocks contained in a block copolymer is not limited to 2, and may be 3 or more.
• the block copolymer containing a polyimide block (BI) and a polyamic acid block (BA) contains imide bonds (also called “imide groups”) and amic acid bonds (also called “amido acid structures” or “amido acid groups”) in the polymer chain.
• the hydrocarbon group (X) may be 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).
• the copolymer has a block structure, which makes it possible to obtain a polyimide with a low thermal expansion coefficient.
• the block copolymer has a hydrocarbon group (X), which makes it possible to obtain a polyimide with a low dielectric constant and a low dielectric tangent. Furthermore, the block copolymer has a hydrocarbon group (X), which makes it easy to obtain a polyimide with a low water absorption rate.
• the block copolymer includes a polyimide block (BI) and a polyamic acid block (BA), and includes a structural unit (X) having a group (X).
• 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" may be simply referred to as a "structural unit (X)".
• the block copolymer may contain structural units other than the structural unit (X).
• An example of a 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).
• either 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).
• the block copolymer contains the structural unit (Y)
• either one of the polyimide block (BI) and the polyamic acid block (BA) may contain the structural unit (Y)
• 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).
• 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 at least one non-aromatic hydrocarbon group in the hydrocarbon group (X).
• 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 any group other than the hydrocarbon group (X), the imide group, and the amic acid group.
• the arbitrary group may be, for example, an organic group that does not fall under the category of the hydrocarbon group (X).
• the organic group is a group containing at least one carbon atom.
• 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 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 the organic group (Y) in the polymer chain.
• the hydrocarbon group (X) contains at least one non-aromatic hydrocarbon group.
• the total number of carbon atoms in the at least one non-aromatic hydrocarbon group is 9 or more.
• the total number of carbon atoms means the total number of carbon atoms contained in the one non-aromatic hydrocarbon group.
• 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.
• the non-aromatic hydrocarbon groups may be the same or different from each other.
• the hydrocarbon group (X) may further contain any group other than the 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 contains a divalent or tetravalent hydrocarbon group (X), and even more preferably contains a divalent hydrocarbon group (X).
• a non-aromatic hydrocarbon group is a non-aromatic hydrocarbon group that does not contain an aromatic ring.
• a 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.
• 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.
• an example of an organic group (Y) and the total number of carbon atoms in at least one non-aromatic hydrocarbon group contained in the organic group (Y) is given.
• the number of carbon atoms contained in -C(O)- groups is not included in the total number of carbon atoms.
• "*" in the formula indicates the bonding position with other atoms.
• the total number of carbon atoms of at least one non-aromatic hydrocarbon group contained in the hydrocarbon group (X) may be 9 to 50.
• the carbon number is, for example, 12 or more, 16 or more, 20 or more, 24 or more, 28 or more, 32 or more, or 36 or more.
• the carbon number is, for example, 48 or less, 44 or less, 40 or less, or 36 or less.
• the carbon number is, for example, 12 to 48, 20 to 44, or 28 to 40.
• the block copolymer has a group in which the total number of carbon atoms of the aromatic hydrocarbon group and the 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 tangent cannot be obtained because of a small free volume.
• 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.
• the following examples can be applied to the saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, saturated alicyclic hydrocarbon groups, unsaturated alicyclic hydrocarbon groups, and groups consisting of two or more selected from these in this disclosure.
• 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 obtained by removing 1 to 4 hydrogen atoms from a linear or branched alkane.
• alkanes examples 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.
• 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 number of carbon-carbon unsaturated bonds contained in the unsaturated aliphatic hydrocarbon group is one or more, and may be, for example, 5 or less, 4 or less, 3 or less, or 2 or less.
• the unsaturated aliphatic hydrocarbon may be an alkene containing one carbon-carbon double bond, or an alkyne containing one carbon-carbon triple bond.
• the unsaturated aliphatic hydrocarbon group is, for example, 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.
• 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.
• alkynes examples 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.
• the number of carbon atoms in the saturated alicyclic hydrocarbon group is, for example, 3 to 20, 4 to 16, 5 to 10, or 6 to 8.
• the saturated alicyclic hydrocarbon group is, for example, an atomic group obtained by removing 1 to 4 hydrogen atoms from a cycloalkane.
• cycloalkanes examples include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, decalin, bicyclobutane, bicyclohexane, bicyclooctane, spiropentane, spiroheptane, guadricyclane, and adamantane.
• 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 number of carbon-carbon unsaturated bonds contained in the unsaturated aliphatic hydrocarbon group is one or more, and may be, for example, 5 or less, 4 or less, 3 or less, or 2 or less.
• the unsaturated aliphatic hydrocarbon may be a cycloalkene containing one carbon-carbon double bond, or a cycloalkyne containing one carbon-carbon triple bond.
• the unsaturated alicyclic hydrocarbon group is, for example, 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.
• unsaturated alicyclic hydrocarbons include cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, norbornene, norbornadiene, and bicyclooctadiene.
• 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, and 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.
• the optional groups that the hydrocarbon group (X) may contain include, for example, aromatic hydrocarbon groups, aromatic heterocyclic compound groups, and groups containing heteroatoms.
• aromatic hydrocarbon groups aromatic heterocyclic compound groups, and groups containing heteroatoms.
• the following examples may be applied to the aromatic hydrocarbon groups, aromatic heterocyclic compound groups, and groups containing heteroatoms in this disclosure.
• 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.
• 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.
• aromatic heterocyclic compounds include pyridine, furan, benzofuran, thiophene, and benzothiophene.
• Examples of groups containing heteroatoms include linking groups containing heteroatoms (excluding imide groups and amide acid groups) and substituents containing heteroatoms.
• Examples of linking groups containing heteroatoms include oxy groups, thio groups, sulfonyl groups, sulfinyl groups, carbonyl groups, carbonyloxy groups, and imino groups.
• Examples of substituents containing heteroatoms include hydroxy groups, mercapto groups, sulfo groups, sulfino groups, carboxy groups, fluoro groups, and chloro groups.
• the carbon number of -C(O)- groups contained in groups containing heteroatoms is not included in the total carbon number of at least one non-aromatic hydrocarbon group.
• the hydrocarbon group (X) is, for example, a non-aromatic hydrocarbon group having 9 or more carbon atoms.
• the hydrocarbon group (X) does not include 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 types selected from a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, a saturated alicyclic hydrocarbon group, and an unsaturated alicyclic hydrocarbon group.
• the saturated aliphatic hydrocarbon group may be linear or branched.
• the unsaturated aliphatic hydrocarbon group may be linear or branched.
• the hydrocarbon group (X) is a non-aromatic hydrocarbon group having 9 or more carbon atoms, it is easy to reduce the concentration of polar groups contained in the block copolymer.
• 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.
• a polyimide having a lower dielectric constant tends to be obtained. This is presumably because the polyimide has an alicyclic structure, which increases the free volume.
• the present invention is not limited by the above presumption.
• 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.
• 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 having a lower dielectric tangent tends to be obtained.
• the concentration of imide groups in the polyimide is lowered due to the polyimide having a long chain structure, that is, the number of polar groups in the polyimide is relatively reduced.
• the present invention is not limited by the above presumption.
• the hydrocarbon group (X) preferably contains a group represented by the following formula (G1):
• R x represents a group (X) containing at least one non-aromatic hydrocarbon group, the total number of carbon atoms of the at least one non-aromatic hydrocarbon group being 9 or more.
• the hydrocarbon group (X) contains at least one selected from the group consisting of groups represented by the following formulas (G2) to (G6):
• R a each independently represents a linear or branched saturated aliphatic hydrocarbon group (carbon number is, for example, 1 or more, 6 or more, or 8 or more), or a linear or branched unsaturated aliphatic hydrocarbon group (carbon number is, for example, 1 or more, 6 or more, or 8 or more), preferably a linear saturated aliphatic hydrocarbon group (carbon number is, for example, 1 or more, 6 or more, or 8 or more) or a linear unsaturated aliphatic hydrocarbon group (carbon number is, for example, 1 or more, 6 or more, or 8 or more).
• R b each independently represents a saturated alicyclic hydrocarbon group or an unsaturated alicyclic hydrocarbon group, preferably a saturated alicyclic hydrocarbon group (carbon number is, for example, 6 (cyclohexane group) or 7 (norbornane group)).
• L represents a single bond or a linking group containing a hetero atom (excluding imide group and amic acid group).
• R a and R b each independently may or may not have a substituent.
• the upper limit of the number of carbon atoms in R a and R b is, for example, 48 or less, 44 or less, 40 or less, or 36 or less.
• 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).
• the structural unit (X) contains at least one selected from the group consisting of a group represented by the formula (G7), a group represented by the formula (G8), and a group represented by the formula (G9), sufficient effects of low dielectric constant, low dielectric tangent, and low thermal expansion coefficient tend to be easily obtained.
• R c each independently represents a linear alkylene group or a linear alkenylene group (having, for example, 6 or more, 8 or more, or 9 or more carbon atoms)
• R d each independently represents a linear alkyl group or a linear alkenyl group (having, for example, 6 or more, 8 or more, or 9 or more carbon atoms).
• R c and R d each independently may or may not have a substituent.
• the upper limit of the number of carbon atoms of R c and R d is, for example, 48 or less, 44 or less, 40 or less, or 36 or less.
• the structural unit (X) may 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.
• 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).
• the organic group (Y) preferably contains a group represented by the following formula (G11):
• R y represents an organic group (Y).
• the organic group (Y) more preferably includes at least one selected from the group consisting of groups represented by the following formulas (G12) to (G14):
• R e each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic compound group, preferably an aromatic hydrocarbon group, more preferably a benzene group.
• R f represents a linear or branched saturated aliphatic hydrocarbon group, or a linear or branched unsaturated aliphatic hydrocarbon group. The carbon number of R f is 8 or less.
• L represents a single bond or a linking group containing a hetero atom (excluding imide groups and amic acid groups).
• R e and R f each independently may or may not have a substituent.
• the structural unit (X) examples include the structural unit represented by formula (XI) and the 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 the structural unit represented by formula (XI) and the structural unit represented by formula (XA). An example of the structural unit (X) includes the structural unit (Xd) described below. In a preferred embodiment, the structural unit (X) includes the structural unit (Xd).
• 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, for example, have 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.
• 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).
• 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 formula (G12) to formula (G14) and at least one selected from the group consisting of groups represented by the following formula (G16) to formula (G18).
• R y represents an organic group (Y).
• Each of R e independently represents an aromatic hydrocarbon group or an aromatic heterocyclic compound group, preferably an aromatic hydrocarbon group, more preferably a benzene group.
• R f represents a linear or branched saturated aliphatic hydrocarbon group, or a linear or branched unsaturated aliphatic hydrocarbon group. The carbon number of R f is 8 or less.
• L represents a single bond or a linking group containing a hetero atom (excluding imide groups and amic acid groups).
• Each of R e and R f may independently have a substituent or may not have a substituent.
• the structural unit (Y) examples include the structural unit represented by the formula (YI) and the structural unit represented by the formula (YA) described below.
• the structural unit (Y) includes at least one selected from the group consisting of the structural unit represented by the formula (YI) and the structural unit represented by the formula (YA).
• An example of the structural unit (Y) includes the structural unit (Yd) described below.
• the structural unit (Y) includes the structural unit (Yd).
• 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).
• block copolymer examples 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); 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), and the like.
• the block copolymer may contain structural units 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 the structural unit represented by the formula (YI) and the 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).
• 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 an example of the structural unit represented by formula (XI) and the structural unit represented by formula (XA) is 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 an example of the structural unit represented by formula (YI) and the structural unit represented by formula (YA) is the structural unit (Yd) described below.
• R 1 and R 2 each independently represent an organic group, and at least one of R 1 and R 2 is a hydrocarbon group (X).
• R 1 is a hydrocarbon group (X) and R 2 is an organic group (Y).
• R 1 is a group selected from the group consisting of groups represented by formulae (G2) to (G6)
• R 2 is a group selected from the group consisting of groups represented by formulae (G12) to (G14); more preferably, R 1 is a group selected from the group consisting of groups represented by formulae (G4) and groups represented by formulae (G7) to (G9)
• R 2 is a group represented by formula (G12); even more preferably, R 1 is a group represented by formula (G8), R 2 is represented by formula (G12), and R e is a benzene group.
• R3 and R4 each independently represent an organic group, and at least one of R3 and R4 is a hydrocarbon group (X).
• organic groups include a hydrocarbon group (X) and an organic group (Y).
• R3 is a hydrocarbon group (X) and R4 is an organic group (Y).
• R3 is a group selected from the group consisting of groups represented by formulae (G2) to (G6)
• R4 is a group selected from the group consisting of groups represented by formulae (G12) to (G14); more preferably, R3 is a group selected from the group consisting of groups represented by formulae (G4) and groups represented by formulae (G7) to (G9)
• R4 is a group represented by formula (G12); even more preferably, R3 is a group represented by formula (G9), R4 is represented by formula (G12), and Re is a benzene group.
• R5 and R6 each independently represent an organic group (Y).
• R 5 is a group selected from the group consisting of groups represented by formulae (G16) to (G18), and R 6 is a group selected from the group consisting of groups represented by formulae (G12) to (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 represented by formula (G16) and R e is a benzene group or represented by formula (18) and R e is a benzene group, and R 6 is represented by formula (G12) and R e is a benzene group, or represented by formula (14) and R e is a benzene group.
• R 7 and R 8 each independently represent an organic group (Y).
• R 7 is a group selected from the group consisting of groups represented by formulae (G16) to (G18), and R 8 is a group selected from the group consisting of groups represented by formulae (G12) to (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 represented by formula (G16) and R e is a benzene group or represented by formula (18) and R e is a benzene group, and R 8 is represented by formula (G12) and R e is a benzene group, or represented by formula (14) and R e is a benzene group.
• 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.
• 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 R 1 to R 8. 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.
• the content of the organic group (Y) is preferably 0 to 60 mass%, 2 to 50 mass%, or 4 to 40 mass%, based on the total mass of R 1 to R 8.
• the mass of any one or more of R 1 to R 8 in the “total mass of R 1 to R 8 " may be 0.
• 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.
• the content of the hydrocarbon group (X) is preferably 0 to 80 mass%, 0 to 50 mass%, or 0 to 30 mass%, based on the total mass of R 1 to R 8.
• the content of the organic group (Y) is preferably 20 to 100 mass%, 30 to 80 mass%, or 40 to 60 mass%, based on the total mass of R 1 to R 8.
• 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.
• 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 R 1 to R 8. 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 easily obtained.
• 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 R 1 to R 8. 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 an organic group (Y) is large. In particular, when the content of the organic group (Y) containing at least one of an aromatic hydrocarbon group and an aromatic heterocyclic compound group is 50 mass% or more, a polyimide having good mechanical strength and heat resistance is likely to be obtained.
• the block copolymer may further contain other optional structural units in addition to the structural units represented by formula (YI) and the structural units represented by formula (YA).
• the content of the other optional structural units in the block copolymer is, for example, 0 to 10 mass% or 0 to 5 mass% based on the total mass of all structural units contained in the block copolymer.
• optional structural units such as a structural unit 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 called 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 may be included.
• a structural unit 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 called 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 may be included.
• These optional structural units may or may not contain a hydrocarbon group (X).
• 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, and at least one of the structure derived from the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride includes a structure having a hydrocarbon group (X).
• BI polyimide block
• BA polyamic acid block
• X hydrocarbon group
• 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).
• diamine or diisocyanate means “at least one compound selected from the group consisting of diamines and diisocyanates”.
• the structure derived from at least a diamine or diisocyanate includes a structure derived from a diamine or 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).
• 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 diisocyanate may include a structure derived from a diamine or diisocyanate having an organic group (Y).
• 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)."
• the diamine having a hydrocarbon group (X) can be represented, for example, by the following formula (Ax).
• R x represents a hydrocarbon group (X).
• R x include the groups represented by the above formulae (G2) to (G9).
• diamine having a hydrocarbon group (X) examples 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 an unsaturated aliphatic hydrocarbon group and having 9 or more carbon atoms such as 1,9-diaminononene, 1,10-diaminodecene, 1,11-diaminoundecene, 1,12-diaminododecene, 1,14-diaminotetradecene, and 1,16-diaminohexadecene
• dimer diamines with 9 or more carbon atoms include, for example, “PRIAMINE 1075” and “PRIAMINE 1074” manufactured by Croda Japan Co., Ltd.
• the diamine having an organic group (Y) can be represented, for example, by the following formula (Ay).
• R y represents an organic group (Y).
• R y include the groups represented by the above formulae (G16) to (G18).
• diamine having an organic group (Y) examples include the following.
• Diamines having a carbon number of 8 or less and having a saturated aliphatic hydrocarbon group such as 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane;
• Diamines having a carbon number of 8 or less and having a saturated aliphatic hydrocarbon group such as 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, and 1,4-bis(aminomethyl)cyclohexane;
• Diamines having an aromatic hydrocarbon group and a non-aromatic hydrocarbon group having 8 or less carbon atoms such as 1,4-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diamino
• the diisocyanate having a hydrocarbon group (X) can be represented, for example, by the following formula (Ix).
• R x represents a hydrocarbon group (X).
• R x include the groups represented by the above formulae (G2) to (G9).
• diisocyanates having a hydrocarbon group (X) include compounds that have the same structure as the compounds shown as specific examples of diamines above, except that the amino group is replaced with an isocyanate group.
• the diisocyanate having an organic group (Y) can be represented, for example, by the following formula (Iy).
• R y represents an organic group (Y).
• R y include the groups represented by the above formulae (G16) to (G18).
• diisocyanates having an organic group (Y) include compounds that have the same structure as the compounds shown as specific examples of diamines above, except that the amino groups are replaced with isocyanate groups.
• the tetracarboxylic acid dianhydride having a hydrocarbon group (X) can be represented, for example, by the following formula (Cx).
• Rx represents a hydrocarbon group (X).
• Preferred examples of the hydrocarbon group (X) are as described above.
• tetracarboxylic dianhydrides having a hydrocarbon group (X) include the following.
• the "carbon number” below refers to the carbon number of the hydrocarbon group (X), and does not include the number of carbon atoms contained in the carboxylic anhydride group.
• the tetracarboxylic dianhydride having the organic group (Y) can be represented, for example, by the following formula (Cy).
• R y represents an organic group (Y).
• R y include the groups represented by the above formulae (G12) to (G14).
• 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 anhydride group.
• Tetracarboxylic acid dianhydrides having a saturated aliphatic hydrocarbon group and a carbon number of 8 or less such as 1,2,3,4-butanetetracarboxylic acid dianhydride and 1,2,5,6-hexanetetracarboxylic acid dianhydride; tetracarboxylic acid dianhydrides having a saturated alicyclic hydrocarbon group and a carbon number of 8 or less, such as 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride; tetracarboxylic acid dianhydrides having an aromatic hydrocarbon group and a carbon number of 8 or less, such as pyromellitic dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 3,3',4,4'-biphenyltetrac
• 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.
• 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.
• the structure derived from the diamine or diisocyanate contained in the polyamic acid block (BA) includes a structure derived from a diamine or diisocyanate having an aromatic hydrocarbon group.
• 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.
• 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.
• 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 loss tangent is likely to be obtained.
• 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.
• 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 10% by mass or more, a polyimide having good mechanical strength and heat resistance is likely to be obtained.
• 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 the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride.
• 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 tangent is easily obtained.
• 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 the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride.
• 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 easily obtained.
• 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 tangent, it is preferable that the content of the structure having a hydrocarbon group (X) is large. In particular, when the content of the structure having a hydrocarbon group (X) is 5 mass% or more, it is easy to obtain a polyimide having a low dielectric constant and a low dielectric tangent.
• the content of the structure having an organic group (Y) is preferably 40 to 97 mass%, 50 to 95 mass%, or 60 to 90 mass%, based on the total mass of the structure derived from the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride. From the viewpoint of obtaining 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 a structure having an organic group (Y) is large. 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 mass% or more, a polyimide having good mechanical strength and heat resistance is likely to be obtained.
• the block copolymer may further include another optional structure in addition to the structure derived from the diamine or diisocyanate and the structure derived from the tetracarboxylic dianhydride.
• the content of the other optional structural unit is, for example, 0 to 10 mass% or 0 to 5 mass% based on the total mass of all structures contained in the block copolymer.
• an optional structure such as a structure derived from a trifunctional or higher polyamine or polyisocyanate, a structure derived from a dicarboxylic acid compound, or a structure derived from a tricarboxylic acid compound may be included.
• These optional structures may or may not include a hydrocarbon group (X).
• the block copolymer is obtained by using a polyimide (PI) obtained by using a diamine or a diisocyanate and a tetracarboxylic dianhydride, and a polyamic acid (PA) obtained by using a diamine and a tetracarboxylic dianhydride, and at least one selected from the group consisting of the diamine or the diisocyanate and the tetracarboxylic dianhydride used to obtain the polyimide (PI) and the diamine and the tetracarboxylic dianhydride used to obtain the polyamic acid (PA) has a hydrocarbon group (X).
• X hydrocarbon group
• Polyimide block (BI) By including the polyimide block (BI) in the block copolymer, it is possible to prevent an exchange reaction or the formation of crosslinks when obtaining the block copolymer or when ring-closing the amic acid group.
• the polyimide block (BI) has an imide group content relative to the total of imide groups and amide 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%.
• the content can be measured by a Fourier Transform Infrared Spectroscopy (FTIR).
• 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).
• 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. If the number average molecular weight is 500 or more, a polyimide having a low expansion coefficient tends to be obtained. If the number average molecular weight is 10,000 or less, the solubility of the block copolymer in a solvent tends to be easily ensured.
• the number average molecular weight of the polyimide block (BI) is, for example, 500 to 10,000, 1,000 to 8,000, 2,000 to 7,000, or 3,000 to 5,000. In the present disclosure, the number average molecular weight can be 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.
• the polyimide block (BI) may be a linear block or a branched block, and is preferably a linear block.
• Block copolymer contains a polyamic acid block, good solubility in a solvent tends to be easily obtained.
• the polyamic acid block (BA) has a content of amide acid groups relative to the total of imide groups and amide 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 amide acid groups may be 100 mol%.
• the content can be measured by FTIR.
• 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).
• 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.
• the number average molecular weight is 500 or more, good film-forming properties tend to be easily obtained.
• the number average molecular weight is 30,000 or less, the composition containing the block copolymer and the solvent tends to be easily adjusted to a viscosity 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.
• the polyamic acid block (BA) may be a linear block or a branched block, and is preferably a linear block.
• 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 believed to be because the block structure makes it easier for the polyimide molecules to be oriented.
• BI polyimide block
• BA polyamic acid block
• either one of the polyimide block (BI) and the polyamic acid block (BA) contains a hydrocarbon group (X), or both the polyimide block (BI) and the polyamic acid block (BA) contain a hydrocarbon group (X).
• the polyimide block (BI) and the polyamic acid block (BA) may each independently contain one or more types of hydrocarbon groups (X).
• 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.
• good film-forming properties tend to be easily obtained.
• the number average molecular weight is 100,000 or less, the composition containing the block copolymer and the solvent tends to be easily adjusted to a viscosity 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.
• 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.
• the content of the polyamic acid block (BA) 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 polyamic acid block (BA) 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 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, 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, 40 to 90% by mass or 50 to 80% by mass.
• the number average molecular weight of the polyimide block (BI) is smaller than the number average molecular weight of the polyamic acid block (BA).
• 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).
• the block copolymer tends to be easier to synthesize and the solubility of the block copolymer tends to be ensured.
• a block copolymer having a sufficient number average molecular weight tends to be easier to synthesize.
• the block copolymer is preferably such that the polyimide obtained by using the block copolymer satisfies one or more of the dielectric constant, dielectric dissipation factor, thermal expansion coefficient, and water absorption coefficient described below. It is particularly preferable that the block copolymer is such that the polyimide obtained by using the block copolymer satisfies one or more of the dielectric constant, dielectric dissipation factor, and thermal expansion coefficient described below.
• a polyimide having a low dielectric constant, a low dielectric loss tangent, and a low thermal expansion coefficient can be obtained by using a block copolymer.
• the obtained polyimide can be used in various electronic and mechanical parts, such as displays, solar cells, touch panels, organic EL lighting, millimeter-wave radar, high-frequency antennas, and high-speed transmission substrates.
• the polyimide can be preferably used in devices used in high-frequency regions, such as millimeter-wave radar, high-frequency antennas, and high-speed transmission substrates.
• a millimeter-wave radar is a radar that transmits millimeter waves to an object and receives reflected waves from the object to detect the object, and an on-board millimeter-wave radar mounted on a vehicle or the like is applied to a collision prevention system, an automatic driving system, and the like.
• a high-frequency antenna there is a demand for high frequency and high-speed transmission for high-speed communication in communication devices, etc., and when a high-frequency antenna is housed in a housing in a small communication device, etc., a material having a lower dielectric constant and a lower dielectric loss tangent is desired.
• Examples of high-speed transmission substrates include high-speed transmission cables and high-speed transmission connectors.
• 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).
• the block copolymer of the above-mentioned embodiment can be easily produced.
• PI polyimide
• PA polyamic acid
• the monomer reaction can be carried out by solution polymerization.
• solvents that can be used during the reaction include polar solvents such as N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), ⁇ -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), ⁇ -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), ⁇ -butyrolactone (GBL), and 3-methoxy-N,N-dimethylpropanamide (MPA).
• NMP N-methyl-2-pyrrolidone
• NEP N-ethyl-2-pyrrolidone
• GBL ⁇ -butyrolactone
• MPA 3-methoxy-N,N-dimethylpropanamide
• 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.
• the amount of solvent used is 100 parts by mass or more, each monomer can be reacted homogeneously.
• the amount of solvent used is 600 parts by mass or less, the polymerization reaction can be promoted.
• 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.
• 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 remaining amino groups or isocyanate groups, etc., and the reaction time may be adjusted so that the desired reaction product is obtained.
• the temperature at which polyimide is obtained using polyamic acid is not particularly limited.
• the imidization temperature may be, for example, 120 to 200°C, or 160 to 180°C.
• the reaction time is, 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 that the desired reaction product is obtained.
• the end of the polymer chain of the polyimide (PI) is a carboxylic acid anhydride group, and the end of the polymer chain of the polyamic acid (PA) is an amino group.
• the ratio of the diamine or diisocyanate used to obtain the polyimide (PI) and the tetracarboxylic acid dianhydride 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 and 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.
• a block copolymer is synthesized using polyimide (PI) and polyamic acid (PA). Any polymer may also be used in the synthesis.
• PI polyimide
• PA polyamic acid
• the reaction between polyimide (PI) and polyamic acid (PA) can be carried out by solution polymerization.
• the above-mentioned solvents can be used as the solvent during the reaction.
• 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, etc., and the reaction time can be adjusted so that the desired reaction product is obtained.
• the insulating material and the heat-resistant insulating material contain the block copolymer according to any one of the above-mentioned embodiments.
• the block copolymer can be preferably used as the insulating material or the heat-resistant insulating material because the polyimide obtained by using the block copolymer has excellent insulating properties and heat-resistant insulating properties.
• the composition contains the block copolymer of any of the above-mentioned embodiments and a solvent.
• the solvent contained in the composition include the above-mentioned reaction solvents that can be used in the synthesis of the block copolymer.
• the solvent preferably contains at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), ⁇ -butyrolactone (GBL), and 3-methoxy-N,N-dimethylpropanamide (MPA), and more preferably contains at least one selected from the group consisting of N-ethyl-2-pyrrolidone (NEP), ⁇ -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.
• the composition may further contain optional components such as polyamide, polyethersulfone, acrylic polymer, epoxy compound, isocyanate compound, melamine compound, filler, defoamer, preservative, surfactant, etc.
• the composition can be produced, for example, by mixing and stirring the block copolymer, the solvent, and optional components used as necessary.
• the content of the block copolymer can be in a range suitable for the application of the composition.
• the content of the block copolymer is, for example, 5 to 50 mass%, 8 to 40 mass%, or 10 to 30 mass%, based on the mass of the composition.
• the viscosity of the composition at 30°C is preferably 2 to 30 Pa ⁇ s, more preferably 5 to 20 Pa ⁇ s, and even more preferably 10 to 15 Pa ⁇ s.
• the viscosity can be measured using a rotational B-type viscometer at 30°C using a No. 3 rotor.
• a polyimide can be obtained using the block copolymer of any of the above-mentioned embodiments or the composition of any of the above-mentioned embodiments.
• the block copolymer contains a polyamic acid block (BA)
• a polyimide can be obtained by converting an amic acid group into an imide group by ring closure (this conversion may be referred to as "imidization" in the present disclosure).
• the method of imidization is not particularly limited.
• a method of heating the block copolymer can be preferably used because it is simple. The heating temperature is, for example, 250 to 400°C.
• the polyimide obtained from the block copolymer contains a polyimide block (BI) and a polyimide block (BI-A) which is a block in which the polyamic acid block (BA) is imidized.
• the polyimide block (BI) and the polyimide block (BI-A) are different blocks.
• the polyimide has a block structure, and therefore exhibits a low coefficient of thermal expansion.
• the polyimide has a hydrocarbon group (X), and therefore exhibits a low dielectric constant and a low dielectric tangent. Furthermore, the polyimide has a tendency to exhibit a low water absorption rate, and therefore, exhibits a hydrocarbon group (X).
• the dielectric constant of polyimide is, for example, 3.5 or less, 3.0 or less, or 2.5 or less from the viewpoint of obtaining excellent insulation.
• the dielectric constant of 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 ⁇ m 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 it is thoroughly dried and then allowed to stand for 24 hours in an atmosphere at a temperature of 23°C and a relative humidity of 50%.
• the dielectric tangent 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 tangent of the polyimide is not particularly limited, but is, for example, 0.0005 or more.
• the dielectric tangent (Df) can be measured using a polyimide film (e.g., 25 ⁇ m 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 tangent (Df) may be a value obtained by measuring the polyimide film immediately after it is thoroughly dried and then allowed to stand for 24 hours in an atmosphere at a temperature of 23°C and a relative humidity of 50%.
• 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 is used by being attached to other materials.
• the coefficient of thermal expansion can be calculated by converting the average linear thermal expansion coefficient (ppm/°C) from 30 to 200°C measured using a polyimide film (for example, 25 ⁇ m thick) at a heating rate of 10°C/min using a thermomechanical analyzer.
• the glass transition temperature (Tg) of polyimide is, for example, 200°C or higher, 250°C or higher, or 300°C or higher from the viewpoint of heat resistance of the molded body.
• the glass transition temperature (Tg) of 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 the linear thermal expansion coefficient curve from 30 to 200°C measured using a polyimide film (e.g., thickness 25 ⁇ m) at a heating rate of 10°C/min using a thermomechanical analyzer.
• the water absorption rate of the polyimide is, for example, 1.0% or less, 0.5% or less, or 0.3% or less from the viewpoint of preventing a change in dielectric properties due to moisture absorption.
• the water absorption rate of the polyimide is not particularly limited, but is, for example, 0.0% or more.
• the relative dielectric constant, dielectric loss tangent, coefficient of thermal expansion, glass transition temperature, and water absorption of 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.
• the molded body, the insulator, and the heat-resistant insulator are obtained using the block copolymer, material, or composition of any of the above-mentioned embodiments, or include the polyimide of the above-mentioned embodiment.
• the insulator preferably has a relative dielectric constant of 3.5 or less and a dielectric loss tangent of 0.0100 or less.
• the heat-resistant insulator preferably has a relative dielectric constant of 3.5 or less, a dielectric loss tangent of 0.0100 or less, and a thermal expansion coefficient of 80 ppm/K or less.
• the shapes of the molded body, insulator, and heat-resistant insulator may be in any shape suitable for the application.
• they may be in the shape of a film, plate, membrane, layer, etc.
• the molded body, insulator, and heat-resistant insulator can be used in various electronic and mechanical parts.
• a printed circuit board is obtained using the block copolymer, material, or composition of any of the above-mentioned embodiments, or includes the polyimide, molding, insulator, or heat-resistant insulator of the above-mentioned embodiments.
• the printed circuit board of the embodiment of the present invention has low transmission loss and excellent heat resistance.
• 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 multi-layer boards. For example, the materials, protective films, insulating layers, etc. of these boards are obtained using block copolymers or include polyimides, etc.
• 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.
• 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
• 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. Or, a block copolymer satisfying the above items [1] and [2].
• R1 and R2 each independently represent an organic group, and at least one of R1 and R2 is a group (X) containing at least one non-aromatic hydrocarbon group, the total number of carbon atoms of the at least one non-aromatic hydrocarbon group being 9 or more.
• R3 and R4 each independently represent an organic group, and at least one of R3 and R4 is a group (X) containing at least one non-aromatic hydrocarbon group, the total number of carbon atoms of the at least one non-aromatic hydrocarbon group being 9 or more.
• a polymer comprising a polyimide block (BI) and a polyamic acid block (BA), having a structure derived from a diamine or 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 includes a structure having a group (X) which contains at least one non-aromatic hydrocarbon group and has a total carbon number of 9 or more in the at least one non-aromatic hydrocarbon group.
• Block copolymer Block copolymer.
• a method for producing a block copolymer which satisfies any one or more of the above [1], [2], and [7], and also satisfies [21].
• a composition comprising the block copolymer according to any one of [1] to [20] above and a solvent.
• a composition for an insulator comprising the block copolymer according to any one of [1] to [20] above or the insulating material according to [22] above, and a solvent.
• a composition for heat-resistant insulation comprising 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.
• a composition for printed circuit boards comprising 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.
• Polyimides (PI-2) to (PI-5) Solutions of polyimides (PI-2) to (PI-5) were obtained in the same manner as for polyimide (PI-1), except that the diamines and tetracarboxylic dianhydrides shown in Table 2 were used.
• PA-1 Polyamic acid (PA-1)] A diamine solution was obtained by dissolving 32.6 g (0.30 mol) of p-phenylenediamine (hereinafter referred to as "PPD") in 485.6 g of dimethylacetamide. 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 an amine structure derived from PPD at its terminal. The reaction was carried out by stirring the solution at 50°C or less for 8 hours or more. The number average molecular weight of the polyamic acid (PA-1) was 9,100.
• PPD p-phenylenediamine
• BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
• Example 1 506.5 g of the polyimide (PI-1) solution and 603.1 g of the polyamic acid (PA-1) solution 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 the block polyamic acid imide 1 was 25,240. The concentration of the block polyamic acid imide 1 was 19.5 mass % based on the mass of the varnish.
• the varnish is a composition containing a block copolymer and a solvent.
• 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.
• 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 third-order equation using a set of five standard polystyrene samples ("TSK standard POLYSTYRENE", manufactured by Tosoh Corporation). The GPC conditions are shown below.
• Example 1 Using the obtained varnish (composition), a film was produced 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 ⁇ m. 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 a nitrogen atmosphere at 350° C. for 1 hour using an inert gas oven 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.
• Examples 2 to 5 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 5 and Comparative Examples 1 to 6.
• 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 the conditions of temperature: 23°C and relative humidity: 50%.
• the dielectric properties (relative dielectric constant Dk and dielectric loss tangent Df) of the film were measured by a cavity resonator method (TE mode).
• TE mode cavity resonator method
• Anritsu Corporation's "MS46122B” was used for the measurement. The conditions were a frequency of 10 GHz and a measurement temperature of 25°C.
• thermomechanical analyzer (TMA7100", manufactured by Hitachi High-Tech Science Corporation) was used for the measurement.
• 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).
• the film was cut into a size of 10 mm wide and 60 mm long to prepare a test piece.
• a tensile test was performed under the following measurement conditions, and the maximum tensile stress applied during the tensile test was taken as the tensile strength (MPa).
• the breaking elongation (%) was calculated by dividing the elongation of the test piece until it broke by the chuck distance of 20 mm.
• the 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 taken as the tensile modulus (MPa).

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