Copolymers, resin compositions, resin films, metal-clad laminates, circuit boards, electronic devices and electronic equipment

Abstract

A copolymer with excellent heat resistance and high-frequency transport characteristics is provided. The copolymer of the embodiment is a copolymer comprising a first structure containing two or more aromatic rings and a balance structure. The first structure is a structure in which the aromatic rings are bonded to each other by single bonds or linking groups. In the balance structure, the mass ratio of the sum of carbon atoms and hydrogen atoms to the total mass of the balance structure is 77 wt% or more, the mass ratio of carbon atoms to hydrogen atoms in the balance structure is 6.5 or more and 12.5 or less, the mass ratio of the first structure to the total mass of the copolymer is 15 wt% or more and 85 wt% or less, and in the linking groups, the number of atoms directly bonded to each other by the aromatic rings is 2 or less.

Description

Technical Field

[0001] This disclosure relates to copolymers, resin compositions, resin films, metal-clad laminates, circuit boards, electronic devices, and electronic equipment.

[0002] This application claims priority based on Japanese Patent Application No. 2024-232959, filed on December 27, 2024, the contents of which are incorporated herein by reference. Background Technology

[0003] In recent years, with the miniaturization and weight reduction of electronic devices, the application of thin, lightweight and flexible printed circuit boards (FPCs) is expanding.

[0004] When the resin used in the insulating layer of a flexible printed circuit board has a large coefficient of thermal expansion, it may cause positional displacement during component mounting. Therefore, a resin with excellent heat resistance is required.

[0005] As a resin with excellent heat resistance, Patent Document 1 discloses a polyimide resin obtained by reacting a polymer obtained by reacting a styrene / maleic anhydride copolymer (A) with an aromatic amine and / or an aliphatic amine, and then reacting the polymer with an aromatic tetracarboxylic dianhydride and an aromatic diamine and / or an aliphatic diamine.

[0006] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2003-335858 Non-patent literature Non-patent literature 1: RFFedors: Polym. Eng. Sci., 14[2], 147-154 (1974) Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] However, when the resin of Patent Document 1 is used in flexible printed circuit boards, the transmission loss at high frequencies is large, which limits its application.

[0009] The present invention was made in view of the above circumstances, and its object is to provide copolymers with excellent heat resistance and excellent high-frequency transmission characteristics, resin compositions containing the copolymers, resin films, metal-clad laminates, circuit boards, electronic devices, and electronic devices.

[0010] means for solving problems

[0011] To address the aforementioned issues, the present invention proposes the following methods.

[0012] (1) The copolymer of Scheme 1 of the present invention is a copolymer comprising a first structure containing two or more aromatic rings and the balance structure. The first structure described above is a structure in which the aromatic rings are bonded to each other by single bonds or connecting groups. In the aforementioned balance structure, the sum of carbon and hydrogen atoms accounts for more than 77 wt% of the total mass of the balance structure. In the aforementioned balance structure, the mass ratio of the aforementioned carbon atoms to the aforementioned hydrogen atoms is 6.5 or more and 12.5 or less. The first structure described above accounts for 15 wt% to 85 wt% of the total mass of the copolymer. In the above-mentioned linking groups, the number of atoms directly bonded to each other by the aromatic rings is 2 or less.

[0013] (2) Scheme 2 of the present invention is that, in the copolymer of Scheme 1, The combined mass ratio of the imide structure and the ammonium acid structure of the first structure to the total mass of the first structure is 15.5 wt% or more.

[0014] (3) Scheme 3 of the present invention is that, in the copolymer of Scheme 1, The above-mentioned residual structure has a chain hydrocarbon structure consisting of more than 6 carbon atoms bonded together by single bonds.

[0015] (4) Scheme 4 of the present invention is that, in the copolymer of Scheme 1, The difference in SP value between the first structure and the surplus structure is 3 (J / cm). 3 ) 1 / 2 Above and 10 (J / cm) 3 ) 1 / 2 the following.

[0016] (5) Solution 5 of the present invention is that, in the copolymer of Solution 1, The difference between the products of δP and δH in the HSP values ​​of the first structure and the residual structure described above is 50 (J / cm). 3 ) or above and 120 (J / cm 3 )the following.

[0017] (6) Solution 6 of the present invention is that, in the copolymer of Solution 1, The copolymers mentioned above are at least one of block copolymers and graft copolymers.

[0018] (7) Scheme 7 of the present invention is that, in the copolymer of Scheme 1, The mass ratio of the first structure to the remaining structure is 15:85 to 85:15.

[0019] (8) Solution 8 of the present invention is that, in the copolymer of Solution 1, The total mass of the carbon atoms and hydrogen atoms is 90 wt% or more, and the mass ratio of the carbon atoms to the hydrogen atoms is 6.5 or more and 12.5 or less.

[0020] (9) The resin composition of Scheme 9 of the present invention comprises the copolymer of Scheme 1.

[0021] (10) The resin film of Scheme 10 of the present invention comprises the copolymer of Scheme 1.

[0022] (11) The resin film of embodiment 11 of the present invention is, in the resin film of embodiment 10, The dielectric loss tangent Df1 of the above copolymer at 10 GHz, measured using a split dielectric resonator (SPDR) at a temperature of 24~26℃ and a relative humidity of 45~55%, and the second dielectric loss tangent Df2 calculated based on two or more repeating units constituting the above copolymer, satisfy the following equation (1). The second dielectric loss tangent mentioned above is calculated based on the dielectric loss tangent of the homopolymer of the repeating unit at 10 GHz and the mass ratio of the repeating unit according to the additive law. Df1 <Df2×0.97…(1)

[0023] (12) Solution 12 of the present invention is that, in the resin film of Solution 10, The linear thermal expansion coefficient at 180~100℃ is below 50ppm / K.

[0024] (13) The metal-clad laminate of embodiment 13 of the present invention is a metal-clad laminate having an insulating resin layer formed of a single layer or multiple layers, and a metal layer laminated on one or both sides of the insulating resin layer. At least one of the aforementioned insulating resin layers is composed of the resin film of Scheme 10.

[0025] (14) The circuit board of embodiment 14 of the present invention is a circuit board having an insulating resin layer formed of a single layer or multiple layers, and a conductor circuit layer stacked on one or both sides of the insulating resin layer. At least one of the aforementioned insulating resin layers is composed of the resin film of Scheme 10.

[0026] (15) The electronic device of embodiment 15 of the present invention includes the circuit board of embodiment 14.

[0027] (16) The electronic device of embodiment 16 of the present invention includes the circuit board of embodiment 14.

[0028] Invention Effects

[0029] According to the above-described embodiments of the present invention, copolymers with excellent high-frequency transmission characteristics and resin compositions containing such copolymers, resin films, metal-clad laminates, circuit boards, electronic devices, and electronic devices can be provided. Detailed Implementation

[0030] The copolymers disclosed herein are copolymers comprising a first structure containing two or more aromatic rings and the balance structure. Here, a copolymer refers to a polymer generated by polymerizing two or more substrates.

[0031] (First Structure)

[0032] The first structure contains two or more aromatic rings. Here, an aromatic ring refers to a ring structure that satisfies Hückel's rule. Examples of aromatic rings include benzene rings, naphthalene rings, anthracene rings, pyrrole rings, pyridine rings, thiophene rings, etc. The aromatic ring is preferably composed of only carbon and hydrogen atoms. Examples of such aromatic rings include benzene rings or fused rings with two or more benzene rings (naphthalene, anthracene, etc.). By having two or more aromatic rings in the first structure, an ordered structure can be formed through intermolecular interactions such as π-π interactions, for example, when forming resin substrates such as resin films from copolymers. This can improve the tensile modulus of the resin substrate and reduce the coefficient of linear thermal expansion (CTE). As a result, the heat resistance of resin substrates using the copolymers of this disclosure can be improved. In addition, the formation of this ordered structure can suppress molecular motion and reduce the dielectric loss tangent of the resin substrate. As a result, the high-frequency transmission characteristics of resin substrates using the copolymers of this disclosure can be improved.

[0033] The first structure preferably contains 3 or more aromatic rings, more preferably 5 or more, and even more preferably 10 or more. The number of aromatic rings can be 14 or more. A higher number of aromatic rings enhances the effect of π-π interactions, and is therefore preferred.

[0034] The first structure is a structure in which aromatic rings in the first structure are bonded to each other by single bonds (i.e., bonds in which carbons constituting one aromatic ring are directly bonded to carbons constituting another aromatic ring) or by connecting groups.

[0035] In the linking groups connecting aromatic rings, the number of atoms directly bonded between the aromatic rings is 2 or less. By making the number of atoms directly bonded between aromatic rings 2 or less, it is easier to form an ordered structure, which can further reduce the linear thermal expansion coefficient and the dielectric loss tangent. Here, "the number of atoms directly bonded between aromatic rings" refers to the total number of atoms along the shortest path connecting the aromatic rings. Here, "the bond connecting the aromatic rings" refers to the bond existing between aromatic rings, and "the atoms along the shortest path connecting the aromatic rings" do not include atoms constituting the aromatic rings. For example, when benzene rings are bonded by COO bonds, there is 1 C-C bond and 2 CO bonds. In this case, the atoms along the shortest path connecting the aromatic rings are 2, namely carbon and oxygen atoms. In the linking groups connecting aromatic rings, the number of atoms directly bonded between the aromatic rings can be more than 1.

[0036] In the first structure, examples of connecting groups that link aromatic rings together include -O-, -CH2-, -CH2-CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -CF2-, -COO-, -OOC-, -SO-, -SO2-, -S-, -CO-, and -CONH-.

[0037] As a first structure, examples include structures with the following formula (1) and structures with the following formula (2). Y in formula (1) 1 It is a single bond (i.e., a bond where a carbon in one aromatic ring is directly bonded to a carbon in another aromatic ring), a divalent linking group, or a structure as shown in formula (3) below. Formula (1) below Indicates the bonding end.

[0038] As Y 1 There are no particular limitations on the number of divalent linking groups as long as the number of atoms directly bonded to each other in the aromatic ring is 2 or less. Examples of divalent linking groups include -O-, -CH2-, -CH2-CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -CF2-, -COO-, -OOC-, -SO-, -SO2-, -S-, -CO-, and -CONH-.

[0039] [Chemical Formula 1]

[0040] Y in the following equation (2) 2 It is a single bond, a divalent linker, or a structure as shown in formula (3) below. Formula (2) below Indicates the bonding end. As Y...2 The number of divalent linking groups directly bonded to each other within the aromatic rings is not particularly limited, as long as the number of atoms directly bonded to each other within the aromatic rings is 2 or less. As Y 2 The divalent linker can be used with Y 1 Same group.

[0041] Ar in the following equation (2) 1 Ar is a divalent group containing an aromatic imide ring, having a structure formed by fused cyclic imide groups onto a divalent aromatic ring or an aromatic ring. 1 The aromatic ring contained therein may have substituents.

[0042] Ar in the following equation (2) 2 Ar is a divalent group containing an aromatic imide ring, having a structure formed by fused cyclic imide groups onto a divalent aromatic ring or an aromatic ring. 2 The aromatic ring contained therein may have substituents. Ar 1 and Ar 2 They can be the same or different.

[0043] The substituents in the aromatic ring of formula (2) below are, for example, alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, phenyl groups, hydroxyl groups, or carboxyl groups. The substituents are preferably alkyl groups having 1 to 3 carbon atoms. The position of the substituents in the aromatic ring is not particularly limited. When the aromatic ring is not substituted, it is bonded to hydrogen atoms.

[0044] In the following formula (3), X 1 and X 2 Indicates a divalent linker or single bond. X 1 and X 2 Linking groups can include -O-, -CH2-, -CH2-CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -CF2-, -COO-, -OOC-, -SO-, -SO2-, -S-, -CO-, -CONH-, etc. 1 and X 2 They can be the same or different.

[0045] In formula (3) below, A represents a divalent group containing an aromatic ring such as a benzene ring or a naphthalene ring. The benzene ring and the naphthalene ring may have any substituents. Examples of substituents include alkyl groups, alkoxy groups, etc., with methyl and ethyl groups being preferred. The number of substituents is preferably 0 to 2.

[0046] [Chemical Formula 2]

[0047] [Chemical Formula 3]

[0048] The first structure preferably has at least one of an imide structure (imide bond) and an amide acid structure.

[0049] The first structure preferably has a structure containing an imide bond and an aromatic ring.

[0050] A structure containing an imide bond and an aromatic ring can be, for example, the structure shown in formula (4) below. The ring Ar in formula (4) below... 3 This refers to the aforementioned aromatic ring. This refers to the bonding end. Ring Ar 3 The aromatic ring can have substituents. (The text abruptly ends here, seemingly mid-sentence.) 3 The substituents in the aromatic ring are, for example, alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, phenyl groups, hydroxyl groups, or carboxyl groups. The substituents are preferably alkyl groups having 1 to 3 carbon atoms. Cyclic Ar 3 The position of the substituent in the aromatic ring is not particularly limited. Preferably, it is related to the ring Ar. 3 A cyclic imide is formed on one side of a ring (e.g., a benzene ring). In the case of aromatic rings with multiple rings, such as anthracene rings, two cyclic imides can be formed for the same ring, or cyclic imides can be formed for different rings one by one.

[0051] [Chemical Formula 4]

[0052] The amic acid structure included in the first structure is a structure containing a carboxyl group and an amide bond for forming an imide bond. A preferred structure containing an amic acid structure is, for example, the structure shown in formula (5) below. The ring Ar in formula (5) below... 4 This refers to the aforementioned aromatic ring. This refers to the bonding end. Ring Ar 4 The aromatic ring can have substituents. (The text abruptly ends here, seemingly mid-sentence.) 4 The substituents in the aromatic ring are, for example, alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, phenyl groups, hydroxyl groups, or carboxyl groups. The substituents are preferably alkyl groups having 1 to 3 carbon atoms. Cyclic Ar 4 The position of the substituent in the aromatic ring is not particularly limited. In order to achieve the desired effect, the position of the substituent in the aromatic ring is not particularly limited. 4 A cyclic imide is formed on one side of a ring (e.g., a benzene ring), preferably having a carboxyl group and an amide bond. In the case where there are multiple aromatic rings, such as anthracene rings, the carboxyl group and amide bond can exist in such a way that two cyclic imides are formed for the same ring, or in such a way that cyclic imides are formed one by one for different rings.

[0053] [Chemical Formula 5]

[0054] The combined mass ratio of the imide structure (imide bond) and the amic acid structure to the total mass of the first structure is preferably 15.5 wt% or more. By making the combined mass ratio of the imide structure (imide bond) and the amic acid structure to the total mass of the first structure 15.5 wt% or more, the CTE can be reduced and the storage modulus at high temperatures can be increased, thus imparting heat resistance. The combined mass ratio of the imide structure and the amic acid structure to the total mass of the first structure is preferably 18 wt% or more. The combined mass ratio of the imide structure and the amic acid structure to the total mass of the first structure is preferably 35 wt% or less. The combined mass ratio of the imide structure and the amic acid structure to the total mass of the first structure is more preferably 30 wt% or less. By making the combined mass ratio of the imide structure and the amic acid structure to the total mass of the first structure 35 wt% or less, the deterioration of the dielectric loss tangent caused by the imide group can be suppressed.

[0055] The total mass ratio of the imide and amic acid structures relative to the total mass of the first structure is calculated as follows. Let the imide structure be (-(CO)₂-N-) and the amic acid structure be (-CO₂H, -CO₂-NH-). Calculate the total mass of the imide and amic acid structures contained in the repeating units of the first structure. Next, calculate the total mass of the repeating units of the first structure, and divide the total mass of the imide and amic acid structures by the total mass to obtain the synthetic mass ratio of the imide and amic acid structures. It should be noted that when the first structure has multiple repeating units, the total mass ratio of the imide and amic acid structures relative to the total mass of the first structure can be calculated by calculating the mass ratio of each repeating unit relative to the total mass of the first structure and then using a weighted average of the mass ratios of each repeating unit relative to the entire first structure.

[0056] Specific structures of the first structure include, for example, structures formed by repeating units of polymers such as fully aromatic polyimide (PI), non-thermoplastic polyimide, liquid crystal polymer (LCP), polyphenylene ether (PPE), polyether ether ketone (PEEK), polyphenylene sulfide (PPS), polyamide, polyamide-imide, polyether sulfone (PES), polysulfone (PS), polybenzimidazole (PBI), polybenzoxazole (PBO), and polyarylate (PAR), as well as structures formed by their combinations.

[0057] Here, a non-thermoplastic polyimide or a precursor of a non-thermoplastic polyimide serving as the first structure is described in more detail, but the first structure of the copolymer disclosed herein is not limited to non-thermoplastic polyimides. Non-thermoplastic polyimides can be obtained by heat-treating a precursor of a non-thermoplastic polyimide. It should be noted that, in this specification, "non-thermoplastic polyimide" refers to a polyimide that generally does not exhibit softening or stickiness even when heated; in this specification, it refers to a storage modulus of 1.0 × 10⁻⁶ at 30°C, measured using a dynamic viscoelasticity measuring device (DMA). 9 The energy storage modulus in the temperature range above Pa and within +30°C of the glass transition temperature is shown to be 1.0 × 10⁻⁶. 8 Polyimide with a strength of Pa or higher.

[0058] The non-thermoplastic polyimide precursor comprises a tetracarboxylic acid residue and a diamine residue. It should be noted that, in this specification, a tetracarboxylic acid residue refers to a tetravalent group derived from a tetracarboxylic dianhydride, and a diamine residue refers to a divalent group derived from a diamine compound. The polyimide preferably comprises an aromatic tetracarboxylic acid residue derived from an aromatic tetracarboxylic dianhydride and an aromatic diamine residue derived from an aromatic diamine.

[0059] The tetracarboxylic anhydride used in the synthesis of non-thermoplastic polyimide precursors can be used without particular restrictions. Examples of such acid anhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,3',3,4'-biphenyltetracarboxylic dianhydride, 4,4'-biphenyl-bis(triphenyl ester anhydride), 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 4,4'-oxobisphthalic anhydride, 2,2',3,3'-, 2,3,3',4'- or 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl) ether dianhydride, 3,3”,4,4”-, 2,3,3”,4”- or 2,2”,3,3”-p-terphenyltetracarboxylic dianhydride. Acid dianhydride, 2,2-bis(2,3- or 3,4-dicarboxyphenyl)-propane dianhydride, bis(2,3- or 3,4-dicarboxyphenyl)methane dianhydride, bis(2,3- or 3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3- or 3,4-dicarboxyphenyl)ethane dianhydride, 1,2,7,8-, 1,2,6,7- or 1,2,9,10-phenanthroline tetracarboxylic dianhydride, 2,3,6,7-anthracite tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)tetrafluoropropane dianhydride, 2,3,5,6-cyclohexane dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride (NTCDA), 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 4 8-Dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6- or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7- (or 1,4,5,8-)tetrachloronaphthalene-1,4,5,8- (or 2,3,6,7-)tetracarboxylic dianhydride, 2,3,8,9-, 3,4,9,10-, 4,5,10,11- or 5,6,11,12-perylene-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-bis(2,3) -Dicarboxyphenoxy)diphenylmethane dianhydride, ethylene glycol dihydrotriphenylene ester, p-Bis(triphenylene oxide monoester dianhydride) (BP-TME), 2,2',3,3',5,5'-hexamethyl[1,1'-biphenyl]-4,4'-diyl=bis(1,3-dioxo-1,3-dihydro-2-benzofuran-5-carboxylate) (TMPBP-TME), 2,6-naphthalenebis(triphenylene oxide monoester dianhydride) (26DHN-TME), 1,3-dihydro-1,3-dioxo-5,5'-(3,3'-dimethyl[1,1'-biphenyl]-4,4'-diyl) ester, 1,3-dihydro-1,3-dioxo-5,5'-(3,3'-dimethyl[1,1'-biphenyl]-4,4'-diyl) ester, 1,3-dihydro-1,3-dioxo-5,5'-(3,3',5,Aromatic tetracarboxylic acid dianhydrides such as 5'-tetramethyl[1,1'-biphenyl]-4,4'-diyl ester and 1,4-phenylene bis(trimethacrylate) dianhydride (TAHQ).

[0060] Among them, dianhydrides with intramolecular ester groups as shown in the following general formula (6) are particularly preferred, as they improve the linearity of the polyimide molecular chain, are expected to improve the tensile modulus and reduce CTE due to in-plane orientation, and are 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 2,3,6,7-naphthalenetetracarboxylic dianhydride (NTCDA) as dianhydrides with biphenyl or naphthalene skeletons. These tetracarboxylic anhydrides can be used alone or in combination of two or more. It should be noted that sometimes the tetracarboxylic dianhydride residues derived from the tetracarboxylic dianhydride shown in general formula (6) are referred to as "acid dianhydride residue (1)".

[0061] [Chemical Formula 6] In general formula (6), Ar represents a divalent group containing one or more aromatic rings, preferably a divalent group selected from the following formulas. In general formula (6), Ar represents a divalent group containing one or more aromatic rings, preferably a divalent group selected from the following formulas.

[0062] [Chemical Formula 7] In the above formula, R1 represents an alkyl group having 1 to 3 carbon atoms, and m independently represents an integer from 0 to 4, more preferably without substituents (m=0).

[0063] The compound represented by general formula (6) is an acid dianhydride containing an ester group and has a relatively large molecular weight. Therefore, although the concentration of imide groups can be reduced, the coefficient of linear thermal expansion (CTE) can also be suppressed to a low level. In addition, the ester structure has the effect of imparting an ordered structure to the polymer as a whole through intermolecular interactions. In particular, when the molecule has a biphenyl backbone or naphthalene backbone and two ester structures (-CO-O-) bonded to the biphenyl backbone or naphthalene backbone, the biphenyl backbone and naphthalene backbone are rigid and therefore easily form an ordered structure, which is preferred. Therefore, by containing acid dianhydride residues (1), the CTE can be reduced (low CTE), and the improvement of the ordered structure of the molecule and the suppression of motion also contribute to the reduction of the dielectric loss tangent (low dielectric loss tangent).

[0064] Examples of tetracarboxylic acid dianhydrides represented by formula (6) above include: p-phenylenebis(triphenylene dianhydride) (BP-TME), 2,2',3,3',5,5'-hexamethyl[1,1'-biphenyl]-4,4'-diyl=bis(1,3-dioxo-1,3-dihydro-2-benzofuran-5-carboxylate) (TMPBP-TME), and 2,6-naphthobis(triphenylene dianhydride) The dianhydrides include BP-TME (26DHN-TME), 1,3-dihydro-1,3-dioxo-5,5'-(3,3'-dimethyl[1,1'-biphenyl]-4,4'-diyl) ester, 1,3-dihydro-1,3-dioxo-5,5'-(3,3',5,5'-tetramethyl[1,1'-biphenyl]-4,4'-diyl) ester, and 1,4-phenylene bis(trimethacrylate) dianhydride (TAHQ). Among these, BP-TME and 26DHN-TME are particularly preferred due to their significant reduction in CTE and dielectric loss tangent.

[0065] Amine compounds used to synthesize precursors of non-thermoplastic polyimide can be used without restriction.

[0066] Examples of such diamine compounds include 1,4-diaminobenzene (p-PDA; p-phenylenediamine), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), 2,2'-diethyl-4,4'-diaminobiphenyl (m-EB), 2,2'-diethoxy-4,4'-diaminobiphenyl (m-EOB), 2,2'-dipropoxy-4,4'-diaminobiphenyl (m-POB), 2,2'-di-n-propyl-4,4'-diaminobiphenyl (m-NPB), 2,2'-divinyl-4,4'-diaminobiphenyl (VAB), 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB), and 4-aminophenyl- 4'-Aminobenzoate (APAB), 3,3'-Diaminodiphenylmethane, 3,3'-Diaminodiphenylpropane, 3,3'-Diaminodiphenylsulfide, 3,3'-Diaminodiphenylsulfone, 3,3'-Diaminodiphenylether, 3,4'-Diaminodiphenylether, 3,4'-Diaminodiphenylmethane, 3,4'-Diaminodiphenylpropane, 3,4'-Diaminodiphenylsulfide, 3,3'-Diaminobenzophenone, (3,3'-Diamino)diphenylamine, 1,4-bis(3-aminophenoxy)benzene, 3-[4-(4-aminophenoxy)phenoxy]aniline, 3-[3-(4-aminophenoxy)phenoxy]aniline, 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1 3-Bis(3-aminophenoxy)benzene (APB), 4,4'-[2-methyl-(1,3-phenylene)dioxy]bisaniline, 4,4'-[4-methyl-(1,3-phenylene)dioxy]bisaniline, 4,4'-[5-methyl-(1,3-phenylene)dioxy]bisaniline, bis[4,4'-(3-aminophenoxy)]benzoylaniline, 4-[3-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline, 4,4'-[oxybis(3,1-phenylene)]bisaniline, bis[4-(4-aminophenoxy)phenyl]ether (BAPE), bis[4-(4-aminophenoxy)phenyl]sulfone (BAPS), bis[4-(4-aminophenoxy)phenyl]ketone (BAPK) ), 2,2-bis-[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)]benzophenone, 9,9-bis[4-(3-aminophenoxy)phenyl]fluorene, 2,2-bis-[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis-[4-(3-aminophenoxy)phenyl]hexafluoropropane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-Dimethylbenzylamine, 4,4'-methylene-2,6-diethylaniline, 3,3'-diaminodiphenylethane, 3,3'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 4,4”-diamino-p-terphenyl, 3,3”-diamino-p-terphenyl, 4,4'-[1,4-phenylenebis(1-methylethoxy)]bisaniline, 4,4'-[1,3-phenylenebis(1-methylethoxy)] Bisaniline, bis(p-aminocyclohexyl)methane, bis(p-β-aminotert-butylphenyl) ether, bis(p-β-methyl-d-aminopentyl)benzene, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis(β-amino-tert-butyl)toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-di Toluene-2,5-diamine, m-phenylenediamine, p-phenylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, piperazine, 2'-methoxy-4,4'-diaminobenzoylaniline, 4,4'-diaminobenzoylaniline, 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene, 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene Aromatic diamine compounds such as 1,4-bis(4-aminophenoxy)-2,5-di-tert-butylbenzene, 6-amino-2-(4-aminophenoxy)benzoxazole, 2,6-diamino-3,5-diethyltoluene, 2,4-diamino-3,5-diethyltoluene, 2,4-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, and bis(4-amino-3-ethyl-5-methylphenyl)methane are preferred. Among these, diamines of the following general formula (7) and diamines with a naphthalene skeleton are particularly preferred, as they enhance the linearity of the polyimide molecular chain and are expected to provide a low CTE effect due to in-plane orientation. These diamine compounds can be used alone or in combination of two or more. It should be noted that in this specification, diamine residues derived from diamine compounds of general formula (7) are sometimes referred to as "diamine residue (2)".

[0067] [Chemical Formula 8] In formula (7), the linking group X represents a single bond, a divalent group selected from -CONH- or -COO-, Y independently represents hydrogen, a monovalent hydrocarbon group or alkoxy group with 1 to 3 carbon atoms, n represents an integer from 0 to 2, and p and q independently represent integers from 0 to 4.

[0068] Preferred examples of the diamine compounds represented by formula (7) above include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), 2,2'-diethyl-4,4'-diaminobiphenyl (m-EB), 2,2'-diethoxy-4,4'-diaminobiphenyl (m-EOB), and 2,2'-dipropoxy-4,4'-diaminobiphenyl (m-EB). Compounds such as m-POB, 2,2'-di-n-propyl-4,4'-diaminobiphenyl (m-NPB), 2,2'-divinyl-4,4'-diaminobiphenyl (VAB), 4,4'-diaminobiphenyl, and 4,4”-diamino-p-terphenyl are preferred. Among these, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) is the most effective compound for reducing the CTE and dielectric loss tangent of the resin film.

[0069] By selecting the types of tetracarboxylic dianhydride residues and diamine residues, and the molar ratios of two or more tetracarboxylic dianhydride residues or diamine residues, the hygroscopicity, dielectric properties, toughness, CTE, storage modulus, and tensile modulus of the non-thermoplastic polyimide precursor can be controlled. In the case of multiple structural units (constituent units) in the non-thermoplastic polyimide precursor, they can exist as blocks or randomly, preferably randomly.

[0070] The tetracarboxylic dianhydride residues and diamine residues in the non-thermoplastic polyimide precursor preferably include aromatic tetracarboxylic dianhydride residues derived from aromatic tetracarboxylic dianhydrides and aromatic diamine residues derived from aromatic diamines.

[0071] The non-thermoplastic polyimide precursor of this disclosure can be synthesized by known methods. For example, the non-thermoplastic polyimide precursor can be produced by reacting the aforementioned tetracarboxylic anhydride with a diamine compound in a solvent. The tetracarboxylic anhydride and the diamine compound are dissolved in an organic solvent at approximately equimolar amounts, and the polymerization reaction is carried out by stirring at a temperature in the range of 0 to 100°C for 30 minutes to 24 hours, thereby obtaining the non-thermoplastic polyimide precursor (polyamic acid) of this disclosure. During the reaction, the reaction components (tetracarboxylic anhydride compound and diamine compound) are dissolved in the organic solvent in a manner that the generated precursor accounts for 5 to 50% by mass, preferably 10 to 40% by mass. Examples of organic solvents used in the polymerization reaction include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 2-butanone, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, methylcyclohexane, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methanol, ethanol, benzyl alcohol, and cresol. Two or more of these solvents may be used in combination, and aromatic hydrocarbons such as xylene and toluene may also be used. Furthermore, there are no particular limitations on the amount of such organic solvents used, but it is preferable to adjust the concentration of the solution of the non-thermoplastic polyimide precursor obtained by the polymerization reaction to approximately 5 to 50% by mass.

[0072] Synthesized non-thermoplastic polyimide precursors typically exhibit excellent solvent solubility, making them advantageous for use as reaction solvent solutions. However, they can be concentrated, diluted, or replaced with other organic solvents as needed. The viscosity of the solution of the non-thermoplastic polyimide precursor is preferably in the range of 100 cP to 100,000 cP.

[0073] The mass proportion of the first structure relative to the total mass of the copolymer of this disclosure is 15 wt% or more and 85 wt% or less. By ensuring that the mass proportion of the first structure relative to the total mass of the copolymer of this disclosure is 15 wt% or more and 85 wt% or less, the coefficient of linear thermal expansion of the resin substrate formed from the copolymer of this disclosure can be reduced, and positional misalignment during component installation can be suppressed. The mass proportion of the first structure relative to the total mass of the copolymer of this disclosure is preferably 20 wt% or more. The mass proportion of the first structure relative to the total mass of the copolymer of this disclosure is preferably 30 wt% or more. The mass proportion of the first structure relative to the total mass of the copolymer of this disclosure is preferably 80 wt% or less. The mass proportion of the first structure relative to the total mass of the copolymer of this disclosure is preferably 75 wt% or less.

[0074] "Method for determining the first structure"

[0075] In the copolymers disclosed herein, the first structure is a structure containing two or more aromatic rings, wherein the aromatic rings are bonded to each other by single bonds or linking groups, and the number of atoms directly bonded between the aromatic rings in the linking groups is 2 or less. For example, the structures shown in formula (1) and formula (2) can coexist. In addition, if an aromatic ring (aromatic ring A) is present at the front end of the bonded end shown in formula (1), and the aromatic ring in formula (1) is bonded to aromatic ring A by single bonds or the linking groups described above, then aromatic ring A is also included in the first structure. When the number of atoms directly bonded between the aromatic ring (aromatic ring B) contained in the first structure and the next aromatic ring is 4 or more, aromatic ring B is the end of the first structure. That is, both ends of the first structure become aromatic rings. Here, when the aromatic rings have a ring structure with a shared aromatic ring side as shown in formula (1), the ring structure with a shared aromatic ring side is also considered as part of the first structure (here, the cyclic imide portion). It should be noted that when the structure of the repeating unit is clearly defined, the repeating unit can be considered as the first structure. Furthermore, when the proportions of monomers used in the synthesis of each copolymer are clearly defined, the calculation can be based on the mixing amounts of each monomer.

[0076] (Spare structure)

[0077] The surplus structure is a structure other than the first structure. That is, the copolymer of this disclosure includes the first structure and the surplus structure. In the surplus structure, the mass ratio of the sum of carbon atoms and hydrogen atoms in the surplus structure to the total mass of the surplus structure is 77 wt% or more. By having the mass ratio of the sum of carbon atoms and hydrogen atoms to the total mass of the surplus structure be 77 wt% or more, the dielectric loss tangent can be reduced, and high-frequency transmission characteristics can be improved. The mass ratio of the sum of carbon atoms and hydrogen atoms to the total mass of the surplus structure is preferably 83 wt% or more. More preferably, the mass ratio of the sum of carbon atoms and hydrogen atoms to the total mass of the surplus structure is 88 wt% or more. Particularly preferably, the mass ratio of the sum of carbon atoms and hydrogen atoms to the total mass of the surplus structure is 91.5 wt% or more. More preferably, the mass ratio of the sum of carbon atoms and hydrogen atoms to the total mass of the surplus structure is 95% or more. The mass ratio of the sum of carbon atoms and hydrogen atoms to the total mass of the surplus structure can be 100%. By reducing the proportion of atoms other than carbon and hydrogen atoms, such as nitrogen and oxygen atoms, which easily increase polarity in the balance structure, the reduction effect of dielectric loss tangent can be further improved. The mass ratio of the sum of carbon and hydrogen atoms to the total mass of the balance structure is preferably 99 wt% or less.

[0078] In the balance structure, the mass ratio (C / H) of carbon atoms (C) to hydrogen atoms (H) is 6.5 or more and 12.5 or less. By making the mass ratio (C / H) of carbon atoms (C) to hydrogen atoms (H) in the balance structure 6.5 or more and 12.5 or less, the polarity of the copolymer can be reduced, and the high-frequency transmission characteristics can be further improved. More preferably, the mass ratio (C / H) of carbon atoms (C) to hydrogen atoms (H) in the balance structure is 10 or less. More preferably, the mass ratio (C / H) of carbon atoms (C) to hydrogen atoms (H) in the balance structure is 8 or less.

[0079] The mass ratio (O / C+H) of oxygen atoms (O) in the balance structure relative to the sum of carbon atoms (C) and hydrogen atoms (H) is preferably 0.20 or less. By making the mass ratio (O / C+H) of oxygen atoms (O) in the balance structure relative to the sum of carbon atoms (C) and hydrogen atoms (H) 0.20 or less, the polarity of the copolymer can be reduced, and the high-frequency transmission characteristics can be further improved. The mass ratio (O / C+H) of oxygen atoms (O) in the balance structure relative to the sum of carbon atoms (C) and hydrogen atoms (H) is preferably 0.10 or less.

[0080] The mass ratio (N / C+H) of nitrogen atoms (N) in the balance structure relative to the sum of carbon atoms (C) and hydrogen atoms (H) is preferably 0.20 or less. By making the mass ratio (N / C+H) of nitrogen atoms (N) in the balance structure relative to the sum of carbon atoms (C) and hydrogen atoms (H) 0.20 or less, the polarity of the copolymer can be reduced, and the high-frequency transmission characteristics can be further improved. The mass ratio (N / C+H) of nitrogen atoms (N) in the balance structure relative to the sum of carbon atoms (C) and hydrogen atoms (H) is preferably 0.10 or less.

[0081] The balance structure preferably has a chain structure in which carbon atoms are bonded together by single bonds. The number of carbon atoms in the chain structure (first chain structure) constituting the balance structure is preferably 6 or more. The chain structure of the balance structure can be a straight chain structure in which carbon atoms are connected in a row, or it can be a branched molecular chain or a ring structure with branched carbon atoms.

[0082] The number of carbon atoms constituting the first chain structure is preferably 6 or more. More preferably, it is 10 or more, and even more preferably 20 or more. By increasing the number of carbon atoms constituting the first chain structure, the dielectric loss tangent can be reduced.

[0083] In addition to carbon atoms, the carbon atoms constituting the first chain structure are preferably bonded to hydrogen atoms. For example, -CH2- can be used as a repeating unit in the first chain structure.

[0084] The first chain structure may have side chains. Here, a side chain refers to an oligomer-level branch extending from the first chain structure. Examples of side chains include aryl groups such as phenyl, maleimide groups, allyl groups, and phosphate groups.

[0085] Examples of modified structures include modified polystyrene, modified polyolefins, modified cyclic olefin polymers, modified styrene-based elastomers, polyimides, polyamides, maleimides, polyesters, polyurethanes, polymethylpentene, and copolymers thereof. Modified functional groups include anhydride groups (derived from maleic anhydride), amino groups, vinyl groups, ethynyl groups, carboxyl groups, hydroxyl groups, and thiol groups. From the viewpoint of the polarity of the functional groups and ease of modification, anhydride groups, amino groups, and vinyl groups are preferred. Examples of modified polystyrene include modified polystyrene, modified styrene-ethylene copolymers, and modified styrene-divinylbenzene copolymers. Examples of modified polyolefins include modified polyethylene, modified polypropylene, modified ethylene-polypropylene, modified propylene-butene copolymers, and modified propylene-ethylene-butene copolymers. Examples of modified cyclic olefin polymers include modified polynorbornene and modified norbornene-ethylene copolymers. Examples of modified styrene-based elastomers include modified styrene-butadiene-styrene block copolymers (SBS), modified styrene-butadiene-butene-styrene block copolymers (SBBS), modified styrene-ethylene-butene-styrene block copolymers (SEBS), modified styrene-ethylene-propylene-styrene block copolymers (SEPS), and modified styrene-ethylene-ethylene-propylene-styrene block copolymers (SEEPS). When the balance structure has multiple structural units (constituent units), these constituent units can exist as blocks or randomly. It should be noted that the balance structure can also include components other than those mentioned above, within the range that satisfies the conditions for the balance structure.

[0086] Examples of copolymers include alternating copolymers, random copolymers, block copolymers, and graft copolymers.

[0087] The copolymer is preferably at least one of block copolymers and graft copolymers. Here, a graft copolymer refers to a polymer with a main polymer as the backbone, and branches of other types of polymers attached to the backbone polymer. A block copolymer refers to a polymer formed from two or more repeating units, with polymer chains formed from the same type of repeating unit bonded in one chain. By including at least one of block copolymers and graft copolymers, a three-dimensional structure can be formed, and the movement between molecular chains can be suppressed, thus further reducing the coefficient of linear thermal expansion. Furthermore, by suppressing the movement of molecular chains, the responsiveness to an electric field can be reduced, and the dielectric loss tangent can be reduced. Here, if the target structure (copolymer) contains polymer chains formed from the same type of repeating unit, the target structure is determined to be a block copolymer. Similarly, if the target structure (copolymer) contains different types of molecular chains branching from the main chain, the target structure is determined to be a graft copolymer. If the structure (copolymer) being studied contains polymer chains formed from the same repeating unit, and if the structure (copolymer) being studied contains different kinds of molecular chains branching from the main chain, then the copolymer is judged to be a block copolymer and a graft copolymer.

[0088] (Method for determining the margin structure)

[0089] In the copolymers disclosed herein, the portion (remaining portion) that was not considered as the first structure in the determination of the first structure described above will be determined as the remaining portion structure.

[0090] (First structure and spare structure)

[0091] The difference (absolute value of the difference) between the SP value (solubility parameter) of the first structure and the residual structure is preferably 3 (J / cm³). 3 ) 1 / 2 Above and 10 (J / cm) 3 ) 1 / 2 The following is an example of achieving a difference of 3 (J / cm³) between the SP values ​​(solubility parameters) of the first structure and the remaining structure. 3 ) 1 / 2 Above and 10 (J / cm) 3 ) 1 / 2 The following design allows the first structure to easily exist around the filler structure, reducing the dielectric loss tangent and the coefficient of linear thermal expansion (CTE). The difference in SP value (solubility parameter) between the first structure and the filler structure is preferably 3 (J / cm²). 3 ) 1 / 2 The above. The preferred difference between the SP value (solubility parameter) of the first structure and the residual structure is 9 (J / cm³). 3 ) 1 / 2 the following.

[0092] The SP values ​​(solubility parameters) of the first structure and the residual structure can be calculated based on the Fedors method described in Non-Patent Document 1. The SP value δ based on the Fedors method is calculated using the following formula (A1). In the following formula (1), E represents the cohesive energy (J / mol), and V represents the molecular capacity (cm³). 3 / mol). The cohesive energy and molecular capacity of each structure constituting the resin are calculated. The SP value can be obtained by multiplying the sum of the cohesive energies of each component by the sum of the molecular capacities. For example, when the first structure is polyimide or polyamic acid, considering the acid-amine ratio, it is preferable to perform the calculation using the imide-amic acid structure. δ = (E / V) 1 / 2 …(A1)

[0093] The difference between the products of δP and δH in the Hansen solubility parameters (HSP values) of the first structure and the aforementioned residual structure (δP×δH of the first structure - δP×δH of the residual structure) is preferably 50 (J / cm³). 3 ) or above and 120 (J / cm 3 Below. Here, δP represents the polar term, and δH represents the hydrogen bonding term. By making the δP×δH of the first structure minus the δP×δH of the balance structure 50 (J / cm²). 3 ) or above and 120 (J / cm 3 The following can make it easier for a first structure to exist around the margin structure, reduce the dielectric loss tangent, and easily reduce the coefficient of linear thermal expansion (CTE).

[0094] The HSP values ​​δP and δH for the first structure and the surplus structure can be calculated using commercially available software. For example, δP and δH can be calculated using Hansen Solubility Parameter in Practice (HSPiP), a software developed by Dr. Hansen.

[0095] The mass ratio of the first structure to the remaining structure in the copolymer disclosed herein (first structure: remaining structure) is preferably 15:85 to 85:15. With a mass ratio of 15:85 to 85:15, the dielectric loss tangent is easily reduced, and the CTE is also easily reduced. A more preferred mass ratio is 25:75 to 75:25.

[0096] (Mass ratio of the first structure)

[0097] The primary and residual structures can be determined by identifying the chemical structure of the copolymer using known methods, based on the aforementioned criteria. Regarding identification, for example, if the copolymer is soluble, nuclear magnetic resonance analysis can be used. 1 H-NMR, 13 Analysis was performed using methods such as C-NMR. After identifying the chemical structure of the copolymer, the first structure was determined based on the obtained structure according to the above-mentioned criteria. The portion not allocated to the first structure was taken as the balance structure, and the mass ratio of each structure could be determined by calculating the molecular weight of each structure. It should be noted that even if the copolymer is insoluble, it can be decomposed to the monomer level to determine the monomer ratio, thereby calculating the mass ratio of each structure.

[0098] The weight-average molecular weight of the copolymer is preferably 500,000 or less. The weight-average molecular weight of the copolymer is preferably 300,000 or less. The weight-average molecular weight of the copolymer is more preferably 250,000 or less. When the weight-average molecular weight of the copolymer is low, the phase separation state of the resin composition changes, making it easier to form a homogeneous phase. Furthermore, in the case of a coating liquid, viscosity adjustment becomes easier.

[0099] The number-average molecular weight of the copolymer is preferably 250,000 or less. More preferably, the number-average molecular weight of the copolymer is 200,000 or less. When the number-average molecular weight of the copolymer is low, the phase separation state of the resin composition changes, making it easier to form a homogeneous phase.

[0100] "Determination of weight-average molecular weight (Mw) and number-average molecular weight (Mn)" Weight-average molecular weight and number-average molecular weight were determined using a gel permeation chromatography system (e.g., Tosoh Corporation, HLC-8420GPC). Polystyrene was used as the standard, and the developing solvent was selected appropriately based on the resin's solubility. Suitable solvents included tetrahydrofuran (THF) and N,N-dimethylacetamide (DMAc).

[0101] By selecting a substrate (monomer) in a manner that constitutes the first and residual structures described above, and polymerizing it using known methods, the copolymer of this disclosure can be obtained. Alternatively, the copolymer of this disclosure can be obtained by bonding the ends of the polymer together using a known reaction, or by elongating the polymer by reacting it from the ends using a substrate or the like. For example, it can be manufactured by adding a resin solution of the residual structural component to a resin solution of the first structural component and mixing them, or by adding a raw material monomer of the first structural component to a resin solution of the residual structural component and mixing them. A solvent may also be added along with the added raw material monomer. In the following description, polyimide is used as an example, but the present invention is not limited to polyimide.

[0102] The composition of the first structure can be adjusted to have either an acid terminator or an amine terminator based on the molar ratio of the tetracarboxylic anhydride to the diamine in the raw materials. For example, by making the molar ratio of the tetracarboxylic anhydride to the diamine (tetracarboxylic anhydride / diamine) less than 1.0, the first structure can be made to have an amine terminator. On the other hand, by setting the molar ratio of the tetracarboxylic anhydride to the diamine (tetracarboxylic anhydride / diamine) to a range greater than 1.0, the first structure can be made to have an anhydride terminator.

[0103] When preparing the first structural component (in this case, non-thermoplastic polyimide), there are no particular restrictions on the order of addition of the raw material monomers; they can be added simultaneously or in a prescribed order.

[0104] The following describes in more detail the method for manufacturing the copolymer of the present disclosure using raw materials containing the residual structural component and the first structural component as representative examples.

[0105] In this case, the method for manufacturing the copolymer disclosed herein includes: Step 1: Prepare the resin solution for the remaining structural components; Step 2 involves adding the first raw material monomer of the first structural component to the resin solution containing the remaining structural component to prepare a mixed solution; and Step 3: Add a second raw material monomer that reacts with the first raw material monomer to the above mixed solution to synthesize a copolymer.

[0106] (Resin composition)

[0107] The resin compositions disclosed herein comprise the copolymers disclosed herein.

[0108] "Any ingredients"

[0109] In the resin composition disclosed herein, in addition to the copolymers disclosed herein, organic fillers, inorganic fillers, ring-closing agents, curing agents, curing accelerators, plasticizers, elastomers, coupling agents, pigments, flame retardants, heat dissipation agents, etc., may be appropriately blended as optional components, within a range that does not impair the effects of the invention. Examples of inorganic fillers include, for instance, silica, alumina, beryllium oxide, niobium oxide, titanium oxide, magnesium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride, magnesium fluoride, potassium fluorosilicate, and metal salts of phosphonates. One or more of these may be used in combination.

[0110] The resin composition disclosed herein exhibits excellent flexibility and thermoplasticity when used to form an adhesive layer. Therefore, it has preferred properties for applications such as materials for insulating layers in circuit boards, including FPCs, rigid substrates, rigid-flexible substrates, multilayer substrates, build-up substrates, and high-frequency substrates, as well as for coatings.

[0111] <Resin Substrate>

[0112] The resin substrate disclosed herein comprises the copolymers disclosed herein. The resin substrate disclosed herein can be formed from the resin composition disclosed herein. The shape of the resin substrate disclosed herein is not particularly limited. The shape of the resin substrate may be, for example, a film, a plate, or a layer. Hereinafter, a film-shaped substrate will be described in more detail as an example.

[0113] <Resin Film>

[0114] The resin film disclosed herein is a resin film formed of a single layer or multiple layers, wherein at least one layer contains a copolymer. The resin film of this disclosure preferably comprises a resin layer formed of the resin composition of this disclosure. The resin film of this disclosure, having a layer formed of the resin composition of this disclosure, therefore exhibits excellent tensile modulus and high-frequency properties.

[0115] The method for manufacturing the resin film disclosed herein is not particularly limited, and known methods can be used. For example, it is preferably manufactured by repeating the operation of coating the resin composition of this disclosure onto a support substrate and drying it once or more. As for the method of coating the resin composition of this disclosure onto the support substrate, there are no particular limitations; for example, coating machines such as comma, die head, doctor blade, and die lip can be used. It should be noted that by using metal foil as the support substrate, the metal-clad laminate of this disclosure, described later, can be manufactured.

[0116] The resin film disclosed herein may be a film (sheet) composed solely of insulating resin, or it may be an insulating resin film laminated on a substrate such as a copper foil, glass plate, polyimide film, polyamide film, polyester film, or other resin sheet.

[0117] The thickness of the resin film disclosed herein is preferably in the range of 5 to 150 μm, and more preferably in the range of 8 to 125 μm. When the thickness of the resin film disclosed herein is less than 5 μm, there is a risk of defects such as wrinkling during handling in the manufacturing process of the resin film, and there is a risk that it cannot exhibit sufficient toughness and thus cannot obtain a self-supporting film. On the other hand, when the thickness of the resin film exceeds 150 μm, the productivity of the resin film may decrease.

[0118] "Mean linear coefficient of thermal expansion (CTE)"

[0119] The CTE of the resin film disclosed herein is preferably 50 ppm / K or less, more preferably in the range of 0 to 30 ppm / K. With a CTE of 50 ppm / K or less, the dimensional change rate can be easily controlled when manufacturing the resin film and the metal-coated laminate.

[0120] "Determination of the coefficient of linear thermal expansion"

[0121] The linear thermal expansion coefficient of the resin can be determined by the following method. Using a thermomechanical analysis apparatus (e.g., Hitachi High-Tech Technology Co., Ltd. (formerly Seiko Instruments Inc.), trade name: TMA / 7100), while applying a load of 5.0 g to the sample (3 mm wide × 20 mm long), the temperature is increased from 30 °C to 180 °C at a certain rate, held at this temperature for 10 minutes, and then cooled at a rate of 5 °C / min. The average thermal expansion coefficient (linear thermal expansion coefficient) from 180 °C to 100 °C is then calculated.

[0122] Relative permittivity

[0123] To ensure impedance matching when used in circuit boards such as FPCs, and to reduce signal loss, the relative permittivity (Dk) of the resin film disclosed herein at 10 GHz after 24 hours of conditioning at a temperature of 24-26°C and a relative humidity of 45-55% is preferably 3.5 or less, more preferably 3.0 or less. When the relative permittivity exceeds 3.5, it can easily lead to signal loss and other adverse effects on the high-frequency signal transmission path when used in circuit boards such as FPCs. The relative permittivity can be determined by the method described above.

[0124] "Dielectric loss tangent"

[0125] Furthermore, in order to reduce electrical signal loss when used in circuit boards such as FPCs, the dielectric loss tangent (Tanδ) of the resin film disclosed herein, after being conditioned for 24 hours at a temperature of 24~26°C and a relative humidity of 45~55%, is preferably 0.0030 or less, more preferably 0.0025 or less, and most preferably 0.0023 or less at 10 GHz, as measured by a split dielectric resonator (SPDR). When the dielectric loss tangent exceeds 0.0030, adverse conditions such as electrical signal loss are easily generated in the transmission path of high-frequency signals when used in circuit boards such as FPCs.

[0126] The relative permittivity and dielectric loss tangent can be evaluated by the following method. A resin film is obtained by molding a resin composition into a thin film. The molding method is not particularly limited. For example, a resin film for evaluation can be obtained by coating a substrate with a solution made by dissolving the resin composition in a solvent and then drying it. Next, the relative permittivity (Dk) and dielectric loss tangent (Df) of the resin film at a specified frequency (e.g., 10 GHz) are measured using a vector network analyzer (e.g., Agilent Technologies E8363C) and a split dielectric resonator (SPDR resonator). It should be noted that the relative permittivity and dielectric loss tangent are measured after the film used in the measurement has been placed at a temperature of 24–26 °C and a relative humidity of 45–55% for 24 hours.

[0127] The dielectric loss tangent Df1 (dielectric loss tangent at 10 GHz) of the resin film containing the copolymer and the second dielectric loss tangent Df2 (dielectric loss tangent at 10 GHz) calculated based on two or more repeating units constituting the copolymer preferably satisfy the following formula (A2). By making the dielectric loss tangent Df1 (dielectric loss tangent at 10 GHz) of the copolymer and the second dielectric loss tangent Df2 calculated based on two or more repeating units constituting the copolymer satisfy the following formula (A2), the dielectric loss when using high-frequency signals can be reduced more effectively.

[0128] Here, the second dielectric loss tangent Df2 is calculated based on the dielectric loss tangent (Dfn) of the homopolymer of the repeating unit at 10 GHz and the mass ratio (mn / M) of the repeating unit according to the following equation (A3) (additive law). In equation (A3), N is the total number of components, n is 1 to N, Dfn is the dielectric loss tangent of the nth component, mn is the mass of the nth component, and M is the total mass. The dielectric loss tangent of each component can be used to prepare a resin film of the homopolymer and then measured.

[0129] Df1 <Df2×0.97…(A2) Df2=Df1×m1 / M+…+Dfn×mn / M+…+DfN×(mN / M)…(A3)

[0130] "Energy storage modulus"

[0131] The preferred storage modulus of the resin film disclosed herein at 180°C is 1.0 × 10⁻⁶. 6 Pa or higher, more preferably 1.0 × 10 Pa 7 Above Pa, the optimal value is 1.0 × 10⁻⁶. 7 ~1.0×10 10Within the range of Pa. Furthermore, the storage modulus of the resin film disclosed herein at 260°C is preferably 1 × 10⁻⁶. 5 Pa or higher, more preferably 1.0 × 10 Pa 6 Above Pa, the optimal value is 1.0 × 10⁻⁶. 6 Pa ~ 5.0 × 10 9 Within the range of Pa. By satisfying the storage modulus at the above temperatures, heat resistance suitable for installation and use in high-temperature environments can be achieved.

[0132] Glass transition temperature

[0133] When the resin film disclosed herein is an amorphous material without a melting point, the glass transition temperature (Tg) is preferably 180°C or higher, more preferably in the range of 180 to 400°C. By setting the Tg of the resin film to 180°C or higher, heat resistance suitable for installation and use in high-temperature environments can be achieved.

[0134] Storage modulus and glass transition temperature can be determined by the following method. A 5mm × 20mm thin film or resin sheet is cut to prepare an evaluation sample. Then, using a dynamic viscoelastic apparatus (e.g., DMA: TA Instruments, trade name: RSA-G2), the sample is heated in stages from 30°C to 500°C at a heating rate of 4°C / min, and measured at a frequency of 1Hz. The temperature of the tanδ peak is set as the glass transition temperature Tg. It should be noted that if multiple tanδ peaks appear, the highest of the peak temperatures is set as Tg. Here, tanδ refers to the loss coefficient, which is the ratio of loss modulus G” to storage modulus G’ (G” / G’).

[0135] Melting point

[0136] When the resin film of this disclosure is crystalline and has a melting point, the melting point (Tm) is preferably 260°C or higher, more preferably in the range of 260 to 450°C. By setting the melting point Tm of the resin film to 260°C or higher, heat resistance suitable for installation and use in high-temperature environments can be achieved. The melting point can be determined by the method described above. In the case of multiple peaks appearing in the differential scanning calorimeter measurement, the maximum temperature among the peak temperatures is taken as the melting point.

[0137] The melting point of the resin can be determined, for example, according to the method of JIS K7121:2012. In the case of multiple peaks originating from melting, the highest peak temperature is taken as the melting point.

[0138] (Tensive modulus)

[0139] The tensile modulus of the resin film disclosed herein is preferably 1.0 GPa or higher. More preferably, the tensile modulus of the resin film disclosed herein is in the range of 1.5 to 6.0 GPa, and even more preferably in the range of 1.5 to 5.0 GPa. When the tensile modulus is less than 1.0 GPa, stickiness occurs, making it impossible to obtain a film that is easy to process.

[0140] (Elongation)

[0141] The elongation of the resin film disclosed herein is preferably 0.1% or more, more preferably 0.5% or more and 150% or less. It is even more preferably 100% or less. A high elongation leads to a deterioration of the CTE (Chemical Elongation Tolerance) of the resin film.

[0142] The tensile modulus and elongation disclosed herein can be determined by the following method. For example, a tensile test is performed on a resin film with a width of 12.7 mm and a length of 127 mm using a Strograph R-1 (manufactured by Toyo Seiki Co., Ltd.) at a speed of 50 mm / min under conditions of 23°C and 50% RH. Based on the results obtained, the tensile modulus and elongation of the resin film can be calculated.

[0143] <Metal-clad laminate>

[0144] The metal-clad laminate of this disclosure comprises an insulating resin layer formed of one or more layers, and a metal layer laminated on one or both sides of the insulating resin layer, wherein at least one layer of the insulating resin layer is formed of a resin film of this disclosure. It should be noted that the metal-clad laminate of this disclosure may include any layer other than those described above.

[0145] There are no particular limitations on the material of the metal layer, and examples include copper, stainless steel, iron, nickel, beryllium, aluminum, zinc, indium, silver, gold, tin, zirconium, tantalum, titanium, lead, magnesium, manganese, and their alloys. Among these, copper or copper alloys are particularly preferred. It should be noted that the material of the wiring layer in the circuit board of this embodiment, described later, is also the same as that of the metal layer.

[0146] The thickness of the metal layer is not particularly limited. For example, when using metal foil such as copper foil, it is preferably 35 μm or less, and more preferably in the range of 5 to 25 μm. From the viewpoint of production stability and operability, the lower limit of the metal foil thickness is preferably set to 5 μm. It should be noted that when using copper foil, it can be rolled copper foil or electrolytic copper foil. In addition, commercially available copper foil can be used.

[0147] The surface roughness of the metal layer is not particularly limited. From the viewpoint of balancing adhesion with the adhesive layer and conductor loss, a roughened surface with a maximum height (Rz) in the range of 0.3 to 1.5 μm is preferred. In addition, for the purpose of rust prevention and improving adhesion, the metal foil can be subjected to surface treatments based on siding, aluminum alkoxides, aluminum chelates, silane coupling agents, etc.

[0148] <Circuit substrate>

[0149] The circuit board disclosed herein is formed by wiring the metal layers of the metal-clad laminate of the present disclosure. By processing one or more metal layers of the metal-clad laminate into a pattern using conventional methods to form a wiring layer (conductor circuit layer), circuit boards such as FPCs can be manufactured. It should be noted that the circuit board may also have a cover film covering the wiring layer.

[0150] <Electronic Components & Electronic Devices>

[0151] The electronic devices and electronic equipment disclosed herein include the circuit board of this disclosure. Examples of electronic devices in this embodiment include liquid crystal displays, organic EL displays, electronic paper, organic EL lighting, solar cells, touch panels, camera modules, inverters, converters, and their constituent components. Examples of electronic devices include hard disk drives (HDDs), DVDs, mobile phones, smartphones, tablet computers, electronic control units (ECUs) and power control units (PCUs) in automobiles. In these electronic devices and electronic equipment, the circuit board is preferably used as a component such as wiring, cables, and connectors for movable parts.

[0152] The copolymers, resin compositions comprising the copolymers, resin films, metal-clad laminates, circuit boards, electronic devices, and electronic devices disclosed herein have been described in detail above. It should be noted that the scope of the present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the invention. Furthermore, without departing from the spirit of the invention, the constituent elements in the above embodiments can be appropriately replaced with known constituent elements, and the above-described variations can also be appropriately combined.

[0153] Example

[0154] The following examples illustrate the features of the invention in more detail. However, the scope of the invention is not limited to these examples. It should be noted that, unless otherwise specified, various measurements and evaluations are described in the following examples.

[0155] "Determination of weight-average molecular weight (Mw) and number-average molecular weight (Mn)"

[0156] Weight-average molecular weight and number-average molecular weight were determined by gel permeation chromatography (using two TSKgel GMHHR-M columns (Tosoh Corporation, 7.8 mm inner diameter × 30 cm length)). Sample solutions were prepared with a solids concentration of 0.1%. The solutions were then filtered using a 0.45 μm filter. The resulting filtrate was used as the test solution. Polystyrene was used as the standard, and tetrahydrofuran (THF) or N,N-dimethylacetamide (DMAc) were used as the developing solvent depending on the resin's solubility. The flow rate was 0.8 mL / min, the measurement temperature was 40 °C, and the sample injection volume was 100 μL. The results are shown in Table 2. Note that for YOUMEX 1010, the values ​​in the catalog are used.

[0157] "Viscosity Measurement"

[0158] Viscosity at 25°C was measured using a Type E viscometer (Brookfield, trade name: DV-II+Pro). The rotational speed was set to 10%–90% torque, and the viscosity was recorded after 2 minutes from the start of measurement when it stabilized. The results are shown in Tables 6A and 6B.

[0159] "Determination of Energy Storage Modulus"

[0160] Regarding the storage modulus, a dynamic viscoelasticity measuring apparatus (DMA: RSA-G2, manufactured by TA Instruments) was used to measure the temperature of a resin film with dimensions of 5 mm wide × 70 mm long, from 30°C to 500°C at a heating rate of 4°C / min and a frequency of 1 Hz. The peak temperature of the loss coefficient was also determined. The results are shown in Tables 4, 7A, and 7B.

[0161] "Determination of the coefficient of linear thermal expansion"

[0162] Using a Hitachi High-Tech Technology (formerly Seiko Instruments Inc.) product, TMA / 7100, a sample (3 mm wide × 20 mm long) was heated from 30 °C to 180 °C at a controlled rate while being subjected to a 5.0 g load. This temperature was then maintained for 10 minutes and subsequently cooled at a rate of 5 °C / min. The average coefficient of thermal expansion (linear thermal expansion) from 180 °C to 100 °C was determined. The results are shown in Tables 3, 7A, and 7B.

[0163] "SP value"

[0164] The SP values ​​(solubility parameters) of each sample were calculated based on the Fedors method described in Non-Patent Document 1. The SP value δ based on the Fedors method was calculated using the above formula (A1). Specifically, the cohesive energy and molecular capacity of each structure constituting the resin were calculated, and the sum of the cohesive energies of each component was divided by the sum of the molecular capacities. The resulting value was then multiplied by 1 / 2 to obtain the SP value and the difference between the SP value of the first structure and the SP value of the remaining structures. The obtained SP values ​​are shown in Table 4.

[0165] “δP、δH、δP×δH”

[0166] In addition, the δP and δH of each sample were determined using the Hansen Solubility Parameter in Practice. The product of δP and δH (δP×δH) and the difference between the products of δP and δH were then calculated using the methods described above. The results are shown in Table 4.

[0167] [Determination of relative permittivity (Dk) and dielectric loss tangent (Df)]

[0168] For the samples listed as SPDR in the Measurement Method column of Table 3 and the samples in Tables 7A and 7B, the relative permittivity (Dk) and dielectric loss tangent (Df) of the resin film at a frequency of 10 GHz were measured using a vector network analyzer (Agilent Technologies, trade name: E8363C) and a split dielectric resonator (SPDR resonator). It should be noted that Dk and Df during conditioning are values ​​measured after the resin film used in the measurement was placed at a temperature of 24~26℃ and a relative humidity of 45~55% for 24 hours. The results are shown in Tables 3, 7A, and 7B. Furthermore, the calculation results and judgment results of the above formula (A2) are also shown in Tables 7A and 7B. The measured Df < the summation law Df is considered satisfactory. Set the value of 0.97 to 0, and set the value of the unsatisfactory value to ×.

[0169] Table 3, under the "Measurement Method" column, records that the cavity resonator sample was measured using a vector network analyzer (Keysight Technologies, E8363C) and a relative permittivity measuring device based on the cavity resonator perturbation method, manufactured by Kanto Electronics Application Development Co., Ltd. The relative permittivity measurement mode was set to TM020, and the relative permittivity (ε1) and dielectric loss tangent (Tanδ1) of the sample were measured at a frequency of 10 GHz. It should be noted that the sample was in powder form, filled into a sample tube (inner diameter 1.68 mm, outer diameter 2.28 mm, height 8 cm) and then measured. Measurements were performed after 24 hours of exposure at 24–26 °C and 45–55% humidity, and the measured values ​​were calculated as the average of n=3. The results are shown in Table 3.

[0170] [Determination of tensile modulus and elongation]

[0171] Using a Strograph R-1 (manufactured by Toyo Seiki Co., Ltd.), tensile tests were conducted on resin films with a width of 12.7 mm and a length of 127 mm at a speed of 50 mm / min under conditions of 23°C and 50% RH. The tensile modulus and elongation of the resin films were calculated. The results are shown in Tables 4, 7A, and 7B.

[0172] "Mass ratio of the first structure"

[0173] The mass ratio of the first structure is determined based on the aforementioned "method for determining the first structure," and the remaining structures are considered the surplus structures. The mass ratio of each structure is calculated by determining its molecular weight. The results are shown in Tables 6A and 6B. The mass ratio of the imide structure and the ammonium acid structure is calculated using the same method. The results are shown in Tables 6A and 6B.

[0174] "The mass ratio of carbon atoms to hydrogen atoms, and the mass proportion of carbon atoms to hydrogen atoms mentioned above."

[0175] In the remaining structures that constitute samples No. 1 to No. 5, the number of hydrogen atoms and the number of carbon atoms were determined. The mass of each atom in the remaining structure was calculated by multiplying the number of atoms by the atomic weight of that atom. From the obtained mass of each atom, the mass ratio of carbon atoms to hydrogen atoms (C / H) and the total mass ratio of carbon atoms to hydrogen atoms in the remaining structure (wt%) were calculated. Furthermore, the carbon content (wt%), hydrogen content (wt%), oxygen content (wt%), and nitrogen content (wt%) in the remaining structures were determined. The results are shown in Table 2.

[0176] The abbreviations used in the examples and comparative examples refer to the following compounds.

[0177] XIRAN 6000: Styrene-maleic anhydride copolymer (Baroko Co., Ltd., styrene:maleic acid ratio = 6:1, weight average molecular weight (Mw): 10000) XIRAN 1000: Styrene-maleic anhydride copolymer (Baroko Co., Ltd., styrene:maleic acid ratio = 1:1, weight average molecular weight (Mw): 10000) FG1901: Maleic anhydride (MA) modified styrene-ethylene-butene-styrene block copolymer (Kraton, coportaion, weight average molecular weight (Mw): 68000) FG1924: Maleic anhydride (MA) modified styrene-ethylene-butene-styrene block copolymer (Kraton, coportaion, weight average molecular weight (Mw): 170,000) YOUMEX 1010: Acid-modified polypropylene (Sanyo Chemical Industries, Ltd., weight-average molecular weight (Mw): 30,000) m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl BP-TME: p-Phenylene bis(trimethoxymethyl ... BPDA: 3,3',4,4'-Biphenyltetracarboxylic dianhydride 26DHN-TME: 2,6-Naphthobis(Trimethicone Monoester Anhydride) BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane ODPA: Oxyphthalic anhydride TPE-R: 1,3-Bis(3-aminophenoxy)benzene PMDA: Pyromellitic anhydride p-PDA: p-phenylenediamine NMP: N-methyl-2-pyrrolidone DMAc: N,N-dimethylacetamide Xylene: (a mixture of ortho, meta, and para-xylene isomers)

[0178] (Synthesis example 1)

[0179] Synthesis of Copolymers

[0180] (Resin Composition 1A)

[0181] In a 500 mL separable flask, 8.00 g of XIRAN 6000 and 160 g of NMP were added and stirred under a nitrogen stream to dissolve the XIRAN 6000. Next, 22.5299 g of BP-TME was added, followed by 9.4701 g of m-TB and 200 g of NMP. The mixture was stirred continuously at room temperature for 24 hours to carry out the polymerization reaction, preparing resin composition No. 1A (solids concentration: 10%, viscosity: 21,634 cP).

[0182] In addition to the raw material composition shown in Table 5A, resin compositions 2A to 17A were prepared in the same manner as resin composition No. 1A.

[0183] <Preparation of Single-Sided Copper Clad Laminates>

[0184] A resin composition is uniformly coated onto copper foil (electrolytic copper foil, thickness: 12 μm, resin side roughness Rzjis: 0.6 μm) to achieve a cured thickness of 25 μm. The coating is then heated and dried at 100–120 °C for 10 minutes to remove the solvent. Subsequently, heat treatment is performed from room temperature to 320 °C at a heating rate of 5 °C / min to complete imidization, thus preparing a single-sided copper-clad laminate.

[0185] <Preparation of Resin Films>

[0186] The copper foil of the single-sided copper-clad laminate was etched away using an aqueous ferric chloride solution to obtain the resin film of the embodiment. Various evaluation results of the resin film are shown in Table 7A.

[0187] According to Table 7A, in resin films No. 2B to 16B, the first structure and the balance structure meet the specified conditions, so the CTE is less than 50.0 ppm / K, and a resin film with a dielectric loss tangent of less than 0.0030 is obtained.

[0188] (See Example 1 for reference)

[0189] (Resin Composition No. 17A)

[0190] Resin composition No. 17A was prepared by adding 30.0 g of XIRAN 6000 and 70.0 g of xylene at a solid content concentration of 30% by mass to a 300 mL separable flask under a nitrogen flow and stirring.

[0191] (See Example 2 for reference)

[0192] (Resin Composition No. 18A)

[0193] 8.8782 g of m-TB and 120 g of NMP were added to a 500 mL separable flask, and the mixture was stirred until m-TB dissolved. Then, 21.1218 g of BP-TME and 50 g of NMP were added, and the mixture was stirred continuously at room temperature for 24 hours to carry out the polymerization reaction, thus preparing resin composition No. 18A (solids concentration: 15%, viscosity: 10,453 cP).

[0194] (Refer to Examples 3-5)

[0195] (Resin compositions No. 19A~21A)

[0196] In addition to the raw material composition shown in Table 5B, resin compositions No. 19A to 21A were prepared in the same manner as resin composition No. 1A.

[0197] In resin compositions No. 17A to 21A, single-sided copper-clad laminates and resin films were prepared in the same manner as in resin composition No. 1A, and the results of measuring various physical properties are shown in Table 7B.

[0198] According to Table 7B, resin film No. 17B does not have the first structure, therefore the elastic modulus of the film is low, making it difficult to produce a film.

[0199] According to Table 7B, resin film No. 18B does not have a surplus structure and therefore does not exhibit a reduction effect on Df relative to the addition law.

[0200] According to Table 7B, in resin film No. 19B, the mass ratio of carbon atoms to hydrogen atoms is less than 77 wt%, therefore it does not show a reduction effect on Df relative to the addition law.

[0201] According to Table 7B, in resin films No. 20B and 21B, the first structure and the reserve structure are not in the specified proportions, so it is impossible to achieve both low CTE and low dielectric loss tangent.

[0202] The effects of this invention are based on the structure of the first structure and the atomic ratios in the remaining structure. Therefore, it is believed that by replacing the first structure (polyimide structure) used in this embodiment with other structures, desired results based on the properties of the replaced structure can be obtained.

[0203] The embodiments of the present invention have been described in detail above for illustrative purposes, but the present invention is not limited to the above embodiments and can be modified in various ways.

[0204]

[0205] [Industry availability] The copolymers of the embodiments exhibit both low CTE and low dielectric loss tangent, thus having high industrial applicability.

Claims

1. A copolymer comprising a first structure containing two or more aromatic rings and the balance structure. The first structure is one in which the aromatic rings are bonded to each other by single bonds or connecting groups. In the balance structure, the sum of carbon atoms and hydrogen atoms accounts for 77 wt% or more of the total mass of the balance structure. In the remaining structure, the mass ratio of the carbon atoms to the hydrogen atoms is 6.5 or more and 12.5 or less. The first structure accounts for 15 wt% to 85 wt% of the total mass of the copolymer. In the linking group, the number of atoms directly bonded to each other by the aromatic rings is 2 or less.

2. The copolymer according to claim 1, wherein, The combined mass ratio of the imide structure and the ammonium acid structure of the first structure to the total mass of the first structure is 15.5 wt% or more.

3. The copolymer according to claim 1, wherein, The remaining structure has a chain-like hydrocarbon structure consisting of six or more carbon atoms bonded together by single bonds.

4. The copolymer according to claim 1, wherein, The difference in SP values ​​between the first structure and the remaining structure is 3 (J / cm). 3 ) 1 / 2 Above and 10 (J / cm) 3 ) 1 / 2 the following.

5. The copolymer according to claim 1, wherein, The difference between the products of δP and δH in the HSP values ​​of the first structure and the surplus structure is 50 (J / cm). 3 ) or above and 120 (J / cm 3 )the following.

6. The copolymer according to claim 1, wherein, The copolymer is at least one of block copolymer and graft copolymer.

7. The copolymer according to claim 1, wherein, The mass ratio of the first structure to the remaining structure is 15:85 to 85:

15.

8. The copolymer according to claim 1, wherein, The total mass of the carbon atom and the hydrogen atom is 90 wt% or more, and the mass ratio of the carbon atom to the hydrogen atom is 6.5 or more and 12.5 or less.

9. A resin composition comprising the copolymer of claim 1.

10. A resin film comprising the copolymer of claim 1.

11. The resin film according to claim 10, wherein, The dielectric loss tangent Df1 of the copolymer at 10 GHz, measured using a split dielectric resonator (SPDR) at a temperature of 24-26°C and a relative humidity of 45-55%, and the second dielectric loss tangent Df2 calculated based on two or more repeating units constituting the copolymer, satisfy the following equation (1). The second dielectric loss tangent is calculated based on the dielectric loss tangent of the homopolymer of the repeating unit at 10 GHz and the mass ratio of the repeating unit according to the additive law. Df1 <Df2×0.97…(1)。 12. The resin film according to claim 10, wherein, The linear thermal expansion coefficient at 180~100℃ is below 50ppm / K.

13. A metal-clad laminate comprising an insulating resin layer formed of a single layer or multiple layers, and a metal layer laminated on one or both sides of the insulating resin layer. At least one layer of the insulating resin layer is composed of the resin film as described in claim 10.

14. A circuit board comprising an insulating resin layer formed of a single layer or multiple layers, and conductive circuit layers stacked on one or both sides of the insulating resin layer. At least one layer of the insulating resin layer is composed of the resin film as described in claim 10.

15. An electronic device comprising the circuit board of claim 14.

16. An electronic device comprising the circuit board of claim 14.

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