Resin, polyimide production method, polyamic acid, functional material, diamine compound, diamine compound production method, resin composition, high-frequency substrate film, metal-clad laminate, and circuit board

Abstract

The purpose of the present disclosure is to provide a novel resin, a polyimide production method, a polyamic acid, a functional material, a diamine compound, a diamine compound production method, a resin composition, a high-frequency substrate film, a metal-clad laminate, and a circuit board. The present disclosure relates to a resin which has a repeating unit represented by formula (1) and which is constituted by a polyimide, a polyetherimide, or a polyamide-imide. (In the formula: X1 and X2 are the same or different and are each a direct bond, a C1-10 alkylene group, a C3-10 alicyclic hydrocarbon group, or a C5-10 aromatic hydrocarbon group; Y1 and Y2 are the same or different and are each a C1-10 alkyl group, a C3-10 alicyclic hydrocarbon group, or a C5-10 aromatic hydrocarbon group; R1 and R2 are the same or different and are each a C1-10 alkyl group; and the groups represented by X1, X2, Y1, Y2, R1, and R2 may each have a substituent.)

Description

Resins, methods for producing polyimides, polyamic acids, functional materials, diamine compounds, methods for producing diamine compounds, resin compositions, films for high-frequency substrates, metal-clad laminates, and circuit boards

[0001] This disclosure relates to resins, methods for producing polyimides, polyamic acids, functional materials, diamine compounds, methods for producing diamine compounds, resin compositions, films for high-frequency substrates, metal-clad laminates, and circuit boards.

[0002] Heat-resistant resins such as polyimide are used in a variety of products. For example, Patent Document 1 discloses a molded article using a resin composition containing polyimide and a fluorine-containing copolymer.

[0003] The synthesis of polyimides is generally carried out by converting aromatic diamines and aromatic tetracarboxylic dianhydrides into polyimides via polyamic acids (Non-Patent Document 1).

[0004] One compound that can form the aromatic skeleton of an aromatic diamine is an aromatic compound called divanillic acid. There have been reports of synthesizing diisocyanate monomers from divanillic acid and then synthesizing polyimides in a single step. However, this method has not achieved high molecular weight (Non-Patent Literature 2).

[0005] In recent years, methods for synthesizing diamine monomers using divanillic acid have been reported (Non-Patent Documents 3 and 4). It is expected that by using this method, it will be possible to synthesize high molecular weight polyimides via polyamic acid using divanillic acid diamine.

[0006] Furthermore, there are very few examples of polyimide synthesis using biomass-derived compounds as raw materials (Non-Patent Document 5, Non-Patent Document 6).

[0007] Japanese Patent Publication No. 2024-119765

[0008] Progress in Organic Coatings Volume 172, November 2022, 107103 (https: / / doi.org / 10.1016 / j.porgcoat.2022.107103) European Polymer Journal Volume 109, December 2018, Pages 257-264 (https: / / doi.org / 10.1016 / j.eurpolymj.2018.09.054) Polymer Volume 256, 21 September 2022, 125222 (https: / / doi.org / 10.1016 / j.polymer.2022.125222) Frontiers in Chemistry September 2019 | Volume 7 | Article 606 doi: 10.3389 / fchem. 2019.00606 Macromolecules 2022, 55, 15, 6787-6800 (https: / / doi.org / 10.1021 / acs.macromol.2c01288) Polymer Chemistry, Volume56, Issue10 May 15, 2018, 1058-1066

[0009] To realize a decarbonized society, there is a need to use biomass in resins. In response to this, the inventors investigated the biomass production of heat-resistant resins and focused on divanillin, which can be synthesized from biomass materials. They discovered that polyimides and the like can be synthesized from divanillin via diamines and polyamic acids, and that the resulting polyimides have novel structures and excellent electrical properties, which led to this disclosure.

[0010] This disclosure provides novel resins, methods for producing polyimides, polyamic acids, functional materials, diamine compounds, methods for producing diamine compounds, resin compositions, films for high-frequency substrates, metal-clad laminates, and circuit boards.

[0011] (1) of this disclosure is a resin having repeating units represented by the following formula (1), and being a polyimide, polyetherimide, or polyamideimide. (In the formula, X １, X ２ is, independently or differently, a direct bond, an alkylene group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. Y １ , Y ２ is, independently or differently, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. R １ , R ２ is, independently or differently, an alkyl group having 1 to 10 carbon atoms. X １ , X ２ , Y １ , Y ２ , R １ , R ２ The groups represented by may have substituents. )

[0012] The present disclosure (2) is the resin described in the present disclosure (1) which is a polyimide.

[0013] The present disclosure (3) is the resin described in the present disclosure (2) in which the polyimide is a copolymer of two or more tetracarboxylic dianhydrides.

[0014] The present disclosure (4) is the resin described in the present disclosure (2) or (3) in which the polyimide is a copolymer of a diamine compound represented by the following formula (2) and another diamine compound. (In the formula, X １ , X ２ is, independently or differently, a direct bond, an alkylene group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. Y １ , Y ２ is, independently or differently, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. R １ , R ２ is, independently or differently, an alkyl group having 1 to 10 carbon atoms. X １ , X ２ , Y １ , Y ２ , R １ , R ２ The groups represented by may have substituents. )

[0015] This disclosure (5) states that in formula (1), X １ , X ２ The resin is the same or different resin according to any of (1) to (4) of this disclosure, which is an alkylene group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms.

[0016] This disclosure (6) states that in formula (1), X １ , X ２ is a methylene group or a direct bond, Y １ , Y ２ R is a methyl group, cyclopentyl group, cyclohexyl group, benzyl group, or n-butyl group. １ , R ２ The resin is a methyl group as described in any of (1) to (4) of this disclosure.

[0017] Disclosure (7) is a resin according to any of Disclosures (1) to (6) having a weight-average molecular weight of 76,000 or more.

[0018] Disclosure (8) is a resin according to any one of Disclosures (1) to (7) wherein the weight-average molecular weight / number-average molecular weight is 4 or less.

[0019] Disclosure (9) is a resin according to any of Disclosures (1) to (8), wherein the glass transition temperature is 180°C or higher.

[0020] Disclosure (10) is a resin according to any one of Disclosures (1) to (9), wherein the dielectric constant measured at a frequency of 10 GHz is 4 or less.

[0021] Disclosure (11) is a resin according to any one of Disclosures (1) to (10), wherein the dielectric loss tangent measured at a frequency of 10 GHz is 0.045 or less.

[0022] Disclosure (12) is a resin according to any of Disclosures (1) to (11) having a tensile strength of 60 MPa or more.

[0023] Disclosure (13) is a resin according to any one of Disclosures (1) to (12), wherein the ratio of amide bonds to imide bonds is 1% or less.

[0024] Disclosure (14) is a resin according to any of Disclosures (1) to (13) having a total light transmittance of 60% or more.

[0025] This disclosure (15) is a method for producing polyimide, comprising a polycondensation step of polycondensing a tetracarboxylic dianhydride with a diamine compound represented by the following formula (2). (In the formula, X １ , X ２ These are identical or different, directly bonded, a C1-C10 alkylene group, a C3-C10 alicyclic hydrocarbon group, or a C5-C10 aromatic hydrocarbon group. １ , Y ２ These are, either identical or different, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. １ , R ２ X is an alkyl group having 1 to 10 carbon atoms, either identical or different. １ , X ２ , Y １ , Y ２ , R １ , R ２ The group represented by may have substituents.

[0026] This disclosure (16) is a method for producing polyimide according to this disclosure (15), which includes an imidation step of imidizing the polyamic acid obtained in the polycondensation step.

[0027] This disclosure (17) states that in formula (2), X １ , X ２ is a methylene group or a direct bond, Y １ , Y ２ R is a methyl group, cyclopentyl group, cyclohexyl group, benzyl group, or n-butyl group. １ , R ２ This is a method for producing polyimide according to the disclosure (15) or (16), wherein the polyimide is a methyl group.

[0028] The present disclosure (18) is a polyamic acid having repeating units represented by the following formula (1). (In the formula, X １ , X ２These are identical or different, directly bonded, a C1-C10 alkylene group, a C3-C10 alicyclic hydrocarbon group, or a C5-C10 aromatic hydrocarbon group. １ , Y ２ These are, either identical or different, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. １ , R ２ X is an alkyl group having 1 to 10 carbon atoms, either identical or different. １ , X ２ , Y １ , Y ２ , R １ , R ２ The group represented by may have substituents.

[0029] The present disclosure (19) is a polyamic acid according to the present disclosure (18), having a viscosity of 500 to 100,000 cP when measured with a 15% by mass N-methyl-2-pyrrolidone solution.

[0030] This disclosure (20) states that in formula (1), X １ , X ２ is a methylene group or a direct bond, Y １ , Y ２ R is a methyl group, cyclopentyl group, cyclohexyl group, benzyl group, or n-butyl group. １ , R ２ is a polyamic acid according to disclosure (18) or (19), which is a methyl group.

[0031] Disclosure (21) is a functional material comprising a polyamic acid as described in any of Disclosures (18) to (20), and used as a paint, adhesive, electrode binder, or coating agent.

[0032] The present disclosure (22) is a diamine compound represented by the following formula (2). (In the formula, X １ , X ２ These are identical or different, directly bonded, a C1-C10 alkylene group, a C3-C10 alicyclic hydrocarbon group, or a C5-C10 aromatic hydrocarbon group. １ , Y ２These are, either identical or different, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. １ , R ２ X is an alkyl group having 1 to 10 carbon atoms, either identical or different. １ , X ２ , Y １ , Y ２ , R １ , R ２ The group represented by may have substituents.

[0033] This disclosure (23) states that in formula (2), X １ , X ２ is a methylene group or a direct bond, Y １ , Y ２ R is a methyl group, a cyclopentyl group, a cyclohexyl group, a benzyl group, or an n-butyl group. １ , R ２ This is a methyl group, which is a diamine compound as described in disclosure (22).

[0034] The present disclosure (24) is a method for producing a diamine compound as described in the present disclosure (22) or (23), wherein the diamine compound represented by formula (2) is synthesized from vanillin via divanillin.

[0035] Disclosure (25) is a resin composition comprising the resin described in any of Disclosures (1) to (14).

[0036] The present disclosure (26) is a resin composition according to the present disclosure (25) comprising a resin (excluding polyimide, polyetherimide, and polyamideimide) having repeating units represented by formula (1).

[0037] The present disclosure (27) is a component used as a mobility component, an information and communication component, a semiconductor component, a precision machinery component, a medical component, an industrial machinery component, a building component, a wire insulation component, or a composite matrix component.

[0038] The present disclosure (28) is a member described in the present disclosure (27) that is a fiber, film, or sheet.

[0039] The present disclosure (29) is a film for a high-frequency substrate including the member described in the present disclosure (27) or (28).

[0040] The present disclosure (30) is a metal-clad laminate including the film for a high-frequency substrate described in the present disclosure (29).

[0041] The present disclosure (31) is a circuit board including the metal-clad laminate described in the present disclosure (30).

[0042] According to the present disclosure, a novel resin, a method for producing polyimide, polyamic acid, functional material, diamine compound, resin composition, film for a high-frequency substrate, metal-clad laminate, and circuit board can be provided.

[0043] Hereinafter, the present disclosure will be specifically described.

[0044] <Resin and Resin Composition> The resin of the present disclosure has a repeating unit represented by the following formula (1) and is polyimide, polyetherimide, or polyamideimide.

[0045] The resin of the present disclosure has a novel structure and is excellent in electrical properties, mechanical strength, transparency, etc. Further, since it has a high molecular weight, it can be easily formed into a film.

[0046] X １ and X ２ are the same or different and are a direct bond, an alkylene group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. Note that the form in which X １ and X ２ are direct bonds is a form in which O and Y １ and Y ２ are directly bonded.

[0047] X １ and X ２ The alkylene group of is 1 to 10 carbon atoms, preferably 1 to 8, and more preferably 1 to 4. X １ and X [[ID=4''7]] ２The alkylene group may have a branched structure. Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and the like.

[0048] X １ , X ２ The alicyclic hydrocarbon group of X ２ has 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms. Specific examples include a cyclopropenyl group, a cyclobutinyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, and the like.

[0049] X １ , X ２ The aromatic hydrocarbon group of X ２ has 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms. Specific examples include a phenylene group, a tolylene group, a xylylene group, a naphthyl group, and the like.

[0050] X １ , X ２ X ２ and X １ are preferably the same or different and are an alkylene group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably a methylene group.

[0051] X １ , X ２ X ２ and X １ may be the same or different groups, but are preferably the same group.

[0052] Y １ , Y ２ Y ２ and Y １ are the same or different and are an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms.

[0053] Y １ , Y ２ The alkyl group of Y ２ has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. Y １ , Y ２ The alkyl group of Y ２ may have a branched structure. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and the like. Preferred are a methyl group and an n-butyl group, and more preferred is a methyl group. Also, Y １ , Y２ The alkyl group may have 2 to 10 carbon atoms.

[0054] Y １ , Y ２ The alicyclic hydrocarbon group has 3 to 10 carbon atoms, preferably 3 to 8. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups, with cyclopentyl and cyclohexyl groups being preferred, and cyclopentyl groups being more preferred.

[0055] Y １ , Y ２ The aromatic hydrocarbon group has 5 to 10 carbon atoms, preferably 5 to 8. Specific examples include phenyl, benzyl, tolyl, xylyl, and naphthyl groups, with benzyl and phenyl groups being preferred, and benzyl groups being more preferred.

[0056] Y １ , Y ２ These are preferably the same or different alkyl groups having 1 to 10 carbon atoms, more preferably alkyl groups having 1 to 3 carbon atoms, and even more preferably methyl groups.

[0057] Y １ , Y ２ These may be the same group or different groups, but it is preferable that they be the same group.

[0058] R １ , R ２ These are identical or different alkyl groups having 1 to 10 carbon atoms.

[0059] R １ , R ２ The alkyl group has 1 to 10 carbon atoms, preferably 1 to 6, and more preferably 1 to 4. A specific example is Y １ , Y ２ Examples of alkyl groups similar to those mentioned above include a methyl group, with the methyl group being preferred.

[0060] R １ , R ２ These may be the same group or different groups, but it is preferable that they be the same group.

[0061] X１ , X ２ , Y １ , Y ２ , R １ , R ２ The group represented by may have substituents. Examples of substituents include C1-C4 alkyl groups (which may have a branched structure), cyclic hydrocarbon groups (which may have a branched structure or a double bond), halogens, hydroxyl groups, formyl groups, carbonyl groups, carboxyl groups, nitro groups, amino groups, sulfo groups, ether bonds, ester bonds, and the like.

[0062] The resin of this disclosure may be polyimide, polyetherimide, or polyamideimide, but is preferably polyimide, and more preferably polyimide having repeating units represented by the following formula (1A). (In the formula, X １ , X ２ These are identical or different, directly bonded, a C1-C10 alkylene group, a C3-C10 alicyclic hydrocarbon group, or a C5-C10 aromatic hydrocarbon group. １ , Y ２ These are, either identical or different, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. １ , R ２ These are identical or different alkyl groups having 1 to 10 carbon atoms. Z is an organic group. X １ , X ２ , Y １ , Y ２ , R １ , R ２ (The group represented by Z may have substituents.)

[0063] In equation (1A), X １ , X ２ , Y １ , Y ２ , R １ , R ２ The contents and preferred form are the same as those described in formula (1).

[0064] The organic group Z is not particularly limited, but it preferably includes a cyclic group such as an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and more preferably includes an aromatic hydrocarbon group. In other words, the resin of this disclosure is preferably an aromatic polyimide.

[0065] The alicyclic hydrocarbon group Z preferably has 3 to 10 carbon atoms, more preferably 3 to 9, and even more preferably 3 to 8. Specific examples include alicyclic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane from which four hydrogen atoms have been removed.

[0066] The aromatic hydrocarbon group Z preferably has 5 to 15 carbon atoms, more preferably 5 to 10, even more preferably 5 to 8, and particularly preferably 5 to 6 carbon atoms. Specific examples include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, cumene, naphthalene, and biphenyl from which four hydrogen atoms have been removed, with benzene from which four hydrogen atoms have been removed being preferred.

[0067] Furthermore, the alicyclic hydrocarbon group and aromatic hydrocarbon group of Z may contain heteroatoms such as oxygen atoms. In this case, the heteroatom may be contained in the ring, or it may bond multiple alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

[0068] The group represented by Z may have substituents. Examples of substituents include X. １ , X ２ , Y １ , Y ２ , R １ , R ２ This is similar to the substituents that the group represented by may have.

[0069] If the resin of the present disclosure is a polyimide, it is preferable that the polyimide is a copolymer of a diamine compound represented by the following formula (2) and a tetracarboxylic dianhydride. (In the formula, X １ , X ２These are identical or different, directly bonded, a C1-C10 alkylene group, a C3-C10 alicyclic hydrocarbon group, or a C5-C10 aromatic hydrocarbon group. １ , Y ２ These are, either identical or different, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. １ , R ２ X is an alkyl group having 1 to 10 carbon atoms, either identical or different. １ , X ２ , Y １ , Y ２ , R １ , R ２ The group represented by may have substituents.

[0070] In equation (2), X １ , X ２ , Y １ , Y ２ , R １ , R ２ The contents and preferred form are the same as those described in formula (1). The diamine compound represented by formula (2) may be used alone, in combination of two or more types, or in combination with the diamine compound represented by formula (2) and other diamine compounds. The structure of the other diamine compound is not particularly limited and may be, for example, a commonly used petroleum-derived diamine compound.

[0071] Examples of tetracarboxylic dianhydrides include benzene-1,2,4,5-tetracarboxylic dianhydride (PMDA (pyromellitic acid)), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic anhydride (ODPA), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 4,4'-carbonyldiphthalic anhydride (BTDA), and 4,4'-sulfonyldiphthalic anhydride (DSD). A) Examples include 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA), 4,4'-(1,4-phenylenedioxy)bisphthalic anhydride, dibromopyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid 2,3:6,7-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and bicyclo[2.2.2]octa-7-ene-2,3,5,6-tetracarboxylic acid dianhydride. In addition, tetracarboxylic acid dianhydrides having an isosorbide skeleton are also examples, such as the compound represented by the following formula (ISS-TME). The isosorbide skeleton is a biomass-derived skeleton made from starch and sugars derived from plants such as corn. Therefore, tetracarboxylic acid dianhydrides having an isosorbide skeleton are known to be biomass-derived tetracarboxylic acid dianhydrides. Among these, PMDA, BPDA, ODPA, BTDA, and ISS-TME are preferred, with ODPA being more preferred. Tetracarboxylic acid dianhydrides may be used individually or in combination of two or more.

[0072] If the resin of this disclosure is a polyimide, the polyimide may be a copolymer of two or more tetracarboxylic dianhydrides (copolymer (A)), or a copolymer of a diamine compound represented by formula (2) and another diamine compound (copolymer (B)). Copolymer (A) is preferably a copolymer of two or more tetracarboxylic dianhydrides and a diamine compound represented by formula (2), and copolymer (B) is preferably a copolymer of a diamine compound represented by formula (2), another diamine compound, and a tetracarboxylic dianhydride.

[0073] The weight-average molecular weight of the resins of this disclosure is preferably 76,000 or more, more preferably 80,000 or more, even more preferably 82,000 or more, and also preferably 300,000 or less, more preferably 250,000 or less, and even more preferably 200,000 or less. The number-average molecular weight of the resins of this disclosure is preferably 10,000 or more, more preferably 15,000 or more, even more preferably 20,000 or more, also preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 120,000 or less. The weight-average molecular weight / number-average molecular weight ratio is preferably 4 or less, more preferably 3.8 or less, and also preferably 1 or more, more preferably 1.2 or more. The weight-average molecular weight and number-average molecular weight of the resins can be determined in accordance with the PS-converted average molecular weight in GPC measurement.

[0074] The glass transition temperature of the resins of this disclosure is preferably 180°C or higher, more preferably 350°C or lower, more preferably 320°C or lower, and even more preferably 300°C or lower. The glass transition temperature is measured by the following method: Using a thermomechanical analyzer (TMA, Rigaku Corporation, EVO2G), the sample (resin film) is heated at 5°C / min and measured in tensile mode. The temperature is determined as the midpoint of the intersection of the extension of the baseline of the TMA curve before and after the second-order transition and the tangent line at the inflection point of the TMA curve.

[0075] The dielectric constant of the resin of this disclosure, measured at a frequency of 10 GHz, is preferably 4 or less, more preferably 3.8 or less, even more preferably 3.6 or less, and also preferably 2 or more, more preferably 2.5 or more, and even more preferably 2.7 or more. The dielectric constant is a value measured using a split cylinder resonator.

[0076] The dielectric loss tangent of the resin of this disclosure, measured at a frequency of 10 GHz, is preferably 0.045 or less, more preferably 0.042 or less, and also preferably 0.005 or more, more preferably 0.010 or more. The dielectric loss tangent is a value measured using a split-cylinder resonator.

[0077] The tensile strength of the resin disclosed herein is preferably 60 MPa or higher, more preferably 65 MPa or higher, and also preferably 150 MPa or lower, more preferably 130 MPa or lower. The tensile strength is determined by a tensile test performed under the following conditions: Tensile test conditions: Tensile speed: 10 mm / min Sample shape: Micro dumbbell

[0078] The ratio of amide bonds to imide bonds in the resin of this disclosure is preferably 1% or less, more preferably 0.01% or less, even more preferably 0.001% or less, particularly preferably 0.0001% or less, and most preferably 0%. In other words, it is preferable that the resin of this disclosure does not contain amide bonds. When thermal imidation is carried out by heat treatment at 400°C for 1 hour, the ratio of amide bonds is usually 0.01% or less. The ratio of amide bonds can be determined from the ratio of the peak area derived from amide bonds to the peak area derived from imide bonds using X-ray photoelectron spectroscopy (XPS).

[0079] The total light transmittance of the resins disclosed herein is preferably 60% or more, more preferably 80% or more, even more preferably 85% or more, and also preferably 100% or less, more preferably 98% or less, and even more preferably 95% or less. The total light transmittance can be measured using a cast film with a thickness of 20 μm according to JIS K 7461-1 (ISO 13468-1) Plastics - Test method for total light transmittance of transparent materials.

[0080] The resins of this disclosure may be used in combination with other materials as a resin composition. This disclosure also relates to resin compositions containing the resins of this disclosure (resin compositions of this disclosure). Examples of other materials include resins having repeating units represented by formula (1) (excluding polyimides, polyetherimides, and polyamideimides).

[0081] The resin used in combination with the resin of this disclosure is not particularly limited as long as it is a resin other than polyimide, polyetherimide, or polyamideimide, but polyetheretherketone, aromatic polyamide, polyphenylene sulfide, liquid crystal polymer, polysulfone, and polyethersulfone are preferred.

[0082] In resins used in combination with the resins of this disclosure, the content and preferred form of the repeating unit represented by formula (1) are the same as those described for the resins of this disclosure.

[0083] In the resin composition of the present disclosure, the content of the resin of the present disclosure is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and also preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 93% by mass or less.

[0084] The resin of this disclosure can be manufactured, for example, by a method for manufacturing the polyimide of this disclosure as described later.

[0085] <Method for producing polyimide> The method for producing polyimide according to the present disclosure includes a polycondensation step of polycondensing a tetracarboxylic dianhydride with a diamine compound represented by the following formula (2). (In the formula, X １ , X ２ These are identical or different, directly bonded, a C1-C10 alkylene group, a C3-C10 alicyclic hydrocarbon group, or a C5-C10 aromatic hydrocarbon group. １ , Y ２ These are, either identical or different, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. １ , R ２ X is an alkyl group having 1 to 10 carbon atoms, either identical or different. １ , X ２ , Y １ , Y ２ , R １ , R ２ The group represented by may have substituents.

[0086] The content and preferred form of the tetracarboxylic dianhydride and the diamine compound represented by formula (2) are the same as those described for the resins of this disclosure.

[0087] The polycondensation method is not particularly limited, and general methods such as solution polycondensation, molten polycondensation, interfacial polycondensation, and solid-phase polycondensation can be applied.

[0088] In the polycondensation process, the polymerization temperature, polymerization time, and polymerization pressure are not particularly limited and can be adjusted as appropriate according to the type and amount of material used, but it is preferable that they be 12 to 60°C, 1 to 72 hours, and atmospheric pressure, respectively.

[0089] When polycondensation is carried out in a solvent, an organic solvent is preferred, and an amide-based organic solvent such as N-methyl-2-pyrrolidone (NMP) or N,N-dimethylacetamide (DMAc) is more preferred, with N-methyl-2-pyrrolidone (NMP) being particularly preferred.

[0090] The polycondensate obtained in the polycondensation process is preferably a polyamic acid, and more preferably a compound represented by the following formula (2A) (polyamic acid). (In the formula, X １ , X ２ These are identical or different, directly bonded, a C1-C10 alkylene group, a C3-C10 alicyclic hydrocarbon group, or a C5-C10 aromatic hydrocarbon group. １ , Y ２ These are, either identical or different, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. １ , R ２ These are identical or different alkyl groups having 1 to 10 carbon atoms. Z is an organic group. X １ , X ２ , Y １ , Y ２ , R １ , R ２ (The group represented by Z may have substituents.)

[0091] In equation (2A), X １ , X ２ , Y １ , Y ２ , R １ , R ２ The content and preferred form of Z are the same as those described in equations (1) and (1A).

[0092] The method for producing polyimide according to this disclosure preferably includes an imidation step after the polycondensation step, in which the polyamic acid obtained in the polycondensation step is imidized.

[0093] The imidation process may be carried out by heating or by reaction with a dehydrating agent such as acetic anhydride. Furthermore, the imidation may be carried out in a solvent such as an organic solvent or in the absence of a solvent.

[0094] When imidization is carried out by heating, the heating temperature can be adjusted appropriately according to the type and amount of material used, but 380 to 450°C is preferred. Furthermore, it is preferable to carry out the heating under an inert gas atmosphere.

[0095] <Polyamic Acids> The polyamic acids of this disclosure have repeating units represented by the following formula (1). (In the formula, X １ , X ２ These are identical or different, directly bonded, a C1-C10 alkylene group, a C3-C10 alicyclic hydrocarbon group, or a C5-C10 aromatic hydrocarbon group. １ , Y ２ These are, either identical or different, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. １ , R ２ X is an alkyl group having 1 to 10 carbon atoms, either identical or different. １ , X ２ , Y １ , Y ２ , R １ , R ２ The group represented by may have substituents.

[0096] The contents and preferred form of formula (1) are the same as those described for the resins of this disclosure.

[0097] The polyamic acid of this disclosure has a viscosity, when measured with a 15% by mass N-methyl-2-pyrrolidone solution, preferably 500 cP or more, more preferably 1000 cP or more, even more preferably 2500 cP or more, and also preferably 100,000 cP or less, more preferably 50,000 cP or less, and even more preferably 30,000 cP or less. In particular, when the viscosity is in the range of 2500 cP to 30,000 cP, the film thickness in the film-forming process becomes uniform, and a film with a good surface shape free of scratches, etc., is obtained. If the viscosity is too low, a thin film may be formed and a film with a uniform film thickness may not be obtained, and if the viscosity is too high, coating becomes difficult and a film with a good surface shape may not be obtained. When a 50 mm x 50 mm film is peeled off a glass plate after film formation, and there are no cracks or tears in the film, the viscosity is usually 500 to 100,000 cP. Viscosity was measured at 20°C using an E-type viscometer (cone plate, TV-100BH) manufactured by Toki Sangyo Co., Ltd., after preparing an N-methyl-2-pyrrolidone solution with a polyamic acid concentration of 15% by mass.

[0098] The polyamic acid of this disclosure preferably has repeating units based on an acid anhydride, and more preferably is a polyamic acid represented by formula (2A). The resin of this disclosure can be obtained by imidizing this polyamic acid. That is, the polyamic acid of this disclosure can be used as a precursor of the resin of this disclosure.

[0099] Furthermore, the polyamic acid of this disclosure can also be used as a functional material for use in paints, adhesives, electrode binders, or coatings.

[0100] <Diamine Compounds> The diamine compounds of this disclosure are represented by the following formula (2). (In the formula, X １ , X ２ These are identical or different, directly bonded, a C1-C10 alkylene group, a C3-C10 alicyclic hydrocarbon group, or a C5-C10 aromatic hydrocarbon group. １ , Y ２ These are, either identical or different, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms.１ , R ２ X is an alkyl group having 1 to 10 carbon atoms, either identical or different. １ , X ２ , Y １ , Y ２ , R １ , R ２ The group represented by may have substituents.

[0101] The contents and preferred form of formula (2) are the same as those described for the resins of this disclosure.

[0102] The diamine compounds of this disclosure are synthesized, for example, from vanillin via divanillin. This disclosure also relates to a method for producing diamine compounds, which involves synthesizing a diamine compound represented by formula (2) from vanillin via divanillin.

[0103] Vanillin may be synthetic vanillin synthesized from guaiacol or the like, or natural vanillin extracted from biomass materials such as wood or vanilla beans, but natural vanillin is preferred.

[0104] The reaction pathway for synthesizing the diamine compound represented by formula (2) from vanillin via divanillin is not particularly limited, but an example of the reaction pathway is shown below. This example uses MeDVA-NH, which will be used in the experimental example described later. ２ This is the reaction pathway. As in this example, divanillin may also be synthesized from vanillin via derivatives such as vanillic acid.

[0105] <Components> The components of the present disclosure include at least one selected from the group consisting of the resins of the present disclosure and the resin compositions of the present disclosure, and are used as mobility components, information and communication components, semiconductor components, precision machinery components, medical components, industrial machinery components, building components, wire insulation components, or composite material matrix components, but are particularly preferably used as mobility components, information and communication components, semiconductor components, and medical components, and are especially preferably used as mobility components and information and communication components.

[0106] Mobility components include parts used in ferries, railways, automobiles, motorcycles, drones, robots, etc. Information and communication components include parts for wireless LAN transceiver circuits and other devices, circuit boards, and parts for optical communication devices. Semiconductor components include process materials used in semiconductor manufacturing and parts for semiconductor manufacturing equipment. Precision machinery components include parts used in laser processing machines, optical instruments, measuring instruments, etc. Medical components include parts used in medical sensors and diagnostic equipment, piping materials such as medical infusion tubes, blood collection tubes, drain tubes, catheters, catheter connectors, stents, pipes, fittings, tube connectors, valves, and filters; liquid, powder, or solid drug containers such as packaging packages, bottles, bottle caps, vials, ampoules, pre-filled syringes, infusion bags, infusion bag connectors, sealed drug bags, press-through packages, and eye drop containers; and sample containers such as urine collection bags, blood sampling test tubes, blood collection tubes, test cells, and specimen containers. Among these, from the viewpoint of requiring high mechanical strength, the materials can be particularly suitably used in medical infusion tubes, blood collection tubes, drain tubes, catheters, catheter connection parts, piping, fittings, tube connectors, valves, packaging, bottles, bottle caps, vials, ampoules, pre-filled syringes, infusion bags, urine collection bags, test tubes for blood sampling, blood collection tubes, test cells, and specimen containers. Furthermore, the materials of this disclosure can be used to constitute a part of the above medical supplies. As part of the above medical supplies, a component formed by laminating the materials of this disclosure with other materials may also be used. Examples of industrial machinery components include parts used in motors, gearboxes, conveyors, etc. Examples of building components include interior building materials such as baseboards, ceiling materials, and plumbing materials, exterior building materials such as waterproof sheets, water-stopping materials, exterior wall materials, and roofing materials, and structural members such as beams, columns, flooring materials, and wall materials. Examples of wire insulation components include insulating layers that cover conductors. Examples of composite material matrix components include matrices such as fiber-reinforced plastics.

[0107] The shape of the component of this disclosure is not particularly limited, but it is preferably a fiber, film, or sheet.

[0108] <Film for high-frequency substrates> The film for high-frequency substrates of this disclosure includes the components of this disclosure.

[0109] A high-frequency circuit board is a circuit board that can operate in a high-frequency band. The high-frequency band may be 1 GHz or higher, preferably 3 GHz or higher, and more preferably 5 GHz or higher. There is no particular upper limit, but it may be 100 GHz or lower.

[0110] The high-frequency substrate film of this disclosure can be suitably used in metal-clad laminates.

[0111] <Metal-clad laminate> The metal-clad laminate of this disclosure includes the film for high-frequency substrates of this disclosure.

[0112] The metal-clad laminates of this disclosure typically further include metal foil. Examples of metal foil include copper, aluminum, iron, nickel, chromium, molybdenum, tungsten, zinc, platinum, or alloys thereof, with copper foil being preferred. Furthermore, to improve adhesion, chemical or mechanical surface treatments such as siding, nickel plating, copper-zinc alloy plating, or aluminum alkoxide, aluminum chelate, or silane coupling agents may be applied.

[0113] The metal-clad laminate of this disclosure can be suitably used in circuit boards.

[0114] <Circuit board> The circuit board of this disclosure includes the metal-clad laminate of this disclosure.

[0115] The circuit boards of this disclosure are suitably used as printed circuit boards, multilayer circuit boards (multilayer substrates), and high-frequency substrates.

[0116] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims.

[0117] The present disclosure will now be explained with reference to examples, but the present disclosure is not limited to such examples.

[0118] Each value in the examples was measured by the following method.

[0119] <Weight-average molecular weight (Mw), number-average molecular weight (Mn)> Measurement device: APC system manufactured by Waters Japan Ltd. Measurement conditions: N-methyl-2-pyrrolidone was used as the eluent, and polystyrene with a known molecular weight was used as the standard sample for molecular weight.

[0120] <Glass Transition Temperature (Tg)> The glass transition temperature was determined by measuring the temperature in tensile mode using a thermomechanical analyzer (TMA, Rigaku Corporation, EVO2G) by increasing the temperature of the sample (resin film) at 5°C / min. It was determined as the temperature at the midpoint of the intersection of two points: the extension of the baseline of the TMA curve before and after the second-order transition, and the tangent line at the inflection point of the TMA curve.

[0121] <Tensile Strength> Tensile strength was determined by a tensile test performed on the resin under the following conditions: Tensile test conditions: Tensile speed: 10 mm / min Sample shape: Micro dumbbell

[0122] <Tensile Modulus of Elasticity, Tensile Elongation> Using an ASTM V-type dumbbell in the MD direction, test specimens with a gauge distance of 7.6 mm were punched out from the resin on the dumbbell. In accordance with ASTM D638, the tensile modulus of elasticity (MPa) and tensile elongation (%) were measured at 25°C, a chuck distance of 24.5 mm, and a tensile speed of 50 mm / min.

[0123] <Linear Expansion Coefficient> The coefficient of linear expansion was determined by performing TMA measurements using the TMA-7100 (manufactured by Hitachi High-Tech Science Co., Ltd.) in the following modes. [Tensile Mode Measurement] An extruded film with a thickness of 25 μm, cut to a length of 20 mm and a width of 4 mm, was used as the sample piece. The linear expansion coefficient was determined from the displacement of the sample at a heating rate of 2 °C / min while being pulled with a load of 49 mN from 30 to 200 °C.

[0124] <Relative permittivity, dielectric loss tangent> Strip-shaped samples measuring 50 mm in width and 50 mm in length were prepared from resin, and the relative permittivity and dielectric loss tangent were measured at 25°C and 10 GHz using an EM Labs split-cylinder resonator.

[0125] <Total Light Transmittance> Total light transmittance was measured using a 20 μm thick cast film according to JIS K 7461-1 (ISO 13468-1) Plastics - Test method for total light transmittance of transparent materials. <Film Formation> The condition of the polyimide film after casting polyamic acid onto a glass plate and heating was evaluated according to the following criteria. ○: No cracks or tears were found in the 50 mm x 50 mm film when peeled from the glass plate. ×: In all other cases (e.g., the film is brittle and cannot be removed, or cracks or tears have occurred in the 50 mm x 50 mm film).

[0126] <Synthesis of Diamine Compounds> MeDVA-NH ２ The diamine compounds were synthesized using the synthetic route described for the diamine compounds of this disclosure. The other diamine compounds were synthesized using the same route as MeDVA-NH, except that the starting materials were different. ２ It was synthesized using a similar synthesis route.

[0127] <Experimental Example> Under the conditions shown in Table 1 below, a diamine compound and an acidic dianhydride were polycondensed in a solvent to obtain polyamic acid. Next, the polyamic acid was coated onto a glass plate and heated at 400°C for 1 hour to obtain a resin (polyimide).

[0128]

[0129] The abbreviations in the table are as follows: <Diamine Compounds> MeDVA-NH ２ : In formula (2), X １ , X ２ They are directly bonded, Y １ , Y ２ , R １ , R ２ The compound with a methyl group is c-PenDVA-NH ２ : In formula (2), X １ , X ２ They are directly bonded, Y １ , Y ２ is a cyclopentyl group, R １ , R ２ The compound with a methyl group is c-PenCH ２ DVA-NH ２ : In formula (2), X １ , X ２ is a methylene group, Y １ , Y２ is a cyclopentyl group, R １ , R ２ The compound with a methyl group is c-HexCH ２ DVA-NH ２ : In formula (2), X １ , X ２ is a methylene group, Y １ , Y ２ is a cyclohexyl group, R １ , R ２ The compound BnCH contains a methyl group. ２ DVA-NH ２ : In formula (2), X １ , X ２ is a methylene group, Y １ , Y ２ is a benzyl group, R １ , R ２ Compounds with a methyl group <Acid dianhydrides> ODPA: 4,4'-oxydiphthalic anhydride BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride ISS-TME: Compound represented by the following formula <Solvent> NMP: N-methyl-2-pyrrolidone

Claims

1. A resin which has a repeating unit represented by the following formula (1) and is a polyimide, a polyetherimide or a polyamideimide. (In the formula, X １ , X ２ are the same or different and are a direct bond, an alkylene group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms or an aromatic hydrocarbon group having 5 to 10 carbon atoms. Y １ , Y ２ are the same or different and are an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms or an aromatic hydrocarbon group having 5 to 10 carbon atoms. R １ , R ２ are the same or different and are an alkyl group having 1 to 10 carbon atoms. The groups represented by X １ , X ２ , Y １ , Y ２ , R １ , R ２ may have a substituent.) 2. The resin according to claim 1, which is polyimide.

3. The resin according to claim 2, wherein the polyimide is a copolymer of two or more tetracarboxylic dianhydrides.

4. The resin according to claim 2 or 3, wherein the polyimide is a copolymer of a diamine compound represented by the following formula (2) and another diamine compound. (In the formula, X １ , X ２ These are identical or different, directly bonded, a C1-C10 alkylene group, a C3-C10 alicyclic hydrocarbon group, or a C5-C10 aromatic hydrocarbon group. １ , Y ２ These are, either identical or different, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. １ , R ２ X is an alkyl group having 1 to 10 carbon atoms, either identical or different. １ , X ２ , Y １ , Y ２ , R １ , R ２ The group represented by may have substituents.

5. In equation (1) above, X １ , X ２ The resin according to any one of claims 1 to 4, wherein is the same or different alkylene group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms.

6. In the above formula (1), X １ , X ２ is a methylene group or a direct bond, Y １ , Y ２ R is a methyl group, cyclopentyl group, cyclohexyl group, benzyl group, or n-butyl group. １ , R ２ The resin according to any one of claims 1 to 4, wherein is a methyl group.

7. The resin according to any one of claims 1 to 6, wherein the weight-average molecular weight is 76,000 or more.

8. The resin according to any one of claims 1 to 7, wherein the weight-average molecular weight / number-average molecular weight is 4 or less.

9. The resin according to any one of claims 1 to 8, wherein the glass transition temperature is 180°C or higher.

10. The resin according to any one of claims 1 to 9, wherein the dielectric constant measured at a frequency of 10 GHz is 4 or less.

11. The resin according to any one of claims 1 to 10, wherein the dielectric loss tangent measured at a frequency of 10 GHz is 0.045 or less.

12. The resin according to any one of claims 1 to 11, wherein the tensile strength is 60 MPa or more.

13. The resin according to any one of claims 1 to 12, wherein the ratio of amide bonds to imide bonds is 1% or less.

14. The resin according to any one of claims 1 to 13, wherein the total light transmittance is 60% or more.

15. A method for producing polyimide, comprising a polycondensation step of polycondensing a tetracarboxylic dianhydride with a diamine compound represented by the following formula (2). (In the formula, X １ , X ２ These are identical or different, directly bonded, a C1-C10 alkylene group, a C3-C10 alicyclic hydrocarbon group, or a C5-C10 aromatic hydrocarbon group. １ , Y ２ These are, either identical or different, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. １ , R ２ X is an alkyl group having 1 to 10 carbon atoms, either identical or different. １ , X ２ , Y １ , Y ２ , R １ , R ２ The group represented by may have substituents.

16. A method for producing polyimide according to claim 15, comprising an imidation step of imidizing the polyamic acid obtained in the polycondensation step.

17. In equation (2) above, X １ , X ２ is a methylene group or a direct bond, Y １ , Y ２ R is a methyl group, cyclopentyl group, cyclohexyl group, benzyl group, or n-butyl group. １ , R ２ The method for producing polyimide according to claim 15 or 16, wherein is a methyl group.

18. A polyamic acid having repeating units represented by the following formula (1). (In the formula, X １ , X ２ These are identical or different, directly bonded, a C1-C10 alkylene group, a C3-C10 alicyclic hydrocarbon group, or a C5-C10 aromatic hydrocarbon group. １ , Y ２ These are, either identical or different, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. １ , R ２ X is an alkyl group having 1 to 10 carbon atoms, either identical or different. １ , X ２ , Y １ , Y ２ , R １ , R ２ The group represented by may have substituents.

19. The polyamic acid according to claim 18, wherein the viscosity measured with a 15% by mass N-methyl-2-pyrrolidone solution is 500 to 100,000 cP.

20. In the above equation (1), X １ , X ２ is a methylene group or a direct bond, Y １ , Y ２ R is a methyl group, cyclopentyl group, cyclohexyl group, benzyl group, or n-butyl group. １ , R ２ The polyamic acid according to claim 18 or 19, wherein the group is a methyl group.

21. A functional material comprising the polyamic acid described in any of claims 18 to 20, which is used as a paint, adhesive, electrode binder, or coating agent.

22. A diamine compound represented by the following formula (2). (In the formula, X １ , X ２ These are identical or different, directly bonded, a C1-C10 alkylene group, a C3-C10 alicyclic hydrocarbon group, or a C5-C10 aromatic hydrocarbon group. １ , Y ２ These are, either identical or different, an alkyl group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms. １ , R ２ X is an alkyl group having 1 to 10 carbon atoms, either identical or different. １ , X ２ , Y １ , Y ２ , R １ , R ２ The group represented by may have substituents.

23. In the above equation (2), X １ , X ２ is a methylene group or a direct bond, Y １ , Y ２ R is a methyl group, cyclopentyl group, cyclohexyl group, benzyl group, or n-butyl group. １ , R ２ The diamine compound according to claim 22, wherein is a methyl group.

24. A method for producing a diamine compound according to claim 22 or 23, comprising synthesizing a diamine compound represented by formula (2) from vanillin via divanillin.

25. A resin composition comprising the resin according to any one of claims 1 to 14.

26. The resin composition according to claim 25, comprising a resin (excluding polyimide, polyetherimide, and polyamideimide) having repeating units represented by formula (1).

27. A component comprising at least one selected from the group consisting of the resin described in any one of claims 1 to 14 and the resin composition described in claim 25 or 26, which is used as a mobility component, an information and communication component, a semiconductor component, a precision machinery component, a medical component, an industrial machinery component, a building component, a wire insulation component, or a composite material matrix component.

28. The member according to claim 27, which is a fiber, film, or sheet.

29. A film for a high-frequency substrate comprising the member described in claim 27 or 28.

30. A metal-clad laminate containing the high-frequency substrate film according to claim 29.

31. A circuit board comprising a metal-clad laminate according to claim 30.

Images