JP2006321229A - Polyimide film laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide film laminate suppressed of foaming and delaminating in a high temperature stage in its production by enhancing rate of gas and moisture permeation through the use of a diamine component of a specified structure as to the polyimide obtained from a tetracarboxylic acid dianhydride component and a diamine component. <P>SOLUTION: This polyimide film laminate comprises a metal layer and a polyimide layer directly laminated thereon, which is produced by applying a polyamic acid solution composition, obtained from a tetracarboxylic acid dianhydride component and a diamine containing 0.5-30 mol% diamine of a specific structure in 100 mol% diamine, on a metal foil in a film state, and vaporizing the solvent and concurrently imidizing the polyamic acid. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention can be suitably used as a copper-clad wiring board or the like for manufacturing a printed wiring board used in the electronic / electrical industry. Depending on the type of metal material, other electronic materials such as heaters can be used. -A polyimide formed from a polyamic acid solution composition used as a dope liquid for forming a polyimide film layer, which can also be used as a heat sink, a heat responsive element, a hard disk suspension, etc. The present invention relates to a polyimide film laminate in which a layer and a metal layer are directly laminated.
More specifically, a tetracarboxylic dianhydride having 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as an essential component is a starting tetracarboxylic dianhydride component, and has a specific structure. Aromatic polyimide formed by casting a polyamic acid solution composition in which a diamine containing an aromatic diamine as an essential component is a starting diamine component into a film on a metal thin film, volatilizing the solvent and imidizing the polyamic acid It is related with the polyimide film laminated body which consists of a layer and a metal layer.

  3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride-based polyimide that gives heat-resistant polyimide includes 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, paraphenylenediamine, Are generally known to have a starting acid dianhydride component and a starting diamine component, respectively, and are known to give a polyimide having a low coefficient of linear expansion and a high elastic modulus.

  Moreover, since the film which consists of this polyimide is excellent in a thermal property and an electrical property, it is widely used for the use of electronic devices. However, an adhesive usually used in the electronic field does not provide a large adhesive strength, and a laminate provided with a metal layer by metal deposition or sputtering has a relatively low peel strength.

  Furthermore, this polyimide film has a low saturated water absorption rate and a low hygroscopic expansion coefficient, and therefore has the advantage of having dimensional stability against environmental changes. However, since the moisture permeation rate is relatively small, the laminate produced by the casting method tends to foam or peel off at the metal-polyimide interface.

  Conventionally, a polyimide laminate comprising an aromatic polyimide film layer and a metal material layer and a method for producing the same are described and suggested in, for example, Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4. It was done.

  Patent Document 5 discloses an aromatic tetracarboxylic acid component composed of biphenyltetracarboxylic acid anhydrides and pyromellitic acid anhydrides, and an aromatic diamine component composed of phenylenediamines and diaminodiphenyl ethers. A polyimide comprising an aromatic polyimide film layer and a metal film layer formed by casting an aromatic polyamic acid solution composition obtained by polymerization onto a metal thin film, drying the film and imidizing at a high temperature A composite sheet has been proposed.

  Patent Document 6 discloses an aromatic tetracarboxylic acid component composed of biphenyltetracarboxylic anhydrides and pyromellitic acid anhydride, and an aromatic diamine component composed of phenylenediamines and diaminodiphenyl ethers. Aromatic polyimide film layer and metal film formed by casting and imidizing an aromatic polyamic acid solution composition obtained by polymerization onto an alkali-etchable metal substrate and then etching the metal substrate A printed wiring board composed of layers has been proposed.

  Patent Document 7 discloses a polyimide film formed by casting and imidizing a polyamic acid solution composition obtained by polymerizing a component comprising an aliphatic tetracarboxylic acid anhydride and a diamine on a metal substrate. A flexible printed wiring board composed of a layer and a metal film layer has been proposed.

Japanese Patent Publication No.59-18221 JP-A-57-181857 JP-A-62-212140 Japanese Patent Publication No. 1-52843 JP-A-61-111359 Japanese Unexamined Patent Publication No. 3-85789 JP 2004-358916 A

The object of the present invention is to use a diamine component having a specific structure as a polyimide obtained from a tetracarboxylic dianhydride component and a diamine component, thereby improving the gas permeation rate and moisture permeation rate. It is providing the polyimide film laminated body which suppressed foaming peeling in the high temperature process at the time of manufacture of.
In particular, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is used as an essential component as a tetracarboxylic dianhydride component, and paraphenylenediamine is used as an essential component as a diamine component. A polyamic acid solution obtained from a diamine component is applied in the form of a film on a metal foil, the solvent is volatilized and the polyamic acid is imidized, and a polyimide film laminate in which a polyimide layer and a metal layer are directly laminated is obtained. When manufacturing, foam peeling may occur in a high temperature process at the time of manufacturing, and it is to provide a polyimide film laminate in which this foam peeling is suppressed.

（但し、式（１）中において、Ａは直接結合あるいは架橋基であり、Ｒ_１〜Ｒ_４は水素原子、炭素数１〜６の炭化水素基、ヒドロキシル基、カルボキシル基、炭素数１〜６のアルコキシ基、カルボアルコキシ基から選ばれる置換基を表し、Ｒ_１およびＲ_２の少なくとも１つは水素原子ではなく、Ｒ_３およびＲ_４の少なくとも１つは水素原子ではない。） The first of the present invention is a polyamic acid solution obtained from a tetracarboxylic dianhydride component and a diamine component containing 0.5 to 30 mol% of a diamine represented by the following general formula (1) in 100 mol% of the diamine. Is applied to a metal foil in the form of a film, the solvent is volatilized and polyamic acid is imidized, and the polyimide layer and the metal layer are directly laminated.

(However, in the formula (1), A is a direct bond or a bridging _group, R 1 to R ₄ is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, hydroxyl group, carboxyl group, 1 to 6 carbon atoms And at least one of R ₁ and R ₂ is not a hydrogen atom, and at least one of R ₃ and R ₄ is not a hydrogen atom.)

  2nd of this invention is related with the polyimide film laminated body by which the base material is laminated | stacked on the polyimide layer of the 1st polyimide film laminated body of this invention directly or through a heat resistant adhesive agent.

The 1st preferable aspect of this invention is shown, These can be combined multiplely.
1) In the diamine of the general formula (1), A in the formula represents a direct bond or a crosslinking group, and R _{1 to} R ₄ represent a substituent selected from a hydrocarbon group having 1 to 6 carbon atoms.
2) The diamine component contains paraphenylenediamine.
3) The tetracarboxylic dianhydride component contains 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride.
4) The elastic modulus of the polyimide film after removing the metal foil is 4 GPa or more and less than 9 GPa.
5) The polyamic acid solution contains a silane coupling agent.
6) The metal foil is a copper foil.
7) The metal foil is a 1-10 μm thick copper foil having a peelable carrier layer, more preferably a 1-10 μm thick copper layer obtained by peeling the carrier layer from the polyimide film laminate. Having

The 2nd preferable aspect of this invention is shown, These can be combined multiplely.
1) The substrate is a metal layer.

According to the first aspect of the present invention, by introducing a diamine component having a specific structure, it is possible to suppress foam peeling in a high-temperature process during the production of a polyimide film laminate, and an excellent breaking strength and excellent A polyimide film laminate having a tensile elastic modulus and excellent peel strength can be provided.
In particular, according to the first aspect of the present invention, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is used as a main component as a tetracarboxylic dianhydride component, and paraphenylenediamine is mainly used as a diamine component. As a component, a polyamic acid solution obtained from these acid component and diamine component is applied in a film form on a metal foil, the solvent is volatilized and the polyamic acid is imidized, and a polyimide layer and a metal layer When manufacturing a polyimide film laminate that is directly laminated, foam peeling may occur in the high-temperature process during manufacturing, and by introducing a diamine component having a specific structure, foam peeling is suppressed during manufacturing. And providing a polyimide film laminate having excellent breaking strength, excellent tensile elastic modulus, and excellent peel strength It can be.
In the first polyimide film laminate of the present invention, the polyimide layer has high mechanical properties and maintains characteristics such as a low coefficient of linear expansion, while improving adhesiveness and moisture transmission rate. It is difficult for foaming and peeling at the adhesive interface.
The first polyimide film laminate of the present invention can provide a laminate with improved surface adhesion and moisture transmission rate.
In addition, the second laminate of the present invention has a high adhesive strength between the polyimide layer and the substrate, a high moisture permeability rate of the polyimide layer, and foaming and peeling at the adhesive interface due to the high temperature treatment process are unlikely to occur.

（但し、式（１）中において、Ａは直接結合あるいは架橋基であり、Ｒ_１〜Ｒ_４は水素原子、炭素数１〜６の炭化水素基、ヒドロキシル基、カルボキシル基、炭素数１〜６のアルコキシ基、カルボアルコキシ基から選ばれる置換基を表し、Ｒ_１およびＲ_２の少なくとも１つは水素原子ではなく、Ｒ_３およびＲ_４の少なくとも１つは水素原子ではない。） The polyimide film laminate of the present invention is a polyamic acid obtained from a tetracarboxylic dianhydride component and a diamine component containing 0.5 to 30 mol% of a diamine represented by the following general formula (1) in 100 mol% of a diamine. It is a polyimide film laminate in which an acid solution is applied in a film form on a metal foil, the solvent is volatilized and polyamic acid is imidized, and a polyimide layer and a metal layer are directly laminated.

(However, in the formula (1), A is a direct bond or a bridging _group, R 1 to R ₄ is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, hydroxyl group, carboxyl group, 1 to 6 carbon atoms And at least one of R ₁ and R ₂ is not a hydrogen atom, and at least one of R ₃ and R ₄ is not a hydrogen atom.)

  The polyimide film laminate of the present invention can be obtained by applying a polyamic acid solution to a metal foil in the form of a film or spraying, volatilizing the solvent and imidizing the polyamic acid to form a polyimide layer. it can.

As the metal foil, a single metal or alloy, for example, metal foil such as copper, aluminum, gold, silver, nickel, and stainless steel, metal plating layer (preferably vapor deposition metal underlayer-metal plating layer or chemical metal plating layer, etc. Many known techniques can be used), and copper foils such as rolled copper foil and electrolytic copper foil are preferable.
The thickness of the metal foil is not particularly limited as long as it has a thickness that is practically used or manufactured, but is preferably 0.1 μm to 10 mm, more preferably 1 to 100 μm, and particularly preferably 2 to 18 μm. .
Further, for the purpose of further improving the adhesive strength to these metal foils, siding, nickel plating, copper-zinc alloy plating, or aluminum alcoholate, aluminum chelate, silane coupling agent, triazine thiol on the surface thereof. Chemical or mechanical surface treatment may be carried out with benzene, benzotriazoles, acetylene alcohols, acetylacetones, catechols, o-benzoquinones, tannins, quinolinols, and the like.

When an ultrathin copper foil having a thickness of 0.1 to 10 μm, preferably 1 to 5 μm is used as the metal foil, a copper foil with a carrier having good handleability can be suitably used.
Although there is no restriction | limiting in particular as a carrier layer of copper foil with a carrier, Rolled copper foil and electrolytic copper foil with a thickness of 5 micrometers-150 micrometers are preferable. The carrier layer is preferably easily and mechanically peelable from the ultrathin copper foil, and preferably has a peel strength of 0.01 to 0.3 Kg / cm.

  As tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) methane, bis ( 3,4-dicarboxyphenyl) ether, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) sulfide, p-phenylenebis (trimellitic acid monoester anhydride) Aromatic tetracarboxylic acids such as ethylene bis (trimellitic acid monoester acid anhydride) and bisphenol A bis (trimellitic acid monoester acid anhydride) Anhydride, etc., may be used singly or in combination of two or more.

  As tetracarboxylic dianhydride, in 100 mol% of tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is 50 mol% or more, preferably 60 mol% or more, More preferably 70 mol% or more, still more preferably 80 mol% or more, particularly preferably 90 mol% or more, and within the range not impairing the properties of the present invention, pyromellitic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4 -Dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) ether, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphe) A) aromatic tetra, such as sulfide, p-phenylenebis (trimellitic acid monoester acid anhydride), ethylene bis (trimellitic acid monoester acid anhydride), bisphenol A bis (trimellitic acid monoester acid anhydride) Carboxylic dianhydrides may be included alone or in combination of two or more.

In the diamine of general formula (1):
Examples of the bridging group A in the general formula (1) include an oxygen atom, a sulfur atom, a methylene group, a carbonyl group, a sulfoxyl group, a sulfone group, a 1,1′-ethylidene group, a 1,2-ethylidene group, and 2,2 ′. -Isopropylidene group, 2,2'-hexafluoroisopropylidene group, cyclohexylidene group, phenylene group, 1,3-phenylenedimethylene group, 1,4-phenylenedimethylene group, 1,3-phenylenediethylidene group 1,4-phenylenediethylidene group, 1,3-phenylenedipropylidene group, 1,4-phenylenedipropylidene group, 1,3-phenylenedioxy group, 1,4-phenylenedioxy group, biphenylenedi Oxy group, methylene diphenoxy group, ethylidene diphenoxy group, propylidene diphenoxy group, hexafluoropropylidenediphenoxy group Oxy diphenoxy group, Chiojifenokishi group, there may be mentioned a sulfonic diphenoxy group may be bonded directly without via a bridging group.

In the diamine of general formula (1):
R _{1 to} R ₄ in the general formula (1) are a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms (preferably a hydrocarbon group having 1, 2, 3, 4, 5 or 6 carbon atoms), a hydroxyl group Represents a substituent selected from a carboxyl group, an alkoxy group having 1 to 6 carbon atoms (preferably an alkoxy group having 1, 2, 3, 4, 5 or 6 carbon atoms), and a carboalkoxy group, and R ₁ and R ₂ At least one is not a hydrogen atom and at least one of R ₃ and R ₄ is not a hydrogen atom.

Examples of R _{1 to} R _{4 in} the general formula (1) include
a) R _{1 to} R ₄ are each a hydrocarbon group having 1 to 6 carbon atoms (preferably a hydrocarbon group having 1, 2, 3, 4, 5 or 6 carbon atoms), a hydroxyl group, a carboxyl group, 1 to 1 carbon atom. 6 alkoxy groups (preferably alkoxy groups having 1, 2, 3, 4, 5 or 6 carbon atoms), a combination of substituents selected from carboalkoxy groups,
b) R _{1 to} R ₃ are each a hydrocarbon group having 1 to 6 carbon atoms (preferably a hydrocarbon group having 1, 2, 3, 4, 5 or 6 carbon atoms), a hydroxyl group, a carboxyl group, 1 to 1 carbon atom. 6 is a substituent selected from an alkoxy group (preferably an alkoxy group having 1, 2, 3, 4, 5 or 6 carbon atoms), a carboalkoxy group, and only R ₄ is a combination of hydrogen atoms,
c) R ₁ and R ₃ are each a hydrocarbon group having 1 to 6 carbon atoms (preferably a hydrocarbon group having 1, 2, 3, 4, 5 or 6 carbon atoms), a hydroxyl group, a carboxyl group, 1 to 1 carbon atom. An alkoxy group having 6 carbon atoms (preferably an alkoxy group having 1, 2, 3, 4, 5 or 6 carbon atoms), a carboalkoxy group, and R ₂ and R ₄ are a combination of hydrogen atoms,
Can be mentioned.

Specific examples of R _{1 to} R _{4 in} the general formula (1) include hydrogen, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i- Hydrocarbon group such as butyl group, t-butyl group, pentyl group, cyclohexyl group, phenyl group, alkoxy group such as hydroxyl group, methoxy group, ethoxy group, propoxy group, butoxy group, carboxyl group, carbomethoxy group, carboethoxy And carboalkoxy groups such as carbopropoxy group and carbobutoxy group. R _{1 to} R ₄ may all be the same or different from each other.

As a specific example of the aromatic diamine represented by a) of the general formula (1),
3,3 ′, 5,5′-tetramethyl-4,4′-diaminobiphenyl,
3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenyl ether,
3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane,
3,3 ′, 5,5′-tetraethyl-4,4′-diaminobiphenyl,
3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether,
3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane,
4,4-methylene-bis (2,6-diisopropylaniline),
3,3′-dicarboxy-4,4′-diamino-5,5′-dimethyldiphenylmethane, and the like.

As a specific example of the aromatic diamine represented by c) of the general formula (1),
3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-diethyl-4,4′-diaminobiphenyl, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′- Dicarboxy-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl,
3,3′-dimethyl-4,4′-diaminodiphenyl ether, 3,3′-diethyl-4,4′-diaminodiphenyl ether, 3,3′-dihydroxy-4,4′-diaminodiphenyl ether, 3,3′- Dicarboxy-4,4′-diaminodiphenyl ether, 3,3′-dimethoxy-4,4′-diaminodiphenyl ether,
3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dihydroxy-4,4′-diaminodiphenylmethane, 3,3′- And dicarboxy-4,4′-diaminodiphenylmethane, 3,3′-dimethoxy-4,4′-diaminodiphenylmethane, and the like.

The diamine of the polyimide of this invention is 0.5-30 mol% of the diamine represented by General formula (1), Preferably it is 1-20 mol%, More preferably, it is 8-20 mol%, General formula (1) Diamines other than the diamines represented by, for example, p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylpropane, 4,4-diaminodiphenylmethane, benzidine, 3,3′-dichlorobenzidine, 4,4 ′ -Diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-oxydianiline, 3,3'-oxydianiline, 3,4'-oxydianiline, 1,5-diaminonaphthalene, 4,4′-diaminodiphenyldiethylsilane, 4,4′-diaminodiphenylsilane, 4,4′-dia Nodiphenylethylphosphine oxide, 1,4-diaminobenzene (p-phenylenediamine), bis {4- (4-aminophenoxy) phenyl} sulfone, bis {4- (3-aminophenoxy) phenyl} sulfone, 4,4 '-Bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone and the like, and the like. 5 to 70 mol%, preferably 99 to 80 mol%, more preferably 92 to 80 mol% (A diamine represented by general formula (1), a total of 100 mol% of a diamine excluding diamine represented by general formula (1).).
The diamine except the diamine represented by the general formula (1) and the diamine represented by the general formula (1) can be used alone or in combination of two or more.

  In particular, the diamine of the polyimide of the present invention is 0.5 to 30 mol%, preferably 1 to 20 mol%, more preferably 8 to 20 mol% of the diamine represented by the general formula (1), and p-phenylenediamine. Diamine containing 70 mol% or more, preferably 80 mol% or more, and further diamine represented by the general formula (1) is 0.5 to 30 mol%, preferably 1 to 20 mol%, more preferably 8 to 20 By using a diamine containing 10% by mole and 99.5 to 70% by mole of p-phenylenediamine, preferably 99 to 80% by mole, and more preferably 92 to 80% by mole, it has excellent heat resistance and has a saturated water absorption rate. A polyimide having a small linear expansion coefficient and a high relative moisture transmission rate, and more preferably a polyimide having a high tensile elastic modulus can be obtained.

In the polyimide of the present invention, as an example of the most excellent combination,
A tetracarboxylic acid dihydrate containing 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride in an amount of 50 mol% or more, preferably 60 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more. 0.5 to 30 mol%, preferably 1 to 20 mol%, more preferably 8 to 20 mol% of the anhydride and the tetrasubstituted diamine represented by a) in the general formula (1), and the remaining diamine A combination of p-phenylenediamine as a component is preferable because it can provide a polyimide film laminate having a high elastic modulus, a high moisture transmission rate, improved adhesion, and suppressed foam peeling.

In the polyimide of the present invention, in 100 mol% of the diamine component,
A) of the general formula (1) such as 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane A 4-substituted diamine represented by
1) By containing 0.5 to 30 mol%, preferably 1 to 20 mol%, more preferably 8 to 20 mol%, the linear expansion coefficient is small, the saturated water absorption is small, and the relative moisture transmission rate is large. A polyimide having excellent breaking stress, tensile modulus and elongation at break can be obtained,
2) Preferably 6 to 30 mol%, more preferably 6 to 20 mol%, further preferably 8 to 17 mol%, further preferably 9 to 17 mol%, particularly preferably 9 to 13 mol%, A polyimide having an extremely high relative moisture transmission rate, a low linear expansion coefficient, a low saturated water absorption rate, and an excellent breaking stress, tensile elastic modulus and breaking elongation can be obtained.

  As a polyamic acid solution composition that gives the polyimide film laminate of the present invention, the ratio of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride to pyromellitic dianhydride is aromatic tetracarboxylic acid dihydric acid. In the total amount of anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is 7.5 to 100 mol%, particularly 15 to 100 mol%, and pyromellitic dianhydride is 0 to 92.5 It is preferable that it is mol%, and among these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is particularly preferably used alone.

The polyamic acid solution that gives the polyimide of this invention is:
(A) a polyamic acid solution obtained by polymerizing tetracarboxylic dianhydride and a diamine other than the aromatic diamine represented by the general formula (1) in an organic solvent;
(B) A tetramic dianhydride and a polyamic acid solution obtained by polymerizing a diamine containing the aromatic diamine represented by the general formula (1) in an organic solvent are mixed and contained in the polyamic acid. In 100 mol% of the diamine, the aromatic diamine represented by the general formula (1) is 0.5 mol% to 30 mol%, preferably 1 mol% to 25 mol%, more preferably 8 mol% to 20 mol. % Or less polyamic acid solution can be obtained.

Moreover, the polyamic acid solution which gives the polyimide of this invention is
(C) an organic solvent containing tetracarboxylic dianhydride, an aromatic diamine represented by the general formula (1), and a diamine such as paraphenylene diamine excluding the aromatic diamine represented by the general formula (1) The polyamic acid solution copolymerized in (in 100 mol% of the diamine contained in the polyamic acid, the aromatic diamine represented by the general formula (1) is 0.5 mol% or more and 30 mol% or less, preferably 1 mol. % To 25 mol%, more preferably 8 mol% to 20 mol%).

In particular, as a polyamic acid solution that gives the polyimide of the present invention,
(A) Diamine components such as paraphenylene diamine except for acid dianhydride including 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and aromatic diamine represented by the general formula (1) And a polyamic acid solution obtained by polymerizing in an organic solvent,
(B) An acid dianhydride containing 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and a diamine component containing an aromatic diamine represented by the general formula (1) in an organic solvent By mixing with the polymerized polyamic acid solution, the aromatic diamine represented by the general formula (1) is 0.5 mol% or more and 30 mol% or less, preferably 100 mol% of the diamine contained in the polyamic acid, preferably A polyamic acid solution having a concentration of 1 mol% to 25 mol%, more preferably 8 mol% to 20 mol% can be obtained.

Moreover, as a polyamic acid solution that gives the polyimide of the present invention,
(C) Acid dianhydride including 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, aromatic diamine represented by the general formula (1), and fragrance represented by the general formula A polyamic acid solution obtained by copolymerizing a diamine such as paraphenylene diamine excluding an aromatic diamine in an organic solvent (0.5 mol of the aromatic diamine represented by the general formula in 100 mol% of the diamine contained in the polyamic acid) % To 30 mol%, preferably 1 mol% to 25 mol%, and more preferably 8 mol% to 20 mol%.

  As an organic polar solvent for producing a polyamic acid solution, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, Examples thereof include amides such as hexamethylsulfuramide, sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide, and sulfones such as dimethyl sulfone and diethyl sulfone. These solvents may be used alone or in combination.

  In carrying out the polymerization reaction of the polyamic acid solution, the concentration of all monomers in the organic polar solvent may be appropriately selected according to the coating method used and the purpose of production. For example, the polyamic acid solution is used in the organic polar solvent. The total monomer concentration is preferably 1 to 40% by mass, more preferably 3 to 35% by mass, and particularly preferably 5 to 30% by mass.

  As an example of production examples of (a) polyamic acid solution and (b) polyamic acid solution, or (c) polyamic acid solution, the polymerization reaction of the aromatic tetracarboxylic acid component and the aromatic diamine component is, for example, Substantially equimolar or either component (acid component or diamine component) is mixed slightly in excess, and the reaction is carried out at a reaction temperature of 100 ° C. or lower, preferably 80 ° C. or lower for about 0.2 to 60 hours. By carrying out, it can carry out and a polyamic acid (polyimide precursor) solution can be obtained.

  In carrying out the polymerization reaction of the polyamic acid (polyimide precursor) solution, the solution viscosity may be appropriately selected according to the purpose of use (coating, casting, spraying, etc.) and the purpose of production. The polyamic acid solution has a rotational viscosity measured at 30 ° C. of about 0.1 to 5000 poise, particularly 0.5 to 2000 poise, more preferably about 1 to 2000 poise. It is preferable from the viewpoint of workability in handling. Therefore, it is desirable to carry out the polymerization reaction to such an extent that the produced polyamic acid exhibits the above viscosity.

In addition, after mixing both components of (a) polyamic acid solution and (b) polyamic acid solution, dicarboxylic acid anhydride, such as phthalic anhydride and its substitution product (for example, (3-methyl or 4-methylphthalic anhydride), hexahydrophthalic anhydride and substituted products thereof, succinic anhydride and substituted products thereof, and the like, preferably phthalic anhydride may be added.
In any case, a copolymerized polyimide having a block bond or a random sequence is obtained in the process in which the polyamic acid is imidized by heating, resulting in cleavage-recombination of the polymer chains. In the process of heating and drying the cast product of the polyamic acid solution, once the viscosity has been increased by heating, further heating further reduces the viscosity to a low viscosity. A polyimide film made of a high molecular weight polyimide is obtained.

  (C) In order to seal the amine terminal of the polyamic acid in the polyamic acid solution, dicarboxylic acid anhydrides such as phthalic anhydride and its substitutes (eg 3-methyl or 4-methylphthalic anhydride), hexahydrophthalic anhydride An phthalic anhydride such as an acid and a substituted product thereof, a succinic anhydride and a substituted product thereof may be preferably added.

Further, for the purpose of limiting the gelation of the film, a phosphorus stabilizer such as triphenyl phosphite, triphenyl phosphate or the like is added at the time of polyamic acid polymerization or to a solid content (polymer) concentration in the polyamic acid solution. It can be added in the range of 01 to 1%.
For the purpose of promoting imidization, an imidizing agent can be added to the dope solution (polyamic acid solution). For example, imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, benzimidazole, isoquinoline, substituted pyridine and the like are 0.05 to 10% by mass, particularly preferably 0.1 to 2% by mass, based on the polyamic acid. Can be used in proportions. With these, imidization can be completed at a relatively low temperature.

Although there is no restriction | limiting in particular in the formation method of the polyimide layer in manufacture of a polyimide film laminated body, A polyamic acid solution is apply | coated (casting, spraying, coating, etc.) on metal foil, and it can imidize by drying and heat processing. It is advantageous. Also, as the imidization reaction, a polyamic acid solution is applied (casting, spraying, coating, etc.), dried, and further subjected to a heat treatment at 200 ° C. or higher, preferably 300 ° C. or higher, to obtain an imidization reaction. I do.
As an imidation reaction, any method can be used, but a layer containing a pre-dried uncured polyamic acid solution is allowed to stand for a certain period of time in a hot air drying furnace that can be set to a predetermined temperature, Alternatively, a method of performing heat treatment at a high temperature (200 ° C. or higher, preferably 300 ° C. or higher) by continuously moving within the drying furnace area range and securing a predetermined drying and curing time is common. In addition, in consideration of work efficiency, yield, etc., a batch processing method is applied in which a pre-dried uncured body is wound into a roll shape after applying a polyamic acid solution, and a thermal effect is further obtained at a high temperature. Is also possible. In the batch processing method, it is preferable to perform heat treatment at a high temperature (200 ° C. or higher) under reduced pressure and reduced pressure in a reducing gas atmosphere for the purpose of preventing the conductor from being oxidized. In the drying and curing step, the polyamic acid solution is uniformly applied on the metal foil, then the solvent is removed by heat treatment, and the imide is ring-closed. At this time, if the heat treatment is suddenly performed at a high temperature, a skin layer may be formed on the resin surface, and the solvent may not easily evaporate or foam, so the heat treatment may be performed while gradually raising the temperature from a low temperature to a high temperature. preferable. The maximum heat treatment temperature for this heat drying is preferably in the range of 350-600 ° C.

  Usually, after applying a polyamic acid solution on a metal foil and drying the solvent, the imidization reaction proceeds by applying a heat treatment at a higher temperature. In this case, amines such as pyridine and quinoline and acetic anhydride are used. Etc. can be added to promote the imidization reaction.

  In order to control warpage or the like in the laminate of the present invention, a polyimide resin layer having a relatively high thermal expansion property contacting the metal foil may be provided between the metal foil and the polyimide film layer of the present invention.

When showing an example of a production example of a laminate,
1) A diamine component and tetracarboxylic dianhydride are polymerized in an organic solvent to prepare a polyamic acid solution (which may be partially imidized as long as a uniform solution state is maintained). , If necessary, mixing two or more polyimic acids, if necessary, compounding phosphorus stabilizers and imidizing agents,
2) A polyamic acid solution can be produced by applying a film on a metal thin film and drying, imidizing, and heat drying (curing).

In the polyimide film laminate, it is preferable that the polyimide layer after removing the metal layer has at least one of the following characteristics.
1) The tensile modulus is preferably 4 GPa or more, more preferably 5 to 10 GPa, more preferably 6 to 9 GPa, and particularly preferably 6 to 8.5 GPa.
2) The breaking strength is 200 MPa or more, particularly 200 to 500 MPa.
3) The linear expansion coefficient (100 to 250 ° C.) is 1 × 10 ^{−5 to} 3 × 10 ⁻⁵ cm / cm / ° C., particularly 1 × 10 ^{−5 to} 2.5 × 10 ⁻⁵ cm / cm / ° C. .

When the polyimide used for this invention manufactures a polyimide film independently, it is preferable to have at least one of the following characteristics.
1) The saturated water absorption is 3% or less, and further 1.3 to 3%.
2) The relative moisture transmission rate is 3 or more, further 4 or more at a thickness of 25 μm.
3) The tensile elastic modulus is 400 kg / mm ² or more, further 400 kg / mm ² or more and less than 900 kg / mm ² , particularly 470 kg / mm ² or more and less than 900 kg / mm ² .
4) The linear expansion coefficient (25 μm thickness) is 10 to 40 × 10 ⁻⁶ cm / cm / ° C., more preferably 12 to 30 × 10 ⁻⁶ cm / cm / ° C., and particularly 12 to 25 × 10 ⁻⁶ cm / cm / ° C. Must be in ° C.

  When etching to process the polyimide film laminate of the present invention, the etching solution is preferably an aqueous alkali solution, preferably an aqueous alkali metal solution or a mixed solution containing the same. As the alkali, potassium hydroxide is preferred because etching is most efficient, but in addition, sodium hydroxide and lithium hydroxide can be used, and alkaline earth metal hydroxides can also be used. From the viewpoint of sex, potassium, sodium or a mixture thereof is preferred. Furthermore, in order to increase the affinity with polyimide, the alkali metal aqueous solution may contain primary amines such as ethanolamine, propanolamine and butanolamine, and secondary amines such as diethylamine and dipropanolamine. It is also advantageous to contain an alcoholic or organic solvent such as oxyalkylamine, hydrazine monohydrate, ethylenediamine, dimethylamine, dimethylformamide, cresol, ethylene glycol. The solvent is not limited to the organic solvent as long as it has a high affinity with the polyimide resin.

In the case of an alkali metal hydroxide, the concentration of the alkali aqueous solution is preferably 30 to 70% by mass of the alkali metal hydroxide with respect to the total of water and the alkali metal hydroxide, and the etching temperature range is temperature. Is higher, the etching rate is higher, preferably 50 ° C. or higher.

In the polyimide film laminate of the present invention, another substrate such as a metal layer can be laminated directly or via an adhesive on the polyimide layer.
In this invention, a silane coupling agent such as 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane is used for the purpose of improving the adhesive strength and mechanical strength of the polyimide film. , 3-glycidylpropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, etc., in the polyamic acid polymerization, 0.01 to 10% with respect to the solid content (polymer) concentration, especially Preferably it can add in the ratio of 0.1-5 mass%.

The second polyimide film laminate of the present invention can be obtained by laminating a substrate such as a metal layer, preferably a metal layer such as a copper layer, directly or via an adhesive on the polyimide surface layer.
The base material such as the metal layer can be formed by laminating metal foils by a laminating method or by using a thin film forming method and an electroplating method. Moreover, as a method of laminating the metal thin film and the copper layer for forming the copper plating layer using the thin film deposition method and the electroplating method, all methods known per se can be adopted.

In the above laminating method, a laminate can be obtained by providing an adhesive layer such as a heat-resistant adhesive on the polyimide layer, and further superposing a base material such as a metal foil, and heating and pressing.
The heat-resistant adhesive is not particularly limited as long as it is a heat-resistant adhesive used in the electronic field. For example, a polyimide-based adhesive, an epoxy-modified polyimide-based adhesive, a phenol resin-modified epoxy resin adhesive. , Epoxy-modified acrylic resin-based adhesives, epoxy-modified polyamide-based adhesives, and the like. This heat-resistant adhesive layer can be provided by any method used in the electronic field itself. For example, an adhesive solution may be applied to the polyimide layer or laminate and dried, or formed separately. It may be laminated with a film adhesive.

  A metal layer can be used as the substrate, and the metal layer can be a single metal or an alloy, for example, copper, aluminum, gold, silver, nickel, stainless steel metal foil, metal plating layer (preferably a deposited metal underlayer- Many known techniques such as a metal plating layer or a chemical metal plating layer can be applied), and a rolled copper foil, an electrolytic copper foil and the like are preferable. The thickness of the metal foil is not particularly limited, but is preferably 0.1 μm to 10 mm, particularly 1 to 18 μm.

  When an ultrathin copper foil having a thickness of 1 to 10 μm is used as a substrate, a copper foil with a carrier having good handleability can be suitably used. Although there is no restriction | limiting in particular as a carrier layer of copper foil with a carrier, Rolled copper foil and electrolytic copper foil with a thickness of 5 micrometers-150 micrometers are preferable. The carrier layer is preferably easily and mechanically peelable from the ultrathin copper foil, and preferably has a peel strength of 0.01 to 0.3 Kg / cm.

The laminate has improved adhesiveness and moisture permeation rate while maintaining characteristics such as heat resistance, high elastic modulus, and low linear expansion coefficient, and foaming and peeling at the adhesion interface due to a high-temperature treatment process hardly occur.
For example, ceramics, glass substrates, silicon wafers, the same or different metals, or polyimide films may be further bonded to the laminate by a heat resistant adhesive.

  This invention is excellent in gas permeation rate and moisture permeation rate, has a low expansion coefficient, and has a polyimide layer having excellent mechanical properties. A polyimide film laminate in which foaming / peeling in a high-temperature process is suppressed can be provided.

  The first and second laminates of the present invention can be suitably used as an electronic component substrate. For example, it can be suitably used as a printed circuit board, a power circuit board, a flexible heater, a resistor board, a heat sink, a thermal response element, and a hard disk suspension.

  Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited by the following examples.

(Synthesis example 1 of raw material dope)
N, N-dimethylacetamide (DMAc) was added to the reaction vessel, paraphenylenediamine (PPD) was added under stirring and nitrogen flow, and the mixture was kept at 50 ° C. and completely dissolved. To this solution, gradually add 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) in an equimolar amount of the diamine component and the dicarboxylic acid component while paying attention to heat generation. The reaction was continued for 3 hours while maintaining the temperature at 50 ° C. to obtain a polyamic acid solution having a monomer concentration of 18% by mass (yellow viscous liquid, solution viscosity at 25 ° C. was about 1000 poise). This solution is referred to as the first liquid.

(Synthesis example 2 of raw material dope)
The same reaction as in Synthesis Example 1 was conducted except that 3,3′-dicarboxy-4,4′-diaminodiphenylmethane (MBAA) was added in place of PPD, and a polyamic acid solution (a light 18% by weight monomer concentration) was obtained. A brown viscous liquid having a solution viscosity of about 500 poise at 25 ° C. was obtained. This solution is referred to as the second liquid.

(Synthesis example 3 of raw material dope)
A polyamic acid solution having a monomer concentration of 18% by mass was prepared by performing the same reaction as in Synthesis Example 1 except that 4,4′-methylene-bis (2,6-dimethylaniline) (MDX) was added instead of PPD. A light brown viscous liquid having a solution viscosity of about 1000 poise at 25 ° C. was obtained. This solution is referred to as the third liquid.

(Synthesis example 4 of raw material dope)
A polyamic acid solution (dark red color) having a monomer concentration of 18% by mass was prepared in the same manner as in Synthesis Example 1 except that 4,4′-methylene-bis (2-methylaniline) (MDT) was added instead of PPD. A viscous liquid, a solution viscosity at 25 ° C. of about 1000 poise) was obtained. This solution is referred to as the fourth liquid.

(Synthesis example 5 of raw material dope)
The same reaction as in Synthesis Example 1 was performed except that 3,3′-dimethoxy-4,4′-diaminobiphenyl (DANS) was added instead of PPD, and a polyamic acid solution (light blackish brown having a monomer concentration of 18% by mass) was obtained. A viscous liquid having a solution viscosity at 25 ° C. of about 1500 poise) was obtained. This solution is referred to as the fifth solution.

(Synthesis Example 6 of raw material dope)
A polyamic acid solution (light brown) having a monomer concentration of 18% by mass was prepared in the same manner as in Synthesis Example 1 except that 3,3′-dimethyl-4,4′-diaminobiphenyl (TB) was added instead of PPD. A viscous liquid, a solution viscosity at 25 ° C. of about 800 poise) was obtained. This solution is referred to as the sixth liquid.

(Synthesis example 7 of raw material dope)
The same reaction as in Synthesis Example 1 was conducted except that pyromellitic dianhydride (PMDA) instead of BPDA and 4,4′-diaminodiphenyl ether (ODA) were added instead of PPD. An 18 mass% polyamic acid solution (light yellow viscous liquid, solution viscosity at 25 ° C. was about 600 poise) was obtained. This solution is referred to as the seventh solution.

(Measurement method)
1. Measurement of elastic modulus and breaking strength of polyimide film obtained after etching:
A test piece punched into a 4 mm width dumbbell was measured according to ASTM D882 using TENSILONUTM-II-20 manufactured by Orientec Corporation. The measurement conditions were 30 mm between chucks, 2 mm / min pulling speed, 23 ° C. temperature and 55% humidity. The measurement is performed on 5 samples, and the measurement result is an average value of 5 samples.
2. Measurement of 180 ° peel strength:
In accordance with JIS C6471, the peel strength in the 180 ° direction was measured under the condition of a tensile speed of 40 mm / min using TENSILONUTM-II-20 manufactured by Orientec.
3. Measurement of linear expansion coefficient:
Using a TMA-50 manufactured by Shimadzu Corporation, a linear expansion coefficient of 100 to 250 ° C. was measured at an initial load of 5 g and a heating rate of 5 ° C./min.
4). Measurement of solution viscosity:
Measured at 25 ° C using an E-type rotational viscometer (VISCOMETERTOKIMEC).
5. Observation of “foaming and peeling” of the laminate:
The appearance of the obtained laminate was visually observed to determine whether foaming or peeling was observed.

  In the following examples and comparative examples, the polyamic acid solution was applied to the rough surface side of the copper foil.

(Examples 1-5)
The ratio (molar ratio) between the molar amount of the diamine contained in the first liquid and the molar amount of the diamine contained in the second to sixth liquids is 90 mol%: 10. A solution in which 1,2-dimethylimidazole was added in an amount of 2% by weight with respect to polyamic acid was mixed with copper foil (manufactured by Nippon Electrolytic Co., Ltd .: SLP copper foil, thickness 18 μm). ) After coating to a final film thickness of about 25 μm and heating at 135 ° C. for 3 minutes to form a solidified film, fixing to a stainless steel frame and heating at 130 ° C. for 3 minutes and 180 ° C. for 1 minute The temperature was raised to 450 ° C. over 5 minutes, and the temperature was maintained at 450 ° C. for 2 minutes for heat treatment to obtain a polyimide copper foil laminate. Foaming, peeling and the like were not observed in the obtained laminate. The 180 ° peel strength at the interface of this laminate was measured to evaluate the adhesive strength. Furthermore, the elastic modulus and breaking strength of the polyimide film obtained after etching the copper foil of the laminate with 40% ferric chloride aqueous solution were measured. The results are shown in Table 1.

(Comparative Example 1)
A polyimide copper foil laminate was obtained in the same manner as in Example 1 except that only the first liquid was used. Foaming and peeling were observed in a wide range, and a homogeneous laminate was not obtained. The 180 ° peel strength at a partial interface where adhesion of the laminate was observed was measured to evaluate the adhesive strength. Furthermore, the elastic modulus and breaking strength of the polyimide film obtained after etching the copper foil of the laminate with 40% ferric chloride aqueous solution were measured. The results are shown in Table 1.

(Comparative Example 2)
The first liquid and the seventh liquid are such that the ratio (molar ratio) between the molar amount of the diamine contained in the first liquid and the molar amount of the diamine contained in the seventh liquid is 50 mol%: 50 mol%. A polyimide copper foil laminate was obtained in the same manner as in Example 1 except that the mixture was used at a ratio. Foaming and peeling were observed in part, and a homogeneous laminate was not obtained. The 180 ° peel strength at a partial interface where adhesion of the laminate was observed was measured to evaluate the adhesive strength. Furthermore, the elastic modulus and breaking strength of the polyimide film obtained after etching the copper foil of the laminate with 40% ferric chloride aqueous solution were measured. The results are shown in Table 1.

(Examples 6 to 9, Comparative Example 3)
The first liquid and the third liquid are mixed so that the ratio (molar ratio) between the molar amount of the diamine contained in the first liquid and the molar amount of the diamine contained in the third liquid is the ratio shown in Table 2. Further, a solution in which 2% by weight of 1,2-dimethylimidazole was added to the polyamic acid was applied on a copper foil (SLP thickness 18 μm, manufactured by Nihon Electrolytic Co., Ltd.) so as to have a final film thickness of 25 μm. In the same manner as in Example 1, a polyimide copper foil laminate was obtained. Foaming, peeling and the like were not observed in the obtained laminate. The 180 ° peel strength at the interface of this laminate was measured to evaluate the adhesive strength. Furthermore, the elastic modulus and breaking strength of the polyimide film obtained after etching the copper foil of the laminate with 40% ferric chloride aqueous solution were measured. The results are shown in Table 2.

(Example 10)
A polyimide copper foil laminate was obtained in the same manner as in Example 2 except that the final film thickness was 15 μm. Foaming, peeling and the like were not observed in the obtained laminate. The results are shown in Table 2.

(Example 11)
A polyimide copper foil laminate was obtained in the same manner as in Example 2 except that USLPR2 (Nippon Electrolytic Co., Ltd., thickness 9 μm) was used as the copper foil. Foaming, peeling and the like were not observed in the obtained laminate. The results are shown in Table 3.

(Example 12)
A polyimide copper foil laminate was obtained in the same manner as in Example 2 except that 3EC-VLP (Mitsui Metal Mining Co., Ltd., thickness 9 μm) was used as the copper foil. Foaming, peeling and the like were not observed in the obtained laminate. The results are shown in Table 3.

(Example 13)
A polyimide copper foil laminate was obtained in the same manner as in Example 2 except that USLPR2 (Nippon Electrolytic Co., Ltd., thickness 12 μm) was used as the copper foil. Foaming, peeling and the like were not observed in the obtained laminate. The results are shown in Table 3.

(Example 14)
A polyimide copper foil laminate was obtained in the same manner as in Example 2 except that HLA2 (Nippon Electrolytic Co., Ltd., thickness 12 μm) was used as the copper foil. Foaming, peeling and the like were not observed in the obtained laminate. The results are shown in Table 3.

(Example 15)
A polyimide copper foil laminate was obtained in the same manner as in Example 2 except that F2WS (thickness 12 μm, manufactured by Furukawa Sakit Foil Co., Ltd.) was used as the copper foil. Foaming, peeling and the like were not observed in the obtained laminate. The results are shown in Table 3.

(Example 16)
A polyimide copper foil laminate was obtained in the same manner as in Example 2 except that YSNAP-1B (manufactured by Nippon Electrolytic Co., Ltd., carrier layer thickness 18 μm, copper foil thickness 1 μm) was used as the copper foil. By peeling off the carrier layer, a laminate having a metal layer of 1 μm and a polyimide layer of 25 μm was obtained. No foaming or peeling was observed in the laminate.

(Example 17)
A polyimide copper foil laminate was obtained in the same manner as in Example 2 except that YSNAP-3B (carrier layer thickness 18 μm, copper foil thickness 3 μm, manufactured by Nippon Electrolytic Co., Ltd.) was used as the copper foil. By peeling off the carrier layer, a laminate having a metal layer of 3 μm and a polyimide layer of 25 μm was obtained. No foaming or peeling was observed in the laminate.

(Example 18)
A polyimide copper foil laminate was obtained in the same manner as in Example 2 except that XTF-1 (Carrier layer thickness 35 μm, copper foil thickness 1 μm, manufactured by Nippon Olympus Co., Ltd.) was used as the copper foil. By peeling off the carrier layer, a laminate having a metal layer of 1 μm and a polyimide layer of 25 μm was obtained. No foaming or peeling was observed in the laminate.

(Example 19)
A polyimide copper foil laminate was obtained in the same manner as in Example 2, except that XTF-3 (Carrier layer thickness 35 μm, copper foil thickness 3 μm, manufactured by Nippon Olympus Co., Ltd.) was used as the copper foil. By peeling off the carrier layer, a laminate having a metal layer of 3 μm and a polyimide layer of 25 μm was obtained. No foaming or peeling was observed in the laminate.

(Example 20)
The first liquid and the third liquid are such that the ratio (molar ratio) between the molar amount of the diamine contained in the first liquid and the molar amount of the diamine contained in the third liquid is 590 mol%: 10 mol%. In addition, 1,2-dimethylimidazole was added at 2% by weight with respect to the polyamic acid, and N-phenyl-3-aminopropyltrimethoxysilane was added at 1% by weight with respect to the polyamic acid. did. This solution was applied onto a copper foil (SLP thickness 18 μm, manufactured by Nippon Electrolytic Co., Ltd.) so as to have a final film thickness of 25 μm, and a polyimide copper foil laminate was obtained in the same manner as in Example 1. Foaming, peeling and the like were not observed in the obtained laminate.
The 180 ° peel strength at the interface of this laminate was measured to evaluate the adhesive strength. Furthermore, the elastic modulus and breaking strength of the polyimide film obtained after etching the copper foil of the laminate with 40% ferric chloride aqueous solution were measured. The results are shown in Table 4.

(Example 21)
A polyimide copper foil laminate was obtained in the same manner as in Example 20, except that N-phenyl-3-aminopropyltrimethoxysilane was added to 3 wt% with respect to the polyamic acid. Foaming, peeling and the like were not observed in the obtained laminate. The results are shown in Table 4.

(Example 22)
A polyimide copper foil laminate was obtained in the same manner as in Example 20 except that N-phenyl-3-aminopropyltrimethoxysilane was added to 5 wt% with respect to the polyamic acid. Foaming, peeling and the like were not observed in the obtained laminate. The results are shown in Table 4.

(Example 23)
The first liquid and the third liquid are such that the ratio (molar ratio) between the molar amount of the diamine contained in the first liquid and the molar amount of the diamine contained in the third liquid is 90 mol%: 10 mol%. Further, 3-mercaptopropyltrimethoxysilane was added at 1% by weight with respect to the polyamic acid, and 1,2-dimethylimidazole was added at 2% by weight with respect to the polyamic acid. This solution was applied onto a copper foil (SLP thickness 18 μm, manufactured by Nippon Electrolytic Co., Ltd.) so as to have a final film thickness of 25 μm, and a polyimide copper foil laminate was obtained in the same manner as in Example 1. Foaming, peeling and the like were not observed in the obtained laminate. The 180 ° peel strength at the interface of this laminate was measured to evaluate the adhesive strength. Furthermore, the elastic modulus, breaking strength, and breaking elongation of the polyimide film obtained after etching the copper foil of the laminate with 40% ferric chloride aqueous solution were measured. The results are shown in Table 4.

(Example 24)
A polyimide copper foil laminate was obtained in the same manner as in Example 23, except that 3-mercaptopropyltrimethoxysilane was added to 3 wt% with respect to the polyamic acid. Foaming, peeling and the like were not observed in the obtained laminate. The results are shown in Table 4.

(Example 25)
A polyimide copper foil laminate was obtained in the same manner as in Example 23, except that 3-mercaptopropyltrimethoxysilane was added to 5% by weight with respect to the polyamic acid. Foaming, peeling and the like were not observed in the obtained laminate. The results are shown in Table 4.

About the laminated board obtained in Examples 1-25 and Comparative Examples 1-2, the presence or absence of generation | occurrence | production of foaming and peeling in the adhesion interface by a high-temperature treatment process was evaluated by the following evaluation method.
Evaluation method: The obtained laminate was immersed in pure water at 23 ° C. for 24 hours, wiped off the adhered water, and then immersed in a solder bath at 280 ° C. for 10 seconds. The results were as follows.
-Foaming and peeling were observed: Comparative Example 1 and Comparative Example 2.
-No foaming was observed: Examples 1 to 10, Examples 12 to 25.

(Reference Examples 1 to 10)
The first liquid and the third liquid are mixed at a ratio shown in Table 5 and applied onto a glass substrate so as to have a final film thickness of 25 μm and 50 μm, and at 135 ° C. for 3 minutes (final film thickness 25 μm) or 5 minutes (final) (Film thickness 50 μm) Heated to form a solidified film, peeled off from the glass substrate, and then attached to a pin tenter and heated at 130 ° C. for 5 minutes, 180 ° C. for 5 minutes, 210 ° C. for 5 minutes, and 320 ° C. for 2 minutes Then, the temperature was raised to 450 ° C. in 5 minutes, and the polyimide film was obtained by heat-treating at 450 ° C. for 2 minutes.
Saturated water absorption, relative moisture transmission rate, linear expansion coefficient and mechanical properties (breaking stress, tensile elastic modulus, breaking elongation) of the obtained polyimide film were measured, and the results are shown in Table 5.

(Evaluation of polyimide film characteristics obtained in Reference Examples 1 to 10)
1) Saturated water absorption (%): The polyimide film was dried to a constant weight in a dry nitrogen atmosphere, the film weight at the time of drying was measured, and then immersed in pure water at 23 ° C. for 24 hours. After wiping off, the film weight at the time of water absorption was measured, and the saturated water absorption was calculated according to the formula (1).

2) Relative moisture permeation rate: The obtained polyimide film was dried to a constant weight in a dry nitrogen atmosphere, and the film weight at the time of drying was measured. Thereafter, the dried polyimide film was measured at a temperature of 27 ° C. and a humidity of 55% RH. The change in weight was traced for 1 hour in the atmosphere, the initial weight increase rate (the slope of the weight change curve) was taken as the moisture transmission rate, and the relative value with the moisture transmission rate of the 50 μ film in Comparative Example 2 as 1 was measured as relative permeability. The wet speed was used.

3) Linear expansion coefficient: measured using TMA-50 in the range of 5 ° C / min and 100 ° C to 250 ° C.

4) Mechanical properties (breaking stress, tensile modulus, breaking elongation): Measured according to ASTM D882 using a polyimide film with a film thickness of 25 μm. The measurement conditions were performed using TENSILON in an environment of a pulling speed of 2 mm / min, a temperature of 23 ° C., and a humidity of 55%. The measurement is performed on 5 samples, and the measurement result is an average value of 5 samples.

5) Glass transition temperature: Dynamic viscoelasticity was measured in the range of room temperature to 500 ° C. using a dynamic viscoelasticity measuring device RSAIII.

Claims (11)

A polyamic acid solution obtained from a tetracarboxylic dianhydride component and a diamine component containing 0.5 to 30 mol% of a diamine represented by the following general formula (1) in 100 mol% of a diamine is formed on a metal foil as a film. The polyimide film laminate is characterized in that the polyimide layer and the metal layer are directly laminated by applying in the shape of a liquid, volatilizing the solvent and imidizing the polyamic acid.

(However, in the formula (1), A is a direct bond or a bridging _group, R 1 to R ₄ is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, hydroxyl group, carboxyl group, 1 to 6 carbon atoms And at least one of R ₁ and R ₂ is not a hydrogen atom, and at least one of R ₃ and R ₄ is not a hydrogen atom.) The diamine of the general formula (1) is characterized in that A in the formula is a direct bond or a crosslinking group, and R _{1 to} R ₄ represent a substituent selected from a hydrocarbon group having 1 to 6 carbon atoms. The polyimide film laminate according to claim 1.   The polyimide film laminate according to claim 1 or 2, wherein the diamine component contains paraphenylenediamine.   The polyimide film laminate according to any one of claims 1 to 3, wherein the tetracarboxylic dianhydride component includes 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. .   The polyimide film laminate according to any one of claims 1 to 4, wherein the elastic modulus of the polyimide film after removing the metal foil is 4 GPa or more and less than 9 GPa.   The polyimide film laminate according to any one of claims 1 to 5, wherein the polyamic acid solution further contains a silane coupling agent comprising an alkoxysilane compound.   The polyimide film laminate according to any one of claims 1 to 6, wherein the metal foil is a copper foil.   The polyimide film laminate according to any one of claims 1 to 6, wherein the metal foil is a copper foil having a thickness of 1 to 10 µm having a peelable carrier layer.   The polyimide film laminated body which has a copper layer with a thickness of 1-10 micrometers obtained by peeling a carrier layer from the polyimide film laminated body of Claim 8.   The polyimide film laminated body by which the base material is laminated | stacked directly or via the heat resistant adhesive on the polyimide layer of the polyimide film laminated body of any one of Claims 1-9. The polyimide film laminate according to claim 10, wherein the substrate is a metal layer.