KR20210116311A - Polyimide, crosslinked polyimide, adhesive film, laminate, coverlay film, copper foil with resin, metal-clad laminate, circuit board and multilayer circuit board - Google Patents

Abstract

The present invention relates to an adhesive film using a polyimide based on a dimeric diamine, having improved dielectric properties and providing effectively reduced transmission loss of high-frequency signals. The present invention provides a polyimide satisfying the following conditions of: a) a content of diamine residues derived from a dimeric diamine composition containing a dimeric diamine as a main ingredient of 60 mmol% or more, based on the total diamine residues; b1) a content of carbon atoms derived from 6-membered aromatic rings (except carbon atoms of 6-membered aromatic rings derived from the dimeric diamine composition) of 12-40 wt% based on the total content of the atoms in the polyimide; b2) a content of diamine residues derived from a diamine compound represented by chemical formula (A1) of 5-40 mol% based on the total diamine residues (wherein each of Y and Z in chemical formula (A1) independently represents a C1-C6 alkyl group, or the like, the linking group X represents a divalent group selected from -O-, -C(CH_3)_2-, or the like, and m represents an integer of 1-4); and c) a weight average molecular weight of 5,000-200,000.

Description

Polyimide, crosslinked polyimide, adhesive film, laminate, coverlay film, copper foil with resin, metal clad laminate, circuit board and multilayer circuit board {POLYIMIDE, CROSSLINKED POLYIMIDE, ADHESIVE FILM, LAMINATE, COVERLAY FILM, COPPER FOIL WITH RESIN, METAL-CLAD LAMINATE, CIRCUIT BOARD AND MULTILAYER CIRCUIT BOARD}

The present invention relates to a polyimide useful as a material for an electronic component, a crosslinked polyimide using the same, an adhesive film, a laminate, a coverlay film, a copper foil provided with a resin, a metal clad laminate, a circuit board, and a multilayer circuit board .

In recent years, with the progress of miniaturization, weight reduction, and space saving of electronic devices, the demand for flexible printed circuits (FPCs) that are thin, light, flexible, and have excellent durability even after repeated bending is increasing. have. Since FPC enables three-dimensional and high-density mounting even in a limited space, its use is expanding to wiring of movable parts of electronic devices such as HDDs, DVDs, and smartphones, and parts such as cables and connectors.

As one aspect of FPC, a circuit pattern is formed on a polyimide film excellent in heat resistance and flexibility, and a structure in which a coverlay film having an adhesive layer is bonded to the surface thereof is mentioned. Polyimide is used as a material of the adhesive layer of the coverlay film of such a structure. For example, a crosslinked polyimide obtained by reacting a polyimide using a diamine compound derived from dimer acid as a raw material with an amino compound having at least two primary amino groups as functional groups is applied to the adhesive layer of the coverlay film. is proposed (for example, Patent Document 1).

Further, it is a metal-clad laminate as a material for circuit boards such as FPC, and a three-layer metal-clad laminate in which a metal layer to be subjected to wiring and an insulating resin layer are adhered through an adhesive layer. It is proposed to apply a polyimide containing a predetermined amount or more of a diamine residue derived from dimer diamine in which a carboxylic acid group is substituted with a primary aminomethyl group or an amino group (for example, Patent Document 2).

By the way, in addition to the above-mentioned densification, it is necessary to cope with the increase in the frequency of the transmission signal because the performance of the equipment has progressed. When a high-frequency signal is transmitted, if the transmission loss in the transmission path is large, problems such as loss of an electrical signal and a long delay time of the signal occur. Therefore, reduction of transmission loss becomes important also in FPC from now on. For this reason, in a circuit board provided with a polyimide insulating layer, a circuit wiring layer laminated on at least one surface thereof, and a coverlay film laminated on the circuit wiring layer, the thickness, dielectric constant and dielectric constant of the polyimide insulating layer and the coverlay film Considering the relationship of tangents has been proposed (for example, Patent Document 3).

Japanese Patent Laid-Open No. 2013-1730 Japanese Patent Laid-Open No. 2018-140544 Japanese Patent Laid-Open No. 2016-192531

As in Patent Documents 1 and 2, the adhesive layer using polyimide using dimer diamine as a raw material exhibits excellent adhesion, low dielectric constant, and dielectric loss tangent. Improvement is required.

Accordingly, it is an object of the present invention to further improve the dielectric properties of an adhesive layer using polyimide using dimer diamine as a raw material, and to more effectively reduce transmission loss of high-frequency signals.

As a result of diligent research, the present inventors have found that the dielectric properties of polyimides can be improved by controlling the amount of aromatic rings contained in a polyimide using dimer diamine as a raw material, or making it a copolymer composition of dimer diamine and diamine having a specific structure. It was found that the present invention was completed.

The polyimide of the present invention is a polyimide containing a tetracarboxylic acid residue derived from a tetracarboxylic acid anhydride component and a diamine residue derived from a diamine component. The polyimide of the present invention is characterized in that the following conditions a, b1 and c, or conditions a, b2 and c are satisfied.

a) 60 mol% or more of diamine residues derived from a dimer diamine composition containing dimer diamine as a main component in which two terminal carboxylic acid groups of dimer acid are substituted with primary aminomethyl groups or amino groups with respect to all diamine residues .

b1) The content of carbon atoms derived from the 6-membered aromatic ring (excluding the carbon atoms of the 6-membered aromatic ring derived from the dimer diamine composition) with respect to the total content of all atoms in the polyimide is within the range of 12 to 40 wt% .

b2) Containing the diamine residue derived from the diamine compound represented by the following general formula (A1) with respect to all the diamine residues within the range of 5 mol% or more and 40 mol% or less.

In the general formula (A1), Y and Z each independently represent an alkyl group, alkoxy group, alkenyl group or alkynyl group having 1 to 6 carbon atoms, and the linking group X is -O-, -S-, -CO-, -SO- , -SO ₂ -, -COO-, -CH ₂ -, -CH ₂ -O-, -C(CH ₃ ) ₂ -, -NH- or -CONH- represents a divalent group selected from, m is 1 to Represents an integer of 4. However, when several linking groups X are included in a molecule|numerator, it may be same or different.

c) a weight average molecular weight in the range of 5,000 to 200,000;

The polyimide of the present invention may further satisfy the following condition d when the above conditions a, b1 and c are satisfied.

d) the following formula (i),

CM value = (C/Mw) × 10 ⁴ ... (i)

[Wherein, C means the weight content of carbon atoms derived from the 6-membered aromatic ring (excluding the carbon atoms of the 6-membered aromatic ring derived from the dimer diamine composition) with respect to the total content of all atoms in the polyimide, and Mw is It means the weight average molecular weight of polyimide]

The CM value, which is an index indicating the amount of the 6-membered aromatic ring contained in the polyimide, calculated based on , is in the range of 3 to 38.

The polyimide of the present invention may further satisfy the following condition e when the above conditions a, b1 and c are satisfied.

e) The content of carbon atoms derived from the 6-membered aromatic ring (excluding the carbon atoms of the 6-membered aromatic ring derived from the dimer diamine composition) with respect to the total content of all atoms in all the diamine components of the raw material exceeds 0 and is 32% by weight Within the following ranges.

The polyimide of the present invention may further satisfy the following condition f when the above conditions a, b1 and c are satisfied.

f) the formula (ii),

DM value = (D/Mw) × 10 ⁴ ... (ii)

[Wherein, D means the weight content of carbon atoms derived from the 6-membered aromatic ring (excluding the carbon atoms of the 6-membered aromatic ring derived from the dimer diamine composition) with respect to the total content of all atoms in the total diamine residues, Mw means the weight average molecular weight of polyimide]

DM value which is an index|index which shows the quantity of the 6-membered aromatic ring derived from the diamine component contained in a polyimide computed based on 0 exceeds 0, and exists in 32 or less range.

The polyimide of the present invention, when the above conditions a, b1 and c are satisfied, with respect to the total amount of the diamine residues,

You may contain the diamine residue derived from the said dimer diamine composition within the range of 60 mol% or more and 99 mol% or less. In this case, you may contain the diamine residue induced|guided|derived from the at least 1 sort(s) of diamine compound chosen from the diamine compound represented by the following general formula (B1) - (B7) within the range of 1 mol% or more and 40 mol% or less.

In formulas (B1) to (B7), R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms, and the linking group A is independently -O-, -S-, -CO-, -SO- , -SO ₂ -, -COO-, -CH ₂ -, -C(CH ₃ ) ₂ -, -NH- or -CONH- represents a divalent group selected from, n ₁ is independently an integer of 0 to 4 indicates. However, the thing which overlaps with Formula (B2) in Formula (B3) shall be excluded, and shall exclude the thing which overlaps with Formula (B4) in Formula (B5).

The polyimide of the present invention, with respect to the total amount of the acid anhydride residue,

You may contain 90 mol% or more of tetracarboxylic-acid residues derived from the tetracarboxylic-acid anhydride represented by following General formula (2) and/or (3) in total.

In the general formula (2), X ₁ represents a single bond or a divalent group selected from the following formulae, and in the general formula (3), _{the cyclic moiety represented by Y 1} is a 4-membered ring, a 5-membered ring, a 6-membered ring, or 7 It represents that a cyclic saturated hydrocarbon group selected from a membered ring or an 8 membered ring is formed.

In the above formula, Z ₁ represents -C ₆ H ₄ -, -(CH ₂ ) _m1 - or -CH ₂ -CH(-OC(=O)-CH ₃ )-CH ₂ -, but m1 is 1 An integer of -20 is represented.

When the polyimide of the present invention satisfies the above conditions a, b2 and c, the group X ₁ in the general formula (2) is -CO- with respect to all the tetracarboxylic acid residues, benzophenonetetracarboxylic dianhydride The tetracarboxylic acid residue derived from water may be contained within the range of 10 mol% or more and 90 mol% or less, and the tetracarboxylic acid anhydride represented by the general formulas (2) and/or (3) (provided that the above You may contain 10 mol% or more of at least 1 sort(s) of the tetracarboxylic-acid residue derived from benzophenonetetracarboxylic dianhydride).

In the crosslinked polyimide of the present invention, the polyimide contains a ketone group in a molecule,

The ketone group and the amino group of the amino compound having at least two primary amino groups as functional groups form a crosslinked structure by a C=N bond.

The adhesive film of this invention contains the said polyimide or the said crosslinked polyimide.

The adhesive film of the present invention, when the polyimide satisfies the above a, b1 and c, after 24 hours of humidity control under constant temperature and humidity conditions (states) of 23 ° C. and 50% RH, split post dielectric resonator (SPDR) The measured dielectric loss tangent (Tanδ ₁ ) at 10 GHz may be 0.005 or less, and the relative dielectric constant (E ₁ ) may be 3.0 or less.

The adhesive film of the present invention, when the polyimide satisfies the above conditions a, b1 and c, is subjected to a split post dielectric resonator (SPDR) after 24 hours of humidity control under constant temperature and humidity conditions (states) of 23° C. and 50% RH. The dielectric loss tangent (Tanδ ₂ ) at 20 GHz measured by 0.005 or less and the relative dielectric constant (E ₂ ) may be 3.0 or less.

The adhesive film of the present invention, when the polyimide satisfies the above conditions a, b1 and c, is subjected to a split post dielectric resonator (SPDR) after 24 hours of humidity control under constant temperature and humidity conditions (states) of 23° C. and 50% RH. dielectric loss tangent of the 10㎓ measured by (Tanδ ₁₎ and the difference in dielectric loss tangent (Tanδ ₂₎ in 20㎓ (Tanδ ₂ -Tanδ ₁₎ is or may be less than or equal to zero.

The adhesive film of the present invention, when the polyimide satisfies the above conditions a, b2 and c, is subjected to a split post dielectric resonator (SPDR) after 24 hours of humidity control under constant temperature and constant humidity conditions (states) of 23° C. and 50% RH. The dielectric loss tangent (Tanδ ₁ ) at 10 GHz as measured by 0.002 may be less than 0.002, and the relative dielectric constant (E ₁ ) may be 3.0 or less.

The adhesive film of the present invention, when the polyimide satisfies the above conditions a, b2 and c, is subjected to a split post dielectric resonator (SPDR) after 24 hours of humidity control under constant temperature and constant humidity conditions (states) of 23° C. and 50% RH. _{The dielectric loss tangent (Tanδ 2} ) at 20 GHz as measured by the above 0.002 may be less than 0.002, and the relative dielectric constant (E ₂ ) may be 3.0 or less.

The laminate of the present invention is a laminate having a substrate and an adhesive layer laminated on at least one surface of the substrate,

The said adhesive layer contains the said any adhesive film.

The coverlay film of the present invention is a coverlay film having a film material layer for a coverlay and an adhesive layer laminated on the film material layer for the coverlay,

The said adhesive layer contains the said any adhesive film.

The copper foil provided with resin of this invention is copper foil provided with resin which laminated|stacked the adhesive bond layer and copper foil,

The said adhesive layer contains the said any adhesive film.

The metal-clad laminate of the present invention is a metal-clad laminate having an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer,

At least 1 layer of the said insulating resin layer contains the said any adhesive film.

A metal-clad laminate of another aspect of the present invention is a metal-coated laminate having an insulating resin layer, an adhesive layer laminated on at least one side of the insulating resin layer, and a metal layer laminated on the insulating resin layer via the adhesive layer. is a laminate,

The said adhesive layer contains the said any adhesive film.

A metal-clad laminate of another aspect of the present invention includes a first single-sided metal-clad laminate having a first metal layer and a first insulating resin layer laminated on at least one side of the first metal layer;

a second single-sided metal-clad laminate having a second metal layer and a second insulating resin layer laminated on at least one side of the second metal layer;

and an adhesive layer disposed in contact with the first insulating resin layer and the second insulating resin layer and laminated between the first single-sided metal-clad laminate and the second single-sided metal-clad laminate. And in the metal-clad laminate of this invention, the said adhesive bond layer contains the said any adhesive film.

A metal-clad laminate of another aspect of the present invention includes an insulating resin layer, a single-sided metal-clad laminate having a metal layer laminated on one side of the insulating resin layer, and an adhesive layer laminated on the other side of the insulating resin layer. and the adhesive layer includes any of the adhesive films.

The circuit board of this invention is formed by wiring the said metal layer of the said metal clad laminated board.

A circuit board according to another aspect of the present invention includes a first substrate, a wiring layer laminated on at least one surface of the first substrate, and an adhesive layer laminated to cover the wiring layer on the surface of the first substrate on the wiring layer side. A circuit board having a

The said adhesive layer contains the said any adhesive film.

A circuit board according to another aspect of the present invention includes a first substrate, a wiring layer laminated on at least one surface of the first substrate, and an adhesive laminated to cover the wiring layer on the surface of the first substrate on the wiring layer side. A circuit board comprising a layer and a second substrate laminated on a surface opposite to the first substrate of the adhesive layer,

The said adhesive layer contains the said any adhesive film.

A circuit board according to another aspect of the present invention includes a first substrate, an adhesive layer laminated on at least one surface of the first substrate, and a second substrate laminated on a surface opposite to the first substrate of the adhesive layer. and a circuit board having a wiring layer laminated on a surface of the first substrate and the second substrate opposite to the adhesive layer,

The said adhesive layer contains the said any adhesive film.

The multilayer circuit board of the present invention is a multilayer circuit board comprising a laminate including a plurality of laminated insulating resin layers, and at least one or more wiring layers embedded in the laminate,

At least one of the plurality of insulating resin layers is formed of an adhesive layer that has adhesive properties and covers the wiring layer,

The said adhesive layer contains the said any adhesive film.

The polyimide of the present invention has excellent adhesion and low dielectric constant by controlling the amount of aromatic rings contained in the polyimide using dimer diamine as a raw material or by making it a copolymer composition of dimer diamine and diamine having a specific structure. and low dielectric loss tangent, so that transmission loss in high-frequency signal transmission can be effectively suppressed. Therefore, when the polyimide of the present invention is applied to a circuit board or the like that transmits a high-frequency signal having a frequency of a GHz band (for example, 1 to 20 GHz), it becomes possible to effectively reduce transmission loss.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the cross-sectional structure of the laminated body which concerns on embodiment of this invention.
It is a schematic diagram which shows the structure of the cross section of the metal-clad laminated board which concerns on embodiment of this invention.
It is a schematic diagram which shows the structure of the cross section of the metal-clad laminated board which concerns on another embodiment of this invention.
It is a schematic diagram which shows the structure of the cross section of the metal-clad laminated board which concerns on still another embodiment of this invention.
5 is a schematic diagram showing a configuration of a cross section of a circuit board according to an embodiment of the present invention.
6 is a schematic diagram showing a configuration of a cross section of a circuit board according to another embodiment of the present invention.
7 is a schematic diagram showing the configuration of a cross section of a circuit board according to still another embodiment of the present invention.
8 is a schematic diagram showing the configuration of a cross section of a multilayer circuit board according to an embodiment of the present invention.
Fig. 9 is a diagram schematically expressing the relationship between the aromatic ring concentration and the dielectric loss tangent in the adhesive polyimide.

EMBODIMENT OF THE INVENTION Embodiment of this invention is suitably demonstrated with reference to drawings.

The polyimide which concerns on one Embodiment of this invention is a polyimide which has adhesiveness. Hereinafter, the polyimide of this embodiment may be described as "adhesive polyimide." The adhesive polyimide contains a tetracarboxylic acid residue derived from a tetracarboxylic acid anhydride component and a diamine residue derived from a diamine component. In the present invention, "tetracarboxylic acid residue" represents a tetravalent group derived from tetracarboxylic dianhydride, and "diamine residue" represents a divalent group derived from a diamine compound. When the tetracarboxylic acid anhydride and the diamine compound, which are raw materials, are reacted in substantially equimolar amounts, the kinds and molar ratios of the tetracarboxylic acid residues and diamine residues contained in the polyimide can be made substantially corresponding to the kinds and molar ratios of the raw materials.

In the present invention, when "polyimide" is used, in addition to polyimide, a polymer having an imide group in its molecular structure, such as polyamideimide, polyetherimide, polyesterimide, polysiloxaneimide, and polybenzimidazolimide, is used. It means a resin containing.

The adhesive polyimide of the present embodiment satisfies the following conditions a, b1 and c, or conditions a, b2 and c. In addition, the detail of the raw material monomer of an adhesive polyimide, a tetracarboxylic acid residue, and a diamine residue is mentioned later.

condition a)

With respect to the total diamine residues, 60 mol% or more of diamine residues derived from a dimer diamine composition containing as a main component dimer diamine in which two terminal carboxylic acid groups of dimer acid are substituted with primary aminomethyl groups or amino groups:

With respect to all the diamine residues, the content of the diamine residues derived from the dimer diamine composition is 60 mol% or more, preferably in the range of 60 to 99 mol%, more preferably in the range of 60 to 95 mol%, still more preferably is in the range of 65 to 95 mol%, most preferably in the range of 70 to 90 mol%, so that the relative dielectric constant and dielectric loss tangent of the polyimide can be reduced. When the content of the diamine residue derived from the dimer diamine composition is less than 60 mol%, the relative permittivity and dielectric loss tangent increase easily because the polar groups contained in the polyimide relatively increase. Moreover, with respect to all the diamine residues, when content of the diamine residue derived from a dimer diamine composition exceeds 99 mol%, the mobility of the molecular chain of a polyimide may become high excessively, and a dielectric loss tangent may raise. In addition, by containing the dimer diamine in the above amount, the dielectric properties of the polyimide are improved, and the thermocompression bonding properties by lowering the glass transition temperature (lower Tg) of the polyimide and lowering the elastic modulus Internal stress can be relieved.

condition b1)

The content of the carbon atoms derived from the 6-membered aromatic ring (excluding the carbon atoms of the 6-membered aromatic ring derived from the dimer diamine composition) with respect to the total content of all atoms in the polyimide is within the range of 12 to 40% by weight:

The content rate of the carbon atom derived from a 6-membered aromatic ring means content (aromatic ring density|concentration) of the aromatic ring contained in adhesive polyimide. When the content of carbon atoms derived from the six-membered aromatic ring is within the range of 12 to 40% by weight, the movement of the molecule is restricted due to the interaction between the aromatic rings in the polyimide, and the effect of reducing the dielectric loss tangent is expressed. If the content of carbon atoms derived from the 6-membered aromatic ring is less than 12% by weight, the motion of the molecular chain of the polyimide cannot be suppressed, so that the dielectric loss tangent increases. When the content of the carbon atoms derived from the 6-membered aromatic ring exceeds 40 wt%, the molecular polarity becomes large and the dielectric loss tangent increases. The content of carbon atoms derived from the 6-membered aromatic ring is preferably in the range of 17 to 38% by weight, and more preferably in the range of 20 to 30% by weight.

condition b2)

What contains the diamine residue derived from the diamine compound represented by general formula (A1) with respect to all the diamine residues within the range of 5 mol% or more and 40 mol% or less:

With respect to all the diamine residues, the content of the diamine residue derived from the diamine compound represented by the general formula (A1) is within the range of 5 mol% or more and 40 mol% or less, preferably within the range of 10 to 30 mol%. It is possible to lower the dielectric constant and dielectric loss tangent of the mid. When content of the diamine residue induced|guided|derived from the diamine compound represented by General formula (A1) is less than 5 mol%, the mobility of the molecular chain of a polyimide may become high excessively, and a dielectric loss tangent may raise. Moreover, when content of the diamine residue derived from the diamine compound represented by general formula (A1) with respect to all the diamine residues exceeds 40 mol%, the polarity of the molecular chain of a polyimide becomes high excessively, and a dielectric loss tangent rises. There are cases.

condition c)

having a weight average molecular weight in the range of 5,000 to 200,000:

When the weight average molecular weight of an adhesive polyimide is less than 5,000, it becomes easy to become brittle when it forms into a film. On the other hand, when a weight average molecular weight exceeds 200,000, when it is set as a varnish, it becomes high viscosity, and it becomes easy to generate|occur|produce thickness nonuniformity at the time of coating.

Further, the preferred range of the weight average molecular weight of the adhesive polyimide is in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 60,000, still more preferably in the range of 20,000 to 55,000. When the weight average molecular weight is less than 10,000, the high polarity of the polyimide molecular chain increases, so that the relative dielectric constant and dielectric loss tangent are likely to rise in some cases. When a weight average molecular weight exceeds 100,000, since molecular chain length becomes long and it becomes difficult to take an ordered structure, a dielectric constant and a dielectric loss tangent may become easy to raise.

When the polyimide of the present embodiment satisfies the conditions a, b1, and c, it is preferable to further satisfy any one or more of the following conditions d, e, and f.

condition d)

The following formula (i),

CM value = (C/Mw) × 10 ⁴ ... (i)

[Wherein, C means the weight content of carbon atoms derived from the 6-membered aromatic ring (excluding the carbon atoms of the 6-membered aromatic ring derived from the dimer diamine composition) with respect to the total content of all atoms in the polyimide, and Mw is It means the weight average molecular weight of polyimide]

CM value, which is an index indicating the amount of the 6-membered aromatic ring contained in the polyimide, calculated based on

Setting the CM value within an appropriate range is effective for reducing the dielectric loss tangent of the polyimide, and when the CM value is less than 3, the aromatic ring concentration decreases, so molecular mobility increases and the dielectric loss tangent increases. On the other hand, when a CM value exceeds 38, an aromatic ring density|concentration becomes excess, it becomes highly polarized, and a dielectric loss tangent rises.

condition e)

The weight content of carbon atoms derived from the 6-membered aromatic ring (excluding the carbon atoms of the 6-membered aromatic ring derived from the dimer diamine composition) with respect to the total content of all atoms in all the diamine components of the raw material exceeds 0 and is 32% by weight or less within the scope of:

In the adhesive polyimide, by controlling the content of the aromatic ring within an appropriate range, the movement of the molecule is restricted by the interaction between the aromatic rings in the polyimide, and the effect of low dielectric dissipation tangent is expressed. For this purpose, also about the diamine component of a raw material, it is effective to make the content rate of the carbon atom derived from a 6-membered aromatic ring with respect to the total content of carbon atoms into the said range. When the content rate of the carbon atom derived from a 6-membered aromatic ring in all the diamine components of a raw material exceeds 32 weight%, the polarity of the polyimide molecule obtained will become large, and a dielectric loss tangent will become high.

condition f)

The following formula (ii),

DM value = (D/Mw) × 10 ⁴ ... (ii)

[Wherein, D means the weight content of carbon atoms derived from the 6-membered aromatic ring (excluding the carbon atoms of the 6-membered aromatic ring derived from the dimer diamine composition) with respect to the total content of all atoms in the total diamine residues, Mw means the weight average molecular weight of polyimide]

DM value, which is an index indicating the amount of the 6-membered aromatic ring derived from the diamine component contained in the polyimide, which is calculated based on

It is effective to carry out the content rate of the carbon atom derived from the 6-membered aromatic ring in the diamine residue in the said range with respect to the total content of all the atoms in a polyimide for the same reason as condition e.

(acid anhydride)

As the adhesive polyimide, tetracarboxylic anhydride generally used for thermoplastic polyimide can be used without particular limitation as a raw material, but the following general formulas (2) and/or (3) for all tetracarboxylic acid anhydride components It is preferable to use the raw material which contains 90 mol% or more of tetracarboxylic anhydride in total represented by ). In other words, the adhesive polyimide contains tetracarboxylic acid residues derived from tetracarboxylic acid anhydrides represented by the following general formulas (2) and/or (3) with respect to all tetracarboxylic acid residues in total. It is preferable to contain 90 mol% or more. Adhesive property by containing 90 mol% or more of tetracarboxylic acid residues derived from tetracarboxylic acid anhydride represented by the following general formulas (2) and/or (3) in total with respect to all the tetracarboxylic acid residues It is easy to achieve coexistence of the flexibility and heat resistance of a polyimide, and it is preferable. When the total of the tetracarboxylic acid residues derived from the tetracarboxylic acid anhydride represented by the following general formulas (2) and/or (3) is less than 90 mol%, the solvent solubility of the adhesive polyimide tends to decrease. do.

In the general formula (2), X ₁ represents a single bond or a divalent group selected from the following formulae, and in the general formula (3), _{the cyclic moiety represented by Y 1} is a 4-membered ring, a 5-membered ring, a 6-membered ring, or 7 It represents that a cyclic saturated hydrocarbon group selected from a membered ring or an 8 membered ring is formed.

In the above formula, Z ₁ represents -C ₆ H ₄ -, -(CH ₂ ) _m1 - or -CH ₂ -CH(-OC(=O)-CH ₃ )-CH ₂ -, but m1 is 1 An integer of -20 is represented.

Examples of the tetracarboxylic anhydride represented by the general formula (2) include 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA), 2,3',3,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride , 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-oxydihydride Phthalic anhydride (ODPA), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride ( BPADA), p-phenylenebis(trimellitic acid monoester acid anhydride) (TAHQ), ethylene glycol bisanhydrotrimellitate (TMEG), etc. are mentioned. Among these, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) is especially preferable. In the case of using BTDA, the carbonyl group (ketone group) present in the molecular skeleton contributes to the adhesiveness, so that the adhesiveness of the adhesive polyimide can be improved. In addition, in BTDA, a C=N bond may be formed by reacting a ketone group present in the molecular skeleton with an amino group of an amino compound for crosslinking to be described later, and it is easy to exhibit an effect of improving heat resistance. From such a viewpoint, it is preferable to contain the tetracarboxylic acid residue derived from BTDA with respect to all the tetracarboxylic acid residues, Preferably it is 50 mol% or more, More preferably, it is 60 mol% or more.

Moreover, as tetracarboxylic acid anhydride represented by General formula (3), 1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2,3,4- cyclopentane tetracarboxyl Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cycloheptanetetracarboxylic dianhydride, 1,2,5,6-cyclooctanetetracarboxylic Acid dianhydride etc. are mentioned.

Here, when the adhesive polyimide satisfies the conditions a, b2 and c, it is preferable that it further satisfies the following condition g regarding the acid anhydride.

condition g)

With respect to all tetracarboxylic acid residues, 10 mol% or more and 90 mol% or less of tetracarboxylic acid residues derived from benzophenonetetracarboxylic dianhydride _{in which group X 1} in the general formula (2) is -CO- A tetracarboxylic acid residue derived from the tetracarboxylic acid anhydride (provided that the benzophenonetetracarboxylic dianhydride is excluded) contained within the range and represented by the general formulas (2) and/or (3). What contains 10 mol% or more of at least one of:

Flexibility and heat resistance of the adhesive polyimide by containing the tetracarboxylic acid residue derived from benzophenonetetracarboxylic dianhydride in a range of 10 mol% or more and 90 mol% or less in total with respect to all tetracarboxylic acid residues. coexistence is easy to achieve, and since the ketone group contributes to the adhesiveness, the adhesiveness of the adhesive polyimide can be improved. When the amount of tetracarboxylic acid residues derived from benzophenonetetracarboxylic acid dianhydride is less than 10 mol% with respect to all tetracarboxylic acid residues, the ketone group serving as a crosslinking point may decrease and solder heat resistance may not be expressed. Moreover, when content of the tetracarboxylic-acid residue derived from benzophenone tetracarboxylic dianhydride with respect to all tetracarboxylic-acid residues exceeds 90 mol%, the diamine residue derived from a diamine compound and benzophenone tetracarboxylic When the ketone group derived from an acid dianhydride reacts, solubility falls remarkably. That is, benzophenonetetracarboxylic dianhydride may react with a ketone group present in the molecular skeleton and an amino group derived from a diamine compound to form a C=N bond, resulting in high molecular weight and gelation. below. In addition, benzophenone tetracarboxylic dianhydride is 3,3',4,4'-, 2,3',3,4'-, 2,2',3,3'- or 2,3,3 Both ',4'-benzophenonetetracarboxylic dianhydride can be used.

On the other hand, the tetracarboxylic acid anhydride represented by the general formulas (2) and/or (3) (however, excluding the benzophenonetetracarboxylic dianhydride) is a functional group that reacts with a diamine residue derived from a diamine compound. Since it does not have, the effect of a solder heat resistance improvement is acquired, suppressing the fall of solvent solubility by using in combination with benzophenone tetracarboxylic dianhydride.

Therefore, when the conditions a, b2 and c are satisfied, the content of the tetracarboxylic acid residues derived from benzophenonetetracarboxylic dianhydride with respect to all the tetracarboxylic acid residues is in the range of 10 mol% or more and 90 mol% or less. , preferably within the range of 10 mol% or more and 50 mol% or less, tetracarboxylic anhydride represented by general formulas (2) and/or (3) (provided that the benzophenone tetracarboxylic dianhydride Storage stability can be improved by making content of at least 1 sort(s) of the tetracarboxylic acid residue derived from ) into the range of 10 mol% or more, preferably 10 mol% or more and 50 mol% or less.

The adhesive polyimide contains a tetracarboxylic acid residue derived from an acid anhydride other than the tetracarboxylic acid anhydride represented by the general formulas (2) and (3) in the range that does not impair the effects of the invention. can do. Although there is no restriction|limiting in particular as such a tetracarboxylic acid residue, For example, pyromellitic dianhydride, 2,3',3,4'- biphenyltetracarboxylic dianhydride, 2,3',3,4'- Diphenylethertetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, 3,3",4,4"-, 2,3,3",4"- or 2,2" ,3,3"-p-terphenyltetracarboxylic dianhydride, 2,2-bis(2,3- or 3,4-dicarboxyphenyl)-propane dianhydride, bis(2,3- or 3, 4-dicarboxyphenyl)methane dianhydride, bis(2,3- or 3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3- or 3,4-dicarboxyphenyl)ethane dianhydride Water, 1,2,7,8-, 1,2,6,7- or 1,2,9,10-phenanthrene-tetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxyl Acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) tetrafluoropropane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5 ,6-tetracarboxylic dianhydride, 2,6- or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7- (or 1,4 ,5,8-)tetrachloronaphthalene-1,4,5,8-(or 2,3,6,7-)tetracarboxylic dianhydride, 2,3,8,9-, 3,4,9 ,10-, 4,5,10,11- or 5,6,11,12-perylene-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrol Dean-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy) ) tetracarboxylic acid residues derived from aromatic tetracarboxylic dianhydrides such as diphenylmethane dianhydride.

(diamine)

For the adhesive polyimide, a diamine compound generally used for thermoplastic polyimide can be used as a raw material without particular limitation, but with respect to the entire diamine component, two terminal carboxylic acid groups of the dimer acid are substituted with primary aminomethyl groups or amino groups The raw material containing 60 mol% or more of the dimer diamine composition which has the dimer diamine formed as a main component is used. In other words, the adhesive polyimide is a dimer mainly composed of dimer diamine in which two terminal carboxylic acid groups of the dimer acid are substituted with primary aminomethyl groups or amino groups with respect to all the diamine residues, as described in condition a. It contains 60 mol% or more of diamine residues derived from a diamine composition.

The dimer diamine composition is a purified product in which the amounts of components (b) and (c) are controlled while containing the following component (a) as a main component.

(a) dimer diamines;

The dimer diamine of the component (a) is a diamine in which two terminal carboxylic acid groups (-COOH) of the dimer acid are substituted with a _{primary aminomethyl group (-CH 2} -NH ₂ ) or an amino group (-NH _{2 ).} it means. Dimer acid is a known dibasic acid obtained by intermolecular polymerization of unsaturated fatty acids, and its industrial production process is almost standardized in the industry, and is obtained by dimerizing unsaturated fatty acids having 11 to 22 carbon atoms in a clay catalyst or the like. The industrially obtained dimer acid is mainly composed of a dibasic acid having 36 carbon atoms obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms, such as oleic acid, linoleic acid, and linolenic acid. acid (54 carbon atoms), and other polymerized fatty acids having 20 to 54 carbon atoms. In addition, although a double bond remains after a dimerization reaction, in this invention, the thing which further reduced the unsaturation by hydrogenation shall be included in the dimer acid. (a) The dimer diamine of the component is defined as a diamine compound obtained by substituting a primary aminomethyl group or an amino group for the terminal carboxylic acid group of a dibasic acid compound within the range of 18 to 54 carbon atoms, preferably 22 to 44 carbon atoms. can do.

As a characteristic of dimer diamine, the characteristic derived from the backbone of a dimer acid can be provided. That is, since dimer diamine is a macromolecular aliphatic having a molecular weight of about 560 to 620, it is possible to increase the molar volume of the molecule to relatively reduce the polar group of the polyimide. It is thought that the characteristic of such a dimer acid type diamine contributes to improving a dielectric characteristic by making a dielectric constant and a dielectric loss tangent small, suppressing the fall of the heat resistance of a polyimide. In addition, since it has two freely moving minor chains of 7 to 9 carbon atoms and two chain aliphatic amino groups having a length close to 18 carbon atoms, not only provides flexibility to the polyimide, but also allows the polyimide to have an asymmetric chemical structure Since it can be set as a non-planar chemical structure, it is thought that the low dielectric constant of a polyimide can be aimed at.

As the dimer diamine composition, the dimer diamine content of component (a) is increased to 96 wt% or more, preferably 97 wt% or more, more preferably 98 wt% or more by a purification method such as molecular distillation. good. (a) Expansion of molecular weight distribution of a polyimide can be suppressed by making dimer diamine content of a component 96 weight% or more. In addition, if technically possible, it is best that all (100 weight%) of dimer diamine composition is comprised with the dimer diamine of (a) component. Moreover, the dimer diamine composition may contain the dimer diamine which has a 6-membered aromatic ring as molecular skeleton. In the polyimide of the present embodiment, control is made focusing on the ratio of the aromatic monomer directly linked to the imide bond site, but in the dimer diamine having a 6-membered aromatic ring, the 6-membered aromatic ring has a length of 7 or more carbon atoms Since it is an imide bond via a fatty chain, it does not become a control object of the 6-membered aromatic ring in the polyimide of this embodiment. Therefore, the 6-membered aromatic ring derived from dimer diamine shall be excluded from the condition b1, the condition d, the condition e, and the condition f in an adhesive polyimide. Moreover, it is preferable that the ratio of the aromatic ring derived from dimer diamine is 20 mol or less with respect to 1 mol of amino groups by quantification by 1H-NMR.

(b) a monoamine compound obtained by substituting a terminal carboxylic acid group of a monobasic acid compound having 10 to 40 carbon atoms with a primary aminomethyl group or an amino group;

The monobasic acid compound in the range of 10 to 40 carbon atoms is a monobasic unsaturated fatty acid in the range of 10 to 20 carbon atoms derived from the raw material of the dimer acid, and a by-product in the production of dimer acid in the range of 21 to 40 carbon atoms. It is a mixture of monobasic acid compounds. The monoamine compound is obtained by substituting a terminal carboxylic acid group of these monobasic acid compounds with a primary aminomethyl group or an amino group.

(b) The monoamine compound of a component is a component which suppresses the molecular weight increase of a polyimide. During polymerization of polyamic acid or polyimide, the monofunctional amino group of the monoamine compound reacts with the terminal acid anhydride group of the polyamic acid or polyimide to seal the terminal acid anhydride group, and the molecular weight of the polyamic acid or polyimide suppress the increase.

(c) an amine compound obtained by substituting a terminal carboxylic acid group of a polybasic acid compound having a hydrocarbon group in the range of 41 to 80 carbon atoms with a primary aminomethyl group or an amino group (with the proviso that the dimer diamine is excluded);

The polybasic acid compound having a hydrocarbon group in the range of 41 to 80 carbon atoms is a polybasic acid compound mainly comprising a tribasic acid compound in the range of 41 to 80 carbon atoms, which is a by-product during the production of dimer acid. Moreover, polymeric fatty acids other than a C41-C80 dimer acid may be included. The amine compound is obtained by substituting a terminal carboxylic acid group of these polybasic acid compounds with a primary aminomethyl group or an amino group.

(c) The amine compound of the component is a component which promotes the molecular weight increase of a polyimide. A trifunctional or higher amino group containing a triamine compound derived from trimer acid as a main component reacts with a terminal acid anhydride group of a polyamic acid or polyimide to rapidly increase the molecular weight of the polyimide. In addition, amine compounds derived from polymerized fatty acids other than dimer acids having 41 to 80 carbon atoms also increase the molecular weight of polyimides and cause gelation of polyamic acids or polyimides.

When quantifying each component by measurement using gel permeation chromatography (GPC), in order to facilitate identification of the peak start, peak top, and peak end of each component of the dimer diamine composition, the dimer diamine composition is mixed with acetic anhydride and A sample treated with pyridine is used, and also cyclohexanone is used as an internal standard. Using the sample thus prepared, each component is quantified by area percent of the chromatogram of GPC. The peak start and peak end of each component can be set as the local minimum of each peak curve, and the area percent of the chromatogram can be calculated based on this.

In addition, the dimer diamine composition is an area percent of the chromatogram obtained by GPC measurement, and the sum total of components (b) and (c) is 4 % or less, Preferably less than 4 % is good. By making the sum total of components (b) and (c) into 4 % or less, the expansion of molecular weight distribution of a polyimide can be suppressed.

In addition, the area percentage of the chromatogram of component (b) becomes like this. Preferably it is 3 % or less, More preferably, it is 2 % or less, More preferably, 1 % or less is good. By setting it as such a range, the molecular weight fall of a polyimide can be suppressed and the range of the preparation molar ratio of a tetracarboxylic-acid anhydride component and a diamine component can be expanded. In addition, (b) component does not need to be contained in the dimer diamine composition.

Moreover, the area percent of the chromatogram of (c) component is 2 % or less, Preferably it is 1.8 % or less, More preferably, 1.5 % or less is good. By setting it as such a range, the rapid increase of the molecular weight of a polyimide can be suppressed and the raise of the dielectric loss tangent in the wide frequency range of a resin film can be suppressed. In addition, (c) component does not need to be contained in the dimer diamine composition.

In addition, when the ratio (b/c) of the area percent of the chromatograms of the components (b) and (c) is 1 or more, the molar ratio of the tetracarboxylic anhydride component and the diamine component (tetracarboxylic anhydride component/diamine component) Preferably, it is good to set it as 0.97 or more and less than 1.0, and control of the molecular weight of a polyimide becomes easier by setting it as such a molar ratio.

In addition, when the ratio (b/c) of the area percent of the chromatograms of the components (b) and (c) is less than 1, the molar ratio of the tetracarboxylic anhydride component and the diamine component (tetracarboxylic anhydride component/diamine component) ), Preferably it is good to set it as 0.97 or more and 1.1 or less, and control of the molecular weight of a polyimide becomes easier by setting it as such a molar ratio.

Commercially available dimer diamine composition is available, and it is preferable to refine|purify for the purpose of reducing components other than dimer diamine of (a) component, For example, it is preferable to make component into 96 weight% or more in (a). . Although it does not restrict|limit especially as a purification method, Well-known methods, such as a distillation method and precipitation purification, are suitable. As a commercial item of a dimer diamine composition, the Croda Japan company PRIAMINE1073 (brand name), the copper PRIAMINE1074 (brand name), the copper PRIAMINE1075 (brand name), etc. are mentioned, for example.

The adhesive polyimide may contain a diamine residue derived from the diamine compound represented by the general formula (A1) as described as condition b2. Since the aromatic rings are couple|bonded with the diamine represented by general formula (A1) at the para position with respect to an amino group, molecular chains are easy to orientate, and can be used advantageously for the purpose of low dielectric dissipation tangent.

In the formula (A1), Y and Z each independently represent a monovalent alkyl group, alkoxy group, alkenyl group or alkynyl group having 1 to 6 carbon atoms, and the linking group X is -O-, -S-, -CO-, - represents a divalent group selected from SO-, -SO ₂ -, -COO-, -CH ₂ -, -CH ₂ -O-, -C(CH ₃ ) ₂ -, -NH- or -CONH-, and m is An integer of 1 to 4 is independently represented. However, when several linking groups X are included in a molecule|numerator, it may be same or different. In the above formula (A1), and optionally a hydrogen atom in the two amino groups of the terminal may be substituted, for example, -NR ₂ R ₃ (wherein, R _2, R ₃ is any alkyl group independently means a substituent of).

The diamine represented by the formula (A1) (hereinafter, may be described as "diamine (A1)") is an aromatic diamine having two or more benzene rings. It is thought that this diamine (A1) contributes to the improvement of the orientation of a polyimide molecular chain by having the amino group directly connected to at least 1 benzene ring and the divalent coupling group X at the para position. Therefore, the low dielectric characterization of the polyimide is enhanced by using the diamine (A1). Here, as linking group X, -O-, -S-, -CO-, -SO-, -SO ₂ -, -COO-, -CH ₂ -, -CH ₂ -O-, -C(CH ₃ ) ₂ -, -NH-, -CONH- are preferable.

As the diamine (A1), for example, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,4,4'-triaminodiphenyl ether, 4,4'-bis(4- aminophenyl sulfide), 4,4'-diaminodiphenylsulfone, 2,2'-bis(4-aminobenzyloxyphenyl)propane, bis[4-(4-aminophenoxy)phenyl]sulfone, 4, 4'-diaminobenzanilide, 4,4'-methylenedianiline, 4,4'- diaminobenzophenone, etc. are mentioned. Among these, 2,2-bis[4-(4-aminophenoxy)phenyl]propane is especially preferable.

The adhesive polyimide contains 5 mol% or more and 40 mol% or less of the diamine residue derived from at least one diamine compound selected from diamine (A1) with respect to all the diamine residues, preferably 10 mol% or more. It is preferable to contain within the range of 30 mol% or less. Since diamine (A1) has a structure with high linearity, by using at least one diamine compound selected therefrom in an amount within the above range, the orientation of the polyimide molecular chains can be improved and low dielectric properties can be imparted. have. When the diamine residue derived from at least one diamine compound selected from diamine (A1) exceeds 40 mol%, the molecular polarity of the polyimide increases and the dielectric loss tangent increases. Moreover, the solubility of a polyimide falls and it becomes a cause of gelatinization. On the other hand, when it is less than 5 mol%, it becomes impossible to suppress the movement of molecular chains, and the dielectric loss tangent rises.

Moreover, when the said conditions a, b1, and c are satisfy|filled, the adhesive polyimide may contain the diamine residue mentioned below. As such a diamine residue, for example, bisanilinefluorene (BAFL), 9,9-bis(3-methyl-4-aminophenyl)fluorene, 9,9-bis(3-fluoro-4-aminophenyl) Diamine residues derived from fluorene, 9,9-bis[4-(aminophenoxy)phenyl]fluorene and diamine compounds represented by general formulas (B1) to (B7) are preferable. In particular, diamine having a fluorene skeleton represented by BAFL can be advantageously used for the purpose of controlling the concentration of aromatic rings in that it contains four aromatic rings.

In formulas (B1) to (B7), R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms, and the linking group A is independently -O-, -S-, -CO-, -SO- , -SO ₂ -, -COO-, -CH ₂ -, -C(CH ₃ ) ₂ -, -NH- or -CONH- represents a divalent group selected from, n ₁ is independently an integer of 0 to 4 indicates. However, the thing which overlaps with Formula (B2) in Formula (B3) shall be excluded, and shall exclude the thing which overlaps with Formula (B4) in Formula (B5). Here, "independently" means that in one or two or more of the formulas (B1) to (B7), a plurality of linking groups A, a plurality of R _{1 ,} or a plurality of n ₁ may be the same or different. it means. Further, in the formulas (B1) to (B7), the hydrogen atoms in the two amino groups at the terminals may be substituted, for example, -NR ₂ R ₃ (here, R ₂ and R ₃ are independently An alkyl group or the like means an arbitrary substituent).

The diamine represented by the formula (B1) (hereinafter, may be described as "diamine (B1)") is an aromatic diamine having two benzene rings. In this diamine (B1), the degree of freedom of the polyimide molecular chain is increased by having the amino group directly connected to at least one benzene ring and the divalent linking group A in the meta position, and thus has high flexibility, and the flexibility of the polyimide molecular chain is thought to contribute to the improvement of Therefore, the thermoplasticity of a polyimide becomes high by using a diamine (B1). Here, as linking group A, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -SO ₂ -, -S- are preferable.

As the diamine (B1), for example, 3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenylpropane, 3,3'-diaminodiphenylsulfide, 3,3'-diamino Diphenylsulfone, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylpropane, 3, 4'-diaminodiphenyl sulfide, 3,3'-diamino benzophenone, (3,3'-bisamino) diphenylamine, etc. are mentioned.

The diamine (henceforth "diamine (B2)" may be described) represented by Formula (B2) is aromatic diamine which has three benzene rings. This diamine (B2) has a high degree of flexibility by increasing the degree of freedom of the polyimide molecular chain by having an amino group directly connected to at least one benzene ring and a divalent linking group A in the meta position. I think it contributes to improvement. Therefore, the thermoplasticity of a polyimide becomes high by using a diamine (B2). Here, as the coupling group A, -O- is preferable.

As the diamine (B2), for example, 1,4-bis(3-aminophenoxy)benzene, 3-[4-(4-aminophenoxy)phenoxy]benzeneamine, 3-[3-(4-amino) phenoxy) phenoxy] benzeneamine etc. are mentioned.

The diamine represented by the formula (B3) (hereinafter, may be described as "diamine (B3)") is an aromatic diamine having three benzene rings. In this diamine (B3), two divalent linking groups A directly linked to one benzene ring are in meta positions with each other, so that the degree of freedom of the polyimide molecular chain is increased, and thus has high flexibility, It is thought to contribute to the improvement of flexibility. Therefore, the thermoplasticity of a polyimide becomes high by using a diamine (B3). Here, as the coupling group A, -O- is preferable.

Examples of the diamine (B3) include 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,3-bis(3-aminophenoxy)benzene (APB), 4,4'- [2-methyl-(1,3-phenylene)bisoxy]bisaniline, 4,4'-[4-methyl-(1,3-phenylene)bisoxy]bisaniline, 4,4'-[5 -methyl-(1,3-phenylene)bisoxy]bisaniline etc. are mentioned.

The diamine (henceforth "diamine (B4)" may be described) represented by Formula (B4) is an aromatic diamine which has four benzene rings. This diamine (B4) has high flexibility by having the amino group directly linked to at least one benzene ring and the divalent linking group A at the meta position, and is considered to contribute to the improvement of the flexibility of the polyimide molecular chain. Therefore, the thermoplasticity of a polyimide becomes high by using a diamine (B4). Here, as linking group A, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -SO ₂ -, -CO-, -CONH- are preferable.

Examples of the diamine (B4) include bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]propane, and bis[4-(3-aminophenoxy)phenyl]ether. , bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)]benzophenone, bis[4,4'-(3-aminophenoxy)]benzanilide, etc. can be heard

The diamine represented by Formula (B5) (henceforth "diamine (B5)" may be described) is an aromatic diamine which has four benzene rings. This diamine (B5) has high flexibility by increasing the degree of freedom of the polyimide molecular chain by having two divalent linking groups A directly connected to at least one benzene ring at meta positions with each other, and It is thought to contribute to the improvement of flexibility. Therefore, the thermoplasticity of a polyimide becomes high by using a diamine (B5). Here, as the coupling group A, -O- is preferable.

As the diamine (B5), 4-[3-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline, 4,4'-[oxybis(3,1-phenyleneoxy)]bisaniline, etc. can be heard

The diamine represented by the formula (B6) (hereinafter, may be described as "diamine (B6)") is an aromatic diamine having four benzene rings. This diamine (B6) has high flexibility by having at least two ether bonds, and it is thought that it contributes to the improvement of the softness|flexibility of a polyimide molecular chain. Therefore, the thermoplasticity of a polyimide becomes high by using a diamine (B6). Here, as the linking group A, -C(CH ₃ ) ₂ -, -O-, -SO ₂ -, -CO- are preferable.

Examples of the diamine (B6) include 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), bis[4-(4-aminophenoxy)phenyl]ether (BAPE), bis [4-(4-aminophenoxy)phenyl]sulfone (BAPS), bis[4-(4-aminophenoxy)phenyl]ketone (BAPK), etc. are mentioned.

The diamine (henceforth "diamine (B7)" may be described) represented by Formula (B7) is aromatic diamine which has four benzene rings. Since this diamine (B7) has a highly flexible divalent coupling group A on both sides of a diphenyl skeleton, respectively, it is thought that it contributes to the improvement of the softness|flexibility of a polyimide molecular chain. Therefore, the thermoplasticity of a polyimide becomes high by using a diamine (B7). Here, as the coupling group A, -O- is preferable.

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

The adhesive polyimide contains the diamine residues derived from at least one diamine compound selected from diamines (B1) to diamines (B7) with respect to all the diamine residues, preferably 1 mol% or more and 40 mol% or less. It is good to contain within the range of 5 mol% or more and 35 mol% or less more preferably. Since diamines (B1) to diamines (B7) have a molecular structure having flexibility, by using at least one diamine compound selected from them in an amount within the above range, the flexibility of the polyimide molecular chain is improved, and thermoplasticity is improved. can be given

The adhesive polyimide may further contain diamine residues other than the above in the range which does not impair the effect of invention.

The adhesive polyimide can be produced by reacting the acid anhydride component and the diamine component described above in a solvent to produce a polyamic acid and then heating and ring closure. For example, an acid anhydride component and a diamine component are dissolved in an organic solvent in substantially equimolar amounts, stirred at a temperature within the range of 0 to 100° C. for 30 minutes to 24 hours, and subjected to polymerization reaction to obtain polyamic acid, which is a precursor of polyimide. In the reaction, the reaction component is dissolved in the organic solvent so that the resulting precursor is in the range of 5 to 50% by weight, preferably in the range of 10 to 40% by weight. Examples of the organic solvent used for the polymerization reaction include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, and N-methyl-2-pi. Rollidone (NMP), 2-butanone, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, methylcyclohexane, dioxane, tetrahydrofuran, diglyme , triglyme, methanol, ethanol, benzyl alcohol, cresol, and the like. Two or more of these solvents may be used in combination, and further, an aromatic hydrocarbon such as xylene or toluene may be used in combination. In addition, although there is no restriction|limiting in particular as the usage-amount of such an organic solvent, It is preferable to adjust and use it so that the density|concentration of the polyamic acid solution obtained by a polymerization reaction will be about 5 to 50 weight%.

The synthesized polyamic acid is usually advantageously used as a reaction solvent solution, but may be concentrated, diluted or substituted with another organic solvent if necessary. In addition, polyamic acids are generally used advantageously because of their excellent solvent solubility. It is preferable that the viscosity of the solution of polyamic acid exists in the range of 500 mPa*s - 100000 mPa*s. When it deviates from this range, it will become easy to generate|occur|produce defects, such as thickness nonuniformity and a stripe, in a film at the time of the coating operation by a coater etc.

The method of imidating the polyamic acid to form the polyimide is not particularly limited, and for example, heat treatment such as heating in the above solvent at a temperature condition within the range of 80 to 400° C. over 1 to 24 hours is suitable are hired In addition, the temperature may be heated under constant temperature conditions, and the temperature may be changed in the middle of the process.

In the adhesive polyimide, dielectric properties, thermal expansion coefficient, tensile modulus, glass transition Physical properties such as temperature can be controlled. Moreover, when an adhesive polyimide has two or more structural units, although it may exist as a block or it may exist at random, it is preferable to exist at random.

The imide group concentration of the adhesive polyimide is preferably 22 wt% or less, more preferably 20 wt% or less. Here, "imide group concentration" _{means the value obtained by dividing the molecular weight of the imide group moiety (-(CO) 2} -N-) in the polyimide by the molecular weight of the entire structure of the polyimide. When the imide group concentration exceeds 22% by weight, the molecular weight of the resin itself decreases, and the low hygroscopicity also deteriorates due to an increase in the polar group, and the Tg and the elastic modulus increase.

The adhesive polyimide is most preferably a fully imidized structure. However, a part of polyimide may be made into amic acid. The imidation rate was determined by measuring the infrared absorption spectrum of the polyimide thin film by a single reflection ATR method using a Fourier transform infrared spectrophotometer (commercially available product: FT/IR620 manufactured by Nippon Bunko), a benzene ring absorber in the vicinity of ^{1015 cm -1} Based on , it can be calculated from the absorbance of C = O stretching derived from an imide group of ^{1780 cm -1 .}

The adhesive polyimide is an optional component, for example, a plasticizer, another cured resin component such as an epoxy resin, a curing agent, a curing accelerator, an organic filler, an inorganic filler, a coupling agent, a solvent, a flame retardant, etc. by appropriately blending the adhesive polyimide It can be set as a mid composition.

(Formation of crosslinking of adhesive polyimide)

When the adhesive polyimide has a ketone group, the ketone group reacts with an amino group of an amino compound having at least two primary amino groups as functional groups (hereinafter, sometimes referred to as “amino compound for crosslinking”) A crosslinked structure can be formed by forming a C=N bond. A polyimide having such a crosslinked structure (hereinafter sometimes referred to as "crosslinked polyimide") is an application example of an adhesive polyimide, and becomes a preferable form. Moreover, since the weight average molecular weight fluctuates greatly due to crosslinking formation, the adhesive polyimide before crosslinking formation should just satisfy the said condition c, and crosslinked polyimide does not need to satisfy condition c. Moreover, the adhesive resin composition which mix|blended the crosslinking agent with the adhesive polyimide which has a ketone group is another application example of adhesive polyimide, and becomes a preferable form. By forming the crosslinked structure, the heat resistance of the adhesive polyimide can be improved. As a preferable tetracarboxylic anhydride for forming the adhesive polyimide which has a ketone group, for example, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) is used as a diamine compound, For example, Examples thereof include aromatic diamines such as 4,4'-bis(3-aminophenoxy)benzophenone (BABP) and 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene (BABB). .

For the purpose of forming a crosslinked structure, in particular, the above-described adhesive polyi containing BTDA residues derived from BTDA, preferably 50 mol% or more, more preferably 60 mol% or more, with respect to all the tetracarboxylic acid residues. It is preferable to make the amino compound for crosslinking|crosslinking act with respect to the imide. In addition, in this invention, "BTDA residue" means a tetravalent group derived from BTDA.

As an amino compound for crosslinking, (I) a dihydrazide compound, (II) aromatic diamine, (III) aliphatic amine, etc. can be illustrated. Among these, a dihydrazide compound is preferable. Aliphatic amines other than the dihydrazide compound easily form a crosslinked structure even at room temperature, and there is a risk of storage stability of the varnish, while the aromatic diamine needs to be heated to a high temperature for forming the crosslinked structure. Thus, when a dihydrazide compound is used, the storage stability of a varnish and shortening of hardening time can be made compatible. As the dihydrazide compound, for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, and azelaic acid dihydrazide. Zide, sebacic acid dihydrazide, dodecane diacid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartrate dihydrazide, malic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide Zide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4-bisbenzene dihydrazide, 1,4-naphthoic acid dihydrazide, 2,6-pyridine diacid dihydrazide, itaconic acid di Dihydrazide compounds, such as hydrazide, are preferable. The above dihydrazide compounds may be used individually or in mixture of 2 or more types.

Further, amino compounds such as (I) dihydrazide compound, (II) aromatic diamine, and (III) aliphatic amine are, for example, a combination of (I) and (II), and a combination of (I) and (III). , like a combination of (I) and (II) and (III), it is also possible to use a combination of two or more types beyond categories.

In addition, from the viewpoint of making the network structure formed by crosslinking with the amino compound for crosslinking more dense, the amino compound for crosslinking used in the present invention has a molecular weight (when the amino compound for crosslinking is an oligomer) Weight average molecular weight) is preferably 5,000 or less, more preferably 90 to 2,000, still more preferably 100 to 1,500. Among these, the amino compound for crosslinking which has a molecular weight of 100-1,000 is especially preferable. When the molecular weight of the amino compound for crosslinking is less than 90, one amino group of the amino compound for crosslinking only forms a C=N bond with the ketone group of the adhesive polyimide, and the periphery of the remaining amino group becomes sterically bulky. Therefore, the remaining amino groups tend to be difficult to form C=N bonds.

When the ketone group in the adhesive polyimide is crosslinked and the amino compound for crosslinking is formed, the amino compound for crosslinking is added to the resin solution containing the adhesive polyimide, and the ketone group in the adhesive polyimide is used for crosslinking. The primary amino group of the amino compound is subjected to a condensation reaction. By this condensation reaction, the resin solution is hardened|cured and becomes hardened|cured material. In this case, the addition amount of the amino compound for crosslinking is 0.004 to 1.5 moles, preferably 0.005 to 1.2 moles, more preferably 0.03 moles to 0.9 moles of primary amino groups in total with respect to 1 mole of ketone groups, Most preferably, it may be 0.04 mol to 0.6 mol. With the addition amount of the amino compound for crosslinking in which the total of the primary amino groups is less than 0.004 moles in total with respect to 1 mole of the ketone group, the crosslinking by the amino compound for crosslinking is not sufficient, so that heat resistance after curing is difficult to develop. If the amount of the amino compound for crosslinking exceeds 1.5 mol, the unreacted amino compound for crosslinking will act as a thermoplastic and tend to decrease the heat resistance as an adhesive layer.

The conditions for the condensation reaction for crosslinking are not particularly limited as long as the conditions for the reaction of the ketone group in the adhesive polyimide with the primary amino group of the amino compound for crosslinking to form an imine bond (C=N bond) . The temperature of the heat condensation is set to release the water generated by the condensation to the outside of the system, or to simplify the condensation process in the case where the heat condensation reaction is continuously performed after the synthesis of the adhesive polyimide. The inside of the range of 120-220 degreeC is preferable, and the inside of the range of 140-200 degreeC is more preferable. The reaction time is preferably about 30 minutes to 24 hours. The end point of the reaction is, for example, by measuring an infrared absorption spectrum using a Fourier transform infrared spectrophotometer (commercial product: FT/IR620 manufactured by Nippon Bunko), derived from a ketone group in a polyimide resin near ^{1670 cm -1 .} It can be confirmed by the decrease or disappearance of the absorption peak, and the appearance of the absorption peak derived from the imine group in the vicinity of ^{1635 cm -1 .}

Heat condensation of the ketone group of the adhesive polyimide and the primary amino group of the amino compound for crosslinking is, for example,

(1) A method of heating by adding an amino compound for crosslinking formation following synthesis (imidization) of the adhesive polyimide;

(2) As the diamine component, an excess amount of an amino compound is added in advance, and following the synthesis (imidization) of the adhesive polyimide, the remaining amino compound not involved in imidization or amidation is used as an amino compound for crosslinking. heating with adhesive polyimide, or

(3) A method of heating the adhesive polyimide composition to which the amino compound for crosslinking has been added after processing it into a predetermined shape (for example, after coating on an arbitrary substrate or forming into a film)

and the like.

In order to impart heat resistance to the adhesive polyimide, an example of a crosslinked polyimide having a crosslinked structure by formation of an imine bond has been described. It is also possible to mix|blend and harden the compound etc. which have unsaturated bonds, such as a resin hardening agent, maleimide, an activated ester resin, and resin which has a styrene skeleton.

[Adhesive Resin Composition]

Since the adhesive polyimide is solvent-soluble, it can be used in the form of a composition containing a solvent. That is, the adhesive resin composition contains an adhesive polyimide and the solvent which can melt|dissolve this adhesive polyimide. Moreover, the adhesive resin composition can contain the amino compound for crosslinking formation as an arbitrary component. The adhesive resin composition contains, as a main component of the resin component, preferably 70% by weight or more of the resin component, more preferably 90% by weight or more of the resin component, and most preferably an adhesive polyimide as all of the resin component. do. In addition, the main component of a resin component means the component contained in excess of 50 weight% with respect to all the resin components.

The solvent is not particularly limited as long as it can dissolve the adhesive polyimide, for example, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-diethylacetate. Amide, N-methyl-2-pyrrolidone (NMP), 2-butanone, dimethyl sulfoxide (DMSO), hexamethyl phosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, methylcyclohexane, Dioxane, tetrahydrofuran, diglyme, triglyme, methanol, ethanol, benzyl alcohol, cresol, acetone, etc. are mentioned. Two or more of these solvents may be used in combination, and further, an aromatic hydrocarbon such as xylene or toluene may be used in combination.

The adhesive resin composition WHEREIN: There is no restriction|limiting in particular as long as the compounding ratio of adhesive polyimide and a solvent can maintain the viscosity of the grade which can coat a composition. It is preferable that the viscosity of an adhesive resin composition exists in the range of 500 mPa*s - 100000 mPa*s, for example. When it deviates from this range, it will become easy to generate|occur|produce defects, such as thickness nonuniformity and a stripe, in a resin film at the time of a coating operation.

The adhesive resin composition contains, as an optional component, other cured resin components such as plasticizers and epoxy resins, curing agents, curing accelerators, organic fillers, inorganic fillers, coupling agents, flame retardants, etc., as long as the effects of the invention are not impaired. It can be properly combined.

[Adhesive Film]

An adhesive film according to an embodiment of the present invention is obtained by processing the adhesive polyimide or crosslinked polyimide into a film shape. The adhesive film, as a main component of the resin component, is preferably 70% by weight or more of the resin component, more preferably 90% by weight or more of the resin component, and most preferably all of the resin component. It will not specifically limit if it is a film containing a polyimide. In addition, the main component of a resin component means the component contained in excess of 50 weight% with respect to all the resin components. The adhesive film may be a film (sheet) containing an adhesive polyimide or a crosslinked polyimide, for example, a base material of an inorganic material such as copper foil or a glass plate, a polyimide-based film, a polyamide-based film, or a polyester-based film The state laminated|stacked on resin base materials, such as a film, may be sufficient. The adhesive film can mix|blend suitably other hardening resin components, such as a plasticizer and an epoxy resin, a hardening|curing agent, a hardening accelerator, an organic filler, an inorganic filler, a coupling agent, a flame retardant, etc. as an arbitrary component, for example.

The adhesive film formed of the adhesive polyimide satisfying the conditions a, b1 and c was measured by a split post dielectric resonator (SPDR) after 24 hours of humidity control under constant temperature and humidity conditions (states) of 23° C. and 50% RH. It is preferable that the dielectric loss tangent (Tanδ ₁ ) at 10 GHz to be used is 0.005 or less, and the relative dielectric constant (E ₁ ) is 3.0 or less. When the dielectric loss tangent (Tanδ ₁ ) and the relative dielectric constant (E ₁ ) exceed the above values, it leads to an increase in dielectric loss when applied to a circuit board, and problems such as loss of electrical signals in the transmission path of high-frequency signals are likely to occur lose

In addition, the adhesive film formed of the adhesive polyimide satisfying the conditions a, b1 and c was subjected to a split post dielectric resonator (SPDR) after 24 hours of humidity control under constant temperature and humidity conditions (states) of 23° C. and 50% RH. It is preferable that the dielectric loss tangent (Tanδ ₂ ) at 20 GHz measured by 0.005 or less and the relative permittivity (E ₂ ) be 3.0 or less. When the dielectric loss tangent (Tanδ ₂ ) and the relative permittivity (E ₂ ) exceed the above values, it leads to an increase in dielectric loss when applied to a circuit board, and problems such as loss of electrical signals on the transmission path of high-frequency signals are likely to occur lose

In addition, the adhesive film formed of the adhesive polyimide satisfying the conditions a, b1 and c was subjected to a split post dielectric resonator (SPDR) after 24 hours of humidity control under constant temperature and humidity conditions (states) of 23° C. and 50% RH. It is preferable that the difference (Tanδ _{2 -Tanδ 1} ) between the dielectric loss tangent (Tanδ ₁ ) at 10 GHz and the dielectric loss tangent ( _{Tanδ 2) at 20 GHz measured by the above is 0 or less.} The difference (Tanδ _{2 -Tanδ 1} ) of 0 or less means that the transmission loss does not increase even if the frequency is increased from 10 GHz to 20 GHz, but is the same or rather decreases.

On the other hand, the adhesive film formed of the adhesive polyimide satisfying the conditions a, b2 and c was subjected to a split post dielectric resonator (SPDR) after 24 hours of humidity control under constant temperature and humidity conditions (states) of 23° C. and 50% RH. _{It is preferable that the dielectric loss tangent (Tanδ 1} ) at 10 GHz as measured by the above is less than 0.002, and the relative dielectric constant (E ₁ ) is 3.0 or less. When the dielectric loss tangent (Tanδ ₁ ) and the relative dielectric constant (E ₁ ) exceed the above values, it leads to an increase in dielectric loss when applied to a circuit board, and problems such as loss of electrical signals in the transmission path of high-frequency signals are likely to occur lose

In addition, the adhesive film formed of the adhesive polyimide satisfying the conditions a, b2 and c was subjected to a split post dielectric resonator (SPDR) after 24 hours of humidity control under constant temperature and humidity conditions (states) of 23° C. and 50% RH. It is preferable that the dielectric loss tangent (Tanδ ₂ ) at 20 GHz as measured by the above is less than 0.002, and the relative dielectric constant (E ₂ ) is 3.0 or less. When the dielectric loss tangent (Tanδ ₂ ) and the relative permittivity (E ₂ ) exceed the above values, it leads to an increase in dielectric loss when applied to a circuit board, and problems such as loss of electrical signals on the transmission path of high-frequency signals are likely to occur lose

The tensile modulus of elasticity of the adhesive film is preferably 3000 MPa or less, preferably 100 MPa or more and 2500 MPa or less, and more preferably 200 MPa or more and 2000 MPa or less. When the tensile modulus of elasticity is less than 100 MPa, the film tends to wrinkle, and handling properties such as the occurrence of entrapment of air at the time of lamination may deteriorate. In addition, when the tensile modulus exceeds 3000 MPa and the base material and the adhesive film are laminated, warpage or dimensional stability is reduced. By setting it as said tensile elasticity modulus, handleability is favorable, curvature is suppressed, and the laminated body excellent in dimensional stability can be obtained.

Although it does not specifically limit about the manufacturing method of the adhesive agent film of this embodiment, The method of the following [1] - [3] can be illustrated.

[1] An optional substrate is coated with an adhesive polyimide in the state of a solution (for example, in the state of an adhesive resin composition) to form a coating film, which is dried at a temperature of, for example, 80 to 180° C. to form a film A method of peeling from a base material if necessary after forming.

[2] A method in which a solution of polyamic acid, which is a precursor of an adhesive polyimide, is applied to an arbitrary substrate and dried, then imidized to form a film, and then peeled off from the substrate if necessary.

[3] A method of applying and drying a solution of polyamic acid, a precursor of an adhesive polyimide, to an arbitrary substrate, then peeling the polyamic acid gel film from the substrate and imidizing it to obtain an adhesive film.

The method for applying the adhesive polyimide solution (or polyamic acid solution) onto the substrate is not particularly limited, and it is possible to apply, for example, with a comma, die, knife, or lip coater or the like.

Next, the laminated body, the metal-clad laminated board, a circuit board, and a multilayer circuit board which are preferable embodiment to which the adhesive agent film is applied are given and demonstrated with specific examples.

[Laminate]

A laminate 100 according to an embodiment of the present invention includes, for example, as shown in FIG. 1 , a substrate 10 and an adhesive layer 20 laminated on at least one surface of the substrate 10 . and the adhesive layer 20 includes the adhesive film. In addition, the laminated body 100 may contain arbitrary layers other than the above. As the base material 10 in the laminate 100, for example, a base material of an inorganic material such as copper foil or a glass plate, or a base material of a resin material such as a polyimide-based film, a polyamide-based film, or a polyester-based film. can be heard The laminated body 100 can be manufactured according to any one of [1] to [3] of the manufacturing method of the said adhesive film except the point which does not peel from the base material 10. Moreover, you may manufacture the laminated body 100 by preparing and bonding the base material 10 and an adhesive film, respectively.

As a preferable aspect of the laminated body 100, a coverlay film, copper foil provided with resin, etc. are mentioned.

(Coverlay Film)

The coverlay film, which is an aspect of the laminate 100, is not shown, but the film material layer for the coverlay as the base material 10, and the adhesive layer 20 laminated on one side of the film material layer for the coverlay. and the adhesive layer 20 includes the adhesive film. In addition, the coverlay film may contain the arbitrary layers other than the above.

Although the material of the film material layer for the coverlay is not particularly limited, for example, a polyimide-based film such as a polyimide resin, a polyetherimide resin, or a polyamide-imide resin, a polyamide-based film, or a polyester-based film can be used. have. Among these, it is preferable to use a polyimide-based film having excellent heat resistance. In addition, the film material layer for a coverlay may contain a black pigment in order to effectively express light-shielding property, hiding property, design property, etc., and suppress the glossiness of the surface in the range which does not impair the improvement effect of a dielectric property. may contain optional components such as matting pigments.

Although the thickness of the film material layer for coverlays is not specifically limited, For example, the inside of the range of 5 micrometers or more and 100 micrometers or less is preferable.

In addition, the thickness of the adhesive bond layer 20 is although it does not specifically limit, For example, the inside of the range of 10 micrometers or more and 75 micrometers or less is preferable.

The coverlay film of this embodiment can be manufactured by the method illustrated below.

First, as a first method, the polyimide serving as the adhesive layer 20 is placed on one side of the film material layer for a coverlay in the state of a solution (for example, a varnish containing solvent is preferable, preferably the adhesive resin composition good), for example, by drying at a temperature of 80 to 180 ° C. to form the adhesive layer 20, a coverlay film having a film material layer for a coverlay and an adhesive layer 20 can be formed. .

In addition, as a second method, the polyimide for the adhesive layer 20 is applied to an arbitrary base material in a solution state (for example, a varnish containing a solvent is preferable, preferably an adhesive resin composition is good) After coating with, for example, drying at a temperature of 80 to 180° C., and peeling, an adhesive film for the adhesive layer 20 is formed, and this adhesive film is combined with a film material layer for a coverlay, for example, 60 To form a coverlay film by thermocompression bonding at a temperature of 220 ℃.

(Copper foil with resin)

The copper foil with resin, which is another aspect of the laminate 100 , is not illustrated, but an adhesive layer 20 is laminated on at least one side of the copper foil as the substrate 10 , and the adhesive layer 20 is the adhesive including film. In addition, the copper foil provided with resin of this embodiment may contain arbitrary layers other than the above.

It is preferable to exist in the range of 0.1-125 micrometers, for example, and, as for the thickness of the adhesive bond layer 20 in copper foil with resin, the inside of the range of 0.3-100 micrometers is more preferable. If the thickness of the adhesive layer 20 is less than the lower limit, there may be problems such as not being able to ensure sufficient adhesiveness. On the other hand, when the thickness of the adhesive layer 20 exceeds the upper limit, problems such as a decrease in dimensional stability occur. Moreover, it is preferable that the thickness of the adhesive bond layer 20 shall be 3 micrometers or more from a viewpoint of low-dielectric constant-ization and a low-dielectric dissipation tangent.

It is preferable that the material of the copper foil in copper foil provided with resin has copper or a copper alloy as a main component. The thickness of copper foil becomes like this. Preferably it is 35 micrometers or less, More preferably, the inside of the range of 5-25 micrometers is good. It is preferable that the lower limit of the thickness of copper foil shall be 5 micrometers from a viewpoint of production stability and handling property. In addition, a rolled copper foil may be sufficient as copper foil, and an electrolytic copper foil may be sufficient as it. In addition, as copper foil, commercially available copper foil can be used.

Copper foil with resin may be prepared by, for example, sputtering a metal on an adhesive film to form a seed layer, and then forming a copper layer by, for example, copper plating, or thermocompression bonding of an adhesive film and copper foil, etc. You may prepare by laminating by the method of In addition, the copper foil with resin is prepared by casting a coating liquid of an adhesive polyimide or a precursor thereof to form an adhesive layer 20 on the copper foil, drying it to form a coating film, and then performing necessary heat treatment. You can do it.

[Metal Covered Laminate]

(first aspect)

A metal clad laminate according to an embodiment of the present invention includes an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer, wherein at least one of the insulating resin layers comprises the adhesive film will be. In addition, the metal clad laminated board of this embodiment may contain arbitrary layers other than the above.

(Second aspect)

The metal-clad laminate according to another embodiment of the present invention is, for example, as shown in FIG. 2 , an insulating resin layer 30 and an adhesive layer 20 laminated on at least one side of the insulating resin layer 30 . ) and a so-called three-layer metal clad laminate 101 having a metal layer M laminated on the insulating resin layer 30 via the adhesive layer 20, wherein the adhesive layer 20 is the adhesive film will include In addition, the three-layer metal clad laminated board 101 may contain arbitrary layers other than the above. In the three-layer metal clad laminate 101 , the adhesive layer 20 may be provided on one or both sides of the insulating resin layer 30 , and the metal layer M is formed with the insulating resin layer 30 through the adhesive layer 20 . ) may be provided on one or both sides of the That is, the three-layer metal-clad laminate 101 may be a single-sided metal-clad laminate, or a double-sided metal-clad laminate. Single-sided FPC or double-sided FPC can be manufactured by etching the metal layer M of the three-layer metal clad laminated board 101, etc. and processing a wiring circuit.

The insulating resin layer 30 in the three-layer metal clad laminate 101 is not particularly limited as long as it is composed of a resin having electrical insulation properties, for example, polyimide, epoxy resin, phenol resin, polyethylene, polypropylene. , polytetrafluoroethylene, silicone, ETFE, etc., but preferably made of polyimide. Although a single layer or multiple layers may be sufficient as the polyimide layer which comprises the insulating resin layer 30, it is preferable that a non-thermoplastic polyimide layer is included.

It is preferable to exist in the range of 1-125 micrometers, for example, and, as for the thickness of the insulating resin layer 30 in the three-layer metal clad laminated board 101, the inside of the range of 5-100 micrometers is more preferable. If the thickness of the insulating resin layer 30 does not reach the lower limit, a problem such as not being able to guarantee sufficient electrical insulation may occur. On the other hand, when the thickness of the insulating resin layer 30 exceeds the said upper limit, problems, such as becoming easy to generate|occur|produce the curvature of a metal clad laminated board, will arise.

It is preferable to exist in the range of 0.1-125 micrometers, for example, and, as for the thickness of the adhesive bond layer 20 in the three-layer metal clad laminated board 101, the inside of the range of 0.3-100 micrometers is more preferable. In the three-layer metal-clad laminate 101 of this embodiment, if the thickness of the adhesive bond layer 20 does not reach the said lower limit, the problem that sufficient adhesiveness cannot be ensured may generate|occur|produce. On the other hand, when the thickness of the adhesive layer 20 exceeds the upper limit, problems such as a decrease in dimensional stability occur. In addition, from the viewpoint of low dielectric constant and low dielectric loss tangent of the entire insulating layer, which is a laminate of the insulating resin layer 30 and the adhesive layer 20 , the thickness of the adhesive layer 20 is preferably 3 µm or more.

In addition, the ratio of the thickness of the insulating resin layer 30 to the thickness of the adhesive layer 20 (thickness of the insulating resin layer 30/thickness of the adhesive layer 20) is, for example, preferably within the range of 0.1 to 3.0. and the inside of the range of 0.15-2.0 is more preferable. By setting it as such a ratio, the curvature of the three-layer metal clad laminated board 101 can be suppressed. In addition, the insulating resin layer 30 may contain a filler as needed. As a filler, silicon dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride, the metal salt of organic phosphinic acid, etc. are mentioned, for example. These can be used 1 type or in mixture of 2 or more types.

(Third aspect)

A metal-clad laminate according to another embodiment of the present invention is a bonding-type metal-clad laminate formed by bonding at least two single-sided metal-clad laminates to each other via an adhesive layer 20, for example, as shown in FIG. 3 . (102). The bonded metal-clad laminate 102 includes a first single-sided metal-clad laminate 41, a second single-sided metal-clad laminate 42, a first single-sided metal-clad laminate 41, and a second single-sided metal-clad laminate 42 It has an adhesive layer 20 laminated therebetween, and the adhesive layer 20 includes the adhesive film.

Here, the 1st single-sided metal clad laminated board 41 has the 1st metal layer M1, and the 1st insulating resin layer 31 laminated|stacked on the surface of at least one side of this 1st metal layer M1. The second single-sided metal-clad laminate 42 has a second metal layer M2 and a second insulating resin layer 32 laminated on at least one side of the second metal layer M2. The adhesive layer 20 is arrange|positioned so that the 1st insulating resin layer 31 and the 2nd insulating resin layer 32 contact|abut. In addition, the bonding type metal clad laminated board 102 may contain arbitrary layers other than the above.

The first insulating resin layer 31 and the second insulating resin layer 32 of the bonding type metal-clad laminate 102 are formed of the insulating resin layer 30 of the three-layer metal-clad laminate 101 of the second aspect and The same configuration may be used.

The bonding type metal-clad laminate 102 is prepared by preparing a first single-sided metal-clad laminate 41 and a second single-sided metal-clad laminate 42, respectively, and a first insulating resin layer 31 and a second insulating resin layer 32 ) by placing and bonding an adhesive film between them.

(4th aspect)

A metal clad laminate according to another embodiment of the present invention is, for example, as shown in FIG. 4 , an insulating resin layer 33 and a metal layer M laminated on one surface of the insulating resin layer 33 . A single-sided metal-clad laminate having a single-sided metal-clad laminate having to include an adhesive film. In addition, the metal-clad laminated board 103 provided with the adhesive bond layer may contain the arbitrary layers other than the above.

The insulating resin layer 33 in the metal-clad laminate 103 provided with an adhesive bond layer may have the same structure as the insulating resin layer 30 of the three-layer metal-clad laminate 101 of the second aspect.

The metal-clad laminate with an adhesive layer 103 is manufactured by preparing a single-sided metal-clad laminate having an insulating resin layer 33 and a metal layer M, and bonding an adhesive film to the side of the insulating resin layer 33. can do.

In any of the first to fourth aspects of the above examples, in the metal-clad laminate, the material of the metal layer M (including the first metal layer M1 and the second metal layer M2. The same applies hereinafter) is not particularly limited. However, examples thereof include copper, stainless steel, iron, nickel, beryllium, aluminum, zinc, indium, silver, gold, tin, zirconium, tantalum, titanium, lead, magnesium, manganese, and alloys thereof. Among these, copper or a copper alloy is especially preferable. In addition, the material of the wiring layer in the circuit board mentioned later is also the same as that of the metal layer M.

Although the thickness of the metal layer M is not specifically limited, For example, when using metal foils, such as copper foil, Preferably it is 35 micrometers or less, More preferably, it is good in the range of 5-25 micrometers. It is preferable that the lower limit of the thickness of metal foil shall be 5 micrometers from a viewpoint of production stability and handling property. In addition, when using copper foil, a rolled copper foil may be sufficient and an electrolytic copper foil may be sufficient. In addition, as copper foil, commercially available copper foil can be used. In addition, metal foil may surface-treat by, for example, siding, aluminum alcoholate, aluminum chelate, a silane coupling agent, etc. for the purpose of a rust prevention process and the improvement of adhesive force, for example.

[circuit board]

(first aspect)

A circuit board according to an embodiment of the present invention is formed by wiring the metal layer of the metal-clad laminate according to any of the above embodiments. Circuit boards, such as an FPC, can be manufactured by processing one or more metal layers of a metal clad laminated board into pattern shape by an ordinary method to form a wiring layer (conductor circuit layer). Moreover, the circuit board may be equipped with the coverlay film which coat|covers a wiring layer.

(Second aspect)

A circuit board 200 according to another embodiment of the present invention is, for example, as shown in FIG. 5 , a first base material 11 and a wiring layer 50 laminated on at least one surface of the first base material 11 . ) and an adhesive layer 20 laminated to cover the wiring layer 50 on the surface of the first substrate 11 on the wiring layer 50 side, wherein the adhesive layer 20 includes the adhesive film will be. In addition, the circuit board 200 may contain arbitrary layers other than the above.

The 1st base material 11 in the circuit board 200 may have the structure similar to the insulating resin layer of the said metal clad laminated board. The circuit board 200 is formed by bonding an adhesive film to the wiring layer 50 side of a circuit board having a first substrate 11 and a wiring layer 50 laminated on at least one surface of the first substrate 11 . can be manufactured.

(Third aspect)

A circuit board 201 according to still another embodiment of the present invention includes, for example, as shown in FIG. 6 , a first substrate 11 and a wiring layer laminated on at least one surface of the first substrate 11 ( 50) and the adhesive layer 20 laminated so as to cover the wiring layer 50 on the surface of the first substrate 11 on the wiring layer 50 side, and the side opposite to the first substrate 11 of the adhesive layer 20 and a second substrate 12 laminated on the surface of the , and the adhesive layer 20 includes the adhesive film. In addition, the circuit board 201 may contain arbitrary layers other than the above. The structure similar to the insulating resin layer of the said metal clad laminated board may be sufficient as the 1st base material 11 and the 2nd base material 12 in the circuit board 201.

The circuit board 201 is formed by interposing an adhesive film on the wiring layer 50 side of the circuit board including the first substrate 11 and the wiring layer 50 laminated on at least one surface of the first substrate 11 . It can manufacture by bonding the 2nd base material 12.

(4th aspect)

A circuit board 202 according to still another embodiment of the present invention is, for example, as shown in FIG. 7 , a first base material 11 and an adhesive layer laminated on at least one surface of the first base material 11 . (20), the second substrate 12 laminated on the surface opposite to the first substrate 11 of the adhesive layer 20, and the adhesive layer of the first substrate 11 and the second substrate 12 ( 20) is provided with the wiring layers 50 and 50 respectively laminated on the surface opposite to the side surface, and the adhesive layer 20 includes the adhesive film. In addition, the circuit board 202 may contain arbitrary layers other than the above. The structure similar to the insulating resin layer of the said metal clad laminated board may be sufficient as the 1st base material 11 and the 2nd base material 12 in the circuit board 202.

The circuit board 202 includes a first circuit board including a first base material 11, a wiring layer 50 laminated on at least one surface of the first base material 11, a second base material 12; A second circuit board having a wiring layer 50 laminated on at least one surface of the second substrate 12 is prepared, respectively, the first substrate 11 of the first circuit board and the second circuit board of the second circuit board It can be manufactured by arranging and bonding an adhesive film between the substrates 12 .

[Multilayer Circuit Board]

A multilayer circuit board according to an embodiment of the present invention includes a laminate in which a plurality of insulating resin layers are laminated, and one or more wiring layers embedded in the laminate, at least one of the plurality of insulating resin layers. As mentioned above, it has adhesiveness and is formed of the adhesive bond layer 20 which coat|covers a wiring layer, and this adhesive bond layer 20 contains the said adhesive film. In addition, the multilayer circuit board of this embodiment may contain arbitrary layers other than the above.

For example, as shown in FIG. 8 , the multilayer circuit board 203 of this embodiment has at least two or more insulating resin layers 34 and at least two or more wiring layers 50 , and among the wiring layers 50 , At least one layer is covered with an adhesive layer (20). The adhesive layer 20 covering the wiring layer 50 may partially cover the surface of the wiring layer 50 or may cover the entire surface of the wiring layer 50 . Further, the multilayer circuit board 203 may optionally have a wiring layer 50 exposed on the surface of the multilayer circuit board 203 . In addition, an interlayer connection electrode (via electrode) in contact with the wiring layer 50 may be provided. The wiring layer 50 has a conductor circuit formed on one side or both sides of the insulating resin layer 34 in a predetermined pattern. The conductor circuit may be pattern-formed on the surface of the insulating resin layer 34, or may be pattern-formed in a damascene (buried) type. The insulating resin layer 34 in the multilayer circuit board 203 may have the same configuration as the insulating resin layer of the metal-clad laminate.

Since the circuit board and multilayer circuit board of each said embodiment are equipped with the adhesive bond layer 20 containing the adhesive polyimide whose aromatic ring density|concentration was controlled, reduction of transmission loss is possible also in high frequency transmission.

[Action]

Fig. 9 is a diagram schematically expressing the relationship between the aromatic ring concentration and dielectric loss tangent when the adhesive polyimide of the present invention satisfies the above conditions a, b1 and c. The ordinate in Fig. 9 is the dielectric loss tangent at 10 GHz measured by the same method as in the later examples, and the abscissa is the weight content of carbon atoms derived from 6-membered aromatic rings with respect to the total content of all atoms in the polyimide (aromatic rings). concentration). Aromatic rings, such as a benzene ring, vibrate by high frequency, and increase heat loss. Therefore, as a general tendency, the dielectric loss tangent increases as the concentration of the aromatic ring contained in the polyimide increases. However, in adhesive polyimide, when the aromatic ring concentration is within the range of 12 to 40% by weight, the dielectric loss tangent does not increase even if the aromatic ring concentration increases, but rather shows a tendency for the dielectric loss tangent to decrease up to a certain aromatic ring concentration. gave out Although the cause showing such a behavior is not yet clear, a rational analysis is possible if it considers as follows.

The adhesive polyimide uses a dimer diamine composition as a raw material, and has relatively low aromatic ring density|concentration compared with the polyimide which uses aromatic diamine as a raw material. As described above, when the concentration of the aromatic ring is gradually increased from the low concentration of the aromatic ring, the movement of the molecule is restricted by the interaction between the aromatic rings, and it is estimated that the dielectric loss tangent is suppressed even lower. And it is thought that it shows a sufficiently low dielectric loss tangent until an aromatic ring density|concentration reaches 40 weight%.

[Example]

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

[Method for measuring amine value]

About 2 g of dimer diamine composition is weighed into a 200 to 250 mL Erlenmeyer flask, and phenolphthalein is used as an indicator, and 0.1 mol/L ethanolic potassium hydroxide solution is added dropwise until the solution exhibits a pale pink color and neutralized butanol drug Dissolve in 100 mL. Add 3 to 7 drops of phenolphthalein solution thereto, and titrate with stirring in 0.1 mol/L ethanolic potassium hydroxide solution until the sample solution turns pale pink. 5 drops of bromophenol blue solution are added thereto, and titrated with stirring in 0.2 mol/L hydrochloric acid/isopropanol solution until the sample solution turns yellow.

An amine titer is computed by following formula (1).

Amine value = {(V ₂ ×C ₂ )-(V ₁ ×C ₁ )} × M _KOH /m ... (1)

Here, the amine value is a value expressed in mg-KOH/g, and M _KOH is the molecular weight of potassium hydroxide 56.1. In addition, V and C are the volume and concentration of the solution used for titration, respectively, and subscripts 1 and 2 represent 0.1 mol/L ethanolic potassium hydroxide solution and 0.2 mol/L hydrochloric acid/isopropanol solution, respectively. Also, m is the sample weight in grams.

[Measurement of weight average molecular weight (Mw) of polyimide]

The weight average molecular weight was measured with a gel permeation chromatograph (the Tosoh Corporation make, HLC-8220GPC is used). Polystyrene was used as a standard material, and tetrahydrofuran (THF) was used as a developing solvent.

[Calculation method of CM value]

The weight content ratio (C) of the carbon atoms derived from the 6-membered aromatic ring (excluding the carbon atoms of the 6-membered aromatic ring derived from the dimer diamine composition) with respect to the total content of the weight average molecular weight (Mw) of the polyimide and all atoms in the polyimide (C _From the relationship of p), the CM value was computed based on the following formula.

CM = (C _p /Mw) × 10 ⁴ ... (i)

[Calculation method of DM value]

The content (C) of the carbon atoms derived from the 6-membered aromatic ring (excluding the carbon atoms of the 6-membered aromatic ring derived from the dimer diamine composition) with respect to the total content of the weight average molecular weight (Mw) of the polyimide and all atoms in all the diamine components (C _From the relationship of d), the DM value was computed based on the following formula.

DM = (C _d /Mw) × 10 ⁴ ... (ii)

[Calculation of the aromatic ring ratio of the dimer diamine composition]

The aromatic ring ratio of the dimer diamine composition was computed with the following procedure. First, about 50 µl of the dimer diamine composition was dissolved in THF-d8550 µl to prepare a sample. The prepared sample was subjected to liquid 1H-NMR measurement at room temperature using an FT-NMR apparatus (JNM-ECA400 manufactured by JEOL). From the ratio of the integral value of the 1H peak derived from the aromatic ring seen at 6.6 to 7.2 ppm to the integral value of the 1H peak derived from the CH _{2 group directly linked to the NH 2} group seen at 2.6 to 2.9 ppm, the aromatic ring ratio as shown in the following formula calculated.

Aromatic ring ratio [mol%] = (Z/Y) × 100

[Here, Y means the integral value of the 1H peak at 2.6 to 2.9 ppm, and Z means the integral value of the 1H peak (derived from the aromatic ring) at 6.6 to 7.2 ppm.]

[Calculation of area percent of GPC and chromatogram]

(a) dimer diamine

(b) a monoamine compound obtained by substituting a terminal carboxylic acid group of a monobasic acid compound having 10 to 40 carbon atoms with a primary aminomethyl group or an amino group

(c) an amine compound obtained by substituting a terminal carboxylic acid group of a polybasic acid compound having a hydrocarbon group within the range of 41 to 80 carbon atoms with a primary aminomethyl group or an amino group (provided that the dimer diamine is excluded)

For GPC, a sample of 100 mg of a 20 mg dimer diamine composition was pretreated with 200 µL of acetic anhydride, 200 µL of pyridine and 2 mL of THF, diluted with 10 mL of THF (containing 1000 ppm of cyclohexanone) to prepare a sample. . The prepared sample is manufactured by Tosoh Corporation, brand name; HLC-8220GPC was used, column: TSK-gel G2000HXL, G1000HXL, flow amount: 1 mL/min, column (oven) temperature: 40°C, injection amount: 50 µL. In addition, cyclohexanone was treated as a standard for calibration of the runoff time.

At this time, the peak top of the main peak of cyclohexanone is adjusted so that the retention time is 27 to 31 minutes, and the peak end is 2 minutes from the peak start of the main peak of cyclohexanone. Each of the above components (a) to (c) under the condition that the peak top is 18 minutes to 19 minutes, and the peak start to the peak end of the main peak excluding the peak of cyclohexanone is 2 minutes to 4 minutes and 30 seconds as,

(a) the component displayed in the main peak;

(b) a component displayed in the GPC peak detected later than the local minimum on the time side when the retention time in the main peak is late as a reference;

(c) a component displayed in the GPC peak detected earlier than the local minimum on the time side when the retention time in the main peak is earlier as a reference;

was detected.

[Measurement of viscosity]

Using a type E viscometer (type DV-II+ProCP), the polyimide solution was measured by temperature; 25°C, number of revolutions; 100 RPM, measurement time; The viscosity (cP) immediately after polymerization was measured under the conditions of 2 minutes.

[Measurement of dielectric constant and dielectric loss tangent]

The resin sheet was subjected to temperature using a Vector Network Analyzer (manufactured by Agilent, trade name; Vector Network Analyzer E8363C) and an SPDR resonator; 23°C, humidity; After standing for 24 hours under the condition of 50%, the relative dielectric constant (ε ₁ ) and dielectric loss tangent ( _{Tanδ 1} ) at a frequency of 10 GHz, and the relative dielectric constant (ε ₂ ) and dielectric loss tangent (Tanδ) at a frequency of 20 GHz ₂ ) was measured. In addition, the R value used as an index of the frequency dependence of the dielectric loss tangent was calculated by the following formula.

R value = Tanδ _{2 -Tanδ 1}

[Glass Transition Temperature (Tg)]

The glass transition temperature (Tg) is a resin sheet having a size of 5 mm × 20 mm, using a thermomechanical analysis apparatus (TMA: manufactured by Netchi Corporation, trade name; TMA4000SA), the temperature increase rate from 0°C to 300°C is 5°C/ The measurement was performed in minutes. The temperature used as the inflection point of extending|stretching at the time of temperature rise was made into glass transition temperature.

[Tensile Modulus]

The tensile modulus of elasticity was measured in the following procedure. First, a test piece (width 12.7 mm x length 127 mm) was produced from a resin sheet using a tension tester (manufactured by Orientec, trade name; Tensilon). A tensile test was performed at 50 mm/min using this test piece, and the tensile modulus in 25 degreeC was calculated|required.

[Method for evaluating warpage]

Evaluation of curvature was performed with the following method. A polyimide solution was applied on a 25 µm-thick polyimide film (manufactured by Toray DuPont, trade name; Kapton 100EN) or on a 12 µm copper foil to a thickness of 25 µm after drying to prepare a test piece. In this state, the polyimide film or copper foil was placed so as to be the lower surface, the average of the heights of the four corners of the test piece was measured, and 5 mm or less was considered "good", and the case exceeding 5 mm was called "impossible".

The abbreviation used in this Example shows the following compounds.

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

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

ODPA: 4,4'-oxydiphthalic anhydride

BPADA: 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride

DDA: dimer diamine having 36 carbon atoms (manufactured by Croda Japan Co., Ltd., trade name; distilled and purified PRIAMINE1074, amine value; 210 mgKOH/g, mixture of dimer diamines having a cyclic structure and a chain structure, component (a); 97.9 area%, component (b);0.3 area%, component (c); area 1.8%, aromatic ring ratio; 8.2 mol%)

BAFL: Bisanilinefluorene

APB: 1,3-bis(3-aminophenoxy)benzene

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

N-12: dodecane diacid dihydrazide

NMP: N-methyl-2-pyrrolidone

OP935: aluminum salt of phosphinic acid (Clary not Itza, product name; Exolit OP935, diethyl phosphinic acid aluminum, phosphorus content; 23%, average particle diameter D _50; 2㎛)

SR-3000: phosphoric acid ester (manufactured by Daihachi Chemical Industries, Ltd., trade name; SR-3000, non-halogen aromatic condensed phosphoric acid ester, phosphorus content; 7.0%)

In addition, the molecular weight of the said DDA was computed by the following formula.

Molecular weight = 56.1 x 2 x 1000 / amine value

[Example A1]

In a 1000 ml separable flask, 46.43 g of BTDA (0.1441 mol), 68.60 g of DDA (0.1284 mol), 4.97 g of BAFL (0.0143 mol), 168 g of NMP and 112 g of xylene were charged and charged at 40° C. for 1 hour. It mixed well to prepare a polyamic acid solution. This polyamic acid solution was heated to 190° C., heated and stirred for 5 hours, and imidized by adding 98 g of xylene. Polyimide solution A1 (solid content; 30% by weight, weight average molecular weight; 28,850, 6-way direction) ring content _{C d; 5.59%, C p} ; 21.57%, DM value; 1.9, CM value; to 7.5) was prepared.

[Examples A2 to A18]

Except having set it as the raw material composition shown in Table 1 and Table 2, it carried out similarly to Example A1, and prepared polyimide solutions A2 - A18.

[Example A19]

Polyimide solution A1 was applied to one side of a release PET film 1 (manufactured by Higashiyama Film Co., Ltd., trade name; HY-S05, length × width × thickness = 200 mm × 300 mm × 25 μm), and dried at 120 ° C. for 10 minutes, , An adhesive film A19 having a thickness of 25 µm was obtained by peeling the adhesive layer from the release PET film 1. Various evaluation results of adhesive film A19 are as follows.

ε ₁ ; 2.6, Tanδ ₁ ; 0.0017, ε ₂ ; 2.6, Tanδ ₂ ; 0.0014, R value; -0.0003, Tg; 45°C, tensile modulus; 630 MPa

[Examples A20 to A36]

Except having used polyimide solution A2 - A18, it carried out similarly to Example A19, and obtained adhesive bond film A20 - A36. Various characteristic evaluation results are shown in Table 3.

[Example A37]

In 100 g of polyimide solution A1 (30 g as solid content), 1.1 g of N-12 (0.004 mol) was blended, 7.5 g of OP935, 2.0 g of NMP and 12.0 g of xylene were added to dilute, and stirred for another hour. By doing so, adhesive composition A37 was prepared.

[Examples A38 to A54]

Except having used polyimide solutions A2 - A18, it carried out similarly to Example A37, and prepared adhesive composition A38 - A54.

[Example A55]

In 100 g of polyimide solution A17 (30 g as solid content), 0.6 g of N-12 (0.002 mol) was mixed, diluted by adding 7.5 g of OP935, 1.5 g of NMP and 11.4 g of xylene, and stirred for another hour By doing so, adhesive composition A55 was prepared.

[Example A56]

1.1 g of N-12 (0.004 mol) was mix|blended with 100 g of polyimide solution A11 (30 g as solid content), 6.0 g of SR-3000, 0.3 g of NMP, and 10.3 g of xylene were added and diluted, and 1 hour By further stirring, adhesive composition A56 was prepared.

[Example A57]

The adhesive composition A37 was applied to one side of the release PET film 1, dried at 80° C. for 15 minutes to obtain a resin sheet A57 having an adhesive layer thickness of 25 μm, and then the adhesive layer was peeled from the mold release PET film 1 to have a thickness of 25 μm. A phosphorous adhesive film A57 was obtained.

[Examples A58 to A76]

After carrying out similarly to Example A57 except having used adhesive composition A38-A56, and obtaining resin sheet A58-A76, adhesive film A58-A76 was obtained.

[Example A77]

Adhesive composition A37 was applied to one side of polyimide film 1 (manufactured by Toray DuPont, trade name; Kapton 50EN, ε ₁ = 3.6, tanδ ₁ = 0.0084, length × width × thickness = 200 mm × 300 mm × 12 μm), and , dried at 80°C for 15 minutes to obtain a coverlay film A77 having a thickness of an adhesive layer of 25 µm. The state of the curvature of the obtained coverlay film A77 was "good|favorableness".

[Examples A78 to A81]

Except having used adhesive composition A40, A54, A55, and A56, it carried out similarly to Example A77, and obtained coverlay film A78-A81. The state of the curvature of the obtained coverlay films A78 - A81 was "good|favorableness" in all.

[Example A82]

It laminated|stacked so that the release PET film 1 might be in contact with the adhesive bond layer side of coverlay film A77, and it was press-bonded for 2 minutes at the temperature of 160 degreeC, and the pressure of 0.8 MPa using the vacuum laminator. Thereafter, the adhesive composition A37 was applied to the polyimide film 1 side of the coverlay film A77 in which the release PET film 1 was pressed to the adhesive layer side so that the thickness after drying was 25 μm, and dried at 80° C. for 15 minutes. Then, the adhesive composition A37 was laminated so that the release PET film 1 was in contact with the coated and dried side, and was compressed for 2 minutes at a temperature of 160 ° C. and a pressure of 0.8 MPa using a vacuum laminator, and polyimide having an adhesive layer on both sides of the polyimide film. A laminate A82 with a mid adhesive layer was obtained.

[Examples A83 to A86]

Using the coverlay film A78, A79, A80 or A81, except having applied the adhesive composition A40, A54, A55 or A56, it carried out similarly to Example A82, and obtained the laminated body A83-A86 with a polyimide adhesive bond layer.

[Example A87]

The adhesive composition A37 was apply|coated to the single side|surface of the 12-micrometer-thick electrolytic copper foil, and it dried at 80 degreeC for 15 minutes, and obtained the copper foil A87 provided with the resin whose thickness of an adhesive bond layer is 25 micrometers. The state of the curvature of copper foil A87 provided with the obtained resin was "favorable".

[Examples A88 to A91]

Except having used adhesive composition A40, A54, A55, or A56, it carried out similarly to Example A87, and obtained copper foil A88-A91 provided with resin. All the states of the curvature of copper foil A88 - A91 provided with obtained resin were "good|favorableness".

[Example A92]

The adhesive composition A37 was apply|coated to the single side|surface of the 12-micrometer-thick electrolytic copper foil, and it dried at 80 degreeC for 30 minute(s), and obtained the copper foil A92 provided with the resin whose thickness of an adhesive bond layer is 50 micrometers. The state of the curvature of copper foil A92 provided with the obtained resin was "favorable".

[Example A93]

On the surface of the adhesive bond layer of copper foil A92 provided with resin, adhesive composition A37 was further apply|coated, and it dried at 80 degreeC for 30 minutes, and the total thickness of the adhesive bond layer was 100 micrometers of resin-equipped copper foil A93. . The state of the curvature of copper foil A93 provided with the obtained resin was "favorable".

[Example A94]

The adhesive composition A37 was apply|coated to the single side|surface of the release PET film 1, and it dried at 80 degreeC for 30 minutes, and peeled the adhesive bond layer from the release PET film 1, The 50-micrometer-thick adhesive film A94 was obtained.

On an electrolytic copper foil having a thickness of 12 µm, adhesive film A94, polyimide film 2 (manufactured by DuPont, trade name; Kapton 100-EN, thickness 25 µm, ε ₁ =3.6, tanδ ₁ =0.0084), adhesive film A94 and thickness 12 μm electrolytic copper foils were sequentially laminated and pressed using a vacuum laminator at a temperature of 160° C. and a pressure of 0.8 MPa for 2 minutes, then heated from room temperature to 160° C. and heat treated at 160° C. for 4 hours to obtain a copper-clad laminate A94 .

[Examples A95 to A98]

Except having used adhesive composition A40, A54, A55, and A56, it carried out similarly to Example A94, and obtained copper clad laminated boards A95 - A98.

[Example A99]

On an electrolytic copper foil having a thickness of 12 μm, the coverlay film A77 is laminated so that the adhesive layer side of the coverlay film A77 is in contact with the copper foil, and is pressed using a vacuum laminator at a temperature of 160° C. and a pressure of 0.8 MPa for 2 minutes, and then from room temperature to 160° C. It heat-processed at the temperature rise and 160 degreeC for 2 hours, and obtained copper-clad laminated board A99.

[Examples A100 to A103]

Except having used coverlay films A78, A79, A80, and A81, it carried out similarly to Example A99, and obtained copper clad laminated boards A100 - A103.

[Example A104]

An adhesive film A57 is laminated on a rolled copper foil having a thickness of 12 µm, and the polyimide film side of the coverlay film A77 is laminated so as to be in contact with the adhesive film A57, and the coverlay film A77 is rolled with a thickness of 12 µm on the adhesive layer side of the film A77. Copper foils were further laminated sequentially, and after pressing for 2 minutes at a temperature of 160 ° C. and a pressure of 0.8 MPa using a vacuum laminator, the temperature was raised from room temperature to 160 ° C., and heat treatment was performed at 160 ° C. for 2 hours to obtain a copper clad laminate A104.

[Examples A105 to A108]

Copper-clad laminate A105 in the same manner as in Example A104 except that the adhesive films A60, A74, A75, and A76 were respectively used instead of the adhesive film A57, and the coverlay films A78, A79, A80, and A81 were respectively used instead of the coverlay film A77. to A108 were prepared.

[Example A109]

2 sheets of copper foil A93 provided with resin were prepared, and polyimide film 3 (manufactured by DuPont, trade name; Kapton 200-EN, 50 µm thick, ε ₁ = 3.6, tanδ ₁ = 0.0084), laminated so as to be in contact with each other, and compressed using a vacuum laminator at a temperature of 160°C and a pressure of 0.8 MPa for 5 minutes, then heated from room temperature to 160°C and heat treated at 160°C for 4 hours, copper-clad laminate A109 got

[Example A110]

A resin layer (polyimide layer) of adhesive composition A55 single-sided copper clad laminate 1 (manufactured by Nittetsu Chemical & Materials, trade name; Espanex MC12-25-00UEM, length × width × thickness = 200 mm × 300 mm × 25 μm) It apply|coated to the side, it dried at 80 degreeC for 30 minute(s), and obtained the copper clad laminated board A110 with an adhesive bond layer whose thickness of an adhesive bond layer is 50 micrometers. The adhesive layer side of the copper clad laminate A110 provided with the adhesive layer is laminated so that the resin layer side of the other single-sided copper clad laminate 1 is in contact, and the copper clad laminate is pressed using a small precision press at a temperature of 160°C and a pressure of 4.0 MPa for 120 minutes. A laminated sheet A110 was obtained.

[Example A111]

The copper clad laminate A110 provided with two adhesive layers was laminated so that the side on the adhesive layer side was in contact, and was pressed using a small precision press at a temperature of 160° C. and a pressure of 4.0 MPa for 120 minutes to obtain a copper clad laminate A111.

[Example A112]

On the resin layer side of the single-sided copper clad laminate 1, an adhesive film A73 is laminated, and the resin layer side of the single-sided copper clad laminate 1 is further laminated on it so that the adhesive film A73 is in contact with the adhesive film A73, using a small precision press machine at a temperature of 160°C, a pressure of 4.0 It was crimped|bonded by MPa for 120 minutes, and copper clad laminated board A112 was obtained.

[Example A113]

The adhesive composition A37 was apply|coated to the single side|surface of the mold release PET film 1, dried at 80 degreeC for 15 minutes, and peeling the adhesive bond layer from the mold release PET film 1, the adhesive film A113 with a thickness of 15 micrometers was obtained.

On the resin layer side of the single-sided copper clad laminate 1, the adhesive film A113 is laminated, and the resin layer side of the single-sided copper clad laminate 1 is further laminated on it so that the adhesive film A113 is in contact with the adhesive film A113, using a small precision press machine at a temperature of 160 ° C, a pressure of 4.0 It was crimped|bonded for 120 minutes at MPa, and copper clad laminated board A113 was obtained.

[Example A114]

A double-sided copper-clad laminate 2 (manufactured by Nittetsu Chemical & Materials, trade name; Espanex MB12-25-00UEG) was prepared, and a copper foil on one side was subjected to circuit processing by etching to form a conductor circuit layer. A114A was obtained.

The copper foil of one surface of the double-sided copper clad laminated board 2 was removed by etching, and copper clad laminated board A114B was obtained.

The adhesive film A73 was sandwiched between the surface on the conductor circuit layer side of the wiring board A114A and the resin layer side surface of the copper clad laminate A114B, in a laminated state, thermocompression bonded at a temperature of 160°C and a pressure of 4.0 MPa for 120 minutes, and a multilayer circuit board I got A114.

[Example A115]

A liquid crystal polymer film (manufactured by Kuraray, trade name; CT-Z, thickness; 50 µm, CTE; 18 ppm/K, heat deflection temperature; 300°C, ε ₁ =3.40, tan δ ₁ =0.0022) was used as an insulating substrate, and both sides thereof A copper-clad laminate A115 provided with an electrolytic copper foil having a thickness of 18 µm was prepared, and circuit processing by etching was performed on one side of the copper foil to obtain a wiring board A115A on which a conductor circuit layer was formed.

The copper foil of the single side|surface of copper clad laminated board A115 was removed by etching, and copper clad laminated board A115B was obtained.

The adhesive film A73 was sandwiched between the surface on the side of the conductor circuit layer of the wiring board A115A and the surface on the side of the insulating base layer of the copper clad laminate A115B, in a laminated state, thermocompression-bonded at a temperature of 160° C. and a pressure of 4.0 MPa for 120 minutes, and a multilayer circuit board I got the A115.

[Example B1]

In a 500 ml separable flask, 27.90 g BTDA (0.08642 mol), 6.702 g ODPA (0.02161 mol), 46.50 g DDA (0.08703 mol), 8.932 g BAPP (0.02176 mol), 126 g NMP and 84 g xylene was charged and mixed well at 40°C for 1 hour to prepare a polyamic acid solution. This polyamic acid solution was heated to 190° C., heated and stirred for 5 hours, and imidized by adding 60 g of xylene to polyimide solution B1 (solid content; 30 wt%, weight average molecular weight; 35,332, viscosity; 2,627). cP) was prepared.

[Examples B2 to B11]

Except having set it as the raw material composition shown in Table 4, it carried out similarly to Example B1, and prepared polyimide solutions B2 - B11.

[Example B12]

Polyimide solution B1 was applied to one side of release PET film 1 (manufactured by Higashiyama Film, trade name; HY-S05, length × width × thickness = 200 mm × 300 mm × 25 μm), and dried at 100° C. for 5 minutes. , The resin sheet B12 whose thickness is 25 micrometers was obtained by drying at 120 degreeC for 5 minutes and peeling an adhesive bond layer from the mold release PET film 1. Various evaluation results of resin sheet B12 are as follows.

ε ₁ ; 2.6, Tanδ ₁ ; 0.0017, ε ₂ ; 2.6, Tanδ ₂ ; 0.0015, R value; -0.0002, Tg; 47°C, tensile modulus; 1230 MPa

[Examples B13 to B22]

Except having used polyimide solutions B2 - B11, it carried out similarly to Example B12, and obtained resin sheet B13 - B22. Various characteristic evaluation results are shown in Table 5.

[Example B23]

1.1 g of N-12 (0.004 mol) was blended with 100 g of polyimide solution B1 (30 g as solid content), diluted by adding 7.5 g of OP935, 0.5 g of NMP and 10.5 g of xylene, and stirred for 1 hour more By doing so, adhesive composition B23 was prepared.

[Examples B24 to B33]

Except having used polyimide solutions B2-B11, it carried out similarly to Example B23, and prepared adhesive composition B24-B33.

[Example B34]

0.6 g of N-12 (0.002 mol) was blended with 100 g of polyimide solution B9 (30 g as solid content), 7.4 g of OP935, 1.8 g of NMP and 11.7 g of xylene were added to dilute, and stirred for 1 hour more By doing so, adhesive composition B34 was prepared.

[Example B35]

The adhesive composition B23 was applied to one side of the release PET film 1, dried at 80° C. for 15 minutes to obtain a resin sheet B35 having an adhesive layer thickness of 25 μm, and then the adhesive layer was peeled from the release PET film 1 to have a thickness of 25 μm. Phosphorous adhesive film B35 was obtained.

[Examples B36 to B46]

Except having used adhesive composition B24-B34, it carried out similarly to Example B35, and obtained adhesive bond film B36-B46.

[Example B47]

Adhesive composition B31 was applied to one side of polyimide film 1 (manufactured by Toray DuPont, trade name; Kapton 50EN, ε ₁ = 3.6, tanδ ₁ = 0.0084, length × width × thickness = 200 mm × 300 mm × 12 μm), and , dried at 80°C for 15 minutes to obtain a coverlay film B47 having a thickness of an adhesive layer of 25 µm. The state of the curvature of the obtained coverlay film B47 was "favorable".

[Examples B48, B49]

Except having used adhesive composition B24, B25, it carried out similarly to Example B47, and obtained coverlay film B48, B49. Both the obtained coverlay films B48 and the state of the curvature of B49 were "good|favorableness".

[Example B50]

It laminated|stacked so that the release PET film 1 might contact with the adhesive bond layer side of coverlay film B47, and it was press-bonded for 2 minutes at the temperature of 160 degreeC and the pressure of 0.8 MPa using the vacuum laminator. Then, the adhesive composition B31 was applied to the polyimide film 1 side of the polyimide film 1 side of the coverlay film B47 which pressed the release PET film 1 to the adhesive layer side so that the thickness after drying might be 25 micrometers, and it dried at 80 degreeC for 15 minutes. Then, the adhesive composition B31 was laminated so that the release PET film 1 was in contact with the coated and dried surface, and was compressed for 2 minutes at a temperature of 160 ° C. and a pressure of 0.8 MPa using a vacuum laminator, and polyimide having an adhesive layer on both sides of the polyimide film A laminate B50 with a mid adhesive layer was obtained.

[Examples B51, B52]

Except having apply|coated adhesive composition B24, B25 using coverlay film B48, B49, it carried out similarly to Example B50, and obtained laminated body B51 and B52 with a polyimide adhesive bond layer.

[Example B53]

The adhesive composition B31 was apply|coated to the single side|surface of the 12-micrometer-thick electrolytic copper foil, and it dried at 80 degreeC for 15 minutes, and obtained the copper foil B53 provided with the resin whose thickness of an adhesive bond layer is 25 micrometers. The state of the curvature of copper foil B53 provided with the obtained resin was "favorable".

[Examples B54 to B56]

Except having used adhesive composition B24, B25, and B26, it carried out similarly to Example B53, and obtained copper foil B54 - B56 provided with resin. All of the curvature states of copper foil B54 - B56 provided with obtained resin were "good|favorableness".

[Example B57]

The adhesive composition B31 was apply|coated to the single side|surface of the 12-micrometer-thick electrolytic copper foil, and it dried at 80 degreeC for 30 minute(s), and obtained the copper foil B57 provided with the resin whose thickness of an adhesive bond layer is 50 micrometers. The state of the curvature of copper foil B57 provided with the obtained resin was "favorable".

[Example B58]

The adhesive composition B31 was further apply|coated to the surface of the adhesive bond layer of copper foil B57 with resin, and it dried at 80 degreeC for 30 minutes, and the total thickness of the adhesive bond layer was 100 micrometers of resin-equipped copper foil B58 was obtained. . The state of the curvature of copper foil B58 provided with the obtained resin was "favorable".

[Example B59]

The adhesive composition B31 was apply|coated to the single side|surface of the release PET film 1, and it dried at 80 degreeC for 30 minutes, The adhesive bond layer was peeled from the release PET film 1, and the adhesive film B59 whose thickness is 50 micrometers was obtained.

[Example B60]

On an electrolytic copper foil having a thickness of 12 µm, adhesive film B59, polyimide film 2 (manufactured by DuPont, trade name; Kapton 100-EN, thickness 25 µm, ε ₁ =3.6, tanδ ₁ =0.0084), adhesive film B44 and thickness 12 µm electrolytic copper foils were sequentially laminated and pressed using a vacuum laminator at a temperature of 160 ° C. and a pressure of 0.8 MPa for 2 minutes, then heated from room temperature to 160 ° C. and heat treated at 160 ° C. for 4 hours to obtain a copper clad laminate B60 .

[Examples B61 to B63]

Except having used adhesive film B36, B37, and B38, it carried out similarly to Example B60, and obtained copper-clad laminated board B61-B63.

[Example B64]

On an electrolytic copper foil having a thickness of 12 μm, the coverlay film B47 is laminated so that the adhesive layer side of the coverlay film B47 is in contact with the copper foil, and is pressed using a vacuum laminator at a temperature of 160° C. and a pressure of 0.8 MPa for 2 minutes, and then from room temperature to 160° C. It heat-processed at the temperature rise and 160 degreeC for 2 hours, and obtained copper-clad laminated board B64.

[Examples B65, B66]

Except having used coverlay film B48, B49, it carried out similarly to Example B64, and obtained copper clad laminated board B65 and B66.

[Example B67]

On a 12 µm-thick rolled copper foil, an adhesive film B44 is laminated, the polyimide film side of the coverlay film B47 is in contact with the adhesive film B44, and the 12 µm-thick rolled copper on the adhesive layer side of the coverlay film B47. The foils were further laminated sequentially, and after pressing for 2 minutes at a temperature of 160°C and a pressure of 0.8 MPa using a vacuum laminator, the temperature was raised from room temperature to 160°C, and heat treatment was performed at 160°C for 2 hours to obtain a copper-clad laminate B67.

[Examples B68, B69]

Copper-clad laminates B68 and B69 were produced in the same manner as in Example B67 except that the adhesive films B35 and B36 were used instead of the adhesive film B44, respectively, and the coverlay films B48 and B49 were used instead of the coverlay film B47, respectively.

[Example B70]

2 sheets of copper foil B57 provided with resin were prepared, and polyimide film 3 (manufactured by DuPont, trade name; Kapton 200-EN, thickness 50 µm, ε ₁ = 3.6, tanδ ₁ = 0.0084), laminated so as to be in contact with each other, and compressed using a vacuum laminator at a temperature of 160°C and a pressure of 0.8MPa for 5 minutes, then heated from room temperature to 160°C and heat treated at 160°C for 4 hours, copper-clad laminate B70 got

[Example B71]

Adhesive composition B31 was applied to the resin layer (polyimide layer) of single-sided copper clad laminate 1 (manufactured by Nittetsu Chemical & Materials, trade name; Espanex MC12-25-00UEM, length × width × thickness = 200 mm × 300 mm × 25 μm) It apply|coated to the side, it dried at 80 degreeC for 30 minute(s), and obtained the copper clad laminated board B71 provided with the adhesive bond layer whose thickness of an adhesive bond layer is 50 micrometers. The adhesive layer side of the copper clad laminate B71 having an adhesive layer is laminated so that the resin layer side of the other single-sided copper clad laminate 1 is in contact, and the copper clad laminate is pressed using a small precision press at a temperature of 160°C and a pressure of 4.0 MPa for 120 minutes. A laminated sheet B71 was obtained.

[Example B72]

The copper-clad laminate B71 having two adhesive layers was laminated so that the surface on the adhesive layer side was in contact, and was pressed using a small precision press at a temperature of 160° C. and a pressure of 4.0 MPa for 120 minutes to obtain a copper-clad laminate B72.

[Example B73]

On the resin layer side of the single-sided copper clad laminate 1, the adhesive film B44 is laminated, and the resin layer side of the single-sided copper clad laminate 1 is further laminated on it so that the adhesive film B44 is in contact with the adhesive film B44, using a small precision press machine at a temperature of 160 ° C, a pressure of 4.0 It crimped|bonded by MPa for 120 minutes, and obtained copper clad laminated board B73.

[Example B74]

The adhesive composition B31 was apply|coated to the single side|surface of the mold release PET film 1, dried at 80 degreeC for 15 minutes, and peeling the adhesive bond layer from the mold release PET film 1, 15 micrometers in thickness adhesive film B74 was obtained.

[Example B75]

On the resin layer side of the single-sided copper clad laminate 1, an adhesive film B74 is laminated, and the resin layer side of the single-sided copper clad laminate 1 is further laminated on it so that the adhesive film B74 is in contact with the adhesive film B74, using a small precision press machine at a temperature of 160 ° C, a pressure of 4.0 It was crimped|bonded for 120 minutes at MPa, and copper clad laminated board B75 was obtained.

[Example B76]

A wiring board on which a double-sided copper clad laminate 2 (manufactured by Nittetsu Chemical & Materials, trade name; Espanex MB12-25-00UEG) was prepared, and a copper foil on one side was subjected to circuit processing by etching to form a conductor circuit layer. B76A was obtained.

The copper foil of one surface of the double-sided copper clad laminated board 2 was removed by etching, and copper clad laminated board B76B was obtained.

The adhesive film B44 was sandwiched between the surface on the conductor circuit layer side of the wiring board B76A and the surface on the resin layer side of the copper clad laminate B76B. I got B76.

[Example B77]

A liquid crystal polymer film (manufactured by Kuraray, trade name; CT-Z, thickness; 50 µm, CTE; 18 ppm/K, heat deflection temperature; 300°C, ε ₁ =3.40, tan δ ₁ =0.0022) was used as an insulating substrate, and both sides thereof A copper clad laminated board B77 provided with an electrolytic copper foil having a thickness of 18 µm was prepared, and circuit processing by etching was performed on one side of the copper foil to obtain a wiring board B77A on which a conductor circuit layer was formed.

The copper foil of the single side|surface of copper clad laminated board B77 was etched away, and copper clad laminated board B77B was obtained.

The adhesive film B44 was sandwiched between the surface on the conductor circuit layer side of the wiring board B77A and the surface on the insulating base layer side of the copper clad laminate B77B, and in a laminated state, thermocompression bonding at a temperature of 160°C and a pressure of 4.0 MPa for 120 minutes, the multilayer circuit board I got B77.

As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention can be variously modified without being limited to the said embodiment.

This application claims priority based on Japanese Patent Application No. 2020-046163, filed in Japan on March 17, 2020, and Japanese Patent Application No. 2020-064081, filed in Japan on March 31, 2020 and the entire contents of the application are incorporated herein by reference.

10: description
11: first description
12: second substrate
20: adhesive layer
30, 33, 34: insulating resin layer
31: first insulating resin layer
32: second insulating resin layer
41: first single-sided metal clad laminate
42: second single-sided metal clad laminate
50: wiring layer
M: metal layer
M1: first metal layer
M2: second metal layer
100: laminate
101: 3-layer metal clad laminate
102: bonded metal clad laminate
103: metal clad laminate with adhesive layer
200, 201, 202: circuit board
203: multilayer circuit board

Claims (26)

A polyimide containing a tetracarboxylic acid residue derived from a tetracarboxylic acid anhydride component and a diamine residue derived from a diamine component, wherein the following conditions a, b1 and c, or conditions a, b2 and c;
a) 60 mol% or more of diamine residues derived from a dimer diamine composition containing dimer diamine as a main component in which two terminal carboxylic acid groups of dimer acid are substituted with primary aminomethyl groups or amino groups with respect to all diamine residues ;
b1) The content of carbon atoms derived from the 6-membered aromatic ring (excluding the carbon atoms of the 6-membered aromatic ring derived from the dimer diamine composition) with respect to the total content of all atoms in the polyimide is within the range of 12 to 40 wt% ;
b2) containing the diamine residue derived from the diamine compound represented by the following general formula (A1) with respect to all the diamine residues within the range of 5 mol% or more and 40 mol% or less;

[In general formula (A1), Y and Z each independently represent an alkyl group, alkoxy group, alkenyl group or alkynyl group having 1 to 6 carbon atoms, and the linking group X is -O-, -S-, -CO-, -SO -, -SO ₂ -, -COO-, -CH ₂ -, -CH ₂ -O-, -C(CH ₃ ) ₂ -, -NH- or -CONH- represents a divalent group selected from, m is 1 represents an integer of to 4. However, when a plurality of linking groups X are included in the molecule, they may be the same or different.]
c) a weight average molecular weight in the range of 5,000 to 200,000;
Characterized in meeting the, polyimide. According to claim 1,
When the above conditions a, b1 and c are satisfied, the following condition d;
d) the following formula (i),
CM value = (C/Mw) × 10⁴ . . . (i)
[Wherein, C means the weight content of carbon atoms derived from the 6-membered aromatic ring (excluding the carbon atoms of the 6-membered aromatic ring derived from the dimer diamine composition) with respect to the total content of all atoms in the polyimide, and Mw is It means the weight average molecular weight of polyimide]
CM value, which is an index indicating the amount of the 6-membered aromatic ring contained in the polyimide, calculated based on , is in the range of 3 to 38;
Characterized in that it further satisfies, polyimide. According to claim 1,
When the above conditions a, b1 and c are satisfied, the following condition e;
e) The content of carbon atoms derived from the 6-membered aromatic ring (excluding the carbon atoms of the 6-membered aromatic ring derived from the dimer diamine composition) with respect to the total content of all atoms in all the diamine components of the raw material exceeds 0 and is 32% by weight within the following ranges;
Characterized in that it further satisfies, polyimide. According to claim 1,
When the above conditions a, b1 and c are satisfied, the following condition f;
f) the formula (ii),
DM value = (D/Mw) × 10 ⁴ ... (ii)
[Wherein, D means the weight content of carbon atoms derived from the 6-membered aromatic ring (excluding the carbon atoms of the 6-membered aromatic ring derived from the dimer diamine composition) with respect to the total content of all atoms in the total diamine residues, Mw means the weight average molecular weight of polyimide]
DM value, which is an index indicating the amount of the 6-membered aromatic ring derived from the diamine component contained in the polyimide, calculated based on the above 0 and within the range of 32 or less;
Characterized in that it further satisfies, polyimide. According to claim 1,
When the conditions a, b1 and c are satisfied, for the total amount of the diamine residues,
It contains the diamine residue derived from the said dimer diamine composition within the range of 60 mol% or more and 99 mol% or less,
A diamine residue derived from at least one diamine compound selected from diamine compounds represented by the following general formulas (B1) to (B7) is contained within the range of 1 mol% or more and 40 mol% or less, polyimide.

[In formulas (B1) to (B7), R ₁ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms, and the linking group A is independently -O-, -S-, -CO-, -SO represents a divalent group selected from -, -SO ₂ -, -COO-, -CH ₂ -, -C(CH ₃ ) ₂ -, -NH-, or -CONH-, and n ₁ is independently an integer of 0 to 4 indicates. However, those overlapping with formula (B2) in formula (B3) are excluded, and those overlapping with formula (B4) in formula (B5) are excluded.] The method of claim 1,
with respect to the total amount of the acid anhydride residues,
The polyimide characterized by containing 90 mol% or more in total of the tetracarboxylic-acid residue derived from the tetracarboxylic-acid anhydride represented by following General formula (2) and/or (3).

[In the general formula (2), X ₁ represents a single bond or a divalent group selected from the following formula, and in the general formula (3), _{the cyclic moiety represented by Y 1} is a 4-membered ring, a 5-membered ring, or a 6-membered ring , indicating that a cyclic saturated hydrocarbon group selected from a 7-membered ring or an 8-membered ring is formed.]

[In the above formula, Z ₁ represents -C ₆ H ₄ -, -(CH ₂ ) _m1 - or -CH ₂ -CH(-OC(=O)-CH ₃ )-CH ₂ -, but m1 is Represents an integer from 1 to 20.] 7. The method of claim 6,
When the above conditions a, b2 and c are satisfied, tetracarboxyl derived from benzophenonetetracarboxylic dianhydride _{in which the group X 1 in the general formula (2) is —CO— with respect to all tetracarboxylic acid residues} The acid residue is contained within the range of 10 mol% or more and 90 mol% or less, and the tetracarboxylic acid anhydride represented by the general formulas (2) and/or (3) (however, the benzophenone tetracarboxylic dianhydride A polyimide characterized by containing 10 mol% or more of at least one tetracarboxylic acid residue derived from ). The polyimide according to claim 1 contains a ketone group in a molecule,
A crosslinked polyimide, wherein the ketone group and the amino group of an amino compound having at least two primary amino groups as functional groups form a crosslinked structure by a C=N bond. An adhesive film comprising the polyimide according to claim 1 or the crosslinked polyimide according to claim 8. 10. The method of claim 9,
When the polyimide satisfies the above conditions a, b1 and c, after 24 hours of humidity control under a constant temperature and humidity condition (state) of 23° C. and 50% RH, 10 GHz measured by a split post dielectric resonator (SPDR) The dielectric loss tangent (Tanδ ₁ ) of 0.005 or less, the relative dielectric constant (E ₁ ) of 3.0 or less, characterized in that the adhesive film. 10. The method of claim 9,
When the polyimide satisfies the above conditions a, b1 and c, after 24 hours of humidity control under a constant temperature and humidity condition (state) of 23° C. and 50% RH, at 20 GHz as measured by a split post dielectric resonator (SPDR) The dielectric loss tangent of (Tanδ ₂ ) is 0.005 or less, and the dielectric constant (E ₂ ) is 3.0 or less, the adhesive film. 10. The method of claim 9,
When the polyimide satisfies the above conditions a, b1 and c, after 24 hours of humidity control under a constant temperature and humidity condition (state) of 23° C. and 50% RH, 10 GHz measured by a split post dielectric resonator (SPDR) The difference between the dielectric loss tangent ( _{Tanδ 1} ) and the dielectric loss tangent (Tanδ ₂ ) at ₂₀ GHz _{(Tanδ 2 -Tanδ 1} ) is zero or less, the adhesive film. 10. The method of claim 9,
When the polyimide satisfies the above conditions a, b2 and c, after 24 hours of humidity control under a constant temperature and humidity condition (state) of 23° C. and 50% RH, 10 GHz measured by a split post dielectric resonator (SPDR) The dielectric loss tangent of (Tanδ ₁ ) is less than 0.002, and the relative dielectric constant (E ₁ ) is 3.0 or less, the adhesive film. 10. The method of claim 9,
When the polyimide satisfies the above conditions a, b2 and c, after 24 hours of humidity control under a constant temperature and humidity condition (state) of 23° C. and 50% RH, at 20 GHz measured by a split post dielectric resonator (SPDR) The dielectric loss tangent of (Tanδ ₂ ) is less than 0.002, and the relative dielectric constant (E ₂ ) is 3.0 or less, the adhesive film. A laminate having a substrate and an adhesive layer laminated on at least one surface of the substrate,
The said adhesive bond layer contains the adhesive bond film of Claim 9, The laminated body characterized by the above-mentioned. A coverlay film having a film material layer for a coverlay and an adhesive layer laminated on the film material layer for the coverlay,
The said adhesive layer contains the adhesive film of Claim 9, The coverlay film characterized by the above-mentioned. It is a copper foil provided with a resin laminated with an adhesive layer and copper foil,
The said adhesive bond layer contains the adhesive bond film of Claim 9, The copper foil with resin characterized by the above-mentioned. A metal clad laminate having an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer,
At least one layer of the said insulating resin layer contains the adhesive film of Claim 9, The metal clad laminated board characterized by the above-mentioned. A metal-clad laminate having an insulating resin layer, an adhesive layer laminated on at least one side of the insulating resin layer, and a metal layer laminated on the insulating resin layer via the adhesive layer,
The said adhesive bond layer contains the adhesive agent film of Claim 9, The metal clad laminated board characterized by the above-mentioned. A first single-sided metal-clad laminate having a first metal layer and a first insulating resin layer laminated on at least one side of the first metal layer;
a second single-sided metal-clad laminate having a second metal layer and a second insulating resin layer laminated on at least one side of the second metal layer;
A metal clad laminate having an adhesive layer disposed in contact with the first insulating resin layer and the second insulating resin layer and laminated between the first single-sided metal-clad laminate and the second single-sided metal-clad laminate,
The said adhesive bond layer contains the adhesive agent film of Claim 9, The metal clad laminated board characterized by the above-mentioned. A single-sided metal-clad laminate having an insulating resin layer, a metal layer laminated on one side of the insulating resin layer, and an adhesive layer laminated on the other side of the insulating resin layer, wherein the adhesive layer is according to claim 9 An adhesive film is included, The metal-clad laminated board characterized by the above-mentioned. A circuit board formed by wiring the metal layer of the metal-clad laminate according to claim 18 . A circuit board comprising a first substrate, a wiring layer laminated on at least one surface of the first substrate, and an adhesive layer laminated to cover the wiring layer on the surface of the first substrate on the wiring layer side,
The said adhesive bond layer contains the adhesive bond film of Claim 9, The circuit board characterized by the above-mentioned. A first substrate, a wiring layer laminated on at least one surface of the first substrate, an adhesive layer laminated to cover the wiring layer on the surface of the first substrate on the wiring layer side, and the first substrate of the adhesive layer It is a circuit board provided with a second substrate laminated on the surface opposite to the
The said adhesive bond layer contains the adhesive bond film of Claim 9, The circuit board characterized by the above-mentioned. A first substrate, an adhesive layer laminated on at least one surface of the first substrate, a second substrate laminated on a surface opposite to the first substrate of the adhesive layer, the first substrate and the second substrate A circuit board having a wiring layer laminated on a surface opposite to the adhesive layer of
The said adhesive bond layer contains the adhesive bond film of Claim 9, The circuit board characterized by the above-mentioned. A multilayer circuit board comprising: a laminate including a plurality of laminated insulating resin layers; and at least one or more wiring layers embedded in the laminate;
At least one of the plurality of insulating resin layers is formed of an adhesive layer that has adhesive properties and covers the wiring layer,
The said adhesive layer contains the adhesive film of Claim 9, The multilayer circuit board characterized by the above-mentioned.

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