Polyimide, crosslinked polyimide, adhesive film, laminate, cover lay film, copper foil with resin, metal-clad laminate, circuit board, and multilayer circuit board

Abstract

To further improve dielectric characteristics, and reduce a transmission loss of a high frequency signal more effectively concerning an adhesive layer using a polyimide using aliphatic diamine as a raw material.SOLUTION: A polyimide contains: 50 to 95 mol% of a residual group derived from a dimer amine composition with respect to a total diamine residue; 5 to 50 mol% of a residual group derived from one or more kinds of diamine compounds having an amino group directly bonded to a benzene ring and a bivalent linking group at a para position, and selected from the group consisting of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,4,4'-triaminodiphenyl ether, 4,4'-bis(4-aminophenyl sulfide), 4,4'-diaminodiphenyl sulphone, 2,2'-bis(4-aminobenzyloxyphenyl)propane, bis[4-(4-aminophenoxy)phenyl]sulphone, 4,4'-diaminobenzanilide, 4,4'-methylenedianiline, and 4,4'-diaminobenzophenone; and 10 to 90 mol% of a residual group derived from benzophenontetracarboxylic acid dianhydride with respect to a total tetracarboxylic acid residue, wherein a dielectric tangent at 20 GHz in a state of a film is less than 0.002, and a dielectric constant is 3.0 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyimide useful as a material for electronic components, and to a crosslinked polyimide, adhesive film, laminate, coverlay film, resin-coated copper foil, metal-clad laminate, circuit board, and multilayer circuit board using the polyimide. [Background technology]

[0002] In recent years, with the progress in miniaturization, weight reduction, and space-saving of electronic devices, there has been an increasing demand for flexible printed circuits (FPCs), which are thin, lightweight, flexible, and have excellent durability even when repeatedly bent. Because FPCs allow for three-dimensional, high-density packaging even in limited spaces, their applications are expanding to include wiring for moving parts in electronic devices such as hard disk drives, DVDs, and smartphones, as well as components such as cables and connectors.

[0003] One type of FPC has a structure in which a circuit pattern is formed on a polyimide film that has excellent heat resistance and flexibility, and a coverlay film having an adhesive layer is laminated to the surface. Polyimide is used as the material for the adhesive layer of a coverlay film with such a structure. For example, it has been proposed to use a crosslinked polyimide obtained by reacting a polyimide made from a diamine compound derived from an aliphatic diamine such as dimer acid with an amino compound having at least two primary amino groups as functional groups in the adhesive layer of the coverlay film (for example, Patent Document 1).

[0004] Furthermore, in a three-layer metal-clad laminate, which is a material for circuit boards such as FPCs, in which a metal layer to be processed for wiring and an insulating resin layer are bonded via an adhesive layer, it has been proposed to use a polyimide in the adhesive layer that contains a predetermined amount or more of diamine residues derived from a dimer acid type diamine in which the two terminal carboxylic acid groups of a dimer acid are substituted with primary aminomethyl groups or amino groups (for example, Patent Document 2).

[0005] In addition to the above-mentioned trend toward higher density, the advancement of device performance has created a need to accommodate higher transmission signal frequencies. When transmitting high-frequency signals, if transmission loss along the transmission path is large, problems such as electrical signal loss and long signal delay times occur. Therefore, reducing transmission loss will become important in FPCs in the future. For this reason, it has been proposed to consider the relationship between the thickness, dielectric constant, and dielectric loss tangent of the polyimide insulating layer and the coverlay film in a circuit board that includes a polyimide insulating layer, a circuit wiring layer laminated on at least one surface of the polyimide insulating layer, and a coverlay film laminated on the circuit wiring layer (see, for example, Patent Document 3). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-1730 [Patent Document 2] Japanese Patent Application Publication No. 2018-140544 [Patent Document 3] Japanese Patent Application Laid-Open No. 2016-192531 Summary of the Invention [Problem to be solved by the invention]

[0007] As in Patent Document 1, adhesive layers using polyimides made from aliphatic diamines exhibit excellent adhesion and low dielectric constants and dielectric dissipation factors, but further improvements in dielectric properties are required to accommodate the increasing frequency of transmission signals.

[0008] Therefore, an object of the present invention is to further improve the dielectric properties of an adhesive layer using a polyimide made from an aliphatic diamine, and to more effectively reduce the transmission loss of high frequency signals. [Means for solving the problem]

[0009] As a result of extensive research, the present inventors have found that the dielectric properties of polyimide can be improved by copolymerizing an aliphatic diamine with a diamine having a specific structure, and have thus completed the present invention.

[0010] 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 by satisfying the following conditions a to c:

[0011] a) The content of diamine residues derived from a dimer diamine composition containing as its main component a dimer diamine in which the two terminal carboxylic acid groups of a dimer acid are substituted with primary aminomethyl groups or amino groups is in the range of 50 mol% to 95 mol% relative to the total diamine residues.

[0012] b) The diamine residues derived from the diamine compound represented by the following general formula (1) are contained in an amount of 5 mol % to 50 mol % based on the total diamine residues:

[0013] [ka]

[0014] In general formula (1), Y and Z each independently represent an alkyl group, alkoxy group, alkenyl group, or alkynyl group having 1 to 6 carbon atoms, the linking group X represents a divalent group selected from -O-, -S-, -CO-, -SO-, -SO2-, -COO-, -CH2-, -CH2-O-, -C(CH3)2-, -NH-, or -CONH-, and m represents an integer of 1 to 4. However, when a molecule contains multiple linking groups X, they may be the same or different.

[0015] c) The content of tetracarboxylic acid residues derived from benzophenonetetracarboxylic dianhydride is in the range of 10 mol % to 90 mol % of all tetracarboxylic acid residues, and the content of at least one tetracarboxylic acid residue derived from tetracarboxylic acid anhydride represented by the following general formula (2) and / or (3) is 10 mol % or more:

[0016] [ka]

[0017] In general formula (2), R represents a single bond or a divalent group represented by the following formula, and in general formula (3), the cyclic moiety represented by S represents the formation of a cyclic saturated hydrocarbon group selected from a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered ring.

[0018] [ka]

[0019] In the above formula, Z1 represents -C6H4-, -(CH2)n- or -CH2-CH(-OC(=O)-CH3)-CH2-, where n represents an integer of 1 to 20.

[0020] The crosslinked polyimide of the present invention is a crosslinked polyimide in which a ketone group contained in the polyimide and an amino group of an amino compound having at least two primary amino groups as functional groups form a crosslinked structure via a C=N bond.

[0021] The adhesive film of the present invention contains the above polyimide or crosslinked polyimide.

[0022] The adhesive film of the present invention may have a dielectric loss tangent (Tanδ1) of less than 0.002 and a relative dielectric constant (E1) of 3.0 or less at 10 GHz, as measured using a split post dielectric resonator (SPDR), after being conditioned for 24 hours under constant temperature and humidity conditions (normal state) of 23°C and 50% RH.

[0023] The adhesive film of the present invention may have a dielectric loss tangent (Tanδ2) of less than 0.002 and a relative dielectric constant (E2) of 3.0 or less at 20 GHz, as measured using a split post dielectric resonator (SPDR), after being conditioned for 24 hours under constant temperature and humidity conditions (normal state) of 23°C and 50% RH.

[0024] 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 adhesive layer is made of any of the adhesive films described above.

[0025] The coverlay film of the present invention is a coverlay film having a coverlay film material layer and an adhesive layer laminated on the coverlay film material layer, The adhesive layer is made of any of the adhesive films described above.

[0026] The resin-coated copper foil of the present invention is a resin-coated copper foil obtained by laminating an adhesive layer and a copper foil, The adhesive layer is made of any of the adhesive films described above.

[0027] 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 one of the insulating resin layers is made of any of the adhesive films described above.

[0028] A metal-clad laminate according to another aspect of the present invention is a metal-clad laminate having an insulating resin layer, an adhesive layer laminated on at least one surface of the insulating resin layer, and a metal layer laminated on the insulating resin layer via the adhesive layer, The adhesive layer is made of any of the adhesive films described above.

[0029] A metal-clad laminate according to yet 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 surface 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 surface of the second metal layer; and an adhesive layer disposed so as to abut 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 metal-clad laminate of the present invention is characterized in that the adhesive layer is made of any of the adhesive films described above.

[0030] A metal-clad laminate according to yet another aspect of the present invention comprises a single-sided metal-clad laminate having an insulating resin layer and 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 made of any of the adhesive films described above.

[0031] The circuit board of the present invention is obtained by wiring the metal layer of the metal-clad laminate.

[0032] A circuit board according to another aspect of the present invention is a circuit board including a first base material, a wiring layer laminated on at least one surface of the first base material, and an adhesive layer laminated on the surface of the first base material facing the wiring layer so as to cover the wiring layer, The adhesive layer is made of any of the adhesive films described above.

[0033] A circuit board according to yet another aspect of the present invention is a circuit board including: a first base material; a wiring layer laminated on at least one surface of the first base material; an adhesive layer laminated on a surface of the first base material facing the wiring layer so as to cover the wiring layer; and a second base material laminated on a surface of the adhesive layer opposite to the first base material, The adhesive layer is made of any of the adhesive films described above.

[0034] A circuit board according to yet another aspect of the present invention is a circuit board including: a first base material; an adhesive layer laminated on at least one surface of the first base material; a second base material laminated on a surface of the adhesive layer opposite to the first base material; and wiring layers laminated on each of the first base material and the second base material opposite to the adhesive layer, The adhesive layer is made of any of the adhesive films described above.

[0035] The multilayer circuit board of the present invention is a multilayer circuit board including a laminate including a plurality of laminated insulating resin layers, and at least one wiring layer embedded inside the laminate, At least one of the plurality of insulating resin layers is formed of an adhesive layer that has adhesiveness and covers the wiring layer, The adhesive layer is made of any of the adhesive films described above. [Effects of the Invention]

[0036] The polyimide of the present invention has a copolymer composition of an aliphatic diamine and a diamine having a specific structure, and thus has excellent adhesive properties, a low dielectric constant, and a low dielectric loss tangent, and can effectively reduce transmission loss in high-frequency signal transmission. Therefore, when the polyimide of the present invention is applied to a circuit board or the like that transmits high-frequency signals in the GHz frequency range (e.g., 1 to 20 GHz), the polyimide can effectively reduce transmission loss. [Brief explanation of the drawings]

[0037] [Figure 1] 1 is a schematic diagram showing a cross-sectional configuration of a laminate according to an embodiment of the present invention. [Figure 2] 1 is a schematic diagram showing a cross-sectional configuration of a metal-clad laminate according to an embodiment of the present invention. [Figure 3] FIG. 4 is a schematic diagram showing a cross-sectional configuration of a metal-clad laminate according to another embodiment of the present invention. [Figure 4] FIG. 10 is a schematic diagram showing a cross-sectional configuration of a metal-clad laminate according to yet another embodiment of the present invention. [Figure 5] 1 is a schematic diagram showing a cross-sectional configuration of a circuit board according to an embodiment of the present invention; [Figure 6] FIG. 10 is a schematic diagram showing a cross-sectional configuration of a circuit board according to another embodiment of the present invention. [Figure 7] FIG. 10 is a schematic diagram showing a cross-sectional configuration of a circuit board according to yet another embodiment of the present invention. [Figure 8] 1 is a schematic diagram showing a cross-sectional configuration of a multilayer circuit board according to an embodiment of the present invention; DETAILED DESCRIPTION OF THE INVENTION

[0038] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described with reference to the accompanying drawings.

[0039] A polyimide according to one embodiment of the present invention is a polyimide having adhesive properties. Hereinafter, the polyimide of this embodiment may be referred to as an "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, the "tetracarboxylic acid residue" refers to a tetravalent group derived from a tetracarboxylic acid dianhydride, and the "diamine residue" refers to a divalent group derived from a diamine compound. When the raw materials, tetracarboxylic acid anhydride and diamine compound, are reacted in approximately equimolar amounts, the types and molar ratios of the tetracarboxylic acid residues and diamine residues contained in the polyimide can be made to correspond approximately to the types and molar ratios of the raw materials. In the present invention, the term "polyimide" refers to a resin made of a polymer having an imide group in the molecular structure, such as polyimide, polyamideimide, polyetherimide, polyesterimide, polysiloxaneimide, or polybenzimidazoleimide.

[0040] The adhesive polyimide satisfies the following conditions a to c: The raw material monomers, tetracarboxylic acid residues, and diamine residues of the adhesive polyimide will be described in detail later.

[0041] Condition a) The content of diamine residues derived from a dimer diamine composition containing as a main component a dimer diamine obtained by substituting two terminal carboxylic acid groups of a dimer acid with primary aminomethyl groups or amino groups is in the range of 50 mol % to 95 mol % relative to the total diamine residues: By controlling the content of diamine residues derived from the dimer diamine composition to be within the range of 50 mol% to 95 mol%, preferably 70 to 90 mol%, relative to the total diamine residues, the dielectric constant and dielectric dissipation factor of the polyimide can be reduced. If the content of diamine residues derived from the dimer diamine composition is less than 50 mol%, the relative dielectric constant and dielectric dissipation factor tend to increase due to the increase in polar groups contained in the polyimide. If the content of diamine residues derived from the dimer diamine composition exceeds 95 mol% relative to the total diamine residues, the mobility of the molecular chains of the polyimide may be excessively increased, resulting in an increase in the dielectric dissipation factor. Furthermore, by incorporating an aliphatic diamine in the above amount, the dielectric properties of the polyimide can be improved, and thermocompression bonding properties can be improved by lowering the glass transition temperature (Tg) of the polyimide, and internal stress can be alleviated by lowering the elastic modulus.

[0042] Condition b) The diamine residues derived from the diamine compound represented by general formula (1) are contained in an amount of 5 mol % to 50 mol % relative to the total diamine residues: By setting the content of diamine residues derived from the diamine compound represented by general formula (1) within the range of 5 mol % to 50 mol % and preferably within the range of 10 to 30 mol % relative to the total diamine residues, the relative dielectric constant and dielectric loss tangent of the polyimide can be reduced. If the content of diamine residues derived from the diamine compound represented by general formula (1) is less than 5 mol %, the mobility of the molecular chain of the polyimide may be excessively increased, resulting in an increase in the dielectric loss tangent. If the content of diamine residues derived from the diamine compound represented by general formula (1) is more than 50 mol % relative to the total diamine residues, the polarity of the molecular chain of the polyimide may be excessively increased, resulting in an increase in the dielectric loss tangent.

[0043] Condition c) The content of tetracarboxylic acid residues derived from benzophenonetetracarboxylic dianhydride is in the range of 10 mol % to 90 mol % relative to all tetracarboxylic acid residues, and the content of at least one tetracarboxylic acid residue derived from a tetracarboxylic acid anhydride represented by general formula (2) and / or (3) is 10 mol % or more: Storage stability can be improved by controlling the content of tetracarboxylic acid residues derived from benzophenonetetracarboxylic dianhydride to 10 mol% to 90 mol%, preferably 10 mol% to 50 mol%, relative to the total tetracarboxylic acid residues, and controlling the content of at least one tetracarboxylic acid residue derived from tetracarboxylic acid anhydrides represented by general formulas (2) and / or (3) to 10 mol% or more, preferably 10 mol% to 50 mol%. If the content of tetracarboxylic acid residues derived from benzophenonetetracarboxylic dianhydride is less than 10 mol%, the number of carbonyl groups serving as crosslinking points may decrease, resulting in a failure to exhibit solder heat resistance. Furthermore, if the content of tetracarboxylic acid residues derived from benzophenonetetracarboxylic dianhydride exceeds 90 mol%, the diamine residues derived from the diamine compound react with the carbonyl groups derived from benzophenonetetracarboxylic dianhydride, significantly reducing solubility.

[0044] (diamine) The adhesive polyimide is made from raw materials containing 50 mol% to 95 mol% of a dimer diamine composition, the main component of which is a dimer diamine in which the two terminal carboxylic acid groups of a dimer acid are substituted with primary aminomethyl groups or amino groups, relative to the total diamine components.

[0045] The dimer diamine composition is a purified product containing the following component (a) as a main component, with the amounts of components (b) and (c) controlled:

[0046] (a) dimer diamine; The dimer diamine of component (a) refers to a diamine in which the two terminal carboxylic acid groups (—COOH) of a dimer acid are replaced with primary aminomethyl groups (—CH—NH) or amino groups (—NH). Dimer acids are known dibasic acids obtained by the intermolecular polymerization of unsaturated fatty acids. Their industrial production process is largely standardized in the industry, and they are obtained by dimerizing unsaturated fatty acids with 11 to 22 carbon atoms using a clay catalyst or the like. Industrially obtained dimer acids are primarily composed of a 36-carbon dibasic acid obtained by dimerizing 18-carbon unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid. However, depending on the degree of purification, they may contain arbitrary amounts of monomer acid (18 carbon atoms), trimer acid (54 carbon atoms), and other polymerized fatty acids with 20 to 54 carbon atoms. Although double bonds remain after the dimerization reaction, in the present invention, dimer acids that have been further hydrogenated to reduce the degree of unsaturation are also included in the definition of dimer acids. The dimer diamine of component (a) can be defined as a diamine compound obtained by substituting the terminal carboxylic acid group of a dibasic acid compound having 18 to 54 carbon atoms, preferably 22 to 44 carbon atoms, with a primary aminomethyl group or an amino group.

[0047] Dimer diamine is characterized by its ability to impart properties derived from the dimer acid skeleton. Dimer diamine is a macromolecular aliphatic compound with a molecular weight of approximately 560 to 620, which increases the molecular molar volume and reduces the relative polarity of the polyimide. These characteristics of dimer diamine are believed to contribute to improving the dielectric properties of polyimides by reducing their dielectric constant and dielectric dissipation factor while suppressing a decrease in their heat resistance. Furthermore, the presence of two freely movable hydrophobic chains with 7 to 9 carbon atoms and two linear aliphatic amino groups with a length approaching 18 carbon atoms not only imparts flexibility to polyimides but also allows them to have asymmetric or nonplanar chemical structures, thereby potentially lowering the dielectric constant of polyimides.

[0048] The dimer diamine composition used should be one in which the dimer diamine content of component (a) has been increased to 96% by weight or more, preferably 97% by weight or more, and more preferably 98% by weight or more, by a purification method such as molecular distillation. By increasing the dimer diamine content of component (a) to 96% by weight or more, the broadening of the molecular weight distribution of the polyimide can be suppressed. If technically possible, it is best for the entire dimer diamine composition (100% by weight) to be composed of component (a) dimer diamine.

[0049] (b) a monoamine compound obtained by substituting the 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 having 10 to 40 carbon atoms is a mixture of a monobasic unsaturated fatty acid having 10 to 20 carbon atoms derived from the raw material of dimer acid, and a monobasic acid compound having 21 to 40 carbon atoms that is a by-product during the production of dimer acid. The monoamine compound is obtained by substituting the terminal carboxylic acid group of these monobasic acid compounds with a primary aminomethyl group or an amino group.

[0050] The monoamine compound (b) is a component that suppresses an increase in the molecular weight of the polyimide. During polymerization of the polyamic acid or polyimide, the monofunctional amino group of the monoamine compound reacts with the terminal acid anhydride groups of the polyamic acid or polyimide, thereby capping the terminal acid anhydride groups and suppressing an increase in the molecular weight of the polyamic acid or polyimide.

[0051] (c) Amine compounds obtained by substituting the terminal carboxylic acid group of a polybasic acid compound having a hydrocarbon group having 41 to 80 carbon atoms with a primary aminomethyl group or an amino group (excluding the dimer diamine); The polybasic acid compound having a hydrocarbon group having 41 to 80 carbon atoms is a polybasic acid compound whose main component is a tribasic acid compound having 41 to 80 carbon atoms, which is a by-product during the production of dimer acid. It may also contain a polymerized fatty acid other than dimer acid having 41 to 80 carbon atoms. The amine compound is obtained by substituting the terminal carboxylic acid group of these polybasic acid compounds with a primary aminomethyl group or an amino group.

[0052] The amine compound (c) is a component that promotes an increase in the molecular weight of the polyimide. The tri- or higher functional amino group, primarily composed of a triamine derived from a trimer acid, reacts with the terminal acid anhydride group of the polyamic acid or polyimide, rapidly increasing the molecular weight of the polyimide. Furthermore, amine compounds derived from polymerized fatty acids other than dimer acids having 41 to 80 carbon atoms also increase the molecular weight of the polyimide, causing gelation of the polyamic acid or polyimide.

[0053] When quantifying each component by gel permeation chromatography (GPC), a sample of the dimer diamine composition treated with acetic anhydride and pyridine is used, and cyclohexanone is used as an internal standard to facilitate confirmation of the peak start, peak top, and peak end of each component of the dimer diamine composition. Using the sample thus prepared, each component is quantified by area percent in the GPC chromatogram. The peak start and peak end of each component are the minimum values ​​of each peak curve, and the area percent of the chromatogram can be calculated based on these values.

[0054] Furthermore, the dimer diamine composition has a total area percentage of components (b) and (c) of 4% or less, preferably less than 4%, in a chromatogram obtained by GPC measurement. By keeping the total area percentage of components (b) and (c) at 4% or less, broadening of the molecular weight distribution of the polyimide can be suppressed.

[0055] The area percentage of the chromatogram of component (b) is preferably 3% or less, more preferably 2% or less, and even more preferably 1% or less. By setting the area percentage within this range, it is possible to suppress a decrease in the molecular weight of the polyimide and to widen the range of the molar ratio of the tetracarboxylic anhydride component and the diamine component. Note that component (b) does not necessarily have to be contained in the dimer diamine composition. The area percentage of the chromatogram of component (c) is 2% or less, preferably 1.8% or less, and more preferably 1.5% or less. By setting the area percentage within this range, a rapid increase in the molecular weight of the polyimide can be suppressed, and an increase in the dielectric loss tangent of the resin film over a wide frequency range can be suppressed. Note that component (c) does not necessarily have to be contained in the dimer diamine composition.

[0056] Furthermore, when the ratio (b / c) of the area percentages of the chromatograms of the components (b) and (c) is 1 or more, the molar ratio of the tetracarboxylic anhydride component to the diamine component (tetracarboxylic anhydride component / diamine component) is preferably 0.97 or more and less than 1.0, and such a molar ratio makes it easier to control the molecular weight of the polyimide.

[0057] Furthermore, when the ratio (b / c) of the area percentages of the components (b) and (c) in the chromatogram is less than 1, the molar ratio of the tetracarboxylic anhydride component to the diamine component (tetracarboxylic anhydride component / diamine component) is preferably 0.97 or more and 1.1 or less, and by setting such a molar ratio, it becomes easier to control the molecular weight of the polyimide.

[0058] Commercially available dimer diamine compositions are available, and are preferably purified to reduce the content of components other than the dimer diamine in component (a). For example, it is preferable to reduce the content of component (a) to 96% by weight or more. The purification method is not particularly limited, but known methods such as distillation and precipitation purification are suitable. Commercially available dimer diamine compositions include, for example, PRIAMINE 1073 (trade name), PRIAMINE 1074 (trade name), and PRIAMINE 1075 (trade name) manufactured by Croda Japan.

[0059] The adhesive polyimide contains a diamine residue derived from a diamine compound represented by general formula (1) as a diamine residue derived from a diamine component other than those mentioned above. In the diamine represented by general formula (1), aromatic rings are bonded to each other at para-positions relative to the amino groups, so that molecular chains are easily oriented, making it advantageous for use in achieving a low dielectric loss tangent.

[0060] [ka]

[0061] In formula (1), Y and Z each independently represent a monovalent alkyl group, alkoxy group, alkenyl group, or alkenyl or alkynyl group having 1 to 6 carbon atoms; the linking group X represents a divalent group selected from -O-, -S-, -CO-, -SO-, -SO2-, -COO-, -CH2-, -CH2-O-, -C(CH3)2-, -NH-, or -CONH-; and m independently represents an integer of 1 to 4. However, when multiple linking groups X are contained in a molecule, they may be the same or different. In formula (1), the hydrogen atoms in the two terminal amino groups may be substituted, for example, -NR2R3 (where R2 and R3 independently represent any substituent such as an alkyl group).

[0062] Diamines represented by formula (1) (hereinafter sometimes referred to as diamine (1)) are aromatic diamines having two or more benzene rings. Diamine (1) is thought to contribute to improving the orientation of polyimide molecular chains because the amino group directly bonded to at least one benzene ring and the divalent linking group X are in the para position. Therefore, the use of diamine (1) enhances the low dielectric properties of polyimides. Here, preferred linking groups X are -O-, -S-, -CO-, -SO-, -SO2-, -COO-, -CH2-, -CH2-O-, -C(CH3)2-, -NH-, and -CONH-.

[0063] Examples of diamine (1) include 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,4,4'-triaminodiphenyl ether, 4,4'-bis(4-aminophenyl sulfide), 4,4'-diaminodiphenyl sulfone, 2,2'-bis(4-aminobenzyloxyphenyl)propane, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4'-diaminobenzanilide, 4,4'-methylenedianiline, 4,4'-diaminobenzophenone, etc. Among these, 2,2-bis[4-(4-aminophenoxy)phenyl]propane is particularly preferred.

[0064] The adhesive polyimide preferably contains diamine residues derived from at least one diamine compound selected from diamine (1) in a range of 5 mol % to 50 mol %, preferably 10 mol % to 30 mol %, based on the total diamine residues. Because diamine (1) has a highly linear structure, using at least one diamine compound selected from this in an amount within the above range can improve the orientation of the polyimide molecular chains and impart low dielectric properties. If the diamine residues derived from at least one diamine compound selected from diamine (1) exceed 50 mol %, the polarity of the polyimide molecules increases, resulting in an increase in the dielectric loss tangent. Furthermore, the solubility of the polyimide decreases, leading to gelation. On the other hand, if the content is less than 5 mol %, the molecular chain motion cannot be suppressed, resulting in an increase in the dielectric loss tangent.

[0065] The adhesive polyimide may further contain diamine residues other than those mentioned above, provided that the effects of the invention are not impaired.

[0066] (acid anhydride) The adhesive polyimide is made from a raw material containing benzophenone tetracarboxylic dianhydride in a range of 10 mol% to 90 mol% based on the total tetracarboxylic acid anhydride components. In other words, the adhesive polyimide contains tetracarboxylic acid residues derived from benzophenone tetracarboxylic dianhydride in a range of 10 mol% to 90 mol% based on the total tetracarboxylic acid residues. By containing tetracarboxylic acid residues derived from benzophenone tetracarboxylic dianhydride in a total range of 10 mol% to 90 mol% based on the total tetracarboxylic acid residues, it is easy to achieve both flexibility and heat resistance of the adhesive polyimide, and the carbonyl group (ketone group) contributes to adhesion, thereby improving the adhesiveness of the adhesive polyimide. Furthermore, since the ketone group present in the molecular skeleton of benzophenone tetracarboxylic dianhydride may react with the amino group derived from the diamine compound to form a C=N bond, resulting in high molecular weight and gelation, the upper limit is set to 90 mol%. The benzophenonetetracarboxylic dianhydride may be any of 3,3',4,4'-, 2,3',3,4'-, 2,2',3,3'-, or 2,3,3',4'-benzophenonetetracarboxylic dianhydride.

[0067] The adhesive polyimide contains tetracarboxylic acid residues derived from tetracarboxylic acid anhydrides represented by the following general formula (2) and / or (3) in a total amount of 10 mol % or more, preferably 10 mol % to 50 mol % as tetracarboxylic acid residues derived from tetracarboxylic acid anhydrides other than those mentioned above. The tetracarboxylic acid anhydrides represented by the general formula (2) and / or (3) do not have functional groups that react with diamine residues derived from diamine compounds, so by using them in combination with benzophenonetetracarboxylic dianhydride, the effect of improving solder heat resistance can be obtained while suppressing a decrease in solvent solubility.

[0068] [ka]

[0069] In general formula (2), R represents a single bond or a divalent group selected from the following formulae, and in general formula (3), the cyclic moiety represented by S represents the formation of a cyclic saturated hydrocarbon group selected from a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, or an 8-membered ring.

[0070] [ka]

[0071] In the above formula, Z1 represents -C6H4-, -(CH2)n- or -CH2-CH(-OC(=O)-CH3)-CH2-, where n represents an integer of 1 to 20.

[0072] Examples of the tetracarboxylic acid anhydride represented by the general formula (2) include 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride (DSDA), 4,4'-oxydiphthalic anhydride (ODPA), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), p-phenylenebis(trimellitic acid monoester anhydride) (TAHQ), and ethylene glycol bisanhydrotrimellitate (TMEG).

[0073] Examples of the tetracarboxylic acid anhydride represented by the general formula (3) include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,4,5-cycloheptanetetracarboxylic acid dianhydride, and 1,2,5,6-cyclooctanetetracarboxylic acid dianhydride.

[0074] The adhesive polyimide may contain tetracarboxylic acid residues derived from acid anhydrides other than the above-mentioned benzophenonetetracarboxylic dianhydride and the tetracarboxylic acid anhydrides represented by general formula (2) and general formula (3), within the scope of not impairing the effects of the present invention.Such tetracarboxylic acid residues are not particularly limited, and examples thereof include 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)-propanhydride, and the like. 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, 1,2,7,8-, 1,2,6,7- or 1,2,9,10-phenanthrene-tetracarboxylic acid dianhydride, 2,3,6,7-anthracenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)tetrafluoropropane dianhydride, 1,2, 5,6-Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic 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 Examples of the tetracarboxylic acid residue include tetracarboxylic acid residues derived from aromatic tetracarboxylic acid dianhydrides such as carboxylic acid dianhydride, 2,3,8,9-, 3,4,9,10-, 4,5,10,11-, or 5,6,11,12-perylene-tetracarboxylic acid dianhydride, pyrazine-2,3,5,6-tetracarboxylic acid dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid dianhydride, thiophene-2,3,4,5-tetracarboxylic acid dianhydride, and 4,4'-bis(2,3-dicarboxyphenoxy)diphenylmethane dianhydride.

[0075] Adhesive polyimides can be produced by reacting the acid anhydride and diamine components in a solvent to form polyamic acid, followed by heating and ring closure. For example, the acid anhydride and diamine components are dissolved in approximately equimolar amounts in an organic solvent, and the mixture is stirred at a temperature in the range of 0 to 100°C for 30 minutes to 24 hours to cause a polymerization reaction, thereby producing polyamic acid, a precursor to polyimide. During the reaction, the reaction components are dissolved in the organic solvent so that the resulting precursor is in the range of 5 to 50 wt %, preferably 10 to 40 wt %, of the organic solvent. Examples of organic solvents used in the polymerization reaction include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 2-butanone, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, methylcyclohexane, dioxane, tetrahydrofuran, diglyme, triglyme, methanol, ethanol, benzyl alcohol, and cresol. Two or more of these solvents can be used in combination, and aromatic hydrocarbons such as xylene and toluene can also be used in combination. The amount of such organic solvents used is not particularly limited, but it is preferable to adjust the amount so that the concentration of the polyamic acid solution obtained by the polymerization reaction is approximately 5 to 50 wt %.

[0076] The synthesized polyamic acid is usually advantageously used as a solution in a reaction solvent, but it can be concentrated, diluted, or replaced with another organic solvent as needed. Polyamic acid is also advantageously used because it generally has excellent solvent solubility. The viscosity of the polyamic acid solution is preferably within the range of 500 mPa·s to 100,000 mPa·s. If the viscosity is outside this range, defects such as uneven thickness and streaks are likely to occur in the film during coating using a coater or the like.

[0077] The method for imidizing polyamic acid to form polyimide is not particularly limited, and a suitable method is, for example, heat treatment in the solvent at a temperature in the range of 80 to 400° C. for 1 to 24 hours. The temperature may be constant, or the temperature may be changed during the process.

[0078] In the adhesive polyimide, by selecting the types of the acid anhydride component and diamine component, or by selecting the molar ratio of each when two or more types of acid anhydride component or diamine component are used, it is possible to control physical properties such as dielectric characteristics, thermal expansion coefficient, tensile modulus, glass transition temperature, etc. Furthermore, when the adhesive polyimide has a plurality of structural units, they may be present as blocks or randomly, but random presence is preferred.

[0079] The imide group concentration of the adhesive polyimide is preferably 22% by weight or less, more preferably 20% by weight or less. Here, "imide group concentration" refers to the value obtained by dividing the molecular weight of the imide group (-(CO)2-N-) in the polyimide by the molecular weight of the entire polyimide structure. If the imide group concentration exceeds 22% by weight, the molecular weight of the resin itself decreases, and the increase in polar groups deteriorates the low moisture absorption property, resulting in an increase in Tg and elastic modulus.

[0080] The adhesive polyimide is most preferably a completely imidized structure. However, a portion of the polyimide may be an amic acid. The imidization rate can be determined by measuring the infrared absorption spectrum of the polyimide thin film by the single-reflection ATR method using a Fourier transform infrared spectrophotometer (commercially available: FT / IR620 manufactured by JASCO Corporation) at 1015 cm -1 Based on the benzene ring absorber near 1780cm -1 It can be calculated from the absorbance of the C=O stretching derived from the imide group.

[0081] The weight-average molecular weight (Mw) of the adhesive polyimide is preferably within the range of, for example, 10,000 to 200,000. If Mw is less than 10,000, the film tends to be brittle. On the other hand, if Mw exceeds 200,000, the varnish tends to have high viscosity, which can easily cause thickness unevenness during coating. The Mw of the adhesive polyimide is preferably in the range of 20,000 to 100,000. If Mw is less than 20,000, the number of highly polar ends in the polyimide molecular chain increases, which may lead to an increase in the dielectric constant and dielectric loss tangent. If Mw is more than 100,000, the molecular chain length becomes long, making it difficult to form an ordered structure, which may lead to an increase in the dielectric constant and dielectric loss tangent.

[0082] (Crosslinking of adhesive polyimide) When an adhesive polyimide has a ketone group, the ketone group can be reacted with the amino group of an amino compound having at least two primary amino groups as functional groups (hereinafter sometimes referred to as a "crosslinking amino compound") to form a C=N bond, thereby forming a crosslinked structure. A polyimide having such a crosslinked structure (hereinafter sometimes referred to as a "crosslinked polyimide") is an application example of an adhesive polyimide and is a preferred embodiment. Since the Mw value varies significantly due to crosslinking, the Mw value of the crosslinked polyimide differs from the Mw value of the adhesive polyimide before crosslinking. An adhesive resin composition obtained by blending a crosslinking agent with an adhesive polyimide having a ketone group is another application example of an adhesive polyimide and is a preferred embodiment. The formation of a crosslinked structure can improve the heat resistance of the adhesive polyimide. A preferred tetracarboxylic acid anhydride for forming an adhesive polyimide having a ketone group is, for example, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride (BTDA), and a preferred diamine compound is, for example, an aromatic diamine such as 4,4'-bis(3-aminophenoxy)benzophenone (BABP) or 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene (BABB).

[0083] For the purpose of forming a crosslinked structure, it is particularly preferred to react a crosslinking amino compound with the above adhesive polyimide containing BTDA residues derived from BTDA in an amount of preferably 50 mol % or more, more preferably 60 mol % or more, based on the total tetracarboxylic acid residues. In the present invention, the term "BTDA residue" refers to a tetravalent group derived from BTDA.

[0084] Examples of amino compounds for crosslinking include (I) dihydrazide compounds, (II) aromatic diamines, and (III) aliphatic amines. Among these, dihydrazide compounds are preferred. Aliphatic amines other than dihydrazide compounds tend to form crosslinked structures even at room temperature, raising concerns about the storage stability of the varnish. On the other hand, aromatic diamines require high temperatures to form crosslinked structures. In this way, when a dihydrazide compound is used, it is possible to achieve both the storage stability of the varnish and a shortened curing time. Examples of dihydrazide compounds include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, and diglycerides. Preferred dihydrazide compounds include cholic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthoedioic acid dihydrazide, 4,4-bisbenzenedihydrazide, 1,4-naphthoic acid dihydrazide, 2,6-pyridinedioic acid dihydrazide, and itaconic acid dihydrazide. These dihydrazide compounds may be used alone or in combination of two or more.

[0085] Furthermore, the amino compounds such as (I) dihydrazide compounds, (II) aromatic diamines, and (III) aliphatic amines can also be used in combination of two or more types across categories, such as a combination of (I) and (II), a combination of (I) and (III), or a combination of (I), (II), and (III).

[0086] Furthermore, from the viewpoint of making the network structure formed by crosslinking with the crosslinking amino compound denser, the crosslinking amino compound used in the present invention preferably has a molecular weight (weight average molecular weight when the crosslinking amino compound is an oligomer) of 5,000 or less, more preferably 90 to 2,000, and even more preferably 100 to 1,500. Among these, crosslinking amino compounds having a molecular weight of 100 to 1,000 are particularly preferred. If the molecular weight of the crosslinking amino compound is less than 90, only one amino group of the crosslinking amino compound will form a C=N bond with a ketone group of the adhesive polyimide, and the surroundings of the remaining amino groups will be sterically bulky, making it difficult for the remaining amino groups to form C=N bonds.

[0087] When crosslinking a ketone group in an adhesive polyimide with a crosslinking amino compound, the crosslinking amino compound is added to a resin solution containing an adhesive polyimide to cause a condensation reaction between the ketone group in the adhesive polyimide and the primary amino group of the crosslinking amino compound. This condensation reaction hardens the resin solution to form a cured product. In this case, the amount of crosslinking amino compound added can be 0.004 to 1.5 mol, preferably 0.005 to 1.2 mol, more preferably 0.03 to 0.9 mol, and most preferably 0.04 to 0.6 mol of primary amino groups per 1 mol of ketone group. If the amount of crosslinking amino compound added is such that the total number of primary amino groups per mole of ketone groups is less than 0.004 moles, crosslinking by the crosslinking amino compound will be insufficient, and heat resistance after curing will tend to be difficult to achieve. If the amount of crosslinking amino compound added exceeds 1.5 moles, the unreacted crosslinking amino compound will act as a thermoplasticizer, tending to reduce the heat resistance of the adhesive layer.

[0088] The conditions for the condensation reaction for crosslinking are not particularly limited, as long as they are conditions under which the ketone group in the adhesive polyimide reacts with the primary amino group of the crosslinking amino compound to form an imine bond (C=N bond). The temperature for the thermal condensation is preferably within the range of, for example, 120 to 220°C, more preferably within the range of 140 to 200°C, for reasons such as discharging water produced by the condensation outside the system or simplifying the condensation step when the thermal condensation reaction is carried out subsequently to the synthesis of the adhesive polyimide. The reaction time is preferably about 30 minutes to 24 hours. The end point of the reaction can be determined by measuring the infrared absorption spectrum using, for example, a Fourier transform infrared spectrophotometer (commercially available: FT / IR620 manufactured by JASCO Corporation) at 1670 cm -1 The decrease or disappearance of the absorption peak due to the ketone group in the polyimide resin near 1635 cm -1 This can be confirmed by the appearance of an absorption peak derived from a nearby imine group.

[0089] The thermal condensation of the ketone group of the adhesive polyimide with the primary amino group of the crosslinking amino compound can be carried out, for example, by the following method: (1) A method in which an amino compound for crosslinking is added and heated after synthesis (imidization) of adhesive polyimide; (2) A method in which an excess amount of an amino compound is charged in advance as a diamine component, and following the synthesis (imidization) of an adhesive polyimide, the remaining amino compound that is not involved in imidization or amidation is used as a crosslinking amino compound and heated together with the adhesive polyimide; Or, (3) A method in which the adhesive polyimide composition containing the above-mentioned crosslinking-forming amino compound is processed into a predetermined shape (for example, after being applied to a substrate or formed into a film), and then heated; This can be done by, etc.

[0090] In the above description, an example of a crosslinked polyimide in which a crosslinked structure is formed by the formation of an imine bond is given to impart heat resistance to the adhesive polyimide. However, the present invention is not limited to this example. As a method for curing the polyimide, it is also possible to compound and cure the polyimide with, for example, an epoxy resin, an epoxy resin curing agent, a compound having an unsaturated bond, such as a maleimide, an activated ester resin, or a resin having a styrene skeleton.

[0091] [Adhesive resin composition] Since adhesive polyimides are solvent-soluble, they can be used in the form of a composition containing a solvent. That is, the adhesive resin composition contains an adhesive polyimide and a solvent capable of dissolving the adhesive polyimide. The adhesive resin composition may also contain an amino compound for crosslinking as an optional component. The adhesive resin composition contains adhesive polyimide as the main component of the resin component, preferably at least 70% by weight of the resin component, more preferably at least 90% by weight of the resin component, and most preferably as the entire resin component. Here, the main component of the resin component means a component that accounts for more than 50% by weight of the total resin component.

[0092] The solvent is not particularly limited as long as it can dissolve the adhesive polyimide, and examples thereof include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 2-butanone, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, methylcyclohexane, dioxane, tetrahydrofuran, diglyme, triglyme, methanol, ethanol, benzyl alcohol, cresol, acetone, etc. Two or more of these solvents can be used in combination, and aromatic hydrocarbons such as xylene and toluene can also be used in combination.

[0093] In the adhesive resin composition, the blending ratio of adhesive polyimide to solvent is not particularly limited as long as the viscosity of the composition can be maintained at a level that allows coating. The viscosity of the adhesive resin composition is preferably, for example, within the range of 500 mPa·s to 100,000 mPa·s. If the viscosity is outside this range, defects such as uneven thickness and streaks are likely to occur in the resin film during coating.

[0094] The adhesive resin composition may contain, as appropriate, optional components, such as plasticizers, other curable resin components such as epoxy resins, curing agents, curing accelerators, organic fillers, inorganic fillers, coupling agents, and flame retardants, within the scope of the invention.

[0095] [Adhesive film] An adhesive film according to one embodiment of the present invention is a film obtained by processing the adhesive polyimide or crosslinked polyimide into a film. The adhesive film is not particularly limited as long as it contains the adhesive polyimide or crosslinked polyimide as the main resin component, preferably at least 70% by weight of the resin component, more preferably at least 90% by weight of the resin component, and most preferably the entire resin component. The term "main resin component" refers to a component that accounts for more than 50% by weight of the total resin component. The adhesive film may be a film (sheet) made of adhesive polyimide or crosslinked polyimide, or may be laminated on a resin substrate such as an inorganic material substrate, such as copper foil or glass plate, or a polyimide film, polyamide film, or polyester film. The adhesive film may contain optional components, such as plasticizers, other curable resin components such as epoxy resins, curing agents, curing accelerators, organic fillers, inorganic fillers, coupling agents, and flame retardants.

[0096] After 24 hours of conditioning at constant temperature and humidity (normal conditions) of 23°C and 50% RH, the adhesive film preferably has a dielectric loss tangent (Tanδ1) of less than 0.002 and a relative dielectric constant (E1) of 3.0 or less at 10 GHz, as measured with a split post dielectric resonator (SPDR). If the dielectric loss tangent (Tanδ1) and relative dielectric constant (E1) exceed the above values, this will lead to increased dielectric loss when applied to a circuit board, making it more likely to cause problems such as electrical signal loss in the transmission path of high-frequency signals.

[0097] Furthermore, the adhesive film preferably has a dielectric loss tangent (Tan δ2) of less than 0.002 and a relative dielectric constant (E2) of 3.0 or less at 20 GHz, as measured with a split post dielectric resonator (SPDR), after 24 hours of conditioning under constant temperature and humidity conditions (normal conditions) of 23°C and 50% RH. If the dielectric loss tangent (Tan δ2) and relative dielectric constant (E2) exceed the above values, this will lead to increased dielectric loss when applied to a circuit board, making it more likely to cause problems such as electrical signal loss in the transmission path of high-frequency signals.

[0098] The tensile modulus of the adhesive film is preferably 3000 MPa or less, preferably 100 MPa to 2500 MPa, and more preferably 200 MPa to 2000 MPa. If the tensile modulus is less than 100 MPa, the film may wrinkle easily, and handling may be impaired due to air entrapment during lamination. If the tensile modulus exceeds 3000 MPa, warping may occur and dimensional stability may be reduced when the substrate and adhesive film are laminated. By achieving the above tensile modulus, a laminate with good handling properties, reduced warping, and excellent dimensional stability can be obtained.

[0099] Next, laminates, metal-clad laminates, circuit boards, and multilayer circuit boards, which are preferred embodiments to which the adhesive film is applied, will be described with specific examples.

[0100] [Laminate] As shown in FIG. 1, a laminate 100 according to one embodiment of the present invention includes a substrate 10 and an adhesive layer 20 laminated on at least one surface of the substrate 10, the adhesive layer 20 being made of the adhesive film described above. The laminate 100 may also include any other layer. Examples of the substrate 10 in the laminate 100 include substrates made of inorganic materials such as copper foil and glass plates, and substrates made of resin materials such as polyimide films, polyamide films, and polyester films. The laminate 100 can be manufactured according to any of the adhesive film manufacturing methods [1] to [3] described above, except that the laminate 100 is not peeled from the substrate 10. Alternatively, the laminate 100 may be manufactured by separately preparing the substrate 10 and the adhesive film and bonding them together. Preferred embodiments of the laminate 100 include a coverlay film, a resin-coated copper foil, and the like.

[0101] (Coverlay film) Although not shown, the coverlay film, which is one embodiment of the laminate 100, has a coverlay film material layer as a substrate 10 and an adhesive layer 20 laminated on one side of the coverlay film material layer, the adhesive layer 20 being made of the adhesive film. The coverlay film may also include any layer other than those described above.

[0102] The material of the coverlay film material layer is not particularly limited, but examples thereof include polyimide-based films such as polyimide resins, polyetherimide resins, and polyamideimide resins, as well as polyamide-based films and polyester-based films. Among these, it is preferable to use polyimide-based films, which have excellent heat resistance. Furthermore, the coverlay film material layer may contain a black pigment to effectively exhibit light-blocking properties, concealing properties, and design properties, and may also contain optional components such as matte pigments that suppress surface gloss, as long as the effect of improving the dielectric properties is not impaired.

[0103] The thickness of the coverlay film material layer is not particularly limited, but is preferably within the range of, for example, 5 μm or more and 100 μm or less. The thickness of the adhesive layer 20 is not particularly limited, but is preferably within the range of 10 μm to 75 μm, for example.

[0104] The coverlay film of the present embodiment can be produced by the following method. First, as a first method, polyimide that will become the adhesive layer 20 is applied in solution form (for example, in the form of a varnish containing a solvent, preferably an adhesive resin composition) to one side of a film material layer for the coverlay, and then the adhesive layer 20 is formed by drying at a temperature of, for example, 80 to 180°C, thereby forming a coverlay film having a film material layer for the coverlay and the adhesive layer 20.

[0105] As a second method, polyimide for adhesive layer 20 is applied to any substrate in a solution state (for example, a varnish containing a solvent is preferable, and an adhesive resin composition is preferable), dried at a temperature of, for example, 80 to 180°C, and then peeled off to form an adhesive film for adhesive layer 20, and this adhesive film can be thermocompressed to a film material layer for coverlay at a temperature of, for example, 60 to 220°C to form a coverlay film.

[0106] (Copper foil with resin) Although not shown, a resin-coated copper foil, which is another embodiment of the laminate 100, is obtained by laminating an adhesive layer 20 on at least one side of a copper foil as a substrate 10, and the adhesive layer 20 is made of the above-mentioned adhesive film. Note that the resin-coated copper foil of this embodiment may include any layer other than those described above.

[0107] The thickness of the adhesive layer 20 in the resin-coated copper foil is preferably, for example, in the range of 0.1 to 125 μm, and more preferably in the range of 0.3 to 100 μm. If the thickness of the adhesive layer 20 is less than the above-mentioned lower limit, problems such as insufficient adhesion may occur. On the other hand, if the thickness of the adhesive layer 20 exceeds the above-mentioned upper limit, problems such as reduced dimensional stability may occur. Furthermore, from the viewpoint of lowering the dielectric constant and the dielectric loss tangent, it is preferable that the thickness of the adhesive layer 20 be 3 μm or more.

[0108] The material of the copper foil in the resin-coated copper foil is preferably one containing copper or a copper alloy as a main component. The thickness of the copper foil is preferably 35 μm or less, more preferably in the range of 5 to 25 μm. From the viewpoint of production stability and handleability, the lower limit of the copper foil thickness is preferably 5 μm. The copper foil may be a rolled copper foil or an electrolytic copper foil. Furthermore, commercially available copper foils can be used as the copper foil.

[0109] The resin-coated copper foil may be prepared, for example, by sputtering a metal onto an adhesive film to form a seed layer, and then forming a copper layer by, for example, copper plating, or by laminating an adhesive film and a copper foil by a method such as thermocompression bonding. Furthermore, the resin-coated copper foil may be prepared by casting a coating solution of an adhesive polyimide or its precursor onto the copper foil, drying it to form a coating film, and then performing the necessary heat treatment to form the adhesive layer 20 on the copper foil.

[0110] [Metal-clad laminate] (First aspect) A metal-clad laminate according to one embodiment of the present invention comprises an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer, at least one of the insulating resin layers being made of the adhesive film described above. Note that the metal-clad laminate of this embodiment may also include any other layer(s) besides those described above.

[0111] (Second aspect) As shown in FIG. 2 , a metal-clad laminate according to another embodiment of the present invention is a so-called three-layer metal-clad laminate 101 including an insulating resin layer 30, an adhesive layer 20 laminated on at least one side of the insulating resin layer 30, and a metal layer M laminated on the insulating resin layer 30 via the adhesive layer 20, where the adhesive layer 20 is made of the adhesive film described above. The three-layer metal-clad laminate 101 may also include any other layer. The three-layer metal-clad laminate 101 may include the adhesive layer 20 on one or both sides of the insulating resin layer 30, and the metal layer M may be provided on one or both sides of the insulating resin layer 30 via the adhesive layer 20. In other words, the three-layer metal-clad laminate 101 may be a single-sided or double-sided metal-clad laminate. A single-sided or double-sided FPC can be manufactured by etching or otherwise processing the metal layer M of the three-layer metal-clad laminate 101 into a wiring circuit.

[0112] The insulating resin layer 30 in the three-layer metal-clad laminate 101 is not particularly limited as long as it is made of a resin having electrical insulation properties, and examples thereof include polyimide, epoxy resin, phenolic resin, polyethylene, polypropylene, polytetrafluoroethylene, silicone, ETFE, etc., but is preferably made of polyimide. The polyimide layer that makes up the insulating resin layer 30 may be a single layer or multiple layers, but preferably includes a non-thermoplastic polyimide layer.

[0113] The thickness of the insulating resin layer 30 in the three-layer metal-clad laminate 101 is preferably in the range of 1 to 125 μm, and more preferably in the range of 5 to 100 μm. If the thickness of the insulating resin layer 30 is less than the above-mentioned lower limit, problems such as insufficient electrical insulation may occur. On the other hand, if the thickness of the insulating resin layer 30 exceeds the above-mentioned upper limit, problems such as the metal-clad laminate becoming more prone to warping may occur.

[0114] The thickness of the adhesive layer 20 in the three-layer metal-clad laminate 101 is preferably, for example, in the range of 0.1 to 125 μm, and more preferably in the range of 0.3 to 100 μm. In the three-layer metal-clad laminate 101 of the present embodiment, if the thickness of the adhesive layer 20 is less than the above-mentioned lower limit, problems such as insufficient adhesion may occur. On the other hand, if the thickness of the adhesive layer 20 exceeds the above-mentioned upper limit, problems such as reduced dimensional stability may occur. Furthermore, from the viewpoint of reducing the dielectric constant and 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.

[0115] 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 preferably in the range of 0.1 to 3.0, and more preferably in the range of 0.15 to 2.0. By adjusting the ratio in this manner, warping of the three-layer metal-clad laminate 101 can be suppressed. The insulating resin layer 30 may contain a filler as needed. Examples of fillers include silicon dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride, and metal salts of organic phosphinic acid. These can be used alone or in combination of two or more.

[0116] (Third aspect) 3, a metal-clad laminate according to yet another embodiment of the present invention is a laminated metal-clad laminate 102 formed by laminating at least two single-sided metal-clad laminates together via an adhesive layer 20. The laminated metal-clad laminate 102 comprises a first single-sided metal-clad laminate 41, a second single-sided metal-clad laminate 42, and an adhesive layer 20 laminated between the first single-sided metal-clad laminate 41 and the second single-sided metal-clad laminate 42, and the adhesive layer 20 is made of the adhesive film described above. Here, the first single-sided metal-clad laminate 41 has a first metal layer M1 and a first insulating resin layer 31 laminated on at least one surface of the first 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 surface of the second metal layer M2. The adhesive layer 20 is disposed so as to abut the first insulating resin layer 31 and the second insulating resin layer 32. Note that the laminated metal-clad laminate 102 may include any layers other than those described above.

[0117] The first insulating resin layer 31 and the second insulating resin layer 32 in the laminated metal-clad laminate 102 may have the same configuration as the insulating resin layer 30 in the three-layer metal-clad laminate 101 of the second embodiment. The laminated metal-clad laminate 102 can be manufactured by preparing a first single-sided metal-clad laminate 41 and a second single-sided metal-clad laminate 42, and then placing an adhesive film between the first insulating resin layer 31 and the second insulating resin layer 32 and laminating them together.

[0118] (Fourth aspect) 4, a metal-clad laminate according to yet another embodiment of the present invention is an adhesive-layered single-sided metal-clad laminate 103 including a single-sided metal-clad laminate having an insulating resin layer 33 and a metal layer M laminated on one side of the insulating resin layer 33, and an adhesive layer 20 laminated on the other side of the insulating resin layer 33, wherein the adhesive layer 20 is made of the adhesive film described above. Note that the adhesive-layered metal-clad laminate 103 may include any layer other than those described above. The insulating resin layer 33 in the adhesive layer-attached metal-clad laminate 103 may have the same configuration as the insulating resin layer 30 in the three-layer metal-clad laminate 101 of the second embodiment. The adhesive layer-attached metal-clad laminate 103 can be produced by preparing a single-sided metal-clad laminate having an insulating resin layer 33 and a metal layer M, and then laminating an adhesive film to the insulating resin layer 33 side.

[0119] In the metal-clad laminate of any of the first to fourth embodiments exemplified above, the material of the metal layer M (including the first metal layer M1 and the second metal layer M2; the same applies below) is not particularly limited, but examples 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 copper alloys are particularly preferred. The material of the wiring layer in the circuit board described below is also the same as the metal layer M.

[0120] The thickness of the metal layer M is not particularly limited, but when a metal foil such as copper foil is used, it is preferably 35 μm or less, and more preferably in the range of 5 to 25 μm. From the viewpoint of production stability and handleability, the lower limit of the thickness of the metal foil is preferably 5 μm. When copper foil is used, it may be rolled copper foil or electrolytic copper foil. Commercially available copper foil may be used as the copper foil. Furthermore, the metal foil may be surface-treated with, for example, siding, aluminum alcoholate, aluminum chelate, silane coupling agent, etc., for the purpose of, for example, rust prevention or improving adhesive strength.

[0121] [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. One or more metal layers of the metal-clad laminate are patterned by a conventional method to form a wiring layer (conductor circuit layer), thereby producing a circuit board such as an FPC. The circuit board may also include a coverlay film that covers the wiring layer.

[0122] (Second aspect) 5, a circuit board 200 according to another embodiment of the present invention includes a first base material 11, a wiring layer 50 laminated on at least one surface of the first base material 11, and an adhesive layer 20 laminated on the surface of the first base material 11 facing the wiring layer 50 so as to cover the wiring layer 50, the adhesive layer 20 being made of the adhesive film described above. Note that the circuit board 200 may include any layer other than those described above. The first base material 11 in the circuit board 200 may have the same configuration as the insulating resin layer of the metal-clad laminate. The circuit board 200 can be manufactured by laminating an adhesive film to the side of the wiring layer 50 of a circuit board that includes the first base material 11 and the wiring layer 50 laminated on at least one surface of the first base material 11.

[0123] (Third aspect) 6, a circuit board 201 according to yet another embodiment of the present invention includes a first substrate 11, a wiring layer 50 laminated on at least one surface of the first substrate 11, an adhesive layer 20 laminated on the surface of the first substrate 11 facing the wiring layer 50 so as to cover the wiring layer 50, and a second substrate 12 laminated on the surface of the adhesive layer 20 opposite the first substrate 11, where the adhesive layer 20 is made of the adhesive film. The circuit board 201 may also include any other layers. The first substrate 11 and the second substrate 12 in the circuit board 201 may have a configuration similar to that of the insulating resin layer of the metal-clad laminate. The circuit board 201 can be manufactured by bonding a second substrate 12 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 via an adhesive film.

[0124] (Fourth aspect) 7, a circuit board 202 according to yet another embodiment of the present invention includes a first substrate 11, an adhesive layer 20 laminated on at least one surface of the first substrate 11, a second substrate 12 laminated on the surface of the adhesive layer 20 opposite the first substrate 11, and wiring layers 50, 50 laminated on the surfaces of the first substrate 11 and the second substrate 12 opposite the adhesive layer 20, respectively, where the adhesive layer 20 is made of the adhesive film. The circuit board 202 may also include any layer other than those described above. The first substrate 11 and the second substrate 12 in the circuit board 202 may have a configuration similar to that of the insulating resin layer of the metal-clad laminate. The circuit board 202 can be manufactured by preparing a first circuit board having a first substrate 11 and a wiring layer 50 laminated on at least one surface of the first substrate 11, and a second circuit board having a second substrate 12 and a wiring layer 50 laminated on at least one surface of the second substrate 12, and then placing an adhesive film between the first substrate 11 of the first circuit board and the second substrate 12 of the second circuit board and bonding them together.

[0125] [Multilayer circuit board] A multilayer circuit board according to one embodiment of the present invention includes a laminate formed by stacking a plurality of insulating resin layers and one or more wiring layers embedded within the laminate, wherein at least one of the insulating resin layers is formed by an adhesive layer that has adhesive properties and covers the wiring layer, the adhesive layer being made of the adhesive film described above. Note that the multilayer circuit board of this embodiment may include any layer other than those described above. For example, as shown in FIG. 8 , a multilayer circuit board 203 of this embodiment has at least two insulating resin layers 34 and at least two wiring layers 50, with at least one of the wiring layers 50 being 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. The multilayer circuit board 203 may also have an optional wiring layer 50 exposed on the surface of the multilayer circuit board 203. The multilayer circuit board 203 may also have interlayer connection electrodes (via electrodes) in contact with the wiring layer 50. The wiring layer 50 has a conductor circuit formed in a predetermined pattern on one or both sides of the insulating resin layer 34. The conductor circuit may be patterned on the surface of the insulating resin layer 34 or may be patterned using a damascene (embedded) method. The insulating resin layer 34 in the circuit board 203 may have a configuration similar to that of the insulating resin layer of the metal-clad laminate.

[0126] The circuit board and multilayer circuit board of each of the above embodiments includes the adhesive layer 20 containing adhesive polyimide, and therefore, transmission loss can be reduced even in high frequency transmission. [Example]

[0127] The features of the present invention will be described in more detail below with reference to examples. However, the scope of the present invention is not limited to these examples. In the following examples, various measurements and evaluations are as follows, unless otherwise specified.

[0128] [Method for measuring amine value] Approximately 2 g of dimer diamine composition is weighed into a 200-250 mL Erlenmeyer flask, and 0.1 mol / L ethanolic potassium hydroxide solution is added dropwise using phenolphthalein as an indicator until the solution turns light pink. The mixture is then dissolved in approximately 100 mL of neutralized butanol. 3-7 drops of phenolphthalein solution are added, and the sample solution is titrated with 0.1 mol / L ethanolic potassium hydroxide solution while stirring until the solution turns light pink. Five drops of bromophenol blue solution are added, and the sample solution is titrated with 0.2 mol / L hydrochloric acid / isopropanol solution while stirring until the solution turns yellow. The amine value is calculated by the following formula (1). Amine value = {(V2 × C2) - (V1 × C1)} × 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. V and C are the volume and concentration of the solution used in the titration, respectively, and the subscripts 1 and 2 represent a 0.1 mol / L ethanolic potassium hydroxide solution and a 0.2 mol / L hydrochloric acid / isopropanol solution, respectively. m is the sample weight in grams.

[0129] [Measurement of weight-average molecular weight (Mw) of polyimide] The weight-average molecular weight was measured by gel permeation chromatography (HLC-8220GPC manufactured by Tosoh Corporation). Polystyrene was used as a standard substance, and tetrahydrofuran (THF) was used as a developing solvent.

[0130] [Viscosity measurement] Using an E-type viscometer (DV-II+ProCP type), the viscosity (cP) of the polyimide solution immediately after polymerization was measured under the conditions of a temperature of 25° C., a rotation speed of 100 RPM, and a measurement time of 2 minutes.

[0131] [Measurement of relative permittivity and dielectric loss tangent] Using a vector network analyzer (Agilent, product name: Vector Network Analyzer E8363C) and an SPDR resonator, the resin sheet was left for 24 hours under conditions of temperature: 23°C and humidity: 50%, and then the relative permittivity (ε1) and dielectric loss tangent (Tanδ1) at a frequency of 10 GHz, and the relative permittivity (ε2) and dielectric loss tangent (Tanδ2) at a frequency of 20 GHz were measured. In addition, the R value, which is an index of the frequency dependence of the dielectric loss tangent, was calculated using the following formula. R value = Tanδ2 - Tanδ1

[0132] [Glass transition temperature (Tg)] The glass transition temperature (Tg) was measured using a 5 mm × 20 mm resin sheet at a temperature increase rate of 5°C / min from 0°C to 300°C using a thermomechanical analyzer (TMA: manufactured by Netsch GmbH, product name: TMA4000SA). The temperature at which the elongation changes during heating is defined as the glass transition temperature.

[0133] Tensile modulus The tensile modulus was measured by the following procedure. First, a test piece (width 12.7 mm × length 127 mm) was prepared from the resin sheet using a tension tester (trade name: Tensilon, manufactured by Orientec Co., Ltd.). A tensile test was performed at 50 mm / min using this test piece, and the tensile modulus at 25°C was determined.

[0134] [Warp evaluation method] Warpage was evaluated using the following method. Test specimens were prepared by applying a polyimide solution to a 25 μm thick polyimide film (manufactured by DuPont-Toray Co., Ltd., product name: Kapton 100EN) or a 12 μm thick copper foil, so that the dry thickness would be 25 μm. In this state, the test specimen was placed with the polyimide film or copper foil facing downwards, and the average height of the warpage at the four corners of the test specimen was measured. A value of 5 mm or less was rated "good," and a value of more than 5 mm was rated "unacceptable."

[0135] [GPC and chromatogram area percentage calculation] (a) Dimer diamine (b) Monoamine compounds obtained by substituting the 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) Amine compounds obtained by substituting the terminal carboxylic acid group of a polybasic acid compound having a hydrocarbon group having 41 to 80 carbon atoms with a primary aminomethyl group or an amino group (excluding the dimer diamine).

[0136] For GPC, 20 mg of the dimer diamine composition was pretreated with 200 μL of acetic anhydride, 200 μL of pyridine, and 2 mL of THF to prepare a 100 mg solution, which was then diluted with 10 mL of THF (containing 1,000 ppm of cyclohexanone). The prepared sample was measured using a Tosoh Corporation HLC-8220GPC column (TSK-gel G2000HXL, G1000HXL), with a flow rate of 1 mL / min, a column (oven) temperature of 40°C, and an injection volume of 50 μL. Cyclohexanone was used as a standard substance to correct for elution time.

[0137] At this time, the peak top of the cyclohexanone main peak was adjusted to a retention time of 27 to 31 minutes, and the period from the peak start to the peak end of the cyclohexanone main peak was adjusted to 2 minutes, and the peak top of the main peak excluding the cyclohexanone peak was adjusted to 18 to 19 minutes, and the period from the peak start to the peak end of the main peak excluding the cyclohexanone peak was adjusted to 2 minutes to 4 minutes 30 seconds. (a) The component represented by the main peak; (b) Components represented by GPC peaks detected at times later than the minimum retention time of the main peak; (c) Components represented by GPC peaks detected at earlier retention times than the minimum value of the main peak; was detected.

[0138] The abbreviations used in the examples represent 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: aliphatic diamine having 36 carbon atoms (manufactured by Croda Japan Co., Ltd., trade name: PRIAMINE 1074, distilled and purified; amine value: 210 mg KOH / g; mixture of dimer diamines with cyclic and chain structures; component (a): 97.9% by weight; component (b): 0.3%; component (c): 1.8%) BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane N-12: Dodecanedioic acid dihydrazide NMP: N-methyl-2-pyrrolidone OP935: Aluminum salt of phosphinic acid (manufactured by Clariant, trade name: Exolit OP935, aluminum diethylphosphinate, phosphorus content: 23%, average particle size D 50 ;2μm) The molecular weight of the DDA was calculated using the following formula: Molecular weight = 56.1 x 2 x 1000 / amine value

[0139] [Example 1] A 500 ml separable flask was charged with 27.90 g of BTDA (0.08642 mol), 6.702 g of ODPA (0.02161 mol), 46.50 g of DDA (0.08703 mol), 8.932 g of BAPP (0.02176 mol), 126 g of NMP, and 84 g of xylene, and the mixture was mixed thoroughly at 40° C. for 1 hour to prepare a polyamic acid solution. The polyamic acid solution was heated to 190° C. and stirred for 5 hours. 60 g of xylene was added to complete the imidization, preparing Polyimide Solution 1 (solids content: 30 wt %, weight average molecular weight: 35,332, viscosity: 2,627 cP).

[0140] [Examples 2 to 11] Polyimide solutions 2 to 11 were prepared in the same manner as in Example 1, except that the raw material compositions shown in Table 1 were used.

[0141] [Table 1]

[0142] [Example 12] The polyimide solution 1 was applied to one side of a release PET film 1 (manufactured by Higashiyama Film Co., Ltd., product name: HY-S05, length x width x thickness = 200 mm x 300 mm x 25 μm), dried at 100°C for 5 minutes, and then dried at 120°C for 5 minutes, and the adhesive layer was peeled off from the release PET film 1 to obtain a resin sheet 12 with a thickness of 25 μm. The various evaluation results of the resin sheet 12 are as follows. ε1;2.6, Tanδ1;0.0017 、 ε2; 2.6, Tanδ2; 0.0015, R value; -0.0002, Tg; 47°C, Tensile modulus; 1230 MPa

[0143] [Examples 13 to 22] Resin sheets 13 to 22 were obtained in the same manner as in Example 12, except that polyimide solutions 2 to 11 were used. Table 2 shows the results of evaluation of various properties.

[0144] [Table 2]

[0145] [Example 23] 1.1 g of N-12 (0.004 mol) was mixed with 100 g of polyimide solution 1 (30 g as solid content), diluted with 7.5 g of OP935, 0.5 g of NMP, and 10.5 g of xylene, and stirred for an additional hour to prepare adhesive composition 23.

[0146] [Examples 24 to 33] Adhesive compositions 24 to 33 were prepared in the same manner as in Example 23, except that polyimide solutions 2 to 11 were used.

[0147] [Example 34] 0.6 g of N-12 (0.002 mol) was mixed with 100 g of polyimide solution 9 (30 g as solid content), and the mixture was diluted with 7.4 g of OP935, 1.8 g of NMP, and 11.7 g of xylene, and further stirred for 1 hour to prepare adhesive composition 34.

[0148] [Example 35] The adhesive composition 23 was applied to one side of a release PET film 1 and dried at 80°C for 15 minutes to obtain a resin sheet 35 with an adhesive layer thickness of 25 μm. The adhesive layer was then peeled off from the release PET film 1 to obtain an adhesive film 35 with a thickness of 25 μm.

[0149] [Examples 36 to 46] Adhesive films 36 to 46 were obtained in the same manner as in Example 35, except that adhesive compositions 24 to 34 were used.

[0150] [Example 47] Adhesive composition 31 was applied to one side of polyimide film 1 (manufactured by DuPont-Toray Co., Ltd., product name: Kapton 50EN, ε1 = 3.6, tanδ1 = 0.0084, length × width × thickness = 200 mm × 300 mm × 12 μm) and dried at 80°C for 15 minutes to obtain coverlay film 47 with an adhesive layer thickness of 25 μm. The warpage state of the obtained coverlay film 47 was "good".

[0151] [Examples 48 and 49] Coverlay films 48 and 49 were obtained in the same manner as in Example 47, except that adhesive compositions 24 and 25 were used. The warpage state of the obtained coverlay films 48 and 49 was both "good".

[0152] [Example 50] The release PET film 1 was laminated so that it was in contact with the adhesive layer side of the coverlay film 47, and the laminate was pressed using a vacuum laminator at a temperature of 160°C and a pressure of 0.8 MPa for 2 minutes. Then, adhesive composition 31 was applied to the polyimide film 1 side of the coverlay film 47 with the release PET film 1 pressed onto the adhesive layer side so that the thickness after drying was 25 μm, and dried at 80°C for 15 minutes. The release PET film 1 was then laminated so that it was in contact with the surface onto which the adhesive composition 31 had been applied and dried, and the laminate was pressed using a vacuum laminator at a temperature of 160°C and a pressure of 0.8 MPa for 2 minutes to obtain a polyimide adhesive layer-attached laminate 50 having adhesive layers on both sides of the polyimide film.

[0153] [Examples 51 and 52] Laminates 51 and 52 with polyimide adhesive layers were obtained in the same manner as in Example 50, except that coverlay films 48 and 49 were used and adhesive compositions 24 and 25 were applied.

[0154] [Example 53] The adhesive composition 31 was applied to one side of an electrolytic copper foil having a thickness of 12 μm and dried at 80° C. for 15 minutes to obtain a resin-coated copper foil 53 having an adhesive layer thickness of 25 μm. The warpage state of the obtained resin-coated copper foil 53 was “good”.

[0155] [Examples 54 to 56] Resin-coated copper foils 54 to 56 were obtained in the same manner as in Example 53, except that adhesive compositions 24, 25 and 26 were used. The warpage state of the obtained resin-coated copper foils 54 to 56 was all "good".

[0156] [Example 57] The adhesive composition 31 was applied to one side of an electrolytic copper foil having a thickness of 12 μm and dried at 80° C. for 30 minutes to obtain a resin-coated copper foil 57 having an adhesive layer thickness of 50 μm. The warpage state of the obtained resin-coated copper foil 57 was “good”.

[0157] [Example 58] Adhesive composition 31 was further applied to the surface of the adhesive layer of resin-coated copper foil 57 and dried at 80°C for 30 minutes to obtain resin-coated copper foil 58 having a total adhesive layer thickness of 100 µm. The warpage state of the obtained resin-coated copper foil 58 was "good".

[0158] [Example 59] The adhesive composition 31 was applied to one side of a release PET film 1, dried at 80° C. for 30 minutes, and the adhesive layer was peeled off from the release PET film 1 to obtain an adhesive film 59 with a thickness of 50 μm.

[0159] [Example 60] An adhesive film 59, a polyimide film 2 (manufactured by DuPont, trade name: Kapton 100-EN, thickness 25 μm, ε1=3.6, tanδ1=0.0084), an adhesive film 44, and a 12 μm thick electrolytic copper foil were laminated in this order on a 12 μm thick electrolytic copper foil, and the laminate was pressure-bonded using a vacuum laminator at a temperature of 160°C and a pressure of 0.8 MPa for 2 minutes. The temperature was then increased from room temperature to 160°C, and the laminate was heat-treated at 160°C for 4 hours, thereby obtaining a copper-clad laminate 60.

[0160] [Examples 61 to 63] Copper clad laminates 61 to 63 were obtained in the same manner as in Example 60, except that adhesive films 36, 37, and 38 were used.

[0161] [Example 64] The coverlay film 47 was laminated onto a 12 μm thick electrolytic copper foil so that the adhesive layer side was in contact with the copper foil, and then pressed using a vacuum laminator at a temperature of 160°C and a pressure of 0.8 MPa for 2 minutes.Then, the temperature was increased from room temperature to 160°C and heat-treated at 160°C for 2 hours to obtain a copper-clad laminate 64.

[0162] [Examples 65 and 66] Copper clad laminates 65 and 66 were obtained in the same manner as in Example 64, except that coverlay films 48 and 49 were used.

[0163] [Example 67] An adhesive film 44 was laminated onto a 12 μm thick rolled copper foil, and the polyimide film side of the coverlay film 47 was laminated so that it was in contact with the adhesive film 44. Further, a 12 μm thick rolled copper foil was laminated onto the adhesive layer side of the coverlay film 47 in sequence, and the laminate was pressed using a vacuum laminator at a temperature of 160°C and a pressure of 0.8 MPa for 2 minutes. After that, the temperature was raised from room temperature to 160°C and the laminate was heat-treated at 160°C for 2 hours to obtain a copper-clad laminate 67.

[0164] [Examples 68 and 69] Copper-clad laminates 68 and 69 were produced in the same manner as in Example 67, except that adhesive films 35 and 36 were used instead of adhesive film 44, and coverlay films 48 and 49 were used instead of coverlay film 47.

[0165] [Example 70] Two sheets of resin-coated copper foil 57 were prepared, and the two resin-coated copper foils 57 were laminated so that the adhesive layer sides of the two sheets of resin-coated copper foil 57 were in contact with a polyimide film 3 (manufactured by DuPont, product name: Kapton 200-EN, thickness 50 μm, ε1=3.6, tanδ1=0.0084). The laminate was then pressed together using a vacuum laminator at a temperature of 160°C and a pressure of 0.8 MPa for 5 minutes, after which the temperature was raised from room temperature to 160°C and heat-treated at 160°C for 4 hours to obtain a copper-clad laminate 70.

[0166] [Example 71] Adhesive composition 31 was applied to the resin layer (polyimide) side of single-sided copper-clad laminate 1 (manufactured by Nippon Steel Chemical & Material Co., Ltd., product name: ESPANEX MC12-25-00UEM, length × width × thickness = 200 mm × 300 mm × 25 μm) and dried at 80°C for 30 minutes to obtain an adhesive layer-attached copper-clad laminate 71 with an adhesive layer thickness of 50 μm. Another single-sided copper-clad laminate 1 was laminated so that the resin layer side of the adhesive layer-attached copper-clad laminate 71 was in contact with the adhesive layer side, and the laminate 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 copper-clad laminate 71.

[0167] [Example 72] Two adhesive layer-attached copper-clad laminates 71 were stacked with the adhesive layer sides facing each other, and then pressed together using a small precision press at a temperature of 160°C and a pressure of 4.0 MPa for 120 minutes to obtain copper-clad laminate 72.

[0168] [Example 73] An adhesive film 44 was laminated on the resin layer side of the single-sided copper-clad laminate 1, and then another single-sided copper-clad laminate 1 was laminated on top of that so that the resin layer side of the single-sided copper-clad laminate 1 was in contact with the adhesive film 44.Then, using a small precision press, the laminate was pressed at a temperature of 160°C and a pressure of 4.0 MPa for 120 minutes to obtain a copper-clad laminate 73.

[0169] [Example 74] The adhesive composition 31 was applied to one side of a release PET film 1, dried at 80° C. for 15 minutes, and the adhesive layer was peeled off from the release PET film 1 to obtain an adhesive film 74 with a thickness of 15 μm.

[0170] [Example 75] An adhesive film 74 was laminated on the resin layer side of the single-sided copper-clad laminate 1, and then another adhesive film 74 was laminated on top of that so that the resin layer side of the single-sided copper-clad laminate 1 was in contact with the adhesive film 74.Then, using a small precision press, the laminate was pressed at a temperature of 160°C and a pressure of 4.0 MPa for 120 minutes to obtain a copper-clad laminate 75.

[0171] [Example 76] A double-sided copper-clad laminate 2 (manufactured by Nippon Steel Chemical & Material Co., Ltd., trade name: Espanex MB12-25-00UEG) was prepared, and the copper foil on one side was subjected to circuit processing by etching to form a conductor circuit layer, thereby obtaining a wiring board 76A.

[0172] The copper foil on one side of the double-sided copper-clad laminate 2 was removed by etching to obtain a copper-clad laminate 76B.

[0173] An adhesive film 44 was sandwiched between the conductive circuit layer side of the wiring board 76A and the resin layer side of the copper-clad laminate 76B, and the laminated sheets were thermocompressed at a temperature of 160°C and a pressure of 4.0 MPa for 120 minutes to obtain the multilayer circuit board 76.

[0174] [Example 77] A copper-clad laminate 77 was prepared using an insulating substrate made of a liquid crystal polymer film (manufactured by Kuraray Co., Ltd., product name: CT-Z, thickness: 50 μm, CTE: 18 ppm / K, heat distortion temperature: 300°C, ε1 = 3.40, tanδ1 = 0.0022) with 18 μm-thick electrolytic copper foil provided on both sides thereof. The copper foil on one side was subjected to circuit processing by etching to obtain a wiring board 77A with a conductor circuit layer formed thereon.

[0175] The copper foil on one side of the copper clad laminate 77 was removed by etching to obtain a copper clad laminate 77B.

[0176] An adhesive film 44 was sandwiched between the conductive circuit layer side of wiring board 77A and the insulating substrate layer side of copper-clad laminate 77B, and the laminated sheets were thermocompressed at a temperature of 160°C and a pressure of 4.0 MPa for 120 minutes to obtain multilayer circuit board 77.

[0177] Although the embodiments of the present invention have been described in detail above for the purpose of illustration, the present invention is not limited to the above-described embodiments and various modifications are possible. [Explanation of symbols]

[0178] DESCRIPTION OF SYMBOLS 10...substrate, 11...first substrate, 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...laminated body, 101...three-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

1. 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 satisfying the following conditions a to c: a) the content of diamine residues derived from a dimer diamine composition containing, as a main component, a dimer diamine obtained by substituting two terminal carboxylic acid groups of a dimer acid with primary aminomethyl groups or amino groups is in the range of 50 mol % or more and 95 mol % or less relative to the total diamine residues; b) A diamine compound in which an amino group directly bonded to a benzene ring and a divalent linking group are at the para position relative to all diamine residues, and which contains diamine residues derived from one or more diamine compounds selected from 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,4,4'-triaminodiphenyl ether, 4,4'-bis(4-aminophenyl sulfide), 4,4'-diaminodiphenyl sulfone, 2,2'-bis(4-aminobenzyloxyphenyl)propane, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4'-diaminobenzanilide, 4,4'-methylenedianiline, and 4,4'-diaminobenzophenone in an amount of 5 mol % to 50 mol %; c) containing 10 mol % or more and 90 mol % or less of tetracarboxylic acid residues derived from benzophenonetetracarboxylic dianhydride relative to all tetracarboxylic acid residues, and containing 10 mol % or more of at least one tetracarboxylic acid residue derived from tetracarboxylic acid anhydride represented by the following general formula (2) and / or (3); 【Chemical 1】 [In general formula (2), R represents a single bond or a divalent group represented by the following formula, and in general formula (3), the cyclic moiety represented by S represents the formation of a cyclic saturated hydrocarbon group selected from a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered ring.] 【Chemistry 2】 [In the above formula, Z １ Ha-C ６ H ４ -, -(CH ２ )n- or -CH ２ -CH(-OC(=O)-CH ３ )-CH ２ -, and n is an integer of 1 to 20. and the dielectric loss tangent (Tanδ) at 20 GHz measured by a split post dielectric resonator (SPDR) after 24 hours of humidity conditioning under constant temperature and humidity conditions (normal conditions) of 23°C and 50% RH in the film state. ２ ) is less than 0.002, and the relative dielectric constant (E ２ ) is 3.0 or less.

2. A crosslinked polyimide in which a ketone group contained in the polyimide according to claim 1 and an amino group of an amino compound having at least two primary amino groups as functional groups form a crosslinked structure via a C=N bond.

3. An adhesive film comprising the polyimide according to claim 1 or the crosslinked polyimide according to claim 2.

4. After 24 hours of humidity conditioning under constant temperature and humidity conditions (normal conditions) of 23°C and 50% RH, the dielectric loss tangent (Tanδ) at 10 GHz measured by a split post dielectric resonator (SPDR) was １ ) is less than 0.002, and the relative dielectric constant (E １ 4. The adhesive film according to claim 3, wherein the value of (a) is 3.0 or less.

5. After 24 hours of humidity conditioning under constant temperature and humidity conditions (normal conditions) of 23°C and 50% RH, the dielectric loss tangent (Tanδ) at 20 GHz measured by a split post dielectric resonator (SPDR) was ２ ) is less than 0.002, and the relative dielectric constant (E ２ 5. The adhesive film according to claim 3, wherein the value of the tensile strength is 3.0 or less.

6. A laminate having a substrate and an adhesive layer laminated on at least one surface of the substrate, A laminate, wherein the adhesive layer comprises the adhesive film according to any one of claims 3 to 5.

7. A coverlay film having a coverlay film material layer and an adhesive layer laminated on the coverlay film material layer, A coverlay film, wherein the adhesive layer comprises the adhesive film according to any one of claims 3 to 5.

8. A resin-coated copper foil in which an adhesive layer and a copper foil are laminated, A resin-coated copper foil, wherein the adhesive layer comprises the adhesive film according to any one of claims 3 to 5.

9. A metal-clad laminate having an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer, A metal-clad laminate, wherein at least one of the insulating resin layers is made of the adhesive film according to any one of claims 3 to 5.

10. A metal-clad laminate having an insulating resin layer, an adhesive layer laminated on at least one surface of the insulating resin layer, and a metal layer laminated on the insulating resin layer via the adhesive layer, A metal-clad laminate, wherein the adhesive layer comprises the adhesive film according to any one of claims 3 to 5.

11. a first single-sided metal-clad laminate having a first metal layer and a first insulating resin layer laminated on at least one surface 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 surface of the second metal layer; an adhesive layer disposed so as to contact 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, A metal-clad laminate, wherein the adhesive layer comprises the adhesive film according to any one of claims 3 to 5.

12. A metal-clad laminate comprising: a single-sided metal-clad laminate having an insulating resin layer and 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 made of the adhesive film described in any one of claims 3 to 5.

13. A circuit board obtained by wiring the metal layer of the metal-clad laminate according to claim 9.

14. A circuit board comprising: a first base material; a wiring layer laminated on at least one surface of the first base material; and an adhesive layer laminated on a surface of the first base material facing the wiring layer so as to cover the wiring layer, A circuit board, wherein the adhesive layer comprises the adhesive film according to any one of claims 3 to 5.

15. A circuit board comprising: a first base material; a wiring layer laminated on at least one surface of the first base material; an adhesive layer laminated on a surface of the first base material facing the wiring layer so as to cover the wiring layer; and a second base material laminated on a surface of the adhesive layer opposite to the first base material, A circuit board, wherein the adhesive layer comprises the adhesive film according to any one of claims 3 to 5.

16. A circuit board comprising: a first base material; an adhesive layer laminated on at least one surface of the first base material; a second base material laminated on a surface of the adhesive layer opposite to the first base material; and wiring layers laminated on the surfaces of the first base material and the second base material opposite to the adhesive layer, A circuit board, wherein the adhesive layer comprises the adhesive film according to any one of claims 3 to 5.

17. A multilayer circuit board comprising a laminate including a plurality of laminated insulating resin layers, and at least one wiring layer embedded inside the laminate, At least one of the plurality of insulating resin layers is formed of an adhesive layer that has adhesiveness and covers the wiring layer, A multilayer circuit board, wherein the adhesive layer comprises the adhesive film according to any one of claims 3 to 5.

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