TWI781901B - Polyimide film, copper laminate and circuit substrate - Google Patents

Abstract

A polyimide film, which has a non-thermoplastic polyimide layer, and the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer is preferably totaled with respect to 100 mole parts of tetracarboxylic acid residues Contains more than 80 molar parts of BPDA residues derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 1,4-phenylene bis(trimellitic acid mono At least one of TAHQ residues derived from ester) dianhydride (TAHQ) and PMDA residues derived from pyromellitic dianhydride (PMDA) and 2,3,6,7-naphthalene tetracarboxylic dianhydride (NTCDA) at least one of the NTCDA residues derived, and preferably a dielectric tangent (Df) of 0.004 or less.

Description

Polyimide film, copper tension laminate and circuit board

The invention relates to a polyimide film, a copper tension laminate and a circuit substrate.

In recent years, with the advancement of miniaturization, weight reduction, and space saving of electronic equipment, flexible printed wiring boards (flexible printed wiring boards) that are thin, lightweight, flexible, and have excellent durability even after repeated bending Circuit (Flexible Printed Circuits, FPC)) needs to increase. Regarding FPC, it can achieve three-dimensional and high-density installation even in a limited space, so it can be used in hard disk drives (Hard Disk Drive, HDD), digital video disks (Digital Video Disk, DVD), smart phones and other electronic devices. Its use is gradually expanding in the wiring of movable parts of equipment, or in parts such as cables and connectors.

In addition to the above-mentioned increase in density, the increase in performance of equipment is being promoted, and therefore it is also necessary to deal with the increase in the frequency of transmission signals. When transmitting a high-frequency signal, if the transmission loss of the signal transmission path is large, there will be disadvantages such as loss of the electrical signal or a longer delay time of the signal. Therefore, reduction of transmission loss of FPC becomes important. In order to cope with higher frequencies, FPCs using liquid crystal polymers featuring low dielectric constant and low dielectric tangent as the dielectric layer are used. However, although liquid crystal polymers are excellent in dielectric properties, there is room for improvement in heat resistance and adhesion to metal foil.

In order to improve heat resistance and adhesiveness, a metal tension laminate using polyimide as an insulating layer has been proposed (Patent Document 1). According to Patent Document 1, it can be seen that the dielectric constant is generally lowered by using aliphatic monomers as monomers of polymer materials, and the heat resistance of polyimides obtained by using aliphatic (chain) tetracarboxylic dianhydrides is remarkably low. , Therefore, there is a practical problem because it cannot be used for processing such as welding, but if an alicyclic tetracarboxylic dianhydride is used, a polyimide having improved heat resistance can be obtained compared with a chain tetracarboxylic dianhydride. However, the polyimide film formed of such polyimide has a dielectric constant of 3.2 or less at 10 GHz, but a dielectric tangent of more than 0.01, and the dielectric properties are not yet sufficient. In addition, polyimides using such aliphatic monomers have problems in that many have a large coefficient of linear expansion, the dimensional change rate of the polyimide film is large, or the flame retardancy is lowered. [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-358961

[Problem to be Solved by the Invention] The object of the present invention is to provide a polyimide film which has high dimensional stability and low hygroscopicity, and can reduce transmission loss by making the dielectric tangent of the insulating layer small, and can be preferably used for high frequency circuit boards. [Means to solve the problem]

The inventors of the present invention conducted diligent research and found that, in the circuit board, the non-thermoplastic polyimide layer mainly functions to control the dimensional change rate, and further, the thermoplastic polyimide layer which functions as the bonding with the copper foil if necessary. For the imide layer, by selecting the monomer used as the raw material of polyimide, it is possible to ensure the necessary dimensional stability as a circuit board and to control the order (crystallinity) of polyimide. The low moisture absorption rate and low dielectric tangent, thus completing the present invention.

That is, the polyimide film according to the first viewpoint of the present invention is a polyimide film having a thermoplastic polyimide layer containing thermoplastic polyimide on at least one side of a non-thermoplastic polyimide layer containing non-thermoplastic polyimide. imide film. Furthermore, the polyimide film according to the first viewpoint of the present invention satisfies the following conditions (a-i) to (a-iv). (a-i) the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer is one containing tetracarboxylic acid residues and diamine residues, and With respect to 100 mole parts of said tetracarboxylic acid residues, Tetracarboxylic acid residues (BPDA residues) derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride (3,3',4,4'-biphenyl tetracarboxylic dianhydride, BPDA) and At least one of the tetracarboxylic acid residues (TAHQ residues) derived from 1,4-phenylene bis(trimellitic acid monoester)dianhydride (TAHQ) One and tetracarboxylic acid residues (PMDA residues) derived from pyromellitic dianhydride (PMDA) and 2,3,6,7-naphthalene tetracarboxylic dianhydride (2,3,6, The total amount of at least one of the tetracarboxylic acid residues (NTCDA residues) derived from 7-naphthalene tetracarboxylic dianhydride (NTCDA) is 80 mole parts or more, The molar ratio of at least one of the BPDA residue and the TAHQ residue to at least one of the PMDA residue and the NTCDA residue {(BPDA residue+TAHQ residue)/(PMDA residue base + NTCDA residue)} in the range of 0.6 to 1.3. (a-ii) The thermoplastic polyimide constituting the thermoplastic polyimide layer contains tetracarboxylic acid residues and diamine residues, and relative to 100 mole parts of the diamine residues, The number of diamine residues derived from at least one diamine compound selected from diamine compounds represented by the following general formulas (B1) to (B7) is 70 mole parts or more. (a-iii) The coefficient of thermal expansion is within the range of 10 ppm/K to 30 ppm/K. (a-iv) The dielectric tangent (Dissipation factor, Df) at 10 GHz is 0.004 or less.

[式（B1）～式（B7）中，R ₁獨立地表示碳數1～6的一價烴基或烷氧基，連結基A獨立地表示選自-O-、-S-、-CO-、-SO-、-SO ₂-、-COO-、-CH ₂-、-C(CH ₃) ₂-、-NH-或-CONH-中的二價基，n ₁獨立地表示0～4的整數。其中，自式（B3）中去除與式（B2）重複者，自式（B5）中去除與式（B4）重複者] [chemical 1]

[In formulas (B1) to (B7), R ₁ independently represents a monovalent hydrocarbon group or alkoxy group with 1 to 6 carbons, and the linking group A independently represents a group selected from -O-, -S-, -CO- , -SO-, -SO ₂ -, -COO-, -CH ₂ -, -C(CH ₃ ) ₂ -, -NH- or -CONH-, n ₁ independently represents 0-4 integer. Among them, the duplicates of formula (B2) are removed from formula (B3), and the duplicates of formula (B4) are removed from formula (B5)]

Regarding the polyimide film according to the first aspect of the present invention, the following general formula The diamine residue derived from the diamine compound represented by (A1) may be 80 mole parts or more.

[式（A1）中，連結基X表示單鍵或-COO-，Y獨立地表示氫、碳數1～3的一價烴基或烷氧基，n表示0～2的整數，p及q獨立地表示0～4的整數] [Chem 2]

[In the formula (A1), the linking group X represents a single bond or -COO-, Y independently represents hydrogen, a monovalent hydrocarbon group or an alkoxy group with 1 to 3 carbons, n represents an integer of 0 to 2, and p and q are independently represent an integer from 0 to 4]

The polyimide film according to the first aspect of the present invention may be a polyimide film selected from the group consisting of: The diamine residue derived from at least one diamine compound among the diamine compounds represented by the general formulas (B1) to (B7) is within the range of 70 mole parts or more and 99 mole parts or less. The diamine residue derived from the diamine compound represented by the general formula (A1) is in the range of not less than 1 mol part and not more than 30 mol parts.

The polyimide film according to the second aspect of the present invention is a polyimide having a thermoplastic polyimide layer containing thermoplastic polyimide on at least one side of a non-thermoplastic polyimide layer containing non-thermoplastic polyimide. Amine film. In addition, the polyimide film according to the second viewpoint of the present invention satisfies the following conditions (b-i) to (b-iv). (b-i) The coefficient of thermal expansion is within the range of 10 ppm/K to 30 ppm/K. (b-ii) the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer contains tetracarboxylic acid residues and diamine residues, and With respect to 100 mole parts of said tetracarboxylic acid residues, It is composed of at least one tetracarboxylic acid dianhydride (BPDA) and 1,4-phenylene bis(trimellitic acid monoester) dianhydride (TAHQ) selected from 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) The tetracarboxylic acid residue derived from carboxylic acid dianhydride is within the range of 30 mole parts to 60 mole parts, and the tetracarboxylic acid residue derived from pyromellitic dianhydride (PMDA) is 40 mole parts Parts or more and 70 mole parts or less. (b-iii) relative to 100 mole parts of diamine residues in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer, The diamine residue derived from the diamine compound represented by the following general formula (A1) is 80 mol parts or more. (b-iv) The thermoplastic polyimide constituting the thermoplastic polyimide layer contains tetracarboxylic acid residues and diamine residues, and relative to 100 mole parts of the diamine residues, The diamine residue derived from at least one diamine compound selected from the diamine compounds represented by the following general formula (B1) to general formula (B7) is within the range of 70 mole parts or more and 99 mole parts or less , The diamine residue derived from the diamine compound represented by the following general formula (A1) exists in the range of 1 mol part or more and 30 mol parts or less.

[式（A1）中，連結基X表示單鍵或-COO-，Y獨立地表示氫、碳數1～3的一價烴基或烷氧基，n表示0～2的整數，p及q獨立地表示0～4的整數] [Chem 3]

[In the formula (A1), the linking group X represents a single bond or -COO-, Y independently represents hydrogen, a monovalent hydrocarbon group or an alkoxy group with 1 to 3 carbons, n represents an integer of 0 to 2, and p and q are independently represent an integer from 0 to 4]

[式（B1）～式（B7）中，R ₁獨立地表示碳數1～6的一價烴基或烷氧基，連結基A獨立地表示選自-O-、-S-、-CO-、-SO-、-SO ₂-、-COO-、-CH ₂-、-C(CH ₃) ₂-、-NH-或-CONH-中的二價基，n ₁獨立地表示0～4的整數。其中，自式（B3）中去除與式（B2）重複者，自式（B5）中去除與式（B4）重複者] [chemical 4]

[In formulas (B1) to (B7), R ₁ independently represents a monovalent hydrocarbon group or alkoxy group with 1 to 6 carbons, and the linking group A independently represents a group selected from -O-, -S-, -CO- , -SO-, -SO ₂ -, -COO-, -CH ₂ -, -C(CH ₃ ) ₂ -, -NH- or -CONH-, n ₁ independently represents 0-4 integer. Among them, the duplicates of formula (B2) are removed from formula (B3), and the duplicates of formula (B4) are removed from formula (B5)]

In the polyimide film according to the first aspect or the second aspect of the present invention, both the non-thermoplastic polyimide and the thermoplastic polyimide may have an imide group concentration of 33% by weight or less.

The polyimide film according to the third aspect of the present invention is a polyimide film having at least one non-thermoplastic polyimide layer, and the polyimide film is characterized in that it satisfies the following conditions (c-i) to Condition (c-iii). (c-i) the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer contains tetracarboxylic acid residues and diamine residues, and 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) contained in the range of 30-60 mole parts with respect to 100 mole parts of the tetracarboxylic acid residue And at least one tetracarboxylic acid residue derived from 1,4-phenylene bis(trimellitic acid monoester) dianhydride (TAHQ), containing in the range of 40 mole parts to 70 mole parts Tetracarboxylic acid residues derived from at least one of pyromellitic dianhydride (PMDA) and 2,3,6,7-naphthalenetetracarboxylic dianhydride (NTCDA), The diamine residue derived from the diamine compound represented by the following general formula (A1) contains 70 mol parts or more with respect to 100 mol parts of the said diamine residue. (c-ii) The glass transition temperature is 300° C. or higher. (c-iii) The dielectric tangent (Df) at 10 GHz is 0.004 or less.

[式（A1）中，連結基X表示單鍵或-COO-，Y獨立地表示氫、碳數1～3的一價烴基或烷氧基，n表示0～2的整數，p及q獨立地表示0～4的整數] [chemical 5]

[In the formula (A1), the linking group X represents a single bond or -COO-, Y independently represents hydrogen, a monovalent hydrocarbon group or an alkoxy group with 1 to 3 carbons, n represents an integer of 0 to 2, and p and q are independently represent an integer from 0 to 4]

The polyimide film according to the third aspect of the present invention may contain the following general formula (C1 ) to the diamine residue derived from the diamine compound represented by the general formula (C4).

[式（C1）～式（C4）中，R ₂獨立地表示碳數1～6的一價烴基、烷氧基或烷硫基，連結基A’獨立地表示選自-O-、-SO ₂-、-CH ₂-或-C(CH ₃) ₂-中的二價基，連結基X1獨立地表示-CH ₂-、-O-CH ₂-O-、-O-C ₂H ₄-O-、-O-C ₃H ₆-O-、-O-C ₄H ₈-O-、-O-C ₅H ₁₀-O-、-O-CH ₂-C(CH ₃) ₂-CH ₂-O-、-C(CH ₃) ₂-、-C(CF ₃) ₂-或-SO ₂-，n ₃獨立地表示1～4的整數，n ₄獨立地表示0～4的整數，但於式（C3）中，連結基A’不含-CH ₂-、-C(CH ₃) ₂-、-C(CF ₃) ₂-或-SO ₂-的情況下，n ₄的任一者為1以上。其中，於n ₃=0的情況下，式（C1）中的兩個胺基並非對位] [chemical 6]

[In formula (C1) to formula (C4), R ₂ independently represents a monovalent hydrocarbon group, alkoxy group or alkylthio group with 1 to 6 carbons, and the linking group A' independently represents a group selected from -O-, -SO ₂ -, -CH ₂ - or -C(CH ₃ ) ₂ -, the linking group X1 independently represents -CH ₂ -, -O-CH ₂ -O-, -OC ₂ H ₄ -O- , -OC ₃ H ₆ -O-, -OC ₄ H ₈ -O-, -OC ₅ H ₁₀ -O-, -O-CH ₂ -C(CH ₃ ) ₂ -CH ₂ -O-, -C( CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or -SO ₂ -, n ₃ independently represents an integer of 1 to 4, n ₄ independently represents an integer of 0 to 4, but in formula (C3), When the linking group A' does not contain -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or -SO ₂ -, any one of n ₄ is 1 or more. Wherein, in the case of n ₃ =0, the two amino groups in the formula (C1) are not in the para position]

The copper tension-laminated board according to the first aspect, the second aspect, or the third aspect of the present invention has an insulating layer, and at least one surface of the insulating layer is provided with copper foil, and the copper tension-laminated board is characterized in that: The insulating layer includes the polyimide film according to any one of the above viewpoints.

The circuit board of the 1st viewpoint of this invention, a 2nd viewpoint, or a 3rd viewpoint is what processed the copper foil of the said copper tension laminated board into wiring. [Effect of the invention]

The polyimide film of the first aspect to the third aspect of the present invention can ensure the physical properties of the matrix resin layer and reduce the moisture absorption rate by forming a non-thermoplastic polyimide layer using a specific acid anhydride as a raw material. Coexistence, and can achieve low dielectric tangent. In addition, the polyimide film according to the first viewpoint or the second viewpoint of the present invention can realize low moisture absorption rate and Low dielectric tangent. Furthermore, the multilayer film combining two resin layers has low hygroscopicity and a dielectric tangent, and is excellent in dimensional stability after thermocompression bonding of copper foil. Therefore, by using the polyimide film of the present invention and the copper tension laminated board using it as the FPC material, the improvement of reliability and yield can be realized in the circuit board, for example, it can also be applied to transmission of more than 10 GHz Circuit boards for high-frequency signals, etc.

Next, embodiments of the present invention will be described.

[Polyimide film] The polyimide film according to the first embodiment of the present invention has a thermoplastic polyimide layer containing thermoplastic polyimide on at least one side of the non-thermoplastic polyimide layer containing non-thermoplastic polyimide, and satisfies The above-mentioned conditions (a-i) to conditions (a-iv). In addition, the polyimide film of the second embodiment of the present invention has a thermoplastic polyimide layer containing thermoplastic polyimide on at least one side of the non-thermoplastic polyimide layer containing non-thermoplastic polyimide, And those who satisfy the conditions (b-i) to (b-iv) above. Furthermore, in the first embodiment or the second embodiment, the thermoplastic polyimide layer is provided on one or both surfaces of the non-thermoplastic polyimide layer. For example, when the polyimide film and copper foil of the first embodiment or the second embodiment are laminated to form a copper tensioned laminate, the copper foil may be laminated on the surface of the thermoplastic polyimide layer. In the case of having a thermoplastic polyimide layer on both sides of a non-thermoplastic polyimide layer, as long as the thermoplastic polyimide layer on one side satisfies the condition (a-ii) or condition (b-iv) That is enough, but preferably, the thermoplastic polyimide layers on both sides satisfy the condition (a-ii) or condition (b-iv). In addition, the polyimide film according to the third embodiment of the present invention has at least one non-thermoplastic polyimide layer containing non-thermoplastic polyimide, and satisfies the above-mentioned conditions (c-i) to conditions (c-iii) By.

Hereinafter, regarding the first embodiment to the third embodiment, common points will be collectively described, and different points will be described separately.

The so-called "non-thermoplastic polyimide" is usually a polyimide that does not show softening and adhesion even when heated, but in the present invention refers to a dynamic viscoelasticity measurement device (Dynamic Mechanical Analyzer (Dynamic Mechanical Analyzer) Analysis, DMA)) and the storage modulus of elasticity measured at 30°C is 1.0×10 ⁹ Pa or more, and the storage modulus of elasticity at 280°C is 3.0×10 ⁸ Pa or more. In addition, "thermoplastic polyimide" is usually a polyimide whose glass transition temperature (Tg) can be clearly confirmed, but in the present invention refers to the storage elastic coefficient at 30°C measured using DMA A polyimide having a storage modulus of elasticity at 280°C of 1.0×10 ⁹ Pa or more and less than 3.0×10 ⁸ Pa.

In the polyimide film of the first embodiment, the second embodiment or the third embodiment, the resin component of the non-thermoplastic polyimide layer preferably contains non-thermoplastic polyimide, and the first embodiment or the second embodiment In an embodiment, the resin component of the thermoplastic polyimide layer preferably contains thermoplastic polyimide. In addition, the non-thermoplastic polyimide layer constitutes a low thermal expansion polyimide layer, and the thermoplastic polyimide layer constitutes a high thermal expansion polyimide layer. Here, the polyimide layer with low thermal expansion means that the coefficient of thermal expansion (Coefficient of Thermal Expansion, CTE) is preferably in the range of 1 ppm/K or more and 25 ppm/K or less, more preferably 3 ppm/K or more And the polyimide layer in the range below 25 ppm/K. In addition, the highly thermally expandable polyimide layer means that the CTE is preferably 35 ppm/K or more, more preferably 35 ppm/K or more and 80 ppm/K or less, and more preferably 35 ppm/K or more and Polyimide layer in the range below 70 ppm/K. The polyimide layer can be made into a polyimide layer having a desired CTE by appropriately changing the combination of raw materials used, the thickness, and drying and curing conditions.

Generally, polyimide can be produced by reacting tetracarboxylic dianhydride and diamine compound in a solvent, and heating and ring-closing after producing polyamic acid. For example, approximately equimolar tetracarboxylic dianhydride and a diamine compound are dissolved in an organic solvent, stirred at a temperature in the range of 0° C. to 100° C. for 30 minutes to 24 hours to perform a polymerization reaction, whereby the Polyamic acid is obtained as a polyimide precursor. During the reaction, the reaction components are dissolved so that the generated precursor is within the range of 5% by weight to 30% by weight, more preferably within the range of 10% by weight to 20% by weight, in the organic solvent. Examples of the organic solvent used in the polymerization reaction include: N,N-dimethylformamide (N,N-dimethyl formamide, DMF), N,N-dimethylacetamide (N,N-dimethyl acetamide, DMAc), N,N-diethylacetamide, N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), 2-butanone, dimethylsulfoxide (Dimethyl sulfoxide, DMSO), hexamethylphosphamide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diglyme, triethylene glycol Methyl ether, cresol, etc. These solvents may be used in combination of two or more, and further aromatic hydrocarbons such as xylene and toluene may also be used in combination. In addition, the amount of the organic solvent used is not particularly limited, but it is preferably adjusted so that the concentration of the polyamic acid solution obtained by the polymerization reaction becomes about 5% by weight to 30% by weight. use.

The synthesized polyamic acid is usually advantageously used as a reaction solvent solution, but it may be concentrated, diluted or replaced with other organic solvents if necessary. In addition, polyamic acid is generally excellent in solvent solubility, so it can be used advantageously. The viscosity of the solution of polyamide acid is preferably in the range of 500 cps to 100,000 cps. If it deviates from the above-mentioned range, defects such as thickness variation and streaks are likely to occur in the film at the time of coating operation with a coater or the like. The method of imidizing the polyamide is not particularly limited, and for example, heat treatment in which the solvent is heated at a temperature in the range of 80°C to 400°C for 1 hour to 24 hours can be preferably used. .

Polyimide is obtained by imidizing the above-mentioned polyamic acid, and is produced by reacting a specific acid anhydride and a diamine compound. Therefore, by describing the acid anhydride and the diamine compound, the first Specific examples of the non-thermoplastic polyimide of the embodiment, the second embodiment or the third embodiment, and the thermoplastic polyimide of the first embodiment or the second embodiment are understood.

＜Non-thermoplastic polyimide＞ In the polyimide film of the first embodiment, the second embodiment, or the third embodiment, the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer contains tetracarboxylic acid residues and diamine residues. . In addition, in this invention, a tetracarboxylic-acid residue shows the tetravalent group derived from tetracarboxylic dianhydride, and a diamine residue shows the divalent group derived from a diamine compound. The polyimide film of the first embodiment, the second embodiment, or the third embodiment preferably includes an aromatic tetracarboxylic acid residue derived from an aromatic tetracarboxylic dianhydride and an aromatic diamine derived polyimide film. aromatic diamine residues.

(tetracarboxylic acid residue) In the first embodiment, the second embodiment or the third embodiment, containing 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 1,4-phenylene bis( Tetracarboxylic acid residues derived from at least one of tricarboxylic acid dianhydride (TAHQ) and pyromellitic dianhydride (PMDA) and 2,3,6,7-naphthalene tetracarboxylic dianhydride (NTCDA ) as a tetracarboxylic acid residue contained in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer.

Tetracarboxylic acid residues derived from BPDA (hereinafter also referred to as "BPDA residues") and tetracarboxylic acid residues derived from TAHQ (hereinafter also referred to as "TAHQ residues") easily form polymers The ordered structure can reduce the dielectric tangent or hygroscopicity by inhibiting the movement of molecules. However, on the other hand, BPDA residues can impart self-supporting properties to the gel film of polyamic acid, which is a precursor of polyimide, but appear to increase the CTE after imidization and lower the glass transition temperature. And the tendency to reduce heat resistance.

From this point of view, in the polyimide film of the first embodiment, the second embodiment, or the third embodiment, the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer has a higher proportion than the tetracarboxylic acid residue. 100 mol parts of BPDA residues and TAHQ residues are contained within a range of preferably 30 mol parts or more and 60 mol parts or less in total, more preferably 40 mol parts or more and 50 mol parts or less. base control. If the total of BPDA residues and TAHQ residues is less than 30 mole parts, the formation of the ordered structure of the polymer becomes insufficient, the moisture absorption resistance decreases, or the reduction of the dielectric tangent becomes insufficient. If it exceeds 60 If the molar portion is used, in addition to an increase in CTE or an increase in the amount of change in in-plane retardation (RO), there is a possibility that heat resistance will decrease.

In addition, tetracarboxylic acid residues derived from pyromellitic dianhydride (hereinafter also referred to as "PMDA residues") and tetracarboxylic acid residues derived from 2,3,6,7-naphthalene tetracarboxylic dianhydride Acid residues (hereinafter, also referred to as “NTCDA residues”) have rigidity, and therefore are residues that improve in-plane alignment, lower CTE suppression, and play a role in RO control or glass transition temperature control. On the other hand, since the PMDA residue has a small molecular weight, if its amount becomes too much, the concentration of the imide group of the polymer becomes high, the polar group increases and the hygroscopicity becomes large, and due to the influence of moisture inside the molecular chain. Electric tangent increases. In addition, the NTCDA residue tends to increase the modulus of elasticity by easily making the film brittle due to the highly rigid naphthalene skeleton.

Therefore, in the first embodiment, the second embodiment, or the third embodiment, the total of the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer is preferable with respect to 100 mole parts of the tetracarboxylic acid residue. It is contained within the range of 40 mole parts to 70 mole parts, more preferably 50 mole parts to 60 mole parts, and more preferably 50 mole parts to 55 mole parts PMDA residues and NTCDA residues. If the total of PMDA residues and NTCDA residues is less than 40 molar parts, there is a possibility that the CTE increases or the heat resistance decreases, and if it exceeds 70 molar parts, the concentration of the imide group of the polymer becomes high, and the polar group Increase and low hygroscopicity may be impaired, the dielectric tangent may increase, or the film may become brittle and the self-supporting property of the film may decrease.

In addition, in the first embodiment, as specified in the condition (a-i), the total of at least one of BPDA residues and TAHQ residues and at least one of PMDA residues and NTCDA residues is relative to the tetracarboxylic acid residues 100 mole parts of 80 mole parts or more, preferably 90 mole parts or more.

In addition, in the first embodiment, as defined in the condition (a-i), the molar ratio of at least one of BPDA residues and TAHQ residues to at least one of PMDA residues and NTCDA residues {(BPDA residue+TAHQ residue)/(PMDA residue+NTCDA residue)} is set within the range of 0.6 to 1.3, preferably 0.7 to 1.3, more preferably 0.8 to 1.2 Within the range, control the CTE and the formation of the ordered structure of the polymer.

In the first embodiment, the second embodiment, or the third embodiment, PMDA and NTCDA have rigid skeletons, so compared with other common acid anhydride components, the in-plane alignment of molecules in polyimide can be controlled, and thermal expansion Coefficient of suppression (CTE) and glass transition temperature (Tg) enhancement effect. In addition, since BPDA and TAHQ have larger molecular weights than PMDA, the concentration of imide groups decreases due to an increase in the loading ratio, which is effective in reducing the dielectric tangent or the moisture absorption rate. On the other hand, when the loading ratio of BPDA and TAHQ increases, the in-plane alignment of molecules in polyimide decreases, leading to an increase in CTE. Furthermore, the formation of an ordered structure in the molecule is promoted, and the haze value increases. From this point of view, the total loading amount of PMDA and NTCDA can be within the range of 40 mole parts to 70 mole parts, preferably 50 mole parts relative to 100 mole parts of all the acid anhydride components of the raw material. It is in the range of ∼60 molar parts, more preferably in the range of 50 molar parts to 55 molar parts. If the total loading amount of PMDA and NTCDA is less than 40 mole parts with respect to 100 mole parts of all the acid anhydride components of the raw material, the in-plane alignment of the molecules will decrease, and it will be difficult to achieve a low CTE, and the Tg will also decrease. The resulting heat resistance or dimensional stability of the film during heating decreases. On the other hand, if the total charge of PMDA and NTCDA exceeds 70 molar parts, the moisture absorption rate will deteriorate due to the increase of the imide group concentration, or the modulus of elasticity will tend to increase.

In addition, BPDA and TAHQ have effects on the suppression of molecular motion or the reduction of the dielectric tangent and the reduction of the moisture absorption rate caused by the reduction of the concentration of imide groups, but they will cause the polyimide film after imidization to be damaged. Increased CTEs. From this point of view, the total charged amount of BPDA and TAHQ may be in the range of 30 to 60 mole parts, preferably 40 mole parts, with respect to 100 mole parts of all acid anhydride components of the raw material. It is in the range of ˜50 molar parts, more preferably in the range of 40 molar parts to 45 molar parts.

Tetracarboxylic acid residues other than the BPDA residue, TAHQ residue, PMDA residue, and NTCDA residue contained in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer include, for example, 3 ,3',4,4'-Diphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride , 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride or 3,3',4,4' -Benzophenone tetracarboxylic dianhydride, 2,3',3,4'-diphenylether tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, 3,3' ',4,4''-terphenyltetracarboxylic dianhydride, 2,3,3'',4''-terphenyltetracarboxylic dianhydride or 2,2'',3,3''- p-terphenyltetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-propane dianhydride or 2,2-bis(3,4-dicarboxyphenyl)-propane dianhydride, bis (2,3-dicarboxyphenyl)methane dianhydride or bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)pyridine dianhydride or bis(3,4- Dicarboxyphenyl) dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride or 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1 ,2,7,8-phenanthrene-tetracarboxylic dianhydride, 1,2,6,7-phenanthrene-tetracarboxylic dianhydride or 1,2,9,10-phenanthrene-tetracarboxylic dianhydride, 2,3 ,6,7-anthracene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)tetrafluoropropane dianhydride, 2,3,5,6-cyclohexane dianhydride, 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-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride 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-perylene-tetracarboxylic dianhydride, 3,4,9,10-perylene-tetracarboxylic dianhydride, 4,5,10,11-perylene-tetracarboxylic Carboxylic dianhydride 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- Tetracarboxylic acid residues derived from aromatic tetracarboxylic dianhydrides such as dicarboxyphenoxy)diphenylmethane dianhydride and ethylene glycol bis-trimellitic anhydride.

(diamine residue) In the first embodiment, the second embodiment, or the third embodiment, as the diamine residue contained in the non-thermoplastic polyimide layer constituting the non-thermoplastic polyimide layer, it is preferable to have the formula (A1) Diamine residues derived from the indicated diamine compounds.

[chemical 7]

In the formula (A1), the linking group X represents a single bond or -COO-, Y independently represents hydrogen, a monovalent hydrocarbon group or an alkoxy group with 1 to 3 carbons, n represents an integer of 0 to 2, and p and q independently Represents an integer from 0 to 4. Here, the term "independently" means that the plurality of linking groups X, the plurality of substituents Y, and the integers p and q in the formula (A1) may be the same or different. Furthermore, in the formula (A1), the hydrogen atoms in the two terminal amine groups may be substituted, for example, -NR ₃ R ₄ (here, R ₃ and R ₄ independently represent any substituents).

The diamine compound represented by the general formula (A1) (hereinafter, may be referred to as “diamine (A1)”) is an aromatic diamine having two benzene rings. Since diamine (A1) has a rigid structure, it has the effect of imparting an ordered structure to the entire polymer. Therefore, polyimide with low gas permeability and low hygroscopicity can be obtained, and the moisture inside the molecular chain can be reduced, so the dielectric tangent can be reduced. Here, the linking group X is preferably a single bond.

Examples of the diamine (A1) include 1,4-diaminobenzene (p-phenylenediamine (p-PDA)), 2,2'-dimethyl-4,4'-di Aminobiphenyl (2,2'-dimethyl-4,4'-diamino biphenyl, m-TB), 2,2'-n-propyl-4,4'-diaminobiphenyl (2,2'- n-propyl-4,4'-diamino biphenyl, m-NPB), 4-aminophenyl-4'-amino benzoate (4-aminophenyl-4'-amino benzoate, APAB), etc.

The non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer of the first embodiment or the second embodiment may contain preferably 80 mole parts or more, more preferably 100 mole parts of diamine residues. It is a diamine residue derived from diamine (A1) at least 85 mole parts. By using the diamine (A1) in an amount within the above range, it is easy to form an ordered structure for the entire polymer by utilizing the rigid structure derived from the monomer, and it is easy to obtain low air permeability, low hygroscopicity and low dielectric properties. Tangential non-thermoplastic polyimide.

In addition, in the first embodiment or the second embodiment, the diamine residue derived from the diamine (A1) is 80 mol parts with respect to 100 mol parts of the diamine residue in the non-thermoplastic polyimide. When it is within the range of 1 part or more and 85 mol parts or less, it is preferable to use 1,4-diamine as the diamine (A1) from the viewpoint of a more rigid structure with excellent in-plane alignment. Benzene.

In the first embodiment or the second embodiment, as other diamine residues contained in the non-thermoplastic polyimide layer constituting the non-thermoplastic polyimide layer, for example, 2,2-bis-[4- (3-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]pyridine, bis[4-(3-aminophenoxy)]biphenyl, bis [1-(3-aminophenoxy)]biphenyl, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl] Ether, bis[4-(3-aminophenoxy)]benzophenone, 9,9-bis[4-(3-aminophenoxy)phenyl] fennel, 2,2-bis-[ 4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis-[4-(3-aminophenoxy)phenyl]hexafluoropropane, 3,3'-dimethyl Base-4,4'-diaminobiphenyl, 4,4'-methylene di-o-toluidine, 4,4'-methylene di-2,6-xylidine, 4,4'- Methylene-2,6-diethylaniline, 3,3'-diaminodiphenylethane, 3,3'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 3,3''-diamino-p-terphenyl, 4,4'-[1,4-phenylenebis(1-methylethylene)]bisaniline, 4,4'-[1,3 -Phenylbis(1-methylethylene)]bisaniline, bis(p-aminocyclohexyl)methane, bis(p-β-amino-tert-butylphenyl)ether, bis(p- β-Methyl-δ-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-diaminotoluene Toluene-2,5-diamine, p-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-Diamino-1,3,4-oxadiazole, piperazine, 2'-methoxy-4,4'-diaminobenzaniline, 4,4'-diaminobenzene Formaniline, 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene, 6-amino-2-(4-aminophenoxy)benzoxazole and other aromatic Diamine residues derived from family diamine compounds, diamine residues derived from aliphatic diamine compounds such as dimer acid-type diamines where the two terminal carboxylic acid groups of dimer acid are substituted with primary aminomethyl or amine groups diamine residues.

In addition, in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer of the third embodiment, the diamine (A1) is as specified in the above-mentioned condition (c-i) relative to 100 moles of all the diamine components of the raw material. The ear part may be more than 70 molar parts, for example, within the range of 70-90 molar parts, preferably within the range of 80-90 molar parts. On the other hand, when the loading amount of diamine (A1) exceeds 90 mole parts, the elongation of a film may fall.

In addition, it is preferable to use at least one aromatic diamine selected from the group consisting of aromatic diamines represented by general formula (C1) to general formula (C4) as the non-thermoplastic polyimide used in the third embodiment. Diamine is used as the diamine component of the raw material. Since diamines (C1) to (C4) have bulky substituents or flexible sites, flexibility can be imparted to polyimide. Moreover, diamine (C1) - diamine (C4) can improve air permeability, and therefore have the effect of suppressing the foaming at the time of manufacture of a multilayer film and a metal tension laminated board. From this point of view, it is preferable to use diamine (C1) to diamine (C4 ) of one or more aromatic diamines. When the charged amount of diamine (C1) to diamine (C4) is less than 2 mole parts, foaming may occur when producing a multilayer film or a metal tension laminate. Moreover, when the loading amount of diamine (C1) - diamine (C4) exceeds 15 mole parts, the alignment property of a molecule will fall and it will become difficult to lower CTE.

[chemical 8]

In the formulas (C1) to (C4), R2 independently represents a monovalent hydrocarbon group, alkoxy group or alkylthio group with ₁ to 6 carbons, and the linking group A' independently represents a group selected from -O-, - The divalent group in SO ₂ -, -CH ₂ - or -C(CH ₃ ) ₂ - preferably represents a divalent group selected from -O-, -CH ₂ - or -C(CH ₃ ) ₂ - The linking group X1 independently represents -CH ₂ -, -O-CH ₂ -O-, -OC ₂ H ₄ -O-, -OC ₃ H ₆ -O-, -OC ₄ H ₈ -O-, - OC ₅ H ₁₀ -O-, -O-CH ₂ -C(CH ₃ ) ₂ -CH ₂ -O-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or -SO ₂ -, n ₃ independently represents an integer of 1 to 4, and n ₄ independently represents an integer of 0 to 4, but in formula (C3), the linking group A' does not contain -CH ₂ -, -C(CH ₃ ) ₂ -, In the case of -C(CF ₃ ) ₂ - or -SO ₂ -, any one of n ₄ is 1 or more. Wherein, in the case of n ₃ =0, the two amine groups in the formula (C1) are not in the para position. Here, the so-called "independently" refers to multiple linking groups A', multiple linking groups X1, and multiple substituents R2 in one or _two or more of the formulas (C1) to (C4) above. Or a plurality of n ₃ and n ₄ may be the same or different. Furthermore, in the formulas (C1) to (C4), the hydrogen atoms in the two terminal amine groups may be substituted, for example, -NR ₃ R ₄ (here, R ₃ and R ₄ are independently represents an arbitrary substituent such as an alkyl group).

Examples of the aromatic diamine represented by the general formula (C1) include 2,6-diamino-3,5-diethyltoluene, 2,4-diamino-3,5-diethyltoluene Wait.

Examples of the aromatic diamine represented by the general formula (C2) include 2,4-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, bis(4 -Amino-3-ethyl-5-methylphenyl)methane and the like.

Examples of the aromatic diamine represented by the general formula (C3) include: 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene, 1,4-bis[2- (4-aminophenyl)-2-propyl]benzene, 1,4-bis(4-aminophenoxy)-2,5-di-tert-butylbenzene, etc.

Examples of the aromatic diamine represented by the general formula (C4) include 2,2-bis[4-(4-aminophenoxy)phenyl]propane and the like.

As mentioned above, the non-thermoplastic polyimide constituting the polyimide film of the third embodiment may be 70 mole parts or more, preferably 70 mole parts to 100 mole parts of diamine residues. Contains residues derived from diamine (A1) in the range of 90 molar parts, and contains residues derived from diamine (C1) to diamine (C4) in the range of 2 to 15 molar parts Residues are controlled.

In the third embodiment, examples of other diamines that can be used as raw materials for polyimide include 2,2-bis-[4-(3-aminophenoxy)phenyl]propane, 2, 2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-trifluoro-4-aminophenoxy)phenyl]hexafluoropropane , 1,4-bis(4-aminophenoxy)2,3,6-trimethyl-benzene, 1,4-bis(4-aminophenoxymethyl)propane, 1,3-bis (4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4 -aminophenoxy)methane, 1,4-bis(4-aminophenoxy)ethane, 1,4-bis(4-aminophenoxy)propane, 1,4-bis(4- Aminophenoxy)butane, 1,4-bis(4-aminophenoxy)pentane, bis[4-(3-aminophenoxy)phenyl]pyridine, bis[4-(4 -aminophenoxy)phenyl]pyridine, bis[4-(3-aminophenoxy)]biphenyl, bis[1-(3-aminophenoxy)]biphenyl, bis[4- (3-aminophenoxy)phenyl]methane, 1,4-bis(4-aminophenoxy)2-phenyl-benzene, 1,4-bis(2-trifluoromethyl-4- Aminophenoxy)benzene, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)]benzophenone, 9,9-bis [4-(3-Aminophenoxy)phenyl]fennel, 2,2-bis-[4-(3-aminophenoxy)phenyl]hexafluoropropane, 3,3'-dimethyl -4,4'-diaminobiphenyl, 4,4'-methylenebis-o-toluidine, 4,4'-methylenebis-2,6-xylaniline, 4,4'- Methylene-2,6-diethylaniline, 3,3'-diaminodiphenylethane, 2-trifluoromethyl-4,4'-diaminodiphenylether, 2,2 '-Di-trifluoromethyl-4,4'-diaminodiphenyl ether, 3,3'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 3,3'' -Diamino-terphenyl, 4,4'-[1,4-Phenylbis(1-methylethylene)]bisaniline, 4,4'-[1,3-Phenylbis (1-methylethylene)]bisaniline, bis(p-aminocyclohexyl)methane, bis(p-β-amino-tert-butylphenyl)ether, bis(p-β-methyl- δ-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-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-di Amino-1,3,4-oxadiazole, piperazine, 2'-methoxy-4,4'-diaminobenzamide, 4,4'-diaminobenzamide and other aromatic family of diamine compounds.

In the third embodiment, by using BPDA, TAHQ, PMDA, and NTCDA as an acid anhydride component used as a raw material of polyimide, and diamine (A1) and diamine ( C1) to diamine (C4), the amount of residues derived from these raw material compounds can be controlled, so that the reduction of dielectric tangent and moisture absorption, and the suppression of foaming in the manufacture of multilayer films and metal tension laminates coexist. .

Regarding the polyimide film of the third embodiment, since low dielectric constant and low dielectric tangent and low hygroscopicity coexist, it is used, for example, as a matrix resin in an insulating resin layer of a copper tensioned laminate used as a raw material for FPC. better. In addition, since aromatic tetracarboxylic acid anhydride and aromatic diamine are used as the monomers used as raw materials for polyimide, it is difficult to cause the problem of dimensional change caused by heating, and it has flame retardancy, and there is no need to formulate flame retardant agent. Therefore, by using the polyimide film of the third embodiment and the copper laminated board using the same, it is possible to improve the reliability and yield of circuit boards such as FPC.

In the non-thermoplastic polyimide of the first embodiment, the second embodiment, or the third embodiment, by selecting the types of the tetracarboxylic acid residues and diamine residues, or using two or more tetracarboxylic acid residues, Residues or diamine residues can control the coefficient of thermal expansion, coefficient of storage elasticity, coefficient of tensile elasticity, etc. by molar ratio of each. In addition, in the case of non-thermoplastic polyimide, in the case of having a plurality of structural units of polyimide, it may exist in the form of a block or randomly, but in order to suppress the deviation of the in-plane retardation (RO) From a viewpoint, random existence is preferable.

Furthermore, in the first embodiment or the second embodiment, by making both the tetracarboxylic acid residues and the diamine residues contained in the non-thermoplastic polyimide an aromatic group, the polyimide can be improved. The dimensional accuracy of the film in a high-temperature environment and the reduction of the variation of the in-plane retardation (RO) are better.

In the first embodiment or the second embodiment, the imide group concentration of the non-thermoplastic polyimide is preferably 33% by weight or less. Here, the "imide group concentration" means a value obtained by dividing the molecular weight of the imide group (-(CO) ₂ -N-) in the polyimide by the molecular weight of the entire structure of the polyimide. If the imide group concentration exceeds 33% by weight, the molecular weight of the resin itself decreases, and the low hygroscopicity also deteriorates due to the increase of polar groups. In the first embodiment or the second embodiment, the alignment of molecules in the non-thermoplastic polyimide is controlled by selecting the combination of the acid anhydride and the diamine compound, thereby suppressing the CTE accompanying the decrease in the concentration of the imide group The increase ensures low moisture absorption.

In the first embodiment, the second embodiment, or the third embodiment, the weight average molecular weight of the non-thermoplastic polyimide is, for example, preferably within a range of 10,000 to 400,000, more preferably within a range of 50,000 to 350,000. When the weight average molecular weight is less than 10,000, the strength of the film tends to decrease and tend to become brittle. On the other hand, if the weight-average molecular weight exceeds 400,000, the viscosity tends to increase excessively, and defects such as film thickness unevenness and streaks tend to easily occur during coating operations.

＜Thermoplastic polyimide＞ In the polyimide film of the first embodiment or the second embodiment, the thermoplastic polyimide constituting the thermoplastic polyimide layer is one containing tetracarboxylic acid residues and diamine residues, preferably containing aromatic An aromatic tetracarboxylic acid residue derived from an aromatic tetracarboxylic dianhydride and an aromatic diamine residue derived from an aromatic diamine.

(tetracarboxylic acid residue) As the tetracarboxylic acid residue used in the thermoplastic polyimide constituting the thermoplastic polyimide layer, the same as the tetracarboxylic acid residue in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer can be used. The bases are the same as those exemplified.

(diamine residue) The diamine residue contained in the thermoplastic polyimide constituting the thermoplastic polyimide layer is preferably a diamine residue derived from a diamine compound represented by general formula (B1) to general formula (B7). base.

[chemical 9]

In formulas (B1) to (B7), R ₁ independently represents a monovalent hydrocarbon group or alkoxy group with 1 to 6 carbons, and the linking group A independently represents a group selected from -O-, -S-, -CO-, A divalent group in -SO-, -SO ₂ -, -COO-, -CH ₂ -, -C(CH ₃ ) ₂ -, -NH- or -CONH-, n ₁ independently represents an integer of 0 to 4 . Among them, the duplicates of formula (B2) are removed from formula (B3), and the duplicates of formula (B4) are removed from formula (B5). Here, the so-called "independently" means that in the formula (B1) to the formula (B7) in one formula or two or more formulas, multiple linking groups A, multiple R ₁ or multiple n ₁ may be the same or different . Furthermore, in the formulas (B1) to (B7), the hydrogen atoms in the two terminal amine groups may be substituted, for example, -NR ₃ R ₄ (here, R ₃ and R ₄ are independently represents an arbitrary substituent such as an alkyl group).

The diamine represented by formula (B1) (hereinafter, sometimes referred to as "diamine (B1)") is an aromatic diamine having two benzene rings. It is considered that the diamine (B1) is in the meta-position between the amine group directly bonded to at least one benzene ring and the divalent linking group A, and the polyimide molecular chain has increased degrees of freedom and high flexibility, Contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, by using diamine (B1), the thermoplasticity of polyimide improves. Here, the linking group A is preferably -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -SO ₂ -, -S-.

Examples of the diamine (B1) include: 3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenylpropane, 3,3'-diaminodiphenylsulfide , 3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl Methane, 3,4'-diaminodiphenylpropane, 3,4'-diaminodiphenylsulfide, 3,3'-diaminobenzophenone, (3,3'-bis Amino) diphenylamine, etc.

The diamine represented by the formula (B2) (hereinafter, may be referred to as “diamine (B2)”) is an aromatic diamine having three benzene rings. It is considered that the diamine (B2) is in the meta-position between the amine group directly bonded to at least one benzene ring and the divalent linking group A, and the polyimide molecular chain has increased degrees of freedom and high flexibility, Contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, by using diamine (B2), the thermoplasticity of polyimide improves. Here, the linking group A is preferably -O-.

Examples of diamines (B2) include: 1,4-bis(3-aminophenoxy)benzene, 3-[4-(4-aminophenoxy)phenoxy]aniline, 3-[ 3-(4-Aminophenoxy)phenoxy]aniline, etc.

The diamine represented by the formula (B3) (hereinafter, sometimes referred to as "diamine (B3)") is an aromatic diamine having three benzene rings. It is considered that the diamine (B3) is in the meta-position to each other through the two divalent linking groups A directly bonded to a benzene ring, and the polyimide molecular chain has an increased degree of freedom and high flexibility. Contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, by using diamine (B3), the thermoplasticity of polyimide improves. Here, the linking group A is preferably -O-.

Examples of the diamine (B3) include: 1,3-bis(4-aminophenoxy)benzene (1,3-Bis(4-aminophenoxy)benzene, TPE-R), 1,3-bis( 3-aminophenoxy)benzene (1,3-Bis(3-aminophenoxy)benzene, APB), 4,4'-[2-methyl-(1,3-phenylene)dioxy]bis Aniline, 4,4'-[4-methyl-(1,3-phenylene)dioxy]bisaniline, 4,4'-[5-methyl-(1,3-phenylene)bis Oxygen] dianiline, etc.

The diamine represented by the formula (B4) (hereinafter, may be referred to as "diamine (B4)") is an aromatic diamine having four benzene rings. It is believed that the diamine (B4) has high flexibility due to the fact that the amine group directly bonded to at least one benzene ring is in the meta-position with the divalent linking group A, which contributes to the flexibility of the polyimide molecular chain improvement. Therefore, by using diamine (B4), the thermoplasticity of polyimide improves. Here, the linking group A is preferably -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -SO ₂ -, -CO-, -CONH-.

Examples of the diamine (B4) include: bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]propane, bis[4- (3-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]phenone, bis[4-(3-aminophenoxy)]benzophenone , Bis[4,4'-(3-aminophenoxy)]benzylaniline, etc.

The diamine represented by the formula (B5) (hereinafter, may be referred to as "diamine (B5)") is an aromatic diamine having four benzene rings. It is considered that the diamine (B5) is in the meta-position with two divalent linking groups A directly bonded to at least one benzene ring, and the polyimide molecular chain has increased degrees of freedom and high flexibility, Contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, by using diamine (B5), the thermoplasticity of polyimide improves. Here, the linking group A is preferably -O-.

Examples of the diamine (B5) include 4-[3-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline, 4,4'-[oxybis(3,1- Extended phenoxy)] dianiline, etc.

The diamine represented by the formula (B6) (hereinafter, may be referred to as "diamine (B6)") is an aromatic diamine having four benzene rings. It is considered that the diamine (B6) has high flexibility by having at least two ether bonds, and contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, by using diamine (B6), the thermoplasticity of polyimide improves. Here, the linking group A is preferably -C(CH ₃ ) ₂ -, -O-, -SO ₂ -, -CO-.

Examples of diamines (B6) include 2,2-bis[4-(4-aminophenoxy)phenyl]propane (2,2-Bis[4-(4-aminophenoxy)phenyl]propane, BAPP), bis[4-(4-aminophenoxy)phenyl]ether (Bis[4-(4-aminophenoxy)phenyl]ether, BAPE), bis[4-(4-aminophenoxy) Phenyl]sulfone (Bis[4-(4-aminophenoxy)phenyl]sulfone, BAPS), bis[4-(4-aminophenoxy)phenyl]ketone (Bis[4-(4-aminophenoxy)phenyl] ketone, BAPK), etc.

The diamine represented by formula (B7) (hereinafter, sometimes referred to as "diamine (B7)") is an aromatic diamine having four benzene rings. Since the diamine (B7) has a highly flexible divalent linking group A on both sides of the diphenyl skeleton, it is considered that it contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, by using diamine (B7), the thermoplasticity of polyimide improves. Here, the linking group A is preferably -O-.

Examples of diamine (B7) include bis[4-(3-aminophenoxy)]biphenyl, bis[4-(4-aminophenoxy)]biphenyl, and the like.

In the first embodiment or the second embodiment, the amount of thermoplastic polyimide constituting the thermoplastic polyimide layer is 70 mole parts or more, preferably 70 mole parts relative to 100 mole parts of diamine residues. Contains at least one diamine compound selected from diamine (B1) to diamine (B7) within the range of 99 mol parts or more, more preferably 80 mol parts or more and 95 mol parts or less Derivatized diamine residues. Diamine (B1) to diamine (B7) have a flexible molecular structure, so by using at least one diamine compound selected from these compounds in an amount within the above-mentioned range, the polyimide can be improved. Molecular chain flexibility, and impart thermoplasticity. If the total amount of diamine (B1) to diamine (B7) is less than 70 mol parts with respect to 100 mol parts of all diamine components, the flexibility of the polyimide resin is insufficient and sufficient thermoplasticity cannot be obtained. .

Moreover, as a diamine residue contained in the thermoplastic polyimide which comprises a thermoplastic polyimide layer, the diamine residue derived from the diamine compound represented by General formula (A1) is also preferable. The diamine compound [diamine (A1)] represented by the formula (A1) is as described in the description of the non-thermoplastic polyimide. Diamine (A1) has a rigid structure and has the effect of imparting an ordered structure to the entire polymer, so it can reduce the dielectric tangent or hygroscopicity by inhibiting the movement of molecules. Furthermore, by using it as a raw material for thermoplastic polyimide, polyimide having low air permeability and excellent long-term heat-resistant adhesion can be obtained.

In the first embodiment or the second embodiment, the amount of thermoplastic polyimide constituting the thermoplastic polyimide layer can be within the range of preferably 1 mole part or more and 30 mole parts or less, more preferably 5 mole parts The diamine residue derived from diamine (A1) is contained in the range of 20 mole parts or more and 20 mole parts or less. By using the diamine (A1) in an amount within the above range, the polymer as a whole forms an ordered structure by utilizing the rigid structure derived from the monomer, so that it is thermoplastic and has low air permeability and hygroscopicity, and long-term heat resistance can be obtained. Polyimide with excellent adhesion.

The thermoplastic polyimide constituting the thermoplastic polyimide layer may include those derived from diamine compounds other than diamine (A1), diamine (B1) to diamine (B7) within the range that does not impair the effect of the invention. of diamine residues.

In thermoplastic polyimides, by selecting the types of the tetracarboxylic acid residues and diamine residues, or the respective molar ratios when two or more tetracarboxylic acid residues or diamine residues are used, it is possible to control Coefficient of thermal expansion, tensile modulus of elasticity, glass transition temperature, etc. In addition, in thermoplastic polyimide, when having a plurality of structural units of polyimide, it may exist in the form of a block or may exist randomly, but it is preferably present randomly.

Furthermore, in the first embodiment or the second embodiment, by making both the tetracarboxylic acid residue and the diamine residue contained in the thermoplastic polyimide an aromatic group, the polyimide film can be improved. Dimensional accuracy in high temperature environment, and suppress the variation of in-plane retardation (RO).

The imide group concentration of the thermoplastic polyimide is preferably 33% by weight or less. Here, the "imide group concentration" means a value obtained by dividing the molecular weight of the imide group (-(CO) ₂ -N-) in the polyimide by the molecular weight of the entire structure of the polyimide. If the imide group concentration exceeds 33% by weight, the molecular weight of the resin itself decreases, and the low hygroscopicity also deteriorates due to the increase of polar groups. In the first embodiment or the second embodiment, by selecting the combination of the above-mentioned diamine compounds, the orientation of molecules in the thermoplastic polyimide is controlled, thereby suppressing an increase in CTE accompanying a decrease in the concentration of imide groups, Ensure low moisture absorption.

The weight average molecular weight of the thermoplastic polyimide is, for example, preferably within a range of 10,000 to 400,000, more preferably within a range of 50,000 to 350,000. When the weight average molecular weight is less than 10,000, the strength of the film tends to decrease and tend to become brittle. On the other hand, if the weight-average molecular weight exceeds 400,000, the viscosity tends to increase excessively, and defects such as film thickness unevenness and streaks tend to easily occur during coating operations.

In the polyimide film of the first embodiment or the second embodiment, the thermoplastic polyimide constituting the thermoplastic polyimide layer can improve the adhesiveness with the copper foil. The glass transition temperature of the thermoplastic polyimide is in the range of not less than 200°C and not more than 350°C, preferably not less than 200°C and not more than 320°C.

The thermoplastic polyimide constituting the thermoplastic polyimide layer is, for example, an adhesive layer in an insulating resin of a circuit board. Therefore, in order to suppress diffusion of copper, a completely imidized structure is preferable. Among them, a part of the polyimide may also be an amide acid. The imidization rate is measured using a Fourier transform infrared spectrophotometer (commercially available: FT/IR620 manufactured by JASCO) and using a once-reflection attenuated total reflectance (Attenuated Total Reflectance, ATR) method to measure the polyimide film. The infrared absorption spectrum of , based on the benzene ring absorber around 1015 cm ^-1 , was calculated from the absorbance derived from the C=O stretching of the imide group at 1780 cm ^-1 .

<Morphology of polyimide film> The polyimide film of the first embodiment, the second embodiment, or the third embodiment is not particularly limited as long as it satisfies the above conditions, and may be a film (sheet) made of an insulating resin, or may be laminated on A film of an insulating resin in a state on a substrate such as a resin sheet such as a copper foil, a glass plate, a polyimide film, a polyamide film, or a polyester film.

＜Thickness＞ The thickness of the polyimide film of the first embodiment, the second embodiment, or the third embodiment can be set to a thickness within a predetermined range according to the purpose of use. The thickness of the polyimide film is, for example, preferably within a range of 8 μm to 50 μm, more preferably within a range of 11 μm to 26 μm. When the thickness of the polyimide film is less than the lower limit, electrical insulation may not be ensured, or handling may become difficult due to a reduction in handling properties. On the other hand, if the thickness of the polyimide film exceeds the above-mentioned upper limit, for example, it is necessary to control the production conditions for controlling the in-plane retardation (RO) with high precision, which causes problems such as a decrease in productivity.

In addition, in the polyimide film of the first embodiment or the second embodiment, the thickness ratio of the non-thermoplastic polyimide layer to the thermoplastic polyimide layer (non-thermoplastic polyimide layer/thermoplastic polyimide layer) can be in the range of 1.5 to 6.0. If the value of the ratio is less than 1.5, the non-thermoplastic polyimide layer becomes thinner relative to the entire polyimide film, so the deviation of the in-plane retardation (RO) tends to become large. If it exceeds 6.0, the thermoplastic polyimide layer becomes thinner. Since the amine layer becomes thinner, the bonding reliability between the polyimide film and the copper foil tends to decrease. The control of the in-plane retardation (RO) is related to the resin composition and thickness of each polyimide layer constituting the polyimide film. With regard to the thermoplastic polyimide layer composed of a resin that imparts adhesiveness, that is, has high thermal expansion or softening, the greater its thickness, the more it will significantly affect the RO value of the polyimide film. Therefore, the non-thermoplastic polyimide The ratio of the thickness of the amine layer is increased, and the ratio of the thickness of the thermoplastic polyimide layer is decreased, and the value of RO of the polyimide film is reduced from its deviation.

＜Film width＞ In the second embodiment, the polyimide film preferably has a film width of 490 mm to 1100 mm, Long strips with a length of 20 m or more. In the case of continuously producing the polyimide film according to the second embodiment, the effect of the invention becomes particularly remarkable as the film is wider in the width direction (hereinafter also referred to as the TD direction). In addition, when manufacturing the polyimide film of 2nd Embodiment continuously, the longitudinal direction of the long polyimide film is called MD direction.

＜Retardation in plane (RO)＞ Regarding the polyimide film according to the second embodiment, the in-plane retardation (RO) value is within the range of 5 nm to 50 nm, preferably 5 nm to 20 nm, more preferably 5 nm. nm to 15 nm or less. In addition, the RO deviation (ΔRO) in the TD direction is 10 nm or less, preferably 5 nm or less, and more preferably 3 nm or less. Since it is controlled within the above range, especially even for a film with a thickness of 25 μm or more, the size The precision is also high.

The polyimide film according to the second embodiment preferably has an in-plane retardation (RO) change of 20 nm or less before and after pressurization at a pressure of 340 MPa/m ² and a holding time of 15 minutes in an environment of a temperature of 320°C. 10 nm or less, more preferably 5 nm or less. Even if the polyimide film of the second embodiment is at a temperature exceeding the glass transition temperature of the polyimide constituting the thermoplastic polyimide layer, the amount of change in RO is controlled to be below the upper limit. Before and after the step of bonding the polyimide film and the copper foil according to the second embodiment by thermal lamination, RO hardly changes, so it becomes a polyimide film excellent in dimensional stability.

＜Coefficient of thermal expansion＞ When the polyimide film of the first embodiment or the second embodiment is used, for example, as an insulating layer of a circuit board, in order to prevent the generation of warpage or the decline of dimensional stability, the conditions (a-iii) ) or condition (b-i), it is important that the coefficient of thermal expansion (CTE) of the film as a whole is in the range of 10 ppm/K to 30 ppm/K, preferably 10 ppm/K to 25 ppm/K In the range of, more preferably in the range of 10 ppm/K～20 ppm/K. When the CTE is less than 10 ppm/K or exceeds 30 ppm/K, warping occurs or dimensional stability decreases. In addition, the coefficient of thermal expansion (CTE) of the polyimide film of 3rd Embodiment is also the same as 1st Embodiment or 2nd Embodiment.

＜Dielectric tangent＞ The polyimide film of the first embodiment, the second embodiment, or the third embodiment is applied, for example, as an insulating layer of a circuit board as specified in the above-mentioned condition (a-iv) or condition (c-iii). In the case of , in order to ensure impedance matching, the dielectric tangent ( Tanδ) may be 0.004 or less, more preferably 0.001 to 0.004, and still more preferably 0.002 to 0.003. In order to improve the dielectric characteristics of the circuit board, it is particularly important to control the dielectric tangent of the insulating layer, and by setting the dielectric tangent within the above-mentioned range, the effect of reducing the transmission loss is increased. Therefore, when the polyimide film is applied, for example, as an insulating layer of a high-frequency circuit board, transmission loss can be efficiently reduced. If the dielectric tangent of the insulating layer at 10 GHz exceeds 0.004, when used in circuit boards such as FPC, problems such as loss of electrical signals are likely to occur on the transmission path of high-frequency signals. The lower limit value of the dielectric tangent at 10 GHz of the insulating layer is not particularly limited, but it takes into consideration physical property control when polyimide is applied as an insulating layer of a circuit board.

＜Dielectric constant＞ When the polyimide film of the first embodiment, the second embodiment, or the third embodiment is applied, for example, as an insulating layer of a circuit board, in order to ensure impedance matching, as the entire insulating layer, it is preferable to use a frequency of 10 GHz. The lower dielectric constant is 4.0 or less. If the dielectric constant of the insulating layer at 10 GHz exceeds 4.0, when used in circuit boards such as FPC, the dielectric loss of the insulating layer will deteriorate, and electrical signal loss will easily occur on the transmission path of high-frequency signals and other bad situations.

＜Moisture absorption rate＞ Regarding the polyimide film of the first embodiment or the second embodiment, in order to reduce the influence of humidity when used in circuit boards such as FPC, the moisture absorption rate at 23°C and 50%RH is preferable 0.7% by weight or less. If the moisture absorption rate of the polyimide film exceeds 0.7% by weight, when it is used in circuit boards such as FPC, it is easily affected by humidity, and problems such as fluctuations in the transmission speed of high-frequency signals are likely to occur. That is, if the moisture absorption rate of the polyimide film exceeds the above-mentioned range, it is easy to absorb water with a high dielectric constant and a high dielectric tangent, thus causing an increase in the dielectric constant and a dielectric tangent, and it is easy to transmit high-frequency signals. Unfavorable conditions such as loss of electrical signals on the path.

In addition, considering the influence on the dimensional stability and dielectric properties of the polyimide film, the polyimide film of the third embodiment is preferably moisture-absorbing when the humidity is adjusted for 24 hours at 23°C and 50%RH. The rate is 0.65% by weight or less. When the moisture absorption rate exceeds 0.65% by weight, the dimensional stability and dielectric properties of the polyimide film may deteriorate. Regarding the fact that the moisture absorption rate is 0.65% by weight or less, it is considered that the concentration of polar groups in polyimide is low, and it is easy to form an ordered structure of polymer chains, so it is relatively low for the improvement of dimensional stability or dielectric properties. good. However, since the haze value tends to become high with formation of the ordered structure of a polymer chain as a moisture absorption rate becomes low, it is preferable to also consider the haze value mentioned later.

＜Modulus of Tensile Elasticity＞ In addition, the tensile modulus of the polyimide film according to the second embodiment is preferably within a range of 3.0 GPa to 10.0 GPa, and may be within a range of 4.5 GPa to 8.0 GPa. If the tensile modulus of the polyimide film is less than 3.0 GPa, the strength of the polyimide itself decreases, which may cause handling problems such as cracking of the film when the copper tension laminate is processed into a circuit board. Conversely, when the tensile modulus of the polyimide film exceeds 10.0 GPa, the rigidity against bending of the copper tension laminate increases, and as a result, the bending stress applied to the copper wiring when the copper tension laminate is bent increases, And the bending resistance is reduced. By setting the tensile modulus of the polyimide film within the above range, the strength and flexibility of the polyimide film can be ensured.

＜Glass transition temperature＞ The polyimide film of the third embodiment has a glass transition temperature of 300° C. or higher as specified in the condition (c-ii). If the glass transition temperature is less than 300°C, expansion of the film or peeling from the wiring is likely to occur when manufacturing a copper-clad plate (CCL) or FPC using the polyimide film of the third embodiment. question. On the other hand, the solder heat resistance and dimensional stability of a polyimide film improve by making a glass transition temperature 300 degreeC or more.

＜Haze value＞ In addition, when the polyimide film of the third embodiment is processed into a polyimide film having a thickness of 25 μm as follows, the haze (HAZE) based on Japanese Industrial Standards (Japanese Industrial Standards, JIS) K 7136 ) value in the range of 62% to 75%, the polyimide film is removed by etching. A solution of polyamic acid as a precursor of polyimide is applied to the ten-point average roughness (Rz ) is obtained from the copper foil of a laminate formed by imidization on a copper foil of 0.6 μm. When the haze value exceeds 75%, the visibility through the polyimide film of the third embodiment decreases. Therefore, in the process of photolithography of a copper laminate (CCL) obtained using a polyimide film, or in the process of mounting an FPC (flexible printed circuit board) using the CCL, there are counter parts placed on the CCL. When the visibility of the alignment mark is lowered, alignment with the alignment mark becomes difficult, and practicality is reduced. On the other hand, if the haze value is less than 62%, the visibility becomes high and the formation of an ordered structure of polyimide polymer chains does not advance, which may impair hygroscopic properties or dielectric properties. In the third embodiment, in order to achieve low dielectric tangent and low moisture absorption due to the formation of the ordered structure, and maintain visibility, the preferred value of the haze value is set to 62% to 75%. %In the range.

＜Film elongation＞ The polyimide film of the third embodiment preferably has a film elongation of 30% or more. When the polyimide film of the third embodiment is used, for example, as an insulating layer of an FPC, it needs to be bent and accommodated in a small space inside a housing of a mobile device or the like. In the above usage form, if the elongation of the film is low, it will cause disconnection of wiring. Therefore, regarding the polyimide film of the third embodiment, a preferable film elongation is set to be 30% or more.

＜Filling＞ The polyimide film of the first embodiment, the second embodiment, or the third embodiment may optionally contain an inorganic filler in the non-thermoplastic polyimide layer or the thermoplastic polyimide layer. Specifically, for example, silicon dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride, etc. are mentioned. These may be used alone or in combination of two or more.

[Production method] As an aspect of the production method of the polyimide film of the first embodiment, the second embodiment, or the third embodiment, for example, there are [1] after coating the polyamide acid solution on the support substrate and drying it, A method for producing a polyimide film by imidization; [2] After coating a polyamic acid solution on a support substrate and drying it, the gel film of the polyamide acid is peeled off from the support substrate, and carried out A method of producing a polyimide film by imidization. In addition, since the polyimide film of the first embodiment or the second embodiment is a polyimide film including a multilayer polyimide layer, as an aspect of its production method, for example, [3] repeating multiple A method in which a polyamic acid solution is coated on a support substrate and dried, and then imidized (hereinafter, casting method); A method in which layers are laminated, coated and dried, followed by imidization (hereinafter, multilayer extrusion method), etc. The same applies to the case where the polyimide film of the third embodiment is applied as one layer of a multilayer polyimide film including a multilayer polyimide layer. The method of coating the polyimide solution (or polyamic acid solution) on the base material is not particularly limited, for example, it can be applied using a coating machine such as a chipped wheel, a mold, a doctor blade, or a die lip. When forming multiple polyimide layers, it is preferable to repeat the operation of applying polyimide solution (or polyamic acid solution) on the substrate and drying.

The method of [1] may include, for example, the following steps 1a to 1c: (1a) a step of coating a polyamic acid solution on a support substrate and drying it; (1b) A step of forming a polyimide layer by heat-treating and imidizing polyamic acid on the support substrate; (1c) A step of obtaining a polyimide membrane by separating the support substrate from the polyimide layer.

The method of [2] may include, for example, the following steps 2a to 2c: (2a) a step of coating a polyamide acid solution on a support substrate and drying it; (2b) a step of separating the support substrate from the polyamide gel film; (2c) A step of obtaining a polyimide membrane by heat-treating and imidizing a gel membrane of polyamic acid.

Regarding the method of [3], in addition to repeating Step 1a or Step 2a multiple times in the method of [1] or [2] to form a laminated structure of polyamic acid on the support substrate , can be implemented in the same manner as the method of [1] or [2].

Regarding the method of [4], except that in step 1a of the method of [1] or step 2a of the method of [2], the laminated structure of polyamic acid is coated simultaneously by multi-layer extrusion and Except drying, it can carry out similarly to the method of the said [1] or the method of [2].

In the polyimide film produced in the first embodiment, the second embodiment, or the third embodiment, it is preferable that imidization of polyamic acid is completed on a support substrate. Since the resin layer of polyamic acid is imidized while being fixed on the support substrate, the stretching and contraction of the polyimide layer during the imidization process can be suppressed and the polyimide film can be maintained. Thickness or dimensional accuracy. In addition, when the polyimide film of the third embodiment is applied as one layer of a multilayer polyimide film including a multilayer polyimide layer, at a temperature ranging from, for example, 120° C. to 360° C. The heat treatment for imidization is carried out step by step under the temperature, and the heat treatment time is controlled to be more than 5 minutes, preferably in the range of 10 minutes to 20 minutes, so that foaming can be effectively suppressed and polyimidization can be prevented. Defects such as swelling of the amine layer.

Regarding the polyimide film in which the imidization of polyamic acid is completed on the support substrate, by the tension applied to the polyimide film when the polyimide film is separated from the support substrate, or for example The polyimide film stretches due to stress on the polyimide film generated during peeling using a blade or the like, and variation in the in-plane retardation (RO) of the polyimide film tends to occur. In particular, regarding the polyimide film of the second embodiment, any of the polyimides constituting the non-thermoplastic polyimide layer and the thermoplastic polyimide layer can easily form an ordered structure, so by making The stress required for peeling is dispersed in each layer of the polyimide membrane, and RO can be controlled.

In addition, the in-plane retardation (RO) can be controlled even by the method of separating the gel film of polyamic acid on the support substrate, and simultaneously or continuously stretching the polyamide with uniaxial stretching or biaxial stretching. The gel film of amide acid is imidized. At this time, in order to control RO more precisely, it is preferable to appropriately adjust the conditions such as the temperature increase rate during stretching operation and imidization, the completion temperature of imidization, and the load.

[copper tension laminate] The copper tensioned laminate of the first embodiment, the second embodiment, or the third embodiment includes an insulating layer, and copper foil is provided on at least one surface of the insulating layer, and only a part or the whole of the insulating layer is used in the first embodiment. , The polyimide film of the second embodiment or the third embodiment may be formed. In addition, in order to improve the adhesion between the insulating layer and the copper foil, the layer in the insulating layer that is in contact with the copper foil is preferably a thermoplastic polyimide layer. Therefore, the polyimide film of the third embodiment is preferably used as a copper tension laminate in a laminated state with thermoplastic polyimide. The copper foil is provided on one or both sides of the insulating layer. That is, the copper tension laminated board of the first embodiment, the second embodiment, or the third embodiment may be a single-sided copper tension laminate (single-sided CCL), or may be a double-sided copper tension laminate (double-sided CCL). In the case of single-sided CCL, the copper foil laminated on one side of the insulating layer is referred to as the "first copper foil layer" in the present invention. In the case of a double-sided CCL, the copper foil laminated on one side of the insulating layer is referred to as the "first copper foil layer" of the present invention, and in the insulating layer, the surface on which the first copper foil is laminated is The copper foil on the surface on the opposite side is referred to as the "second copper foil layer" of the present invention. The copper laminated board of 1st Embodiment, 2nd Embodiment, or 3rd Embodiment etches copper foil etc., performs wiring circuit processing, forms copper wiring, and uses it as FPC.

Copper tension laminated boards can be produced, for example, by preparing a resin film composed of the polyimide film of the first embodiment, the second embodiment, or the third embodiment, sputtering a metal thereon to form a seed layer Thereafter, a copper foil layer is formed, for example, by copper plating.

In addition, the copper tension laminated board can also be produced by preparing a resin film composed of the polyimide film of the first embodiment, the second embodiment, or the third embodiment, and applying a method such as thermocompression bonding to the resin film. Laminated copper foil.

Furthermore, the copper tension laminate can also be produced by casting a coating solution containing polyamic acid as a precursor of polyimide onto a copper foil, drying it to form a coating film, and then performing heat treatment and imidization to form a polyimide layer.

＜1st Copper Foil Layer＞ In the copper tensioned laminate of the first embodiment, the second embodiment, or the third embodiment, the copper foil used for the first copper foil layer (hereinafter, may be described as "first copper foil") is not particularly limited, For example, rolled copper foil or electrolytic copper foil may be used. As the first copper foil, a commercially available copper foil can be used.

In the first embodiment, the second embodiment, or the third embodiment, the thickness of the first copper foil is preferably 18 μm or less, more preferably within a range of 6 μm to 13 μm, and still more preferably 6 μm to 12 μm. within range. By setting the thickness of the first copper foil to 18 μm or less, preferably 13 μm or less, and more preferably 12 μm or less, the bendability of the copper tension laminate (or FPC) can be improved. Moreover, it is preferable that the lower limit of the thickness of the 1st copper foil shall be 6 micrometers from a viewpoint of production stability and handleability.

In addition, in the first embodiment, the second embodiment, or the third embodiment, the tensile modulus of the first copper foil is, for example, preferably within a range of 10 GPa to 35 GPa, more preferably within a range of 15 GPa to 25 GPa. Inside. When using rolled copper foil as the 1st copper foil, if it anneals by heat processing, flexibility will become high easily. Therefore, if the tensile modulus of copper foil is less than the lower limit value, the rigidity of the first copper foil itself will be lowered by heating in the step of forming an insulating layer on the elongated first copper foil. On the other hand, when the tensile modulus of elasticity exceeds the above-mentioned upper limit, a large bending stress is applied by copper wiring when FPC is bent, and the above-mentioned bending resistance decreases. Furthermore, the rolled copper foil tends to have a modulus of tensile elasticity that changes depending on the heat treatment conditions when the insulating layer is formed on the copper foil, the annealing treatment of the copper foil after the insulating layer is formed, or the like. Therefore, in the first embodiment, the second embodiment, or the third embodiment, in the finally obtained copper tension laminate, the tensile modulus of the first copper foil may be within the above range.

＜Second Copper Foil Layer＞ In the first embodiment, the second embodiment, or the third embodiment, the second copper foil layer is laminated on the surface of the insulating layer that is on the opposite side to the first copper foil layer. Although it does not specifically limit as copper foil (2nd copper foil) used for a 2nd copper foil layer, For example, it may be a rolled copper foil or an electrolytic copper foil. Moreover, you may use a commercially available copper foil as a 2nd copper foil. In addition, the thing similar to the 1st copper foil can also be used as a 2nd copper foil.

[circuit substrate] The copper tension laminated board of the first embodiment, the second embodiment, or the third embodiment is mainly useful as a circuit board material such as FPC. That is, the FPC which is one embodiment of the present invention can be manufactured by processing the copper foil of the copper laminated board of the first embodiment, the second embodiment, or the third embodiment into a pattern shape to form a wiring layer by a conventional method. . [Example]

Examples are shown below, and the features of the present invention will be described more specifically. However, the scope of the present invention is not limited to the examples. In addition, in the following examples, unless otherwise specified, various measurements and evaluations used the following.

[Measurement of viscosity] The viscosity at 25° C. was measured using an E-type viscometer (manufactured by Brookfield, trade name: DV-II+Pro). The rotational speed was set so that the torque became 10% to 90%, and after 2 minutes from the start of the measurement, the value when the viscosity was stable was read.

[Measurement of glass transition temperature (Tg)] Regarding the glass transition temperature, using a dynamic viscoelasticity measuring device (DMA: manufactured by UBM Corporation, trade name: E4000F), the temperature rise rate is 4°C/ The measurement was performed on a polyimide film having a size of 5 mm×20 mm at a frequency of 11 Hz, and the temperature at which the elastic coefficient change (tan δ) was maximum was defined as the glass transition temperature. In addition, the storage modulus of elasticity at 30°C measured using DMA is 1.0×10 ⁹ Pa or more and the storage modulus of elasticity at 280°C is less than 3.0×10 ⁸ Pa as "thermoplastic", and the temperature at 30°C is displayed. A storage modulus of 1.0×10 ⁹ Pa or more and a storage modulus of 3.0×10 ⁸ Pa or more at 280° C. were defined as “non-thermoplastic”.

[Measurement of Coefficient of Thermal Expansion (CTE)] Using a thermomechanical analyzer (manufactured by Bruker, trade name: 4000SA), while applying a load of 5.0 g to a polyimide film with a size of 3 mm×20 mm, the temperature was raised from 30°C at a constant rate. After raising the temperature to 265°C and maintaining the temperature for 10 minutes, cooling was performed at a rate of 5°C/min, and the average thermal expansion coefficient (thermal expansion coefficient) from 250°C to 100°C was obtained.

[Determination of moisture absorption rate] Two test pieces of polyimide film (width 4 cm x length 25 cm) were prepared and dried at 80°C for 1 hour. Immediately after drying, put it in a constant temperature and humidity room at 23°C/50%RH, let it stand for more than 24 hours, and use the following formula to calculate the weight change before and after. Moisture absorption rate (weight%)=[(weight after moisture absorption-weight after drying)/weight after drying]×100

[Measurement of dielectric constant and dielectric tangent] The dielectric constant and dielectric tangent of the resin sheet at a high frequency of 10 GHz were measured using a vector network analyzer (manufactured by Agilent, trade name E8363C) and a split dielectric resonator (SPDR resonator). In addition, the material used for a measurement is what was left to stand for 24 hours under conditions of temperature: 24 degreeC - 26 degreeC, and humidity: 45% - 55%.

[Calculation of imide group concentration] The value obtained by dividing the molecular weight of the imide group (—(CO) ₂ —N—) by the molecular weight of the entire polyimide structure was defined as the imide group concentration.

[Measurement of Surface Roughness of Copper Foil] Regarding the surface roughness of the copper foil, an atomic force microscope (Atomic Force Microscope, AFM) (manufactured by Bruker AXS (Bruker AXS), trade name: Dimension Icon SPM), a probe (Bruker AXS ( Bruker AXS) company, trade name: TESPA (NCHV), tip curvature radius of 10 nm, spring constant of 42 N/m), using tapping mode (Tapping Mode), on the copper foil surface 80 μm × 80 μm The range is measured, and the ten-point average roughness (Rz) is obtained.

[Measurement of Peel Strength] The copper foil on both sides of the thermocompression bonding side and the casting side of the double-sided copper laminate (copper foil/resin layer/copper foil) is circuit-processed to a width of 0.8 mm (the copper foils on both sides are at the same position After wiring processing), it was cut into width: 8 cm x length: 4 cm, and a measurement sample was prepared. The peel strength of the casting side and the thermocompression bonding side of the sample was measured using a Tensilon Tester (manufactured by Toyo Seiki Seisakusho, trade name: Strograph VE-1D), by double-sided Fix the copper foil surface on the thermocompression bonding side or the casting side of the measurement sample to an aluminum plate with tape, and peel off the other copper foil at a speed of 50 mm/min in a 90° direction, and obtain the time when 10 mm is peeled off from the resin layer. median strength. At this time, the peel strength is ◎ (excellent) if it is 1.0 kN/m or more, ○ (good) if it is 0.7 kN/m or more and less than 1.0 kN/m, and 0.4 kN/m or more and less than 0.7 kN /m is defined as Δ (pass), and those less than 0.4 kN/m is defined as × (fail).

[Measurement of in-plane retardation (RO)] The in-plane retardation (RO) was obtained by using a birefringence meter (manufactured by photonic-lattice, trade name: Wide Range Birefringence Evaluation System WPA-100) to obtain polyimide Retardation in the in-plane direction of the film. The measurement wavelength is 543 nm.

[Measurement of haze value] The haze value was measured using a haze measuring device (nephelometer: manufactured by Nippon Denshoku Kogyo Co., Ltd., trade name: NDH5000), and the measurement method described in JIS K 7136 was used to measure the 5 cm × 5 cm size poly imide membrane.

[Measurement of film elongation] Regarding the polyimide film cut into a width of 12.7 mm×length of 127 mm, a tensile test was performed at 50 mm/min using a tension tester (Tensilon manufactured by Orientec) , and the film elongation at 25°C was obtained.

Abbreviations used in Examples and Reference Examples represent the following compounds. BPDA: 3,3',4,4'-Biphenyltetracarboxylic dianhydride PMDA: pyromellitic dianhydride NTCDA: 2,3,6,7-naphthalene tetracarboxylic dianhydride TAHQ: 1,4-phenylene bis(trimellitic acid monoester) dianhydride TMEG: Ethylene glycol bis-trimellitic anhydride m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl TPE-R: 1,3-bis(4-aminophenoxy)benzene TPE-Q: 1,4-bis(4-aminophenoxy)benzene APB: 1,3-bis(3-aminophenoxy)benzene 3,3'-DAPM: 3,3'-Diamino-diphenylmethane DTBAB: 1,4-bis(4-aminophenoxy)-2,5-di-tert-butylbenzene BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane APAB: 4-Aminophenyl-4'-aminobenzoate Dianiline-M: 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene Dianiline-P: 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene (manufactured by Mitsui Fine Chemicals, trade name: Dianiline-P) AABOZ: 6-amino-2-(4-aminophenoxy)benzoxazole DTAm: a mixture of 2,6-diamino-3,5-diethyltoluene and 2,4-diamino-3,5-diethyltoluene (manufactured and commercialized by Ihara Chemical Industry Co., Ltd. Name: Hardcure 10, amine value: 629 KOHmg/g) BAPM: bis(4-amino-3-ethyl-5-methylphenyl)methane (manufactured by Ihara Chemical Industry, trade name: Curehard MED) DMAc: N,N-Dimethylacetamide

(Synthesis Example A-1) Under nitrogen flow, 1.335 g of m-TB (0.0063 mol) and 10.414 g of TPE-R (0.0356 mol) and the amount of solid content after polymerization to 12% by weight were put into a 300 ml separate flask. DMAc, stirred and dissolved at room temperature. Next, after adding 0.932 g of PMDA (0.0043 mol) and 11.319 g of BPDA (0.0385 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-1. The solution viscosity of polyamide acid solution A-1 is 1,420 cps.

Next, after the polyamic acid solution A-1 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film A-1 (thermoplasticity, Tg: 256° C., moisture absorption rate: 0.36% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-1 was 26.4% by weight.

(Synthesis Example A-2) Under a nitrogen stream, 0.451 g of m-TB (0.0021 mol) and 11.794 g of TPE-R (0.0403 mol) and an amount of 12% by weight of solid content after polymerization were put into a 300 ml separate flask. DMAc, stirred and dissolved at room temperature. Next, after adding 2.834 g of PMDA (0.0130 mol) and 8.921 g of BPDA (0.0303 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-2. The solution viscosity of polyamide acid solution A-2 is 1,510 cps.

Next, after the polyamic acid solution A-2 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film A-2 (thermoplasticity, Tg: 242° C., moisture absorption rate: 0.35% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-2 was 26.5% by weight.

(Synthesis Example A-3) Under nitrogen flow, 0.908 g of m-TB (0.0043 moles) and 11.253 g of TPE-R (0.0385 moles) and the amount of solid content concentration after polymerization to 12% by weight were put into a 300 ml separate flask DMAc, stirred and dissolved at room temperature. Next, after adding 2.855 g of PMDA (0.0131 mol) and 8.985 g of BPDA (0.0305 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-3. The solution viscosity of polyamide acid solution A-3 is 1,550 cps.

Next, after the polyamic acid solution A-3 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film A-3 (thermoplasticity, Tg: 240° C., moisture absorption rate: 0.31% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-3 was 26.9% by weight.

(Synthesis Example A-4) Under a nitrogen stream, 1.372 g of m-TB (0.0065 mol) and 10.704 g of TPE-R (0.0366 mol) and an amount of 12% by weight of solid content after polymerization were put into a 300 ml separate flask. DMAc, stirred and dissolved at room temperature. Next, after adding 2.875 g of PMDA (0.0132 mol) and 9.049 g of BPDA (0.0308 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-4. The solution viscosity of polyamide acid solution A-4 is 1,580 cps.

Next, after the polyamic acid solution A-4 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film A-4 (thermoplasticity, Tg: 240° C., moisture absorption rate: 0.29% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-4 was 27.1% by weight.

(Synthesis Example A-5) Under a nitrogen stream, 1.842 g of m-TB (0.0087 mol) and 10.147 g of TPE-R (0.0347 mol) and an amount of 12% by weight of solid content after polymerization were put into a 300 ml separate flask. DMAc, stirred and dissolved at room temperature. Next, after adding 2.896 g of PMDA (0.0133 mol) and 9.115 g of BPDA (0.0310 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-5. The solution viscosity of polyamide acid solution A-5 is 1,610 cps.

Next, after the polyamic acid solution A-5 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film A-5 (thermoplasticity, Tg: 244° C., moisture absorption rate: 0.27% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-5 was 27.4% by weight.

(Synthesis Example A-6) Under nitrogen flow, 2.804 g of m-TB (0.0132 mol) and 9.009 g of TPE-R (0.0308 mol) and the amount of solid content after polymerization to 12% by weight were put into a 300 ml separate flask. DMAc, stirred and dissolved at room temperature. Next, after adding 2.938 g of PMDA (0.0135 mol) and 9.249 g of BPDA (0.0314 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-6. The solution viscosity of polyamide acid solution A-6 is 1,720 cps.

Next, after the polyamic acid solution A-6 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film A-6 (thermoplasticity, Tg: 248° C., moisture absorption rate: 0.27% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-6 was 27.8% by weight.

(Synthesis Example A-7) Under nitrogen flow, 1.469 g of APAB (0.0064 mol) and 10.658 g of TPE-R (0.0365 mol) and DMAc in an amount of 12% by weight after polymerization were charged into a 300 ml separate flask, Stir and dissolve at room temperature. Next, after adding 2.863 g of PMDA (0.0131 mol parts) and 9.011 g of BPDA (0.0306 mol parts), stirring was continued at room temperature for 3 hours and polymerization reaction was carried out to obtain polyamic acid solution A-7. The solution viscosity of polyamide acid solution A-7 is 1,280 cps.

Next, after the polyamic acid solution A-7 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film A-7 (thermoplasticity, Tg: 239° C., moisture absorption rate: 0.31% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-7 was 27.0% by weight.

(Synthesis Example A-8) Under a nitrogen stream, 1.372 g of m-TB (0.0065 mol) and 10.704 g of APB (0.0366 mol) and DMAc in an amount of 12% by weight of solid content after polymerization were charged into a 300 ml separate flask, Stir and dissolve at room temperature. Next, after adding 2.875 g of PMDA (0.0132 mol) and 9.049 g of BPDA (0.0308 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-8. The solution viscosity of polyamide acid solution A-8 is 1,190 cps.

Next, after the polyamic acid solution A-8 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film A-8 (thermoplasticity, Tg: 235° C., moisture absorption rate: 0.31% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-8 was 27.1% by weight.

(Synthesis Example A-9) Under nitrogen flow, 1.162 g of m-TB (0.0055 mol) and 12.735 g of BAPP (0.0310 mol) and DMAc in an amount of 12% by weight after polymerization were charged into a 300 ml separate flask, Stir and dissolve at room temperature. Next, after adding 2.436 g of PMDA (0.0112 mol) and 7.667 g of BPDA (0.0261 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-9. The solution viscosity of polyamide acid solution A-9 is 1,780 cps.

Next, after the polyamic acid solution A-9 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film A-9 (thermoplasticity, Tg: 278° C., moisture absorption rate: 0.34% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-9 was 22.6% by weight.

(Synthesis Example A-10) Under a nitrogen stream, 1.411 g of m-TB (0.0066 mol) and 11.011 g of TPE-R (0.0377 mol) and an amount of 12% by weight of solid content after polymerization were put into a 300 ml separate flask. DMAc, stirred and dissolved at room temperature. Next, after adding 4.929 g of PMDA (0.0226 mol) and 6.649 g of BPDA (0.0226 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-10. The solution viscosity of polyamide acid solution A-10 is 2,330 cps.

Next, after the polyamic acid solution A-10 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film A-10 (thermoplasticity, Tg: 276° C., moisture absorption rate: 0.41% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-10 was 28.0% by weight.

(Synthesis Example A-11) Under a nitrogen flow, 12.327 parts by weight of TPE-R (0.0422 moles) and DMAc in an amount of 12% by weight of solid content after polymerization were put into a 300 ml separate flask, and stirred and dissolved at room temperature . Next, after adding 2.815 g of PMDA (0.0129 mol) and 8.858 g of BPDA (0.0301 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-11. The solution viscosity of polyamide acid solution A-11 is 1,530 cps.

Next, after the polyamic acid solution A-11 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film A-11 (thermoplasticity, Tg: 244° C., moisture absorption rate: 0.39% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-11 was 26.5% by weight.

(Synthesis Example A-12) Under a nitrogen stream, 12.128 g of m-TB (0.0571 mol) and 1.856 g of TPE-R (0.0063 mol) and an amount of 15% by weight of solid content after polymerization were put into a 300 ml separate flask. DMAc, stirred and dissolved at room temperature. Next, after adding 6.819 g of PMDA (0.0313 mol) and 9.198 g of BPDA (0.0313 mol), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain polyamic acid solution A-12. The solution viscosity of polyamide acid solution A-12 is 29,100 cps.

Next, after the polyamic acid solution A-12 was uniformly applied to one side of the electrolytic copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film A-12 (non-thermoplastic, Tg: 322° C., moisture absorption rate: 0.57% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-12 was 31.8% by weight.

(Synthesis Example A-13) Under a nitrogen stream, 13.707 g of m-TB (0.0646 mol) and DMAc in an amount to have a solid content concentration of 15% by weight after polymerization were charged into a 300 ml separate flask, and stirred and dissolved at room temperature. Next, after adding 6.936 g of PMDA (0.0318 mol) and 9.356 g of BPDA (0.0318 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-13. The solution viscosity of polyamide acid solution A-13 is 29,900 cps.

Next, after the polyamic acid solution A-13 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film A-13 (non-thermoplastic, Tg: 332° C., moisture absorption rate: 0.63% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-13 was 32.4% by weight.

(Synthesis Example A-14) Under nitrogen flow, put 12.061 g of m-TB (0.0568 moles), 0.923 g of TPE-Q (0.0032 moles) and 1.0874 g of dianiline-M (0.0032 moles) into a 300 ml separate flask, and DMAc was stirred and dissolved at room temperature in such an amount that the solid content concentration after polymerization became 15% by weight. Next, after adding 6.781 g of PMDA (0.0311 mol) and 9.147 g of BPDA (0.0311 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-14. The solution viscosity of polyamide acid solution A-14 is 29,800 cps.

Next, after the polyamic acid solution A-14 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film A-14 (non-thermoplastic, Tg: 322° C., moisture absorption rate: 0.61% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-14 was 31.6% by weight.

(Synthesis Example A-15) Under nitrogen flow, 11.978 g of m-TB (0.0564 moles), 0.916 g of TPE-Q (0.0031 moles) and 1.287 g of BAPP (0.0031 moles) were put into a 300 ml separate flask, and after polymerization DMAc in an amount such that the solid content concentration becomes 15% by weight was stirred and dissolved at room temperature. Next, after adding 6.735 g of PMDA (0.0309 mol) and 9.084 g of BPDA (0.0309 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-15. The solution viscosity of polyamide acid solution A-15 is 29,200 cps.

Next, after the polyamic acid solution A-15 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was etched away using an aqueous solution of ferric chloride to prepare a polyimide film A-15 (non-thermoplastic, Tg: 324° C., moisture absorption rate: 0.58% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-15 was 31.4% by weight.

(Synthesis Example A-16) Under a nitrogen stream, 12.128 g of m-TB (0.0571 mol) and 1.856 g of TPE-Q (0.0063 mol) and an amount of 15% by weight of solid content after polymerization were put into a 300 ml separate flask. DMAc, stirred and dissolved at room temperature. Next, after adding 6.819 g of PMDA (0.0313 mol) and 9.198 g of BPDA (0.0313 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-16. The solution viscosity of polyamide acid solution A-16 is 32,800 cps.

Next, after the polyamic acid solution A-16 was uniformly applied to one side of the electrolytic copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was etched away using an aqueous solution of ferric chloride to prepare a polyimide film A-16 (non-thermoplastic, Tg: 330° C., moisture absorption rate: 0.59% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-16 was 31.8% by weight.

(Synthesis Example A-17) Under a nitrogen stream, 12.323 g of m-TB (0.0580 mol) and 1.886 g of TPE-R (0.0064 mol) and an amount of 15% by weight of solid content after polymerization were put into a 300 ml separate flask. DMAc, stirred and dissolved at room temperature. Next, after adding 8.314 g of PMDA (0.0381 mol) and 7.477 g of BPDA (0.0254 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-17. The solution viscosity of polyamide acid solution A-17 is 31,500 cps.

Next, after the polyamic acid solution A-17 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film A-17 (non-thermoplastic, Tg: 342° C., moisture absorption rate: 0.56% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-17 was 32.3% by weight.

(Synthesis Example A-18) Under nitrogen flow, 13.434 g of m-TB (0.0633 mol) and DMAc in an amount to obtain a solid content concentration of 15% by weight after polymerization were charged into a 300 ml separate flask, and stirred and dissolved at room temperature. Next, after adding 6.188 g of PMDA (0.0281 moles), 9.170 g of BPDA (0.0312 moles) and 1.279 g of TMEG (0.0031 moles), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain Polyamide acid solution A-18. The solution viscosity of polyamide acid solution A-18 is 14,100 cps.

Next, after the polyamic acid solution A-18 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film A-18 (non-thermoplastic, Tg: 314° C., moisture absorption rate: 0.59% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-18 was 31.7% by weight.

(Synthesis Example A-19) Under a nitrogen flow, 12.003 g of m-TB (0.0565 mol) and 1.836 g of TPE-R (0.0063 mol) and an amount of 15% by weight of solid content after polymerization were put into a 300 ml separate flask. DMAc, stirred and dissolved at room temperature. Next, after adding 5.399 g of PMDA (0.0248 moles), 9.103 g of BPDA (0.0309 moles) and 1.659 g of NTCDA (0.0062 moles), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain Polyamide acid solution A-19. The solution viscosity of polyamide acid solution A-19 is 31,200 cps.

Next, after the polyamic acid solution A-19 was uniformly applied to one side of the electrolytic copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was etched away using an aqueous solution of ferric chloride to prepare a polyimide film A-19 (non-thermoplastic, Tg: 311° C., moisture absorption rate: 0.58% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-19 was 31.4% by weight.

(Synthesis Example A-20) Under nitrogen flow, 8.778 g of m-TB (0.0414 moles), 1.860 g of TPE-R (0.0064 moles), 3.582 g of AABOZ (0.0159 moles) and polymerized DMAc in an amount having a solid content concentration of 15% by weight was stirred and dissolved at room temperature. Next, after adding 8.309 g of PMDA (0.0381 mol) and 7.472 g of BPDA (0.0254 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-20. The solution viscosity of polyamide acid solution A-20 is 42,300 cps.

Next, after the polyamic acid solution A-20 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was etched away using an aqueous solution of ferric chloride to prepare a polyimide film A-20 (non-thermoplastic, Tg: 312° C., moisture absorption rate: 0.61% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-20 was 32.1% by weight.

(Synthesis Example A-21) Under nitrogen flow, 5.365 g of m-TB (0.0253 moles), 1.847 g of TPE-R (0.0063 moles), 7.116 g of AABOZ (0.0316 moles) and polymerized DMAc in an amount having a solid content concentration of 15% by weight was stirred and dissolved at room temperature. Next, after adding 8.252 g of PMDA (0.0378 mol) and 7.421 g of BPDA (0.0252 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-21. The solution viscosity of polyamide acid solution A-21 is 22,700 cps.

Next, after the polyamic acid solution A-21 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film A-21 (non-thermoplastic, Tg: 320° C., moisture absorption rate: 0.65% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-21 was 31.9% by weight.

(Synthesis Example A-22) Under nitrogen flow, 8.110 g of m-TB (0.0382 moles), 1.861 g of TPE-R (0.0064 moles), 4.360 g of APAB (0.0191 moles) and polymerized DMAc in an amount having a solid content concentration of 15% by weight was stirred and dissolved at room temperature. Next, after adding 8.250 g of PMDA (0.0378 mol) and 7.419 g of BPDA (0.0252 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-22. The solution viscosity of polyamide acid solution A-22 is 24,500 cps.

Next, after the polyamic acid solution A-22 was uniformly applied to one side of the electrolytic copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film A-22 (non-thermoplastic, Tg: 322° C., moisture absorption rate: 0.57% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-22 was 32.0% by weight.

(Synthesis Example A-23) Under a nitrogen stream, 11.755 g of m-TB (0.0554 mol) and 1.799 g of TPE-R (0.0062 mol) and an amount of 15% by weight of solid content after polymerization were put into a 300 ml separate flask. DMAc, stirred and dissolved at room temperature. Next, after adding 3.966 g of PMDA (0.0182 mol) and 12.481 g of BPDA (0.0424 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-23. The solution viscosity of polyamide acid solution A-23 is 26,800 cps.

Next, after the polyamic acid solution A-23 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film A-23 (non-thermoplastic, Tg: 291° C., moisture absorption rate: 0.59% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-23 was 30.7% by weight.

(Synthesis Example A-24) Under a nitrogen stream, 14.405 g of m-TB (0.0679 mol) and DMAc in an amount to have a solid content concentration of 15% by weight after polymerization were charged into a 300 ml separate flask, and stirred and dissolved at room temperature. Next, after adding 11.663 g of PMDA (0.0535 mol) and 3.933 g of BPDA (0.0134 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-24. The solution viscosity of polyamide acid solution A-24 is 33,600 cps.

Next, after the polyamic acid solution A-24 was uniformly applied to one side of the electrolytic copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was etched away using an aqueous solution of ferric chloride to prepare a polyimide film A-24 (non-thermoplastic, Tg: 400° C. or higher, moisture absorption rate: 0.78% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-24 was 34.2% by weight.

(Synthesis Example A-25) Under a nitrogen flow, 12.201 g of m-TB (0.0575 moles) and 1.042 g of dianiline-M (0.0030 moles) were charged into a 300 ml separate flask in such an amount that the solid content concentration after polymerization became 15% by weight DMAc was stirred and dissolved at room temperature. Next, after adding 7.991 g of NTCDA (0.0298 mol) and 8.766 g of BPDA (0.0298 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-25. The solution viscosity of polyamide acid solution A-25 is 30,100 cps.

Next, after the polyamic acid solution A-25 was uniformly applied to one side of the electrolytic copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was etched away using an aqueous solution of ferric chloride to prepare a polyimide film A-25 (non-thermoplastic, Tg: 400° C. or higher, moisture absorption rate: 0.57% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-25 was 30.2% by weight.

(Synthesis Example A-26) Under nitrogen flow, 11.204 g of m-TB (0.0528 moles) and 0.670 g of BAPP (0.0016 moles) and DMAc in an amount of 15% by weight of the solid content concentration after polymerization were charged into a 300 ml separate flask, Stir and dissolve at room temperature. Next, after adding 5.845 g of PMDA (0.0268 mol) and 12.281 g of TAHQ (0.0268 mol), stirring was continued at room temperature for 3 hours and polymerization was carried out to obtain polyamic acid solution A-26. The solution viscosity of polyamide acid solution A-26 is 26,600 cps.

Next, after the polyamic acid solution A-26 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film A-26 (non-thermoplastic, Tg: 304° C., moisture absorption rate: 0.49% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film A-26 was 26.9% by weight.

[Example A-1] After the polyamic acid solution A-1 is uniformly applied to one side of an electrolytic copper foil with a thickness of 12 μm (surface roughness Rz: 0.6 μm) so that the thickness after curing becomes approximately 2 μm to 3 μm , heat-dried at 120° C. to remove the solvent. Next, the polyamic acid solution A-15 was uniformly applied thereon so that the thickness after curing was about 21 μm, and heat-dried at 120° C. to remove the solvent. Furthermore, polyamic-acid solution A-1 was uniformly apply|coated so that the thickness after hardening may become about 2 micrometers - 3 micrometers, and it heat-dried at 120 degreeC, and removed a solvent. In this way, after forming three layers of polyamic acid layers, stepwise heat treatment is carried out from 120°C to 360°C within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was etched away using an aqueous solution of ferric chloride to prepare a multilayer polyimide film A-1 (CTE: 22 ppm/K, moisture absorption rate: 0.54% by weight, dielectric constant : 3.58, dielectric tangent: 0.0031).

[Example A-2 to Example A-21, Reference Example A-1 to Reference Example A-2] Example A-2 to Example A-21, Reference Example A-1 to Reference Example A-2 were obtained in the same manner as in Example A-1, except that the polyamic acid solutions shown in Tables 1 to 4 were used. Multilayer polyimide film A-2 to multilayer polyimide film A-23. The CTE, moisture absorption rate, dielectric constant, and dielectric tangent of the obtained multilayer polyimide films A-2 to A-23 were determined. Each measurement result is shown in Table 1-Table 4.

[Table 1] Example A-2 Example A-3 Example A-4 Example A-5 Example A-6 Example A-7 Types of multilayer polyimide film A-2 A-3 A-4 A-5 A-6 A-7 Types of Polyamide Acid Solutions Used in Multilayer Polyimide Films thermoplastic polyimide layer A-2 A-3 A-4 A-5 A-6 A-7 Non-thermoplastic polyimide layer A-15 A-15 A-15 A-15 A-15 A-15 thermoplastic polyimide layer A-2 A-3 A-4 A-5 A-6 A-7 CTE[ppm/K] twenty two twenty two twenty two twenty two twenty two twenty two Moisture absorption rate [weight%] 0.54 0.54 0.53 0.53 0.53 0.54 Dielectric constant (10 GHz) 3.57 3.58 3.58 3.58 3.59 3.60 Dielectric tangent (10 GHz) 0.0031 0.0031 0.0030 0.0030 0.0030 0.0031

[Table 2] Example A-8 Example A-9 Example A-10 Example A-11 Example A-12 Example A-13 Types of multilayer polyimide film A-8 A-9 A-10 A-11 A-12 A-13 Types of Polyamide Acid Solutions Used in Multilayer Polyimide Films thermoplastic polyimide layer A-8 A-9 A-10 A-11 A-4 A-4 Non-thermoplastic polyimide layer A-15 A-15 A-15 A-15 A-12 A-13 thermoplastic polyimide layer A-8 A-9 A-10 A-11 A-4 A-4 CTE[ppm/K] twenty two twenty two twenty two twenty two 20 twenty two Moisture absorption rate [weight%] 0.54 0.54 0.55 0.55 0.53 0.58 Dielectric constant (10 GHz) 3.59 3.62 3.58 3.57 3.40 3.43 Dielectric tangent (10 GHz) 0.0031 0.0031 0.0032 0.0031 0.0028 0.0035

[table 3] Example A-14 Example A-15 Example A-16 Example A-17 Example A-18 Example A-19 Types of multilayer polyimide film A-14 A-15 A-16 A-17 A-18 A-19 Types of Polyamide Acid Solutions Used in Multilayer Polyimide Films thermoplastic polyimide layer A-4 A-4 A-4 A-4 A-4 A-4 Non-thermoplastic polyimide layer A-14 A-16 A-17 A-18 A-19 A-20 thermoplastic polyimide layer A-4 A-4 A-4 A-4 A-4 A-4 CTE[ppm/K] twenty two twenty two twenty two twenty two 19 twenty two Moisture absorption rate [weight%] 0.56 0.54 0.52 0.54 0.53 0.56 Dielectric constant (10 GHz) 3.38 3.57 3.48 3.46 3.48 3.52 Dielectric tangent (10 GHz) 0.0034 0.0031 0.0033 0.0030 0.0030 0.0035

[Table 4] Example A-20 Example A-21 Reference example A-1 Reference example A-2 Types of multilayer polyimide film A-20 A-21 A-22 A-23 Types of Polyamide Acid Solutions Used in Multilayer Polyimide Films thermoplastic polyimide layer A-4 A-4 A-4 A-4 Non-thermoplastic polyimide layer A-21 A-22 A-23 A-24 thermoplastic polyimide layer A-4 A-4 A-4 A-4 CTE[ppm/K] twenty two 28 32 18 Moisture absorption rate [weight%] 0.59 0.53 0.54 0.70 Dielectric constant (10 GHz) 3.85 3.56 3.42 3.54 Dielectric tangent (10 GHz) 0.0037 0.0030 0.0032 0.0050

[Example A-22 to Example A-23] Except for using the polyamic acid solution shown in Table 5, the multilayer polyimide film A-24 to the multilayer polyimide film of Example A-22 to Example A-23 were obtained in the same manner as in Example A-1. Amine film A-25. The CTE, moisture absorption rate, dielectric constant, and dielectric tangent of the obtained multilayer polyimide films A-24 to A-25 were determined. Each measurement result is shown in Table 5.

[table 5] Example A-22 Example A-23 Types of multilayer polyimide film A-24 A-25 Types of Polyamide Acid Solutions Used in Multilayer Polyimide Films thermoplastic polyimide layer A-4 A-4 Non-thermoplastic polyimide layer A-25 A-26 thermoplastic polyimide layer A-4 A-4 CTE[ppm/K] 17 twenty four Moisture absorption rate [weight%] 0.54 0.46 Dielectric constant (10 GHz) 3.48 3.43 Dielectric tangent (10 GHz) 0.0034 0.0030

(Synthesis Example B-1) Under a nitrogen flow, 66.727 parts by weight of m-TB (0.314 parts by mole) and 520.681 parts by weight of TPE-R (1.781 parts by mole) and the amount of 12 parts by weight of solid content after polymerization were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 46.620 parts by weight of PMDA (0.214 mol parts) and 565.972 parts by weight of BPDA (1.924 mol parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain polyamic acid solution B -1. The solution viscosity of polyamide acid solution B-1 is 1,420 cps.

Next, after the polyamic acid solution B-1 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film B-1 (thermoplasticity, Tg: 256° C., moisture absorption rate: 0.36% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-1 was 26.4% by weight.

(Synthesis Example B-2) Under a nitrogen flow, 22.538 parts by weight of m-TB (0.106 parts by mole) and 589.682 parts by weight of TPE-R (2.017 parts by mole) and the amount of 12 parts by weight of solid content after polymerization were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 141.722 parts by weight of PMDA (0.650 mole parts) and 446.058 parts by weight of BPDA (1.516 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain polyamic acid solution B -2. The solution viscosity of polyamide acid solution B-2 is 1,510 cps.

Next, after the polyamic acid solution B-2 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film B-2 (thermoplasticity, Tg: 242° C., moisture absorption rate: 0.35% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-2 was 26.5% by weight.

(Synthesis Example B-3) Under a nitrogen flow, 45.398 parts by weight of m-TB (0.214 parts by mole) and 562.630 parts by weight of TPE-R (1.925 parts by mole) and the concentration of the solid content after polymerization became 12% by weight. DMAc, stirred and dissolved at room temperature. Next, after adding 142.733 parts by weight of PMDA (0.654 parts by mole) and 449.239 parts by weight of BPDA (1.527 parts by mole), continue to stir at room temperature for 3 hours and carry out polymerization reaction to obtain polyamic acid solution B -3. The solution viscosity of polyamide acid solution B-3 is 1,550 cps.

Next, after the polyamic acid solution B-3 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was etched away using an aqueous solution of ferric chloride to prepare a polyimide film B-3 (thermoplasticity, Tg: 240° C., moisture absorption rate: 0.31% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-3 was 26.9% by weight.

(Synthesis Example B-4) Under a nitrogen stream, 68.586 parts by weight of m-TB (0.323 parts by mole) and 535.190 parts by weight of TPE-R (1.831 parts by mole) and the concentration of the solid content after polymerization became 12% by weight. DMAc, stirred and dissolved at room temperature. Next, after adding 143.758 parts by weight of PMDA (0.659 mole parts) and 452.466 parts by weight of BPDA (1.538 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain polyamic acid solution B -4. The solution viscosity of polyamide acid solution B-4 is 1,580 cps.

Next, after the polyamic acid solution B-4 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film B-4 (thermoplasticity, Tg: 240° C., moisture absorption rate: 0.29% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-4 was 27.1% by weight.

(Synthesis Example B-5) Under nitrogen flow, 92.110 parts by weight of m-TB (0.434 mole parts) and 507.352 parts by weight of TPE-R (1.736 mole parts) and the amount of solid content concentration after polymerization to 12% by weight were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 144.798 parts by weight of PMDA (0.664 parts by mole) and 455.740 parts by weight of BPDA (1.549 parts by mole), continue to stir at room temperature for 3 hours and carry out polymerization reaction to obtain polyamic acid solution B -5. The solution viscosity of polyamide acid solution B-5 is 1,610 cps.

Next, after the polyamic acid solution B-5 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film B-5 (thermoplasticity, Tg: 244° C., moisture absorption rate: 0.27% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-5 was 27.4% by weight.

(Synthesis Example B-6) Under nitrogen flow, 140.193 parts by weight of m-TB (0.660 mol parts) and 450.451 parts by weight of TPE-R (1.541 mol parts) and the amount of solid content concentration after polymerization to 12% by weight were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 146.924 parts by weight of PMDA (0.674 mole parts) and 462.431 parts by weight of BPDA (1.572 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain polyamic acid solution B -6. The solution viscosity of polyamide acid solution B-6 is 1,720 cps.

Next, after the polyamic acid solution B-6 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film B-6 (thermoplasticity, Tg: 248° C., moisture absorption rate: 0.27% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-6 was 27.8% by weight.

(Synthesis Example B-7) Under a nitrogen stream, 73.427 parts by weight of APAB (0.322 parts by mole) and 532.900 parts by weight of TPE-R (1.823 parts by mole) and DMAc in an amount of 12 weight percent of the solid content concentration after polymerization were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 143.143 parts by weight of PMDA (0.656 mole parts) and 450.530 parts by weight of BPDA (1.531 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain polyamic acid solution B -7. The solution viscosity of polyamide acid solution B-7 is 1,280 cps.

Next, after the polyamic acid solution B-7 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was approximately 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film B-7 (thermoplasticity, Tg: 239° C., moisture absorption rate: 0.31% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-7 was 27.0% by weight.

(Synthesis Example B-8) Under a nitrogen flow, 68.586 parts by weight of m-TB (0.323 parts by mole) and 535.190 parts by weight of APB (1.831 parts by mole) and DMAc in an amount of 12 weight percent of the solid content concentration after polymerization were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 143.758 parts by weight of PMDA (0.659 mole parts) and 452.466 parts by weight of BPDA (1.538 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain polyamic acid solution B -8. The solution viscosity of polyamide acid solution B-8 is 1,190 cps.

Next, after the polyamic acid solution B-8 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film B-8 (thermoplasticity, Tg: 235° C., moisture absorption rate: 0.31% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-8 was 27.1% by weight.

(Synthesis Example B-9) Under a nitrogen stream, 58.109 parts by weight of m-TB (0.274 parts by mole) and 636.745 parts by weight of BAPP (1.551 parts by mole) and DMAc in an amount of 12 parts by weight of solid content after polymerization were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 121.798 parts by weight of PMDA (0.558 mole parts) and 383.348 parts by weight of BPDA (1.303 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain polyamic acid solution B -9. The solution viscosity of polyamide acid solution B-9 is 1,780 cps.

Next, after the polyamic acid solution B-9 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was etched away using an aqueous solution of ferric chloride to prepare a polyimide film B-9 (thermoplasticity, Tg: 278° C., moisture absorption rate: 0.34% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-9 was 22.6% by weight.

(Synthesis Example B-10) Under a nitrogen flow, 70.552 parts by weight of m-TB (0.332 parts by mole) and 550.530 parts by weight of TPE-R (1.883 parts by mole) and 12 parts by weight of solid content after polymerization were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 246.465 parts by weight of PMDA (1.130 mole parts) and 332.454 parts by weight of BPDA (1.130 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain polyamic acid solution B -10. The solution viscosity of polyamide acid solution B-10 is 2,330 cps.

Next, after the polyamic acid solution B-10 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film B-10 (thermoplasticity, Tg: 276° C., moisture absorption rate: 0.41% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-10 was 28.0% by weight.

(Synthesis Example B-11) Under a nitrogen flow, 616.353 parts by weight of TPE-R (2.108 parts by mole) and DMAc in an amount to have a solid concentration after polymerization of 12% by weight were charged into the reaction tank, and stirred and dissolved at room temperature. Next, after adding 140.726 parts by weight of PMDA (0.645 mol parts) and 442.921 parts by weight of BPDA (1.505 mol parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain polyamic acid solution B -11. The solution viscosity of polyamide acid solution B-11 is 1,530 cps.

Next, after the polyamic acid solution B-11 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was etched away using an aqueous solution of ferric chloride to prepare a polyimide film B-11 (thermoplasticity, Tg: 244° C., moisture absorption rate: 0.39% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-11 was 26.5% by weight.

(Synthesis Example B-12) Under a nitrogen flow, 240.725 parts by weight of m-TB (1.134 parts by mole) and 331.485 parts by weight of TPE-R (1.134 parts by mole) and the concentration of the solid content after polymerization became 12% by weight. DMAc, stirred and dissolved at room temperature. Next, after adding 151.369 parts by weight of PMDA (0.694 mol parts) and 476.421 parts by weight of BPDA (1.619 mol parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain polyamic acid solution B -12. The solution viscosity of polyamide acid solution B-12 is 3,240 cps.

Next, after the polyamic acid solution B-12 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film B-12 (thermoplasticity, Tg: 260° C., moisture absorption rate: 0.28% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-12 was 28.7% by weight.

(Synthesis Example B-13) Under a nitrogen flow, 596.920 parts by weight of m-TB (2.812 parts by mole) and 91.331 parts by weight of TPE-R (0.312 parts by mole) and 15 parts by weight of solid content after polymerization were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 268.495 parts by weight of PMDA (1.231 mole parts) and 543.255 parts by weight of BPDA (1.846 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain polyamic acid solution B -13. The solution viscosity of polyamide acid solution B-13 is 27,310 cps.

Next, after the polyamic acid solution B-13 was uniformly applied to one side of the electrolytic copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film B-13 (non-thermoplastic, Tg: 305° C., moisture absorption rate: 0.52% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-13 was 31.2% by weight.

(Synthesis Example B-14) Under nitrogen flow, 606.387 parts by weight of m-TB (2.856 mol parts) and 92.779 parts by weight of TPE-R (0.317 mol parts) and the amount of solid content after polymerization to 15% by weight were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 340.941 parts by weight of PMDA (1.563 parts by mole) and 459.892 parts by weight of BPDA (1.563 parts by mole), continue to stir at room temperature for 3 hours and carry out polymerization reaction to obtain polyamic acid solution B -14. The solution viscosity of polyamide acid solution B-14 is 29,100 cps.

Next, after the polyamic acid solution B-14 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film B-14 (non-thermoplastic, Tg: 322° C., moisture absorption rate: 0.57% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-14 was 31.8% by weight.

(Synthesis Example B-15) Under a nitrogen flow, 685.370 parts by weight of m-TB (3.228 parts by mole) and DMAc in an amount to have a solid content concentration of 15% by weight after polymerization were charged into the reaction tank, and stirred and dissolved at room temperature. Next, after adding 346.815 parts by weight of PMDA (1.590 mole parts) and 467.815 parts by weight of BPDA (1.590 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain polyamic acid solution B -15. The solution viscosity of polyamide acid solution B-15 is 29,900 cps.

Next, after the polyamic acid solution B-15 was uniformly applied to one side of the electrolytic copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film B-15 (non-thermoplastic, Tg: 332° C., moisture absorption rate: 0.63% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-15 was 32.4% by weight.

(Synthesis Example B-16) Under nitrogen flow, put 603.059 parts by weight of m-TB (2.841 mole parts), 46.135 parts by weight of TPE-Q (0.158 mole parts) and 54.368 parts by weight of dianiline-M (0.158 mole parts ) and DMAc in such an amount that the solid content concentration after polymerization becomes 15% by weight were stirred and dissolved at room temperature. Next, after adding 339.070 parts by weight of PMDA (1.555 parts by mole) and 457.368 parts by weight of BPDA (1.555 parts by mole), continue to stir at room temperature for 3 hours and carry out polymerization reaction to obtain polyamic acid solution B -16. The solution viscosity of polyamide acid solution B-16 is 29,800 cps.

Next, after the polyamic acid solution B-16 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film B-16 (non-thermoplastic, Tg: 322° C., moisture absorption rate: 0.61% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-16 was 31.6% by weight.

(Synthesis Example B-17) Under nitrogen flow, 598.899 parts by weight of m-TB (2.821 parts by mole), 45.817 parts by weight of TPE-Q (0.157 parts by mole) and 64.339 parts by weight of BAPP (0.157 parts by mole) were put into the reaction tank and polymerized DMAc in an amount having a solid content concentration of 15% by weight was stirred and dissolved at room temperature. Next, after adding 336.731 parts by weight of PMDA (1.544 parts by mole) and 454.214 parts by weight of BPDA (1.544 parts by mole), continue to stir at room temperature for 3 hours and carry out polymerization reaction to obtain polyamic acid solution B -17. The solution viscosity of polyamide acid solution B-17 is 29,200 cps.

Next, after the polyamic acid solution B-17 was uniformly applied to one side of the electrolytic copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film B-17 (non-thermoplastic, Tg: 324° C., moisture absorption rate: 0.58% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-17 was 31.4% by weight.

(Synthesis Example B-18) Under nitrogen flow, 606.387 parts by weight of m-TB (2.856 mole parts) and 92.779 parts by weight of TPE-Q (0.317 mole parts) and the amount of solid content concentration after polymerization to 15% by weight were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 340.941 parts by weight of PMDA (1.563 parts by mole) and 459.892 parts by weight of BPDA (1.563 parts by mole), continue to stir at room temperature for 3 hours and carry out polymerization reaction to obtain polyamic acid solution B -18. The solution viscosity of polyamide acid solution B-18 is 32,800 cps.

Next, after the polyamic acid solution B-18 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film B-18 (non-thermoplastic, Tg: 330° C., moisture absorption rate: 0.59% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-18 was 31.8% by weight.

(Synthesis Example B-19) Under a nitrogen flow, 616.159 parts by weight of m-TB (2.902 parts by mole) and 94.275 parts by weight of TPE-R (0.322 parts by mole) and an amount of 15 parts by weight of solid content after polymerization were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 415.723 parts by weight of PMDA (1.906 mole parts) and 373.843 parts by weight of BPDA (1.271 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain polyamic acid solution B -19. The solution viscosity of polyamide acid solution B-19 is 31,500 cps.

Next, polyamic acid solution B-19 was uniformly applied to one side of a 12-μm-thick electrodeposited copper foil (surface roughness Rz: 2.1 μm) so that the thickness after curing was approximately 25 μm. Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was etched away using an aqueous solution of ferric chloride to prepare a polyimide film B-19 (non-thermoplastic, Tg: 342° C., moisture absorption rate: 0.56% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-19 was 32.3% by weight.

(Synthesis Example B-20) Under nitrogen flow, 626.252 parts by weight of m-TB (2.950 mole parts) and 95.819 parts by weight of TPE-R (0.328 mole parts) and the amount of solid content concentration after polymerization to 15% by weight were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 492.954 parts by weight of PMDA (2.260 mole parts) and 284.975 parts by weight of BPDA (0.969 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to obtain polyamic acid solution B -20. The solution viscosity of polyamide acid solution B-20 is 34,100 cps.

Next, after the polyamic acid solution B-20 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was etched away using an aqueous solution of ferric chloride to prepare a polyimide film B-20 (non-thermoplastic, Tg: 364° C., moisture absorption rate: 0.68% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-20 was 32.9% by weight.

(Synthesis Example B-21) Under nitrogen flow, 517.831 parts by weight of m-TB (2.439 parts by mole) and 79.230 parts by weight of TPE-R (0.271 parts by mole) and the amount of solid content concentration after polymerization to 15% by weight were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 291.151 parts by weight of PMDA (1.335 parts by mole) and 611.788 parts by weight of TAHQ (1.335 parts by mole), continue to stir at room temperature for 3 hours and carry out polymerization reaction to obtain polyamic acid solution B -twenty one. The solution viscosity of polyamide acid solution B-21 is 33,200 cps.

Next, after the polyamic acid solution B-21 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film B-21 (non-thermoplastic, Tg: 296° C., moisture absorption rate: 0.54% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-21 was 26.8% by weight.

(Synthesis Example B-22) Under a nitrogen flow, 587.744 parts by weight of m-TB (2.769 parts by mole) and 89.927 parts by weight of TPE-R (0.308 parts by mole) and the amount of 15% by weight of solid content after polymerization were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 198.275 parts by weight of PMDA (0.909 parts by mole) and 624.054 parts by weight of BPDA (2.121 parts by mole), continue to stir at room temperature for 3 hours and carry out polymerization reaction to obtain polyamic acid solution B -twenty two. The solution viscosity of polyamide acid solution B-22 is 26,800 cps.

Next, after the polyamic acid solution B-22 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film B-22 (non-thermoplastic, Tg: 291° C., moisture absorption rate: 0.59% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-22 was 30.7% by weight.

(Synthesis Example B-23) Under nitrogen flow, 456.183 parts by weight of m-TB (2.149 parts by mole) and 269.219 parts by weight of TPE-R (0.921 parts by mole) and the amount of 15% by weight of solid content after polymerization were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 329.772 parts by weight of PMDA (1.512 parts by mole) and 444.826 parts by weight of BPDA (1.512 parts by mole), continue to stir at room temperature for 3 hours and carry out polymerization reaction to obtain polyamic acid solution B -twenty three. The solution viscosity of polyamide acid solution B-23 is 26,400 cps.

Next, after the polyamic acid solution B-23 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film B-23 (non-thermoplastic, Tg: 285° C., moisture absorption rate: 0.53% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-23 was 30.7% by weight.

(Synthesis Example B-24) Under nitrogen flow, 720.230 parts by weight of m-TB (3.393 parts by mole) and DMAc in an amount of 15% by weight of solid content after polymerization were charged into the reaction tank, and stirred and dissolved at room temperature. Next, after adding 583.127 parts by weight of PMDA (2.673 parts by mole) and 196.644 parts by weight of BPDA (0.668 parts by mole), continue to stir at room temperature for 3 hours and carry out polymerization reaction to obtain polyamic acid solution B -twenty four. The solution viscosity of polyamide acid solution B-24 is 33,600 cps.

Next, after the polyamic acid solution B-24 was uniformly applied to one side of the electrodeposited copper foil with a thickness of 12 μm (surface roughness Rz: 2.1 μm) so that the thickness after curing was about 25 μm, Heat drying was performed at 120° C. to remove the solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. For the obtained metal tension laminate, the copper foil was removed by etching using an aqueous solution of ferric chloride to prepare a polyimide film B-24 (non-thermoplastic, Tg: 400° C. or higher, moisture absorption rate: 0.78% by weight). In addition, the imide group concentration of the polyimide constituting the polyimide film B-24 was 34.2% by weight.

[Example B-1] Using a multi-manifold 3-layer co-extrusion multi-layer die, in the order of polyamide acid solution B-2/polyamide acid solution B-18/polyamide acid solution B-2 The three-layer structure was continuously extruded and coated on an endless belt-shaped stainless steel support substrate, and dried by heating at 130° C. for 3 minutes to remove the solvent. Thereafter, staged heat treatment is carried out from 130°C to 360°C to complete the imidization, and the thickness of the prepared thermoplastic polyimide layer/non-thermoplastic polyimide layer/thermoplastic polyimide layer is 2.0 Polyimide membrane B-1' of μm/21 μm/2.0 μm. The polyimide film B-1' on the support substrate was peeled off by the knife-edge method, and the strip-shaped polyimide film B-1 with the length of 1100 mm in the width direction was prepared. The evaluation results of the elongated polyimide film B-1 are as follows. CTE: 19 ppm/K In-plane retardation (RO): 9 nm Deviation (ΔRO) of in-plane retardation (RO) in the width direction (TD direction): 2 nm In an environment with a temperature of 320°C and a pressure of 340 MPa/m ² , Change in in-plane retardation (RO) before and after pressurization for 15 minutes during holding period: 13 nm Moisture absorption rate: 0.56% by weight Dielectric constant (10 GHz): 3.56, Dielectric tangent (10 GHz): 0.0032

[Example B-2 to Example B-18, Reference Example B-1 to Reference Example B-5] Except for using the polyamic acid solution shown in Table 6 to Table 9, it was the same as Example B-1 The strip-shaped polyimide film B-2 to the strip-shaped polyimide film B-23 of Example B-2 to Example B-18 and Reference Example B-1 to Reference Example B-5 were successfully obtained. Calculate the CTE, in-plane retardation (RO), and in-plane retardation (RO) in the width direction (TD direction) of the obtained long polyimide films B-2 to B-23 Deviation (ΔRO), change in in-plane retardation (RO) before and after pressurization at 320°C, pressure 340 MPa/m ² , and holding period of 15 minutes, and moisture absorption rate. Each measurement result is shown in Table 6 - Table 9.

[Table 6] Example B-2 Example B-3 Example B-4 Example B-5 Example B-6 Example B-7 Types of long polyimide film B-2 B-3 B-4 B-5 B-6 B-7 Types of Polyamide Acid Solutions Used in Long Polyamide Films thermoplastic polyimide layer B-3 B-4 B-5 B-6 B-1 B-7 Non-thermoplastic polyimide layer B-18 B-18 B-18 B-18 B-18 B-18 thermoplastic polyimide layer B-3 B-4 B-5 B-6 B-1 B-7 CTE[ppm/K] 19 19 19 19 19 19 In-plane retardation (RO) [nm] 9 10 11 13 9 9 Deviation of in-plane retardation (RO) in the width direction (TD direction) (⊿RO) [nm] 3 1 2 2 1 1 Change in in-plane retardation (RO) before and after pressurization at a pressure of 340 MPa/m ² and a holding period of 15 minutes at a temperature of 320°C [nm] 8 4 4 3 6 4 Moisture absorption rate [weight%] 0.53 0.52 0.52 0.51 0.53 0.53 Dielectric constant (10 GHz) 3.57 3.57 3.57 3.59 3.57 3.59 Dielectric tangent (10 GHz) 0.0032 0.0031 0.0031 0.0031 0.0032 0.0032

[Table 7] Example B-8 Example B-9 Example B-10 Example B-11 Example B-12 Example B-13 Types of long polyimide film B-8 B-9 B-10 B-11 B-12 B-13 Types of Polyamide Acid Solutions Used in Long Polyamide Films thermoplastic polyimide layer B-8 B-9 B-10 B-4 B-4 B-4 Non-thermoplastic polyimide layer B-18 B-18 B-18 B-13 B-14 B-15 thermoplastic polyimide layer B-8 B-9 B-10 B-4 B-4 B-4 CTE[ppm/K] 19 19 19 19 19 19 In-plane retardation (RO) [nm] 10 9 19 6 11 10 Deviation of in-plane retardation (RO) in the width direction (TD direction) (⊿RO) [nm] 1 1 1 1 2 1 Change in in-plane retardation (RO) before and after pressurization at a pressure of 340 MPa/m ² and a holding period of 15 minutes at a temperature of 320°C [nm] 9 3 1 16 5 4 Moisture absorption rate [weight%] 0.52 0.57 0.58 0.46 0.51 0.55 Dielectric constant (10 GHz) 3.58 3.61 3.57 3.48 3.40 3.43 Dielectric tangent (10 GHz) 0.0032 0.0032 0.0033 0.0028 0.0028 0.0035

[Table 8] Example B-14 Example B-15 Example B-16 Example B-17 Example B-18 Types of long polyimide film B-14 B-15 B-16 B-17 B-18 Types of Polyamide Acid Solutions Used in Long Polyamide Films thermoplastic polyimide layer B-4 B-4 B-4 B-4 B-4 Non-thermoplastic polyimide layer B-16 B-17 B-19 B-20 B-21 thermoplastic polyimide layer B-4 B-4 B-4 B-4 B-4 CTE[ppm/K] 19 19 19 19 19 In-plane retardation (RO) [nm] 12 11 16 twenty one 10 Deviation of in-plane retardation (RO) in the width direction (TD direction) (⊿RO) [nm] 2 2 3 1 1 Change in in-plane retardation (RO) before and after pressurization at a pressure of 340 MPa/m ² and a holding period of 15 minutes at a temperature of 320°C [nm] 4 5 4 2 18 Moisture absorption rate [weight%] 0.54 0.51 0.51 0.62 0.54 Dielectric constant (10 GHz) 3.38 3.58 3.57 3.48 3.48 Dielectric tangent (10 GHz) 0.0034 0.0030 0.0031 0.0033 0.0042

[Table 9] Reference example B-1 Reference example B-2 Reference example B-3 Reference example B-4 Reference example B-5 Types of long polyimide film B-19 B-20 B-21 B-22 B-23 Types of Polyamide Acid Solutions Used in Long Polyamide Films thermoplastic polyimide layer B-11 B-12 B-4 B-4 B-4 Non-thermoplastic polyimide layer B-18 B-18 B-22 B-23 B-24 thermoplastic polyimide layer B-11 B-12 B-4 B-4 B-4 CTE[ppm/K] 19 19 28 26 19 In-plane retardation (RO) [nm] 9 8 10 9 9 Deviation of in-plane retardation (RO) in the width direction (TD direction) (⊿RO) [nm] 2 2 2 3 2 Change in in-plane retardation (RO) before and after pressurization at a pressure of 340 MPa/m ² and a holding period of 15 minutes at a temperature of 320°C [nm] twenty three 3 31 27 2 Moisture absorption rate [weight%] 0.59 0.51 0.52 0.50 0.72 Dielectric constant (10 GHz) 3.56 3.60 3.42 3.54 3.54 Dielectric tangent (10 GHz) 0.0032 0.0031 0.0032 0.0028 0.0050

[Example B-19] Polyamic acid solution B-2 was uniformly applied to a strip-shaped copper foil (rolled copper foil, manufactured by JX Metal Co., Ltd., commercial product) so that the thickness after curing was 2.0 μm. name: GHY5-93F-HA-V2 foil, thickness: 12 μm, tensile modulus of elasticity after heat treatment: 18 GPa), heat-dry at 120°C for 1 minute to remove the solvent. Polyamic acid solution B-18 was uniformly applied thereon so that the thickness after curing was 21 μm, and then heat-dried at 120° C. for 3 minutes to remove the solvent. Furthermore, polyamic-acid solution B-2 was uniformly apply|coated so that the thickness after hardening might become 2.0 micrometers, and it heat-dried at 120 degreeC for 1 minute, and removed the solvent. Thereafter, stepwise heat treatment was performed from 130° C. to 360° C. to complete imidization, and a single-sided copper tension laminate B-1 was prepared. Lay copper foil on the side of the polyimide layer of the single-sided copper tensioned laminate B-1, and perform thermocompression bonding for 15 minutes at a temperature of 320°C and a pressure of 340 MPa/m2 to prepare a ^double -sided copper tensioned laminate Board B-1. Peel strength of casting side: ◎, peeling strength of crimping side: ○

[Example B-20 to Example B-36, Reference Example B-6 to Reference Example B-10] Example B-20 to Example B-36, Reference Example B-6 to Reference Example B-10 were obtained in the same manner as in Example B-19, except that the polyamic acid solutions shown in Tables 10 to 13 were used. Double-sided copper tensioned laminates B-2 to double-sided copper tensioned laminates B-23. The casting surface side peel strength and the crimping surface side peel strength of the obtained double-sided copper tension laminated boards B-2 to B-23 were determined. Each measurement result is shown in Table 10 - Table 13.

[Table 10] Example B-20 Example B-21 Example B-22 Example B-23 Example B-24 Example B-25 Types of double-sided copper tension laminates B-2 B-3 B-4 B-5 B-6 B-7 Types of polyamide acid solutions thermoplastic polyimide layer B-3 B-4 B-5 B-6 B-1 B-7 Non-thermoplastic polyimide layer B-18 B-18 B-18 B-18 B-18 B-18 thermoplastic polyimide layer B-3 B-4 B-5 B-6 B-1 B-7 Cast side peel strength ◎ ◎ ◎ ○ ◎ ◎ Peel strength of crimping side ◎ ◎ ◎ Δ ○ ◎

[Table 11] Example B-26 Example B-27 Example B-28 Example B-29 Example B-30 Example B-31 Types of double-sided copper tension laminates B-8 B-9 B-10 B-11 B-12 B-13 Types of polyamide acid solutions thermoplastic polyimide layer B-8 B-9 B-10 B-4 B-4 B-4 Non-thermoplastic polyimide layer B-18 B-18 B-18 B-13 B-14 B-15 thermoplastic polyimide layer B-8 B-9 B-10 B-4 B-4 B-4 Cast side peel strength ◎ Δ Δ ◎ ◎ ◎ Peel strength of crimping side ◎ Δ Δ ◎ ◎ ◎

[Table 12] Example B-32 Example B-33 Example B-34 Example B-35 Example B-36 Types of double-sided copper tension laminates B-14 B-15 B-16 B-17 B-18 Types of polyamide acid solutions thermoplastic polyimide layer B-4 B-4 B-4 B-4 B-4 Non-thermoplastic polyimide layer B-16 B-17 B-19 B-20 B-21 thermoplastic polyimide layer B-4 B-4 B-4 B-4 B-4 Cast side peel strength ◎ ◎ ◎ ◎ ◎ Peel strength of crimping side ◎ ◎ ◎ ◎ ◎

[Table 13] Reference Example B-6 Reference Example B-7 Reference Example B-8 Reference Example B-9 Reference Example B-10 Types of double-sided copper tension laminates B-19 B-20 B-21 B-22 B-23 Types of polyamide acid solutions thermoplastic polyimide layer B-11 B-12 B-4 B-4 B-4 Non-thermoplastic polyimide layer B-18 B-18 B-22 B-23 B-24 thermoplastic polyimide layer B-11 B-12 B-4 B-4 B-4 Cast side peel strength ◎ Δ ◎ ◎ ◎ Peel strength of crimping side ◎ x ◎ ◎ ◎

(Synthesis Example C-1) Under nitrogen flow, 606.387 parts by weight of m-TB (2.856 mol parts) and 92.779 parts by weight of TPE-R (0.317 mol parts) and the amount of solid content concentration after polymerization to 15% by weight were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 340.941 parts by weight of PMDA (1.563 parts by mole) and 459.892 parts by weight of BPDA (1.563 parts by mole), stirring was continued for 3 hours at room temperature and polymerization was carried out to prepare polyamic acid solution C -1. The solution viscosity of polyamide acid solution C-1 is 29,100 cps.

(Synthesis Example C-2) Under nitrogen flow, 606.387 parts by weight of m-TB (2.856 mole parts) and 92.779 parts by weight of TPE-Q (0.317 mole parts) and the amount of solid content concentration after polymerization to 15% by weight were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 340.941 parts by weight of PMDA (1.563 parts by mole) and 459.892 parts by weight of BPDA (1.563 parts by mole), continue to stir at room temperature for 3 hours and carry out polymerization reaction to prepare polyamic acid solution C -2. The solution viscosity of polyamide acid solution C-2 is 32,800 cps.

(Synthesis Example C-3) Under a nitrogen flow, 616.159 parts by weight of m-TB (2.902 parts by mole) and 94.275 parts by weight of TPE-R (0.322 parts by mole) and an amount of 15 parts by weight of solid content after polymerization were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 415.723 parts by weight of PMDA (1.906 mole parts) and 373.843 parts by weight of BPDA (1.271 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to prepare polyamic acid solution C -3. The solution viscosity of polyamide acid solution C-3 is 31,500 cps.

(Synthesis Example C-4) Under a nitrogen stream, 637.503 parts by weight of m-TB (3.003 parts by mole) and 64.882 parts by weight of BAPP (0.158 parts by mole) and DMAc in an amount of 15% by weight of the solid concentration after polymerization were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 339.571 parts by weight of PMDA (1.557 parts by mole) and 458.044 parts by weight of BPDA (1.557 parts by mole), continue to stir at room temperature for 3 hours and carry out polymerization reaction to prepare polyamic acid solution C -4. The solution viscosity of polyamide acid solution C-4 is 24,100 cps.

(Synthesis Example C-5) Under a nitrogen stream, 591.594 parts by weight of m-TB (2.787 parts by mole) and 127.109 parts by weight of BAPP (0.310 parts by mole) and DMAc in an amount of 15% by weight of the solid concentration after polymerization were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 332.624 parts by weight of PMDA (1.525 mole parts) and 448.673 parts by weight of BPDA (1.525 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to prepare polyamic acid solution C -5. The solution viscosity of polyamide acid solution C-5 is 23,200 cps.

(Synthesis Example C-6) Under nitrogen flow, 641.968 parts by weight of m-TB (3.024 parts by mole) and 54.830 parts by weight of dianiline-M (0.159 parts by mole) were put into the reaction tank, and the concentration of the solid content after polymerization became 15% by weight. DMAc was stirred and dissolved at room temperature. Next, after adding 341.950 parts by weight of PMDA (1.568 mole parts) and 461.252 parts by weight of BPDA (1.568 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to prepare polyamic acid solution C -6. The solution viscosity of polyamide acid solution C-6 is 26,500 cps.

(Synthesis Example C-7) Under a nitrogen flow, 538.432 parts by weight of m-TB (2.536 parts by mole) and 185.359 parts by weight of TPE-R (0.634 parts by mole) and an amount of 15 parts by weight of solid content after polymerization were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 408.690 parts by weight of PMDA (1.874 parts by mole) and 367.519 parts by weight of BPDA (1.249 parts by mole), stirring was continued for 3 hours at room temperature and polymerization was carried out to prepare polyamic acid solution C -7. The solution viscosity of polyamide acid solution C-7 is 31,100 cps.

(Synthesis Example C-8) Under nitrogen flow, 674.489 parts by weight of m-TB (3.177 parts by mole) and DMAc in an amount to have a solid content concentration of 15% by weight after polymerization were charged into the reaction tank, and stirred and dissolved at room temperature. Next, after adding 273.047 parts by weight of PMDA (1.252 mole parts) and 552.465 parts by weight of BPDA (1.878 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to prepare polyamic acid solution C -8. The solution viscosity of polyamide acid solution C-8 is 26,400 cps.

(Synthesis Example C-9) Under a nitrogen flow, 463.290 parts by weight of m-TB (2.182 parts by mole) and 273.414 parts by weight of TPE-R (0.935 parts by mole) and the concentration of the solid content after polymerization became 15% by weight. DMAc, stirred and dissolved at room temperature. Next, after adding 401.891 parts by weight of PMDA (1.843 parts by mole) and 361.405 parts by weight of BPDA (1.228 parts by mole), continue to stir at room temperature for 3 hours and carry out polymerization reaction to prepare polyamic acid solution C -9. The solution viscosity of polyamide acid solution C-9 is 29,000 cps.

(Synthesis Example C-10) Under a nitrogen flow, 589.033 parts by weight of m-TB (2.775 parts by mole) and 111.762 parts by weight of APAB (0.490 parts by mole) and DMAc in an amount of 15% by weight of the solid concentration after polymerization were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 420.798 parts by weight of PMDA (1.929 mole parts) and 378.407 parts by weight of BPDA (1.286 mole parts), stirring was continued at room temperature for 3 hours and polymerization was carried out to prepare polyamic acid solution C -10. The solution viscosity of polyamide acid solution C-10 is 22,700 cps.

(Synthesis Example C-11) Under a nitrogen flow, 500.546 parts by weight of m-TB (2.358 parts by mole) and 229.756 parts by weight of TPE-R (0.786 parts by mole) and an amount of 15 parts by weight of solid content after polymerization were put into the reaction tank. DMAc, stirred and dissolved at room temperature. Next, after adding 405.262 parts by weight of PMDA (1.858 mole parts) and 364.436 parts by weight of BPDA (1.239 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to prepare polyamic acid solution C -11. The solution viscosity of polyamide acid solution C-11 is 29,600 cps.

(Synthesis Example C-12) Under a nitrogen stream, 779.571 parts by weight of BAPP (1.899 parts by mole) and DMAc in an amount to have a solid concentration after polymerization of 12% by weight were charged into the reaction tank, and stirred and dissolved at room temperature. Next, after adding 420.430 parts by weight of PMDA (1.928 mole parts), stirring was continued at room temperature for 3 hours and polymerization was carried out to prepare polyamic acid solution C-12. The solution viscosity of polyamide acid solution C-12 is 2,210 cps.

(Synthesis Example C-13) Under a nitrogen stream, 616.159 parts by weight of m-TB (2.902 parts by mole) and 94.275 parts by weight of APB (0.322 parts by mole) and DMAc in an amount of 15% by weight of the solid concentration after polymerization were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 415.723 parts by weight of PMDA (1.906 mole parts) and 373.843 parts by weight of BPDA (1.271 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to prepare polyamic acid solution C -13. The solution viscosity of polyamide acid solution C-13 is 12,700 cps.

(Synthesis Example C-14) Under nitrogen flow, 628.877 parts by weight of m-TB (2.962 parts by mole) and 65.261 parts by weight of 3,3'-DAPM (0.329 parts by mole) were put into the reaction tank, and the solid content concentration after polymerization became 15% by weight The amount of DMAc was stirred and dissolved at room temperature. Next, after adding 424.303 parts by weight of PMDA (1.945 mole parts) and 381.559 parts by weight of BPDA (1.297 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to prepare polyamic acid solution C -14. The solution viscosity of polyamide acid solution C-14 is 31,400 cps.

(Synthesis Example C-15) Under nitrogen flow, 613.786 parts by weight of m-TB (2.891 moles), 28.652 parts by weight of DTAm (0.161 parts by moles) and 46.956 parts by weight of TPE-Q (0.161 parts by moles) were put into the reaction tank and polymerized DMAc was stirred and dissolved at room temperature so that the final solid content concentration became 15% by weight. Next, after adding 345.102 weight parts of PMDA (1.582 mole parts) and 465.504 weight parts of BPDA (1.582 mole parts), stirring was continued at room temperature for 3 hours and polymerization was carried out to prepare polyamic acid solution C -15. The solution viscosity of polyamide acid solution C-15 is 24,400 cps.

(Synthesis Example C-16) Under nitrogen flow, 607.034 parts by weight of m-TB (2.859 parts by mole), 44.840 parts by weight of BAPM (0.159 parts by mole) and 46.439 parts by weight of TPE-Q (0.159 parts by mole) were put into the reaction tank and polymerized DMAc in an amount having a solid content concentration of 15% by weight was stirred and dissolved at room temperature. Next, after adding 341.305 parts by weight of PMDA (1.565 mole parts) and 460.383 parts by weight of BPDA (1.565 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to prepare polyamic acid solution C -16. The solution viscosity of polyamide acid solution C-16 is 27,100 cps.

(Synthesis Example C-17) Under nitrogen flow, 603.059 parts by weight of m-TB (2.841 mole parts), 54.368 parts by weight of dianiline-P (0.158 mole parts) and 46.135 parts by weight of TPE-Q (0.158 mole parts) were put into the reaction tank ) and DMAc in such an amount that the solid content concentration after polymerization becomes 15% by weight were stirred and dissolved at room temperature. Next, after adding 339.070 parts by weight of PMDA (1.555 parts by mole) and 457.368 parts by weight of BPDA (1.555 parts by mole), continue to stir at room temperature for 3 hours and carry out polymerization reaction to prepare polyamic acid solution C -17. The solution viscosity of polyamide acid solution C-17 is 29,200 cps.

(Synthesis Example C-18) Under nitrogen flow, 599.272 parts by weight of m-TB (2.823 parts by mole), 63.445 parts by weight of DTBAB (0.157 parts by mole) and 45.845 parts by weight of TPE-Q (0.157 parts by mole) were put into the reaction tank and polymerized DMAc in an amount having a solid content concentration of 15% by weight was stirred and dissolved at room temperature. Next, after adding 336.941 parts by weight of PMDA (1.545 parts by mole) and 454.497 parts by weight of BPDA (1.545 parts by mole), continue to stir at room temperature for 3 hours and carry out polymerization reaction to prepare polyamic acid solution C -18. The solution viscosity of polyamide acid solution C-18 is 28,800 cps.

(Synthesis Example C-19) Under nitrogen flow, 610.050 parts by weight of m-TB (2.874 parts by mole) and 52.104 parts by weight of dianiline-M (0.151 parts by mole) were put into the reaction tank so that the concentration of the solid content after polymerization became 15% by weight. DMAc was stirred and dissolved at room temperature. Next, after adding 399.526 parts by weight of NTCDA (1.490 mol parts) and 438.320 parts by weight of BPDA (1.490 mol parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to prepare polyamic acid solution C -19. The solution viscosity of polyamide acid solution C-19 is 29,200 cps.

(Synthesis Example C-20) Under a nitrogen stream, 560.190 parts by weight of m-TB (2.639 parts by mole) and 33.503 parts by weight of BAPP (0.082 parts by mole) and DMAc in an amount of 15% by weight of the solid concentration after polymerization were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 292.237 parts by weight of PMDA (1.340 mole parts) and 614.071 parts by weight of TAHQ (1.340 mole parts), stirring was continued for 3 hours at room temperature and polymerization was carried out to prepare polyamic acid solution C -20. The solution viscosity of polyamide acid solution C-20 is 26,100 cps.

[Example C-1] After the polyamic acid solution C-1 is uniformly applied to one side of a 12 μm thick electrolytic copper foil (surface roughness Rz: 0.6 μm) so that the thickness after hardening becomes about 25 μm, at 120 The drying was carried out at ℃ and the solvent was removed. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. The copper foil was etched and removed using an aqueous ferric chloride solution to prepare polyimide film C-1 (CTE: 18.1 ppm/K, Tg: 322°C, moisture absorption rate: 0.57% by weight, haze: 74.5%, film Elongation: 48%, dielectric constant: 3.42, dielectric tangent: 0.0028).

[Example C-2 to Example C-9 and Reference Example C-1 to Reference Example C-2] Except having used the polyamic acid solution shown in Table 14 and Table 15, it carried out similarly to Example C-1, and produced polyimide membrane C-2 - polyimide membrane C-11. For the polyimide films C-2 to C-11, CTE, Tg, moisture absorption, haze, film elongation, dielectric constant, and dielectric tangent were determined. These measurement results are shown in Table 14 and Table 15.

[Table 14] Example C-2 Example C-3 Example C-4 Example C-5 Example C-6 Example C-7 Types of polyamide acid solutions C-2 C-3 C-4 C-5 C-6 C-7 Types of polyimide membranes C-2 C-3 C-4 C-5 C-6 C-7 CTE[ppm/K] 17.0 15.6 16.1 22.3 15.8 23.8 Moisture absorption rate [weight%] 0.54 0.61 0.59 0.60 0.60 0.58 Tg[°C] 330 342 318 312 322 314 Haze[%] 67.6 67.8 71.4 73.5 68.9 74.7 Film elongation [%] 33 42 35 37 31 42 Dielectric constant 3.50 3.54 3.40 3.50 3.39 3.50 Dielectric tangent (×10 ^-4 ) 32 34 31 32 35 31

[Table 15] Reference example C-1 Reference example C-2 Example C-8 Example C-9 Types of polyamide acid solutions C-8 C-9 C-10 C-11 Types of polyimide membranes C-8 C-9 C-10 C-11 CTE[ppm/K] 15.8 32.7 32.2 26.1 Moisture absorption rate [weight%] 0.60 0.57 0.59 0.58 Tg[°C] 314 296 340 307 Haze[%] 73.6 79.9 87.0 77.8 Film elongation [%] twenty two 47 30 44 Dielectric constant 3.47 3.54 3.49 3.52 Dielectric tangent (×10 ^-4 ) 31 29 33 30

[Example C-10] Polyimide film C-12 (CTE: 10.2 ppm/ K, Tg: 307°C, moisture absorption: 0.61% by weight, haze: 74.2%, film elongation: 41%).

[Example C-11] After the polyamic acid solution C-15 is uniformly applied to one side of an electrolytic copper foil with a thickness of 12 μm (surface roughness Rz: 0.6 μm) so that the thickness after curing becomes approximately 2 μm to 3 μm , heat-dried at 120° C. to remove the solvent. Next, the polyamic acid solution C-1 was uniformly applied thereon so that the thickness after curing was about 21 μm, and heat-dried at 120° C. to remove the solvent. Furthermore, polyamic-acid solution C-15 was uniformly apply|coated so that the thickness after hardening may become about 2 micrometers - 3 micrometers, and it heat-dried at 120 degreeC, and removed a solvent. In this way, after forming three layers of polyamic acid layers, stepwise heat treatment was carried out from 120° C. to 360° C. for 30 minutes to complete imidization, and the metal tension laminate C-11 was prepared. Defects such as expansion of the polyimide layer in the metal tension laminate C-11 were not confirmed.

[Example C-12 to Example C-17] Except for using polyamic acid solution C-2 to polyamic acid solution C-7 instead of polyamic acid solution C-1, metal tension laminates C-12 to metal sheets were prepared in the same manner as in Example C-11. Laminate C-17. No defects such as swelling of the polyimide layer were confirmed in any of the metal tensor laminated boards C-12 to C-17.

(Refer to Example C-3) In Example C-11, except that the stepwise heat treatment was performed from 120° C. to 360° C. for 15 minutes, a metal tension laminate was produced in the same manner as in Example C-11, but expansion was confirmed in the polyimide layer.

[Example C-18 to Example C-20] In addition to using polyamic acid solution C-4 to polyamic acid solution C-6 to replace polyamic acid solution C-1 in Example C-11 and carry out a 15-minute step-by-step process from 120°C to 360°C Except for the heat treatment, metal tension laminates C-18 to metal tension laminates C-20 were prepared in the same manner as in Example C-11. No defects such as swelling of the polyimide layer were confirmed in any of the metal tensor laminated boards C-18 to C-20.

(Reference example C-4 to reference example C-6) In addition to using polyamic acid solution C-2, polyamic acid solution C-3 and polyamic acid solution C-7 to replace polyamic acid solution C-1 in Example C-11 and from 120 ° C to Except for stepwise heat treatment up to 360° C. for 15 minutes, a metal tension laminate was produced in the same manner as in Example C-11, but swelling was observed in the polyimide layer in any metal tension laminate.

[Example C-21 to Example C-26] Except having used the polyamic acid solution shown in Table 16, it carried out similarly to Example C-1, and produced polyimide membrane C-13 - polyimide membrane C-18. For polyimide films C-13 to C-18, CTE, Tg, dielectric constant, and dielectric tangent were obtained. These measurement results are shown in Table 16.

[Table 16] Example C-21 Example C-22 Example C-23 Example C-24 Example C-25 Example C-26 Types of polyamide acid solutions C-13 C-14 C-15 C-16 C-17 C-18 Types of polyimide membranes C-13 C-14 C-15 C-16 C-17 C-18 CTE[ppm/K] 20.0 14.8 16.3 18.0 17.5 19.9 Tg[°C] 322 334 340 320 332 320 Dielectric constant 3.41 3.41 3.70 3.62 3.60 3.66 Dielectric tangent (×10 ^-4 ) 39 38 34 32 33 32

[Example C-27 to Example C-30] In addition to using polyamic acid solution C-15 ~ polyamic acid solution C-18 to replace the polyamic acid solution C-1 in Example C-11 and carry out a 15-minute step-by-step process from 120°C to 360°C Except for the heat treatment, metal tension laminates C-27 to metal tension laminates C-30 were produced in the same manner as in Example C-11. No defects such as swelling of the polyimide layer were confirmed in any of the metal tension laminates C-27 to C-30.

(Reference Example C-7 to Reference Example C-8) In addition to using polyamic acid solution C-13 and polyamic acid solution C-14 to replace polyamic acid solution C-1 in Example C-11 and carry out a step-by-step process from 120°C to 360°C for 15 minutes Except for the heat treatment, a metal tension laminate was produced in the same manner as in Example C-11, but expansion was confirmed in the polyimide layer in any metal tension laminate.

[Example C-31 to Example C-32] Except having used the polyamic acid solution shown in Table 17, it carried out similarly to Example C-1, and produced polyimide membrane C-19 - polyimide membrane C-20. For the polyimide films C-19 to C-20, CTE, Tg, dielectric constant, and dielectric tangent were obtained. These measurement results are shown in Table 17.

[Table 17] Example C-31 Example C-32 Types of polyamide acid solutions C-19 C-20 Types of polyimide membranes C-19 C-20 CTE[ppm/K] 5.4 14.1 Tg[°C] >400 304 Dielectric constant 3.51 3.45 Dielectric tangent (×10 ^-4 ) 35 30

As mentioned above, although the embodiment of this invention was demonstrated in detail for the purpose of illustration, this invention is not restricted by the said embodiment, Various deformation|transformation is possible.

This application claim is based on Japanese Patent Application No. 2016-191786 filed on September 29, 2016, Japanese Patent Application No. 2016-191787 filed on September 29, 2016, and Japanese Patent Application filed on December 28, 2016 Application No. 2016-256927 and Japanese Patent Application No. 2016-256928 filed on December 28, 2016 have priority, and the entire contents of said applications are incorporated into this application.

none

none

Claims (8)

A polyimide film, which has a thermoplastic polyimide layer comprising thermoplastic polyimide on at least one side of the non-thermoplastic polyimide layer comprising non-thermoplastic polyimide, and the polyimide film is characterized by satisfying the following conditions (ai) to (a-iv): (ai) the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer is an aromatic tetracarboxylic acid residue and an aromatic dicarboxylic acid residue. amine residues, and relative to 100 molar parts of the aromatic tetracarboxylic acid residues, tetracarboxylic acid residues derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) (BPDA residue) and at least one of the tetracarboxylic acid residue (TAHQ residue) derived from 1,4-phenylene bis(trimellitic acid monoester) dianhydride (TAHQ) and Tetracarboxylic acid residues (PMDA residues) derived from tetracarboxylic dianhydride (PMDA) and tetracarboxylic acid residues (NTCDA residues) derived from 2,3,6,7-naphthalene tetracarboxylic dianhydride (NTCDA) The total of at least one of ) is 80 mole parts or more, the molar ratio of at least one of the BPDA residue and the TAHQ residue to at least one of the PMDA residue and the NTCDA residue {(BPDA residue+TAHQ residue)/(PMDA residue+NTCDA residue)} is in the range of 0.6 to 1.3; (a-ii) the thermoplastic polyimide constituting the thermoplastic polyimide layer is Aromatic tetracarboxylic acid residues and aromatic diamine residues, and relative to 100 mole parts of the aromatic diamine residues, are represented by the group selected from the following general formula (B1) to general formula (B7) At least 70 mole parts of diamine residues derived from at least one diamine compound among the diamine compounds, and 1 mole part of diamine residues derived from a diamine compound represented by the following general formula (A1) (a-iii) The coefficient of thermal expansion is in the range of 10 ppm/K to 30 ppm/K; (a-iv) The dielectric tangent (Df) at 10 GHz is 0.004 or less ,

In formulas (B1) to (B7), R ₁ independently represents a monovalent hydrocarbon group or alkoxy group with 1 to 6 carbons, and the linking group A independently represents a group selected from -O-, -S-, -CO-, A divalent group in -SO-, -SO ₂ -, -COO-, -CH ₂ -, -C(CH ₃ ) ₂ -, -NH- or -CONH-, n ₁ independently represents an integer of 0 to 4 ; Among them, the duplicates of formula (B2) are removed from formula (B3), and the duplicates of formula (B4) are removed from formula (B5),

In the formula (A1), the linking group X represents a single bond or -COO-, Y independently represents hydrogen, a monovalent hydrocarbon group or an alkoxy group with 1 to 3 carbons, n represents an integer of 0 to 2, and p and q independently Represents an integer from 0 to 4. The polyimide film as described in claim 1, wherein relative to 100 mole parts of the aromatic diamine residues in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer, the The diamine residue derived from the diamine compound represented by general formula (A1) is 80 mol parts or more. The polyimide film according to claim 1, wherein with respect to 100 mole parts of the aromatic diamine residues in the thermoplastic polyimide constituting the thermoplastic polyimide layer, The diamine residue derived from at least one diamine compound among the diamine compounds represented by the general formulas (B1) to (B7) is within the range of 70 mol parts or more and 99 mol parts or less. A polyimide film, which has a thermoplastic polyimide layer comprising thermoplastic polyimide on at least one side of the non-thermoplastic polyimide layer comprising non-thermoplastic polyimide, and the polyimide film is characterized by satisfying the following conditions (bi) to (b-iv): (bi) the thermal expansion coefficient is in the range of 10 ppm/K to 30 ppm/K; (b-ii) the non-thermoplastic polyamide The non-thermoplastic polyimide of the amine layer is an aromatic tetracarboxylic acid residue and an aromatic diamine residue, and with respect to 100 mole parts of the aromatic tetracarboxylic acid residue, is selected from 3,3' , derived from at least one tetracarboxylic dianhydride in 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 1,4-phenylene bis(trimellitic acid monoester) dianhydride (TAHQ) The tetracarboxylic acid residue is in the range of 30 mole parts to 60 mole parts, and the tetracarboxylic acid residue derived from pyromellitic dianhydride (PMDA) is 40 mole parts to 70 mole parts Within the following range; (b-iii) With respect to 100 mole parts of the aromatic diamine residues in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer, the following general formula (A1 ) the diamine residue derived from the diamine compound is more than 80 mole parts; (b-iv) the thermoplastic polyimide constituting the thermoplastic polyimide layer contains aromatic tetracarboxylic acid residues and Aromatic diamine residues, and relative to 100 mole parts of the aromatic diamine residues, at least one of the diamine compounds represented by the following general formula (B1) to general formula (B7) The diamine residue derived from the diamine compound is in the range of 70 mole parts to 99 mole parts, and the diamine residue derived from the diamine compound represented by the following general formula (A1) is 1 mole Parts or more and 30 mole parts or less,

In the formula (A1), the linking group X represents a single bond or -COO-, Y independently represents hydrogen, a monovalent hydrocarbon group or an alkoxy group with 1 to 3 carbons, n represents an integer of 0 to 2, and p and q independently Represents an integer from 0 to 4,

In formulas (B1) to (B7), R ₁ independently represents a monovalent hydrocarbon group or alkoxy group with 1 to 6 carbons, and the linking group A independently represents a group selected from -O-, -S-, -CO-, A divalent group in -SO-, -SO ₂ -, -COO-, -CH ₂ -, -C(CH ₃ ) ₂ -, -NH- or -CONH-, n ₁ independently represents an integer of 0 to 4 ; Among them, the duplicates of formula (B2) are removed from formula (B3), and the duplicates of formula (B4) are removed from formula (B5). The polyimide film according to claim 1 or claim 4, wherein both the non-thermoplastic polyimide and the thermoplastic polyimide have an imide group concentration of 33% by weight or less. A polyimide film, which has at least one non-thermoplastic polyimide layer, and the polyimide film is characterized by satisfying the following conditions (ci) to (c-iii): (ci) forming the The non-thermoplastic polyimide of the non-thermoplastic polyimide layer is an aromatic tetracarboxylic acid residue and an aromatic diamine residue, and relative to 100 mole parts of the aromatic tetracarboxylic acid residue, in The range of 30 mole parts to 60 mole parts contains 3,3',4,4'-biphenyltetracarboxylic dianhydride and 1,4-phenylene bis(trimellitic acid monoester) dianhydride At least one of the tetracarboxylic acid residues derived from it contains pyromellitic dianhydride and 2,3,6,7-naphthalene tetracarboxylic dianhydride in the range of 40 mole parts to 70 mole parts At least one derived tetracarboxylic acid residue, containing 70 mole parts or more of the diamine compound derived from the following general formula (A1) relative to 100 mole parts of the aromatic diamine residue Diamine residues, and contain diamine residues derived from diamine compounds represented by the following general formula (C1) to general formula (C4) within the range of 2 mole parts to 15 mole parts; (c -ii) the glass transition temperature is 300°C or higher; (c-iii) the dielectric tangent (Df) at 10 GHz is 0.004 or lower,

In the formula (A1), the linking group X represents a single bond or -COO-, Y independently represents hydrogen, a monovalent hydrocarbon group or an alkoxy group with 1 to 3 carbons, n represents an integer of 1 or 2, and p and q independently Represents an integer from 0 to 4,

In formulas (C1) to (C4), R ₂ independently represents a monovalent hydrocarbon group, alkoxy group or alkylthio group with 1 to 6 carbons, and the linking group A' independently represents a group selected from -O-, -SO ₂ The divalent group in -, -CH ₂ - or -C(CH ₃ ) ₂ -, the linking group X1 independently represents -CH ₂ -, -O-CH ₂ -O-, -OC ₂ H ₄ -O-, -OC ₃ H ₆ -O-, -OC ₄ H ₈ -O-, -OC ₅ H ₁₀ -O-, -O-CH ₂ -C(CH ₃ ) ₂ -CH ₂ -O-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or -SO ₂ -, n ₃ independently represents an integer of 1 to 4, and n ₄ independently represents an integer of 0 to 4, but in the formula (C3), the link When the group A' does not contain -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or -SO ₂ -, any one of n ₄ is 1 or more. A copper tension-laminated board having an insulating layer and having a copper foil on at least one surface of the insulating layer, wherein the copper tensioned-laminated board is characterized by: The insulating layer comprises the polyimide film as described in any one of Claim 1, Claim 4 or Claim 6. A circuit board obtained by processing the copper foil of the copper tension laminate according to claim 7 into wiring.