KR20220092412A - Polyimide film, metal-clad laminate, method for producing same and circuit substrate - Google Patents

Abstract

The present invention relates to a polyimide film or a metal thin laminated plate capable of realizing good adhesion of an interface between the polyimide film or a polyimide insulating layer and a bonding sheet without deteriorating dielectric properties. The polyimide film or a polyimide insulating layer of the metal thin laminated plate of the present invention comprises: a plurality of polyimide layers and a polyimide layer (P) on an exposure surface. The whole of the polyimide film or the polyimide insulating layer satisfies (i) oxygen transmission coefficient of 2.0 × 10^-18 mol·m/m^2·s·Pa or less; (ii) thermal expansion coefficient of 10-30 ppm/K; (iii) dielectric tangent (Tanδ) of 0.004 or less in 10 GHz; and a thickness of 10-100 ㎛. In addition, polyimide (p) constituting the polyimide layer (P) contains an acid anhydride residue which is induced from a tetracarboxylic anhydride component; and a diamine residue which is induced from a diamine component. The diamine residue contains at least 30 mol% of the diamine residue induced from 1,3-bis (aminophenoxy) benzene with respect to the total diamine residue.

Description

Polyimide film, metal clad laminate, manufacturing method and circuit board thereof

The present invention relates to an electronic material, for example, a polyimide film used to form a circuit board, a metal clad laminate, and a circuit board formed by processing the same.

In the manufacture of circuit boards such as flexible printed circuit boards (FPC), a metal foil laminate in which a metal layer such as copper foil is laminated on one or both sides of a polyimide insulating layer is widely used. Such a polyimide insulating layer is generally required to exhibit a relatively low dielectric constant and dielectric loss tangent for the purpose of improving the high-frequency transmission characteristics of a circuit.

By the way, the formation of the polyimide insulating layer of the metal clad laminate is made by the “cast method” in which imidization heat treatment is performed after applying a polyamic acid solution to the metal layer and drying it. Between the layers of the mid insulating layer, so-called "swelling" or "peeling" phenomena (hereinafter sometimes referred to as foaming phenomenon) may occur due to volume expansion of the residual solvent or water generated by imidization.

For this reason, as a metal clad laminate in which the foaming phenomenon is suppressed without deteriorating the dielectric properties, the polyimide insulating layer in contact with the metal layer has a storage modulus of elasticity equal to or greater than a predetermined value, in 100 moles in total of the acid anhydride residues constituting the polyimide insulating layer. On the other hand, there has been proposed a metal clad laminate in which 40 mole parts or more of a tetracarboxylic dianhydride residue having a ketone group, which is a relatively highly polar group, is contained in the molecule (Patent Document 1).

However, as described above, as a metal clad laminate, a double-sided metal clad laminate in which a metal layer is formed on both sides of a polyimide insulating layer is also widely used. The layers are opposed to each other, and the polyimide insulating layers are bonded to each other by a double-sided adhesive sheet (hereinafter referred to as a bonding sheet (BS)) formed by molding a polyimide-based adhesive into a sheet shape between them. Manufacturing is being done. When the metal clad laminate of Patent Document 1 is used as a double-sided metal clad laminate, it is prepared by the same method.

Japanese Patent Laid-Open No. 2020-104340

However, in the case of the metal clad laminate of Patent Document 1, attention is paid to securing the adhesion between the interface between the metal layer and the polyimide insulating layer adjacent thereto, and the very flat surface of the polyimide insulating layer on the opposite side to the metal layer and the bonding sheet A sufficient examination has not been made about the adhesiveness of the interface between them. In addition, since the acid anhydride residue constituting the polyimide contains 40 mole parts or more of the tetracarboxylic acid dianhydride residue having a ketone group, which is a relatively highly polar group in the molecule, there is a problem that not only the dielectric constant but also the dielectric loss tangent tends to increase. . For this reason, according to Patent Document 1, in the polyimide insulating layer of the metal clad laminate, it is possible to suppress the foaming phenomenon without deteriorating the dielectric properties thereof, as well as to realize good adhesion at the interface with the bonding sheet. Couldn't come up with a configuration.

An object of the present invention is to provide a specific configuration capable of realizing good adhesion at the interface between a polyimide film or a polyimide insulating layer and a bonding sheet without deteriorating dielectric properties in a polyimide film or a metal clad laminate. .

The inventors of the present invention have studied a vast number of specific elements for the polyimide insulating layer of a polyimide film or a metal clad laminate, and controlled extremely limited specific elements shown in (a) to (c) below, thereby achieving the object of the present invention. It has been found that this can be achieved and completed the present invention.

(a) using a polyimide film or a polyimide insulating layer as a some polyimide layer, and arrange|positioning a specific polyimide layer on the exposed surface side;

(b) setting “oxygen permeability”, “coefficient of thermal expansion”, “dielectric loss tangent” and “layer thickness” of the polyimide film or the entire polyimide insulating layer within predetermined ranges; and

(c) The polyimide constituting the polyimide layer on the exposed surface side of the polyimide film or polyimide insulating layer is a diamine residue derived from 1,3-bis(aminophenoxy)benzene as a diamine residue. To be used in more than one content.

That is, the first aspect of the present invention is a polyimide film having a plurality of polyimide layers, under the following conditions (i) to (iv):

(i) an oxygen permeability coefficient of 2.0×10 ^-18 mol·m/m2·s·Pa or less;

(ii) the coefficient of thermal expansion is within the range of 10 to 30 ppm / K;

(iii) a dielectric loss tangent (Tanδ) of 0.004 or less at 10 GHz; and

(iv) having a thickness in the range of 10 μm to 100 μm;

satisfied with

The polyimide film is provided with a polyimide layer (P) on at least one exposed surface side,

The polyimide (p) constituting the polyimide layer (P) contains an acid anhydride residue derived from a tetracarboxylic acid dianhydride component and a diamine residue derived from a diamine component, and the diamine residue is represented by the following general formula ( The polyimide film characterized by containing at least 30 mol% of the diamine residue induced|guided|derived from the diamine compound represented by 1) with respect to all the diamine residues is provided.

In addition, a second aspect of the present invention is a metal clad laminate comprising a metal layer and a polyimide insulating layer including a plurality of polyimide layers,

(a) the polyimide insulating layer is provided with a polyimide layer (P) on the exposed surface side opposite to the metal layer,

(b) the following conditions (i) to (iv) as the whole polyimide insulating layer:

(i) an oxygen permeability coefficient of 2.0×10 ^-18 mol·m/m2·s·Pa or less;

(ii) the coefficient of thermal expansion is within the range of 10 to 30 ppm / K;

(iii) a dielectric loss tangent (Tanδ) of 0.004 or less at 10 GHz; and

(iv) the layer thickness is in the range of 10 μm to 100 μm;

is satisfied with

(c) the polyimide (p) constituting the polyimide layer (P) contains an acid anhydride residue derived from a tetracarboxylic acid dianhydride component and a diamine residue derived from a diamine component, wherein the diamine residue is There is provided a metal clad laminate comprising at least 30 mol% of a diamine residue derived from the diamine compound represented by the general formula (1) with respect to the total diamine residue.

In addition, a third aspect of the present invention is a method for manufacturing a metal clad laminate for manufacturing the above metal clad laminate,

A step of applying a solution of polyamic acid on the metal layer and drying it to form a first polyamic acid layer of a single layer or a plurality of layers;

forming a second polyamic acid layer by coating and drying a solution of polyamic acid, which is a precursor of the polyimide (p), on the first polyamic acid layer;

It provides a manufacturing method comprising the step of forming the polyimide insulating layer by imidizing the polyamic acid contained in the first polyamic acid layer and the polyamic acid contained in the second polyamic acid layer.

In addition, a fourth aspect of the present invention provides a circuit board in which the metal layer of the metal clad laminate is processed as wiring.

The polyimide film and metal clad laminate of the present invention comprises a polyimide film or polyimide insulating layer with a plurality of polyimide layers, and the “oxygen permeability” and “coefficient of thermal expansion” of the entire polyimide film or the entire polyimide insulating layer Since , “dielectric loss tangent” and “layer thickness” are set within predetermined ranges, respectively, dimensional stability is excellent and transmission loss can be reduced. Further, in the polyimide film and metal clad laminate of the present invention, by arranging a specific polyimide layer on the exposed surface side, the dielectric properties of the entire polyimide film or polyimide insulating layer are not reduced, for example, a bonding sheet or the like. Good adhesion at the interface with the resin material can also be realized. Therefore, the metal clad laminate of the present invention can be processed into a double-sided metal clad laminate without impairing the good properties of the single-sided metal clad laminate. Further, the circuit board formed of the metal clad laminate of the present invention is excellent in dimensional stability and heat resistance, and furthermore, good high-frequency transmission characteristics can be obtained.

1 is a cross-sectional view schematically showing the configuration of a metal clad laminate according to an embodiment of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, the polyimide film and metal clad laminated board of this invention are demonstrated, referring drawings.

[Polyimide film of the present invention and metal clad laminate of the present invention]

The polyimide film of this invention is equipped with a some polyimide layer. Further, the metal clad laminate of the present invention is composed of a metal layer and a polyimide insulating layer including a plurality of polyimide layers. Here, the polyimide film of the present invention is different from the metal clad laminate of the present invention in that it does not necessarily contain a metal layer. That is, the polyimide film of the present invention has substantially the same configuration as the "polyimide insulating layer" in the metal clad laminate of the present invention.

In order to avoid duplication of description below, in the detailed description of the metal clad laminate of the present invention, the structure of the polyimide film of the present invention will also be clarified. In the following description, the "polyimide insulating layer" in the metal clad laminate may be substituted for the "polyimide film", except where otherwise specified.

1 is a cross-sectional view schematically showing the basic configuration of one embodiment of a metal clad laminate 30 of the present invention. The metal clad laminate 30 has a structure in which a polyimide insulating layer 20 is formed on one side of the metal layer 10, and has configurations (a), (b) (i) to (iv), (c) ) is provided. Hereinafter, each configuration will be described in detail.

In addition, as described above, the polyimide film of the present invention has the same configuration as the polyimide insulating layer 20 of the metal clad laminate 30 .

<Configuration (a)>

(Polyimide insulating layer 20)

In the present invention, the polyimide insulating layer 20 is a polyimide layer 21 composed of a single layer or a plurality of polyimide layers, and a polyimide layer (P) containing a specific polyimide (p) described later ( 23), and the polyimide layer (P) 23 is formed as a part on the surface side of the polyimide insulating layer 20 on the opposite side to the metal layer 10 . In Fig. 1, the polyimide layer (P) 23 is exposed.

Moreover, in the case of the polyimide film of this invention, the polyimide layer P should just be provided in at least one exposed surface side.

The polyimide layer 21 is composed of a single layer or a plurality of polyimide layers, and the main polyimide layer is a non-thermoplastic polyimide layer composed of non-thermoplastic polyimide in order to ensure high heat resistance and high water stability. Although it is preferable that it is a range which does not impair the effect of this invention, you may contain the thermoplastic polyimide layer comprised from a thermoplastic polyimide. Here, it is preferable that the total thickness of the main polyimide layer shall be 50 % or more with respect to the thickness of the polyimide layer 21. Further, in order to improve the adhesiveness of the polyimide surface of the polyimide insulating layer 20 , a polyimide layer (P) 23 is laminated on the exposed surface side of the polyimide layer 21 . The polyimide constituting the polyimide layer (P) 23 is not limited to a thermoplastic polyimide or a non-thermoplastic polyimide, and can improve adhesiveness with other materials.

Non-thermoplastic polyimides and thermoplastic polyimides are both obtained by imidation reaction of a tetracarboxylic dianhydride component and a diamine component, and as a monomer residue, a tetravalent acid anhydride residue derived from a tetracarboxylic acid dianhydride component, and a diamine component It contains a divalent diamine residue. These tetracarboxylic dianhydride components and diamine components will be described later in relation to the thermoplastic polyimide and the non-thermoplastic polyimide.

In the present invention, the "non-thermoplastic" of "non-thermoplastic polyimide" means that the storage modulus at 30°C measured using a dynamic viscoelasticity measuring device (DMA) is 1.0×10 ⁹ Pa or more, and the glass transition temperature +30 It means that the storage modulus in the temperature range within ℃ is 1.0×10 ⁸ Pa or more. In addition, the "thermoplastic" of "thermoplastic polyimide" is a temperature range in which the storage modulus at 30°C measured using a dynamic viscoelasticity measuring device (DMA) is 1.0×10 ⁹ Pa or more, and the glass transition temperature is within +30°C. It means that the storage modulus at is less than 1.0×10 ⁸ Pa.

Further, the non-thermoplastic polyimide layer constitutes a polyimide layer having low thermal expansion properties, and the thermoplastic polyimide layer constitutes a polyimide layer having high thermal expansion properties. Here, "low thermal expansion property" of the polyimide layer of low thermal expansion property means that the 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 or less. On the other hand, "high thermal expansibility" of the polyimide layer of high thermal expansibility means that the CTE is preferably in the range of 35 ppm/K or more and 80 ppm/K or less, more preferably 35 ppm/K or more and 70 ppm/K or less. The thermal expansibility of the polyimide layer can be adjusted by appropriately changing the monomer composition of the polyimide, the thickness of the polyimide insulating layer, the conditions for forming the polyimide layer (coating, drying, curing), and the like.

<Configuration (b)>

In the metal clad laminate 30 of the present embodiment, the polyimide insulating layer 20 as a whole satisfies the following conditions (i) to (iv).

(i) The oxygen permeability coefficient is 2.0×10 ^-18 mol·m/m2·s·Pa or less.

In the present invention, the oxygen permeability coefficient of the polyimide insulating layer 20 is adjusted to 2.0×10 ⁻¹⁸ mol·m/m 2 ·s·Pa or less. The measurement of the oxygen permeability coefficient can be performed based on the differential pressure method of JISK-7126-1. By adjusting the oxygen permeability coefficient to 2.0×10 ^-18 mol·m/m2·s·Pa or less, it is possible to reduce the dielectric loss tangent by suppressing the motion of molecules of the polyimide constituting the polyimide insulating layer 20 . In addition, in the case where the metal layer 10 of the metal clad laminate 30 is circuit-processed and the polyimide insulating layer 20 is applied as an insulating resin layer of a circuit board, even in an environment repeatedly exposed to high temperatures, the wiring layer and adhesiveness is maintained, and excellent long-term heat-resistance adhesiveness can be obtained. When the oxygen permeability coefficient of the polyimide insulating layer 20 exceeds 2.0×10 ^-18 mol·m/m2·s·Pa, the oxidation of the wiring layer proceeds by oxygen passing through the polyimide insulating layer 20 . , there is a fear that the adhesion between the wiring layer and the polyimide insulating layer 20 may be lowered. In addition, the oxygen permeability coefficient of the polyimide insulating layer 20, in addition to the thickness and thickness ratio of the polyimide layer 21, is the ratio in the polyimide mainly constituting the polyimide layer 21, preferably in the non-thermoplastic polyimide. It can be adjusted by the ratio of a phenyl skeleton containing residue, the presence or absence of an aliphatic skeleton residue, and the kind of substituent of a diamine residue and an acid anhydride residue.

(ii) The coefficient of thermal expansion (CTE) is within the range of 10 to 30 ppm/K.

In the present invention, the coefficient of thermal expansion (CTE) of the polyimide insulating layer 20 as a whole is 10 ppm/K or more and 30 ppm/K or less, preferably 10 ppm/K or more and 25 ppm/K or less, more preferably 15 ppm/K or more and 25 ppm or less. Adjust to /K or less. Accordingly, in the metal clad laminate 30, it is possible to prevent the occurrence of warpage and deterioration of dimensional stability. When the CTE of the entire polyimide insulating layer 20 is out of the range of 10 to 30 ppm/K, there is concern about the occurrence of warpage and a decrease in dimensional stability. In addition, the coefficient of thermal expansion (CTE) of the polyimide insulating layer 20 is mainly a ratio in addition to the thickness ratio of the non-thermoplastic polyimide layer included in the polyimide layer 21 with the main polyimide layer being a non-thermoplastic polyimide layer. The ratio of the rigid monomer residues such as phenyl skeleton-containing residues, naphthalene skeleton-containing residues, and biphenyl skeleton-containing residues in the non-thermoplastic polyimide constituting the thermoplastic polyimide layer, the heat treatment conditions in the imidization step, etc. can be adjusted. have.

(iii) Dielectric loss tangent (Tanδ) at 10 GHz is 0.004 or less.

In the present invention, the dielectric loss tangent (Tan?) at 10 GHz of the entire polyimide insulating layer 20 is adjusted to 0.004 or less. Accordingly, when the polyimide insulating layer 20 of the metal clad laminate 30 is applied as an insulating resin layer of a circuit board, for example, the dielectric loss during transmission of a high-frequency signal can be reduced. Here, the dielectric loss tangent can be measured by a split post dielectric resonator (SPDR). Accordingly, when the polyimide insulating layer 20 is applied as an insulating resin layer of, for example, a high-frequency circuit board, the transmission loss can be effectively reduced. In addition, when the dielectric loss tangent at 10 GHz exceeds 0.004, when the polyimide insulating layer 20 is applied as an insulating resin layer of a circuit board, there is a risk that a problem such as an increase in electrical signal loss on the transmission path of a high frequency signal may occur. have. The lower limit of the dielectric loss tangent at 10 GHz is not particularly limited, but can be determined according to the required characteristics when the polyimide insulating layer 20 is applied as an insulating resin layer of a circuit board. In addition, the dielectric loss tangent (Tanδ) of the polyimide insulating layer 20 is, in addition to the thickness ratio of the polyimide layer 21, the ratio of the residues containing the biphenyl skeleton in the polyimide mainly constituting the polyimide layer 21 and the imide group It can be adjusted according to the ratio.

On the other hand, the polyimide insulating layer 20 is a split post dielectric resonator (SPDR) as a whole polyimide insulating layer 20 in order to ensure impedance matching when applied as an insulating resin layer of a circuit board, for example. It is preferable that the relative permittivity in 10 GHz measured by , is 4.0 or less. When the relative permittivity at 10 GHz exceeds 4.0, when the polyimide insulating layer 20 is applied as an insulating resin layer of a circuit board, it leads to an increase in dielectric loss, resulting in an increase in electrical signal loss on the transmission path of high-frequency signals, etc. This is because there is a risk that the problem of In addition, when the thickness of the polyimide insulating layer 20 is constant, the higher the relative permittivity, the narrower the width of the circuit wiring when impedance matching is performed, which may cause an increase in conductor loss.

(iv) The layer thickness is within the range of 10㎛ ~ 100㎛.

In this invention, the layer thickness of the whole polyimide insulating layer 20 is made into the range of 10 micrometers - 100 micrometers. This is because, if the layer thickness is too thin, the polyimide insulating layer 20 is easily broken, while if the layer thickness is too thick, cracks may occur in the metal layer 10 when the metal clad laminate 30 is bent. to be. In addition, within the range where the entire polyimide insulating layer 20 has a layer thickness of 10 µm to 100 µm, an appropriate layer thickness can be set according to the purpose of use of the metal clad laminate 30 . For example, when the metal clad laminate 30 is applied to a circuit board, it is preferably set within the range of 30 to 60 µm, more preferably 35 to 50 µm.

<Configuration (c)>

(Polyimide layer (P) (23))

In the present invention, the polyimide layer (P) 23 is exposed on the surface of the metal clad laminate 30, and forms an exposed surface to which, for example, a bonding sheet is directly bonded. The polyimide (p) constituting the polyimide layer (P) 23 contains an acid anhydride residue derived from a tetracarboxylic acid dianhydride component and a diamine residue derived from a diamine component, and the diamine residue is The diamine residue derived from the diamine compound (1,3-bis(aminophenoxy)benzene) represented by Formula (1) is at least 30 mol% with respect to all the diamine residues, Preferably it contains at least 50 mol%.

The diamine compound represented by General formula (1) is equipped with two aminophenoxy groups at the meta position of the central benzene ring. For this reason, rotational motion due to meta-bonding is suppressed, and since the molecular weight is relatively larger than that of a general diamine compound such as di(aminophenyl)ether, an increase in the imide group concentration can be suppressed, and the polyimide insulating layer 20 is Therefore, low dielectric constant and low dielectric loss tangent can be realized. In addition, even when reacted with highly polar tetracarboxylic dianhydride, which tends to deteriorate dielectric properties, adhesion to the bonding sheet can be ensured without deteriorating dielectric properties.

Examples of the diamine compound represented by the general formula (1) include 1,3-bis(3-aminophenoxy)benzene (APB) and 1,3-bis(4-aminophenoxy)benzene (TPE-R). have. In particular, 1,3-bis(4-aminophenoxy)benzene (TPE-R) is preferable in that a good inhibitory effect of rotational motion due to meta-bonding can be expected.

The diamine residue of the polyimide (p) contains at least 30 mol%, preferably at least 50 mol%, more preferably at least 70 mol% of the diamine residue derived from the diamine compound represented by the general formula (1) with respect to the total diamine residues. are doing This is because, when the content of the diamine residue derived from the diamine compound represented by the general formula (1) is too small, the polyimide insulating layer 20 may not be able to achieve low dielectric constant and low dielectric loss tangent.

Further, the diamine residue of the polyimide (p) constituting the polyimide layer (P) 23 may contain a diamine residue derived from a known diamine compound within a range that does not impair the effects of the present invention. As such a known diamine compound, for example, 1,4-diaminobenzene (p-PDA; paraphenylenediamine), 4-aminophenyl-4'-aminobenzoate (APAB), 3,3'-diamino Diphenylmethane, 3,3'-diaminodiphenylpropane, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylsulfone, 3,3'-diaminodiphenyl ether, 3 ,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylpropane, 3,4'-diaminodiphenylsulfide, 3,3'-dia minobenzophenone, (3,3'-bisamino)diphenylamine, 1,4-bis(3-aminophenoxy)benzene, 3-[4-(4-aminophenoxy)phenoxy]benzeneamine, 3 -[3-(4-aminophenoxy)phenoxy]benzeneamine, 4,4'-[2-methyl-(1,3-phenylene)bisoxy]bisaniline, 4,4'-[4-methyl -(1,3-phenylene)bisoxy]bisaniline, 4,4'-[5-methyl-(1,3-phenylene)bisoxy]bisaniline, bis[4,4'-(3-amino Phenoxy)]benzanilide, 4-[3-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline, 4,4'-[oxybis(3,1-phenyleneoxy)]bisaniline , bis[4-(4-aminophenoxy)phenyl]ether (BAPE), bis[4-(4-aminophenoxy)phenyl]sulfone (BAPS), bis[4-(4-aminophenoxy)phenyl] Ketone (BAPK), 2,2-bis-[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), bis[4 -(3-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(3-amino) phenoxy)]benzophenone, 9,9-bis[4-(3-aminophenoxy)phenyl]fluorene, 2,2-bis-[4-(4-aminophenoxy)phenyl]hexafluoropropane; 2,2-bis-[4-(3-aminophenoxy)phenyl]hexafluoropropane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenedi-o- Toluidine, 4,4'-methylenedi-2,6-xylidine, 4,4'-methylene-2,6-diethylaniline, 3,3'-diaminodiphenylethane, 3,3'-dia Minobiphenyl, 3,3'-dimethoxybenzidine, 3,3''-diamino-p-terphenyl, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bis Aniline, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, bis(p-aminocyclohexyl)methane, bis(p-β-amino-t-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-t-butyl)toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p -xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3, 4-oxadiazole, piperazine, 2'-methoxy-4,4'-diaminobenzanilide, 4,4'-diaminobenzanilide, 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 , 6-amino-2- (4-aminophenoxy) benzoxazole, 2,6-diamino-3,5-diethyltoluene, 2,4-diamino-3,5-diethyltoluene, 2, Aromatic diamine compounds such as 4-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane and bis(4-amino-3-ethyl-5-methylphenyl)methane, two ends of dimer acid and aliphatic diamine compounds such as dimer acid type diamine in which a carboxylic acid group is substituted with a primary aminomethyl group or an amino group.

In addition, as the acid anhydride residues derived from the tetracarboxylic acid dianhydride component of the polyimide (p), various acid anhydride residues capable of realizing the low dielectric properties of the polyimide insulating layer 20 and high adhesion to the bonding sheet in a balanced way are used. can be hired Among them, the acid anhydride residue is an acid anhydride residue derived from 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) having a highly polar carbonyl group, and an imide group because of its relatively low molecular weight. Preferably at least 60 mol%, more preferably at least 90 mol% of the acid anhydride residues derived from pyromellitic dianhydride (PMDA) having a high concentration in total, based on the total acid anhydride residues. Only BTDA or PMDA may be sufficient, but when both are contained, the preferable ranges are 50-80 mol% of BTDA and 20-50 mol% of PMDA with respect to all acid anhydride residues.

Further, the acid anhydride residue of the polyimide (p) may contain an acid anhydride residue derived from a known tetracarboxylic acid dianhydride within a range not impairing the effects of the present invention. As such a known acid dianhydride, 1,4-phenylenebis(trimellitic acid monoester) dianhydride (TAHQ), 2,3,6,7-naphthalenetetracarboxylic dianhydride (NTCDA), 3,3',4 ,4'-diphenylsulfonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 2,2',3,3'- or 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 2,3',3,4'-diphenylethertetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl)etherdianhydride, 3,3'',4,4''-, 2,3,3' ',4''- or 2,2'',3,3''-p-terphenyltetracarboxylic dianhydride, 2,2-bis(2,3- or 3,4-dicarboxyphenyl)-propane Anhydride, bis(2,3- or 3,4-dicarboxyphenyl)methandianhydride, bis(2,3- or 3,4-dicarboxyphenyl)sulfondianhydride, 1,1-bis(2,3- or 3,4-dicarboxyphenyl)ethane dianhydride, 1,2,7,8-, 1,2,6,7- or 1,2,9,10-phenanthrene-tetracarboxylic dianhydride, 2,3 , 6,7-anthracene tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) tetrafluoropropane dianhydride, 2,3,5,6-cyclohexane dianhydride, 1,2,5 ,6-naphthalenetetracarboxylic 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- or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7- (or 1,4,5,8 -) tetrachloronaphthalene-1,4,5,8- (or 2,3,6,7-) tetracarboxylic dianhydride, 2,3,8,9-, 3,4,9,10-, 4, 5,10,11- or 5,6,11,12-perylene-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetra Carboxylic acid dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-bis(2,3-dicarboxylate) phenoxy ) Aromatic tetracarboxylic dianhydride, such as diphenylmethane dianhydride and ethylene glycol bisanhydro trimellitate, etc. are mentioned.

In the polyimide (p), by selecting the types of the acid anhydride residues and diamine residues, or the molar ratios in the case of applying two or more types of acid anhydride residues or diamine residues, thermal expansion coefficient, tensile modulus of elasticity, glass transition temperature, etc. can be controlled. Moreover, polyimide (p) WHEREIN: When providing two or more structural units of polyimide, even if it exists as a block, although it may exist at random, it is preferable to exist at random. Further, the polyimide (p) preferably contains an aromatic tetracarboxylic acid anhydride residue derived from an aromatic tetracarboxylic acid dianhydride and an aromatic diamine residue derived from an aromatic diamine. By making both the acid anhydride residue and the diamine residue contained in the polyimide (p) into aromatic groups, deterioration of the polyimide in the high-temperature environment of the polyimide insulating layer 20 can be suppressed.

It is preferable that the imide group density|concentration of a polyimide (p) is 30 weight% or less. Here, "imide group concentration" means the value obtained by dividing the molecular weight of the imide group moiety (-(CO) ₂ -N-) in the polyimide by the molecular weight of the entire structure of the polyimide. When the imide group concentration exceeds 30% by weight, the elastic modulus at a temperature equal to or higher than the glass transition temperature is less likely to decrease, and the low hygroscopicity is also deteriorated due to the increase in polar groups.

The weight average molecular weight of the polyimide (p) is, for example, preferably in the range of 10,000 to 400,000, 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 is lowered and the film tends to become brittle. On the other hand, when the weight average molecular weight exceeds 400,000, the viscosity is excessively increased, and defects such as unevenness of film thickness and streaks tend to occur during coating operation.

Further, in the polyimide insulating layer 20 of the present invention, by further laminating a metal layer (not shown) on the polyimide layer (P) 23, the polyimide layer (P) 23 functions as an adhesive layer. can do it

(Polyimide layer 21)

In the present invention, the polyimide layer 21 constituting the polyimide insulating layer 20 of the metal clad laminate 30 is composed of a single layer or a plurality of polyimide layers, and the main polyimide layer is a non-thermoplastic polyimide layer. It is preferable that a mid layer is contained and the said non-thermoplastic polyimide layer satisfy|fills the following conditions (a) - (c). Hereinafter, each condition will be described.

(A) the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer contains 50 mol% or more of monomer residues having a biphenyl skeleton in all monomer residues derived from all monomer components;

(B) The thickness is within the range of 7㎛ ~ 70㎛; and

(C) The ratio of the thickness of the non-thermoplastic polyimide layer to the overall thickness of the polyimide insulating layer 20 is 70% or more.

(Condition (a))

In the polyimide insulating layer (20), a non-thermoplastic polyimide layer is contained as a main layer of the polyimide layer (21). This is to make it easier to control the oxygen permeability coefficient, CTE, and dielectric properties of the polyimide insulating layer 20 . Here, the "main layer" is more than 50% of the thickness of the whole polyimide layer 21, Preferably it means the layer which occupies 60 to 100% of thickness. In addition, the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer is a monomer residue having a biphenyl skeleton among all monomer residues derived from all monomer components constituting the non-thermoplastic polyimide (hereinafter, "biphenyl skeleton-containing residue"). ) is preferably contained in an amount of 50 mol% or more, more preferably 70 mol% or more. Accordingly, it is possible to increase the content of the biphenyl skeleton-containing residues in the entire polyimide constituting the polyimide insulating layer 20, lower the oxygen permeability coefficient, and achieve a low dielectric loss tangent. On the other hand, in order to maintain the physical properties necessary for the polyimide insulating layer 20 of the metal clad laminate 30 used as a circuit board material, the ratio of the residues containing the biphenyl skeleton is preferably 80 mol% or less with respect to the total monomer residues. Here, the biphenyl skeleton is a skeleton in which two phenyl groups are single-bonded. Therefore, as a biphenyl skeleton containing residue, a biphenyldiyl residue, a biphenyltetrayl residue, etc. are mentioned, for example. The aromatic ring contained in these residues may be equipped with arbitrary substituents. Representative examples of the biphenyldiyl group include a biphenyl-3,3'-diyl residue and a biphenyl-4,4'-diyl residue. A typical example of the biphenyltetrayl residue is a biphenyl-3,4,3',4'-tetrayl residue.

In the non-thermoplastic polyimide layer, the ratio of the biphenyl skeleton-containing residues to each of all the diamine residues and all the acid anhydride residues is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more. % or more. By including 20 mol% or more of the biphenyl skeleton-containing residue for each of the total diamine residues and the total acid anhydride residues, the total amount of the polymer is compared to the case where the biphenyl skeleton-containing residue is biased toward either the diamine residue or the acid anhydride residue. The formation of an ordered structure is more accelerated, and the effect of lowering the oxygen permeability coefficient and dielectric loss tangent is increased.

The biphenyl skeleton-containing residue is a structure derived from the raw material monomer, and may be derived from tetracarboxylic dianhydride or may be derived from a diamine compound.

Representative examples of the acid anhydride residue having a biphenyl skeleton include 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,3',3,4'-biphenyltetracarboxylic dianhydride, and residues derived from acid dianhydrides such as 4,4'-biphenol-bis(trimellitate anhydride). Among these, acid anhydride residues derived from BPDA (hereinafter also referred to as "BPDA residues") are preferable because they tend to form an ordered structure of the polymer and reduce the dielectric loss tangent and hygroscopicity by inhibiting molecular motion. Moreover, the BPDA residue can provide the self-supporting property of the gel film|membrane as polyamic acid which is a polyimide precursor.

In addition, the acid anhydride residue of the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer is an acid derived from a known tetracarboxylic acid dianhydride in addition to the acid anhydride residue having a biphenyl skeleton within a range that does not impair the effects of the present invention. may contain anhydride residues. As such a known acid dianhydride, for example, pyromellitic dianhydride (PMDA), 1,4-phenylenebis(trimellitic acid monoester) dianhydride (TAHQ), 2,3,6,7-naphthalenetetracarboxylic acid dianhydride (NTCDA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 2,2',3,3'-, 2,3,3 ',4'- or 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl ) ether dianhydride, 3,3'',4,4''-, 2,3,3'',4''- or 2,2'',3,3''-p-terphenyltetracarboxylic dianhydride , 2,2-bis(2,3- or 3,4-dicarboxyphenyl)-propanedianhydride, bis(2,3- or 3,4-dicarboxyphenyl)methandianhydride, bis(2,3- Or 3,4-dicarboxyphenyl) sulfonic anhydride, 1,1-bis (2,3- or 3,4-dicarboxyphenyl) ethane dianhydride, 1,2,7,8-, 1,2,6 ,7- or 1,2,9,10-phenanthrene-tetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)tetrafluoro Ropropane dianhydride, 2,3,5,6-cyclohexane dianhydride, 1,2,5,6-naphthalenetetracarboxylic 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- or 2,7-dichloronaphthalene-1,4,5,8 -tetracarboxylic dianhydride, 2,3,6,7- (or 1,4,5,8-) tetrachloronaphthalene-1,4,5,8- (or 2,3,6,7-) tetracarboxylic acid dianhydride, 2,3,8,9-, 3,4,9,10-, 4,5,10,11- or 5,6,11,12-perylene-tetracarboxylic dianhydride, cyclopentane-1 ,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3 aromatic tetracarboxylic dianhydride such as ,4,5-tetracarboxylic dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenylmethanedianhydride, and ethylene glycol bisanhydrotrimellitate; can

On the other hand, representative examples of the diamine compound having a biphenyl skeleton include a diamine compound having only two aromatic rings, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), 2 , 2'-diethyl-4,4'-diaminobiphenyl (m-EB), 2,2'-diethoxy-4,4'-diaminobiphenyl (m-EOB), 2,2'- Dipropoxy-4,4'-diaminobiphenyl (m-POB), 2,2'-di-n-propyl-4,4'-diaminobiphenyl (m-NPB), 2,2'- Divinyl-4,4'-diaminobiphenyl (VAB), 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) ) and the like. Since the residues derived from these diamine compounds have a rigid structure, they are acting to impart an ordered structure to the entire polymer. By containing a residue derived from these diamine compounds, a polyimide having a low oxygen permeability coefficient and low hygroscopicity can be obtained, and since moisture inside the molecular chain can be reduced, the dielectric loss tangent can be lowered. Among them, m-TB is preferable.

In addition, the diamine residue of the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer is a diamine residue derived from a known diamine compound in addition to the above-mentioned diamine compound having a biphenyl skeleton within a range that does not impair the effects of the present invention. may contain. As such a known diamine compound, for example, 1,4-diaminobenzene (p-PDA; paraphenylenediamine), 4-aminophenyl-4'-aminobenzoate (APAB), 3,3'-diamino Diphenylmethane, 3,3'-diaminodiphenylpropane, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylsulfone, 3,3'-diaminodiphenyl ether, 3 ,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylpropane, 3,4'-diaminodiphenylsulfide, 3,3'-dia minobenzophenone, (3,3'-bisamino)diphenylamine, 1,4-bis(3-aminophenoxy)benzene, 3-[4-(4-aminophenoxy)phenoxy]benzeneamine, 3 -[3-(4-aminophenoxy)phenoxy]benzeneamine, 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,3-bis(3-aminophenoxy)benzene ( APB), 4,4'-[2-methyl-(1,3-phenylene)bisoxy]bisaniline, 4,4'-[4-methyl-(1,3-phenylene)bisoxy]bisaniline , 4,4′-[5-methyl-(1,3-phenylene)bisoxy]bisaniline, bis[4,4′-(3-aminophenoxy)]benzanilide, 4-[3-[4] -(4-aminophenoxy)phenoxy]phenoxy]aniline, 4,4'-[oxybis(3,1-phenyleneoxy)]bisaniline, bis[4-(4-aminophenoxy)phenyl] Ether (BAPE), bis[4-(4-aminophenoxy)phenyl]sulfone (BAPS), bis[4-(4-aminophenoxy)phenyl]ketone (BAPK), 2,2-bis-[4- (3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), bis[4-(3-aminophenoxy)phenyl]sulfone, bis[ 4-(3-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)]benzophenone, 9,9-bis[4 -(3-aminophenoxy)phenyl]fluorene, 2,2-bis-[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis-[4-(3-aminophenoxy) C)phenyl]hexafluoropropane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6 -xylidine, 4,4'-methylene-2,6-diethylaniline, 3,3'-diaminodiphenylethane, 3,3'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 3,3''-diamino-p-terphenyl, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 4,4'-[1,3-phenyl Lenbis(1-methylethylidene)]bisaniline, bis(p-aminocyclohexyl)methane, bis(p-β-amino-t-butylphenyl)ether, bis(p-β-methyl-δ-aminophen tyl)benzene, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,5-diaminonaphthalene, 2,6-diamino Naphthalene, 2,4-bis(β-amino-t-butyl)toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylyl Lendiamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, piperazine, 2'-methyl Toxy-4,4'-diaminobenzanilide, 4,4'-diaminobenzanilide, 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, 6-amino-2-(4-aminophenoxy) ) Benzoxazole, 2,6-diamino-3,5-diethyltoluene, 2,4-diamino-3,5-diethyltoluene, 2,4-diamino-3,3'-diethyl- In aromatic diamine compounds such as 5,5'-dimethyldiphenylmethane and bis(4-amino-3-ethyl-5-methylphenyl)methane, two terminal carboxylic acid groups of dimer acid are substituted with primary aminomethyl groups or amino groups Aliphatic diamine compounds, such as dimer acid type diamine, etc. are mentioned.

(Condition (B))

In the present invention, the thickness of the non-thermoplastic polyimide layer is preferably in the range of 7 µm to 70 µm. The thickness of the non-thermoplastic polyimide layer can be appropriately set within the range of 7 µm to 70 µm depending on the purpose of use, more preferably 25 µm to 49 µm, still more preferably 30 µm to 49 µm is the range of When the thickness of the non-thermoplastic polyimide layer is within the above range, the effect of improving the dielectric properties of the polyimide insulating layer 20 can be expected, and the oxygen permeability coefficient can be suppressed from increasing, and repeated exposure to high temperature In this case, a decrease in the adhesion between the wiring layer and the insulating resin layer can also be suppressed.

(Condition (C))

In the present invention, the ratio of the thickness of the non-thermoplastic polyimide layer to the overall thickness of the polyimide insulating layer 20 is preferably 70% or more. For this reason, it is possible to suppress an excessive increase in the oxygen permeability coefficient of the polyimide insulating layer 20, to facilitate control of CTE, and to consider a decrease in dielectric loss tangent to a polyimide layer (P) ( 23) increases the freedom of choice. Therefore, when it is used for a circuit board, for example, it becomes easy to control the dimensional change rate and to adapt to high-speed transmission. Moreover, as this ratio becomes large, there exists a tendency for it to become easy to achieve control of an oxygen permeability coefficient and a dimensional change rate, and reduction of a dielectric loss tangent.

In the non-thermoplastic polyimide, oxygen permeability coefficient, dielectric properties, thermal expansion coefficient, storage Elastic modulus, tensile modulus of elasticity, etc. can be controlled. Moreover, in a non-thermoplastic polyimide, when providing two or more structural units of polyimide, even if it exists as a block, although it may exist at random, it is preferable to exist at random. Further, the non-thermoplastic polyimide is preferably composed of an aromatic tetracarboxylic acid anhydride residue derived from an aromatic tetracarboxylic acid dianhydride and an aromatic diamine residue derived from an aromatic diamine. When both the acid anhydride residue and the diamine residue contained in the non-thermoplastic polyimide are aromatic groups, the dimensional accuracy of the polyimide insulating layer 20 in a high-temperature environment can be improved.

It is preferable that the imide group density|concentration of a non-thermoplastic polyimide is 33 weight% or less. Here, "imide group concentration" means the value obtained by dividing the molecular weight of the imide group moiety (-(CO) ₂ -N-) in the polyimide by the molecular weight of the entire structure of the polyimide. When the concentration of the imide group exceeds 33% by weight, the hygroscopicity increases due to an increase in the polar group. In addition, by selecting the combination of the acid dianhydride and the diamine compound, the orientation of molecules in the non-thermoplastic polyimide can be controlled, thereby suppressing an increase in CTE accompanying a decrease in the imide group concentration, and ensuring low hygroscopicity have.

The inside of the range of 10,000-400,000 is preferable, for example, and, as for the weight average molecular weight of a non-thermoplastic polyimide, the inside of the range of 50,000-350,000 is more preferable. When the weight average molecular weight is less than 10,000, the strength of the film is lowered and the film tends to become brittle. On the other hand, when the weight average molecular weight exceeds 400,000, the viscosity is excessively increased, and defects such as unevenness of film thickness and streaks tend to occur during coating operation.

The polyimide insulating layer 20 of this embodiment may contain an inorganic filler or an organic filler in the polyimide layer 21 or the polyimide layer (P) 23 as needed. Specific examples include inorganic fillers such as silicon dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, and calcium fluoride, and organic fillers such as fluorine-based polymer particles and liquid crystal polymer particles. can These can be used 1 type or in mixture of 2 or more types.

In the present invention, the polyimide layer 21 of the polyimide insulating layer 20 may be a single non-thermoplastic polyimide layer, and may be directly laminated on the metal layer 10 .

<Metal layer>

Although there is no particular limitation on the material of the metal layer 10, for example, copper, stainless steel, iron, nickel, beryllium, aluminum, zinc, indium, silver, gold, tin, zirconium, tantalum, titanium, lead, magnesium, manganese and These alloys etc. are mentioned. Among these, copper or copper alloy is especially preferable. In addition, the material of the wiring layer in the circuit board which will be described later is also the same as that of the metal layer 10 .

Although the thickness of the metal layer 10 is not specifically limited, For example, when using the metal foil represented by copper foil, the upper limit of the thickness becomes like this. Preferably it is 35 micrometers or less, More preferably, it is 5-25 micrometers. The range is good, and the lower limit of the thickness is preferably 5 µm from the viewpoints of production stability and handling properties. Moreover, as copper foil used for the metal layer 10, a rolled copper foil or an electrodeposited copper foil may be sufficient. Moreover, as copper foil, commercially available copper foil can be used.

Moreover, it is preferable that it is 1.2 micrometers or less, and, as for the 10-point average roughness Rzjis of the surface in contact with the polyimide layer 21 in the metal layer 10, it is more preferable that it is 1.0 micrometer or less. When the metal layer 10 is made of metal foil as a raw material, by setting the surface roughness (Rzjis) to 1.2 μm or less, fine wiring corresponding to high-density mounting is possible, and conductor loss during high-frequency signal transmission can be reduced. Therefore, it becomes possible to apply to a circuit board for high-frequency signal transmission. When the surface roughness (Rzjis) exceeds 1.2 μm, the wiring shape at the time of fine wiring processing deteriorates, making the processing difficult, and the conductor loss increases, making it unsuitable for transmission of high-frequency signals.

In addition, the metal layer 10 may be subjected to, for example, a surface treatment with siding, aluminum alcoholate, aluminum chelate, a silane coupling agent, etc. for the purpose of anti-rust treatment or improvement of adhesive strength.

[Method of manufacturing metal clad laminate]

The metal clad laminate 30 of the present invention can be manufactured by a manufacturing method comprising the following steps (A), (B) and (C).

<Process (A)>

On the metal foil used as the metal layer 10, a solution of polyamic acid, which is a precursor of polyimide, is applied and dried to form a single or multiple first polyamic acid layer. The method for applying the polyamic acid solution on the metal layer 10 is not particularly limited, and for example, it can be applied with a comma, die, knife, or a coater such as a lip. In addition, when the first polyamic acid layer is made into a plurality of layers, for example, a method of repeatedly applying and drying a solution of polyamic acid on a metal foil a plurality of times, or simultaneously performing multilayer extrusion on a metal foil by extruding a polyamic acid A method of coating and drying in a multi-layered state can be employed.

The polyamic acid solution is prepared by dissolving the acid dianhydride component and the diamine component in approximately equimolar amounts in an organic solvent such as N,N-dimethylformamide (DMF), followed by stirring at a temperature within the range of 0 to 100° C. for 30 minutes to 24 hours. (攪拌) is obtained by polymerization reaction. Usually, it is preferable to adjust the polyamic acid concentration of the polyamic acid solution to a usage amount of about 5 to 30 wt%, and to set the viscosity to 500 cps to 100,000 cps.

<Process (B)>

Next, a solution of polyamic acid, which is a precursor of polyimide (p), is applied on the first polyamic acid layer by the same operation as in step (A), and dried to form a second polyamic acid layer. Further, in the same manner as above, the first polyamic acid layer and the second polyamic acid layer may be simultaneously formed by multi-layer extrusion.

<Process (C)>

Next, by imidizing the polyamic acid contained in the first polyamic acid layer and the polyamic acid contained in the second polyamic acid layer, the polyimide layer 21 and the polyimide layer (P) 23 are changed to polyimide An insulating layer 20 is formed. The method for imidating the polyamic acid is not particularly limited, and for example, a heat treatment of heating at a temperature within the range of 80 to 400° C. for 1 to 24 hours is suitably employed. Accordingly, the metal foil laminate 30 of FIG. 1 is obtained.

In addition, the polyimide film of the present invention, in the method for manufacturing the metal clad laminate 30, removes the metal layer 10 by means such as etching after manufacturing the metal clad laminate 30, or a base material that can be peeled off instead of the metal foil It can manufacture by peeling the metal layer 10 and the polyimide insulating layer 20 after manufacturing the metal foil laminated board 30 using (基材) (a peelable metal foil is included).

[circuit board]

The metal clad laminate 30 of the present invention is useful as a material for circuit boards such as FPC, and a circuit board prepared by processing the clad metal laminate 30 of the present invention is also an aspect of the present invention. In this circuit board, the metal layer 10 of the metal clad laminate 30 of the present invention is wire-processed by a common method, and the features of the configuration inherit the features of the configuration of the metal clad laminate 30 of the present invention. have. Accordingly, this circuit board can obtain stable and good high-frequency transmission characteristics.

(Example)

Examples are shown below, and the characteristics of the present invention will be described in more detail. However, the present invention is not limited to the following examples. In addition, in the following examples, various measurements and evaluations are based on the following unless otherwise indicated.

[Measurement of viscosity]

For the polyamic acid solutions of Synthesis Examples 1 to 16 and Synthesis Examples A to C, the viscosity at 25°C was measured using an E-type viscometer (Brookfield, trade name: DV-II+Pro). The rotation speed was set so that the torque became 10% to 90%, and the value when the viscosity was stabilized after 2 minutes had elapsed from the start of the measurement was read.

[Measurement of glass transition temperature and storage modulus]

The polyimide film was cut into a size of 5 mm × 70 mm, and using a dynamic viscoelasticity measuring device (DMA: manufactured by TA Instruments, trade name: RSA G2), the temperature increase rate from 30°C to 400°C was 4°C/min. , the glass transition temperature and storage modulus were measured at a frequency of 10 Hz. The temperature at which the change in modulus of elasticity (tanδ) becomes the maximum was set as the glass transition temperature. From these measurement results, the "non-thermoplasticity" of the polyimide film was judged. The case where the storage modulus at 30°C was 1.0×10 ⁹ Pa or more and the storage modulus in the temperature range within the glass transition temperature +30° C. was 1.0×10 ⁸ Pa or more was defined as “non-thermoplastic”.

[Measurement of coefficient of thermal expansion (CTE)]

The polyimide film obtained by removing the copper foil of the single-sided copper clad laminates of Examples 1 to 30 and Comparative Examples 1 to 4 was cut into a size of 3 mm × 20 mm, and a thermomechanical analyzer (Hitachi High-Tech Science Co., Ltd.) Science Corporation) (formerly Seiko Instruments Inc.) product, trade name: TMA/SS6100), while applying a load of 5.0 g, the temperature was raised from 30°C to 260°C at a constant temperature increase rate, After holding at that temperature for another 10 minutes, it was cooled at a rate of 5°C/min to obtain an average coefficient of thermal expansion (coefficient of thermal expansion) from 250°C to 100°C. It is preferable that the thermal expansion coefficient exists in the range of 10-30 ppm/K practically.

[Measurement of Peel Strength]

Two polyimide films obtained by removing the copper foil of the single-sided copper clad laminates of Examples 1 to 30 and Comparative Examples 1 to 4 and a bonding sheet (polyimide-based, NIPPON STEEL Chemical & Material Co. Ltd. , Ltd.) product, brand name: NB25A-M, thickness: 25㎛) was laminated so that the side opposite to the side where the copper foil was in contact of the polyimide film was in contact with the bonding sheet, using a vacuum press at a temperature of 160°C , and was heat-pressed for 60 minutes with a surface pressure of 3.5 MPa. The obtained laminated sheet was cut to a width of 5 mm, and one polyimide film was applied with a tensilon tester (trade name: STROGRAPH VE-1D, Toyo Seiki Seisaku-sho, Ltd.). product) was pulled at a speed of 50 mm/min in the 180° direction, and the peel strength was obtained from the median strength when peeled by 20 mm. It is preferable that the peeling strength is 0.7 kN/m or more practically.

[Measurement of dielectric constant and dielectric loss tangent]

A vector network analyzer (manufactured by Agilent, trade name: E8363C) and a split post dielectric resonator (SPDR resonator) for the polyimide films obtained by removing the copper foil of the single-sided copper clad laminates of Examples 1 to 30 and Comparative Examples 1 to 4 was used to measure the relative dielectric constant and dielectric loss tangent of the polyimide film at a frequency of 10 GHz. In addition, the material used for the measurement was left to stand for 24 hours under the conditions of temperature: 24-26 degreeC, and humidity: 45-55%. For practical use, the dielectric constant is preferably 3.5 or less, and the dielectric loss tangent is preferably 0.004 or less.

[Measurement of oxygen permeability coefficient]

With respect to the polyimide film obtained by removing the copper foil of the single-sided copper clad laminates of Examples 1 to 30 and Comparative Examples 1 to 4, under the conditions of a temperature of 23°C±2°C and a humidity of 65%RH±5%RH, JIS K7126-1 Based on the differential pressure method, the oxygen permeability coefficient was measured. In addition, as a vapor permeability measuring device, GTR-30XAD2 manufactured by GTR TEC Corporation and G2700T·F manufactured by Yanako Technical Science Co., Ltd. were used. For practical use, the oxygen permeability coefficient is preferably 2.0×10 ^-18 mol·m/m2·s·Pa or less.

The abbreviation used by the following synthesis example, an Example, and a comparative example shows the following compounds.

PMDA: pyromellitic dianhydride

BTDA: 3,3',4,4'-benzophenonetetracarboxylic dianhydride

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

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

BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane

BAPB: 4,4'-bis(4-aminophenoxy)biphenyl

4,4'-DAPE: 4,4'-diaminodiphenyl ether

Bisaniline-P: 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene (manufactured by Mitsui Fine Chemicals, Inc., trade name: bisaniline-P)

DMAc: N,N-dimethylacetamide

(Synthesis Example 1)

In a 500 ml separable flask under a nitrogen stream, 20.670 g of TPE-R (0.0707 mol) and DMAc in an amount such that the solid content concentration after polymerization was 12 wt% was charged, and stirred at room temperature to dissolve. Next, after adding 15.330 g of PMDA (0.0703 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution 1 having the composition shown in Table 1. The solution viscosity of polyamic acid solution 1 was 4,600 cps.

(Synthesis Example 2)

In a 500 ml separable flask under a nitrogen stream, 19.862 g of TPE-R (0.0680 mol) and DMAc in an amount such that the solid content concentration after polymerization was 12 wt% was charged, and stirred at room temperature to dissolve. Next, after adding 11.785 g of PMDA (0.0540 mol) and 4.353 g of BTDA (0.0135 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution 2. The solution viscosity of the polyamic acid solution 2 of the composition shown in Table 1 was 4,300 cps.

(Synthesis Example 3)

In a 500 ml separable flask under a nitrogen stream, 19.482 g of TPE-R (0.0666 mol) and DMAc in an amount such that the solid content concentration after polymerization was 12 wt% was charged, and stirred at room temperature to dissolve. Next, after adding 10.114 g of PMDA (0.0464 mol) and 6.404 g of BTDA (0.0199 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution 3. The solution viscosity of the polyamic acid solution 3 of the composition shown in Table 1 was 4,000 cps.

(Synthesis Example 4)

In a 500 ml separable flask under a nitrogen stream, 19.116 g of TPE-R (0.0654 mol) and DMAc in an amount such that the solid content concentration after polymerization was 12 wt% was charged, and stirred at room temperature to dissolve. Next, after adding 8.506 g of PMDA (0.0390 mol) and 8.378 g of BTDA (0.0260 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution 4. The solution viscosity of the polyamic acid solution 4 of the composition shown in Table 1 was 4,300 cps.

(Synthesis Example 5)

In a 500 ml separable flask under a nitrogen stream, 18.763 g of TPE-R (0.0642 mol) and DMAc in an amount such that the solid content concentration after polymerization was 12 wt% was charged, and stirred at room temperature to dissolve. Next, after adding 6.958 g of PMDA (0.0319 mol) and 10.279 g of BTDA (0.0319 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution 5. The solution viscosity of the polyamic acid solution 5 of the composition in Table 1 was 4,400 cps.

(Synthesis Example 6)

In a 500 ml separable flask under a nitrogen stream, 18.095 g of TPE-R (0.0619 mol) and DMAc in an amount such that the solid content concentration after polymerization was 12 wt% was charged, and stirred at room temperature to dissolve. Next, after adding 4.026 g of PMDA (0.0185 mol) and 13.879 g of BTDA (0.0431 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution 6. The solution viscosity of the polyamic acid solution 6 of the composition shown in Table 1 was 3,700 cps.

(Synthesis Example 7)

In a 500 ml separable flask under a nitrogen stream, 17.779 g of TPE-R (0.0608 mol) and DMAc in an amount such that the solid content concentration after polymerization was 12 wt% was charged, and stirred at room temperature to dissolve. Next, after adding 2.637 g of PMDA (0.0121 mol) and 15.584 g of BTDA (0.0484 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution 7. The solution viscosity of the polyamic acid solution 7 of the composition shown in Table 1 was 3,400 cps.

(Synthesis Example 8)

In a 500 ml separable flask under a nitrogen stream, 17.178 g of TPE-R (0.0588 mol) and DMAc in an amount such that the solid content concentration after polymerization was 12 wt% was charged, and the mixture was dissolved by stirring at room temperature. Next, after adding 18.822 g of BTDA (0.0584 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution 8 having the composition shown in Table 1. The solution viscosity of the polyamic acid solution 8 was 3,800 cps.

(Synthesis Example 9)

In a 500 ml separable flask under a nitrogen stream, 18.182 g of TPE-R (0.0622 mol) and DMAc in an amount such that the solid content concentration after polymerization was 12 wt% was charged, and stirred at room temperature to dissolve. Next, after adding 4.046 g of PMDA (0.0185 mol), 11.953 g of BTDA (0.0371 mol) and 1.819 g of BPDA (0.0062 mol), the polymerization reaction was continued for 3 hours at room temperature, and the composition shown in Table 1 of polyamic acid solution 9 was obtained. The solution viscosity of the polyamic acid solution 9 was 4,100 cps.

(Synthesis Example 10)

In a 500 ml separable flask under a nitrogen stream, 18.270 g of TPE-R (0.0625 mol) and DMAc in an amount such that the solid content concentration after polymerization was 12 wt% was charged, and stirred at room temperature to dissolve. Next, after adding 4.065 g of PMDA (0.0186 mol), 10.09 g of BTDA (0.0311 mol) and 3.656 g of BPDA (0.0124 mol), the polymerization reaction was continued for 3 hours at room temperature, and the composition shown in Table 1 of polyamic acid solution 10 was obtained. The solution viscosity of the polyamic acid solution 10 was 3,800 cps.

(Synthesis Example 11)

In a 500 ml separable flask under a nitrogen stream, 18.359 g of TPE-R (0.0628 mol) and DMAc in an amount such that the solid content concentration after polymerization was 12 wt% was charged, and stirred at room temperature to dissolve. Next, after adding 4.085 g of PMDA (0.0187 mol), 8.046 g of BTDA (0.0250 mol) and 5.510 g of BPDA (0.0187 mol), the polymerization reaction was continued at room temperature for 3 hours, and the composition shown in Table 1 of polyamic acid solution 11 was obtained. The solution viscosity of the polyamic acid solution 11 was 4,300 cps.

(Synthesis Example 12)

In a 500 ml separable flask under a nitrogen stream, 14.476 g of TPE-R (0.0495 mol), 3.619 g of APB (0.0124 mol) and DMAc in an amount such that the solid content concentration after polymerization is 12 wt% was added, and stirred at room temperature. dissolved. Next, after adding 4.026 g of PMDA (0.0185 mol) and 13.879 g of BTDA (0.0431 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution 12 having the composition shown in Table 1. The solution viscosity of the polyamic acid solution 12 was 3,100 cps.

(Synthesis Example 13)

In a 500 ml separable flask under a nitrogen stream, 8.348 g of TPE-R (0.0286 mol), 11.723 g of BAPP (0.0286 mol) and DMAc in an amount such that the solid content concentration after polymerization is 12 wt% was added, and stirred at room temperature. dissolved. Next, after adding 4.953 g of PMDA (0.0227 mol) and 10.976 g of BTDA (0.0341 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution 13 having the composition shown in Table 1. The solution viscosity of the polyamic acid solution 13 was 4,200 cps.

(Synthesis Example 14)

In a 500 ml separable flask under a nitrogen stream, 6.940 g of TPE-R (0.0237 mol), 13.120 g of BAPB (0.0356 mol) and DMAc in an amount such that the solid content concentration after polymerization is 12 wt% was added, and stirred at room temperature. dissolved. Next, after adding 6.434 g of PMDA (0.0295 mol) and 9.505 g of BTDA (0.0295 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution 14 having the composition shown in Table 1. The solution viscosity of the polyamic acid solution 14 was 3,700 cps.

(Synthesis Example 15)

In a 500 ml separable flask under a nitrogen stream, 15.417 g of TPE-R (0.0527 mol), 2.799 g of m-TB (0.0132 mol), and DMAc in an amount such that the solid content concentration after polymerization is 12 wt % was added, and at room temperature Stir to dissolve. Next, after adding 4.288 g of PMDA (0.0197 mol) and 13.496 g of BPDA (0.0459 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution 15 having the composition shown in Table 1. The solution viscosity of the polyamic acid solution 15 was 3,500 cps.

(Synthesis Example 16)

In a 500 ml separable flask under a nitrogen stream, 13.848 g of 4,4'-DAPE (0.0692 mol) and DMAc in an amount such that the solid content concentration after polymerization was 12 wt% was charged, and stirred at room temperature to dissolve. Then, after adding 22.152 g of BTDA (0.0687 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution 16 having the composition shown in Table 1. The solution viscosity of the polyamic acid solution 16 was 3,300 cps.

(Synthesis Example A)

In a 3000 ml separable flask under a nitrogen stream, 120.612 g of m-TB (0.5681 mol), 9.227 g of TPE-Q (0.0316 mol), 10.873 g of bisaniline-P (0.0316 mol) and a solid content concentration after polymerization were 15 wt. % of DMAc was added, and the mixture was dissolved by stirring at room temperature. Next, after adding 67.814 g of PMDA (0.3109 mol) and 91.474 g of BPDA (0.3109 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution A having the composition shown in Table 1. The solution viscosity of polyamic acid solution A was 28,300 cps.

On the substrate, the polyamic acid solution A was uniformly applied to a thickness of about 25 µm after curing, and then the solvent was removed by heating and drying at 120°C. In addition, by performing stepwise heat treatment from 120°C to 360°C within 10 minutes, imidization was completed and the obtained polyimide film was non-thermoplastic.

(Synthesis Example B)

In a 3000 ml separable flask under a nitrogen stream, 127.501 g of m-TB (0.6006 mol), 12.976 g of BAPP (0.0316 mol), and DMAc in an amount such that the solid content concentration after polymerization is 15 wt% was added, and stirred at room temperature. dissolved. Next, after adding 67.914 g of PMDA (0.3114 mol) and 91.609 g of BPDA (0.3114 mol), the polymerization reaction was continued at room temperature for 3 hours to obtain a polyamic acid solution B having the composition shown in Table 1. The solution viscosity of polyamic acid solution B was 25,600 cps.

On the substrate, the polyamic acid solution B was uniformly applied to a thickness of about 25 µm after curing, and then the solvent was removed by heating and drying at 120°C. In addition, by performing stepwise heat treatment from 120°C to 360°C within 10 minutes, imidization was completed and the obtained polyimide film was non-thermoplastic.

(Synthesis Example C)

In a 3000 ml separable flask under a nitrogen stream, 114.972 g of m-TB (0.5416 mol), 39.580 g of TPE-R (0.1354 mol), and DMAc in an amount such that the solid content concentration after polymerization is 15 wt% was added, and at room temperature Stir to dissolve. Next, after adding 145.447 g of PMDA (0.6668 mol), stirring was continued at room temperature for 3 hours for polymerization reaction to obtain a polyamic acid solution C having the composition shown in Table 1. The solution viscosity of polyamic acid solution C was 27,200 cps.

On the substrate, the polyamic acid solution C was uniformly applied to a thickness of about 25 µm after curing, and then the solvent was removed by heating and drying at 120°C. In addition, by performing stepwise heat treatment from 120°C to 360°C within 10 minutes, imidization was completed and the obtained polyimide film was non-thermoplastic.

[Example 1]

On the copper foil, the polyamic acid solution A as a first layer in contact with the copper foil was uniformly applied to a thickness of 23 μm after curing, and then the solvent was removed by heating and drying at 120° C. for 2 minutes. On the first layer, the polyamic acid solution 1 as the second layer was uniformly applied to a thickness of 2 μm after curing, and then the solvent was removed by heating and drying at 130° C. for 30 seconds. Subsequently, imidization was completed by stepwise heat treatment from 140° C. to 360° C., and a copper clad laminate was manufactured. Thereafter, the copper foil was removed by etching using an aqueous ferric chloride solution to obtain a polyimide film. Table 2 shows the physical properties of the obtained polyimide film.

[Example 2] to [Example 15] and [Comparative Example 1] to [Comparative Example 2]

As shown in Table 2, except having changed the polyamic acid solution of a 1st layer and a 2nd layer, it carried out similarly to Example 1, and obtained the polyimide film.

[Example 16]

On the copper foil, the polyamic acid solution A as a first layer in contact with the copper foil was uniformly applied to a thickness of 47 µm after curing, and then the solvent was removed by heating and drying at 120°C for 4 minutes. On the first layer, the polyamic acid solution 1 as the second layer was uniformly applied to a thickness of 3 μm after curing, and then the solvent was removed by heating and drying at 130° C. for 1 minute. Subsequently, imidization was completed by stepwise heat treatment from 140° C. to 360° C., and a copper clad laminate was manufactured. Thereafter, the copper foil was removed by etching using an aqueous ferric chloride solution to obtain a polyimide film. Table 3 shows the physical properties of the obtained polyimide film.

[Example 17] to [Example 30] and [Comparative Example 3] to [Comparative Example 4]

As shown in Table 3, except having changed the polyamic acid solution of the 1st layer and 2nd layer, it carried out similarly to Example 16, and obtained the polyimide film.

In the polyimide films prepared from the copper clad laminates of Examples 1 to 30, 30 mol% or more of the diamine residues in the polyimide layer of the second layer were 1,3-bis(aminophenoxy)benzene residues, and the first layer and (i) the oxygen permeability coefficient of the polyimide insulating layer laminated with the second layer is 2.0×10 ^-18 mol·m/m2·s·Pa or less, (ii) the coefficient of thermal expansion is within the range of 10 to 30 ppm/K; , (iii) since the dielectric loss tangent (Tanδ) at 10 GHz was 0.004 or less, and the layer thickness was in the range of 10 µm to 100 µm, the dielectric properties did not deteriorate and the peeling strength was 0.7 kN/m or more. Therefore, it can be processed into a double-sided copper clad laminate without impairing the good properties of the single-sided copper clad laminate. In addition, the circuit board formed from the copper clad laminate of the present invention can obtain stable and good high-frequency transmission characteristics.

On the other hand, from the results of Comparative Examples 1 and 3, even if the first layer has low dielectric properties, if the second layer does not contain a 1,3-bis(aminophenoxy)benzene residue, the original low dielectric properties will be impaired. Could know.

In addition, in the polyimide films prepared from the copper clad laminates of Comparative Examples 2 and 4, since the diamine residues of the polyimide film of the second layer consist only of 1,3-bis(aminophenoxy)benzene residues, the peel strength is satisfactory. However, due to the influence of the first layer, the oxygen permeability coefficient exceeded 2.0×10 ^-18 mol·m/m2·s·Pa, and the dielectric loss tangent exceeded 0.004. Moreover, in the case of Comparative Example 4, although the thickness was twice that of the polyimide film in Comparative Example 2, no improvement in dielectric loss tangent was observed.

From the above result, it turned out that the copper clad laminated board excellent in adhesiveness with a bonding sheet|seat was obtained while maintaining a low dielectric property by taking the structure of an Example.

Although the embodiment of the present invention has been described in detail for the purpose of illustration above, it goes without saying that the present invention is not limited to the above embodiment and various modifications are possible.

10: metal layer
20: polyimide insulating layer
21: polyimide layer
23: polyimide layer (P)
30: metal foil laminate

Claims (9)

A polyimide film having a plurality of polyimide layers, the following conditions (i) to (iv):
(i) an oxygen permeability coefficient of 2.0×10 ^-18 mol·m/m2·s·Pa or less;
(ii) the coefficient of thermal expansion is within the range of 10 to 30 ppm / K;
(iii) a dielectric loss tangent (Tanδ) of 0.004 or less at 10 GHz; and
(iv) the thickness is in the range of 10 μm to 100 μm;
satisfied with
The polyimide film is provided with a polyimide layer (P) on at least one exposed surface side,
The polyimide (p) constituting the polyimide layer (P) contains an acid anhydride residue derived from a tetracarboxylic acid dianhydride component and a diamine residue derived from a diamine component, and the diamine residue is represented by the following general formula ( The polyimide film characterized by containing the diamine residue derived from the diamine compound represented by 1) at least 30 mol% with respect to all the diamine residues.

According to claim 1,
The polyimide film whose diamine compound represented by the said General formula (1) is 1, 3-bis (4-aminophenoxy) benzene.
3. The method of claim 2,
With respect to all the acid anhydride residues in the polyimide (p), an acid anhydride residue derived from pyromellitic dianhydride and an acid anhydride residue derived from 3,3',4,4'-benzophenonetetracarboxylic dianhydride A polyimide film containing at least 60 mol% in total.
According to claim 1,
The plurality of polyimide layers contain a non-thermoplastic polyimide layer, and the non-thermoplastic polyimide layer contains the following conditions (A) to (C):
(A) the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer contains 50 mol% or more of monomer residues having a biphenyl skeleton in all monomer residues derived from all monomer components;
(B) The thickness is within the range of 7㎛ ~ 70㎛; and
(C) The ratio of the thickness to the thickness of the entire polyimide film is 70% or more;
A polyimide film that satisfies
5. The method of claim 4,
In the non-thermoplastic polyimide layer, the diamine residue derived from the diamine component constituting the non-thermoplastic polyimide contains 20 mol% or more of the diamine residue having a biphenyl skeleton based on the total diamine residue, tetracarboxylic dianhydride The polyimide film in which the acid anhydride residue derived from a component contains 20 mol% or more of acid anhydride residues with a biphenyl skeleton with respect to all acid anhydride residues.
6. The method according to claim 4 or 5,
A monomer residue having a biphenyl skeleton is derived from a diamine residue derived from 2,2'-dimethyl-4,4'-diaminobiphenyl and a 3,3',4,4'-biphenyltetracarboxylic acid dianhydride A polyimide film that is an acid anhydride residue.
A metal clad laminate comprising a metal layer and a polyimide insulating layer, wherein the polyimide insulating layer comprises the polyimide film of claim 1 .
A method for manufacturing a metal clad laminate for manufacturing the clad metal laminate of claim 7,
A step of applying a solution of polyamic acid on the metal layer and drying it to form a first polyamic acid layer of a single layer or a plurality of layers;
forming a second polyamic acid layer by applying a solution of polyamic acid, which is a precursor of the polyimide (p), on the first polyamic acid layer and drying;
A step of forming the polyimide insulating layer by imidizing the polyamic acid included in the first polyamic acid layer and the polyamic acid included in the second polyamic acid layer
A method of manufacturing a metal clad laminate comprising a.
A circuit board in which the metal layer of the metal clad laminate of claim 7 is processed into wiring.

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