CN114716707A - Polyimide film, copper sheet laminate and circuit substrate - Google Patents

Abstract

A polyimide film, a copper sheet laminate and a circuit substrate having a non-thermoplastic polyimide layer, the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer is preferably relative to tetracarboxylic acid residues. 100 parts by mole and 80 parts by mole or more of BPDA residues derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 1,4-phenylene bis(partial) At least one of TAHQ residues derived from trimellitic acid monoester) dianhydride (TAHQ) and PMDA residues derived from pyromellitic dianhydride (PMDA) and 2,3,6,7-naphthalene At least one of the NTCDA residues derived from tetracarboxylic dianhydride (NTCDA) preferably has a dielectric tangent (Df) of 0.004 or less. By forming the non-thermoplastic polyimide layer using a specific acid anhydride as a raw material, the physical properties as a matrix resin layer can be ensured and the moisture absorption rate can be reduced, and the dielectric tangent can be reduced.

Description

Polyimide film, copper sheet laminate and circuit substrate

The present invention is a divisional application for an invention patent application filed on September 11, 2017 with the application number of 201780059180.2 and the invention name of "polyimide film, copper sheet laminate and circuit substrate".

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims 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 Priority is given to Japanese Patent Application No. 2016-256928 filed on December 28, 2016 and Japanese Patent Application No. 2016-256928 filed on December 28, 2016, and the entire contents of the applications are incorporated herein by reference.

technical field

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

Background technique

In recent years, with the progress of miniaturization, weight reduction, and space saving of electronic devices, flexible printed wiring boards (flexible printed wiring boards (flexible printed wiring boards) that are thin and lightweight, have flexibility, and have excellent durability even if they are repeatedly bent have been developed. The demand for printed circuit boards (Flexible Printed Circuits, FPC) is increasing. As for FPC, three-dimensional and high-density installation can be realized even in a limited space. Therefore, for example, in electronic devices such as Hard Disk Drive (HDD), Digital Video Disk (DVD), and smart phones. Its use is gradually expanding in the wiring of moving parts, or parts such as cables and connectors.

In addition to the above-mentioned densification, the performance of equipment has been advanced, and accordingly, it is also necessary to cope with the increase in the frequency of transmission signals. When a high-frequency signal is transmitted, when the transmission loss of the signal transmission path is large, problems such as loss of an electrical signal and a longer delay time of the signal occur. Therefore, reduction of the transmission loss of the FPC becomes important. In order to cope with the increase in frequency, FPCs using liquid crystal polymers characterized by low dielectric constant and low dielectric tangent as dielectric layers are used. However, although liquid crystal polymers are excellent in dielectric properties, there is room for improvement in heat resistance and adhesion to metal foils.

In order to improve heat resistance or adhesiveness, a metal sheet laminate in which polyimide is used as an insulating layer has been proposed (Patent Document 1). According to Patent Document 1, it is found that the dielectric constant is generally lowered by using an aliphatic monomer as a monomer of a polymer material, and the heat resistance of a polyimide obtained by using an aliphatic (chain) tetracarboxylic dianhydride is remarkably low. Therefore, it cannot be used for processing such as welding, and there is a problem in practice, but when an alicyclic tetracarboxylic dianhydride is used, a polyimide having improved heat resistance can be obtained compared with a chain tetracarboxylic dianhydride. However, in the polyimide film formed of the polyimide, although the dielectric constant at 10 GHz is 3.2 or less, the dielectric tangent exceeds 0.01, and the dielectric properties are still insufficient. Moreover, regarding the polyimide using the said aliphatic monomer, there exists a problem that the linear expansion coefficient is large, the dimensional change rate of a polyimide film is large, or flame retardance falls.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2004-358961

SUMMARY OF THE INVENTION

The problem to be solved by the invention

An object of the present invention is to provide a polyimide film which has high dimensional stability and low hygroscopicity, and which can reduce transmission loss by making the dielectric tangent of an insulating layer small, and which can be preferably used for high-frequency applications circuit board.

technical solutions to problems

As a result of diligent research conducted by the present inventors, it was found that in the circuit board, the non-thermoplastic polyimide layer mainly responsible for the function of controlling the dimensional change rate, and the thermoplastic polyimide layer, which has the function of adhering to the copper foil as necessary, In the imide layer, by selecting the monomer as the raw material of the polyimide, it is possible to ensure the necessary dimensional stability as a circuit board, and to control the order (crystallinity) of the polyimide. The present invention has been completed by lowering the moisture absorption rate and lowering the dielectric tangent.

That is, the polyimide film of the first aspect of the present invention is a polyimide film having a thermoplastic polyimide layer including a thermoplastic polyimide on at least one surface of a non-thermoplastic polyimide layer including a non-thermoplastic polyimide. imide film.

And the polyimide film of the 1st viewpoint of this invention satisfies the following condition (a-i) - condition (a-iv).

(a-i) the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer comprises a tetracarboxylic acid residue and a diamine residue, and

With respect to 100 mole parts of the tetracarboxylic acid residue,

Tetracarboxylic acid residues (BPDA residues) derived from 3,3',4,4'-biphenyl tetracarboxylic dianhydride (3,3',4,4'-biphenyl tetracarboxylicdianhydride, BPDA) and 1 At least one of the tetracarboxylic acid residues (TAHQ residues) derived from ,4-phenylene bis(trimellitic acid monoester) dianhydride (1,4-phenylene bis(trimellitic acid monoester) dianhydride, TAHQ) and tetracarboxylic acid residues (PMDA residues) derived from pyromellitic dianhydride (PMDA) and 2,3,6,7-naphthalenetetracarboxylic dianhydride (2,3,6, 7-naphthalenetetracarboxylic dianhydride, NTCDA) derived at least one of the tetracarboxylic acid residues (NTCDA residues) in total is 80 mole parts or more,

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)} in the range of 0.6 to 1.3.

(a-ii) The thermoplastic polyimide constituting the thermoplastic polyimide layer contains a tetracarboxylic acid residue and a diamine residue, and is based on 100 mole parts of the diamine residue,

The amount of diamine residues derived from at least one diamine compound selected from the group consisting of diamine compounds represented by the following general formula (B1) to (B7) is 70 mole parts or more, and the amount of the diamine residue derived from the following general formula (A1 The amount of the diamine residue derived from the diamine compound represented by ) is in the range of 1 part by mol or more and 30 parts by mol or less.

(a-iii) The thermal expansion coefficient is in 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.

[hua 1]

[In formula (B1) to formula (B7), R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms, and the linking group A independently represents a group selected from -O-, -S-, -CO- A divalent group among , -SO-, -SO ₂ -, -COO-, -CH ₂ -, -C(CH ₃ ) ₂ -, -NH- or -CONH-, n ₁ independently represents 0-4 Integer. Among them, from the formula (B3), remove the duplicate with the formula (B2), from the formula (B5) remove the duplicate with the formula (B4)]

[hua 2]

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

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

The polyimide film of the first aspect of the present invention may be selected from the group consisting of 100 mol parts of the diamine residue in the thermoplastic polyimide constituting the thermoplastic polyimide layer. The amount of the diamine residue derived from at least one of the diamine compounds represented by the general formula (B1) to (B7) is within a range of 70 mol parts or more and 99 mol parts or less.

The polyimide film of the second aspect of the present invention is a polyimide having a thermoplastic polyimide layer containing thermoplastic polyimide on at least one surface of a non-thermoplastic polyimide layer containing non-thermoplastic polyimide Amine film.

Furthermore, the polyimide film of the second aspect of the present invention satisfies the following conditions (b-i) to (b-iv).

(b-i) The thermal expansion coefficient is in the range of 10 ppm/K to 30 ppm/K.

(b-ii) the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer comprises a tetracarboxylic acid residue and a diamine residue, and

With respect to 100 mole parts of the tetracarboxylic acid residue,

At least one selected from 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 1,4-phenylene bis(trimellitic acid monoester) dianhydride (TAHQ) The tetracarboxylic acid residue derived from tetracarboxylic dianhydride is in the range of 30 mole parts or more and 60 mole parts or less,

The tetracarboxylic acid residue derived from pyromellitic dianhydride (PMDA) is in the range of 40 mole parts or more and 70 mole parts or less.

(b-iii) with respect to 100 mole parts of diamine residues in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer,

The amount of the diamine residue derived from the diamine compound represented by the following general formula (A1) is 80 mole parts or more.

(b-iv) The thermoplastic polyimide constituting the thermoplastic polyimide layer contains a tetracarboxylic acid residue and a diamine residue, and relative to 100 mole parts of the diamine residue,

The amount of the diamine residue derived from at least one diamine compound selected from the group consisting of diamine compounds represented by the following general formula (B1) to (B7) is in 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) is in the range of 1 part by mol or more and 30 parts by mol or less.

[hua 3]

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

[hua 4]

[In formula (B1) to formula (B7), R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms, and the linking group A independently represents a group selected from -O-, -S-, -CO- A divalent group among , -SO-, -SO ₂ -, -COO-, -CH ₂ -, -C(CH ₃ ) ₂ -, -NH- or -CONH-, n ₁ independently represents 0-4 Integer. Among them, from the formula (B3), remove the duplicate with the formula (B2), from the formula (B5) remove the duplicate with the formula (B4)]

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

The polyimide film of the third aspect of the present invention is a polyimide film having at least one non-thermoplastic polyimide layer, and the polyimide film satisfies the following conditions (c-i) to (c) -iii).

(c-i) the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer comprises a tetracarboxylic acid residue and a diamine residue, and

Contains 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 1,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) in a range of 30 to 60 mole parts relative to 100 mole parts of the tetracarboxylic acid residue. A tetracarboxylic acid residue derived from at least one of 4-phenylene bis(trimellitic acid monoester) dianhydride (TAHQ), containing pyromellitic acid in a range of 40 to 70 mole parts A tetracarboxylic acid residue derived from at least one of 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) is contained in 70 mol parts or more with respect to 100 mol parts of the diamine residue, and is contained in 2 mol parts to 15 mol parts The diamine residue derived from the diamine compound represented by following general formula (C1) - general formula (C4) is contained in the range.

(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.

[hua 5]

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

[hua 6]

[In formula (C1) to formula (C4), R ₂ independently represents a monovalent hydrocarbon group, alkoxy group or alkylthio group having 1 to 6 carbon atoms, and the linking group A' independently represents a group selected from -O-, -SO A divalent group in ₂ -, -CH ₂ - or -C(CH ₃ ) ₂ -, and 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), 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]

The copper sheet laminate of the first aspect, the second aspect, or the third aspect of the present invention includes an insulating layer, and copper foil is provided on at least one surface of the insulating layer, and the insulating layer of the copper sheet laminate includes The polyimide film according to any one of the above viewpoints.

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

effect of invention

The polyimide films of the first to third aspects of the present invention can achieve the coexistence of ensuring physical properties as a matrix resin layer and reducing moisture absorption by forming a non-thermoplastic polyimide layer using a specific acid anhydride as a raw material , and can achieve low dielectric tangent.

In addition, the polyimide film of the first aspect or the second aspect of the present invention can realize low moisture absorption and low dielectric by forming a thermoplastic polyimide layer using a thermoplastic polyimide into which a specific diamine compound is introduced. Electrical tangentization. Moreover, about the multilayer film combining two resin layers, moisture absorption and dielectric tangent are low, and the dimensional stability after thermocompression bonding of copper foil is also excellent.

Therefore, by using the polyimide film of the present invention and the copper sheet laminate using the same as the FPC material, it is possible to improve the reliability and yield in the circuit board, for example, it can also be applied to the transmission of high frequencies above 10 GHz signal circuit boards, etc.

Detailed ways

Next, embodiments of the present invention will be described.

[Polyimide film]

The polyimide film of the first embodiment of the present invention has a thermoplastic polyimide layer containing thermoplastic polyimide on at least one surface of a non-thermoplastic polyimide layer containing non-thermoplastic polyimide, and satisfies The above conditions (a-i) to conditions (a-iv).

Moreover, the polyimide film of 2nd Embodiment of this invention has a thermoplastic polyimide layer containing thermoplastic polyimide on at least one surface of a non-thermoplastic polyimide layer containing non-thermoplastic polyimide, And those that satisfy the above-mentioned conditions (b-i) to (b-iv).

In addition, in 1st Embodiment or 2nd Embodiment, a thermoplastic polyimide layer is provided in the single side|surface or both surfaces of a non-thermoplastic polyimide layer. For example, when laminating|stacking the polyimide film and copper foil of 1st Embodiment or 2nd Embodiment, and making a copper sheet laminated board, a copper foil can be laminated|stacked on the surface of a thermoplastic polyimide layer. In the case of having thermoplastic polyimide layers on both sides of the 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, but it is preferable that the thermoplastic polyimide layers on both sides satisfy the above-mentioned condition (a-ii) or condition (b-iv).

In addition, the polyimide film of the third embodiment of the present invention has at least one non-thermoplastic polyimide layer containing a non-thermoplastic polyimide, and satisfies the above-mentioned conditions (c-i) to (c-iii) )By.

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

The term "non-thermoplastic polyimide" is usually a polyimide that does not show softening and adhesiveness even when heated, but in the present invention, refers to the use of a dynamic viscoelasticity measuring device (Dynamic Mechanical Analysis). , DMA)), the storage elastic modulus at 30°C is 1.0×10 ⁹ Pa or more, and the storage elastic modulus at 280°C is 3.0×10 ⁸ Pa or more.

In addition, the "thermoplastic polyimide" is usually a polyimide whose glass transition temperature (Tg) can be clearly confirmed, but in the present invention, it means that the storage elastic coefficient at 30° C. measured using DMA is: A polyimide whose storage elastic modulus at 280° C. is 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 a non-thermoplastic polyimide, and the first embodiment or the second embodiment In the form, 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 low thermal expansion polyimide layer means that the thermal expansion coefficient (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 25 ppm/K The polyimide layer in the following range. In addition, the polyimide layer with high thermal expansion refers to one whose CTE is preferably 35 ppm/K or more, more preferably 35 ppm/K or more and 80 ppm/K or less, and still more preferably 35 ppm/K or more and 70 ppm/K or less. range of polyimide layers. The polyimide layer can be a polyimide layer having a desired CTE by appropriately changing the combination of the raw materials used, the thickness, and drying and curing conditions.

Usually a polyimide can be manufactured by making a tetracarboxylic dianhydride and a diamine compound react in a solvent, and heating ring-closure after generating a polyamic acid. For example, it can be obtained by dissolving approximately equimolar amounts of tetracarboxylic dianhydride and diamine compound in an organic solvent, and stirring at a temperature in the range of 0°C to 100°C for 30 minutes to 24 hours to carry out the polymerization reaction. Polyamic acid as a polyimide precursor. During the reaction, the reaction components are dissolved so that the produced precursor is in the range of 5% by weight to 30% by weight, more preferably in the range of 10% by weight to 20% by weight, in the organic solvent. As the organic solvent used in the polymerization reaction, for example, N,N-dimethylformamide (N,N-dimethylformamide, DMF), N,N-dimethylacetamide (N,N-dimethylacetamide, DMAc) can be mentioned. ), N,N-diethylacetamide, N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), 2-butanone, dimethylsulfoxide (DMSO), hexamethylene phosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diglyme, triglyme, cresol and the like. Two or more of these solvents may be used in combination, and aromatic hydrocarbons such as xylene and toluene may be used in combination. Moreover, although the usage-amount of the said organic solvent is not specifically limited, It is preferable to adjust and use so that the density|concentration of the polyamic acid solution obtained by a polymerization reaction may become about 5 weight% - 30weight%.

The synthesized polyamic acid is usually advantageously used as a reaction solvent solution, but can be concentrated, diluted or replaced with other organic solvents as necessary. Moreover, since polyamic acid is generally excellent in solvent solubility, it can be used advantageously. The viscosity of the solution of the polyamic acid is preferably in the range of 500 cps to 100,000 cps. When it deviates from the said range, in the coating operation by a coater etc., the film becomes easy to generate|occur|produce troubles, such as thickness deviation and a streak. The method in particular of imidizing a polyamic acid is not restrict|limited, For example, the heat processing of heating under the temperature conditions in the range of 80 degreeC - 400 degreeC in the said solvent for 1 hour - 24 hours can be preferably used.

The polyimide is obtained by imidizing the above-mentioned polyamic acid, and is produced by reacting a specific acid anhydride and a diamine compound. Therefore, the first embodiment will be described by describing the acid anhydride and the diamine compound. , Specific examples of the non-thermoplastic polyimide of the second embodiment or the third embodiment and the thermoplastic polyimide of the first embodiment or the second embodiment can be 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 a tetracarboxylic acid residue and a diamine residue . In addition, in the present invention, the term "tetracarboxylic acid residue" refers to a tetravalent group derived from tetracarboxylic dianhydride, and the term "diamine residue" refers to a divalent group derived from a diamine compound. The polyimide film of the first embodiment, the second embodiment, or the third embodiment preferably contains an aromatic tetracarboxylic acid residue derived from an aromatic tetracarboxylic dianhydride and an aromatic diamine derived Aromatic diamine residues.

(tetracarboxylic acid residue)

In the first embodiment, the second embodiment, or the third embodiment, the mixture is composed of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 1,4-phenylenebis(trimene) A tetracarboxylic acid residue derived from at least one of tricarboxylic acid monoester) dianhydride (TAHQ) and a tetracarboxylic acid residue derived from pyromellitic acid dianhydride (PMDA) and 2,3,6,7-naphthalenetetracarboxylic dianhydride ( The tetracarboxylic acid residue derived from at least one of NTCDA) is used as the 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") tend to 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 polyimide precursor, but appear to increase the CTE after imidization and lower the glass transition temperature and cause problems. Tendency to decrease heat resistance.

From this viewpoint, the polyimide film of the first embodiment, the second embodiment, or the third embodiment is the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer with respect to the tetracarboxylic acid residue. 100 mol parts of BPDA residues and TAHQ residues are contained in a total of preferably 30 mol parts or more and 60 mol parts or less, more preferably 40 mol parts or more and 50 mol parts or less. If the total of BPDA residues and TAHQ residues is less than 30 mol parts, the formation of the ordered structure of the polymer becomes insufficient, the moisture absorption resistance decreases, or the dielectric tangent decreases insufficiently. If it exceeds 60 mol parts 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 the heat resistance may decrease.

In addition, a tetracarboxylic acid residue (hereinafter, also referred to as "PMDA residue") derived from pyromellitic dianhydride and a tetracarboxylic acid derived from 2,3,6,7-naphthalenetetracarboxylic dianhydride The acid residue (hereinafter, also referred to as "NTCDA residue") has rigidity, and thus is a residue that improves in-plane orientation, suppresses CTE to a low level, and plays a role in RO control or glass transition temperature control. On the other hand, since the molecular weight of the PMDA residue is small, if the amount is too large, the imide group concentration of the polymer increases, the polar group increases, and the hygroscopicity increases, and the hygroscopicity increases due to the influence of the moisture inside the molecular chain. The dielectric tangent increases. In addition, the NTCDA residue tends to become fragile due to the highly rigid naphthalene skeleton and to increase the elastic modulus.

Therefore, in the first embodiment, the second embodiment, or the third embodiment, the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer is preferably 40 parts by mole in total with respect to 100 parts by mole of the tetracarboxylic acid residue. PMDA residues and NTCDA residues are contained within a range of not less than 70 parts by mol and not more than 70 parts by mol, more preferably not less than 50 parts by mol and not more than 60 parts by mol, and still more preferably within a range of 50 parts by mol to 55 parts by mol. If the total of PMDA residues and NTCDA residues is less than 40 mol parts, the CTE may increase or the heat resistance may decrease, and if it exceeds 70 mol parts, the imide group concentration of the polymer may increase and the polar group increase and the low hygroscopicity is impaired, the dielectric tangent increases, or the film becomes brittle and the self-supporting property of the film decreases.

In addition, in the first embodiment, as specified in the condition (a-i), the sum 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 100 mol parts of a residue is 80 mol parts or more, Preferably it is 90 mol parts or more.

In addition, in the first embodiment, as specified in the conditions (a-i), 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 within the range of 0.6 or more and 1.3 or less, preferably 0.7 or more and 1.3 or less, more preferably 0.8 or more and 1.2 or less range, control the formation of the ordered structure of the CTE with the polymer.

In the first embodiment, the second embodiment, or the third embodiment, since PMDA and NTCDA have a rigid skeleton, compared with other general acid anhydride components, the in-plane orientation of the molecules in the polyimide can be controlled, and they have thermal expansion. Inhibition of coefficient (CTE) and improvement of glass transition temperature (Tg). In addition, since the molecular weight of BPDA and TAHQ is larger than that of PMDA, the imide group concentration decreases due to the increase of the loading ratio, which is effective in reducing the dielectric tangent or the moisture absorption rate. On the other hand, when the incorporation ratio of BPDA and TAHQ is increased, the in-plane orientation of the molecules in the polyimide is lowered, resulting in an increase in CTE. Furthermore, the formation of an ordered structure in the molecule is promoted, and the haze value is increased. From this viewpoint, the total amount of PMDA and NTCDA charged may be in the range of 40 to 70 parts by mol, preferably 50 to 60 parts by mol, based on 100 parts by mol of all acid anhydride components in the raw material. within the range, more preferably within the range of 50 to 55 parts by mole. If the total loading amount of PMDA and NTCDA is less than 40 mol parts with respect to 100 mol parts of all the acid anhydride components in the raw material, the in-plane orientation of the molecules decreases, and it becomes difficult to reduce the CTE, and the decrease in Tg is also caused. The heat resistance or dimensional stability of the film upon heating decreases. On the other hand, when the total loading amount of PMDA and NTCDA exceeds 70 mol parts, there exists a tendency for the moisture absorption rate to worsen by the increase of the imide group density|concentration, or to increase the elastic modulus.

In addition, BPDA and TAHQ have effects on the inhibition of molecular motion or on the reduction of the dielectric tangent and the decrease in the moisture absorption rate due to the decrease in the concentration of imide groups, but they degrade the CTE of the imidized polyimide film. increase. From this viewpoint, the total charged amount of BPDA and TAHQ may be in the range of 30 to 60 parts by mol, preferably 40 to 50 parts by mol, based on 100 parts by mol of all the acid anhydride components of the raw material. within the range, more preferably within the range of 40 to 45 parts by mole.

Examples of 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'-diphenylsulfone tetracarboxylic 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'-diphenyl ether tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl) ether dianhydride, 3,3" ,4,4"-p-terphenyltetracarboxylic dianhydride, 2,3,3",4"-p-terphenyltetracarboxylic dianhydride or 2,2",3,3"-p-terphenyltetracarboxylic acid dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-propane dianhydride or 2,2-bis(3,4-dicarboxyphenyl)-propane dianhydride, bis(2,3-di Carboxyphenyl)methane dianhydride or bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)sulfone dianhydride or bis(3,4-dicarboxyphenyl)sulfone 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-cyclohexanedianhydride, 1,2,5,6-naphthalene Tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic 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 acid 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 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-dicarboxyphenoxy) Tetracarboxylic acid residues derived from aromatic tetracarboxylic dianhydrides such as diphenylmethane dianhydride and ethylene glycol bis-trimellitic anhydride.

(diamine residue)

In the first embodiment, the second embodiment or the third embodiment, the diamine residue contained in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer is preferably represented by the general formula (A1). A diamine residue derived from the indicated diamine compound.

[hua 7]

In formula (A1), the linking group X represents a single bond or -COO-, Y independently represents hydrogen, a monovalent hydrocarbon group having 1 to 3 carbon atoms or an alkoxy group, n represents an integer of 0 to 2, and p and q independently Indicates an integer from 0 to 4. Here, "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 amino groups at the terminal may be substituted, for example, -NR ₃ R ₄ (here, R ₃ and R ₄ independently represent an arbitrary group such as an alkyl group). substituent).

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

As the diamine (A1), for example, 1,4-diaminobenzene (p-phenylenediamine (p-PDA)), 2,2'-dimethyl-4,4'-diamino Biphenyl (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-amino phenyl-4'-amino benzoate, APAB) and the like.

The non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer of the first embodiment or the second embodiment can be contained in an amount of preferably 80 mol parts or more, and more preferably 85 mol parts with respect to 100 mol parts of the diamine residue. part or more of the diamine residue derived from the diamine (A1). By using the diamine (A1) in an amount within the above range, it is easy to form an ordered structure in the polymer as a whole by utilizing the rigid structure derived from the monomer, and it is easy to obtain low air permeability, low hygroscopicity, and low dielectric tangent of non-thermoplastic polyimide.

In addition, in the first embodiment or the second embodiment, the amount of the diamine residue derived from the diamine (A1) is 80 parts by mole with respect to 100 parts by mole of the diamine residue in the non-thermoplastic polyimide. In the range of more than or equal to 85 mol parts, it is preferable to use 1, 4- diaminobenzene as a diamine (A1) from a viewpoint of a structure which is more rigid and excellent in in-plane orientation.

In the first embodiment or the second embodiment, as another diamine residue contained in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer, for example, 2,2-bis-[4- (3-Aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]sulfone, 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]fluorene, 2,2-bis-[4-(4-aminophenoxy) base)phenyl]hexafluoropropane, 2,2-bis-[4-(3-aminophenoxy)phenyl]hexafluoropropane, 3,3'-dimethyl-4,4'-diaminobiphenyl Benzene, 4,4'-methylenebis-o-toluidine, 4,4'-methylenebis-2,6-xylidine, 4,4'-methylene-2,6-diethyl Aniline, 3,3'-diaminodiphenylethane, 3,3'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 3,3"-diamino-p-terphenyl, 4 ,4'-[1,4-phenylenebis(1-methylethylene)]dianiline, 4,4'-[1,3-phenylenebis(1-methylethylene)] Dianiline, 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-xylene diamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, piperazine, 2'-methoxy-4 ,4'-Diaminobenzoic anilide, 4,4'-diaminobenzoic anilide, 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene, 6-amino- Diamine residues derived from aromatic diamine compounds such as 2-(4-aminophenoxy)benzoxazole, diamine residues derived from two terminal carboxylic acid groups of dimer acid substituted with primary aminomethyl or amino groups A diamine residue derived from an aliphatic diamine compound such as dimer acid diamine.

In addition, in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer of the third embodiment, the diamine (A1) is defined as the condition (c-i) with respect to 100 mol of all the diamine components in the raw material. The part may be 70 parts by mol or more, for example, in the range of 70 parts by mol to 90 parts by mol, preferably in the range of 80 parts by mol to 90 parts by mol. On the other hand, when the charging amount of the diamine (A1) exceeds 90 mol parts, the elongation of the film may decrease.

Moreover, it is preferable that the non-thermoplastic polyimide used in 3rd Embodiment uses the at least 1 sort(s) of aromatics chosen from the group which consists of the aromatic diamines represented by general formula (C1) - general formula (C4). Diamine is a diamine component of a raw material. Since the diamines (C1) to (C4) have bulky substituents or flexible sites, flexibility can be imparted to the polyimide. Moreover, since the diamine (C1) - diamine (C4) can improve air permeability, it has the effect of suppressing foaming at the time of manufacture of a multilayer film and a metal sheet laminate. From this viewpoint, it is preferable to use one selected from the group consisting of diamine (C1) to diamine (C4) in the range of 2 to 15 mol parts with respect to 100 mol parts of all the diamine components of the raw material. more than one aromatic diamine. When the charged amount of diamine (C1) - diamine (C4) is less than 2 mol parts, foaming may generate|occur|produce when manufacturing a multilayer film and a metal sheet laminate. Moreover, when the charging amount of diamine (C1) - diamine (C4) exceeds 15 mol parts, the orientation of a molecule will fall, and it will become difficult to reduce CTE.

[hua 8]

In the above formulas (C1) to (C4), R ₂ independently represents a monovalent hydrocarbon group, alkoxy group or alkylthio group having 1 to 6 carbon atoms, and the linking group A' independently represents a group selected from -O-, - A divalent group in SO ₂ -, -CH ₂ - or -C(CH ₃ ) ₂ -, preferably 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. Here, "independently" means a plurality of linking groups A', a plurality of linking groups X1, and a plurality of substituents R ₂ in one formula or two or more formulae in the above formulas (C1) to (C4). A plurality of n ₃ and n ₄ may be the same or different. In addition, in the above formulas (C1) to (C4), the hydrogen atoms in the two amino groups at the terminal may be substituted, for example, -NR ₃ R ₄ (here, R ₃ and R ₄ independently represent arbitrary substituents such as alkyl).

As the aromatic diamine represented by general formula (C1), 2,6-diamino-3,5-diethyltoluene, 2,4-diamino-3,5-diethyltoluene, etc. are mentioned, for example.

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, etc.

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.

As the aromatic diamine represented by general formula (C4), 2,2-bis[4-(4-aminophenoxy)phenyl]propane etc. are mentioned, for example.

As described above, the non-thermoplastic polyimide constituting the polyimide film of the third embodiment may be 70 parts by mol or more, preferably 70 parts by mol to 90 parts by mol relative to 100 parts by mol of the diamine residue. It controls so that the residue derived from diamine (A1) is contained in the range, and the residue derived from diamine (C1)-diamine (C4) is contained in the range of 2-15 mol part.

In 3rd Embodiment, as another diamine which can be used as a raw material of polyimide, 2,2-bis-[4-(3-aminophenoxy)phenyl]propane, 2,2-bis-[4-(3-aminophenoxy)phenyl]propane, -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-aminobenzene) oxy)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]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, 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]fluorene, 2,2-bis- [4-(3-Aminophenoxy)phenyl]hexafluoropropane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenedi-o-toluidine , 4,4'-methylenebis-2,6-dimethylaniline, 4,4'-methylene-2,6-diethylaniline, 3,3'-diaminodiphenylethane , 2-trifluoromethyl-4,4'-diaminodiphenyl ether, 2,2'-di-trifluoromethyl-4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether Aminobiphenyl, 3,3'-dimethoxybenzidine, 3,3"-diamino-p-terphenyl, 4,4'-[1,4-phenylenebis(1-methylethylene) )] bisaniline, 4,4'-[1,3-phenylene bis(1-methylethylene)] bisaniline, bis(p-aminocyclohexyl)methane, bis(p-β-amino-tertiary Butylphenyl) ether, bis(p-β-methyl-δ-aminopentyl)benzene, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,1-di) Methyl-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-xylene diamine, p-xylene diamine, 2,6-diaminopyridine, 2,5-diaminopyridine , 2,5-diamino-1,3,4-oxadiazole, piperazine, 2'-methoxy-4,4'-diaminobenzoic anilide, 4,4'-diaminobenzoyl Aromatic diamine compounds such as aniline.

In the third embodiment, BPDA, TAHQ, PMDA, and NTCDA, which are acid anhydride components used as raw materials of polyimide, and diamine (A1) and diamine (C1), which are diamine components, are used in the above molar ratios, respectively. - Diamine (C4), the amount of residues derived from these raw material compounds can be controlled, and the reduction of dielectric tangent and moisture absorption can be combined with the suppression of foaming in the production of multilayer films and metal sheet laminates.

The polyimide film of the third embodiment has low dielectric constant, low dielectric tangent, and low hygroscopicity. Therefore, for example, it is preferable as a matrix resin in an insulating resin layer of a copper sheet laminate serving as a raw material of FPC. . In addition, since aromatic tetracarboxylic acid anhydride and aromatic diamine are used as monomers used as raw materials of polyimide, the problem of dimensional change due to heating is not easily caused, and it has flame retardancy, and it is not necessary to prepare flame retardancy agent. Therefore, by using the polyimide film of 3rd Embodiment and the copper sheet laminated board using the same, the reliability and yield improvement of circuit boards, such as FPC, can be aimed at.

In the non-thermoplastic polyimide of the first embodiment, the second embodiment, or the third embodiment, the types of the tetracarboxylic acid residues and the diamine residues are selected, or two or more kinds of tetracarboxylic acids are used. The molar ratio of the residues or the diamine residues can control the thermal expansion coefficient, storage elasticity coefficient, tensile elasticity coefficient, and the like. In addition, in the non-thermoplastic polyimide, in the case of having a plurality of polyimide structural units, it may exist in the form of a block or may exist randomly, but the variation in in-plane retardation (RO) is suppressed. From a viewpoint, random presence is preferable.

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

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 the value obtained by dividing the molecular weight of the imide group part (-(CO) ₂ -N-) in the polyimide by the molecular weight of the entire structure of the polyimide. When the imide group concentration exceeds 33% by weight, the molecular weight of the resin itself decreases, and the low hygroscopicity also deteriorates due to an increase in polar groups. In the first embodiment or the second embodiment, by selecting the combination of the acid anhydride and the diamine compound, the orientation of the molecules in the non-thermoplastic polyimide is controlled, thereby suppressing the change of CTE accompanying the decrease in the imide group concentration. increase to ensure low hygroscopicity.

In the first embodiment, the second embodiment, or the third embodiment, the weight average molecular weight of the non-thermoplastic polyimide is preferably in the range of, for example, 10,000 to 400,000, and more preferably in the range of 50,000 to 350,000. When the weight-average molecular weight is less than 10,000, the strength of the film decreases and tends to become brittle. On the other hand, when the weight-average molecular weight exceeds 400,000, the viscosity tends to increase excessively and problems such as uneven film thickness and streaks tend to occur during the coating operation.

<Thermoplastic polyimide>

In the polyimide film of the first embodiment or the second embodiment, the thermoplastic polyimide constituting the thermoplastic polyimide layer contains a tetracarboxylic acid residue and a diamine residue, and preferably contains an aromatic An aromatic tetracarboxylic acid residue derived from 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 tetracarboxylic acid residue in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer described above can be used The base and the exemplified are the same.

(diamine residue)

As the diamine residue contained in the thermoplastic polyimide constituting the thermoplastic polyimide layer, diamine residues derived from diamine compounds represented by general formulae (B1) to (B7) are preferred .

[Chemical 9]

In formulas (B1) to (B7), R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms, 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-, and n ₁ independently represents an integer of 0 to 4 . Among them, those repeating with formula (B2) are removed from formula (B3), and those repeating with formula (B4) are removed from formula (B5). Here, "independently" means that a plurality of linking groups A, a plurality of R ₁ , or a plurality of n ₁ may be the same or different in one or two or more of the formulas (B1) to (B7). . In addition, in the above formulas (B1) to (B7), the hydrogen atoms in the two amino groups at the terminal may be substituted, for example, -NR ₃ R ₄ (here, R ₃ and R ₄ independently represent arbitrary substituents such as alkyl).

The diamine represented by formula (B1) (hereinafter, it may be expressed as "diamine (B1)") is an aromatic diamine having two benzene rings. It is considered that the diamine (B1) is in the meta position through the amino group directly bonded to at least one benzene ring and the divalent linking group A, and the polyimide molecular chain has an increased degree of freedom and high flexibility, which helps Due to the improvement of the flexibility of the polyimide molecular chain. Therefore, by using the diamine (B1), the thermoplasticity of the polyimide is improved. Here, as the linking group A, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -SO ₂ -, and -S- are preferable.

As the diamine (B1), for example, 3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenylpropane, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3'-diaminodiphenylsulfone, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 3,4' -Diaminodiphenylpropane, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, (3,3'-bisamino)diphenylamine, etc.

The diamine represented by formula (B2) (hereinafter, it may be expressed as "diamine (B2)") is an aromatic diamine having three benzene rings. It is considered that the diamine (B2) is in the meta position through the amino group directly bonded to at least one benzene ring and the divalent linking group A, and the polyimide molecular chain has an increased degree of freedom and high flexibility, which helps Due to the improvement of the flexibility of the polyimide molecular chain. Therefore, by using the diamine (B2), the thermoplasticity of the polyimide is improved. Here, as the linking group A, -O- is preferable.

As the diamine (B2), for example, 1,4-bis(3-aminophenoxy)benzene, 3-[4-(4-aminophenoxy)phenoxy]aniline, 3-[3- (4-Aminophenoxy)phenoxy]aniline and the like.

The diamine represented by formula (B3) (hereinafter, it may be expressed as "diamine (B3)") is an aromatic diamine having three benzene rings. It is considered that the diamine (B3) is in the meta position with each other through the two divalent linking groups A directly bonded to one benzene ring, and the polyimide molecular chain has an increased degree of freedom and high flexibility, which helps Due to the improvement of the flexibility of the polyimide molecular chain. Therefore, by using the diamine (B3), the thermoplasticity of the polyimide is improved. Here, as the linking group A, -O- is preferable.

As the diamine (B3), for example, 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)bisoxy]dianiline, 4,4'-[4-Methyl-(1,3-phenylene)dioxy]bisaniline, 4,4'-[5-methyl-(1,3-phenylene)dioxy ] Dianiline, etc.

The diamine represented by formula (B4) (hereinafter, it may be expressed as "diamine (B4)") is an aromatic diamine having four benzene rings. It is considered that the diamine (B4) has high flexibility because the amino group directly bonded to at least one benzene ring is in the meta position with the divalent linking group A, and contributes to the improvement of the flexibility of the polyimide molecular chain . Therefore, by using the diamine (B4), the thermoplasticity of the polyimide is improved. Here, as the linking group A, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -SO ₂ -, -CO-, and -CONH- are preferable.

As the diamine (B4), bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]propane, bis[4-(3 -Aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)]benzophenone, bis[4, 4'-(3-aminophenoxy)] benzoic anilide, etc.

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

As the diamine (B5), 4-[3-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline, 4,4'-[oxybis(3,1-idene) phenoxy)] dianiline, etc.

The diamine represented by formula (B6) (hereinafter, it may be expressed 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 the diamine (B6), the thermoplasticity of the polyimide is improved. Here, as the linking group A, -C(CH ₃ ) ₂ -, -O-, -SO ₂ -, and -CO- are preferable.

As the diamine (B6), for example, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (2,2-Bis[4-(4-aminophenoxy)phenyl]propane, BAPP) may be mentioned. ), 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 (BAPK) Wait.

The diamine represented by formula (B7) (hereinafter, it may be expressed as "diamine (B7)") is an aromatic diamine having four benzene rings. Since the diamine (B7) has a highly flexible bivalent 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 the diamine (B7), the thermoplasticity of the polyimide is improved. Here, as the linking group A, -O- is preferable.

As diamine (B7), bis[4-(3-aminophenoxy)]biphenyl, bis[4-(4-aminophenoxy)]biphenyl, etc. are mentioned, for example.

In the first embodiment or the second embodiment, the thermoplastic polyimide constituting the thermoplastic polyimide layer is 70 mol parts or more, preferably 70 mol parts or more and 99 mol parts with respect to 100 mol parts of the diamine residue. Diamine residues derived from at least one diamine compound selected from the group consisting of diamine (B1) to diamine (B7) are contained within a range of part or less, more preferably within a range of 80 parts by mol or more and 95 parts by mol or less base. Since the diamines (B1) to (B7) contain a flexible molecular structure, by using at least one diamine compound selected from these compounds in an amount within the above range, the polyimide molecule can be increased in size. Chain flexibility and imparts thermoplasticity. If the total amount of diamines (B1) to (B7) is less than 70 parts by mol with respect to 100 parts by mol of all the 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. The diamine (A1) has a rigid structure and has a function of imparting an ordered structure to the entire polymer, and thus can reduce the dielectric tangent and hygroscopicity by suppressing the movement of molecules. Furthermore, by using it as a raw material of thermoplastic polyimide, the polyimide which is low in air permeability and excellent in long-term heat-resistant adhesiveness can be obtained.

In the first embodiment or the second embodiment, the thermoplastic polyimide constituting the thermoplastic polyimide layer may be preferably in a range of 1 part by mol or more and 30 parts by mol or less, more preferably 5 parts by mol or more and 20 parts by mol. The diamine residue derived from diamine (A1) is contained in the range below a molar part. By using the diamine (A1) in an amount within the above-mentioned range, the polymer as a whole forms an ordered structure due to the rigid structure derived from the monomer, so that it is thermoplastic and has low air permeability and hygroscopicity, and a long-term heat-resistant adhesive can be obtained. Excellent polyimide.

The thermoplastic polyimide constituting the thermoplastic polyimide layer may contain diamine compounds other than diamine (A1) and diamine (B1) to diamine (B7) within a range that does not impair the effects of the invention. the diamine residue.

In thermoplastic polyimide, thermal expansion can be controlled by selecting the type of the tetracarboxylic acid residue and the diamine residue, or the molar ratio of each when two or more tetracarboxylic acid residues or diamine residues are used. coefficient, tensile elastic coefficient, glass transition temperature, etc. Moreover, in a thermoplastic polyimide, when it has several structural units of polyimide, it may exist in the form of a block or may exist randomly, but it is preferable that it exists 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 aromatic groups, the polyimide film can be improved in Dimensional accuracy in a high temperature environment and suppression of in-plane retardation (RO) variation.

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

The weight average molecular weight of the thermoplastic polyimide is, for example, preferably in the range of 10,000 to 400,000, and more preferably in the range of 50,000 to 350,000. When the weight-average molecular weight is less than 10,000, the strength of the film decreases and tends to become brittle. On the other hand, when the weight-average molecular weight exceeds 400,000, the viscosity tends to increase excessively and problems such as uneven film thickness and streaks tend to occur during the coating operation.

In the polyimide film of 1st Embodiment or 2nd Embodiment, the thermoplastic polyimide which comprises a thermoplastic polyimide layer can improve the adhesiveness with copper foil. The glass transition temperature of the thermoplastic polyimide is in the range of 200°C or higher and 350°C or lower, preferably in the range of 200°C or higher and 320°C or lower.

Since the thermoplastic polyimide constituting the thermoplastic polyimide layer is, for example, an adhesive layer in an insulating resin of a circuit board, it is most preferable to have a completely imidized structure in order to suppress the diffusion of copper. However, a part of polyimide may be an amic acid. The imidization ratio was measured using a Fourier transform infrared spectrophotometer (commercial product: FT/IR620 manufactured by JASCO), and the polyimide film was measured by the Attenuated Total Reflectance (ATR) method. The infrared absorption spectrum of , was calculated from the absorbance derived from the C=O expansion and contraction of the imide group at 1780 cm ^-1 on the basis of the benzene ring absorber near 1015 cm ^-1 .

<Form 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) containing an insulating resin, or may be laminated on The film of insulating resin in the state on the base material, such as a resin sheet, such as a copper foil, a glass plate, a polyimide-type film, a polyamide-type film, and a polyester-type 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 in the range of 8 μm to 50 μm, and more preferably in the range of 11 μm to 26 μm. When the thickness of the polyimide film is less than the lower limit, problems such as failure to secure electrical insulating properties, or difficulty in handling in manufacturing steps due to deterioration in handling properties may occur. On the other hand, when the thickness of the polyimide film exceeds the upper limit value, for example, the manufacturing conditions for controlling the in-plane retardation (RO) need to be controlled with high precision, resulting in problems such as a drop 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) layer) can be in the range of 1.5 to 6.0. When the value of the ratio is less than 1.5, the non-thermoplastic polyimide layer becomes thinner with respect to the entire polyimide film, so that the variation in in-plane retardation (RO) tends to increase, and when it exceeds 6.0, the thermoplastic polyimide Since the amine layer becomes thinner, the adhesion 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. Regarding the thermoplastic polyimide layer, which is a resin that imparts adhesiveness, that is, high thermal expansion or softening, the larger the thickness of the thermoplastic polyimide layer, the more remarkably affects 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 and its deviation are decreased.

＜Film width＞

In the second embodiment, the polyimide film preferably has a film width in the range of 490 mm or more and 1100 mm or less, and has a long shape from the viewpoint of more remarkably showing the effect of improving the dimensional accuracy of the polyimide film. The length of 20m or more. In the case where the polyimide film of the second embodiment is continuously produced, 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.

<In-plane retardation (RO)>

Regarding the polyimide film of the second embodiment, the value of the in-plane retardation (RO) is within the range of 5 nm or more and 50 nm or less, preferably 5 nm or more and 20 nm or less, and more preferably 5 nm or more and 15 nm or less. within the range. In addition, the deviation (ΔRO) of RO 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-mentioned range, the dimensional accuracy is particularly high even for a film having a thickness of 25 μm or more.

In the polyimide film of the second embodiment, the amount of change in in-plane retardation (RO) before and after pressing at a temperature of 320° C., a pressure of 340 MPa/m ² , and a holding time of 15 minutes is 20 nm or less, preferably 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 equal to or less than the upper limit. Even before and after the step of bonding the polyimide film of the second embodiment to the copper foil by thermal lamination, RO is not easily changed, 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 applied as an insulating layer of a circuit board, for example, in order to prevent the occurrence of warpage and the reduction of dimensional stability, the above-mentioned condition (a-iii) ) or condition (b-i), it is important that the coefficient of thermal expansion (CTE) of the entire film is within the range of 10 ppm/K or more and 30 ppm/K or less, preferably 10 ppm/K or more and 25 ppm/K or less, and more It is preferably within the range of 10 ppm/K to 20 ppm/K. When CTE is less than 10 ppm/K or exceeds 30 ppm/K, warpage occurs or dimensional stability decreases. In addition, the coefficient of thermal expansion (CTE) of the polyimide film of the third embodiment is also the same as that of the first embodiment or the second embodiment.

＜Dielectric tangent＞

The polyimide film of the first embodiment, the second embodiment, or the third embodiment is applied to, for example, an insulating layer of a circuit board as defined in the above-mentioned condition (a-iv) or condition (c-iii). In this case, in order to ensure impedance matching, the dielectric tangent (Tanδ) at 10 GHz when measured by a split dielectric resonator (split postdielectric resonator (SPDR)) as a whole insulating layer can be obtained. It is 0.004 or less, more preferably, it is in the range of 0.001 or more and 0.004 or less, and still more preferably, it is in the range of 0.002 or more and 0.003 or less. In order to improve the dielectric properties 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. When the dielectric tangent of the insulating layer at 10 GHz exceeds 0.004, when it is used in a circuit board such as an FPC, problems such as loss of electrical signals are likely to occur in 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 physical property control when polyimide is applied as an insulating layer of a circuit board is considered.

<Dielectric constant>

For example, when the polyimide film of the first embodiment, the second embodiment, or the third embodiment is applied as an insulating layer of a circuit board, in order to ensure impedance matching, the insulating layer as a whole is preferably 10 GHz. The dielectric constant is 4.0 or less. When the dielectric constant of the insulating layer at 10 GHz exceeds 4.0, when used in a circuit board such as an FPC, the dielectric loss of the insulating layer is deteriorated, and the loss of electrical signals is likely to occur in the transmission path of high-frequency signals. bad condition.

＜Moisture absorption rate＞

The polyimide film of the first embodiment or the second embodiment preferably has a moisture absorption rate of 0.7 at 23° C. and 50% RH in order to reduce the influence of humidity when used for circuit boards such as FPC. % by weight or less. When the moisture absorption rate of a polyimide film exceeds 0.7 weight%, when it is used for circuit boards, such as FPC, it is easy to be affected by humidity, and troubles, such as a fluctuation|variation of the transmission speed of a high frequency signal, are easy to arise. That is, if the moisture absorption rate of the polyimide film exceeds the above-mentioned range, it is easy to absorb water with high dielectric constant and dielectric tangent, so that the dielectric constant and dielectric tangent increase, and it is easy to be used in the transmission path of high-frequency signals. There are other problems such as loss of electrical signals.

In addition, in consideration of the influence on the dimensional stability and dielectric properties of the polyimide film, the polyimide film of the third embodiment preferably has a moisture absorption rate when subjected to humidity conditioning at 23° C. and 50% RH for 24 hours. 0.65 wt% or less. When the moisture absorption rate exceeds 0.65% by weight, the dimensional stability and dielectric properties of the polyimide film may be deteriorated. Regarding the moisture absorption rate of 0.65% by weight or less, it is considered that the concentration of polar groups in the polyimide is low and the ordered structure of the polymer chain is easily formed, which is preferable for the improvement of dimensional stability and dielectric properties. . Among them, when the moisture absorption rate is low, the haze value (HAZE) tends to be high along with the formation of the ordered structure of the polymer chain, so it is preferable to also consider the haze value described later.

<tensile elastic modulus>

Moreover, it is preferable that the tensile elastic modulus of the polyimide film of 2nd Embodiment exists in the range of 3.0GPa-10.0GPa, and it may exist in the range of 4.5GPa-8.0GPa. When the tensile modulus of elasticity of the polyimide film is less than 3.0 GPa, the strength of the polyimide itself may decrease, which may cause problems in handling such as film breakage when the copper sheet laminate is processed into a circuit board. Conversely, when the tensile modulus of elasticity of the polyimide film exceeds 10.0 GPa, the rigidity with respect to the bending of the copper-stretched laminate increases, and as a result, the bending stress applied to the copper wiring when the copper-stretched laminate is bent increases. , and the bending resistance decreases. By setting the tensile modulus of elasticity of the polyimide film to be within the above range, the strength and flexibility of the polyimide film are ensured.

＜Glass transition temperature＞

The polyimide film of the third embodiment has a glass transition temperature of 300° C. or higher as prescribed by the above-mentioned condition (c-ii). When the glass transition temperature is less than 300° C., when a copper-clad plate (CCL) or FPC using the polyimide film of the third embodiment is produced, expansion of the film and peeling of the wiring are likely to occur. And other issues. On the other hand, by setting the glass transition temperature to be 300° C. or higher, the solder heat resistance and dimensional stability of the polyimide film are improved.

<Haze value>

The polyimide film of the third embodiment preferably has a haze (HAZE) value based on Japanese Industrial Standards (JIS) K 7136 when processed into a polyimide film having a thickness of 25 μm as follows In the range of 62% to 75%, the polyimide film is removed by etching, and a solution of polyamic acid, which is a precursor of polyimide, is applied to a ten-point average roughness (Rz) of 0.6 μm. The copper foil of the laminated board formed by imidization on the copper foil is obtained. When the haze value exceeds 75%, the visibility through the polyimide film of the third embodiment will be lowered. Therefore, in a photolithography step of a copper sheet laminate (CCL) obtained by using a polyimide film, or a process of mounting an FPC (flexible printed circuit board) using the CCL, there is a When the visibility of the alignment mark is lowered, the position alignment with the alignment mark becomes difficult, and the practicality is lowered. On the other hand, when the haze value is less than 62%, the visibility becomes high and the formation of the ordered structure of the polyimide polymer chain is not promoted, so that the hygroscopic properties and the dielectric properties may be impaired. In the third embodiment, the preferable value of the haze value is set to 62% to 75% in order to achieve a lower dielectric tangent and a lower moisture absorption rate due to the formation of an ordered structure and to maintain visibility. 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 folded and stored in a small space in a casing of a mobile device or the like. In the above-mentioned usage mode, when the film elongation rate is low, it becomes a cause of disconnection of the wiring. Therefore, about the polyimide film of 3rd Embodiment, the preferable film elongation is made into 30 % or more.

＜Packing＞

The polyimide film of 1st Embodiment, 2nd Embodiment, or 3rd Embodiment may contain an inorganic filler in a non-thermoplastic polyimide layer or a thermoplastic polyimide layer as needed. Specifically, for example, silica, alumina, magnesia, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride, etc. are mentioned. These can be used alone or in combination of two or more.

[Manufacturing method]

As an aspect of the manufacturing method of the polyimide film of the first embodiment, the second embodiment, or the third embodiment, for example, [1] after applying a polyamic acid solution on a support substrate and drying, performing A method of producing a polyimide film by imidization; [2] After coating a polyamic acid solution on a support substrate and drying, peeling off the gel film of the polyamic acid from the support substrate to carry out imide A method of producing a polyimide film by chemistry. In addition, since the polyimide film of 1st Embodiment or 2nd Embodiment is a polyimide film containing a multilayer polyimide layer, as an aspect of the manufacturing method, for example, [3] Repeating A method of applying a polyamic acid solution to a support substrate multiple times and drying it, followed by a method of imidization (hereinafter, casting method); [4] Laminate the polyamic acid while extruding through multiple layers A method of applying and drying in a multilayered state, followed by imidization (hereinafter, a multilayer extrusion method) or the like. The same applies to the case where the polyimide film of the third embodiment is applied as one layer in the multilayer polyimide film including the multilayer polyimide layer. It does not specifically limit as a method to apply|coat a polyimide solution (or a polyamic acid solution) to a base material, For example, it can apply|coat using a coater, such as a cutout wheel, a die, a doctor blade, and a die lip. When forming a multilayer polyimide layer, it is preferable to repeat the operation of applying a polyimide solution (or a polyamic acid solution) to a base material and drying it.

For example, the method of [1] may include the following steps 1a to 1c:

(1a) the step of coating the polyamic acid solution on the support substrate and drying;

(1b) a step of forming a polyimide layer by heat-treating and imidizing a polyamic acid on a support substrate;

(1c) A step of obtaining a polyimide film by separating the support substrate from the polyimide layer.

For example, the method of [2] may include the following steps 2a to 2c:

(2a) the step of coating the polyamic acid solution on the support substrate and drying;

(2b) the step of separating the support substrate from the gel film of polyamic acid;

(2c) The step of obtaining a polyimide film by heat-treating and imidizing the gel film of polyamic acid.

With regard to the method of the above [3], except that in the method of the above [1] or the method of [2], the step 1a or the step 2a is repeatedly performed a plurality of times to form the laminated structure of the polyamic acid on the support substrate, It can be implemented in the same manner as the method of [1] or the method of [2].

Regarding the method of the above [4], except that in the step 1a of the method of the [1] or the step 2a of the method of the [2], the laminated structure of the polyamic acid is simultaneously coated and dried by multi-layer extrusion Other than that, it can be implemented in the same manner as the method of [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 the imidization of the polyamic acid is completed on the support substrate. Since the resin layer of the polyamic acid is imidized in a state of being fixed on the support substrate, the change in expansion 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 applying the polyimide film of 3rd Embodiment as one layer of the multilayer polyimide film including the multilayer polyimide layer, for example, at a temperature from 120° C. to 360° C. The heat treatment for imidization is performed stepwise at a temperature within the range, and the heat treatment time is controlled within a range of 5 minutes or more, preferably within a range of 10 minutes to 20 minutes, thereby effectively suppressing foaming and preventing polymerization. Defects such as swelling of the imide layer.

Regarding the polyimide film in which the imidization of the polyamic acid is completed on the supporting substrate, the tension applied to the polyimide film when the polyimide film is separated from the supporting substrate, or, for example, using The polyimide film stretches due to the stress to the polyimide film that occurs when the blade or the like is peeled off, and the variation in the in-plane retardation (RO) of the polyimide film tends to occur. In particular, with regard to the polyimide film of the second embodiment, since any of the polyimides constituting the non-thermoplastic polyimide layer and the thermoplastic polyimide layer easily forms an ordered structure, it is easy to form an ordered structure by peeling off The required stress is dispersed in each layer of the polyimide film, and RO can be controlled.

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

[Copper sheet laminate]

The copper sheet laminate of the first embodiment, the second embodiment, or the third embodiment includes an insulating layer, and includes a copper foil on at least one surface of the insulating layer, and only uses the first embodiment for part or all of the insulating layer. , the polyimide film of the second embodiment or the third embodiment may be formed. Moreover, in order to improve the adhesiveness of an insulating layer and a copper foil, it is preferable that the layer in contact with the copper foil among the insulating layers is a thermoplastic polyimide layer. Therefore, it is preferable that the polyimide film of 3rd Embodiment is used as a copper sheet laminated board in the state laminated|stacked with the thermoplastic polyimide layer. The copper foil is arranged on one side or both sides of the insulating layer. That is, the copper sheet laminate of the first embodiment, the second embodiment, or the third embodiment may be a single-sided copper sheet laminate (single-sided CCL) or a double-sided copper sheet laminate (double-sided CCL). In the case of single-sided CCL, the copper foil laminated on one surface of the insulating layer is referred to as the "first copper foil layer" of 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 the insulating layer has the surface laminated on the first copper foil layered as the “first copper foil layer” of the present invention. The copper foil on the opposite side is referred to as the "second copper foil layer" of the present invention. About the copper sheet laminated board of 1st Embodiment, 2nd Embodiment, or 3rd Embodiment, copper foil is etched etc., wiring circuit processing is performed, and copper wiring is formed, and it is used as an FPC.

The copper sheet laminate can be prepared, for example, by preparing a resin film including the polyimide film of the first embodiment, the second embodiment, or the third embodiment, and sputtering metal to form a seed layer. , for example, a copper foil layer is formed by copper plating.

In addition, the copper sheet laminate can also be prepared by preparing a resin film including the polyimide film of the first embodiment, the second embodiment, or the third embodiment, and layering it by a method such as thermocompression bonding. Pressed copper foil.

Furthermore, a copper sheet laminate can also be produced by casting a coating liquid containing a polyamic acid as a precursor of a polyimide on a copper foil, drying it to obtain a coating film, and then heat-treating and forming a coating film. The imidization is performed to form a polyimide layer.

<1st copper foil layer>

In the copper sheet laminate of the first embodiment, the second embodiment, or the third embodiment, the copper foil (hereinafter, sometimes referred to as "first copper foil") used in the first copper foil layer is not particularly limited. For example, It can be rolled copper foil or electrolytic copper foil. 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 in the range of 6 μm to 13 μm, and still more preferably in the range of 6 μm to 12 μm. By setting the thickness of the first copper foil to be 18 μm or less, preferably 13 μm or less, and more preferably 12 μm or less, the bendability of the copper sheet laminate (or FPC) can be improved. Moreover, it is preferable to make the lower limit of the thickness of a 1st copper foil into 6 micrometers from a viewpoint of production stability and handleability.

Moreover, in 1st Embodiment, 2nd Embodiment, or 3rd Embodiment, it is preferable to exist in the range of 10GPa-35GPa, and it is more preferable to exist in the range of 15GPa-25GPa as the tensile elastic modulus of the 1st copper foil, for example. When the rolled copper foil is used as the first copper foil, when annealing is performed by heat treatment, the flexibility tends to increase. Therefore, when the tensile modulus of elasticity of the copper foil is less than the lower limit value, in the step of forming the insulating layer on the long first copper foil, the rigidity of the first copper foil itself is reduced by heating. On the other hand, when the tensile elastic modulus exceeds the upper limit value, a large bending stress is applied by the copper wiring when the FPC is bent, and the bending resistance decreases. In addition, the rolled copper foil tends to change its tensile elastic modulus by the heat treatment conditions when forming the insulating layer on the copper foil, or the annealing treatment of the copper foil after forming the insulating layer, and the like. Therefore, in the first embodiment, the second embodiment, or the third embodiment, in the finally obtained copper sheet laminate, the tensile modulus of elasticity of the first copper foil may be within the above-described range.

<Second copper foil layer>

In 1st Embodiment, 2nd Embodiment, or 3rd Embodiment, the 2nd copper foil layer is laminated|stacked on the surface on the opposite side to the 1st copper foil layer among the insulating layers. It does not specifically limit as a copper foil (2nd copper foil) used for a 2nd copper foil layer, For example, a rolled copper foil may be sufficient as an electrolytic copper foil. Moreover, a commercially available copper foil can also be used as a 2nd copper foil. In addition, as a 2nd copper foil, the same thing as a 1st copper foil can also be used.

[circuit board]

The copper sheet laminate 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 copper foil of the copper sheet laminate according to the first embodiment, the second embodiment, or the third embodiment can be processed into a pattern by an ordinary method to form a wiring layer, thereby producing the copper foil which is one embodiment of the present invention. FPC.

Example

An Example is shown below, and the characteristic of this invention is demonstrated more concretely. 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 were performed by the following ones.

[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 would be 10% to 90%, and the value when the viscosity was stabilized was read after 2 minutes elapsed after the measurement was started.

[Measurement of glass transition temperature (Tg)]

Regarding the glass transition temperature, using a dynamic viscoelasticity measuring apparatus (DMA: UBM Co., Ltd., trade name: E4000F), from 30° C. to 400° C. at a temperature increase rate of 4° C./min and a frequency of 11 Hz, 5 mm×20 mm The polyimide film of the size was measured, and the temperature at which the elastic modulus change (tan δ) became the largest was set as the glass transition temperature. In addition, those showing that the storage elastic modulus at 30°C measured by DMA is 1.0×10 ⁹ Pa or more and the storage elastic modulus at 280° C. is less than 3.0×10 ⁸ Pa are regarded as “thermoplastic”, A storage elastic modulus of 1.0×10 ⁹ Pa or more and a storage elastic modulus at 280° C. of 3.0×10 ⁸ Pa or more were defined as “non-thermoplastic”.

[Measurement of Coefficient of Thermal Expansion (CTE)]

Using a thermomechanical analyzer (manufactured by Bruker, trade name: 4000SA), the polyimide film having a size of 3 mm×20 mm was heated from 30° C. to a temperature of 5.0 g at a constant temperature increase rate. 265 degreeC, after holding at the said temperature for 10 minutes, it cooled at the rate of 5 degreeC/min, and calculated|required the average thermal expansion coefficient (thermal expansion coefficient) from 250 degreeC to 100 degreeC.

[Measurement of moisture absorption rate]

Two test pieces of polyimide film (width 4 cm×length 25 cm) were prepared, and were dried at 80° C. for 1 hour. Immediately after drying, it was placed in a constant temperature and humidity room of 23°C/50% RH, left to stand for 24 hours or more, and was obtained by the following formula from the weight change before and after.

Moisture absorption rate (% by weight)=[(weight after moisture absorption-weight after drying)/weight after drying]×100

[Determination of dielectric constant and dielectric tangent]

Using a vector network analyzer (manufactured by Agilent, trade name E8363C) and a separation dielectric resonator (SPDR resonator), the dielectric constant and dielectric tangent of the resin sheet at a frequency of 10 GHz were measured. In addition, the material used for the measurement was left to stand for 24 hours under the conditions of temperature: 24°C to 26°C and humidity: 45% to 55%.

[Calculation of imide group concentration]

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

[Measurement of Surface Roughness of Copper Foil]

For the surface roughness of the copper foil, an atomic force microscope (Atomic Force Microscope, AFM) (manufactured by Bruker AXS, trade name: Dimension Icon type SPM), a probe (Bruker AXS (Bruker AXS) Manufactured by Bruker AXS), trade name: TESPA (NCHV), tip curvature radius: 10 nm, spring constant: 42 N/m), using the tapping mode (Tapping Mode), the copper foil surface was measured in the range of 80 μm × 80 μm, The ten-point average roughness (Rz) was 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 sheet laminate (copper foil/resin layer/copper foil) was circuit-processed to have a width of 0.8mm (the copper foil on both sides was 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 on the casting side and the thermocompression bonding side of the sample was measured by using a Tensilon Tester (manufactured by Toyo Seiki Co., Ltd., trade name: Strograph VE-1D). Tape to fix the copper foil surface on the thermocompression bonding side or the casting side of the measurement sample to an aluminum plate, peel off the other copper foil in the 90° direction at a speed of 50 mm/min, and obtain the median value when peeling 10 mm from the resin layer strength. At this time, the peel strength was 1.0 kN/m or more as ⊚ (excellent), 0.7 kN/m or more and less than 1.0 kN/m as ○ (good), and 0.4 kN/m or more and less than 0.7 kN /m was set as △ (pass), and those less than 0.4kN/m were set as × (failure).

[Measurement of in-plane retardation (RO)]

The in-plane retardation (RO) was determined using a birefringence meter (manufactured by Photonic-lattice Co., Ltd., trade name: Wide Range Birefringence Evaluation System WPA-100). Retardation in the in-plane direction of the film. The measurement wavelength was 543 nm.

[Measurement of haze value]

The haze value was measured by using a haze measuring apparatus (turbidity meter: Nippon Denshoku Kogyo Co., Ltd., trade name: NDH5000), and using the measurement method described in JIS K 7136 on a polyimide having a size of 5 cm×5 cm membrane.

[Measurement of film elongation]

The polyimide film cut into a width of 12.7 mm×length of 127 mm was obtained by performing a tensile test at 50 mm/min using a tension tester (Tensilon manufactured by Orientec). Film elongation at 25°C.

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-naphthalenetetracarboxylic dianhydride

TAHQ: 1,4-phenylene bis(trimellitic acid monoester) dianhydride

TMEG: Ethylene Glycol Ditrimellitic 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 by Ihara Chemical Industry, trade name : Hardcure 10, Amine value: 629KOHmg/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 a nitrogen stream, 1.335 g of m-TB (0.0063 mol), 10.414 g of TPE-R (0.0356 mol), and DMAc in such an amount that the solid content concentration after polymerization was 12% by weight were put into a 300-ml separable flask. Stir and dissolve 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 to perform a polymerization reaction to obtain a polyamic acid solution A-1. The solution viscosity of the polyamic acid solution A-1 was 1,420 cps.

Next, after the polyamic acid solution A-1 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after hardening would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-1 (thermoplastic, Tg: 256 degreeC, moisture absorption rate: 0.36weight%) was prepared. 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), 11.794 g of TPE-R (0.0403 mol), and DMAc in an amount such that the solid content concentration after polymerization was 12 wt % were put into a 300-ml separable flask. Stir and dissolve at room temperature. Next, after adding 2.834 g of PMDA (0.0130 mol) and 8.921 g of BPDA (0.0303 mol), the polymerization reaction was continued at room temperature for 3 hours while stirring to obtain a polyamic acid solution A-2. The solution viscosity of the polyamic acid solution A-2 was 1,510 cps.

Next, after the polyamic acid solution A-2 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after hardening would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-2 (thermoplastic, Tg: 242 degreeC, moisture absorption rate: 0.35weight%) was prepared. 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 a nitrogen stream, 0.908 g of m-TB (0.0043 mol), 11.253 g of TPE-R (0.0385 mol), and DMAc in such an amount that the solid content concentration after polymerization was 12% by weight were put into a 300-ml separable flask. Stir and dissolve 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 a polymerization reaction was performed to obtain a polyamic acid solution A-3. The solution viscosity of the polyamic acid solution A-3 was 1,550 cps.

Next, the polyamic acid solution A-3 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after hardening would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-3 (thermoplastic, Tg: 240 degreeC, moisture absorption rate: 0.31weight%) was prepared. 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), 10.704 g of TPE-R (0.0366 mol), and DMAc in an amount such that the solid content concentration after polymerization was 12% by weight were put into a 300-ml separable 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 to perform a polymerization reaction to obtain a polyamic acid solution A-4. The solution viscosity of the polyamic acid solution A-4 was 1,580 cps.

Next, after the polyamic acid solution A-4 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after hardening would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-4 (thermoplastic, Tg: 240 degreeC, moisture absorption rate: 0.29weight%) was prepared. 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), 10.147 g of TPE-R (0.0347 mol), and DMAc in an amount such that the solid content concentration after polymerization was 12 wt % were put into a 300-ml separable flask. Stir and dissolve 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 to perform a polymerization reaction to obtain a polyamic acid solution A-5. The solution viscosity of the polyamic acid solution A-5 was 1,610 cps.

Next, the polyamic acid solution A-5 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-5 (thermoplastic, Tg: 244 degreeC, moisture absorption rate: 0.27weight%) was prepared. 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 a nitrogen stream, 2.804 g of m-TB (0.0132 mol), 9.009 g of TPE-R (0.0308 mol), and DMAc in such an amount that the solid content concentration after polymerization was 12% by weight were put into a 300-ml separable flask. Stir and dissolve 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 to perform a polymerization reaction to obtain a polyamic acid solution A-6. The solution viscosity of the polyamic acid solution A-6 was 1,720 cps.

Next, after the polyamic acid solution A-6 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after hardening would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-6 (thermoplastic, Tg: 248 degreeC, moisture absorption rate: 0.27weight%) was prepared. 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 a nitrogen stream, 1.469 g of APAB (0.0064 mol), 10.658 g of TPE-R (0.0365 mol), and DMAc were put into a 300-ml separable flask in such an amount that the solid content concentration after polymerization was 12% by weight, and the mixture was heated at room temperature. Stir and dissolve. Next, after adding 2.863 g of PMDA (0.0131 mol part) and 9.011 g of BPDA (0.0306 mol), stirring was continued at room temperature for 3 hours, and a polymerization reaction was performed to obtain a polyamic acid solution A-7. The solution viscosity of the polyamic acid solution A-7 was 1,280 cps.

Next, the polyamic acid solution A-7 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-7 (thermoplastic, Tg: 239 degreeC, moisture absorption rate: 0.31weight%) was prepared. 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), 10.704 g of APB (0.0366 mol), and DMAc after polymerization were put into a 300-ml separable flask in such an amount that the solid content concentration after polymerization was 12% by weight, and the mixture was heated at room temperature. Stir and dissolve. 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 to perform a polymerization reaction to obtain a polyamic acid solution A-8. The solution viscosity of the polyamic acid solution A-8 was 1,190 cps.

Next, the polyamic acid solution A-8 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-8 (thermoplastic, Tg: 235 degreeC, moisture absorption rate: 0.31weight%) was prepared. 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 a nitrogen stream, 1.162 g of m-TB (0.0055 mol), 12.735 g of BAPP (0.0310 mol), and DMAc in an amount such that the solid content concentration after polymerization was 12% by weight were put into a 300-ml separable flask at room temperature. Stir and dissolve. 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 to perform a polymerization reaction to obtain a polyamic acid solution A-9. The solution viscosity of the polyamic acid solution A-9 was 1,780 cps.

Next, the polyamic acid solution A-9 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-9 (thermoplastic, Tg: 278 degreeC, moisture absorption rate: 0.34weight%) was prepared. 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), 11.011 g of TPE-R (0.0377 mol), and DMAc in an amount such that the solid content concentration after polymerization was 12% by weight were put into a 300-ml separable flask. Stir and dissolve 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 to perform a polymerization reaction to obtain a polyamic acid solution A-10. The solution viscosity of the polyamic acid solution A-10 was 2,330 cps.

Next, the polyamic acid solution A-10 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing was about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-10 (thermoplastic, Tg: 276 degreeC, moisture absorption rate: 0.41weight%) was prepared. 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 stream, 12.327 parts by weight of TPE-R (0.0422 mol) and DMAc after polymerization were put into a 300-ml separable flask, and the mixture was 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 a polymerization reaction was performed to obtain a polyamic acid solution A-11. The solution viscosity of the polyamic acid solution A-11 was 1,530 cps.

Next, after the polyamic acid solution A-11 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after hardening would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-11 (thermoplastic, Tg: 244 degreeC, moisture absorption rate: 0.39weight%) was prepared. 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), 1.856 g of TPE-R (0.0063 mol), and DMAc in such an amount that the solid content concentration after polymerization was 15% by weight were put into a 300-ml separable flask. Stir and dissolve 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 to perform a polymerization reaction to obtain a polyamic acid solution A-12. The solution viscosity of the polyamic acid solution A-12 was 29,100 cps.

Next, after the polyamic acid solution A-12 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after hardening would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-12 (non-thermoplastic, Tg: 322 degreeC, moisture absorption rate: 0.57weight%) was prepared. 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 after polymerization were put into a 300-ml separable flask, and the mixture was 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 a polymerization reaction was performed to obtain a polyamic acid solution A-13. The solution viscosity of the polyamic acid solution A-13 was 29,900 cps.

Next, after the polyamic acid solution A-13 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after hardening would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-13 (non-thermoplastic, Tg: 332 degreeC, moisture absorption rate: 0.63 weight%) was prepared. 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, 12.061 g of m-TB (0.0568 mol), 0.923 g of TPE-Q (0.0032 mol), 1.0874 g of dianiline-M (0.0032 mol), and the polymerized solid were put into a 300-ml separable flask. DMAc in an amount of a component concentration of 15% by weight was stirred and dissolved at room temperature. 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 a polymerization reaction was performed to obtain a polyamic acid solution A-14. The solution viscosity of the polyamic acid solution A-14 was 29,800 cps.

Next, after the polyamic acid solution A-14 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after hardening would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-14 (non-thermoplastic, Tg: 322 degreeC, moisture absorption rate: 0.61weight%) was prepared. 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 a nitrogen stream, 11.978 g of m-TB (0.0564 mol), 0.916 g of TPE-Q (0.0031 mol), 1.287 g of BAPP (0.0031 mol part), and the solid content concentration after polymerization were put into a 300-ml separable flask. DMAc in an amount of 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 to perform a polymerization reaction to obtain a polyamic acid solution A-15. The solution viscosity of the polyamic acid solution A-15 was 29,200 cps.

Next, after the polyamic acid solution A-15 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after hardening would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-15 (non-thermoplastic, Tg: 324 degreeC, moisture absorption rate: 0.58weight%) was prepared. 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), 1.856 g of TPE-Q (0.0063 mol), and DMAc in such an amount that the solid content concentration after polymerization was 15% by weight were put into a 300-ml separable flask. Stir and dissolve 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 to perform a polymerization reaction to obtain a polyamic acid solution A-16. The solution viscosity of the polyamic acid solution A-16 was 32,800 cps.

Next, the polyamic acid solution A-16 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-16 (non-thermoplastic, Tg: 330 degreeC, moisture absorption rate: 0.59weight%) was prepared. 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), 1.886 g of TPE-R (0.0064 mol), and DMAc in such an amount that the solid content concentration after polymerization was 15% by weight were put into a 300-ml separable flask. Stir and dissolve 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 a polymerization reaction was performed to obtain a polyamic acid solution A-17. The solution viscosity of the polyamic acid solution A-17 was 31,500 cps.

Next, the polyamic acid solution A-17 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-17 (non-thermoplastic, Tg: 342 degreeC, moisture absorption rate: 0.56weight%) was prepared. 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 a nitrogen stream, 13.434 g of m-TB (0.0633 mol) and DMAc in an amount such that the solid content concentration after polymerization was 15 wt % were put into a 300 ml separable flask, and the mixture was stirred and dissolved at room temperature. Next, after adding 6.118 g of PMDA (0.0281 mol), 9.170 g of BPDA (0.0312 mol), and 1.279 g of TMEG (0.0031 mol), stirring was continued at room temperature for 3 hours to carry out the polymerization reaction to obtain a polyamic acid solution A-18. The solution viscosity of the polyamic acid solution A-18 was 14,100 cps.

Next, after the polyamic acid solution A-18 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after curing would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-18 (non-thermoplastic, Tg: 314 degreeC, moisture absorption rate: 0.59weight%) was prepared. 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 stream, 12.003 g of m-TB (0.0565 mol), 1.836 g of TPE-R (0.0063 mol), and DMAc in an amount such that the solid content concentration after polymerization was 15% by weight were put into a 300-ml separable flask. Stir and dissolve at room temperature. Next, after adding 5.399 g of PMDA (0.0248 mol), 9.103 g of BPDA (0.0309 mol), and 1.659 g of NTCDA (0.0062 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution. A-19. The solution viscosity of the polyamic acid solution A-19 was 31,200 cps.

Next, after the polyamic acid solution A-19 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after hardening would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-19 (non-thermoplastic, Tg: 311 degreeC, moisture absorption rate: 0.58weight%) was prepared. 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 a nitrogen stream, 8.778 g of m-TB (0.0414 mol), 1.860 g of TPE-R (0.0064 mol), and 3.582 g of AABOZ (0.0159 mol) were put into a 300-ml separable flask, and the solid content concentration after polymerization was DMAc in an amount 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 to perform a polymerization reaction to obtain a polyamic acid solution A-20. The solution viscosity of the polyamic acid solution A-20 was 42,300 cps.

Next, the polyamic acid solution A-20 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-20 (non-thermoplastic, Tg: 312 degreeC, moisture absorption rate: 0.61weight%) was prepared. 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 a nitrogen stream, 5.365 g of m-TB (0.0253 mol), 1.847 g of TPE-R (0.0063 mol), and 7.116 g of AABOZ (0.0316 mol) were charged into a 300-ml separable flask, and the solid content concentration after polymerization was DMAc in an amount 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 a polymerization reaction was performed to obtain a polyamic acid solution A-21. The solution viscosity of the polyamic acid solution A-21 was 22,700 cps.

Next, the polyamic acid solution A-21 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-21 (non-thermoplastic, Tg: 320 degreeC, moisture absorption rate: 0.65weight%) was prepared. 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 a nitrogen stream, 8.110 g of m-TB (0.0382 mol), 1.861 g of TPE-R (0.0064 mol), and 4.360 g of APAB (0.0191 mol) were put into a 300-ml separable flask, and the solid content concentration after polymerization was DMAc in an amount 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 a polymerization reaction was performed to obtain a polyamic acid solution A-22. The solution viscosity of the polyamic acid solution A-22 was 24,500 cps.

Next, the polyamic acid solution A-22 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after hardening would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-22 (non-thermoplastic, Tg: 322 degreeC, moisture absorption rate: 0.57weight%) was prepared. 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), 1.799 g of TPE-R (0.0062 mol), and DMAc in such an amount that the solid content concentration after polymerization was 15% by weight were put into a 300-ml separable flask. Stir and dissolve 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 a polymerization reaction was performed to obtain a polyamic acid solution A-23. The solution viscosity of the polyamic acid solution A-23 was 26,800 cps.

Next, after the polyamic acid solution A-23 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after curing would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-23 (non-thermoplastic, Tg: 291 degreeC, moisture absorption rate: 0.59weight%) was prepared. 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 nitrogen flow, 14.405 g of m-TB (0.0679 mol) and DMAc after polymerization were put into a 300-ml separable flask, and the mixture was 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 a polymerization reaction was performed to obtain a polyamic acid solution A-24. The solution viscosity of the polyamic acid solution A-24 was 33,600 cps.

Next, the polyamic acid solution A-24 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing was about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-24 (non-thermoplastic, Tg: 400 degreeC or more, moisture absorption rate: 0.78weight%) was prepared. 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 stream, 12.201 g of m-TB (0.0575 mol), 1.042 g of bisaniline-M (0.0030 mol), and DMAc in such an amount that the solid content concentration after polymerization was 15% by weight were put into a 300-ml separable flask. Stir and dissolve 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 to perform a polymerization reaction to obtain a polyamic acid solution A-25. The solution viscosity of the polyamic acid solution A-25 was 30,100 cps.

Next, the polyamic acid solution A-25 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing was about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-25 (non-thermoplastic, Tg: 400 degreeC or more, moisture absorption rate: 0.57weight%) was prepared. 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 a nitrogen stream, 11.204 g of m-TB (0.0528 mol), 0.670 g of BAPP (0.0016 mol), and DMAc were put into a 300-ml separable flask in such an amount that the solid content concentration after polymerization was 15% by weight. Stir and dissolve. 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 to perform a polymerization reaction to obtain a polyamic acid solution A-26. The solution viscosity of the polyamic acid solution A-26 was 26,600 cps.

Next, after the polyamic acid solution A-26 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after curing would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film A-26 (non-thermoplastic, Tg: 304 degreeC, moisture absorption rate: 0.49weight%) was prepared. 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 was uniformly applied to one side (surface roughness Rz: 0.6 μm) of an electrolytic copper foil with a thickness of 12 μm so that the thickness after curing was about 2 μm to 3 μm, it was heated at 120° C. drying under heat and solvent removal. Next, the polyamic acid solution A-15 was uniformly coated thereon so that the thickness after curing was about 21 μm, and the solvent was removed by heating and drying at 120°C. Further, the polyamic acid solution A-1 was uniformly coated thereon so that the thickness after curing was about 2 μm to 3 μm, and then heated and dried at 120° C. to remove the solvent. In this way, after forming the three-layer polyamic acid layer, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was removed by etching using an aqueous ferric chloride solution to prepare a multilayer polyimide film A-1 (CTE: 22 ppm/K, moisture absorption rate: 0.54 wt %, dielectric constant: 3.58, dielectric tangent: 0.0031).

[Example A-2 to Example A-21, Reference Example A-1 to Reference Example A-2]

Except having used the polyamic acid solutions shown in Table 1-Table 4, it carried out similarly to Example A-1, and obtained Example A-2-Example A-21, Reference Example A-1-Reference Example A-2 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. The respective measurement results are shown in Tables 1 to 4.

[Table 1]

[Table 2]

[table 3]

[Table 4]

[Example A-22 to Example A-23]

Except having used the polyamic acid solution shown in Table 5, it carried out similarly to Example A-1, and obtained the multilayer polyimide film A-24 - multilayer polyamide of Example A-22 - Example A-23 Imine 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]

(Synthesis Example B-1)

Under a nitrogen stream, 66.727 parts by weight of m-TB (0.314 parts by mol), 520.681 parts by weight of TPE-R (1.781 parts by mol), and DMAc in such an amount that the solid content concentration after polymerization was 12 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 46.620 parts by weight of PMDA (0.214 parts by mol) and 565.972 parts by weight of BPDA (1.924 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-1. The solution viscosity of the polyamic acid solution B-1 was 1,420 cps.

Next, the polyamic acid solution B-1 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing was about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-1 (thermoplastic, Tg: 256 degreeC, moisture absorption rate: 0.36weight%) was prepared. 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 stream, 22.538 parts by weight of m-TB (0.106 parts by mol), 589.682 parts by weight of TPE-R (2.017 parts by mol), and DMAc in such an amount that the solid content concentration after polymerization was 12 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 141.722 parts by weight of PMDA (0.650 parts by mol) and 446.058 parts by weight of BPDA (1.516 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-2. The solution viscosity of the polyamic acid solution B-2 was 1,510 cps.

Next, the polyamic acid solution B-2 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-2 (thermoplastic, Tg: 242 degreeC, moisture absorption rate: 0.35weight%) was prepared. 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 nitrogen flow, 45.398 parts by weight of m-TB (0.214 parts by mol), 562.630 parts by weight of TPE-R (1.925 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 12 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 142.733 parts by weight of PMDA (0.654 parts by mol) and 449.239 parts by weight of BPDA (1.527 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-3. The solution viscosity of the polyamic acid solution B-3 was 1,550 cps.

Next, the polyamic acid solution B-3 was uniformly coated on one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after hardening would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-3 (thermoplastic, Tg: 240 degreeC, moisture absorption rate: 0.31weight%) was prepared. 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 nitrogen flow, 68.586 parts by weight of m-TB (0.323 parts by mol), 535.190 parts by weight of TPE-R (1.831 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 12 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 143.758 parts by weight of PMDA (0.659 parts by mol) and 452.466 parts by weight of BPDA (1.538 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-4. The solution viscosity of the polyamic acid solution B-4 was 1,580 cps.

Next, the polyamic acid solution B-4 was uniformly coated on one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after hardening would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-4 (thermoplastic, Tg: 240 degreeC, moisture absorption rate: 0.29weight%) was prepared. 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 a nitrogen stream, 92.110 parts by weight of m-TB (0.434 parts by mol), 507.352 parts by weight of TPE-R (1.736 parts by mol), and DMAc in such an amount that the solid content concentration after polymerization was 12 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 144.798 parts by weight of PMDA (0.664 parts by mol) and 455.740 parts by weight of BPDA (1.549 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-5. The solution viscosity of the polyamic acid solution B-5 was 1,610 cps.

Next, after the polyamic acid solution B-5 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after hardening would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-5 (thermoplastic, Tg: 244 degreeC, moisture absorption rate: 0.27weight%) was prepared. 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 a nitrogen stream, 140.193 parts by weight of m-TB (0.660 parts by mol), 450.451 parts by weight of TPE-R (1.541 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 12 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 146.924 parts by weight of PMDA (0.674 parts by mol) and 462.431 parts by weight of BPDA (1.572 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-6. The solution viscosity of the polyamic acid solution B-6 was 1,720 cps.

Next, the polyamic acid solution B-6 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-6 (thermoplastic, Tg: 248 degreeC, moisture absorption rate: 0.27weight%) was prepared. 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 mol), 532.900 parts by weight of TPE-R (1.823 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 12 wt % were put into the reaction tank, and the mixture was heated at room temperature. Stir and dissolve. Next, after adding 143.143 parts by weight of PMDA (0.656 parts by mol) and 450.530 parts by weight of BPDA (1.531 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-7. The solution viscosity of the polyamic acid solution B-7 was 1,280 cps.

Next, the polyamic acid solution B-7 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing was about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-7 (thermoplastic, Tg: 239 degreeC, moisture absorption rate: 0.31weight%) was prepared. 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 stream, 68.586 parts by weight of m-TB (0.323 parts by mol), 535.190 parts by weight of APB (1.831 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 12 wt % were put into the reaction tank. Stir and dissolve. Next, after adding 143.758 parts by weight of PMDA (0.659 parts by mol) and 452.466 parts by weight of BPDA (1.538 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-8. The solution viscosity of the polyamic acid solution B-8 was 1,190 cps.

Next, after the polyamic acid solution B-8 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-8 (thermoplastic, Tg: 235 degreeC, moisture absorption rate: 0.31weight%) was prepared. 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 mol), 636.745 parts by weight of BAPP (1.551 parts by mol), and DMAc in such an amount that the solid content concentration after polymerization was 12 wt % were put into the reaction tank, and the reaction was carried out at room temperature. Stir and dissolve. Next, after adding 121.798 parts by weight of PMDA (0.558 parts by mol) and 383.348 parts by weight of BPDA (1.303 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-9. The solution viscosity of the polyamic acid solution B-9 was 1,780 cps.

Next, the polyamic acid solution B-9 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-9 (thermoplastic, Tg: 278 degreeC, moisture absorption rate: 0.34weight%) was prepared. 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 nitrogen flow, 70.552 parts by weight of m-TB (0.332 parts by mol), 550.530 parts by weight of TPE-R (1.883 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 12 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 246.465 parts by weight of PMDA (1.130 parts by mol) and 332.454 parts by weight of BPDA (1.130 parts by mol), stirring was continued for 3 hours at room temperature, and a polymerization reaction was performed to obtain a polyamic acid solution B-10. The solution viscosity of the polyamic acid solution B-10 was 2,330 cps.

Next, after the polyamic acid solution B-10 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after hardening would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-10 (thermoplastic, Tg: 276 degreeC, moisture absorption rate: 0.41weight%) was prepared. 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 nitrogen flow, 616.353 parts by weight of TPE-R (2.108 parts by mol) and DMAc after polymerization were charged in an amount such that the solid content concentration after polymerization was 12% by weight, and stirred and dissolved at room temperature. Next, after adding 140.726 parts by weight of PMDA (0.645 parts by mol) and 442.921 parts by weight of BPDA (1.505 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-11. The solution viscosity of the polyamic acid solution B-11 was 1,530 cps.

Next, the polyamic acid solution B-11 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-11 (thermoplastic, Tg: 244 degreeC, moisture absorption rate: 0.39weight%) was prepared. 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 nitrogen flow, 240.725 parts by weight of m-TB (1.134 parts by mol), 331.485 parts by weight of TPE-R (1.134 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 12 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 151.369 parts by weight of PMDA (0.694 parts by mol) and 476.421 parts by weight of BPDA (1.619 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-12. The solution viscosity of the polyamic acid solution B-12 was 3,240 cps.

Next, the polyamic acid solution B-12 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-12 (thermoplastic, Tg: 260 degreeC, moisture absorption rate: 0.28weight%) was prepared. 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 nitrogen flow, 596.920 parts by weight of m-TB (2.812 parts by mol), 91.331 parts by weight of TPE-R (0.312 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 15 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 268.495 parts by weight of PMDA (1.231 parts by mol) and 543.255 parts by weight of BPDA (1.846 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-13. The solution viscosity of the polyamic acid solution B-13 was 27,310 cps.

Next, the polyamic acid solution B-13 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-13 (non-thermoplastic, Tg: 305 degreeC, moisture absorption rate: 0.52weight%) was prepared. 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 parts by mol), 92.779 parts by weight of TPE-R (0.317 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 15 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 340.941 parts by weight of PMDA (1.563 parts by mol) and 459.892 parts by weight of BPDA (1.563 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-14. The solution viscosity of the polyamic acid solution B-14 was 29,100 cps.

Next, after the polyamic acid solution B-14 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after curing would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-14 (non-thermoplastic, Tg: 322 degreeC, moisture absorption rate: 0.57weight%) was prepared. 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 stream, 685.370 parts by weight of m-TB (3.228 parts by mol) and DMAc in an amount such that the solid content concentration after polymerization was 15% by weight were put into the reaction tank, and the mixture was stirred and dissolved at room temperature. Next, after adding 346.815 parts by weight of PMDA (1.590 parts by mol) and 467.815 parts by weight of BPDA (1.590 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-15. The solution viscosity of the polyamic acid solution B-15 was 29,900 cps.

Next, the polyamic acid solution B-15 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing was about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-15 (non-thermoplastic, Tg: 332 degreeC, moisture absorption rate: 0.63 weight%) was prepared. 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, 603.059 parts by weight of m-TB (2.841 parts by mol), 46.135 parts by weight of TPE-Q (0.158 parts by mol) and 54.368 parts by weight of dianiline-M (0.158 parts by mol) were put into the reaction tank, and the polymerization The resulting solid content concentration was DMAc in an amount of 15% by weight, and the mixture was stirred and dissolved at room temperature. Next, after adding 339.070 parts by weight of PMDA (1.555 parts by mol) and 457.368 parts by weight of BPDA (1.555 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-16. The solution viscosity of the polyamic acid solution B-16 was 29,800 cps.

Next, after the polyamic acid solution B-16 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after hardening would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-16 (non-thermoplastic, Tg: 322 degreeC, moisture absorption rate: 0.61weight%) was prepared. 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 mol), 45.817 parts by weight of TPE-Q (0.157 parts by mol), 64.339 parts by weight of BAPP (0.157 parts by mol) and the polymerized solid were put into the reaction tank DMAc in an amount of a component 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 mol) and 454.214 parts by weight of BPDA (1.544 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-17. The solution viscosity of the polyamic acid solution B-17 was 29,200 cps.

Next, the polyamic acid solution B-17 was uniformly coated on one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after curing was about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-17 (non-thermoplastic, Tg: 324 degreeC, moisture absorption rate: 0.58weight%) was prepared. 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 a nitrogen stream, 606.387 parts by weight of m-TB (2.856 parts by mol), 92.779 parts by weight of TPE-Q (0.317 parts by mol), and DMAc in such an amount that the solid content concentration after polymerization was 15 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 340.941 parts by weight of PMDA (1.563 parts by mol) and 459.892 parts by weight of BPDA (1.563 parts by mol), stirring was continued for 3 hours at room temperature, and a polymerization reaction was performed to obtain a polyamic acid solution B-18. The solution viscosity of the polyamic acid solution B-18 was 32,800 cps.

Next, the polyamic acid solution B-18 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after hardening would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-18 (non-thermoplastic, Tg: 330 degreeC, moisture absorption rate: 0.59weight%) was prepared. 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 nitrogen flow, 616.159 parts by weight of m-TB (2.902 parts by mol), 94.275 parts by weight of TPE-R (0.322 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 15 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 415.723 parts by weight of PMDA (1.906 parts by mol) and 373.843 parts by weight of BPDA (1.271 parts by mol), stirring was continued for 3 hours at room temperature, and a polymerization reaction was performed to obtain a polyamic acid solution B-19. The solution viscosity of the polyamic acid solution B-19 was 31,500 cps.

Next, after the polyamic acid solution B-19 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after curing would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-19 (non-thermoplastic, Tg: 342 degreeC, moisture absorption rate: 0.56weight%) was prepared. 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 parts by mol), 95.819 parts by weight of TPE-R (0.328 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 15% by weight were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 492.954 parts by weight of PMDA (2.260 parts by mol) and 284.975 parts by weight of BPDA (0.969 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-20. The solution viscosity of the polyamic acid solution B-20 was 34,100 cps.

Next, the polyamic acid solution B-20 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing was about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-20 (non-thermoplastic, Tg: 364 degreeC, moisture absorption rate: 0.68weight%) was prepared. 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 mol), 79.230 parts by weight of TPE-R (0.271 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 15 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 291.151 parts by weight of PMDA (1.335 parts by mol) and 611.788 parts by weight of TAHQ (1.335 parts by mol), stirring was continued at room temperature for 3 hours to perform a polymerization reaction to obtain a polyamic acid solution B-21. The solution viscosity of the polyamic acid solution B-21 was 33,200 cps.

Next, the polyamic acid solution B-21 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after hardening would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-21 (non-thermoplastic, Tg: 296 degreeC, moisture absorption rate: 0.54weight%) was prepared. 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 stream, 587.744 parts by weight of m-TB (2.769 parts by mol), 89.927 parts by weight of TPE-R (0.308 parts by mol), and DMAc with a solid content concentration of 15 wt % were charged into the reaction tank, Stir and dissolve at room temperature. Next, after adding 198.275 parts by weight of PMDA (0.909 parts by mol) and 624.054 parts by weight of BPDA (2.121 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-22. The solution viscosity of the polyamic acid solution B-22 was 26,800 cps.

Next, the polyamic acid solution B-22 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-22 (non-thermoplastic, Tg: 291 degreeC, moisture absorption rate: 0.59weight%) was prepared. 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 mol), 269.219 parts by weight of TPE-R (0.921 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 15 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 329.772 parts by weight of PMDA (1.512 parts by mol) and 444.826 parts by weight of BPDA (1.512 parts by mol), stirring was continued at room temperature for 3 hours and a polymerization reaction was performed to obtain a polyamic acid solution B-23. The solution viscosity of the polyamic acid solution B-23 was 26,400 cps.

Next, after the polyamic acid solution B-23 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after curing would be about 25 μm, it was heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-23 (non-thermoplastic, Tg: 285 degreeC, moisture absorption rate: 0.53weight%) was prepared. 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 a nitrogen stream, 720.230 parts by weight of m-TB (3.393 parts by mol) and DMAc in an amount such that the solid content concentration after polymerization was 15% by weight were put 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 mol) and 196.644 parts by weight of BPDA (0.668 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to obtain a polyamic acid solution B-24. The solution viscosity of the polyamic acid solution B-24 was 33,600 cps.

Next, the polyamic acid solution B-24 was uniformly applied to one side (surface roughness Rz: 2.1 μm) of a 12 μm-thick electrolytic copper foil so that the thickness after curing would be about 25 μm, and then heated at 120° C. drying under heat and solvent removal. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. About the obtained metal sheet laminate, the copper foil was etched and removed using the ferric chloride aqueous solution, and the polyimide film B-24 (non-thermoplastic, Tg: 400 degreeC or more, moisture absorption rate: 0.78weight%) was prepared. 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 type 3-layer co-extrusion multi-layer die, the three-layer structure in the order of polyamic acid solution B-2/polyamic acid solution B-18/polyamic acid solution B-2 was continuously extruded and coated. It was clothed on an endless belt-shaped stainless-steel support substrate, heated and dried at 130° C. for 3 minutes, and the solvent was removed. Thereafter, stepwise heat treatment was performed from 130° C. to 360° C. to complete imidization, and the thicknesses of the thermoplastic polyimide layer/non-thermoplastic polyimide layer/thermoplastic polyimide layer were prepared to be 2.0 respectively. μm/21 μm/2.0 μm polyimide film B-1′. The polyimide film B-1' on the support substrate was peeled off by a knife-edge method to prepare a long polyimide film B-1 having a length in the width direction of 1100 mm.

The evaluation results of the elongated polyimide film B-1 are as follows.

CTE: 19ppm/K

In-plane retardation (RO): 9nm

Variation (ΔRO) of in-plane retardation (RO) in the width direction (TD direction): 2 nm

Variation in in-plane retardation (RO) before and after pressurization with a temperature of 320°C, a pressure of 340MPa/m ² and a holding period of 15 minutes: 13 nm

Moisture absorption rate: 0.56% by weight

Dielectric Constant (10GHz): 3.56, Dielectric Tangent (10GHz): 0.0032

[Example B-2 to Example B-18, Reference Example B-1 to Reference Example B-5]

Except having used the polyamic acid solution shown in Table 6-Table 9, it carried out similarly to Example B-1, and obtained Example B-2-Example B-18, Reference Example B-1-Reference Example B-5 Long polyimide film B-2 to long polyimide film B-23. CTE, in-plane retardation (RO), and in-plane retardation (RO) in the width direction (TD direction) of the obtained elongated polyimide films B-2 to B-23 were determined deviation (ΔRO), change in in-plane retardation (RO) before and after pressurization with a temperature of 320° C., pressure of 340 MPa/m ² , and a holding period of 15 minutes, and moisture absorption rate. The respective measurement results are shown in Tables 6 to 9.

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Example B-19]

The polyamic acid solution B-2 was uniformly applied to a long copper foil (rolled copper foil, manufactured by JX Metal Co., Ltd., trade name: GHY5-93F-HA- The surface of V2 foil, thickness: 12 μm, tensile elastic modulus after heat treatment: 18 GPa) was heated and dried at 120° C. for 1 minute to remove the solvent. After the polyamic acid solution B-18 was uniformly coated thereon so that the thickness after hardening might be 21 μm, it was heated and dried at 120° C. for 3 minutes to remove the solvent. Further, the polyamic acid solution B-2 was uniformly coated thereon so that the thickness after curing was 2.0 μm, and then heated and dried at 120° C. for 1 minute to remove the solvent. After that, stepwise heat treatment was performed from 130°C to 360°C, imidization was completed, and a single-sided copper sheet laminate B-1 was prepared. Copper foil was stacked on the polyimide layer side of the single-sided copper sheet laminate B-1, and thermocompression bonding was performed for 15 minutes under the conditions of a temperature of 320° C. and a pressure of 340 MPa/m ² to prepare a double-sided copper sheet laminate. B-1.

Casting surface side peel strength: ◎, Crimping surface side peel strength: ○

[Example B-20 to Example B-36, Reference Example B-6 to Reference Example B-10]

Except having used the polyamic acid solution shown in Table 10 - Table 13, it carried out similarly to Example B-19, obtained Example B-20 - Example B-36, the reference example B-6 - the reference example B-10 Double-sided copper sheet laminate B-2 to double-sided copper sheet laminate B-23. The casting surface side peeling strength and the pressure-bonding surface side peeling strength of the obtained double-sided copper sheet laminate B-2 to double-sided copper sheet laminate B-23 were determined. The respective measurement results are shown in Tables 10 to 13.

[Table 10]

[Table 11]

[Table 12]

[Table 13]

(Synthesis example C-1)

Under nitrogen flow, 606.387 parts by weight of m-TB (2.856 parts by mol), 92.779 parts by weight of TPE-R (0.317 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 15 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 340.941 parts by weight of PMDA (1.563 parts by mol) and 459.892 parts by weight of BPDA (1.563 parts by mol), stirring was continued at room temperature for 3 hours and a polymerization reaction was performed to prepare a polyamic acid solution C-1. The solution viscosity of the polyamic acid solution C-1 was 29,100 cps.

(Synthesis example C-2)

Under a nitrogen stream, 606.387 parts by weight of m-TB (2.856 parts by mol), 92.779 parts by weight of TPE-Q (0.317 parts by mol), and DMAc in such an amount that the solid content concentration after polymerization was 15 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 340.941 parts by weight of PMDA (1.563 parts by mol) and 459.892 parts by weight of BPDA (1.563 parts by mol), stirring was continued at room temperature for 3 hours and a polymerization reaction was performed to prepare a polyamic acid solution C-2. The solution viscosity of the polyamic acid solution C-2 was 32,800 cps.

(Synthesis example C-3)

Under nitrogen flow, 616.159 parts by weight of m-TB (2.902 parts by mol), 94.275 parts by weight of TPE-R (0.322 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 15 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 415.723 parts by weight of PMDA (1.906 parts by mol) and 373.843 parts by weight of BPDA (1.271 parts by mol), stirring was continued at room temperature for 3 hours and a polymerization reaction was performed to prepare a polyamic acid solution C-3. The solution viscosity of the polyamic acid solution C-3 was 31,500 cps.

(Synthesis example C-4)

Under a nitrogen stream, 637.503 parts by weight of m-TB (3.003 parts by mol), 64.882 parts by weight of BAPP (0.158 parts by mol), and DMAc in such an amount that the solid content concentration after polymerization was 15 wt % were put into the reaction tank, and the reaction was carried out at room temperature. Stir and dissolve. Next, after adding 339.571 parts by weight of PMDA (1.557 parts by weight) and 458.044 parts by weight of BPDA (1.557 parts by weight), stirring was continued for 3 hours at room temperature and polymerization was performed to prepare a polyamic acid solution C-4. The solution viscosity of the polyamic acid solution C-4 was 24,100 cps.

(Synthesis Example C-5)

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

(Synthesis example C-6)

Under a nitrogen stream, 641.968 parts by weight of m-TB (3.024 parts by mol), 54.830 parts by weight of dianiline-M (0.159 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 15% by weight were charged into the reaction tank. , stirred and dissolved at room temperature. Next, after adding 341.950 parts by weight of PMDA (1.568 parts by weight) and 461.252 parts by weight of BPDA (1.568 parts by weight), stirring was continued for 3 hours at room temperature and polymerization was performed to prepare a polyamic acid solution C-6. The solution viscosity of the polyamic acid solution C-6 was 26,500 cps.

(Synthesis Example C-7)

Under nitrogen flow, 538.432 parts by weight of m-TB (2.536 parts by mol), 185.359 parts by weight of TPE-R (0.634 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 15 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 408.690 parts by weight of PMDA (1.874 parts by weight) and 367.519 parts by weight of BPDA (1.249 parts by weight), stirring was continued for 3 hours at room temperature to carry out a polymerization reaction to prepare a polyamic acid solution C-7. The solution viscosity of the polyamic acid solution C-7 was 31,100 cps.

(Synthesis Example C-8)

Under a nitrogen stream, 674.489 parts by weight of m-TB (3.177 parts by mol) and DMAc after polymerization were put into the reaction tank in such an amount that the solid content concentration after polymerization was 15% by weight, and the mixture was stirred and dissolved at room temperature. Next, after adding 273.047 parts by weight of PMDA (1.252 parts by weight) and 552.465 parts by weight of BPDA (1.878 parts by weight), stirring was continued for 3 hours at room temperature and polymerization was performed to prepare a polyamic acid solution C-8. The solution viscosity of the polyamic acid solution C-8 was 26,400 cps.

(Synthesis Example C-9)

Under nitrogen flow, 463.290 parts by weight of m-TB (2.182 parts by mol), 273.414 parts by weight of TPE-R (0.935 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 15 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 401.891 parts by weight of PMDA (1.843 parts by weight) and 361.405 parts by weight of BPDA (1.228 parts by weight), stirring was continued for 3 hours at room temperature to carry out a polymerization reaction to prepare a polyamic acid solution C-9. The solution viscosity of the polyamic acid solution C-9 was 29,000 cps.

(Synthesis example C-10)

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

(Synthesis example C-11)

Under a nitrogen stream, 500.546 parts by weight of m-TB (2.358 parts by mol), 229.756 parts by weight of TPE-R (0.786 parts by mol), and DMAc in an amount such that the solid content concentration after polymerization was 15 wt % were put into the reaction tank, Stir and dissolve at room temperature. Next, after adding 405.262 parts by weight of PMDA (1.858 parts by weight) and 364.436 parts by weight of BPDA (1.239 parts by weight), stirring was continued for 3 hours at room temperature to carry out a polymerization reaction to prepare a polyamic acid solution C-11. The solution viscosity of the polyamic acid solution C-11 was 29,600 cps.

(Synthesis example C-12)

Under a nitrogen stream, 779.571 parts by weight of BAPP (1.899 parts by mol) and DMAc in an amount such that the solid content concentration after polymerization was 12% by weight were put into the reaction tank, and stirred and dissolved at room temperature. Next, after adding 420.430 parts by weight of PMDA (1.928 parts by mol), stirring was continued at room temperature for 3 hours, and a polymerization reaction was performed to prepare a polyamic acid solution C-12. The solution viscosity of the polyamic acid solution C-12 was 2,210 cps.

(Synthesis Example C-13)

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

(Synthesis Example C-14)

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

(Synthesis Example C-15)

Under nitrogen flow, 613.786 parts by weight of m-TB (2.891 parts by mol), 28.652 parts by weight of DTAm (0.161 parts by mol), 46.956 parts by weight of TPE-Q (0.161 parts by mol) and the polymerized solid were put into the reaction tank DMAc in an amount of a component concentration of 15% by weight was stirred and dissolved at room temperature. Next, after adding 345.102 parts by weight of PMDA (1.582 parts by weight) and 465.504 parts by weight of BPDA (1.582 parts by weight), stirring was continued for 3 hours at room temperature to carry out a polymerization reaction to prepare a polyamic acid solution C-15. The solution viscosity of the polyamic acid solution C-15 was 24,400 cps.

(Synthesis example C-16)

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

(Synthesis Example C-17)

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

(Synthesis Example C-18)

Under a nitrogen stream, 599.272 parts by weight of m-TB (2.823 parts by mol), 63.445 parts by weight of DTBAB (0.157 parts by mol), 45.845 parts by weight of TPE-Q (0.157 parts by mol) and the polymerized solid were put into the reaction tank DMAc in an amount of a component 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 mol) and 454.497 parts by weight of BPDA (1.545 parts by mol), stirring was continued for 3 hours at room temperature to carry out a polymerization reaction, and a polyamic acid solution C-18 was prepared. The solution viscosity of the polyamic acid solution C-18 was 28,800 cps.

(Synthesis Example C-19)

Under a nitrogen flow, 610.050 parts by weight of m-TB (2.874 parts by mol), 52.104 parts by weight of dianiline-M (0.151 parts by mol), and DMAc in such an amount that the solid content concentration after polymerization was 15 wt % were charged into the reaction tank. , stirred and dissolved at room temperature. Next, after adding 399.526 parts by weight of NTCDA (1.490 parts by mol) and 438.320 parts by weight of BPDA (1.490 parts by mol), stirring was continued at room temperature for 3 hours to carry out a polymerization reaction to prepare a polyamic acid solution C-19. The solution viscosity of the polyamic acid solution C-19 was 29,200 cps.

(Synthesis example C-20)

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

[Example C-1]

After the polyamic acid solution C-1 was uniformly applied to one side (surface roughness Rz: 0.6 μm) of an electrolytic copper foil having a thickness of 12 μm so that the thickness after curing would be about 25 μm, it was carried out at 120° C. Heat to dry and remove solvent. Furthermore, stepwise heat treatment is performed from 120° C. to 360° C. within 30 minutes to complete imidization. The copper foil was removed by etching using an aqueous ferric chloride solution to prepare a polyimide film C-1 (CTE: 18.1 ppm/K, Tg: 322° C., moisture absorption rate: 0.57% by weight, haze: 74.5%, film elongation Length: 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 the polyimide film C-2 - the polyimide film C-11. Regarding 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]

[Table 15]

[Example C-10]

A polyimide film C-12 (CTE: 10.2 ppm/K) was prepared in the same manner as in Example C-1, except that the polyamic acid solution C-11 was used and the heat treatment was performed stepwise from 120°C to 360°C for 5 hours. , Tg: 307°C, moisture absorption rate: 0.61% by weight, haze: 74.2%, film elongation: 41%).

[Example C-11]

After the polyamic acid solution C-15 was uniformly applied to one side (surface roughness Rz: 0.6 μm) of an electrolytic copper foil with a thickness of 12 μm so that the thickness after curing would be about 2 μm to 3 μm, it was heated at 120° C. drying under heat and solvent removal. Next, the polyamic acid solution C-1 was uniformly coated thereon so that the thickness after curing was about 21 μm, and the solvent was removed by heating and drying at 120°C. Further, the polyamic acid solution C-15 was uniformly coated thereon so that the thickness after curing was about 2 μm to 3 μm, and then heated and dried at 120° C. to remove the solvent. In this way, after forming the three-layer polyamic acid layer, stepwise heat treatment was performed from 120° C. to 360° C. for 30 minutes, imidization was completed, and metal sheet laminate C-11 was prepared. Inconveniences such as expansion of the polyimide layer in the sheet metal laminate C-11 were not confirmed.

[Example C-12 to Example C-17]

Metal sheet laminate C-12 to metal sheet laminate C were prepared in the same manner as in Example C-11, except that polyamic acid solution C-2 to polyamic acid solution C-7 were used instead of polyamic acid solution C-1 -17. In any of sheet metal laminate C-12 to sheet metal laminate C-17, defects such as expansion of the polyimide layer were not confirmed.

(Reference Example C-3)

A metal tension laminate was prepared in the same manner as in Example C-11 except that the heat treatment was performed stepwise from 120° C. to 360° C. for 15 minutes in Example C-11, but swelling was observed in the polyimide layer.

[Example C-18 to Example C-20]

Except that the polyamic acid solution C-4 to the polyamic acid solution C-6 were used instead of the polyamic acid solution C-1 in Example C-11, and the stepwise heat treatment was performed from 120°C to 360°C for 15 minutes, Metal sheet laminates C-18 to metal sheet laminates C-20 were prepared in the same manner as in Example C-11. In any of the sheet metal laminates C-18 to C-20, a defect such as expansion of the polyimide layer was not confirmed.

(Reference Example C-4 to Reference Example C-6)

Except using the polyamic acid solution C-2, the polyamic acid solution C-3 and the polyamic acid solution C-7 instead of the polyamic acid solution C-1 in Example C-11, it was carried out from 120°C to 360°C Except for the stepwise heat treatment for 15 minutes, a metal tension laminate was prepared in the same manner as in Example C-11, but swelling was observed in the polyimide layer in any of the metal tension laminates.

[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 the polyimide film C-13 - the polyimide film C-18. About the polyimide film C-13 - the polyimide film C-18, CTE, Tg, a dielectric constant, and a dielectric tangent were calculated|required. These measurement results are shown in Table 16.

[Table 16]

[Example C-27 to Example C-30]

Except for using polyamic acid solution C-15 to polyamic acid solution C-18 instead of polyamic acid solution C-1 in Example C-11, and performing stepwise heat treatment from 120°C to 360°C for 15 minutes, Metal sheet laminates C-27 to C-30 were prepared in the same manner as in Example C-11. In any of metal sheet laminate C-27 to metal sheet laminate C-30, defects such as expansion of the polyimide layer were not confirmed.

(Reference Example C-7 to Reference Example C-8)

Except that the polyamic acid solution C-13 and the polyamic acid solution C-14 were used instead of the polyamic acid solution C-1 in Example C-11, and the stepwise heat treatment was performed from 120°C to 360°C for 15 minutes, A metal sheet laminate was prepared in the same manner as in Example C-11, but swelling was observed in the polyimide layer in any of the metal sheet laminates.

[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 the polyimide film C-19 - polyimide film C-20. About the polyimide film C-19 - the polyimide film C-20, CTE, Tg, a dielectric constant, and a dielectric tangent were calculated|required. These measurement results are shown in Table 17.

[Table 17]

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

Claims (8)

1. A polyimide film having a thermoplastic polyimide layer containing a thermoplastic polyimide on at least one side of a non-thermoplastic polyimide layer containing a non-thermoplastic polyimide, and characterized in that the following conditions (a-i) to (a-iv) are satisfied:

(a-i) the residue contained in the non-thermoplastic polyimide constituting 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,

the total of at least one of a tetracarboxylic acid residue (BPDA residue) derived from 3,3',4,4' -biphenyltetracarboxylic dianhydride (BPDA), a tetracarboxylic acid residue (TAHQ residue) derived from 1, 4-phenylenebis (trimellitic acid monoester) dianhydride (TAHQ), and at least one of a tetracarboxylic acid residue (PMDA residue) derived from pyromellitic dianhydride (PMDA) and a tetracarboxylic acid residue (NTCDA residue) derived from 2,3,6, 7-naphthalenetetracarboxylic dianhydride (NTCDA) is 80 parts by mole 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 an aromatic tetracarboxylic acid residue and an aromatic diamine residue, and

relative to 100 mole parts of the aromatic diamine residue,

a diamine residue derived from at least one diamine compound selected from diamine compounds represented by general formulae (B1) to (B7) is 70 parts by mole or more, and a diamine residue derived from a diamine compound represented by general formula (a1) is in a range of 1 part by mole or more and 30 parts by mole or less;

(a-iii) a coefficient of thermal expansion in the range of 10ppm/K to 30 ppm/K;

(a-iv) a dielectric tangent (Df) at 10GHz of 0.004 or less,

in the formulae (B1) to (B7), R₁Independently represents a C1-6 monovalent hydrocarbon group or an alkoxy group, and the linking group A independently represents a group selected from-O-, -S-, -CO-, -SO-, -SO₂-、-COO-、-CH₂-、-C(CH₃)₂A divalent radical of-NH-or-CONH-, n₁Independently represent an integer of 0 to 4; wherein the duplication with the formula (B2) is removed from the formula (B3), the duplication with the formula (B4) is removed from the formula (B5),

in the formula (A1), the linking group X represents a single bond or-COO-, Y independently represents hydrogen, C1-3 monovalent hydrocarbon group or alkoxy group, n represents an integer of 0-2, and p and q independently represent an integer of 0-4.

2. The polyimide film according to claim 1, wherein the diamine residue derived from the diamine compound represented by the general formula (a1) is 80 parts by mole or more per 100 parts by mole of the aromatic diamine residue in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer.

3. The polyimide film according to claim 1, wherein a diamine residue derived from at least one diamine compound selected from the group consisting of the diamine compounds represented by the general formulae (B1) to (B7) is in a range of 70 parts by mole or more and 99 parts by mole or less with respect to 100 parts by mole of the aromatic diamine residue in the thermoplastic polyimide constituting the thermoplastic polyimide layer.

4. A polyimide film having a thermoplastic polyimide layer containing a thermoplastic polyimide on at least one side of a non-thermoplastic polyimide layer containing a non-thermoplastic polyimide, and characterized in that the following conditions (b-i) to (b-iv) are satisfied:

(b-i) a thermal expansion coefficient in the range of 10ppm/K to 30 ppm/K;

(b-ii) the residue contained in the non-thermoplastic polyimide constituting 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,

the amount of the tetracarboxylic acid residue derived from at least one tetracarboxylic acid dianhydride selected from the group consisting of 3,3',4,4' -biphenyltetracarboxylic acid dianhydride (BPDA) and 1, 4-phenylenebis (trimellitic acid monoester) dianhydride (TAHQ) is in the range of 30 parts by mole or more and 60 parts by mole or less,

a tetracarboxylic acid residue derived from pyromellitic dianhydride (PMDA) in a range of 40 to 70 parts by mole;

(b-iii) relative to 100 mole parts of aromatic diamine residues in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer,

80 parts by mole or more of diamine residues derived from a diamine compound represented by the following general formula (A1);

(b-iv) the thermoplastic polyimide constituting the thermoplastic polyimide layer is one containing an aromatic tetracarboxylic acid residue and an aromatic diamine residue and is present in an amount of 100 parts by mole based on the aromatic diamine residue,

the diamine residue derived from at least one diamine compound selected from the group consisting of diamine compounds represented by the following general formulae (B1) to (B7) is in the range of 70 parts by mole or more and 99 parts by mole or less,

the diamine residue derived from the diamine compound represented by the following general formula (A1) is in the range of 1 to 30 parts by mole,

in the formula (A1), the linking group X represents a single bond or-COO-, Y independently represents hydrogen, C1-3 monovalent hydrocarbon group or alkoxy group, n represents an integer of 0-2, p and q independently represent an integer of 0-4,

in the formulae (B1) to (B7), R₁Independently represents a C1-6 monovalent hydrocarbon group or an alkoxy group, and the linking group A independently represents a group selected from-O-, -S-, -CO-, -SO-, -SO₂-、-COO-、-CH₂-、-C(CH₃)₂A divalent radical of-NH-or-CONH-, n₁Independently represent an integer of 0 to 4; wherein the duplication of formula (B2) is removed from formula (B3), and the duplication of formula (B4) is removed from formula (B5).

5. The polyimide film according to claim 1 or 4, wherein the imide group concentration of each of the non-thermoplastic polyimide and the thermoplastic polyimide is 33% by weight or less.

6. A polyimide film having at least one non-thermoplastic polyimide layer, and characterized by satisfying the following conditions (c-i) to (c-iii):

(c-i) the residue contained in the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer is an aromatic tetracarboxylic acid residue and an aromatic diamine residue, and

a tetracarboxylic acid residue derived from at least one of 3,3',4,4' -biphenyltetracarboxylic dianhydride and 1, 4-phenylenebis (trimellitic acid monoester) dianhydride in the range of 30 to 60 parts by mole based on 100 parts by mole of the aromatic tetracarboxylic acid residue, a tetracarboxylic acid residue derived from at least one of pyromellitic dianhydride and 2,3,6, 7-naphthalenetetracarboxylic dianhydride in the range of 40 to 70 parts by mole,

a diamine residue derived from a diamine compound represented by the following general formula (a1) in an amount of 70 parts by mole or more per 100 parts by mole of the aromatic diamine residue, and a diamine residue derived from a diamine compound represented by the following general formula (C1) to general formula (C4) in an amount of 2 to 15 parts by mole;

(c-ii) a glass transition temperature of 300 ℃ or higher;

(c-iii) a dielectric tangent (Df) at 10GHz of 0.004 or less,

in the formula (A1), the linking group X represents a single bond or-COO-, Y independently represents hydrogen, C1-3 monovalent hydrocarbon group or alkoxy group, n represents an integer of 1 or 2, p and q independently represent an integer of 0-4,

in the formulae (C1) to (C4), R₂Independently represents a C1-6 monovalent hydrocarbon group, alkoxy group or alkylthio group, and the linking group A' independently represents a group selected from-O-, -SO₂-、-CH₂-or-C (CH)₃)₂The divalent group in (A), the linking group X1 independently represent-CH₂-、-O-CH₂-O-、-O-C₂H₄-O-、-O-C₃H₆-O-、-O-C₄H₈-O-、-O-C₅H₁₀-O-、-O-CH₂-C(CH₃)₂-CH₂-O-、-C(CH₃)₂-、-C(CF₃)₂-or-SO₂-，n₃Independently represents an integer of 1 to 4, n₄Independently represents an integer of 0 to 4, but in the formula (C3), the linking group A' does not contain-CH₂-、-C(CH₃)₂-、-C(CF₃)₂-or-SO₂In the case of-n₄Is 1 or more.

7. A copper sheet laminated plate comprising an insulating layer and a copper foil on at least one side of the insulating layer, and characterized in that:

the insulating layer comprises the polyimide film according to any one of claims 1,4, or 6.

8. A circuit board obtained by processing the copper foil of the copper-clad laminate according to claim 7 into wiring.