TW201700673A - Multilayer adhesive film and flexible metal-clad laminate - Google Patents

Abstract

The present invention provides a film for circuit boards, which has low dielectric constant and low dielectric loss tangent, while having small dimensional change rate. The present invention is able to solve the above-described problem by: a multilayer adhesive film which is obtained by providing at least one surface of a non-thermoplastic polyimide film with an adhesive layer containing a thermoplastic polyimide, and which has a specific physical property; and a flexible metal-clad laminate which uses this multilayer adhesive film.

Description

Multilayer adhesive film and flexible metal foil laminate

The present invention relates to a multilayer adhesive film which can be preferably used for a high-frequency circuit substrate, and a flexible metal foil laminate having a metal foil on one or both sides.

In recent years, in order to improve the information processing capability in electronic devices, the high frequency of electronic signals of transmission circuits has been developed. With the increase in the frequency of the electronic signal, it is desirable to suppress the decrease in the transmission speed of the electronic signal in the circuit and suppress the loss of the electronic signal with respect to the circuit board while maintaining the reliability of the electronic signal, in the high frequency (1 GHz or higher) region. A material that requires a lower dielectric constant and dielectric loss tangent.

On the other hand, a flexible metal foil laminated board for manufacturing a circuit board is obtained by providing a metal foil on one side or both sides of a base resin film. The method for producing the flexible metal foil laminated board may be a casting method in which a ruthenium imidization is carried out after casting or coating a polyimide on a metal foil, followed by sputtering or plating. A metal spray method in which a metal layer is directly provided on the polyimide film, and a thermal lamination method in which a polyimide film and a metal foil are bonded via an adhesive layer such as a thermoplastic polyimide. Among them, the thermal lamination method is superior to other methods from the viewpoint that the thickness of the metal foil which can be handled is wider than the casting method, and the device cost is lower than that of the metal spraying method. In recent years, the demand level of moisture-absorbing solder resistance has been higher than that of the prior art due to the use of lead-free solder, and in order to cope with this, the high Tg (glass transition temperature) of the film connected to the metal foil has progressed. As a result, the temperature required for thermal lamination is also inevitably high. because As a result, the thermal stress applied to the material such as the base resin film and the adhesive layer becomes large, and the dimensional change is likely to occur.

For example, as a flexible metal foil laminated board which can be used as a high-frequency circuit board, a copper-clad laminate which is provided with a copper foil on both surfaces of a fluororesin-containing polyimide resin has been developed (for example, Patent Document 1) ~2).

Patent Document 1 is mainly for the purpose of lowering the dielectric constant of the insulating resin layer for a flexible metal foil laminated board, and specifically discloses that it is composed of 90% by mole of pyromellitic dianhydride and 10% by mole. , 4'-(hexafluoroisopropylidene)diphthalic dianhydride, and 100 mol% of 2,2'-bis(trifluoromethyl)benzidine-derived polydecimide contain poly Insulation layer of tetrafluoroethylene (PTFE) powder.

Patent Document 2 mainly discloses a technique for combining a fluoropolymer fine powder with a polyimide. It is described that a fluoropolymer is melted by heat during hydrazine imidization and is concentrated on a surface of a film.

Patent Document 3 discloses a flexible polyimide foil laminate in which a value of a storage elastic modulus is controlled within a specific range as a flexible metal foil laminate which suppresses occurrence of dimensional change.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication "Japanese Patent Special Publication No. 2014-526399 (published on October 6, 2014)"

[Patent Document 2] Japanese Patent Publication "Japanese Patent No. 4237694 (issued on March 11, 2009)"

[Patent Document 3] Japanese Patent Gazette "Japanese Patent No. 5613300 (issued on October 22, 2014)"

However, a low dielectric constant, low dielectric loss tangent and low moisture absorption were previously unknown. The material, which is suitable for heat lamination and has a small dimensional change rate to reduce transmission loss, requires the design of such a material.

An object of the present invention is to provide a multilayer adhesive film which can reduce the dielectric loss tangent and moisture absorption rate of a resin layer while controlling the stress generated by the thermal lamination method and reducing the dimensional change rate, thereby reducing transmission loss. It is preferably used for a high frequency circuit substrate.

In view of the above circumstances, the inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by the following novel polyimide film and a flexible metal foil laminate using the polyimide film. The present invention has been completed.

That is, the present invention relates to a multilayer adhesive film characterized in that it is provided with an adhesive layer containing a thermoplastic polyimide on at least one side of a non-thermoplastic polyimide film, and the above non-thermoplastic polyimide film satisfies the following (1) ~ (6) conditions.

(1) The recurve point temperature of the storage elastic modulus is 250 ° C ~ 320 ° C

(2) The peak temperature of the loss elastic coefficient (tan δ) is 260 ° C ~ 400 ° C

(3) The storage elastic modulus at 380 ° C is 0.2GPa~2.0GPa

(4) The storage elastic modulus α1 (GPa) under the inflection point and the storage elastic modulus α2 (GPa) at 380 °C are the ranges of the following formula (I)

95≧{(α1-α2)/α1}×100≧65‧‧‧(I)

(5) moisture absorption rate is 0.1wt%~1.5wt%

(6) Dielectric loss tangent (Df) is 0.001~0.010

In a preferred embodiment, the invention relates to a multilayer adhesive film, characterized in that the non-thermoplastic polyimide film comprises a thermoplastic block component (a) and a non-thermoplastic block component (b), and a thermoplastic block component. (a) The conditions of the following (A) to (C) are satisfied, and the non-thermoplastic block component (b) satisfies the conditions of the following (D).

(A) 醯 imine density is below 0.25

(B) Dielectric loss tangent (Df) is 0.001~0.012

(C) moisture absorption rate is 0.1 wt% to 1.3 wt%

(D) Thermal expansion coefficient is 1ppm~10ppm

A preferred embodiment relates to a multilayer adhesive film, characterized in that the non-thermoplastic polyimide film comprises a material selected from the group consisting of 2,2'-bis[4-(4-aminophenoxy)benzene. Single of at least two aromatic diamines in a group consisting of propane (BAPP), p-phenylenediamine (PDA), and 4,4'-bis(4-aminophenoxy)biphenyl (BAPB) The body composition, and from the selected from pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 4,4'-oxydiphthalic acid A monomer component of at least two aromatic acid dianhydrides in the group consisting of anhydrides (ODPA).

As a preferred embodiment, the present invention relates to a multilayer adhesive film characterized in that the non-thermoplastic polyimide film contains a fluororesin.

In a preferred embodiment, the present invention relates to a flexible metal foil laminate which is obtained by laminating a metal foil on the multilayer adhesive film.

As a preferred embodiment, the present invention relates to a flexible metal foil laminate which is obtained by laminating a metal foil on a multilayer adhesive film by a thermal lamination method.

Further, the present invention relates to a multilayer adhesive film characterized in that an adhesive layer containing a thermoplastic polyimide is provided on at least one side of a non-thermoplastic polyimide film containing fluororesin particles, which satisfies the following (1' ) The condition of ~(7').

(1') The storage point of the elastic modulus is 240 ° C ~ 320 ° C

(2') The peak temperature of the loss elastic coefficient (tan δ) is 260 ° C ~ 400 ° C

(3') Storage elastic modulus at 380 ° C is 0.1GPa~2.0GPa

(4') The storage elastic modulus α1 (GPa) under the inflection point and the storage elastic modulus α2 (GPa) at 380 °C are the ranges of the following formula (I)

95≧{(α1-α2)/α1}×100≧65‧‧‧(I)

(5') moisture absorption rate is 0.1wt%~1.5wt%

(6') dielectric loss tangent (Df) is 0.001~0.010

(7') hot line expansion coefficient is 17ppm~30ppm

According to the multilayer adhesive film of the present invention, the flexible metal foil laminate having the metal foil disposed on the multilayer adhesive film has the following effects: it can provide a low transmission loss and a low size compared to the previously used flexible metal foil laminate. Material of rate of change. Therefore, the present invention is useful, for example, in the case of developing a substrate for a high-frequency circuit of 1 GHz or more.

An embodiment of the present invention will be described in detail below. Furthermore, the academic documents and patent documents described in the present specification are hereby incorporated by reference in their entirety. In addition, unless otherwise stated, the meaning of "A~B" of the numerical range is "A or more (including A and larger than A) B or less (including B and smaller than B)". In addition, in this specification, "wt%" means "% by weight".

(non-thermoplastic polyimide film)

The present invention is a multilayer adhesive film comprising an adhesive layer (surface layer) comprising a thermoplastic polyimide, at least one side of a non-thermoplastic polyimide film (core layer), since the non-thermoplastic polyimide film satisfies the following ( Since all of the physical properties of 1) to (6) are low in dielectric loss tangent or moisture absorption rate, it is possible to realize a flexible metal foil laminate having less transmission loss and high dimensional stability.

(1) The recurve point temperature of the storage elastic modulus is 250 ° C ~ 320 ° C

(2) The peak temperature of the loss elastic coefficient (tan δ) is 260 ° C ~ 400 ° C

(3) The storage elastic modulus at 380 ° C is 0.2GPa~2.0GPa

(4) The storage elastic modulus α1 (GPa) under the inflection point and the storage elastic modulus α2 (GPa) at 380 °C are the ranges of the following formula (I)

95≧{(α1-α2)/α1}×100≧65‧‧‧(I)

(5) moisture absorption rate is 0.1wt%~1.5wt%

(6) Dielectric loss tangent (Df) is 0.001~0.010

In addition, the parameters of the above (1) to (6) are values measured in a state in which the fluororesin described later is not contained.

The non-thermoplastic polyimide film is obtained by imidating a polyimine precursor (i.e., polyglycolic acid) obtained by reacting an aromatic diamine with an aromatic acid dianhydride. The ruthenium imidization can be thermal imidization or chemical imidization. Preferably, chemical ruthenium is used as the ruthenium.

Further, the technique disclosed in Patent Document 1 is a method of laminating a metal foil by coating a polyimine resin, and therefore, it is not described that the material for thermal lamination is used (manufacturing of the adhesive film, A method of controlling the dimensional change rate by controlling the stress generated during lamination of the film-attached metal foil flexible metal foil laminate.

Further, in Patent Document 2, a specific example of the ruthenium imidization method is hydrazine imidization. The technique described in Patent Document 2 has a case where it is reproduced when a sufficient heating time is given, but when the chemical imidization method with excellent productivity is used, the heating time becomes short, and the fluororesin is affected. It does not sufficiently concentrate on the surface of the polyimide film, and the adhesion strength to the metal foil via the fluororesin cannot be obtained. Further, Patent Document 2 does not describe a related control method for controlling the dimensional change rate by relaxing the stress generated during lamination.

Patent Document 3 discloses a low transmission loss of a flexible metal foil laminated board, that is, a specific description of a low dielectric constant of a resin film, a low dielectric loss tangent, and a low moisture absorption rate.

(non-thermoplastic block components and thermoplastic block components)

Here, the non-thermoplastic block component and the thermoplastic polyimide component block included in the non-thermoplastic polyimide film of the present invention will be described. In the present specification, the non-thermoplastic polyimine refers to a solution polymerization in which a raw material monomer is combined, and the obtained polyglycine solution is dried, thermally imidated, and chemically imidized. When the molded body (mainly film) is heated at 450 ° C for 1 minute, it does not cause deformation caused by wrinkles or stretching. Shape, shape retention. On the other hand, the polyimine which was deformed or fused by wrinkles or stretching when heated at 450 ° C for 1 minute was judged to be a thermoplastic polyimide. Therefore, the non-thermoplastic block component and the thermoplastic block component in the present invention mean that the polyamic acid solution polymerized by using only the raw material monomers constituting each block is formed in the above manner, according to the above heating. It is determined as a non-thermoplastic block component or a thermoplastic block component based on the judgment criteria. Further, in order to determine whether the block component is thermoplastic or non-thermoplastic and the film-like polyimine is formed, if a combination of rigid monomers is selected, the film may be broken or broken and may be pulverized without being formed into a film. In this case, the chips may also be collected and heated at 450 ° C to visually confirm and judge whether there is deformation or fusion. For example, for polyamic acid in which pyromellitic dianhydride (PMDA) and p-phenylenediamine (PDA) are combined, if the combination is to be film-formed separately, it will be broken and pulverized during drying and hot imidization. However, in the case where the ruptured chips are placed in a metal container and heated at 450 ° C for 1 minute without being deformed, melted and fused, it can be defined as a non-thermoplastic block component in the present invention.

(dynamic viscoelasticity)

The various parameters of the range specified in the present invention can be confirmed by the dynamic viscoelasticity measurement of the resin film. First, the temperature of the inflection point of the storage elastic modulus will be described. The inflection point temperature of the storage elastic modulus of the non-thermoplastic polyimide film of the present invention is preferably from 250 ° C to 320 in terms of mitigating thermal stress when the metal foil is bonded by thermal lamination. The range of °C is further preferably in the range of 270 ° C to 300 ° C. Here, when the temperature at which the inflection point of the storage elastic modulus is 250° C. or more, the temperature at which the dimensional change after heating of the flexible metal foil laminate is evaluated (in the two-layer FPC field, the number is 250 In the evaluation at °C, the core layer does not start to soften, so that the increase in the dimensional change rate can be prevented. When the temperature at which the inflection point of the storage elastic modulus is 320 ° C or less, the temperature at which the core layer starts to soften is too high, so that the thermal stress can be sufficiently alleviated during thermal lamination, and the increase in the dimensional change rate can be prevented.

For the non-thermoplastic polyimide film of the present invention, the dynamic viscoelasticity measuring device The measured loss elastic modulus is divided by the value of the storage elastic modulus, that is, the maximum value of the loss elastic modulus (also referred to as tan δ), and the temperature (hereinafter, also referred to as the peak temperature) is 260 ° C to 400 ° C. Preferably, it is in the range of 270 ° C to 380 ° C, more preferably in the range of 280 ° C to 370 ° C, and further preferably in the range of 290 to 360 ° C. When the peak temperature of tan δ is 260 ° C or higher, the temperature at which tan δ starts to increase is not about 250 ° C or less, and the core layer does not soften when the dimensional change is measured, so that the dimensional change rate is hard to increase. When the peak temperature of tan δ is 400 ° C or less, the temperature required to soften the core layer to sufficiently relax the level of thermal stress does not become too high, and the thermal stress can be sufficiently alleviated by the existing thermal lamination device. Therefore, the dimensional change rate is difficult to increase. When the peak temperature of tan δ is within the above range, the increase in the dimensional change rate can be prevented in the same manner as the temperature of the inflection point of the storage elastic modulus.

For the non-thermoplastic polyimide film of the present invention, the storage elastic modulus at 380 ° C measured by a dynamic viscoelasticity measuring apparatus is 0.2 GPa to 2.0 GPa, preferably in the range of 0.3 GPa to 1.6 GPa, and further preferably It is in the range of 0.3 GPa to 1.4 GPa. When the storage modulus at 380 ° C is 0.2 GPa or more, the film can be sufficiently self-supporting during the imidization or thermal lamination of the film, so that the film can be produced and scratched. The appearance of the metal foil laminate is better. When the storage elastic modulus at 380 ° C is 2.0 GPa or less, the core layer is sufficiently softened, so that the effect of mitigating thermal stress during heat lamination is sufficiently exhibited, so that deterioration in dimensional change can be prevented.

For the non-thermoplastic polyimide film of the present invention, the value of the storage elastic modulus α1 (GPa) at the inflection point of the storage elastic modulus measured by the dynamic viscoelasticity measuring device and the storage elastic modulus α2 at 380 ° C The value of (GPa) is in the range of the following formula (I).

95≧{(α1-α2)/α1}×100≧65‧‧‧(I)

When {(α1-α2)/α1}×100 is 65 or more, the degree of reduction in the storage elastic modulus is sufficient, so that the effect of mitigating thermal stress during heat lamination is sufficiently exhibited, so that the obtained can be prevented. The dimensional change of the flexible metal foil laminate is deteriorated. On {(α1- When α2)/α1}×100 is 95 or less, the film can sufficiently maintain self-supporting property, so that the productivity of the film and the appearance of the obtained flexible metal foil laminate can be better.

The non-thermoplastic polyimide film of the present invention preferably has a moisture absorption rate of from 0.1% by weight to 1.5% by weight. More preferably, it is 0.1 wt% - 1.3 wt%, and further preferably 0.1 wt% - 1.0 wt%. When the moisture absorption rate is 1.5 wt% or less, the water having a large dielectric constant is less abundant in the non-thermoplastic polyimide film, so that the dielectric constant and the dielectric loss tangent are prevented from increasing. Therefore, it is better.

The dielectric loss tangent (Df) of the non-thermoplastic polyimide film of the present invention is preferably from 0.001 to 0.010. More preferably, it is 0.001 to 0.009, and further preferably 0.001 to 0.006. When the dielectric loss tangent (Df) is 0.010 or less, it is preferable to prevent an increase in transmission loss.

(The thermoplastic block component (a) and the non-thermoplastic block component (b) of the non-thermoplastic polyimide film)

In order to exhibit the above (1) to (6), the non-thermoplastic polyimide film of the present invention preferably comprises a thermoplastic block component (a) and a non-thermoplastic block component (b). . When the thermoplastic block component (a) and the non-thermoplastic block component (b) have been previously designed and combined, the polyimine film obtained by simultaneously mixing and polymerizing the monomers used is easier. Design the parameters that satisfy (1) to (6). For the preferred ratios of (a) and (b), it is preferred that the non-thermoplastic block (b) is 50 mol% to 85 mol in consideration of the case where the polyimine film produced by the combination is non-thermoplastic. The combination is carried out in the range of %, more preferably in the range of 60 mol% to 80 mol%. Further, it is preferable that the thermoplastic block component (a) satisfies the following conditions (A) to (C), and the non-thermoplastic block component (b) satisfies the condition (D) below.

(A) 醯 imine density is below 0.25

(B) Dielectric loss tangent (Df) is 0.001~0.012

(C) moisture absorption rate is 0.1 wt% to 1.3 wt%

(D) Thermal expansion coefficient is 1ppm~10ppm

(thermoplastic block composition (a))

In general, the quinone imine group has a high polarity and is easy to absorb moisture in the environment, so that it becomes a factor of an increase in the dielectric constant of the polyimide film. Therefore, the polyimine resin having a lower density of the quinone imine group tends to have a lower moisture absorption rate. However, the various heat resistances of polyimine are largely dependent on the presence of the quinone imine group, and the polyimide having a lower density of quinone imine has a lower heat resistance and contains a property of a thermoplastic polyimide. The thermoplastic block component (a) of the present invention preferably has a quinone imine group density of 0.25 or less. The ruthenium group density can be adjusted by increasing the molecular weight of the monomer used in the polymerization of the polyimide precursor, and more preferably 0.24 or less, further preferably 0.23 or less.

The quinone imine group density of the present invention is a value calculated from the molecular weight of the quinone imine moiety and the molecular weight of all the units in the polyimine resin obtained by imidating the polyimide precursor. Specifically, the ruthenium group density was calculated by the following method.

The density of the quinone imine group from the molecular weight calculation unit of the aromatic diamine and the aromatic acid dianhydride. For example, a polyfluorene imine precursor consisting of pyromellitic dianhydride (PMDA) 1 molar and 3,4'-oxydiphenylamine (3,4'-ODA) 1 molar 2 component In the case of the polyimine obtained, the density of the quinone imine is: 醯imino molecular weight = 140.1

Unit molecular weight = 382.4

The ruthenium base density = (140.1) / (382.4) = 0.366.

The dielectric loss tangent of the thermoplastic block component (a) of the non-thermoplastic polyimide film of the present invention means the dielectric loss tangent of the film obtained by filming only the thermoplastic block component. In the present invention, the dielectric loss tangent of the thermoplastic block component (a) is preferably from 0.001 to 0.012, more preferably from 0.001 to 0.010, still more preferably from 0.001 to 0.008. When the dielectric loss tangent of the thermoplastic block component (a) is 0.012 or less, the dielectric loss tangent of the non-thermoplastic polyimide film is 0.012 or less, thereby preventing an increase in transmission loss, and thus good.

The moisture absorption rate of the thermoplastic block component (a) is preferably from 0.1% by weight to 1.3% by weight, more preferably from 0.1% by weight to 1.1% by weight, still more preferably from 0.1% by weight to 0.9% by weight.

As an example of the aromatic diamine preferably used for designing the thermoplastic block component (a), 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 4, 4 may be mentioned. '-Diaminodiphenylpropane, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Thioether, 3,3'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 4,4'-oxydiphenylamine, 3,3'-oxydiphenylamine, 3 , 4'-oxydiphenylamine, 4,4'-diaminodiphenyldiethyldecane, 4,4'-diaminodiphenylnonane, 4,4'-diaminodiphenyl Phosphine oxide, 4,4'-diaminodiphenyl N-methylamine, 4,4'-diaminodiphenyl N-aniline, 1,4-diaminobenzene (p-phenylenediamine) , bis{4-(4-aminophenoxy)phenyl}anthracene, bis{4-(3-aminophenoxy)phenyl}anthracene, 4,4'-bis(3-aminophenoxyl) Biphenyl, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy) Benzene, 1,3-bis(3-aminophenoxy)benzene, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenoxyphenyl)propane and 3,3'-dihydroxy-4,4' -Diamino-1,1'-biphenyl, etc., may be used singly or in combination. A fluorine-based monomer such as 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl may also be used. Further, in addition to the above aromatic diamine, any aromatic diamine may be used as an accessory component. As an example of the aromatic diamine which can be preferably used in the above, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4- Aminophenoxy)phenyl]propane and/or 1,4-diaminobenzene (p-phenylenediamine), or a plurality of them may be used in combination.

Examples of the aromatic acid dianhydride which is preferably used for designing the thermoplastic block component (a) include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 2,2. ',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propionic acid The dianhydride, the p-phenylene bis(trimellitic acid monoester anhydride), and the 4,4'-oxydiphthalic dianhydride may be used singly or in combination.

As an example of the aromatic acid dianhydride which can be especially preferably used in these, it can be mentioned that it is made individually. 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride and/or pyromellitic dianhydride are used, or a plurality of them are used in combination.

For example, the non-thermoplastic polyimide film preferably comprises: a monomer component derived from at least two aromatic diamines selected from the group consisting of 2,2'-bis[4-(4- a group of aminophenoxy)phenyl]propane (BAPP), p-phenylenediamine (PDA), 4,4'-bis(4-aminophenoxy)biphenyl (BAPB); and from at least a monomer component of two aromatic acid dianhydrides selected from the group consisting of pyromellitic dianhydride (PMDA) and 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), a group consisting of 4,4'-oxydiphthalic dianhydride (ODPA). Further, the non-thermoplastic polyimide film may be an essential component of 4,4'-oxydiphthalic dianhydride.

For the combination of the more preferable aromatic diamine and aromatic acid dianhydride constituting the thermoplastic block component (a), 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-double is exemplified. Examples of the at least one of [4-(4-aminophenoxy)phenyl]propane and 1,4-diaminobenzene (p-phenylenediamine) as the aromatic diamine include pyromellitic dianhydride and At least one of 3,3',4,4'-biphenyltetracarboxylic dianhydride is used as the aromatic acid dianhydride.

(non-thermoplastic block component (b))

In order to suppress the dimensional change rate before and after etching of the flexible metal foil laminate obtained by laminating the metal foil on the multilayer adhesive film of the non-thermoplastic polyimide film of the present invention, the non-thermoplastic polyimide film is not The thermal linear expansion coefficient (CTE) of the thermoplastic block component (b) is preferably from 1 ppm to 10 ppm. The CTE is preferably from 3 ppm to 9 ppm. When the CTE is 10 ppm or less, it is possible to prevent an increase in the dimensional change rate before and after the etching of the flexible metal foil laminate in which the metal foil is placed on the multilayer adhesive film of the non-thermoplastic polyimide film.

Since the dielectric loss tangent has a case where the addition property is not established, the dielectric loss tangent of the non-thermoplastic block component (b) of the present invention is preferably lower. Specifically, the dielectric loss tangent is preferably 0.001 to 0.012, more preferably 0.001 to 0.010.

The moisture absorption rate of the non-thermoplastic block component (b) of the present invention is also preferably lower. specific The moisture absorption rate is preferably from 0.1% by weight to 1.7% by weight, more preferably from 0.1% by weight to 1.4% by weight.

As an example of the aromatic diamine which is preferably used for designing the non-thermoplastic block component (b) of the present invention, 4,4'-diaminodiphenylpropane and 4,4'-bis(4- Aminophenoxy)biphenyl, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylanthracene, 4,4 '-Diaminodiphenylanthracene, 4,4'-oxydiphenylamine, 3,3'-oxydiphenylamine, 3,4'-oxydiphenylamine, 4,4'-diaminodiphenyl Diethyldecane, 4,4'-diaminodiphenylnonane, 4,4'-diaminodiphenylethylphosphine oxide, 4,4'-diaminodiphenyl N-methylamine , 4,4'-diaminodiphenyl N-aniline, 1,4-diaminobenzene (p-phenylenediamine), bis{4-(4-aminophenoxy)phenyl}anthracene, double {4-(3-Aminophenoxy)phenyl}anthracene, 4,4'-bis(3-aminophenoxy)biphenyl, 1,3-bis(3-aminophenoxy)benzene , 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3 , 3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2-double (4-Aminophenoxyphenyl)propane and 3,3'-dihydroxy-4,4'-diamino-1,1'-biphenyl, etc. Use this or use a combination of them. A fluorine-based monomer such as 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl may also be used. Further, in addition to the above aromatic diamine, any aromatic diamine may be used as an accessory component. As an example of the aromatic diamine which can be used especially in these, p-phenylenediamine is mentioned.

Examples of the aromatic acid dianhydride which is preferably used for designing the non-thermoplastic block component (b) include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 2, 2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane The acid dianhydride, the p-phenylene bis(trimellitic acid monoester anhydride), and the 4,4'-oxydiphthalic dianhydride may be used singly or in combination. Examples of the aromatic acid dianhydride which can be preferably used in the above-mentioned examples include pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride alone or in combination. One.

(Polymerization method of polylysine)

A preferred solvent for producing a polyimide precursor, that is, a poly-proline, and any solvent can be used as the solvent capable of dissolving the poly-proline, and is not particularly limited. As the above solution The agent may, for example, be a guanamine-based solvent, that is, N,N-dimethylformamide (DMF), N,N-dimethylacetamide or N-methyl-2-pyrrolidone. Among them, N,N-dimethylformamide or N,N-dimethylacetamide can also be preferably used.

The non-thermoplastic polyimide film of the present invention can be polymerized into a block component by the control of the order of addition of the raw material monomers, in addition to the structure of the aromatic diamine and the aromatic acid dianhydride, which are raw material monomers. Various physical properties. As a typical polymerization method, the following methods are mentioned, ie, the following methods: 1) Aromatic acid dianhydride is reacted with an aromatic diamine having a relatively small amount of moietre in an organic polar solvent to obtain a prepolymer having an acid anhydride group at both terminals. Then, a method of polymerizing an aromatic diamine in such a manner that the aromatic tetracarboxylic dianhydride and the aromatic diamine are substantially equivalent in the entire step; 2) The aromatic acid dianhydride is reacted with an aromatic diamine having an excessive amount of moles in an organic polar solvent to obtain a prepolymer having an amine group at both terminals. Then, an aromatic diamine is added thereto, and a method of polymerizing the aromatic acid dianhydride in such a manner that the aromatic acid dianhydride and the aromatic diamine are substantially equal in the entire step.

Here, there is no limitation on forming the initially obtained prepolymer into a thermoplastic block, or making a non-thermoplastic block, but the synthesis can be carried out by such a polymerization method so that the respective block components are obtained and finally obtained. The polyimide film is non-thermoplastic.

Further, in the non-thermoplastic polyimide of the present invention, a filler may be added for the purpose of improving properties of the film such as slidability, thermal conductivity, electrical conductivity, corona resistance and/or ring rigidity. Any substance may be used as the filler, but preferred examples thereof include cerium oxide, titanium oxide, aluminum oxide, cerium nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, and mica. These fillers may be added to the solution while being dispersed in the above polymerization step, or may be separately prepared in advance, added to the prepared high-viscosity polyamic acid solution, and mixed to form a film.

Can also be used to further reduce the dielectric loss tangent into the non-thermoplastic polyimide film Add fluororesin. That is, the non-thermoplastic polyimide film may also contain a fluororesin. As the fluororesin, for example, a tetrafluoroethylene polymer (PTFE), a tetrafluoroethylene/hexafluoropropylene copolymer (FEP), a tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer (PFA), and/or may be used alone. Either tetrafluoroethylene/ethylene copolymer (ETFE) or the like, or two or more types may be used in combination. Among them, from the viewpoint of thermal decomposition temperature, it is also preferred to use PTFE.

The shape of the fluororesin is not particularly limited as long as it can be uniformly dispersed in the polyimide precursor, and examples thereof include a fibrous form, a scaly form, a powder form, and the like, and are preferably powdery (fluororesin particles). . The blending amount of the fluororesin is preferably 30% by mass to 70% by mass, and more preferably 40% by mass to 60% by mass based on the non-thermoplastic polyimide. When the amount of the fluororesin is 30% by mass or more, the dielectric constant and the dielectric loss tangent are not excessively high, which is preferable. When the blending amount of the fluororesin is 70% by mass or less, it is preferable to prevent deterioration of the dimensional change rate when processing to a flexible metal foil laminate. Further, a fluororesin in a solid state may be added, or a dispersion solution of a fluororesin may be added.

(Method of film formation of non-thermoplastic polyimine)

Examples of the method for producing the polyimine from the poly-proline are, for example, a thermal imidization method and a chemical imidization method, but in terms of shortening the drying time or the calcination time, it is preferably a chemical Amination method.

Moreover, the manufacturing step of the particularly preferred non-thermoplastic polyimide film of the present invention preferably comprises the steps of: i) mixing a film-forming dopant comprising the poly-proline solution with a chemical sulfonating agent; a step of casting a liquid film on the support; ii) a step of peeling off the gel film from the support after heating on the support; iii) further heating, imidating the remaining guanidinium amide, and It is a step of drying to form a film.

In the above steps, the chemical hydrazine imiding agent refers to a solution containing a dehydrating agent represented by an acid anhydride such as acetic anhydride; and isoquinoline, quinoline, and β-methylpyridyl A tertiary amine such as a pyridine, a pyridine or a diethyl pyridine is represented by a ruthenium amide catalyst.

The film forming conditions and heating conditions may vary depending on the type of polyamic acid and the thickness of the film. The dehydrating agent and the ruthenium-imiding catalyst are mixed at a low temperature in a poly-proline solution to obtain a film-forming dopant. Then, the film-forming dopant is film-cast on a support such as a glass plate, an aluminum foil, a ring-shaped stainless steel belt or a stainless steel drum, and the support is 80 ° C to 200 ° C, preferably 100 ° C to 180 The polyhydric acid film (hereinafter referred to as a gel film) is obtained by heating in a temperature range of °C to activate a dehydrating agent and a ruthenium-based catalyst to partially harden and/or dry it, and then peel off from the support. .

The gel film is in the middle stage of hardening from poly-proline to polyimine, and is self-supporting, from formula (II) (A-B) × 100 / B‧‧ (II)

In the formula (II), A and B represent the following.

A: the weight of the gel film

B: The weight of the gel film after heating at 450 ° C for 20 minutes

The calculated volatile content is in the range of 5% by weight to 500% by weight, preferably in the range of 5% by weight to 200% by weight, more preferably in the range of 5% by weight to 150% by weight. When a film of this range is used, it is preferable that an abnormality such as a color unevenness of the film due to film breakage or unevenness in drying, or a difference in characteristics is hard to occur in the calcination process.

The preferred amount of dehydrating agent is from 0.5 moles to 5 moles, preferably from 1.0 moles to 4 moles, relative to the valeric acid unit 1 mole in the polyamic acid. Further, the preferred amount of the ruthenium-aminated catalyst is 0.05 mole to 3 moles, preferably 0.2 moles to 2 moles, relative to the methionine unit 1 mole in the polyamic acid.

When the amount of the dehydrating agent is 0.5 mol or more or the amount of the ruthenium-imiding catalyst is 0.05 mol or more, chemical imidization can be sufficiently performed, so that breakage during the calcination and reduction in mechanical strength can be prevented. Further, when the amount of the dehydrating agent is 5 mol or less or the amount of the quinone imidization catalyst is 3 m or less, the ruthenium imidization does not proceed prematurely, and film casting is easy, which is preferable.

Fixing the end portion of the above gel film to avoid shrinkage during hardening, drying, removing water, residual solvent, residual conversion agent and catalyst, and completely imidating the remaining lysine to obtain the polyphthalamide of the present invention. Amine film.

At this time, it is preferred to finally heat at a temperature of 400 ° C to 650 ° C for 5 seconds to 400 seconds. When the temperature is 650 ° C or lower or the time is 400 seconds or less, thermal deterioration of the film hardly occurs, so that it is difficult to cause a problem. When the temperature is 400 ° C or more or the time is 5 seconds or more, the desired effect is easily exhibited.

The thickness of the non-thermoplastic polyimide film of the present invention is preferably from 10 μm to 50 μm, more preferably from 12.5 μm to 44 μm. When the thickness is 50 μm or less, the flexible wiring board is not too hard and is easily bent, which is preferable. In addition, when the thickness is 10 μm or more, the handleability is increased, so that it is possible to prevent the crack from being able to pass through the production step during the conveyance.

(multilayer film)

The multilayer adhesive film can be produced by providing at least one side of the non-thermoplastic polyimide film of the present invention with an adhesive layer containing a thermoplastic polyimide.

The method of providing the adhesive layer containing the thermoplastic polyimide on the non-thermoplastic polyimide film is not particularly limited, but for example, the coating of the thermoplastic polyimide may be applied to the non-thermoplastic polyimide film. The method of polylysine and the like.

The thickness (single side) of the adhesive layer containing the thermoplastic polyimide is preferably 1.7 μm to 35 μm, more preferably 1.7 μm to 8 μm, still more preferably 1.7 μm to 6 μm, particularly preferably 1.7 μm to 4 μm. When the thickness of the adhesive layer is 1.7 μm or more, it is also determined by the roughness of the surface of the metal foil, but the adhesion is good. Moreover, when the thickness of the adhesive layer is 35 μm or less, it is possible to prevent the dimensional change rate after etching the metal foil attached to the metal foil laminated board from increasing on the negative side. Further, the thermoplastic polyimide film is not too thick, and when the thickness ratio of the non-thermoplastic polyimide film to the entire thickness of the multilayer adhesive film exceeds 50%, the processing can be prevented from being processed to the flexible metal foil laminate. It is preferable that the dimensional change rate at the time is deteriorated. The thickness ratio of the non-thermoplastic polyimide film in the entire thickness of the multilayer adhesive film is preferably a ratio It is 75% to 94%, more preferably 80% to 93%, and further preferably 85% to 92%.

The non-thermoplastic polyimide film in the multilayer adhesive film may contain fluororesin particles as described above. In this case, the multilayer adhesive film preferably satisfies the following conditions (1') to (7').

(1') The storage point of the elastic modulus is 240 ° C ~ 320 ° C

(2') The peak temperature of the loss elastic coefficient (tan δ) is 260 ° C ~ 400 ° C

(3') Storage elastic modulus at 380 ° C is 0.1GPa~2.0GPa

(4') The storage elastic modulus α1 (GPa) under the inflection point and the storage elastic modulus α2 (GPa) at 380 °C are the ranges of the following formula (I)

95≧{(α1-α2)/α1}×100≧65‧‧‧(I)

(5') moisture absorption rate is 0.1wt%~1.5wt%

(6') dielectric loss tangent (Df) is 0.001~0.010

(7') hot line expansion coefficient is 17ppm~30ppm

The definitions of the parameters described in (1') to (7'), the range of the better, and the like are the same as those described in the above (dynamic viscoelasticity). However, the coefficient of thermal linear expansion is more preferably 20 ppm to 25 ppm.

(thermoplastic polyimide)

The thermoplastic polyimine contained in the adhesive layer of the multilayer adhesive film of the present invention can be laminated by an existing apparatus, and the present invention can be considered from the viewpoint of not impairing the heat resistance of the obtained metal foil laminated board. The thermoplastic polyimine in the range preferably has a glass transition temperature (Tg) in the range of from 150 ° C to 300 ° C. Further, when the moisture absorption solder resistance is also considered, the Tg is preferably 230 ° C or higher, more preferably 240 ° C or higher. Further, Tg can be obtained from the value of the inflection point of the storage elastic modulus measured by a dynamic viscoelasticity measuring device (DMA). The polyacrylamide precursor which is a precursor of the thermoplastic polyimine is not particularly limited, and any known polyamic acid can be used. Known raw materials and reaction conditions can also be used for their manufacture. Further, an inorganic or organic filler may be added as needed.

(metal foil)

The metal foil which can be used in the present invention is not particularly limited, but when the flexible metal foil laminate of the present invention is used in an electronic device or an electrical device, for example, copper or a copper alloy, stainless steel or alloy thereof may be mentioned. , nickel or nickel alloy (also contains 42 alloy), and aluminum or aluminum alloy foil. In the conventional flexible metal foil laminate, a copper foil such as a rolled copper foil or an electrolytic copper foil is often used, but it can also be preferably used in the present invention. Further, the surface of the metal foil may be coated with a rustproof layer, a heat resistant layer or an adhesive layer. Moreover, the thickness of the metal foil is not particularly limited, and may be any thickness that exhibits a sufficient function depending on the application. The surface of the metal foil is preferably smooth in order to reduce the transmission loss, and a copper foil having a Ra of 1.0 μm or less can be preferably used. Smooth copper foil for high-speed transmission is available at all companies. In the multilayer adhesive film used in the present invention, since the adhesive layer is a thermoplastic polyimide, the adhesion to the copper foil is high, and a smooth copper foil which is generally difficult to obtain a anchoring effect can be obtained, and in this respect, in this respect, Excellent.

(Flexible metal foil laminate)

The flexible metal foil laminate of the present invention is obtained by laminating a metal foil on a multilayer adhesive film. In other words, the flexible metal foil laminate of the present invention is a metal foil disposed on a multilayer adhesive film. As a method of laminating a multilayer adhesive film and a metal foil for producing the flexible metal foil laminate of the present invention, for example, a hot roll laminating apparatus or a double belt press having one or more metal rolls can be used ( Continuous processing by DBP). Among them, from the viewpoint of a simple device configuration and an advantageous maintenance cost, it is preferable to use a hot roll laminating device having one or more metal rolls. Further, in view of the fact that the metal foil is preferably apt to change in size when the metal foil is laminated by a hot roll laminating apparatus having a pair of metal rolls, the multilayer film of the present invention comprising a polyimide film and an adhesive layer is The hot roll laminating device exhibits a remarkable effect when it is attached to a metal foil. Accordingly, the flexible metal foil laminate of the present invention is preferably obtained by laminating a metal foil on a multilayer adhesive film by a thermal lamination method. The "hot roll laminating device having one or more metal rolls" as described herein does not have a material for heating the material. The apparatus for pressurizing the metal roll is not particularly limited as to the specific device configuration.

The specific configuration of the apparatus for performing the above thermal lamination is not particularly limited. However, in order to make the appearance of the obtained laminated sheet excellent, it is preferable to provide a protective material between the pressing surface and the metal foil. Examples of the protective material include materials resistant to the heating temperature in the thermal lamination step, that is, heat-resistant plastics such as non-thermoplastic polyimide films, and metal foils such as copper foil, aluminum foil, and SUS foil. Among them, a non-thermoplastic polyimide film or a film containing a thermoplastic polyimide having a lamination temperature of 50 ° C or higher is preferably used from the viewpoint of excellent balance between heat resistance and recyclability. Further, from the viewpoint of sufficiently exerting the buffering and protecting action at the time of lamination, the thickness of the non-thermoplastic polyimide film as a protective material is preferably 75 μm or more.

The present invention is not limited to the embodiments described above, and various modifications can be made within the scope of the claims. The embodiments obtained by appropriately combining the technical means disclosed in the different embodiments are also included in the embodiments. Within the technical scope of the present invention. Further, new technical features can be formed by appropriately combining the technical means disclosed in the respective embodiments.

The present invention can also be constructed in the following manner.

[1] A multilayer adhesive film comprising: an adhesive layer having a thermoplastic polyimide, at least one side of a non-thermoplastic polyimide film, wherein the non-thermoplastic polyimide film is an aromatic second The polyimine precursor obtained by reacting an amine with an aromatic acid dianhydride is chemically imidized and satisfies the following conditions (1) to (6).

(1) The recurve point temperature of the storage elastic modulus is 250 ° C ~ 320 ° C

(2) The peak temperature of the loss elastic coefficient (tan δ) is 260 ° C ~ 400 ° C

(3) The storage elastic modulus at 380 ° C is 0.2GPa~2.0GPa

(4) The storage elastic modulus α1 (GPa) under the inflection point and the storage elastic modulus α2 (GPa) at 380 °C are the ranges of the following formula (1)

(Formula 1): 95≧{(α1-α2)/α1}×100≧65

(5) moisture absorption rate is 0.1wt%~1.5wt%

(6) Dielectric loss tangent (Df) is 0.001~0.010

[2] The multilayer adhesive film according to [1], wherein the non-thermoplastic polyimide film comprises a thermoplastic block component (a) and a non-thermoplastic block component (b), and the thermoplastic block component (a) The conditions of the following (A) to (C) are satisfied, and the non-thermoplastic block component (b) satisfies the conditions of the following (D).

(A) 醯 imine density is below 0.25

(B) Dielectric loss tangent (Df) is 0.001~0.012

(C) moisture absorption rate is 0.1 wt% to 1.3 wt%

(D) Thermal expansion coefficient is 1ppm~10ppm

[3] The multilayer adhesive film according to [1] or [2], wherein the non-thermoplastic polyimide film comprises a film selected from 2,2'-bis[4-(4-aminophenoxy)benzene. At least two aromatic diamines of a group consisting of propane (BAPP), p-phenylenediamine (PDA), and 4,4'-bis(4-aminophenoxy)biphenyl (BAPB) as a fragrance Group of diamines selected from pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic dianhydride At least two aromatic acid dianhydrides in the group consisting of (ODPA) are used as the aromatic acid dianhydride.

[4] The multilayer adhesive film according to any one of [1] to [3] wherein the non-thermoplastic polyimide film contains a fluororesin.

[5] A flexible metal foil laminated board obtained by laminating a metal foil to a multilayer adhesive film according to any one of [1] to [4].

[6] The flexible metal foil laminate according to [5], wherein the metal foil is bonded to the multilayer adhesive film by a thermal lamination method.

[Examples]

Hereinafter, the present invention will be more specifically described based on examples and comparative examples. Furthermore, the present invention is not limited to the following examples.

Further, regarding the synthesis of the polyaminic acid solution for determining the thermoplastic block component or the non-thermoplastic block component in the present invention and using only the raw material monomers constituting each block, it is exemplified that only the synthesis example is used. When the thermoplastic block component of 4 was polymerized, as Synthesis Example 2, a case where polymerization was carried out using only the non-thermoplastic block component of Synthesis Example 4 was exemplified as Synthesis Example 3. In the synthesis examples 5 to 14, polymerization was carried out in the same manner as in the synthesis examples 2 and 3, and it was judged to be either a thermoplastic block component or a non-thermoplastic block component. The results are shown in Table 1.

(thickness of film)

The thickness of the film was measured using a LASER HOLOGAGE manufactured by a contact thickness meter Mitsutoyo Corporation.

(Dynamic viscoelasticity measurement)

A non-thermoplastic polyimide film or a multilayer adhesive film (sample) was measured by a dynamic viscoelasticity measuring device (manufactured by SII NanoTechnology, DMS6100). The storage elastic modulus is plotted against the temperature, and the storage elastic modulus at this time, the inflection point temperature of the storage elastic modulus, and the temperature indicating the maximum value of tan δ (the peak temperature of tan δ) are obtained. The measurement conditions are shown below.

Sample measurement range: width 9mm, clamp spacing 20mm

Measuring temperature range: 0 ° C ~ 440 ° C

Heating rate: 3 ° C / min

Atmosphere: under the air atmosphere

Strain amplitude: 10μm

Measuring frequency: 5Hz

Minimum tension / compression: 100mN

Tension / compression gain: 1.5

Initial force amplitude: 100mN

Direction of measurement: 45 degrees in the clockwise direction relative to the molecular orientation axis of the membrane to.

(molecular orientation axis angle)

The molecular orientation axis angle θ was measured by a microwave molecular orientation meter MOA2012A type manufactured by KS Systems. The molecular orientation axis angle θ is defined as follows.

Using a molecular orienter, the molecular orientation direction (the maximum orientation of ε', where ε' is the dielectric constant of the sample) in the plane of the film can be known as the value of the angle. In the present invention, a straight line indicating the orientation direction is referred to as an "orientation axis" of the sample.

Based on the obtained molecular orientation axis angle, the measurement direction of the dynamic viscoelasticity measurement and the coefficient of thermal linear expansion described later is determined.

(Measurement of moisture absorption rate)

The moisture absorption rate was calculated from STD Q600 manufactured by TA Instruments Japan Co., Ltd. by heating at 20 ° C to 120 ° C at 20 ° C / min and holding at 120 ° C for 2 hours. For the sample, the humidity was controlled by standing at 23 ° C / 55% RH for one week.

(Measurement of CTE (Hot Coefficient of Expansion))

The coefficient of thermal linear expansion is temporarily increased to 0 ° C to 400 ° C at 10 ° C / min by a thermomechanical analysis device manufactured by SII NanoTechnology, under the trade name TMA/SS6100, and then cooled to 10 ° C at 40 ° C / min. The temperature was raised at 10 ° C / min, and the value in the range of 100 ° C to 200 ° C at the second temperature rise was determined. The measurement conditions are shown below.

Sample shape: width 3mm, length 10mm

Load: 29.4mN

Measuring temperature range: 0 ° C ~ 400 ° C

Atmosphere: under the air atmosphere

Direction of measurement: 45 degrees in the clockwise direction with respect to the molecular orientation axis of the membrane.

(Measurement of dielectric constant and dielectric loss tangent)

The dielectric constant and the dielectric loss tangent were measured using a network analyzer 8719C manufactured by HEWLETTPACKARD Co., Ltd. and a cavity resonator resonance dielectric constant measuring device CP511 manufactured by Kanto Electronics Application Development Co., Ltd. The sample was cut into 2 mm × 100 mm, and subjected to humidity control in a 23 ° C / 55% RH atmosphere for 24 hours, and then measured. The measurement was carried out at 10 GHz.

(Manufacturing method of flexible metal foil laminate)

A rolled copper foil (GHY5-93F-HA: manufactured by JX Nippon Mining Co., Ltd.) having a thickness of 12 μm was placed on both sides of the multilayer adhesive film, and a protective material (Apical 125 NPI: manufactured by Kaneka, thickness: 125 μm) was disposed on both surfaces thereof, and a heat roller was used. The laminator was continuously thermally laminated at a lamination temperature of 360 ° C, a lamination pressure of 245 N/cm 2 (25 kgf / cm), and a lamination speed of 1.0 m / min to prepare a flexible metal foil laminated board.

(Measurement of dimensional change rate)

Four holes were formed on the flexible metal foil laminate sheet based on JIS C6481, and the respective distances of the respective holes were measured. Next, the etching step was performed to remove the metal foil from the flexible metal foil laminate, and then placed in a constant temperature room at 23 ° C / 55% RH for 24 hours. Thereafter, the distances of the four holes were measured in the same manner as before the etching step. The measured value of the distance between the holes before the removal of the metal foil was D1, and the measured value of the distance between the holes after removing the metal foil was D2, and the dimensional change rate before and after the etching was obtained by the following formula (III).

Dimensional change rate (%) = {(D2-D1) / D1} × 100‧‧‧ (III)

Then, the sample after the etching was heated at 250 ° C for 30 minutes, and then placed in a constant temperature room at 23 ° C and 55% RH for 24 hours. Thereafter, the respective distances were measured for the above four holes. The measured value of the distance between each hole after heating was D3, and the dimensional change rate before and after heating was calculated by the following formula (IV).

Dimensional change rate (%) = {(D3-D2) / D2} × 100‧‧‧ (IV)

Further, the dimensional change rate is measured for both the MD direction and the TD direction, and the average value thereof is the dimensional change rate. Also, the dimensional change rate before and after etching and before heating The value obtained by adding the subsequent dimensional change rates is set to Total, and the dimensional change rate from the pre-etching state to the final state after heating is calculated.

(Measurement of FPC transmission characteristics)

A microstrip line having a line length of 10 cm and a line width of 100 μm was formed using the obtained flexible metal foil laminate. Specifically, after the boring hole opening, the through hole plating, and the patterning step, the Coverlay Film CISV1225 manufactured by Nikkan Industries Co., Ltd. is attached, and the measurement pad portion is plated with gold to prepare a microstrip line shape FPC test. sheet. The obtained microstrip line was heated and dried at 120 ° C / 24 hours, and then placed in an environmental laboratory at 23 ° C / 55% RH for 48 hours for humidity control, using a network analyzer and a probe station. The transmission loss S21 parameter was measured. Record the signal frequency when the signal strength is halved by -3dB/10cm.

(Synthesis Example 1: Synthesis of Polylysine 1 Solution for Adhesive Layer)

To D81 818.3 kg, 102.3 kg of BAPP and 13.2 kg of BPDA were added, and the mixture was stirred for 40 minutes. Then, PMDA 42.9 kg was added and stirred for 40 minutes. The additionally adjusted PMDA DMF solution (7 wt%) was slowly added to the above reaction liquid, and the addition was stopped when the addition amount reached 20.0 kg, and a polyamine acid 1 solution having a viscosity of 3500 poise at 23 ° C was obtained.

(Synthesis Example 2: Specific method of thermoplastic block component (a))

To 340 g of N,N-dimethylformamide (DMF), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) 18.8 g, 4,4'- 16.9 g of bis(4-aminophenoxy)biphenyl (BAPB) and 14.2 g of 4,4'-oxydiphthalic anhydride (ODPA), and further added 10 g of pyromellitic dianhydride (PMDA). Polyurethane 2 having a viscosity of 2500 poise at 23 ° C was obtained as a polyimide precursor.

To the obtained poly-proline 2, a chemical dehydrating agent, a catalyst and DMF (chemical dehydrating agent: 1.6 mol of acetic anhydride relative to polyglycine 2), a catalyst : relative to the polyamine acid 2 of the proline unit 1 molar is 0.5 mole of isoquinoline, DMF: chemical dehydrating agent, catalyst and DMF total weight up to 45% of polyamidite 2 The weight was stirred and defoamed, and cast on an aluminum foil using a notch coater to obtain a liquid film. After the liquid film was heated at 125 ° C for 100 seconds, the self-supporting gel film was peeled off from the aluminum foil and fixed in a metal frame. Then, when drying and bismuthizing at 250 ° C × 15 sec, 350 ° C × 15 sec, 450 ° C × 130 sec, the film is melted in an oven stage placed at 450 ° C, and dropped from the metal frame to the oven. The bottom. In this regard, it is judged that the component is a thermoplastic block component. In the same manner as in the case of obtaining a liquid film, the self-supporting gel film is fixed in a metal frame without being peeled off from the aluminum foil, and is made at 250 ° C × 15 seconds, 350 ° C × 15 seconds, 450 ° C × 130 seconds. Drying and hydrazine imidization, followed by etching the aluminum foil with a hydrochloric acid solution, thereby obtaining a monolayer film of a thermoplastic polyimide film. The properties of the obtained film are shown in Table 1 as characteristics of the thermoplastic block component.

(Synthesis Example 3: Specific method of non-thermoplastic block component (b))

To 340 g of N,N-dimethylformamide (DMF), 16.3 g of p-phenylenediamine (PDA) and 33.8 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) were added. The mixture was stirred under a nitrogen atmosphere for 30 minutes to be dissolved, and polymerization was carried out to obtain polyglycine 3 as a polyimide precursor.

To the obtained polylysine 3, a chemical dehydrating agent, a catalyst and DMF (chemical dehydrating agent: 1.6 mol of acetic anhydride relative to polyglycine 3), a catalyst : relative to the polyamine acid 3 of the proline unit 1 molar is 0.5 mole of isoquinoline, DMF: the total weight of the chemical dehydrating agent, catalyst and DMF reaches 45% of the weight of the polyimine 3 The mixture was stirred and defoamed, and casted on an aluminum foil by a notch coater to obtain a liquid film. After the liquid film was heated at 125 ° C for 100 seconds, the self-supporting gel film was peeled off from the aluminum foil and fixed in a metal frame. Then, it was dried and arniminated at 250 ° C × 15 seconds, 350 ° C × 15 seconds, and 450 ° C × 130 seconds to obtain a non-thermoplastic polyimide film having a thickness of 44 μm. The characteristics of the obtained film as the characteristics of the non-thermoplastic block component are shown in Table 1.

(Synthesis Example 4: Synthesis of poly-proline 4)

Referring to Synthesis Examples 2 and 3, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 4,4'-bis(4-aminophenoxy)biphenyl was selected. (BAPB), 4,4'-oxydiphthalic anhydride (ODPA) and pyromellitic dianhydride (PMDA) as monomers constituting the thermoplastic block component, and selected p-phenylenediamine (PDA) and 3,3',4,4'-biphenyltetracarboxylic acid Anhydride (BPDA) is used as a monomer constituting a non-thermoplastic block component.

To 850 kg of N,N-dimethylformamide (DMF), added 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) 68.74 kg (75 mol%), p-phenylene The amine (PDA) was 23.6 kg (70 mol%), which was then stirred under a nitrogen atmosphere for 30 minutes to dissolve to obtain a polymer. The components added so far are non-thermoplastic block components, and the components added later are thermoplastic block components. To the polymerization solution containing the above non-thermoplastic block component, 14.5 kg (15 mol%) of 4,4'-oxydiphthalic anhydride (ODPA) and 6.8 kg of pyromellitic dianhydride (PMDA) were added ( 10 mol%), and further charged 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) 19.2 kg (15 mol%), 4,4'-bis (4- Aminophenoxy)biphenyl (BAPB) 17.2 kg (15 mol%) was stirred for 1 hour to obtain polyamic acid 4 having a viscosity of 2500 poise at 23 ° C as a polyimide precursor.

(film formation example 1)

To the poly-proline 4 obtained in Synthesis Example 4, a chemical dehydrating agent, a catalyst, and DMF (chemical dehydrating agent: 1.6 mol of the proline unit 1 relative to polyglycolic acid 4 was added) Anhydride, catalyst: relative to the polyamine acid 4, the proline unit 1 mole is 0.5 mole of isoquinoline, DMF: the total weight of the chemical dehydrating agent, catalyst and DMF reaches 45 of the poly-proline 4 The weight of %) was mixed with a stirrer and immediately extruded from a 300 mm T-die and cast on a stainless steel belt. After the casting, the liquid film was heated stepwise in the range of 70 ° C to 130 ° C for 100 seconds to obtain a self-supporting gel film, which was peeled off from the support and fixed to the needle plate. Then, drying and hydrazine imidization were carried out stepwise in the range of 250 ° C to 400 ° C to obtain a non-thermoplastic polyimide film having a thickness of 44 μm.

Regarding the obtained non-thermoplastic polyimide film, dynamic viscoelasticity measurement was performed, and the inflection point temperature of the storage elastic modulus, the peak temperature of tan δ, the storage elastic modulus at 380 ° C, and (α1 - α2) were determined. ÷α1 × 100 (here, α1 is the storage elastic modulus under the inflection point, and α2 is the storage elastic modulus at 380 ° C) (the value of the formula I). Also, the moisture absorption rate and dielectric loss The tangent was measured. The results are shown in Table 1 as the properties of the non-thermoplastic polyimide.

(Synthesis Example 5)

2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) 34.2 g, and 4,4' were added to 340 g of N,N-dimethylformamide (DMF). 2-5.8 g of oxydiphthalic anhydride (ODPA) gave polyamic acid 5 having a viscosity of 2500 poise at 23 °C. A chemical dehydrating agent, a catalyst, and DMF were added in the same manner as in Synthesis Example 2 to obtain a monolayer film of a thermoplastic polyimide film. The properties of the obtained film are shown in Table 1 as characteristics of the thermoplastic block component.

(Synthesis Example 6)

To 340 g of N,N-dimethylformamide (DMF), 4,4'-bis(4-aminophenoxy)biphenyl (BAPB) 32.6 g, and 4,4'-oxygen di-n-butyl Phthalic anhydride (ODPA) 27.4 g gave polyamic acid 6 having a viscosity of 2500 poise at 23 °C. A chemical dehydrating agent, a catalyst, and DMF were added in the same manner as in Synthesis Example 2 to obtain a monolayer film of a thermoplastic polyimide film. The properties of the obtained film are shown in Table 1 as characteristics of the thermoplastic block component.

(Synthesis Example 7)

To 340 g of N,N-dimethylformamide (DMF), 16.0 g of 4,4'-bis(4-aminophenoxy)biphenyl (BAPB) and 2,2-bis[4-( 4-aminophenoxy)phenyl]propane (BAPP) 17.8g, 4,4'-oxydiphthalic anhydride (ODPA) 13.5g and 3,3',4,4'-biphenyltetracarboxylate Acid dianhydride (BPDA) 12.8 g gave polyamic acid 7 having a viscosity of 2500 poise at 23 °C. A chemical dehydrating agent, a catalyst, and DMF were added in the same manner as in Synthesis Example 2 to obtain a monolayer film of a thermoplastic polyimide film. The properties of the obtained film are shown in Table 1 as characteristics of the thermoplastic block component.

(Synthesis Example 8)

To 340 g of N,N-dimethylformamide (DMF), 10.4 g of 3,4'-oxydiphenylamine (3,4'-ODA) and 2,2-bis[4-(4-amine) were added. Benzophenoxy)phenyl]propane (BAPP) 21.4g, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) 16.8g and pyromellitic dianhydride (PMDA) 11.37 g, a polyamine 8 having a viscosity of 2500 poise at 23 ° C was obtained. A chemical dehydrating agent, a catalyst, and DMF were added in the same manner as in Synthesis Example 2 to obtain a single sheet of a thermoplastic polyimide film. Layer film. The properties of the obtained film are shown in Table 1 as characteristics of the thermoplastic block component.

(Synthesis Example 9)

2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) 35.0 g, and 3,3' were added to 340 g of N,N-dimethylformamide (DMF). 2,4'-biphenyltetracarboxylic dianhydride (BPDA) 25.1 g, and a polyamine 9 having a viscosity of 2500 poise at 23 ° C was obtained. A chemical dehydrating agent, a catalyst, and DMF were added in the same manner as in Synthesis Example 2 to obtain a monolayer film of a thermoplastic polyimide film. The properties of the obtained film are shown in Table 1 as characteristics of the thermoplastic block component.

(Synthesis Example 10)

2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) 34.2 g, and 4,4' were added to 340 g of N,N-dimethylformamide (DMF). 2-5.8 g of oxydiphthalic anhydride (ODPA) gave polyamic acid 10 having a viscosity of 2500 poise at 23 °C. A chemical dehydrating agent, a catalyst, and DMF were added in the same manner as in Synthesis Example 2 to obtain a monolayer film of a thermoplastic polyimide film. The properties of the obtained film are shown in Table 1 as characteristics of the thermoplastic block component.

(Synthesis Example 11)

To 340 g of N,N-dimethylformamide (DMF), 19.9 g of p-phenylenediamine (PDA) and 40.1 g of pyromellitic dianhydride (PMDA) were added to obtain a viscosity of 2500 poise at 23 ° C. Poly-proline 11 . A chemical dehydrating agent, a catalyst, and DMF were added in the same manner as in Synthesis Example 3 to obtain a monolayer film, but at this time, when it was taken out from the oven, it was broken into a powder, and a sample of the size evaluated was not obtained. The chips were heated at 450 ° C, but were not melted or deformed, and thus were judged to be non-thermoplastic block components. It is presumed that the reason why the shape cannot be maintained is that it is too hard due to an excessively rigid structure at the time of imidization, and is broken and pulverized by a slight stress.

(Synthesis Example 12)

To 340 g of N,N-dimethylformamide (DMF), 28.7 g of 4,4'-oxydiphenylamine (4,4'-ODA) and 31.3 g of pyromellitic dianhydride (PMDA) were charged. A polyamine 12 having a viscosity of 2500 poise at 23 ° C was obtained. A chemical dehydrating agent, a catalyst, and DMF were added in the same manner as in Synthesis Example 3 to obtain a monolayer film of a non-thermoplastic polyimide film. Taking the characteristics of the obtained film as The properties of the non-thermoplastic block components are shown in Table 1.

(Synthesis Example 13)

To 340 g of N,N-dimethylformamide (DMF), 37.7 g of 4,4'-bis(4-aminophenoxy)biphenyl (BAPB) and pyromellitic dianhydride (PMDA) were charged. 22.31 g, polyamic acid 13 having a viscosity of 2500 poise at 23 ° C was obtained. A chemical dehydrating agent, a catalyst, and DMF were added in the same manner as in Synthesis Example 3 to obtain a monolayer film of a non-thermoplastic polyimide film. The characteristics of the obtained film as the characteristics of the non-thermoplastic block component are shown in Table 1.

(Synthesis Example 14)

In the same manner as in Synthesis Example 4, Synthesis Example 5 and Synthesis Example 3 were referred to, and BPDA, PDA, ODPA, and BAPP were added in this order in the molar ratio shown in Table 1, to obtain polylysine 14. The obtained polyamic acid 14 was formed into a film in the same manner as in Film Formation Example 1, and a film of Film Formation Example 2 was obtained. The properties of the obtained non-thermoplastic polyimide film are shown in Table 1 as characteristics of the non-thermoplastic polyimide.

(Synthesis Example 15)

In the same manner as in Synthesis Example 4, Synthesis Example 6 and Synthesis Example 3 were referred to, and BPDA, PDA, ODPA, and BAPB were added in this order in the molar ratio shown in Table 1, to obtain polylysine 15. The obtained polyamic acid 15 was formed into a film in the same manner as in Film Formation Example 1, and a film of Film Formation Example 3 was obtained. The properties of the obtained non-thermoplastic polyimide film are shown in Table 1 as characteristics of the non-thermoplastic polyimide.

(Synthesis Example 16)

In the same manner as in Synthesis Example 4, Synthesis Example 7 and Synthesis Example 3 were referred to, and BPDA, PDA, ODPA, BPDA, BAPP, and BAPB were added in this order in the molar ratio shown in Table 1, to obtain polylysine 16. The obtained polylysine 16 was formed into a film in the same manner as in the film formation example 1, and the film of the film formation example 4 was obtained. The properties of the obtained non-thermoplastic polyimide film are shown in Table 1 as characteristics of the non-thermoplastic polyimide.

(Synthesis Example 17)

In the same manner as in Synthesis Example 4, Synthesis Example 8 and Synthesis Example 11 were referred to, and 3,4'-ODA, BAPP, BTDA, PMDA, PDA, and PMDA were added in this order in the molar ratio shown in Table 1, to obtain a polyfluorene. Amino acid 17. The obtained polyamic acid 17 was formed into a film in the same manner as in the film formation example 1, and the film of the film formation example 5 was obtained. The properties of the obtained non-thermoplastic polyimide film are shown in Table 1 as characteristics of the non-thermoplastic polyimide.

(Synthesis Example 18)

In the same manner as in Synthesis Example 4, Synthesis Example 9 and Synthesis Example 13 were referred to, and PMDA, BAPB, BPDA, and BAPP were added in this order in the molar ratio shown in Table 1, to obtain polylysine 18. The obtained polyamic acid 18 was formed into a film in the same manner as in Film Formation Example 1, and a film of Film Formation Example 6 was obtained. The properties of the obtained non-thermoplastic polyimide film are shown in Table 1 as characteristics of the non-thermoplastic polyimide.

(Synthesis Example 19)

In the same manner as in Synthesis Example 4, Synthesis Example 10 and Synthesis Example 3 were referred to, and BPDA, PDA, ODPA, and BAPP were added in this order in the molar ratio shown in Table 1, to obtain polylysine 19. The obtained polyaminic acid 19 was formed into a film in the same manner as in Film Formation Example 1, and a film of Film Formation Example 7 was obtained. The properties of the obtained non-thermoplastic polyimide film are shown in Table 1 as characteristics of the non-thermoplastic polyimide.

(Example 1)

The poly-proline 1 solution obtained in Synthesis Example 1 was diluted with DMF until the solid content concentration reached 10% by weight, and then the two sides of the above-mentioned non-thermoplastic polyimide film having a thickness of 44 μm obtained in Film Formation Example 1 were obtained. The polyimine precursor was coated in such a manner that the final single-sided thickness of the thermoplastic polyimide was 3 μm, and then heated at 140 ° C for 50 seconds. Then, heating and hydrazine imidization were carried out for 15 seconds in an infrared heating furnace at an atmospheric temperature of 320 ° C to obtain a multilayer adhesive film having a total thickness of 50 μm. Further, the properties of the multilayer adhesive film were measured. The results are shown in Table 2.

A laminated copper foil having a thickness of 12 μm (GHY5-) was heat-laminated on the obtained multilayer film. 93F-HA: JX Nippon Mining Co., Ltd.), made of flexible copper foil laminate, measuring dimensional change rate and transmission loss. The results are shown in Table 2.

(Example 2)

In addition to mixing the polyimine precursor with a chemical dehydrating agent, catalyst, and DMF as a stirrer, the PTFE-containing masterbatch dispersed in a rotor stator disperser (weight ratio is a polyimide precursor) Multilayer adhesive film and flexibility were obtained in the same manner as in Example 1 except that the weight of the non-thermoplastic polyimide film finally obtained was 3% by weight of PTFE particles. Copper foil laminates were evaluated for characteristics. The results will be shown in Table 2.

(Example 3)

A multilayer adhesive film and a flexible copper foil laminate were obtained in the same manner as in Example 1 except that the non-thermoplastic polyimide film was obtained by using the polyamic acid 14 obtained in Synthesis Example 14, and the characteristics were evaluated. The results are shown in Table 2.

(Example 4)

A multilayer adhesive film and a flexible copper foil laminate were obtained in the same manner as in Example 2 except that the non-thermoplastic polyimide film was obtained by using the polyamic acid 14 obtained in Synthesis Example 14, and the characteristics were evaluated. The results are shown in Table 2.

(Example 5)

A multilayer adhesive film and a flexible copper foil laminate were obtained in the same manner as in Example 1 except that the non-thermoplastic polyimide film was obtained by using the polyamic acid 15 obtained in Synthesis Example 15, and the characteristics were evaluated. The results are shown in Table 2.

(Example 6)

A multilayer adhesive film and a flexible copper foil laminate were obtained in the same manner as in Example 2 except that the non-thermoplastic polyimide film was obtained by using the polyamic acid 15 obtained in Synthesis Example 15, and the characteristics were evaluated. The results are shown in Table 2.

(Example 7)

A multilayer adhesive film and a flexible copper foil laminated plate were obtained in the same manner as in Example 1 except that the polyaminic acid 16 obtained in Synthesis Example 16 was used to obtain a non-thermoplastic polyimide film, and the characteristics were evaluated. The results are shown in Table 2.

(Example 8)

A multilayer adhesive film and a flexible copper foil laminated plate were obtained in the same manner as in Example 2 except that the polyaminic acid 16 obtained in Synthesis Example 16 was used to obtain a non-thermoplastic polyimide film, and the characteristics were evaluated. The results are shown in Table 2.

(Comparative Example 1)

A multilayer adhesive film and a flexible copper foil laminate were obtained in the same manner as in Example 1 except that the polyamic acid 17 obtained in Synthesis Example 17 was used, and the properties were evaluated. The results are shown in Table 2.

(Comparative Example 2)

A multilayer adhesive film and a flexible copper foil laminate were obtained in the same manner as in Example 2 except that the polyamic acid 17 obtained in Synthesis Example 17 was used, and the characteristics were evaluated. The results are shown in Table 2.

(Comparative Example 3)

A multilayer adhesive film and a flexible copper foil laminate were obtained in the same manner as in Example 1 except that the polyamic acid 12 obtained in Synthesis Example 12 was used, and the characteristics were evaluated. The results are shown in Table 2.

(Comparative Example 4)

A multilayer adhesive film and a flexible copper foil laminate were obtained in the same manner as in Example 2 except that the polyamic acid 12 obtained in Synthesis Example 12 was used, and the characteristics were evaluated. The results are shown in Table 2.

(Comparative Example 5)

A multilayer adhesive film and a flexible copper foil laminate were obtained in the same manner as in Example 1 except that the polyamic acid 18 obtained in Synthesis Example 18 was used, and the characteristics were evaluated. Show the results in the table 2.

(Comparative Example 6)

A multilayer adhesive film and a flexible copper foil laminate were obtained in the same manner as in Example 2 except that the polyamic acid 18 obtained in Synthesis Example 18 was used, and the properties were evaluated. The results are shown in Table 2.

(Comparative Example 7)

A multilayer adhesive film and a flexible copper foil laminate were obtained in the same manner as in Example 1 except that the polyamic acid 19 obtained in Synthesis Example 19 was used, and the properties were evaluated. The results are shown in Table 2.

(Comparative Example 8)

A multilayer adhesive film and a flexible copper foil laminate were obtained in the same manner as in Example 2 except that the polyamic acid 19 obtained in Synthesis Example 19 was used, and the characteristics were evaluated. The results are shown in Table 2.

(discussion)

Any of Embodiments 1, 3, 5, and 7 can reduce the dimensional change rate in the case of manufacturing a metal foil laminated board. In Examples 2, 4, 6, and 8, by adding a fluororesin, the dimensional change rate after etching was larger than that of Examples 1, 3, 5, and 7, but the dimensional change rate after heating was small. Fully durable. Further, it can be seen that in any of the examples, the transmission characteristics are good and can be used in a range of higher frequencies. Furthermore, it is shown that the higher the frequency of -3 dB/10 cm, the lower the attenuation, and the signal on the high frequency side (that is, the low transmission loss) can be used.

On the other hand, in Comparative Examples 1 and 2, the dimensional change rate was small and the workability was good, but the transmission characteristics were poor and the usable frequency was low. Further, in Synthesis Example 2 used in Comparative Examples 1 and 2, the moisture absorption rate exceeded 1.5% by weight, and the dielectric loss tangent exceeded 0.010. Further, in Comparative Examples 3 and 4, the non-thermoplastic polyimide did not have a thermoplastic block component, and did not satisfy the various parameters described in the above (1) to (6). Therefore, the dimensional change rate was large and it was not durable. Further, in Comparative Examples 5 to 8, it is found that Synthesis Examples 8 and 9 satisfy "(5) moisture absorption rate of 0.1 wt% to 1.5 wt%" and "(6) dielectric loss tangent (Df) is 0.001 to 0.010" Therefore, the transmission characteristics are good. However, in Comparative Examples 3 to 8, since the various parameters described in the above (1) to (6) are not satisfied, the dimensional change rate is large and it is not durable.

Further, in the characteristics of the multilayered film containing PTFE particles, as in the case of Examples 2, 4, 6 and 8, the dimensional change after heating is satisfied when the conditions of the above (1') to (7') are satisfied. The rate is large and the transmission characteristics are good. On the other hand, in Comparative Examples 2, 4, 6, and 8 which did not satisfy any of the above conditions (1') to (7'), the dimensional change rate or the transmission characteristics were unsatisfactory.

[Industrial availability]

The non-thermoplastic polyimide film according to the present invention has a low dielectric constant, a low dielectric loss tangent, and a low dimensional change rate. Therefore, it is useful for, for example, a substrate film for a high-frequency circuit, and can be used in various industrial fields.

Claims (7)

A multilayer adhesive film comprising: an adhesive layer comprising a thermoplastic polyimide, at least one side of a non-thermoplastic polyimide film, wherein the non-thermoplastic polyimide film satisfies the following (1) to (6) The conditions of (1) storage elastic modulus of the inflection point temperature is 250 ° C ~ 320 ° C (2) loss elastic modulus (tan δ) peak temperature is 260 ° C ~ 400 ° C (3) 380 ° C storage elastic mode The storage elastic modulus α1 (GPa) under the inflection point of 0.2GPa~2.0GPa(4) and the storage elastic modulus α2(GPa) at 380°C are the range of the following formula (I) 95≧{( 1-1-α2)/α1}×100≧65‧‧‧Formula (I)(5) The moisture absorption rate is 0.1 wt% to 1.5 wt% (6) The dielectric loss tangent (Df) is 0.001 to 0.010. The multilayer adhesive film of claim 1, wherein the non-thermoplastic polyimide film comprises a thermoplastic block component (a) and a non-thermoplastic block component (b), and the thermoplastic block component (a) satisfies the following (A) Under the condition of ~(C), the non-thermoplastic block component (b) satisfies the following condition (D), (A) the quinone imine group density is 0.25 or less (B) the dielectric loss tangent (Df) is 0.001 to 0.012 ( C) The moisture absorption rate is 0.1 wt% to 1.3 wt% (D) The coefficient of thermal linear expansion is 1 ppm to 10 ppm. A multilayer adhesive film according to claim 1 or 2, wherein said non-thermoplastic polyimide film comprises: from the group selected from 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) a monomer component of at least two aromatic diamines in a group consisting of p-phenylenediamine (PDA) and 4,4'-bis(4-aminophenoxy)biphenyl (BAPB), and Free pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 4,4'-oxydiphenylene a monomer component of at least two aromatic acid dianhydrides in a group consisting of formic acid dianhydride (ODPA). A multilayer adhesive film according to claim 1 or 2, wherein the non-thermoplastic polyimide film contains a fluororesin. A flexible metal foil laminated board obtained by laminating a metal foil on a multilayer adhesive film as claimed in claim 1 or 2. A flexible metal foil laminate according to claim 5, which is obtained by laminating a metal foil on a multilayer adhesive film by a thermal lamination method. A multilayer adhesive film comprising: an adhesive layer comprising a thermoplastic polyimide on at least one side of a non-thermoplastic polyimide film containing fluororesin particles, and satisfying the following (1')~( 7') condition, (1') storage elastic modulus of the inflection point temperature is 240 ° C ~ 320 ° C (2 ') loss elastic coefficient (tan δ) peak temperature is 260 ° C ~ 400 ° C (3 ') 380 ° C The storage elastic modulus α 0.1 (GPa) under the inversion point of 0.1 GPa to 2.0 GPa (4') and the storage elastic modulus α 2 (GPa) at 380 ° C are the following formula (I) The range of 95 ≧{(α1-α2)/α1}×100≧65‧‧‧(I)(5') moisture absorption rate is 0.1wt%~1.5wt% (6') dielectric loss tangent (Df) The coefficient of thermal linear expansion of 0.001 to 0.010 (7') is 17 ppm to 30 ppm.