Polyimide or polyamic acid, resin composition, laminate, and method for producing laminate

Abstract

The present invention provides: a novel polyimide or polyamic acid; a resin composition comprising the same; a laminate comprising a resin layer that is formed from the resin composition; and a method for producing the laminate.　Provided are: a polyimide or polyamic acid which is a reaction product of a diamine compound represented by general formula (1), an acid anhydride represented by general formula (2), and an acid anhydride represented by general formula (4); a resin composition comprising the polyimide and / or the polyamic acid; a laminate comprising a resin layer that is formed from the resin composition; and a method for producing the laminate.

Description

Polyimide or polyamic acid, resin composition, laminate, and method for producing the laminate

[0001] This disclosure relates to polyimides or polyamic acids, resin compositions, laminates, and methods for producing laminates.

[0002] In electrical products such as mobile phones and portable recorders / playback devices, flexible copper foil wiring boards (hereinafter also known as FCCL; Flexible Copper Clad Laminate) are used between electrical circuit parts to achieve miniaturization and cost reduction.

[0003] FCCL comprises a copper foil and an insulating layer. Polyamic acid can be used as the insulating layer. A polyamic acid resin composition is imidized on the surface of the copper foil to form a polyimide insulating layer (see Patent Document 1, etc.).

[0004] Japanese Patent Application Publication No. 2009-19132

[0005] One embodiment of this disclosure aims to solve the problem of a novel polyimide or polyamic acid, a resin composition comprising at least one thereof, a laminate comprising a resin layer formed on the resin composition, and a method for manufacturing the laminate.

[0006] One embodiment of this disclosure includes the following aspects:

[0007] <1> A polyimide or polyamic acid which is a reaction product of a diamine compound represented by the following general formula (1), an acid anhydride represented by the following general formula (2), and an acid anhydride represented by the following general formula (4).

[0008]

[0009] (In general formula (1), R １ ~R ４ However, it is a hydrogen atom, R ５ ~R ８ At least one of them is an aromatic group having 6 to 10 carbon atoms, a phenoxy group, a benzyl group, or a benzyloxy group, and the other R ５ ~R ８ (This is a hydrogen atom.)

[0010]

[0011] (In general formula (2), E １ and E ２ each represent an ester bond, Z １ and Z ２ each independently represent a single bond, an alkyl group having a substituent or an alkyl group having no substituent, W １ and W ２ each independently represent an oxygen atom, a nitrogen atom having a substituent or a nitrogen atom having no substituent, and R' represents an alkylene group having a substituent, an alkylene group having no substituent, a group represented by the following general formula (3) or a group represented by the following general formula (3').)

[0012]

[0013] (In general formula (3), Z ３ represents a single bond, an alkylene group having a substituent or an alkylene group having no substituent, Z ４ and Z ５ each independently represent an alkyl group having a substituent or an alkyl group having no substituent, o and p each independently represent 0 or an integer of 1 to 4, *1 is a bonding site to E １ , and *2 is a bonding site to E ２ .)

[0014]

[0015] (In general formula (3'), Z ６ and Z ７ each independently represent an alkyl group having a substituent or an alkyl group having no substituent, *1 is a bonding site to E １ , and *2 is a bonding site to E ２ .)

[0016]

[0017] (In general formula (4), Z １０ and Z １１ each independently represent a single bond, an alkyl group having a substituent or an alkyl group having no substituent, W ３ and W ４These are, independently, an oxygen atom, a substituted nitrogen atom, or an unsubstituted nitrogen atom, W ５ (This is an alkene group or an alkyne group.)

[0018] <2> A polyimide or polyamic acid according to <1>, which is a reaction product of a diamine compound represented by the general formula (1), an acid anhydride represented by the general formula (2), wherein R' in general formula (2) is a group represented by the general formula (3) below, and an acid anhydride represented by the general formula (4).

[0019] <3> In the above general formula (3), Z ３ However, the polyimide or polyamic acid described in <2> is a single bond.

[0020] <4> The polyimide or polyamic acid according to <1> or <2>, wherein the acid anhydride represented by the general formula (2) is a compound represented by the general formula (20) below.

[0021]

[0022] (In general formula (20), X is a group represented by general formula (21) or (22), and in general formulas (21) and (22), R ９ ~R ２１ (wherein is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms or a phenyl group, and * represents the bond with the oxygen atom in formula (20).)

[0023] <5> The polyimide or polyamic acid according to any one of <1> to <4>, wherein the general formula (4) is the compound described below.

[0024]

[0025] <6> The polyimide or polyamic acid according to any one of <1> to <5>, wherein the diamine compound represented by the general formula (1) is one of the following compounds.

[0026]

[0027] <7> A polyimide or polyamic acid according to any one of <1> to <6>, wherein the content of the amine compound represented by general formula (1) relative to the diamine component constituting the polyimide or polyamic acid is 30 mol% or more.

[0028] <8> A resin composition comprising the polyimide or polyamic described in any one of <1> to <7>.

[0029] <9> The resin composition according to <8>, wherein the relative permittivity at a dielectric constant of 20 GHz is 3.60 or less and / or the dielectric loss tangent is 0.0050 or less.

[0030] <10> The resin composition according to <8> or <9>, wherein the linear thermal expansion coefficient is 35 ppm / K or less.

[0031] <11> A resin composition according to any one of <8> to <10>, wherein the tensile modulus of elasticity is 5.0 GPa or more.

[0032] <12> A resin composition according to any one of <8> to <11>, wherein the tensile strength is 150 MPa or more.

[0033] <13> A resin composition according to any one of <8> to <12>, wherein the elongation rate is 20% or more.

[0034] <14> A resin composition according to any one of <8> to <13>, wherein the glass transition temperature is 180°C or higher.

[0035] <15> A resin composition according to any one of <8> to <14>, wherein the bonding strength with copper foil is 6.0 N / cm or more.

[0036] <16> A resin composition according to any one of <8> to <15> that can be heat-pressed.

[0037] <17> A laminate comprising a first metal layer (preferably copper foil), a resin layer formed from any one of the resin compositions described in <8> to <16>, and a second metal layer (preferably copper foil).

[0038] <18> A method for manufacturing a laminate, comprising the step of heat-pressing together a first copper foil, a resin layer formed from any one of the resin compositions described in <8> to <16>, and a second copper foil.

[0039] <19> A resin film formed by any one of the resin compositions described in <8> to <16>.

[0040] According to one embodiment of the present disclosure, it is possible to provide a novel polyimide or polyamic acid, a resin composition comprising at least one thereof, a laminate comprising a resin layer formed on the resin composition, and a method for manufacturing the laminate.

[0041] The contents of the present invention will be described in detail below. The following descriptions of constituent elements may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, the "~" indicating a numerical range is used to mean that the numbers described before and after it are included as the lower limit and upper limit. In numerical ranges described in stages in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described in stages. Also, in numerical ranges described in this disclosure, the upper limit or lower limit of that numerical range may be replaced with the values ​​shown in the examples. Furthermore, in this disclosure, "mass%" and "weight%" are synonymous, and "parts by mass" and "parts by weight" are synonymous. Furthermore, in this disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

[0042] [Polyimide or Polyamic Acid] In one embodiment, the polyimide or polyamic acid of the present disclosure is a reaction product of a diamine compound represented by the following general formula (1), an acid anhydride represented by the following general formula (2), and an acid anhydride represented by the following general formula (4). The reaction product may also be a reaction product of a diamine compound other than the diamine compound represented by general formula (1), an acid anhydride other than the acid anhydride represented by general formula (2), and / or an acid anhydride other than the acid anhydride represented by general formula (4).

[0043]

[0044] In general formula (1), R １ ~R ４ However, it is a hydrogen atom, R ５ ~R ８ At least one of them is an aromatic group having 6 to 10 carbon atoms, a phenoxy group, a benzyl group, or a benzyloxy group, and the other R ５ ~R ８ That is a hydrogen atom.

[0045]

[0046] In general formula (2), E １ and E ２ This is an ester bond, Z １ and Z ２ Each of these is independently a single bond, a substituted alkyl group, or an unsubstituted alkyl group, W １ and W ２ Each of the following is independently an oxygen atom, a substituted nitrogen atom, or an unsubstituted nitrogen atom, and R' is a substituted alkylene group, an unsubstituted alkylene group, a group represented by the following general formula (3), or a group represented by the following general formula (3').

[0047]

[0048] In general formula (3), Z ３ Z is a single bond, a substituted alkylene group, or an unsubstituted alkylene group. ４ and Z ５ Each is independently a substituted alkyl group or an unsubstituted alkyl group, o and p are independently 0 or an integer from 1 to 4, and *1 is E １ This is the connection point with E, and *2 is E ２ This is the connection point.

[0049]

[0050] In general formula (3'), Z ６ and Z ７ Each of these is independently a substituted alkyl group or an unsubstituted alkyl group, and *1 is E１ This is the connection point with E, and *2 is E ２ This is the connection point.

[0051]

[0052] In general formula (4), Z １０ and Z １１ Each of these is independently a substituted alkyl group or an unsubstituted alkyl group, W ３ and W ４ These are, independently, an oxygen atom, a substituted nitrogen atom, or an unsubstituted nitrogen atom, W ５ This is an alkene group or an alkyne group.

[0053] Insulating layers used in FCCL and the like are required to have excellent thermal expandability, dielectric properties, and adhesion to substrates such as copper foil, but conventional polyamic acid resin compositions have room for improvement in these properties. According to one embodiment of the present disclosure, it is possible to improve the thermal expandability, dielectric properties, and adhesion to substrates such as copper foil of polyimide or polyamic acid. The reason why the polyimide or polyamic acid of the present disclosure has excellent thermal expandability, dielectric properties, and adhesion to substrates such as copper foil is presumed to be as follows. Note that the present invention is not limited to the following description. First, the polyimide or polyamic acid of the present disclosure is a reaction product of a diamine compound represented by general formula (1). As a result, the polyimide or polyamic acid of the present disclosure contains a rigid aromatic ring and an ester structure, which is presumed to reduce its thermal expandability. Furthermore, the polyimide or polyamic acid of the present disclosure is a reaction product of a diamine compound represented by general formula (1) and an acid anhydride represented by general formula (2), and these have an ester structure in their structure. This is expected to reduce the water absorption rate of the resin layer, thereby lowering the dielectric loss tangent and relative permittivity of the resin layer and improving its dielectric properties. Furthermore, it is expected that the acid anhydride represented by general formula (2) will cause the polyimide or polyamic acid of this disclosure to contain rigid aromatic rings and ester structures, thereby reducing thermal expansion. In addition, laminates with copper foil and insulating layers for FCCL applications usually require applying an adhesive to the surface of the insulating layer and then laminating the copper foil, etc. On the other hand, a resin layer formed from a resin composition containing the polyimide or polyamic acid of this disclosure can be heat-pressed (for example, by a hot plate or hot roll), and a metal layer such as copper foil can be laminated onto the surface of the resin layer without using an adhesive.

[0054] (Regarding General Formula (1)) In General Formula (1), R ５ ~R ８ Preferably, one or two of them are aromatic groups having 6 to 10 carbon atoms, R ５ and R ７ It is more preferable that at least one of them is an aromatic group having 6 to 10 carbon atoms, R ７It is even more preferable that the atom is an aromatic group having 6 to 10 carbon atoms. In this disclosure, the "aromatic group" includes substituents that are bonded to the main skeleton via oxygen atoms, nitrogen atoms, or carbon atoms. Furthermore, the aromatic group includes heteroaromatic groups such as pyrrole groups.

[0055] Examples of aromatic groups having 6 to 10 carbon atoms include phenyl group, tolyl group, methylphenyl group, dimethylphenyl group, ethylphenyl group, diethylphenyl group, propylphenyl group, butylphenyl group, fluorophenyl group, pentafluorophenyl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, dimethoxyphenyl group, ethoxyphenyl group, diethoxyphenyl group, aminophenyl group, nitrophenyl group, nitrobenzyl group, cyanophenyl group, cyanobenzyl group, phenethyl group, phenylpropyl group, phenylamino group, diphenylamino group, biphenyl group, naphthyl group, phenylnaphthyl group, diphenylnaphthyl group, anthryl group, and anthryl group. Examples of heteroaromatic groups include phenyl group, phenylanthryl group, naphthacenyl group, phenanthryl group, phenanthrylphenyl group, phenylphenanthryl group, pyrenyl group, phenylpyrenyl group, fluorenyl group, phenylfluorenyl group, naphthylethyl group, naphthylpropyl group, anthracenylethyl group, phenanthrylethyl group, pyrrole group, imidazole group, thiazole group, oxazole group, furan group, thiophene group, triazole group, pyrazole group, isoxazole group, isothiazole group, pyridine group, pyrimidine group, benzofuran group, benzothiophene group, quinoline group, isoquinoline group, indolyl group, benzothiazolyl group, and carbazolyl group. Among the aromatic groups listed above, phenyl and methylphenyl groups are preferred in terms of ease of obtaining starting materials and synthesis cost.

[0056] The polyimide or polyamic acid of this disclosure may be a polyimide or polyamic acid obtained by using two or more diamine compounds represented by general formula (1).

[0057] As a diamine compound satisfying general formula (1), specifically, 2-phenyl-4-aminophenyl)-4-aminobenzoate, which is represented by the following formula (6), can be preferably used. By using this diamine compound, the solvent solubility, melt moldability, etc., of the resulting polyimide or polyamic acid can be improved.

[0058]

[0059] The diamine compound represented by general formula (1) can be obtained by reacting the compound represented by formula (7) below with the compound represented by formula (8) below, and then reducing the nitro group.

[0060]

[0061]

[0062] In the above formula, R １ ~R ４ , and R ５ ~R ８ The definition of is the same as that of general formula (1) above. Also, Y represents a hydroxyl group, or a halogen group selected from a fluoro group, a chloro group, a bromo group, and an iodo group. From the viewpoint of reactivity with the compound represented by general formula (8), Y is preferably a halogen group, and more preferably a chloro group or a bromo group.

[0063] When Y in general formula (7) is a hydroxyl group, the reaction between the compound represented by general formula (7) and the compound represented by general formula (8) is preferably carried out in the presence of a dehydrating condensation agent such as N,N'-dicyclohexylcarbodiimide (DCC) and an organic acid catalyst such as p-toluenesulfonic acid. Furthermore, when Y in general formula (7) is a halogen group, the reaction between the compound represented by general formula (7) and the compound represented by general formula (8) is preferably carried out in the presence of an acid acceptor such as triethylamine.

[0064] Specifically, the diamine compound represented by formula (6) can be obtained by reacting the compound represented by formula (9) below with the compound represented by formula (10) below.

[0065]

[0066]

[0067] The compound represented by general formula (8) can be obtained by nitrating a commercially available or synthesized compound represented by the following formula (11). The nitration of the compound represented by the following formula (11) can be carried out by conventionally known nitration methods using a mixed acid of concentrated sulfuric acid and concentrated nitric acid, nitric acid, fuming nitric acid, alkali metal acid salts in concentrated sulfuric acid, acetyl nitrate, nitronium salts, nitrogen oxides, etc. Note that R in the formula ５ ~R ８ This is the same as the definition of the general formula (1) above.

[0068]

[0069] From the viewpoint of low thermal expansion, dielectric properties, tensile strength, heat resistance, etc., the content of the amine compound represented by general formula (1) relative to the diamine component constituting the polyimide or polyamic acid is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, particularly preferably 60 mol% or more, and most preferably 70 mol% or more. Furthermore, the upper limit of the content is not particularly limited and may be 100 mol% or less, preferably 95 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less. For example, the content of the amine compound represented by general formula (1) relative to the diamine component constituting the polyimide or polyamic acid can be 30 to 100 mol%, 40 to 100 mol%, 50 to 100 mol%, 60 to 100 mol%, or 70 to 100 mol%.

[0070] (Regarding General Formula (2)) In General Formula (2), E １ and E ２ This is an ester bond. The CO portion in the ester bond is Z １ and Z ２ Even if placed to the side (Z １ or Z ２ -CO-O-R'), may be placed on the R' side (Z １ or Z ２-O-CO-R'), Z １ and Z ２ It is preferable that it be located on the side.

[0071] In general formula (2), Z １ and Z ２ Each of these is independently a single bond, a substituted alkyl group, or an unsubstituted alkyl group, and it is preferable that all are single bonds. The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 3. Examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, chloroethyl group, dichloromethyl Examples of substituents include hydroxyethyl group, trichloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, hydroxymethyl group, hydroxyethyl group, hydroxylpropyl group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentyloxy group, sec-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, trifluoromethoxy group, methylamino group, dimethylamino group, trimethylamino group, ethylamino group, propylamino group, etc. Substituents include alkyl groups, halogen groups such as fluoro groups and chloro groups, amino groups, nitro groups, hydroxyl groups, cyano groups, carboxyl groups, sulfonic acid groups, etc.

[0072] In general formula (2), W １ and W ２Each of these is independently an oxygen atom, a substituted nitrogen atom, or an unsubstituted nitrogen atom, and it is preferable that it is an oxygen atom or a substituted nitrogen atom. Examples of substituents include alkyl groups, halogen groups such as fluoro groups and chloro groups, amino groups, nitro groups, hydroxyl groups, cyano groups, carboxyl groups, sulfonic acid groups, etc. Among these, alkyl groups are preferred, alkyl groups having 1 to 6 carbon atoms are more preferred, and alkyl groups having 1 to 3 carbon atoms are even more preferred. In one embodiment, the nitrogen atom having an alkyl group is a nitrogen atom having a methyl group or an ethyl group. In general formula (2), when R' is a substituted alkylene group, an unsubstituted alkylene group, or a group represented by general formula (3'), W １ and W ２ It is preferable that is a substituted nitrogen atom. In general formula (2), when R' is a group represented by general formula (3), W １ and W ２ It is preferable that it is an oxygen atom.

[0073] In general formula (2), R' is a substituted alkylene group, an unsubstituted alkylene group, a group represented by general formula (3), or a group represented by general formula (3'), and is preferably an unsubstituted alkyl group, a group represented by general formula (3), or a group represented by general formula (3'). From the viewpoint of keeping the glass transition temperature of the polyimide low, R' is preferably an unsubstituted alkylene group. From the viewpoint of tensile strength and elastic modulus, the number of carbon atoms in the alkylene group is preferably 1 to 5, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 2. Substituents that the alkylene group may have include alkyl groups, halogen groups such as fluoro groups and chloro groups, amino groups, nitro groups, hydroxyl groups, cyano groups, carboxyl groups, and sulfonic acid groups.

[0074] (Regarding general formula (3)) In general formula (3), Z ３This is a single bond, a substituted alkylene group, or an unsubstituted alkylene group, and a single bond is preferred. For the alkylene group, the same type as the alkylene group in R' is preferred.

[0075] In general formula (3), Z ４ and Z ５ Each of these is independently a substituted alkyl group or an unsubstituted alkyl group. From the viewpoint of solvent solubility of polyimide or polyamic acid, the structure represented by general formula (3) preferably has an alkyl group (i.e., one or more of either O or P). The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 5. The alkyl group may be linear or branched, but it is preferably branched. Examples of substituents include halogen groups such as fluoro and chloro groups, amino groups, nitro groups, hydroxyl groups, cyano groups, carboxyl groups, and sulfonic acid groups. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, sec-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups, among which isopropyl or tert-butyl groups are preferred. From the viewpoint of dielectric properties, the alkyl group is preferably a fluoroalkyl group. However, the polyimide or polyamic acid of this disclosure is a reaction product of a diamine compound represented by general formula (1) and an acid anhydride represented by general formula (2), and as described above, its dielectric properties are improved. Therefore, the alkyl group does not need to have a fluoro group as a substituent.

[0076] In general formula (3), o and p are each independently 0 or an integer from 1 to 4. When the present invention is polyimide, from the viewpoint of solvent solubility, the sum of o and p is preferably 4 to 8, and more preferably 6 to 8.

[0077] (Regarding general formula (3')) In general formula (3'), Z ６ and Z ７each independently represent an alkyl group having a substituent or an alkyl group having no substituent, and are preferably alkyl groups having no substituent. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 7, and still more preferably 1 to 5. The alkyl group may be linear or branched, and is preferably branched. Examples of the substituent include halogen groups such as fluoro group and chloro group, amino group, nitro group, hydroxyl group, cyano group, carboxyl group, sulfonic acid group and the like. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. Among these, isopropyl group or tert-butyl group is preferred.

[0078] The polyimide or polyamic acid of the present disclosure may be a polyimide or polyamic acid obtained by using two or more types of acid anhydrides represented by general formula (2). From the viewpoints of low thermal expansion, dielectric properties, tensile strength, heat resistance and the like, the sum of the contents of acid anhydrides represented by general formula (2), wherein R' is a group represented by general formula (3) and a group represented by general formula (3'), relative to the acid anhydride component constituting the polyimide or polyamic acid, is preferably 5 mol% or more, more preferably 10 mol% to 80 mol%, still more preferably 20 mol% to 70 mol%.

[0079] From the viewpoints of low thermal expansion, dielectric properties, tensile strength, heat resistance and the like, the acid anhydride represented by general formula (2) is preferably a compound represented by the following general formula (20).

[0080]

[0081] In general formula (20), X is a group represented by general formula (21) or (22). In general formula (21) and (22), R ９ to R ２１ each are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, * represents a bonding site to an oxygen atom. R９ to R ２１ is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. From the viewpoint of improving solvent solubility, R ９ to R ２１ is preferably an alkyl group having 1 to 8 carbon atoms.

[0082] The compound represented by general formula (20) can be obtained by reacting a diol compound having an X structure with trimellitic anhydride chloride and performing esterification. Further, when the X structure is a phenyl skeleton (a group represented by general formula (21)) and R ９ to R １２ is hydrogen, p-phenylenebis(trimellitate anhydride) (TAHQ) is available from Manac Inc. and Nippon Fine Chemical Co., Ltd. When the X structure is a biphenyl skeleton (a group represented by general formula (22)) and R １３ to R ２１ is hydrogen or a methyl group, the various derivatives BP-TME, OCBP-TME, and TMPBP-TME described below can be purchased from Honshu Chemical Industry Co., Ltd. Examples of the compound satisfying general formula (20) include, but are not limited to, the following compounds.

[0083]

[0084]

[0085]

[0086]

[0087]

[0088] (Regarding general formula (4)) Z １０ and Z １１ each independently is preferably a single bond or an unsubstituted alkyl group, more preferably a single bond or an unsubstituted alkyl group having 1 to 6 carbon atoms, still more preferably a single bond or an unsubstituted alkyl group having 1 to 3 carbon atoms, and particularly preferably a single bond.

[0089] W ３ and W４ Each of these atoms is preferably an oxygen atom or a substituted nitrogen atom, and more preferably an oxygen atom.

[0090] W ５ The group is an alkene or alkyne group, preferably an alkene or alkyne group having 1 to 10 carbon atoms, more preferably an alkene or alkyne group having 1 to 6 carbon atoms, and even more preferably an alkene or alkyne group having 1 to 3 carbon atoms. The number of double and triple bonds in the alkene or alkyne group is not particularly limited, but can be, for example, 1 to 3, and preferably 1. ５ It is preferably an alkyne group, more preferably an alkyne group having 1 to 6 carbon atoms and 1 to 3 triple bonds, even more preferably an alkyne group having 1 to 3 carbon atoms and 1 triple bond, and particularly preferably an alkyne group (acetylene group) having 2 carbon atoms and 1 triple bond.

[0091] The polyimide or polyamic acid of this disclosure may be a polyimide or polyamic acid obtained by using two or more acid anhydrides represented by general formula (4). The sum of the content of acid anhydrides represented by general formula (4) relative to the acid anhydride components constituting the polyimide or polyamic acid is preferably 10 mol% or more, more preferably 15 mol% or more, even more preferably 20 mol% or more, and particularly preferably 25 mol% or more. From the viewpoint of low thermal expansion, dielectric properties, tensile strength, heat resistance, etc., the upper limit of the content is preferably 50 mol% or less, more preferably 45 mol% or less, even more preferably 40 mol% or less, and particularly preferably 35 mol% or less. Also, for example, the sum of the content of acid anhydrides represented by general formula (4) relative to the acid anhydride components constituting the polyimide or polyamic acid can be 10 to 45 mol%, 15 to 40 mol%, 20 to 40 mol%, or 25 to 40 mol%.

[0092] Examples of acid anhydrides represented by general formula (4) include, but are not limited to, the following compounds.

[0093]

[0094] (Regarding General Formula (5)) The polyamic acid or polyimide of this disclosure may contain an acid anhydride represented by the following general formula (5) as a component thereof.

[0095]

[0096] In general formula (5), X represents a carbonyl group, an oxygen atom, or a single bond. Among the acid anhydrides represented by general formula (5), 3,4,3',4'-benzophenonetetracarboxylic dianhydride (BTDA) where X is a carbonyl group, 4,4'-oxydiphthalic anhydride (ODPA) where X is an oxygen atom, and 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) where X is a single bond can be preferably used. From the viewpoint of tensile strength and elastic modulus, ODPA or BPDA are preferred. From the viewpoint of solvent solubility, BPDA is preferred.

[0097] The polyimide or polyamic acid of this disclosure may be a polyimide obtained by using two or more acid anhydrides represented by general formula (5). The content of the acid anhydride represented by formula (5) in relation to the acid anhydride component constituting the polyimide or polyamic acid is not particularly limited and can be, for example, 10 to 30 mol%.

[0098] (Other Diamine Compounds) The polyimides or polyamic acids of this disclosure may contain as components diamine compounds other than the diamine compound represented by general formula (1). Other diamine compounds include 4,4'-bis(3-aminophenoxy)biphenyl (BAPB-M), 4,4'-bis(4-aminophenoxy)biphenyl (BODA), 4,4'-diamino-2,2'-dimethylbiphenyl (mTBHG), 3,3',5,5'-tetramethylbenzidine (TMB), paraphenylenediamine (PPD), metaphenylenediamine (MPDA), 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminobiphenyl, 2,5- Dimethyl 1,4-phenylenediamine (DMPDA), 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane (MDA), 2,2-bis-(4-aminophenyl)propane, 3,4'-diaminodiphenyl ether (m-DADE), 4,4' -Diaminodiphenyl ether (p-DADE), 1,5-diaminonaphthalene, 4,4'-diaminodiphenyldiethylsilane, 4,4'-diaminodiphenylsilane, 4,4'-diaminodiphenylethylphosphine oxide, 1,3-bis(3-aminophenoxy)benzene (APB), 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BA Examples of diamine compounds include, but are not limited to, PP), 2-bis(3-aminophenyl)1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)1,1,1,3,3,3-hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 9,9-dimethyl-9H-fluorene-2,7-diamine, 2-(4-aminophenyl)benzoxazole-5-amine, and 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine. These diamine compounds may be used individually or in combination of two or more.

[0099] (Other Acid Anhydrides) The polyimides or polyamic acids of this disclosure may contain as components acid anhydrides other than those represented by general formula (2) and general formula (4). Other acid anhydrides include 4,4'-(p-phenylenedioxy)diphthalic anhydride (HQDA), pyromellitic dianhydride (PMDA), 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-ben Zophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) sulfone dianhydride, bis(2,3-dicarboxyphenyl) methane dianhydride, bis(3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis(2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis[3,4-(dicarboxyphenoxy [Phenyl]propane dianhydride (BPADA), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,3,6,7-anthracenetetracarboxylic acid dianhydride, 1,2,7,8-phenanthrenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4'-dicarboxyphenoxy)phenyl]fluorene dianhydride, etc. Examples of acid anhydrides include, but are not limited to, fragrant tetracarboxylic dianhydrides, cyclobutanetetracarboxylic dianhydrides, 1,2,3,4-cyclopentanetetracarboxylic dianhydrides, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydrides, 1,2,4,5-cyclohexanetetracarboxylic dianhydrides, 3,4-dicarboxy-1-cyclohexylsuccinic acid dianhydrides, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydrides. These acid anhydrides may be used individually or in combination of two or more types.

[0100] (An Embodiment of Polyimide or Polyamic Acid) In one embodiment, the polyimide or polyamic acid of the present disclosure is a reaction product of a diamine compound represented by general formula (1), an acid anhydride represented by general formula (2), in which R' in general formula (2) is a group represented by general formula (3), and an acid anhydride represented by general formula (4). By reacting the above diamine compound and acid anhydride, it is possible to improve low thermal expansion, dielectric properties, tensile strength, heat resistance, etc. Furthermore, with the above configuration, the resin layer can be adhered to a substrate such as copper foil using a hot plate or hot roll without an adhesive layer, and the bonding strength can be improved.

[0101] (Physical properties of polyimide or polyamic acid) The polyimide or polyamic acid of this disclosure is preferably solvent-soluble. In this disclosure, "solvent-soluble" means that 5 g or more dissolves in 100 g of an organic solvent.

[0102] The weight-average molecular weight (Mw) of the polyimide or polyamic acid of this disclosure is preferably 20,000 to 300,000, and more preferably 50,000 to 250,000. Mw is measured using high-performance liquid chromatography and expressed as polystyrene-equivalent molecular weight.

[0103] (Method for producing polyimide or polyamic acid) The polyamic acid of this disclosure can be obtained by reacting a diamine compound with an acid anhydride. Polyimide can be obtained by subjecting this polyamic acid to a cyclization dehydration reaction and converting it to polyimide.

[0104] The mixing ratio of the diamine compound to the acid anhydride is preferably 0.5 mol% to 1.5 mol%, and more preferably 0.9 mol% to 1.1 mol%, of the total amount of the diamine compound per 1 mol% of the total amount of the acid anhydride.

[0105] The reaction between the diamine compound and the acid anhydride is preferably carried out in an organic solvent. The organic solvent is not particularly limited as long as it does not react with the diamine compound and the acid anhydride and can dissolve the reaction product of the diamine compound and the acid anhydride, and examples include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N'-dimethylimidazolidinone, γ-butyrolactone, dimethyl sulfoxide, sulfolane, 1,3-dioxolane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dibutyl ether, dibenzyl ether, methyl lactate, ethyl lactate, butyl lactate, methyl benzoate, ethyl benzoate, triglyme, tetraglyme, toluene, xylene, etc. From the viewpoint of solvent solubility of the diamine compound, N-methyl-2-pyrrolidone, N,N'-dimethylimidazolidinone, and γ-butyrolactone are preferred.

[0106] The reaction temperature between the diamine compound and the acid anhydride is preferably 40°C or lower in the case of chemical imidation. In the case of thermal imidation, it is preferably 150°C to 220°C, and more preferably 170°C to 200°C.

[0107] In the cyclization dehydration reaction, an imidation catalyst may be used, such as methylamine, ethylamine, trimethylamine, triethylamine, propylamine, tripropylamine, butylamine, tributylamine, tert-butylamine, hexylamine, triethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, aniline, benzylamine, toluidine, trichloroaniline, pyridine, colidine, lutidine, picoline, quinoline, isoquinoline, valerolactone, etc. In addition, if necessary, azeotropic dehydrating agents such as toluene, xylene, and ethylcyclohexane, and acid catalysts such as acetic anhydride, propionic anhydride, butyric anhydride, and benzoic anhydride may be used. Furthermore, in the reaction between the diamine compound and the acid anhydride, encapsulating agents such as benzoic acid, phthalic anhydride, and hydrogenated phthalic anhydride may be used. Furthermore, by using maleic anhydride, ethynylphthalic anhydride, methylethynylphthalic anhydride, phenylethynylphthalic anhydride, phenylethynyltrimellitic anhydride, 3- or 4-ethynylaniline, etc., double or triple bonds can be introduced to the ends of the polyimide.

[0108] [Resin Composition] The resin composition of this disclosure comprises at least one of the above-mentioned polyimide and polyamic acid.

[0109] The content of the polyimide and polyamic acid of the disclosed composition, relative to the total mass, is preferably 1% to 30% by mass, more preferably 3% to 25% by mass, and even more preferably 5% to 20% by mass.

[0110] The resin composition of this disclosure may contain a solvent. Examples of solvents include the above-mentioned solvent and water.

[0111] (Physical Properties of Resin Compositions) The glass transition temperature (Tg) of the resin composition of this disclosure is preferably 180°C or higher, more preferably 190°C or higher, even more preferably 195°C or higher, particularly preferably 200°C or higher, and most preferably 210°C or higher. The upper limit of Tg is not particularly limited, but for example it can be 350°C or lower. For example, the Tg of the resin composition can be 180-350°C, 190-350°C, 195-350°C, 200-350°C, or 210-350°C. A method for measuring Tg will be described in the examples. The Tg of the resin composition tends to improve by increasing the content of the diamine compound represented by general formula (1) in the polyimide or polyamic acid of this disclosure.

[0112] The tensile strength of the resin composition of this disclosure is preferably 140 MPa or higher, more preferably 145 MPa or higher, even more preferably 150 MPa or higher, particularly preferably 155 MPa or higher, and most preferably 160 MPa or higher. The upper limit of the tensile strength is not particularly limited and can be, for example, 300 MPa or lower. For example, the tensile strength of the resin composition can be 140 to 300 MPa, 145 to 300 MPa, 150 to 300 MPa, 155 to 300 MPa, or 160 to 300 MPa. A method for measuring tensile strength will be described in the examples. The tensile strength of the resin composition tends to improve by increasing the content of the diamine compound represented by general formula (1) and the acid anhydride represented by general formula (4) in the polyimide or polyamic acid of this disclosure.

[0113] The elongation of the resin composition of this disclosure is preferably 15% or more, more preferably 20% or more, even more preferably 25% or more, and particularly preferably 30% or more. The upper limit of the elongation is not particularly limited and can be, for example, 150% or less. For example, the elongation of the resin composition can be 15-70%, 20-70%, 25-70%, or 30-70%. A method for measuring the elongation is described in the examples. The elongation of the resin composition tends to improve by increasing the content of acid anhydrides and diamine compounds having ether bonds in the polyimide or polyamic acid of this disclosure. It also tends to improve as the molecular weight of the resin composition increases.

[0114] The elastic modulus of the resin composition of this disclosure is preferably 4.5 GPa or higher, more preferably 5.0 GPa or higher, even more preferably 5.5 GPa or higher, particularly preferably 5.7 GPa or higher, and most preferably 6.0 GPa or higher. The upper limit of the tensile strength is not particularly limited and can be, for example, 10.0 GPa or lower. For example, the elastic modulus of the resin composition can be 4.5 to 10.0 GPa, 5.0 to 10.0 GPa, 5.5 to 10.0 GPa, 5.7 to 10.0 GPa, or 6.0 to 10.0 GPa. A method for measuring the elastic modulus is described in the examples. The elastic modulus of the resin composition tends to improve by increasing the content of the diamine compound represented by general formula (1) and the acid anhydride represented by general formula (2) in the polyimide or polyamic acid of this disclosure.

[0115] The relative permittivity of the resin composition of this disclosure at 20 GHz is preferably 3.60 or less, more preferably 3.55 or less, even more preferably 3.52 or less, and may be 3.40 or less. The lower limit of the relative permittivity is not particularly limited, but can be 2.50 or more. For example, the relative permittivity of the resin composition at 20 GHz can be 3.00 to 3.60, 3.00 to 3.55, 3.00 to 3.52, or 3.00 to 3.40. The dielectric loss tangent of the resin composition of this disclosure at 20 GHz is preferably 0.0050 or less, more preferably 0.0045 or less, even more preferably 0.0040 or less, and particularly preferably 0.0035 or less. The lower limit of the dielectric loss tangent is not particularly limited, but can be 0.0002 or more. For example, the dielectric loss tangent of the resin composition at 20 GHz can be 0.0020 to 0.0050, 0.0020 to 0.0045, 0.0020 to 0.0040, 0.0020 to 0.0038, or 0.0020 to 0.0035. The method for measuring the relative permittivity and dielectric loss tangent is described in the examples. The dielectric loss tangent and relative permittivity of the resin composition tend to decrease by increasing the content of the diamine compound represented by general formula (1) and the acid anhydride represented by general formula (2) in the polyimide or polyamic acid of this disclosure.

[0116] The coefficient of thermal expansion (CTE) of the resin composition of this disclosure is preferably 40 ppm / K or less, more preferably 35 ppm / K or less, even more preferably 33 ppm / K or less, particularly preferably 30 ppm / K or less, and most preferably 25 ppm / K or less. By setting the CTE within the above numerical range, it is possible to suppress warping of the resin layer made from the resin composition on a substrate such as copper foil, and to suppress the occurrence of wrinkles in the resin layer when a second substrate is pressed onto the surface of the resin layer of a laminate comprising a substrate and a resin layer. The lower limit of the CTE is not particularly limited, but can be 10 ppm / K or more. For example, the CTE of the resin composition can be 10 to 40 ppm / K, 10 to 35 ppm / K, 10 to 33 ppm / K, 10 to 30 ppm / K, or 10 to 25 ppm / K. The method for measuring the coefficient of thermal expansion is described in the examples. The coefficient of thermal expansion of the resin composition tends to decrease by increasing the content of the diamine compound represented by general formula (1) and the acid anhydride represented by general formula (2) in the polyimide or polyamic acid of this disclosure.

[0117] The bonding strength of the resin composition of this disclosure to copper foil is preferably 6.0 N / cm or more, more preferably 6.5 N / cm or more, even more preferably 7.0 N / cm or more, particularly preferably 7.5 N / cm or more, and most preferably 8.0 N / cm or more. The upper limit of the bonding strength is not particularly limited and can be, for example, 20.0 N / cm or less. Also, for example, the bonding strength of the resin composition to copper foil can be 6.0 to 15.0 N / cm, 6.5 to 15.0 N / cm, 7.0 to 15.0 N / cm, 7.5 to 15.0 N / cm, or 8.0 to 15.0 N / cm. A method for measuring the bonding strength of the resin composition of this disclosure to copper foil is described in the examples.

[0118] The resin composition of this disclosure is preferably thermocompressible. In this disclosure, whether or not it is thermocompressible is determined as follows. A laminate comprising a copper foil and a resin layer is prepared in the same manner as the adhesion measurement method described above. A copper foil (second copper foil) similar to the copper foil in the laminate is placed on the surface of the resin layer of this laminate. For example, using a hot plate or hot roll at 400°C or less, 200 to 400°C or 300 to 400°C, the laminate is heated and pressurized under conditions of a pressure of 5 to 50 MPa and a pressing time of 5 to 60 minutes for vacuum thermocompression that can be used for single-wafer and multi-layer lamination, or under conditions of a pressure of 10 to 200 kN and a line speed of 5 m / sec or less for hot roll pressing that allows continuous thermocompression, thereby preparing a second laminate comprising a copper foil, a resin layer and a second copper foil. The resin composition of this disclosure is said to be thermocompression bondable when the second copper foil is peeled off from this second laminate at a peeling angle of 180 degrees and a peeling speed of 10 mm / min, and the measured load is 6.0 N / cm or more.

[0119] The resin composition of this disclosure can be suitably used as a material for forming an insulating layer in flexible copper foil wiring boards and the like, but is not limited thereto.

[0120] [Laminate] The laminate of the present disclosure comprises a first metal layer, a resin layer formed from the resin composition described above, and a second metal layer.

[0121] The first and second metal layers may be composed of the same material or of different materials. Examples of materials that make up these metal layers include copper, gold, silver, iron, nickel, and aluminum, with copper being preferred. The thickness of the metal layers is preferably 6 to 150 μm, and more preferably 12 to 70 μm. In one embodiment, the first and second metal layers are copper foils.

[0122] The thickness of the resin layer is preferably 5 to 100 μm, and more preferably 10 to 80 μm.

[0123] (Method for manufacturing a laminate) The method for manufacturing a laminate according to the present disclosure includes a step of heat-pressing a first metal layer (preferably copper foil), a resin layer formed from the above resin composition, and a second metal layer (preferably copper foil). The heat-pressing can be carried out using a hot plate, a hot roll, or the like.

[0124] [Resin Film] The resin film of this disclosure is formed from the above-mentioned resin composition. The method for manufacturing the resin film of this disclosure is not particularly limited and may be manufactured by peeling it off from the above-mentioned laminate, or by conventionally known methods.

[0125] The present disclosure will be explained below with reference to examples, but the present disclosure is not limited to the following examples.

[0126] (Example 1) In a 500 ml separable flask equipped with a stirrer, a nitrogen inlet tube, and a Dean-Stark apparatus, 15.22 g (50 mmol) of (2-phenyl-4-aminophenyl)-4-aminobenzoate (PHBAAB), an aromatic diamine compound represented by the following formula, 18.71 g (35 mmol) of biphenyl-4,4'-diyl=bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) (BP-TME), represented by the following formula, 4.77 g (15 mmol) of 4,4'-(ethyn-1,2-diyl)diphthalic anhydride (EBPA), and 95 g of N-methyl-2-pyrrolidone (NMP) were added and heated at 80°C with stirring under a nitrogen atmosphere. Once the raw materials were completely dissolved, the mixture was returned to room temperature and the reaction continued. The mixture was then diluted with NMP as needed while monitoring the viscosity, and finally a polyamic acid solution (resin composition) with a solid content of 12% by mass was obtained. The weight-average molecular weight Mw was measured and found to be 62,000. The PHBAAB used was synthesized according to the method described in the examples of Japanese Patent Publication No. 6240798.

[0127]

[0128]

[0129]

[0130] (Example 2) A 12% by mass polyamic acid solution (resin composition) was obtained in the same manner as in Example 1, except that the amount of PHBAAB used was changed to 7.61 g (25 mmol), 9.21 g (25 mmol) of 4,4'-bis(3-aminophenoxy)biphenyl (BAPB-M) represented by the following formula was further used, and the amount of NMP was changed to 99 g. When the molecular weight was measured, the weight-average molecular weight Mw was 130,000.

[0131]

[0132] (Example 3) In the same apparatus as in Example 1, 8.52 g (28 mmol) of PHBAAB, 5.16 g (14 mmol) of BAPB-M, 5.94 g (28 mmol) of 4,4'-diamino-2,2'-dimethylbiphenyl (mTBHG) represented by the following formula, 7.48 g (14 mmol) of BP-TME, 21.65 g (35 mmol) of 2,2',3,3',5,5'-hexamethyl-[1,1'-biphenyl]-4,4'-diirbis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) (TMPBP-TME) represented by the following formula, 6.68 g (21 mmol) of EBPA, 136 g of NMP, and 14 g of toluene were added and reacted at 180°C with stirring under a nitrogen atmosphere. The reaction was carried out for 6 hours, with toluene being removed from the system during the process, and finally, a polyimide solution (resin composition) was obtained by diluting it to 12% by mass. The weight-average molecular weight Mw was measured and found to be 85,000.

[0133]

[0134]

[0135] (Example 4) A 12% by mass polyimide solution (resin composition) was obtained in the same manner as in Example 3, except that BP-TME was not used, and 12.83 g (28 mmol) of p-phenylenebis(trimellitate anhydride) (TAHQ) represented by the following formula was used, and the amount of TMPBP-TME used was changed to 12.99 g (21 mmol), NMP to 128 g, and toluene to 13 g. The molecular weight was measured and the weight-average molecular weight Mw was 74000.

[0136]

[0137] (Example 5) A 12% by mass polyimide solution (resin composition) was obtained in the same manner as in Example 3, except that BP-TME was not used, and 23.62 g (42 mmol) of 3,3'-dimethyl-[1,1'-biphenyl]-4,4'-diirbis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) (OCBP-TME), represented by the following formula, was used, and the amount of TMPBP-TME used was changed to 4.33 g (7 mmol), NMP to 133 g, and toluene to 13 g. The molecular weight was measured, and the weight-average molecular weight Mw was 99000.

[0138]

[0139] (Comparative Example 1) Instead of 50 mmol of PHBAAB as in Example 1, 10.61 g (50 mmol) of mTBHG was used and the reaction was carried out in the same manner as in Example 1. However, since the viscosity was high at 12% by mass, it was diluted to 7% by mass to obtain a polyamic acid solution (resin composition). When the molecular weight was measured, the weight-average molecular weight Mw was 243,000.

[0140] (Comparative Example 2) Instead of 28 mmol of PHBAAB and 28 mmol of mTBHG in Example 4, 11.89 g (56 mmol) of mTBHG was used and the reaction was carried out in the same manner as in Example 4. However, polyimide precipitated during synthesis and did not become soluble. Therefore, the synthesis was carried out in the same manner as in Example 1 with the same proportions, and finally diluted to 10% by mass to obtain a polyamic acid solution (resin composition). When the molecular weight was measured, the weight-average molecular weight Mw was 223,000.

[0141] (Comparative Example 3) In this comparative example, instead of 50 mmol of PHBAAB in Example 1, 13.70 g (45 mmol) of PHBAAB and 1.46 g (5 mmol) of APB-N were used. BP-TME and EBPA were omitted, and 14.71 g (50 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was added. The synthesis was carried out in the same manner as in Example 1 to obtain a 12% by mass polyamic acid solution (resin composition). The weight-average molecular weight Mw was measured and found to be 61,000.

[0142]

[0143]

[0144]

[0145] <Preparation of Polyimide Films> Polyimide films for measuring thermal properties, film properties, and dielectric properties were prepared as follows. The resin compositions of Examples 1-5 and Comparative Examples 1-3 were applied to glass plates by spin coating. Then, in the case of the polyamic acid solutions of Examples 1 and 2 and Comparative Examples 1-3, heat treatment was performed under a nitrogen atmosphere at 100°C for 30 minutes, 200°C for 30 minutes, and 300°C for 60 minutes, and the films were peeled off the glass plates by immersion in boiling water to obtain single polyimide films. In the case of the polyimide solutions of Examples 3-5, heat treatment was performed under a nitrogen atmosphere at 100°C for 30 minutes, 200°C for 30 minutes, and 250°C for 60 minutes, and the films were peeled off the glass plates by immersion in boiling water to obtain single polyimide films.

[0146] <Preparation of Copper Foil Coating Samples> For bonding tests, coating samples were prepared by coating each resin composition onto copper foil using the bar coating method and then performing the same heat treatment as for polyimide film preparation.

[0147] <Measurement of Glass Transition Temperature (Tg)> Test specimens (3 mm × 3 mm × (25 μm ± 5 μm)) weighing 3-5 mg were cut from the film (polyimide single film) prepared as described above. For each test specimen obtained in this way, the glass transition temperature (Tg) of the test specimen was measured using a DSCQ200 (product name) manufactured by T.A. Instrument Japan Co., Ltd., under a nitrogen atmosphere at a heating rate of 10°C / min. The measurement results are summarized in Table 2.

[0148] <Measurement of Thermal Expansion Coefficient (CTE)> Each polyimide film was prepared as a test specimen measuring 3 mm x 20 mm. Using a thermal analyzer (Hitachi High-Tech Science Corporation, TMA6100), the test specimen was heated from room temperature (30°C) to 400°C at a rate of 10°C / min while applying a load of 5 g. The average thermal expansion coefficient (CTE) of the test specimen was determined from 100°C to 200°C. The results are summarized in Table 2.

[0149] <Measurement of Elastic Modulus> Each polyimide film was prepared as a test specimen measuring 10 mm × 80 mm × (25 μm ± 5 μm), and the elastic modulus was measured using a tensile testing machine (Shimadzu Corporation, product name: EZ-SX, chuck distance 50 mm) at a tensile speed of 10 mm / min. The average value of the elastic modulus of n (3) was used as the elastic modulus and is summarized in Table 2. The elastic modulus was measured in an environment of 23 ± 2°C and 50 ± 10% relative humidity.

[0150] <Measurement of Tensile Strength> Each polyimide film was prepared as a test specimen measuring 10 mm × 80 mm × (25 μm ± 5 μm), and its tensile strength was measured at a tensile speed of 10 mm / min using a tensile testing machine (Shimadzu Corporation, product name: EZ-SX, chuck distance 50 mm). The average tensile strength of n(n) was used as the tensile strength and is summarized in Table 2. The tensile strength was measured in an environment of 23 ± 2°C and 50 ± 10% relative humidity.

[0151] <Measurement of Elongation> Each polyimide film was prepared as a test specimen measuring 10 mm × 80 mm × 10 to 50 μm in size, and the elongation was measured at a tensile speed of 10 mm / min using a tensile testing machine (Shimadzu Corporation, product name: EZ-SX, chuck distance 50 mm). The maximum displacement for n=3 is summarized in Table 2. The elongation (%) was calculated as displacement (mm) / chuck distance 50 mm × 100. The elongation was measured in an environment of 23 ± 2°C and relative humidity of 50 ± 10%.

[0152] <Measurement of Bonding Strength> Each copper foil coated sample was prepared as a test piece measuring 100 mm x 100 mm x 25 ± 5 μm in resin thickness. A 12 mm thick copper foil was superimposed on the unbonded surface of this test piece to create a first laminate comprising the first copper foil, the test piece (resin layer), and the second copper foil. A second laminate was prepared by vacuum heating and pressurizing this laminate at 350-370°C and a pressure of 10 MPa for 30 minutes. The second laminate was cut into 10 mm wide strips to be used as samples for bonding strength measurement. The second copper foil was peeled off at a peeling angle of 180 degrees and a peeling speed of 10 mm / min, and the load (N / cm) was measured as the bonding strength. The results are summarized in Table 2. The bonding strength was measured in accordance with JIS C 6471. The results shown in Table 2 indicate that each solution (resin composition) in the examples had a bonding strength of 6.0 N / cm or higher, demonstrating that heat bonding was possible.

[0153] <Measurement of Dielectric Loss Tangent and Relative Permittivity> Each polyimide film was cut to 35 mm x 50 mm and prepared as a test specimen by conditioned it by standing it at 20°C and 60% RH for more than 72 hours. The dielectric loss tangent and relative permittivity of these test specimens were measured in accordance with JIS C 2565 using a commercially available dielectric constant measuring device (EM Lab 20 GHz split cylinder resonator, Keysight Technologies N5290A vector network analyzer). The measurement was performed at a test frequency of 20 GHz, a test temperature of approximately 22°C, and a humidity of approximately 50%, with two measurements taken. The results shown in Table 2 indicate that each solution (resin composition) in the examples had low dielectric loss tangent and relative permittivity. Furthermore, the measurement of dielectric loss tangent and relative permittivity was performed using test specimens conditioned under high humidity conditions (conditioned at 60% RH for more than 72 hours), which suggests that the water absorption rate was low.

[0154]

[0155] Comparative Examples 1 and 2, which do not contain a diamine compound satisfying general formula (1), exhibit low bond strength. Even Comparative Example 2, which has a glass transition temperature close to that of the example, shows low bond strength, suggesting that the glass transition temperature alone is not the sole factor influencing bond strength. Furthermore, Comparative Example 3, which does not contain general formulas (2) and (4), also clearly exhibits low bond strength.

Claims

1. A polyimide or polyamic acid, which is a reaction product of: a diamine compound represented by the following general formula (1); an acid anhydride represented by the following general formula (2); and an acid anhydride represented by the following general formula (4). (In general formula (1), R １ to R ４ are hydrogen atoms, and at least one of R ５ to R ８ is an aromatic group having 6 to 10 carbon atoms, a phenoxy group, a benzyl group or a benzyloxy group, and the remaining R ５ to R ８ are hydrogen atoms.) (In general formula (2), E １ and E ２ are ester bonds, Z １ and Z ２ are each independently a single bond, an alkyl group having a substituent or an alkyl group having no substituent, W １ and W ２ are each independently an oxygen atom, a nitrogen atom having a substituent or a nitrogen atom having no substituent, and R' is an alkylene group having a substituent, an alkylene group having no substituent, a group represented by the following general formula (3) or a group represented by the following general formula (3').) (In general formula (3), Z ３ is a single bond, an alkylene group having a substituent or an alkylene group having no substituent, Z ４ and Z ５ are each independently an alkyl group having a substituent or an alkyl group having no substituent, o and p are each independently 0 or an integer of 1 to 4, *1 is a bonding site to E １ , and *2 is a bonding site to E ２ .) (In general formula (3'), Z ６ and Z ７ are each independently an alkyl group having a substituent or an alkyl group having no substituent, *1 is a bonding site to E １ , and *2 is a bonding site to E ２ .) (In general formula (4), Z １０ and Z １１ Each of these is independently a single bond, a substituted alkyl group, or an unsubstituted alkyl group, W ３ and W ４ These are, independently, an oxygen atom, a substituted nitrogen atom, or an unsubstituted nitrogen atom, W ５ (This is an alkene group or an alkyne group.) 2. The polyimide or polyamic acid according to claim 1, which is a reaction product of a diamine compound represented by the general formula (1), an acid anhydride represented by the general formula (2), wherein R' in general formula (2) is a group represented by the general formula (3) below, and an acid anhydride represented by the general formula (4).

3. In the above general formula (3), Z ３ The polyimide or polyamic acid according to claim 2, wherein the bond is a single bond.

4. The polyimide or polyamic acid according to claim 1 or 2, wherein the acid anhydride represented by general formula (2) is a compound represented by the following general formula (20). (In general formula (20), X is a group represented by general formula (21) or (22), and in general formulas (21) and (22), R ９ ~R ２１ (wherein is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms or a phenyl group, and * represents the bond with the oxygen atom in formula (20).) 5. The polyimide or polyamic acid according to claim 1 or 2, wherein the general formula (4) is the following compound.

6. The polyimide or polyamic acid according to claim 1 or 2, wherein the diamine compound represented by the general formula (1) is one of the following compounds.

7. The polyimide or polyamic acid according to claim 1 or 2, wherein the content of the amine compound represented by general formula (1) relative to the diamine component constituting the polyimide or polyamic acid is 30 mol% or more.

8. A resin composition comprising the polyimide or polyamic acid described in claim 1 or 2.

9. A laminate comprising a first copper foil, a resin layer formed by the resin composition described in claim 8, and a second copper foil.

10. A method for manufacturing a laminate, comprising the step of heat-pressing together a first copper foil, a resin layer formed from the resin composition described in claim 8, and a second copper foil.

11. A resin film formed by the resin composition described in claim 8.

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