TW202012501A - Resin film, cover film, circuit substrate, resin-attached copper foil, metal-clad laminate, multilayer circuit substrate, polyimide and adhesive resin composition capable of addressing the tendency of higher frequency for electronic equipment - Google Patents

Abstract

The present invention provides a resin film, a polyimide, an adhesive resin composition, and a use thereof, capable of coping with the increase in the frequency of electronic devices due to the improvement of dielectric characteristics, and having dielectric characteristics with reduced humidity dependence. The resin film contains a polyimide obtained by reacting a tetracarboxylic acid anhydride component and a diamine component for serving as a resin component. The diamine component contains a dimer diamine composition of 40 mol% or more with dimer diamine as a main component with respect to the total diamine components.

Description

Resin film, cover film, circuit board, copper foil with resin, metal-clad laminate, multilayer circuit board, polyimide and adhesive resin composition

The present invention relates to a polyimide useful as an adhesive in a circuit board such as a printed wiring board and its use.

In recent years, with the development of miniaturization, weight reduction and space saving of electronic devices, flexible printed circuits (FPC) that are thin and lightweight, have flexibility, and have excellent durability even when repeatedly bent Demand has increased. FPC can also be installed in three-dimensional and high-density in a limited space, so for example in the hard disk drive (Hard Disk Drive, HDD), digital video disk (Digital Video Disk, DVD), mobile phones and other mobile devices The use of wiring, or cables, connectors and other parts is gradually expanding.

In addition to the above-mentioned high-density, high-performance equipment has also been developed, so it is necessary to cope with the high-frequency transmission signals. In information processing or information communication, in order to transmit and process large-capacity information, efforts have been made to increase the transmission frequency, and printed circuit board materials are required to reduce transmission loss by thinning the insulating layer and improving the dielectric properties of the insulating layer. In the future, high-frequency FPC or adhesives will be required, and the reduction of transmission loss will become important.

Furthermore, as a technique related to an adhesive layer mainly composed of polyimide, it has been proposed to apply a cross-linked polyimide resin to the adhesive layer of a cover film, the cross-linked polyimide resin It is obtained by reacting polyimide with an amino compound having at least two primary amino groups as functional groups. The polyimide is a diamine derived from an aliphatic diamine such as dimer acid (dimer fatty acid). An amine compound is used as a raw material (for example, Patent Document 1). In addition, a resin composition in which a thermosetting resin such as polyimide, an epoxy resin, and a crosslinking agent are used in combination is proposed to be applied to a copper-clad laminate (for example, Patent Document 2). However, in Patent Document 1 and Patent Document 2, the influence of by-products other than dimer diamine (Dimer diamine) derived from the dimer acid contained in the raw material is not considered at all.

It is known that dimer acid uses natural fatty acids such as soybean oil fatty acid, tall oil fatty acid, rapeseed oil fatty acid, and oleic acid, linoleic acid, linolenic acid, erucic acid, etc. refined from these acids as raw materials. The dimerized fatty acid obtained by performing the Diels-Alder reaction (Diels-Alder reaction), a polyacid compound derived from a dimer acid can be obtained as a raw material fatty acid or a composition of fatty acids above trimerization (for example , Patent Document 3). [Prior Art Literature]

[Patent Literature] [Patent Document 1] Japanese Patent Laid-Open No. 2013-1730 [Patent Document 2] Japanese Patent Laid-Open No. 2017-119361 [Patent Document 3] Japanese Patent Laid-Open No. 2017-137375

[Problems to be solved by the invention] As a method of controlling the physical properties of a resin mainly composed of polyimide, it is important to control the molecular weight of polyamic acid or polyimide, which is a precursor of polyimide. However, when the dimer diamine is used as a raw material, it is used in a state containing by-products other than the dimer diamine derived from the dimer acid. Such by-products not only make it difficult to control the molecular weight of the polyimide, but also have an influence on the dielectric properties or their humidity dependence at a wide frequency.

An object of the present invention is to provide a resin film and a polyimide that can respond to the increase in the frequency of electronic devices due to the improvement in dielectric characteristics and have dielectric characteristics with reduced humidity dependence. [Technical means to solve the problem]

The resin film of the present invention contains polyimide as a resin component. The polyimide is obtained by reacting a tetracarboxylic anhydride component and a diamine component. The diamine component contains 40 moles relative to the total diamine component. A dimer diamine composition composed mainly of dimer diamines in which two terminal carboxylic acid groups of a dimer acid are replaced with primary aminomethyl groups or amino groups by more than 10%. Furthermore, the resin film of the present invention satisfies the following configuration I and configuration II.

Composition I: Based on the following mathematical formula (i) E ₁ =√ε ₁ ×Tanδ ₁ ･･･(i) [Here, ε ₁ represents downward adjustment at a constant temperature and humidity condition (normal state) at 23°C and 50%RH After 24 hours of humidity, the dielectric constant at 10 GHz measured by a Split Post Dielectric Resonator (SPDR), Tan δ ₁ means that after 24 hours of humidity adjustment at a constant temperature and constant humidity of 23°C and 50%RH , The dielectric loss tangent at 10 GHz measured by SPDR] is calculated, and the index representing the dielectric characteristic at 10 GHz after the humidity is adjusted at a constant temperature and constant humidity of 23°C and 50%RH for 24 hours at 10 GHz, that is, the E ₁ value is 0.010 the following.

Composition II: Based on the following mathematical formula (ii) E ₂ =√ε ₂ ×Tanδ ₂ ･･･(ii) [Here, ε ₂ means that after absorbing water at 23°C for 24 hours, at 10 GHz measured by SPDR The dielectric constant of Tan δ ₂ represents the dielectric loss tangent at 10 GHz measured by SPDR after absorbing water at 23°C for 24 hours] and is calculated to represent the dielectric properties at 10 GHz after absorbing water at 23°C for 24 hours an index value E _2, E ₂ with respect to the value greater than the value E ₁ (E ₂ / E ₁₎ is within the range of 3.0 to 1.0.

In addition, in mathematical formula (i) and mathematical formula (ii), "√ε ₁ "and "√ε ₂ " refer to the square roots of "ε ₁ "and "ε ₂ ", respectively.

The cover film of the present invention is laminated with an adhesive layer and a cover film layer, wherein the adhesive layer contains the resin film.

The circuit board of the present invention includes a base material, a wiring layer formed on the base material, and the cover film covering the wiring layer.

The copper foil with resin of the present invention is laminated with an adhesive layer and a copper foil, wherein the adhesive layer includes the resin film.

The metal-clad laminate of the present invention has an insulating resin layer, an adhesive layer laminated on at least one side of the insulating resin layer, and laminated on the insulating resin via the adhesive layer The metal layer of the layer, wherein the adhesive layer includes the resin film.

The multilayer circuit board of the present invention includes a laminate including a plurality of laminated insulating resin layers, and one or more conductor circuit layers embedded in the laminate. In the multilayer circuit board of the present invention, at least one layer of the plurality of insulating resin layers is formed of an adhesive layer having adhesiveness and covering the conductor circuit layer, the adhesive layer containing the resin membrane.

The polyimide of the present invention is obtained by reacting a tetracarboxylic anhydride component and a diamine component, wherein the diamine component contains 40 mol% or more of both ends of the dimer acid relative to the total diamine component A dimer diamine composition composed mainly of a dimer diamine in which a carboxylic acid group is substituted with a primary aminomethyl group or an amino group. In the polyimide of the present invention, based on the area percentage of a chromatogram obtained by measuring the dimer diamine composition using colloidal permeation chromatography, the following components (a) to (c) The said component (c) is below 2%; (A) Dimer diamine; (B) A monoamine compound obtained by substituting the terminal carboxylic acid group of a monobasic acid compound having a carbon number in the range of 10 to 40 with a primary aminomethyl group or amino group; (C) An amine compound obtained by substituting a terminal carboxylic acid group of a polybasic acid compound having a hydrocarbon group in the range of 41 to 80 with a primary aminomethyl group or an amino group (excluding the dimer diamine) .

The polyimide of the present invention may contain more than 50 mole% of 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA) relative to the total amount of the tetracarboxylic anhydride component .

The adhesive resin composition of the present invention contains the following components (A) and (B): (A) The polyimide, and (B) an amino compound having at least two primary amino groups as functional groups, and Contain the (B) such that the primary amino group is 1 mole relative to the BTDA residue derived from the BTDA in the (A) component in a total range of 0.004 moles to 1.5 moles )ingredient. [Effect of invention]

Since the resin film and the polyimide of the present invention control the content of amine compounds other than the dimer diamine in the dimer diamine composition, the dielectric properties have low humidity dependence and excellent stability. Therefore, the resin film and the polyimide of the present invention can be particularly preferably used for circuit boards such as FPC in electronic devices requiring high-speed signal transmission.

Hereinafter, embodiments of the present invention will be described.

<Resin film> The resin film of this embodiment is formed by forming a resin component as a main component. In order to impart excellent high-frequency characteristics and stability with respect to humidity, the resin film of the present embodiment contains polyimide obtained by reacting a tetracarboxylic anhydride component and a diamine component as a resin component. The diamine component contains a relative Based on all diamine components, it is a dimer dimer with 40 mol% or more of dimer diamines in which two terminal carboxylic acid groups of the dimer acid are substituted with primary aminomethyl groups or amino groups. Amine composition. In addition, the resin film of this embodiment may contain, for example, fillers as optional components other than the resin component.

(Dielectric characteristics) In the resin film of this embodiment, based on the following formula (i) E ₁ =√ε ₁ ×Tanδ ₁ ･･･(i) [Here, ε ₁ represents the temperature at 23°C and 50%RH After 24 hours of humidity adjustment under constant temperature and humidity conditions (normal state), the dielectric constant at 10 GHz measured by a separate dielectric resonator (SPDR), Tanδ ₁ means humidity adjustment under constant temperature and humidity conditions of 23°C and 50%RH after 24 hours, the dielectric loss measured by SPDR tangent's 10 GHz] is calculated, represents 23 ℃, 50% RH constant temperature and humidity conditions of reduced index dielectric properties under wet's 10 GHz after 24 hours, ie E ₁ The value is 0.010 or less, preferably 0.009 or less, and more preferably 0.008 or less. If the E ₁ value exceeds the upper limit, when used in a circuit board such as an FPC, a defect such as a loss of an electric signal is likely to occur in the transmission path of the high-frequency signal.

(Dielectric constant) In the resin film of this embodiment, in order to ensure impedance matching when used in a circuit board such as FPC, and in order to reduce the loss of electrical signals, the humidity is adjusted under a constant temperature and humidity condition of 23°C and 50%RH The dielectric constant (ε ₁ ) at 10 GHz after 24 hours is preferably 3.2 or less, and more preferably 3.0 or less. If this dielectric constant exceeds 3.2, when used in a circuit board such as an FPC, it is easy to cause problems such as loss of electrical signals on the transmission path of high-frequency signals.

(Dielectric loss tangent) In addition, in the resin film of the present embodiment, in order to reduce the loss of electrical signals when used in a circuit board such as FPC, etc., the humidity after constant temperature and humidity conditions at 23°C and 50%RH for 24 hours is 10 The dielectric loss tangent (Tanδ ₁ ) at GHz is preferably less than 0.005, and more preferably 0.004 or less. If the dielectric loss tangent is 0.005 or more, when used in a circuit board such as an FPC, it is easy to cause problems such as loss of electrical signals on the transmission path of high-frequency signals.

(Dependency on moisture absorption) In the resin film of the present embodiment, in order to reduce the loss of electrical signals during drying and wetting when used in a circuit board such as FPC or the like, and to ensure impedance matching, based on the following formula (ii) E ₂ =√ε ₂ ×Tanδ ₂ ･･･(ii) [Here, ε ₂ represents the dielectric constant at 10 GHz measured by SPDR after absorbing water at 23°C for 24 hours, Tan δ ₂ represents absorbing water at 23°C 24 after hour, a dielectric loss lower's 10 GHz through SPDR measured tangent] is calculated, an index dielectric characteristics under's 10 GHz after 23 ℃ lower water absorption 24 hours, ie E ₂ value, E ₂ value with respect to the basis of the The ratio of the E ₁ value (E ₂ /E ₁ ) calculated by the formula (i) is in the range of 3.0 to 1.0, preferably in the range of 2.5 to 1.0, more preferably in the range of 2.2 to 1.0 Is appropriate. If E ₂ /E ₁ exceeds the upper limit, when used in a circuit board such as an FPC, the dielectric constant and the tangent of dielectric loss will increase when wetting, and electricity may easily appear on the transmission path of the high-frequency signal Bad conditions such as signal loss.

(Moisture absorption rate) In addition, in the resin film of the present embodiment, in order to reduce the influence of humidity when used in a circuit board such as FPC, the moisture absorption rate of the resin film is preferably 0.5% by mass or less, and more preferably less than 0.3 The quality% is suitable. Here, "moisture absorption rate" refers to the moisture absorption rate after the passage of 24 hours or more under a constant temperature and constant humidity condition of 23° C. and 50% RH (the same meaning in this specification). If the moisture absorption rate of the resin film exceeds 0.5% by mass, when used in a circuit board such as an FPC, it is easily affected by humidity, and a defect such as a change in the transmission speed of a high-frequency signal is likely to occur. That is, if the moisture absorption rate of the resin film exceeds the above range, water with a high dielectric constant is easily absorbed, so that the dielectric constant and dielectric loss tangent increase, and electricity is likely to appear on the transmission path of the high-frequency signal Bad conditions such as signal loss.

(Storage Elastic Modulus) The resin film of the present embodiment may have a temperature range in which the storage elastic modulus decreases with a steep slope as the temperature rises in the range of 40°C to 250°C. The characteristics of such a resin film are considered to be, for example, main factors for relaxing internal stress during thermocompression bonding and maintaining dimensional stability after circuit processing. In the resin film, the storage elastic modulus at the upper limit temperature in the temperature range is preferably 5×10 ⁷ [Pa] or less. By setting such a storage elastic modulus, even if it is the upper limit of the temperature range, thermocompression bonding can be performed at 250° C. or less, thereby ensuring adhesion and suppressing dimensional changes after circuit processing. Furthermore, the resin film of the present embodiment has high thermal expansion but low elasticity. Therefore, even if the coefficient of thermal expansion (CTE) exceeds 30 ppm/K, internal stress generated during lamination can be alleviated.

(Glass transition temperature) In the resin film of the present embodiment, the glass transition temperature (Tg) is preferably 250° C. or lower, and more preferably 40° C. or higher and 200° C. or lower. By setting the Tg of the resin film to 250° C. or lower, thermocompression bonding can be performed at a low temperature, and therefore, internal stress generated during lamination can be relaxed, and dimensional changes after circuit processing can be suppressed. If the Tg of the resin film exceeds 250°C, the bonding temperature becomes high, which may impair the dimensional stability after circuit processing.

(thickness) The thickness of the resin film of the present embodiment is preferably in the range of, for example, 5 μm or more and 125 μm or less, and more preferably in the range of 8 μm or more and 100 μm or less. If the thickness of the resin film is less than 5 μm, there is a possibility that defects such as wrinkles may occur during transportation of the production of the resin film, etc. On the other hand, if the thickness of the resin film exceeds 125 μm, there may be Possibility of decreased productivity.

<Polyimide> The polyimide of the present embodiment is obtained by reacting a polyimide amide imide which is a precursor obtained by reacting a tetracarboxylic anhydride component and a diamine component, the diamine component containing It is a dimer diamine composition whose main component is a dimer diamine in which 40 mol% or more of the dimer acid has two terminal carboxylic acid groups substituted with primary aminomethyl groups or amino groups.

(Tetracarboxylic anhydride component) The tetracarboxylic anhydride used in the polyimide of the present embodiment may include, without particular limitation, the tetracarboxylic anhydride generally used in thermoplastic polyimide, but it is preferable to contain a total of 90 mol% relative to the total tetracarboxylic anhydride component The above tetracarboxylic anhydride represented by the following general formula (1). By containing the tetracarboxylic anhydride represented by the following general formula (1) at a total of 90 mol% or more with respect to all the tetracarboxylic anhydride components, it is easy to achieve both the flexibility and heat resistance of polyimide, so it is preferable . If the total amount of tetracarboxylic anhydride represented by the following general formula (1) is less than 90 mol%, there is a tendency for the solvent solubility of polyimide to decrease.

[Chemical 1]

In general formula (1), X represents a single bond or a divalent group selected from the following formula.

[Chem 2]

In the above formula, Z represents -C ₆ H ₄ -, -(CH ₂ )n- or -CH ₂ -CH(-OC(=O)-CH ₃ )-CH ₂ -, and n represents 1-20 Integer.

In addition, "thermoplastic polyimide" is usually polyimide whose glass transition temperature (Tg) can be clearly confirmed, but in the present invention, it refers to the use of a dynamic viscoelasticity measuring device (Dynamic thermomechanical analyzer (Dynamic thermomechanical analyzer) Analyzer (DMA)) Polyimide with a storage elastic modulus at 30°C of 1.0×10 ⁸ Pa or more and a storage elastic modulus at 300°C of less than 3.0×10 ⁷ Pa. In addition, "non-thermoplastic polyimide" is usually polyimide that does not show softening and adhesion even when heated, but in the present invention refers to measurement using a dynamic viscoelasticity measuring device (DMA) at 30°C Polyimide having a storage elastic modulus of 1.0×10 ⁹ Pa or more and a storage elastic modulus at 300° C. of 3.0×10 ⁸ Pa or more.

Examples of the tetracarboxylic anhydride represented by the general formula (1) include 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4' -Benzophenone tetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenyl sulfone tetracarboxylic 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-phenylene bis (trimellitic acid monoester anhydride) (TAHQ), ethylene glycol bistrimellitic anhydride (TMEG), etc. Among these, especially in the case of using 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), the adhesion of polyimide can be improved, and it is present in the molecular skeleton When a ketone group reacts with an amino group of the component (B) described later to form a C=N bond, it is easy to exhibit an effect of improving heat resistance. From such a viewpoint, it is preferable to contain BTDA in an amount of preferably 50 mol% or more, and more preferably 60 mol% or more with respect to all tetracarboxylic anhydride components.

The polyimide of the present embodiment may contain a tetracarboxylic acid residue derived from an acid anhydride other than the tetracarboxylic anhydride represented by the general formula (1) within a range that does not impair the effects of the invention. The tetracarboxylic acid residue is not particularly limited, and examples thereof include pyromellitic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, and 2,2',3. ,3'-benzophenone tetracarboxylic dianhydride or 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic acid Acid dianhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, 3,3'',4,4''-p-terphenylphenyl tetracarboxylic dianhydride, 2,3,3'',4 ''-P-terphenylphenyltetracarboxylic dianhydride or 2,2'',3,3''-p-terphenylphenyltetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl) -Propane dianhydride or 2,2-bis(3,4-dicarboxyphenyl)-propane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride or bis(3,4-dicarboxyphenyl) ) Methane dianhydride, bis(2,3-dicarboxyphenyl) lanthanide dianhydride or bis(3,4-dicarboxyphenyl) lanthanide dianhydride, 1,1-bis(2,3-dicarboxyphenyl) Ethane dianhydride or 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,7,8-phenanthrene-tetracarboxylic dianhydride, 1,2,6,7-phenanthrene -Tetracarboxylic dianhydride or 1,2,9,10-phenanthrene-tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxy Phenyl)tetrafluoropropane dianhydride, 2,3,5,6-cyclohexane dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid 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-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-(or 1,4,5,8-)tetrachloronaphthalene-1,4,5,8-(or 2,3,6,7-)tetracarboxylic dianhydride, 2, 3,8,9-perylene-tetracarboxylic dianhydride, 3,4,9,10-perylene-tetracarboxylic dianhydride, 4,5,10,11-perylene-tetracarboxylic dianhydride or 5,6, 11,12-Perylene-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine- 2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl Tetracarboxylic acid residues derived from aromatic tetracarboxylic dianhydride such as methane dianhydride and ethylene glycol trimellitic anhydride.

(Diamine component) The polyimide of the present embodiment contains a dimer diamine composition of 40 mol% or more, more preferably 60 mol% or more with respect to all diamine components. By containing the dimer diamine composition in the stated amount, while improving the dielectric properties of the polyimide, the thermocompression bonding can be improved by lowering the glass transition temperature of the polyimide (lower Tg). Characteristics, and can be quantified by low elastic modulus to relieve internal stress.

(Dimer diamine composition) The dimer diamine composition contains the following component (a), and the amounts of component (b) and component (c) are controlled.

(A) Dimer diamine; (a) Component dimer diamine means that the two terminal carboxylic acid groups (-COOH) of the dimer acid are replaced with primary aminomethyl groups (-CH ₂ -NH ₂ ) Or a diamine formed from an amino group (-NH ₂ ). Dimer acid is a known dibasic acid obtained by intermolecular polymerization of unsaturated fatty acids. Its industrial manufacturing process is roughly standardized in the industry. It is an unsaturated fatty acid with a carbon number of 11-22 using a clay catalyst. Obtained by dimerization. Regarding the industrially obtained dimer acid, the main component is a dimer acid with a carbon number of 36 obtained by dimerizing unsaturated fatty acids having a carbon number of 18, such as oleic acid, linoleic acid, and linolenic acid, depending on the degree of purification. Any amount of monomeric acid (carbon number 18), trimer acid (carbon number 54), and other polymeric fatty acids with carbon number 20-54. In addition, a double bond may remain after the dimerization reaction, but in the present invention, the dimer acid also includes a compound that further undergoes a hydrogenation reaction to reduce unsaturation. (A) The component dimer diamine can be defined as the substitution of the terminal carboxylic acid group of the dibasic acid compound having a carbon number in the range of 18 to 54 and preferably in the range of 22 to 44 with a primary aminomethyl group or amino group The obtained diamine compound.

The dimer diamine composition is obtained by using a purification method such as molecular distillation to increase the content of (a) component dimer diamine to 96% by weight or more, preferably 97% by weight or more, and more preferably 98% by weight or more should. By setting the dimer content of the component dimer (a) to 96% by weight or more, the spread of the molecular weight distribution of the polyimide can be suppressed. Furthermore, if it is technically feasible, it is preferable that the entire dimer diamine composition (100% by weight) consists of (a) component dimer diamine.

(B) A monoamine compound obtained by substituting the terminal carboxylic acid group of a monobasic acid compound having a carbon number in the range of 10 to 40 with a primary aminomethyl group or amino group; The monoacid compound having a carbon number in the range of 10 to 40 is a monounsaturated fatty acid having a carbon number in the range of 10 to 20 from the raw material derived from the dimer acid, and the carbon number as a by-product when producing the dimer acid A mixture of monobasic acid compounds in the range of 21-40. The monoamine compound is obtained by substituting the terminal carboxylic acid group of these monobasic acid compounds with a primary aminomethyl group or amino group.

(B) Component The monoamine compound is a component that suppresses the increase in molecular weight of polyimide. During the polymerization of polyamic acid or polyimide, the monofunctional amino group of the monoamine compound reacts with the terminal acid anhydride group of the polyamic acid or polyimide, whereby the terminal acid anhydride group is blocked, This suppresses the increase in molecular weight of polyamic acid or polyimide.

(C) An amine compound obtained by substituting a terminal carboxylic acid group of a polybasic acid compound having a hydrocarbon group in the range of 41 to 80 with a primary aminomethyl group or an amino group (excluding the dimer diamine) ; The polybasic acid compound having a hydrocarbon group having a carbon number in the range of 41 to 80 is a polybasic acid compound having a tribasic acid compound having a carbon number in the range of 41 to 80 as a by-product when producing a dimer acid as a main component. In addition, polymeric fatty acids other than the dimer acid having 41 to 80 carbon atoms may be included. The amine compound is obtained by substituting the terminal carboxylic acid group of these polybasic acid compounds with a primary aminomethyl group or amino group.

(C) The component amine compound is a component that promotes an increase in the molecular weight of polyimide. By reacting a trifunctional or more amino group derived from a trimer acid as a main component with a terminal acid anhydride group of polyamic acid or polyimide, the molecular weight of the polyimide increases sharply. In addition, amine compounds derived from polymeric fatty acids other than dimer acids having 41 to 80 carbon atoms also increase the molecular weight of polyimide and cause gelation of polyamic acid or polyimide.

The dimer diamine composition is quantified by the use of colloidal permeation chromatography (GPC) measurement, but in order to easily confirm the peak of each component of the dimer diamine composition (Peak start), peak top (peak top) and peak end (peak end), using a sample treated with acetic anhydride and pyridine dimer diamine composition, and using cyclohexanone as an internal standard substance. Using the sample thus prepared, each component was quantified using the area percentage of the GPC chromatogram. Using the peak start and peak end of each component as the minimum value of each peak curve, the area percentage of the chromatogram was calculated based on this.

In addition, in the dimer diamine composition used in the present invention, the total amount of component (b) and component (c) is 4% or less based on the area percentage of the chromatogram obtained by GPC measurement, preferably not 4% is appropriate. By setting the total of component (b) and component (c) to 4% or less, the spread of the molecular weight distribution of polyimide can be suppressed.

In addition, the area percentage of the chromatogram of the component (b) is preferably 3% or less, more preferably 2% or less, and still more preferably 1% or less. By setting it as such a range, the decrease of the molecular weight of polyimide can be suppressed, and the range of the molar ratio of the tetracarboxylic anhydride component and the diamine component input can be expanded. In addition, the component (b) may not be included in the dimer diamine composition.

In addition, the area percentage of the chromatogram of the component (c) is 2% or less, and preferably 1.8% or less, and more preferably 1.5% or less. By setting it as such a range, the molecular weight of polyimide can be suppressed from increasing rapidly, and the dielectric loss tangent of the resin film can be suppressed from rising at a wide frequency. In addition, the component (c) may not be included in the dimer diamine composition.

In addition, when the ratio (b/c) of the area percentage of the chromatogram of component (b) and component (c) is 1 or more, the molar ratio of the tetracarboxylic anhydride component to the diamine component (tetracarboxylic anhydride component/ The diamine component) is preferably set to preferably 0.97 or more and less than 1.0. By setting such a molar ratio, it is easier to control the molecular weight of the polyimide.

In addition, when the ratio (b/c) of the area percentage of the chromatogram of component (b) and component (c) is less than 1, the molar ratio of the tetracarboxylic anhydride component to the diamine component (tetracarboxylic anhydride Component/diamine component) is preferably set to preferably 0.97 or more and 1.1 or less. By setting such a molar ratio, it is easier to control the molecular weight of the polyimide.

The weight average molecular weight of the polyimide is, for example, preferably in the range of 10,000 to 200,000, and if it is in such a range, the control of the weight average molecular weight of the polyimide becomes easy. In addition, for example, when applied as an adhesive for FPC, the weight average molecular weight of polyimide is more preferably in the range of 20,000 to 150,000, and further preferably in the range of 40,000 to 150,000. When the weight average molecular weight of the polyimide is less than 20,000, there is a tendency for the flow resistance to deteriorate. On the other hand, if the weight average molecular weight of the polyimide exceeds 150,000, the viscosity is excessively increased and becomes insoluble in the solvent, which tends to cause defects such as uneven thickness and stripes of the adhesive layer during the coating operation.

The dimer diamine composition used in the present invention is preferably purified to reduce components other than the dimer diamine. The purification method is not particularly limited, and known methods such as distillation and precipitation purification are preferred. The dimer diamine composition before purification can be obtained in the form of a commercial item, and examples include PRIAMINE 1073 (trade name) manufactured by Croda Japan and Croda Japan. ) PRIAMINE 1074 (trade name) made by the company, PRIAMINE 1075 (trade name) made by Croda Japan, etc.

Examples of the diamine compound other than the dimer diamine used in the polyimide include aromatic diamine compounds and aliphatic diamine compounds. Specific examples of these include 1,4-diaminobenzene (p-PDA; p-phenylenediamine), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) , 2,2'-n-propyl-4,4'-diaminobiphenyl (m-NPB), 4-aminophenyl-4'-aminobenzoate (APAB), 2,2-bis-[ 4-(3-Aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]benzene, bis[4-(3-aminophenoxy)]biphenyl, bis[ 1-(3-aminophenoxy)]biphenyl, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]ether, bis[ 4-(3-aminophenoxy)]benzophenone, 9,9-bis[4-(3-aminophenoxy)phenyl] stilbene, 2,2-bis-[4-(4-amino Phenoxy)phenyl]hexafluoropropane, 2,2-bis-[4-(3-aminophenoxy)phenyl]hexafluoropropane, 3,3'-dimethyl-4,4'-di Aminobiphenyl, 4,4'-methylenedi-o-toluidine, 4,4'-methylenebis-2,6-xylidine (Xylidine), 4,4'-methylene-2, 6-diethylaniline, 3,3'-diaminodiphenylethane, 3,3'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 3,3''-diamino -P-terphenyl, 4,4'-[1,4-phenylene bis(1-methylethylene)] bisaniline, 4,4'-[1,3-phenylene bis(1-methyl Ethylidene)] bisaniline, bis(p-aminocyclohexyl)methane, bis(p-β-amino-third butylphenyl) ether, bis(p-β-methyl-δ-aminopentyl) Benzene, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,5-diaminonaphthalene, 2,6-bis Aminonaphthalene, 2,4-bis(β-amino-tert-butyl)toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, M-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, pyrazine, 2' -Methoxy-4,4'-diaminobenzylanilide, 4,4'-diaminobenzylanilide, 1,3-bis[2-(4-aminophenyl)-2-propyl] Diamine compounds such as benzene, 6-amino-2-(4-aminophenoxy)benzoxazole, and 1,3-bis(3-aminophenoxy)benzene.

Polyimide can be produced as follows: the tetracarboxylic anhydride component and the diamine component are reacted in a solvent to form polyamic acid, followed by heating and ring closure. For example, the tetracarboxylic anhydride component and the diamine component are dissolved in an organic solvent at approximately the same mole, and stirred at a temperature in the range of 0°C to 100°C for 30 minutes to 24 hours to carry out the polymerization reaction, thereby obtaining Polyamide acid, the precursor of amide imine. At the time of the reaction, the reaction component is dissolved so that the generated precursor is in the range of 5 to 50% by weight in the organic solvent, preferably 10 to 40% by weight. Examples of the organic solvent used in the polymerization reaction include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N,N-diethylacetamide. Amine, N-methyl-2-pyrrolidone (NMP), 2-butanone, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate , Cyclohexanone, methylcyclohexane, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), methanol, ethanol, benzyl alcohol, cresol, etc. Two or more of these solvents may be used in combination, and aromatic hydrocarbons such as xylene and toluene may be used in combination. In addition, the amount of use of such an organic solvent is not particularly limited, but it is preferably adjusted to be such that the concentration of the polyamic acid solution obtained by the polymerization reaction is about 5% to 50% by weight.

The synthesized polyamic acid is usually advantageously used as a reaction solvent solution, and may be concentrated, diluted or replaced with other organic solvents as necessary. In addition, polyamic acid generally has excellent solvent solubility, so it is advantageously used. The viscosity of the solution of polyamic acid is preferably in the range of 500 cps to 100,000 cps. If it deviates from the above range, defects such as uneven thickness and streaks may easily occur in the film when a coating operation is performed by a coating machine or the like.

The method for forming polyimide by polyimidization of polyimide is not particularly limited. For example, it is preferable to use temperature conditions in the range of 80°C to 400°C in the solvent for 1 hour to 24 Heat treatment such as heating is performed for hours. In addition, regarding the temperature, heating may be performed under a fixed temperature condition, or the temperature may be changed in the middle of the step.

By selecting the kind of the tetracarboxylic anhydride component and the diamine component in the polyimide of the present embodiment, or the respective molar ratios when two or more tetracarboxylic anhydride components or diamine components are applied, the medium can be controlled Electrical properties, thermal expansion coefficient, tensile modulus of elasticity, glass transition temperature, etc. In addition, when the polyimide of the present embodiment has a plurality of structural units of polyimide, it may exist as a block or may exist randomly, preferably randomly.

The concentration of the amide imide group of the polyimide of the present embodiment is preferably 22% by weight or less, and more preferably 20% by weight or less. Here, the "concentration of amide imide group" refers to a value obtained by dividing the molecular weight of the amide imide group portion (-(CO) ₂ -N-) in the polyimide group by the molecular weight of the entire structure of the polyimide group. . If the concentration of the amide imide group exceeds 22% by weight, the molecular weight of the resin itself becomes small, and the low moisture absorption property also deteriorates due to the increase in polar groups, and the Tg and elastic modulus increase.

The polyimide of the present embodiment is most preferably a structure that is completely imidized. However, a part of the polyimide can also become amic acid. The amide imidization ratio can be obtained by using a Fourier conversion infrared spectrophotometer (commercially available product: FT/IR620 manufactured by Nippon Spectroscopy), and using an Attenuated Total Reflection (ATR) method for polyimide The infrared absorption spectrum of the film was measured, and the benzene ring absorber in the vicinity of 1015 cm ^-1 was used as a reference to calculate from the absorbance of C=O expansion and contraction derived from the amide imide group at 1780 cm ^-1 .

<Adhesive resin composition> The adhesive resin composition of the present embodiment contains: as component (A), the content of BTDA derived from BTDA is preferably 50 mol% or more, more preferably 60 mol% or more with respect to all tetracarboxylic acid residues. The above-mentioned polyimide and an amino compound having at least two primary amino groups as functional groups as the component (B). Furthermore, in the present invention, "BTDA residue" refers to a tetravalent group derived from BTDA.

(Amino compound) In the adhesive resin composition of the present embodiment, as the (B) component, the amino compound having at least two primary amino groups as functional groups may be exemplified by dihydrazide compounds, aromatic diamines, aliphatic amines, and the like. Among these, dihydrazide compounds are preferred. Aliphatic amines other than dihydrazide compounds can easily form a cross-linked structure even outdoors, so there is concern about the storage stability of varnishes. On the other hand, aromatic diamines need to be made at a high temperature in order to form a cross-linked structure. In this way, in the case where the dihydrazide compound is used, the storage stability of the varnish and the shortening of the curing time can be balanced. As the dihydrazide compound, for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, Suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycol dihydrazide Hydrazine, dihydrazide tartrate, dihydrazide malate, dihydrazide phthalate, dihydrazide isophthalate, dihydrazide terephthalate, 2,6-naphthoic dihydrazide, 4,4 -Diphenylhydrazine compounds such as bisphenyldihydrazine, 1,4-naphthoic acid dihydrazide, 2,6-pyridinedicarboxylic acid dihydrazide, itaconic acid dihydrazide. The above dihydrazide compounds may be used alone or in combination of two or more.

In addition, the amino compounds such as (I) dihydrazide compound, (II) aromatic diamine, (III) aliphatic amine, etc. may also be a combination of (I) and (II), (I) and (III), for example Like the combination of (I), (II), and (III), two or more super-category combinations are used.

In addition, from the viewpoint of making the network structure formed by crosslinking of the (B) component amino compound more dense, the molecular weight of the (B) component amino compound used in the present invention (when the amino compound is an oligomer is The weight average molecular weight) is preferably 5,000 or less, and more preferably 90 to 2,000, and still more preferably 100 to 1,500. Among these, amino compounds having a molecular weight of 100 to 1,000 are particularly preferred. If the molecular weight of the amino compound is less than 90, there is only one amino group of the amino compound forming a C=N bond with the ketone group of the polyimide resin, and the periphery of the remaining amino group becomes three-dimensionally large, so the remaining amino group is not easy The tendency to form a C=N bond.

In the case of crosslinking the ketone group of the BTDA residue with an amino compound, the amino compound is added to the resin solution containing the component (A) to make the ketone group in the polyimide and the primary amino group of the amino compound Perform condensation reaction. This condensation reaction hardens the resin solution and becomes a hardened product. In this case, the amount of the amino compound added may be 0.004 to 1.5 mol, preferably 0.005 to 1.2 mol, and more preferably 0.03 mol to 1 mol of keto group. The amino compound is added in a manner of 0.9 moles, most preferably 0.04 moles to 0.6 moles. If the amount of the amino compound added is less than 0.004 mol relative to 1 mol of the keto group, the cross-linking of the amino compound will be insufficient, so there is a tendency that it is difficult to express the heat resistance after curing. If the amount of the compound added exceeds 1.5 moles, the unreacted amino compound acts as a thermoplastic agent, and the heat resistance as the adhesive layer tends to decrease.

If the conditions of the condensation reaction for the formation of crosslinks are the conditions in which the ketone group of (A) component polyimide reacts with the primary amino group of (B) component amino compound to form an imine bond (C=N bond), There are no special restrictions. Regarding the temperature of the heating condensation, the condensation step is performed in order to release the water generated by the condensation out of the system, or to perform the heating condensation reaction after the synthesis of (A) component polyimide. For reasons such as simplification, for example, it is preferably in the range of 120°C to 220°C, and more preferably in the range of 140°C to 200°C. The reaction time is preferably about 30 minutes to 24 hours. The end point of the reaction can be measured, for example, by using a Fourier transform infrared spectrophotometer (commercially available product: FT/IR620 manufactured by Nippon Spectroscopy), and using the polyimide-derived resin derived from polyimide resin near 1670 cm ^-1 The decrease or disappearance of the absorption peak of the ketone group and the appearance of the absorption peak derived from the imine group near 1635 cm ^-1 were confirmed.

(A) The ketone group of the component polyimide and (B) the primary condensation of the amino group of the amino compound can be performed by, for example, the following method: (1) Following the synthesis of (A) component polyimide (acrylimination), the method of adding (B) component amino compound and heating, (2) As a diamine component, an excess amount of amino compound is added in advance, and after (A) component polyimide synthesis (amidation), the remaining amino groups that will not participate in the amidation or amidation will be involved Compound (B) component, the method of heating with polyimide, or (3) After the composition of the (A) component polyimide added with the (B) component amino compound is processed into a predetermined shape (for example, after being applied to an arbitrary substrate or after being formed into a film), heating is performed Methods.

In order to impart heat resistance to the component (A) component polyimide, the formation of the imine bond has been described in the formation of the cross-linked structure, but it is not limited to this. As a method for curing the component (A) component polyimide , For example, epoxy resin, epoxy resin hardener, active ester compound, benzoxazine resin, cyanate resin, maleimide, activated ester resin, phenyl ether skeleton with unsaturated bond can also be formulated Or styrene skeleton resin and so on. Here, the active ester compound functions as a hardener for epoxy resin and has an active ester.

In addition, in the adhesive resin composition of the present embodiment, it is preferable to contain (C) component inorganic filler as an optional component in addition to the (A) component polyimide and (B) component amino compound. Furthermore, other resin components such as plasticizers, epoxy resins, fluororesins, olefin resins, curing accelerators, coupling agents, fillers, pigments, solvents, flame retardants, etc. may be appropriately formulated as other optional components as necessary. However, there are those containing a large amount of polar groups in the plasticizer, and it is feared that it will promote the diffusion of copper from the copper wiring, so it is preferable not to use a plasticizer as much as possible.

Regarding the adhesive resin composition of the present embodiment, when it is used to form an adhesive layer, it will have excellent flexibility and thermoplasticity, and be used as a protection for wiring parts such as FPC, rigidity, flexible circuit boards, etc. The adhesive for the cover film has satisfactory characteristics.

<cover film> The cover film of this embodiment includes an adhesive layer including the resin film or the adhesive resin composition, and a cover film layer. The film material for covering is not particularly limited, and for example, a polyimide-based resin film such as a polyimide resin, a polyether amide imide resin, a polyamide amide imide resin, or a polyimide-based resin film, a polymer Ester resin film, etc. Among these, it is preferable to use a polyimide-based resin film having excellent heat resistance. The thickness of the covering film material layer is not particularly limited, but for example, it is preferably 5 μm or more and 100 μm or less. In addition, the thickness of the adhesive layer is not particularly limited. For example, it is preferably 10 μm or more and 50 μm or less.

In addition, the covering film material may contain black pigments in order to effectively exhibit light-shielding properties, concealment properties, design properties, and the like, and may include matting to suppress the gloss of the surface within a range that does not impair the improvement effect of dielectric properties. Optional components such as pigments.

The cover film of this embodiment can be manufactured by the method illustrated below, for example. First, as a first method, after applying the adhesive resin composition as an adhesive layer on one side of the covering film material in a solution state (for example, in the form of a varnish containing a solvent), for example, at 60°C to 220 A temperature of 0° C. allows thermocompression bonding to form a cover film having a cover film layer and an adhesive layer.

In addition, as a second method, an adhesive resin composition for an adhesive layer is applied in a state of a solution (for example, in the form of a varnish containing a solvent) on an arbitrary substrate, and the After drying at a temperature, peeling is performed to form a resin film for the adhesive layer, and the resin film and the covering film material are thermocompression-bonded at a temperature of, for example, 60°C to 220°C. Cover film of an embodiment. Furthermore, the adhesive layer can also be used as follows, that is, an adhesive resin composition is applied in a state of solution on an arbitrary substrate by, for example, a screen printing method to form a coating film, for example, at 80° C. to 180° C. It is used by drying and filming at a temperature of ℃.

<Circuit board> The circuit board of this embodiment includes a base material, a wiring layer formed on the base material, and the cover film covering the wiring layer. The base material of the circuit board is not particularly limited. In the case of FPC, it is preferable to use the same material as the covering film material, and it is more preferable to use a base material made of polyimide-based resin.

<Copper foil with resin> The copper foil with resin of this embodiment includes an adhesive layer and the copper foil including the resin film or the adhesive resin composition.

The thickness of the adhesive layer is, for example, preferably in the range of 0.1 μm to 125 μm, and more preferably in the range of 0.3 μm to 100 μm. If the thickness of the adhesive layer is less than the lower limit value, problems such as insufficient adhesiveness may occur. On the other hand, if the thickness of the adhesive layer exceeds the upper limit, problems such as a decrease in dimensional stability may occur. In addition, from the viewpoints of low dielectric constant and low dielectric loss tangent, the thickness of the adhesive layer is preferably 3 μm or more.

In the resin-coated copper foil of the present embodiment, as the material of the copper foil, it is preferable to use copper or a copper alloy as a main component. The thickness of the copper foil is preferably 35 μm or less, and more preferably in the range of 5 μm to 25 μm. From the viewpoint of production stability and handling, the lower limit of the thickness of the copper foil is preferably 5 μm. Furthermore, the copper foil may be rolled copper foil or electrolytic copper foil. As the copper foil, commercially available copper foil can be used.

The copper foil with resin of this embodiment can be prepared by, for example, preparing a resin film, sputtering a metal to form a shielding layer, and then forming a copper layer by, for example, copper plating, or by thermally pressure bonding the copper foil or the like. Press to prepare.

In addition, the copper foil with resin of the present embodiment may be prepared by casting a coating liquid for forming a resin layer on the copper foil, drying to form a coating film, and then performing heat treatment.

<Metal-clad laminate> The metal-clad laminate of the present embodiment is an adhesive layer including an insulating resin layer and the resin film or the adhesive resin composition laminated on at least one side of the insulating resin layer, And a so-called three-layer metal-clad laminate laminated to the metal layer of the insulating resin layer via the adhesive layer. In the three-layer metal-clad laminate, as long as the adhesive layer is provided on one side or both sides of the insulating resin layer, the metal layer may be provided on one side or both sides of the insulating resin layer via the adhesive layer . That is, the metal-clad laminate of this embodiment may be a single-sided metal-clad laminate or a double-sided metal-clad laminate. By etching the metal layer of the metal-clad laminate of the present embodiment to perform wiring circuit processing, a single-sided FPC or a double-sided FPC can be manufactured.

The insulating resin layer is not particularly limited as long as it includes a resin having electrical insulation, and examples thereof include polyimide, epoxy resin, phenol resin, polyethylene, polypropylene, polytetrafluoroethylene, silicone, ETFE, etc. , Preferably including polyimide. The polyimide layer constituting the insulating resin layer may be a single layer or multiple layers, and preferably contains a non-thermoplastic polyimide layer.

The thickness of the insulating resin layer is, for example, preferably within a range of 1 μm to 125 μm, and more preferably within a range of 5 μm to 100 μm. If the thickness of the insulating resin layer is less than the lower limit, problems such as insufficient electrical insulation may not be guaranteed. On the other hand, if the thickness of the insulating resin layer exceeds the upper limit, defects such as warpage of the metal-clad laminate are likely to occur. In addition, the ratio of the thickness of the insulating resin layer to the thickness of the adhesive layer (thickness of the insulating resin layer/thickness of the adhesive layer) is preferably in the range of 0.5 to 2.0. By setting it as such a ratio, the warpage of a metal-clad laminate can be suppressed.

The insulating resin layer may contain fillers as necessary. Examples of the filler include silicon dioxide, aluminum oxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride, and metal salts of organic phosphonic acids. These can be used alone or in combination of two or more.

The thickness of the adhesive layer is, for example, preferably in the range of 0.1 μm to 125 μm, and more preferably in the range of 0.3 μm to 100 μm. In the three-layer metal-clad laminate of the present embodiment, if the thickness of the adhesive layer is less than the lower limit, there may be a problem that sufficient adhesiveness cannot be ensured. On the other hand, if the thickness of the adhesive layer exceeds the upper limit, problems such as a decrease in dimensional stability may occur. In addition, from the viewpoint of lowering the dielectric constant and lowering the dielectric loss tangent of the entire insulating layer of the laminate of the insulating resin layer and the adhesive layer, the thickness of the adhesive layer is preferably 3 μm the above.

The material of the metal layer in the metal-clad laminate of this embodiment is not particularly limited, and examples include copper, stainless steel, iron, nickel, beryllium, aluminum, zinc, indium, silver, gold, tin, zirconium, tantalum, and titanium , Lead, magnesium, manganese and their alloys. Among them, copper or copper alloy is particularly preferable.

The thickness of the metal layer is not particularly limited. For example, when copper foil is used as the metal layer, it is preferably 35 μm or less, and more preferably in the range of 5 μm to 25 μm. From the viewpoint of production stability and handling, the lower limit of the thickness of the copper foil is preferably 5 μm. Furthermore, when copper foil is used, it may be rolled copper foil or electrolytic copper foil. As the copper foil, commercially available copper foil can be used.

As the metal layer, when a copper foil is used, the copper foil preferably includes a base material copper foil and an adhesive layer (or insulating resin layer) formed on the surface of the base material copper foil forming the surface side The anti-rust treatment layer. In addition to the rust prevention treatment described above, the surface of the copper foil may be subjected to surface treatment using, for example, sidewalls, aluminum alcoholates, aluminum chelate compounds, silane coupling agents, etc. for the purpose of improving adhesion.

<Multilayer circuit board> The multilayer circuit board of the present embodiment includes a laminate including a plurality of laminated insulating resin layers, and one or more conductor circuit layers embedded in the laminate, in the plurality of insulating resin layers At least one layer is formed of an adhesive layer having adhesiveness and covering the conductor circuit layer, and the adhesive layer includes the resin film or the adhesive resin composition.

The multilayer circuit board of this embodiment has at least two or more insulating resin layers and at least two or more conductor circuit layers, and at least one of the conductor circuit layers is a conductor circuit layer covered with an adhesive layer. The adhesive layer covering the conductor circuit layer can partially cover the surface of the conductor circuit layer or the entire surface of the conductor circuit layer. In addition, the multilayer circuit board of the present embodiment may optionally have a conductor circuit layer exposed on the surface of the multilayer circuit board. In addition, it may have an interlayer connection electrode (via electrode) in contact with the conductor circuit layer.

The conductor circuit layer is one in which a conductor circuit is formed in a predetermined pattern on one side or both sides of an insulating resin layer. In addition, the conductor circuit may be patterned on the surface of the insulating resin layer, or may be formed in a damascene (embedded) pattern.

Examples Examples are given below to explain the features of the present invention more specifically. However, the scope of the present invention is not limited to the examples. In the following examples, unless otherwise specified, various measurements and evaluations are in accordance with the following.

[Measurement method of amine value] Weigh about 2 g of the dimer diamine composition into a 200 mL to 250 mL Erlenmeyer flask, use phenolphthalein as an indicator, and add 0.1 mol/L ethanolic potassium hydroxide dropwise The solution was light pink until it was dissolved in about 100 mL of neutralized butanol. Add 3 to 7 drops of phenolphthalein solution to it, and titrate with 0.1 mol/L ethanolic potassium hydroxide solution while stirring, until the sample solution turns pale pink. Add 5 drops of bromophenol blue solution to it and titrate with 0.2 mol/L hydrochloric acid/isopropanol solution until the sample solution turns yellow. The amine value is calculated by the following formula (1). Amine price={(V ₂ ×C ₂ )-(V ₁ ×C ₁ )}×M _KOH /m ･･･（1） Here, the amine price is the value expressed by mg-KOH/g, M _KOH The molecular weight of potassium hydroxide is 56.1. In addition, V and C are the volume and concentration of the solution used in the titration, and the subscripts 1 and 2 indicate the 0.1 mol/L ethanolic potassium hydroxide solution and the 0.2 mol/L hydrochloric acid/isopropanol solution, respectively. And, m is the sample weight expressed by gram.

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

[Calculation of GPC and chromatogram area percentage] Regarding GPC, for 200 mg of acetic anhydride, 200 μL of pyridine, and 2 mL of THF, a 20 mg dimer diamine composition was added to a previously processed 100 mg solution, and 10 mL of THF (containing 1000 ppm cyclohexanone) was diluted to prepare samples. For the prepared samples, use the trade name of Tosoh (TOSOH) Co., Ltd.: HLC-8220 GPC with column TSK-gel G2000HXL, G1000HXL, flow rate 1 mL/min, column (oven) temperature 40 The measurement was performed under the conditions of ℃ and injection volume of 50 μL. In addition, cyclohexanone is treated as a standard substance in order to correct the outflow time.

At this time, the peak top of the main peak of cyclohexanone was adjusted from the retention time (retention time) of 27 minutes to 31 minutes, and adjusted so that the peak of the main peak of cyclohexanone was 2 minutes. And the peak of the main peak except the peak of cyclohexanone is changed from 18 minutes to 19 minutes, and the peak of the main peak except for the peak of cyclohexanone is changed from 2 minutes to the end of the peak from 2 minutes Test each component (a) to component (c) under the condition of 4 minutes and 30 seconds; (A) The composition represented by the main peak; (B) The component represented by the peak value of GPC detected at a later time based on the minimum value on the time side of the retention time later in the main peak; (C) The component represented by the GPC peak detected at an earlier time based on the minimum value on the time side where the retention time in the main peak is earlier.

[Evaluation of dielectric properties] Using a vector network analyzer (manufactured by Agilent, trade name: vector network analyzer E8363C) and SPDR resonator, the resin sheet (hardened resin sheet) was placed at a temperature After 24 hours at 23°C and 50% humidity, the dielectric constant (ε ₁ ) and dielectric loss tangent (Tanδ ₁ ) at a frequency of 10 GHz were measured. E _{1, which} is an index indicating the dielectric properties of the resin laminate, is calculated based on the mathematical formula (i). In addition, after absorbing water at 23° C. for 24 hours, the dielectric constant (ε ₂ ) and dielectric loss tangent (Tanδ ₂ ) at a frequency of 10 GHz of the resin sheet (hardened resin sheet) were measured. E _{2, which} is an index indicating the dielectric properties of the resin laminate, is calculated based on the mathematical formula (ii).

[Measurement of moisture absorption] Two test pieces (width 4 cm×length 25 cm) of resin sheets (hardened resin sheets) were prepared and dried at 80° C. for 1 hour. Immediately after drying, it was placed in a constant temperature and humidity chamber at 23°C/50%RH, and it was allowed to stand for more than 24 hours. The weight change before and after it was determined by the following formula. Moisture absorption rate (wt%) = [(weight after moisture absorption-weight after drying)/weight after drying]×100

[Glass transition temperature (Tg) and storage elastic modulus] The glass transition temperature (Tg) and storage elastic modulus are for a resin sheet (hardened resin sheet) with a size of 5 mm × 20 mm, using a dynamic viscoelasticity measuring device (DMA: manufactured by Dubm, trade name: E4000F) Measured from 30°C to 400°C at a heating rate of 4°C/min and a frequency of 11 Hz. The temperature at which the elastic modulus change (tan δ) is the largest is taken as the glass transition temperature.

[Tensile elastic modulus] The tensile elastic modulus is measured by the following procedure. First, using a tension tester (Tensilon manufactured by Orientec), a test piece (width 12.7 mm × length 127 mm) was produced from a resin sheet (hardened resin sheet). Using this test piece, a tensile test was performed at 50 mm/min, and the tensile modulus at 25°C was determined.

[Warpage evaluation method] The evaluation of warpage was performed by the following method. A polyimide adhesive was applied on a 25 μm thick kapton film or a 12 μm copper foil so that the thickness after drying became 25 μm. In this state, place the Kapton film and the copper foil as the lower surface, measure the average height of the four corners of the film, and set 5 mm or less as "good", and exceed 5 The case of mm is set to "impossible".

The ellipsis used in this example indicate the following compounds. BTDA: 3,3',4,4'-benzophenone tetracarboxylic dianhydride (manufactured by Evonik, trade name: BTDA Ultra Pure) BisDA: 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)] diphthalic dianhydride (SABIC Innovative Plastics Japan LLC .) Manufacturing, trade name: BisDA-1000) BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride ODPA: 4,4'-oxydiphthalic anhydride DDA1: The product name made by Croda Japan Co., Ltd.: PRIAMINE 1075 by distillation and purification (component a: 98.2% by weight, component b: 0%, component c: 1.9% , Amine price: 206 mg KOH/g) DDA2: Made by distillation and purification of the brand name: PRIAMINE 1075 made by Croda Japan Co., Ltd. (component a: 99.2% by weight, component b: 0%, component c: 0.8% , Amine price: 210 mg KOH/g) N-12: Dodecanedioic acid dihydrazide NMP: N-methyl-2-pyrrolidone APB: 1,3-bis(3-aminophenoxy)benzene BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane In addition, in the above-mentioned DDA1 and DDA2, [%] of the component b and the component c refers to the area percentage of the chromatogram in GPC measurement. In addition, the molecular weights of DDA1 and DDA2 are calculated by the following formula (1). Molecular weight=56.1×2×1000/amine price･･･（1）

[Example 1] Fill a 1000 ml separable flask with 55.51 g of BTDA (0.1721 mol), 94.49 g of DDA1 (0.1735 mol), 210 g of NMP and 140 g of xylene, and mix thoroughly at 40°C for 1 hour , Preparation of polyamic acid solution. This polyamic acid solution was heated to 190°C, heated and stirred for 10 hours, and 125 g of xylene was added to prepare polyimide solution 1 (solid content: 30% by weight, weight average molecular weight: 82,900).

[Example 2 to Example 12] The polyimide solution 2 to the polyimide solution 12 were prepared in the same manner as in Example 1, except that the raw material composition shown in Table 1 was used.

[Table 1]

As shown in Table 1, in Examples 1 to 12, polyimide having a weight average molecular weight in the range of 40,000 to 150,000 was obtained.

[Example 13] 169.49 g (50 g in the form of solid content) of the polyimide solution 1 obtained in Example 1 was blended with 2.7 g of N-12 (0.0105 mol; the keto group of BTDA was 1 mol, and the primary amino group (Equivalent to 0.35 mol), 6.0 g of NMP was added for dilution, and the mixture was further stirred for 1 hour, thereby obtaining adhesive resin composition 1.

Apply the obtained adhesive resin composition 1 to one side of a release PET film (manufactured by Dongshan Film Co., Ltd., trade name: HY-S05, vertical×horizontal×thickness=200 mm×300 mm×25 μm), on Drying was performed at 80°C for 15 minutes, and the adhesive layer was peeled from the release PET film, thereby preparing a resin film 1 having a thickness of 25 μm. This resin film 1 was heated in an oven at a temperature of 160° C. for 2 hours to obtain Evaluation Sample 1. Table 2 shows the evaluation results of various characteristics.

[Example 14 to Example 24] Instead of the polyimide solution 1, the polyimide solution 2 to the polyimide solution 12 were used, except that the adhesive resin composition 2 to the adhesive resin composition was prepared in the same manner as in Example 13. After the object 12 and the resin film 2 to the resin film 12, evaluation samples 2 to 12 are obtained. Table 2 shows the evaluation results of various characteristics.

[Table 2]

[Example 25] The adhesive resin composition 1 obtained in Example 13 was applied to a polyimide film (manufactured by Dupont Co., Ltd., trade name: kapton 100EN-S, ε1=3.5, tanδ1=0.012 , Vertical×horizontal×thickness=200 mm×300 mm×25 μm) on one side, and dried at 80° C. for 15 minutes to obtain a cover film 1 with an adhesive layer thickness of 25 μm. The warped state of the obtained cover film was "good".

[Example 26 to Example 36] Instead of the adhesive resin composition 1, the adhesive resin composition 2 to the adhesive resin composition 12 were used, and otherwise, the cover films 2 to 12 were produced in the same manner as in Example 25. The warped states of the obtained cover films 2 to 12 were all “good”.

[Example 37] The adhesive resin composition 1 obtained in Example 13 was applied to one side of an electrolytic copper foil with a thickness of 12 μm, and dried at 80° C. for 15 minutes to obtain a tape with an adhesive layer thickness of 25 μm. Resin copper foil 1. The warped state of the obtained copper foil with resin 1 was “good”.

[Example 38] The adhesive resin composition 4 obtained in Example 16 was applied to one side of an electrolytic copper foil with a thickness of 12 μm, and dried at 80° C. for 30 minutes to obtain a tape with an adhesive layer thickness of 50 μm. Resin copper foil 2.

[Example 39] An adhesive resin composition 4 was coated on the resin surface of the resin-coated copper foil 2 obtained in Example 38, and dried at 80° C. for 30 minutes to obtain a tape having an adhesive layer thickness of 100 μm in total Resin copper foil 3.

[Example 40] The adhesive resin composition 1 obtained in Example 13 was applied to a release PET film (manufactured by Dongshan Film Co., Ltd., trade name: HY-S05, vertical×horizontal×thickness=200 mm×300 mm×25 μm) One side was dried at 80° C. for 30 minutes, and the adhesive layer was peeled from the release PET film, thereby obtaining a resin film 1′ having a thickness of 50 μm. On an electrolytic copper foil with a thickness of 12 μm, a resin film 1′ and a polyimide film (manufactured by Dupont Co., Ltd., trade name: kapton 100-EN, thickness 25 μm, ε1= 3.6, tanδ1=0.084), resin film 1′ and electrolytic copper foil with a thickness of 12 μm, using a vacuum laminator at a temperature of 160° C. and a pressure of 0.8 MPa, pressure bonding for 2 minutes, and then heat treatment at 160° C. for 4 hours ，Get copper-clad laminate 1.

[Example 41] The adhesive resin composition 1 obtained in Example 13 was applied to a polyimide film (manufactured by Dupont Co., Ltd., trade name: kapton 50EN, ε1=3.6, tanδ1=0.086, vertical ×horizontal×thickness=200 mm×300 mm×12 μm) on one side, and dried at 80°C for 15 minutes to prepare a cover film 1′ with an adhesive layer thickness of 25 μm. On an electrolytic copper foil with a thickness of 12 μm, the cover film 1'was laminated so that the adhesive resin composition 1 side was in contact with the copper foil, using a vacuum laminator at a temperature of 160°C and a pressure of 0.8 MPa, and pressed After 2 minutes, heat treatment was performed at 160°C for 2 hours to obtain a copper-clad laminate 2.

[Example 42] On the rolled copper foil with a thickness of 12 μm, the resin film 1 (thickness: 25 μm) obtained in Example 13 was laminated, and the cover film 1′ obtained in Example 41 was separated from the polyimide film side and the resin film Lamination in a continuous manner, followed by lamination of a resin film 1 (thickness: 25 μm) and a rolled copper foil with a thickness of 12 μm, using a vacuum laminator at a temperature of 160°C and a pressure of 0.8 MPa, and pressure bonding for 2 minutes. Thereafter, heat treatment was performed at 160° C. for 2 hours to obtain copper-clad laminate 3.

[Example 43] Two resin-coated copper foils 3 obtained in Example 39 were prepared, and a polyimide film (manufactured by Dupont) was laminated on one side of the adhesive resin composition 4 of one of the resin-coated copper foils 3. Trade name: Kapton 200-EN, thickness 50 μm, ε1=3.6, tanδ1=0.084), and then another resin-coated copper foil 3 with its adhesive resin composition 4 side and polyacrylic acid The imine films were laminated in a contacting manner, using a vacuum laminator at a temperature of 160°C and a pressure of 0.8 MPa for 5 minutes, followed by heat treatment at 160°C for 4 hours to obtain a copper-clad laminate 4.

[Example 44] The adhesive resin composition 1 obtained in Example 13 was applied to a single-sided copper-clad laminate (manufactured by NIPPON STEEL Chemical & Material), trade name: espanex FC12-25-00UEJ, vertical×horizontal×thickness=200 mm×300 mm×25 μm) on the polyimide side, drying at 80°C for 30 minutes to obtain a tape with an adhesive layer thickness of 50 μm Adhesive copper-clad laminate 1. On the side of the adhesive resin composition 1 of the copper-clad laminate with adhesive 1, a single-sided copper-clad laminate (manufactured by NIPPON STEEL Chemical & Material), trade name: Espanay (Espanex FC12-25-00UEJ) Laminated in a polyimide-contacting manner, using a small precision press at a temperature of 160°C and a pressure of 4.0 MPa for 120 minutes to obtain a copper-clad laminate 5.

[Example 45] The adhesive-coated copper-clad laminates 1 obtained in Example 44 were laminated with the adhesive resin composition 1 side in contact with each other, and pressed at a temperature of 160°C and a pressure of 4.0 MPa using a small precision press After 120 minutes, the copper-clad laminate 6 was obtained.

[Example 46] Laminated on the polyimide side of a single-sided copper-clad laminate (manufactured by NIPPON STEEL Chemical & Material, trade name: espanex FC12-25-00UEJ) The resin film 4 (thickness 25 μm) obtained in Example 16, and a single-sided copper-clad laminate (manufactured by NIPPON STEEL Chemical & Material), trade name: espanex FC12-25-00UEJ) Laminated in such a way that the polyimide side was in contact with the resin film 4, and was pressure bonded for 120 minutes at a temperature of 160°C and a pressure of 4.0 MPa using a small precision press to obtain a copper-clad laminate 7.

[Example 47] The adhesive resin composition 1 obtained in Example 13 was applied to a sheet of release PET film (manufactured by Dongshan Film Co., Ltd., trade name: HY-S05, vertical×horizontal×thickness=200 mm×300 mm×25 μm) The surface was dried at 80°C for 15 minutes to peel the adhesive layer from the release PET film, thereby obtaining a resin film 1″ having a thickness of 15 μm. Laminated resin on the polyimide side of single-sided copper-clad laminate (manufactured by NIPPON STEEL Chemical & Material, trade name: espanex FC12-25-00UEJ) Film 1'', and then a single-sided copper-clad laminate (manufactured by NIPPON STEEL Chemical & Material, trade name: espanex FC12-25-00UEJ) to Polyamide The amine side was laminated with the resin film 1'' in contact with it, and it was pressure-bonded for 120 minutes at a temperature of 160°C and a pressure of 4.0 MPa using a small precision press to obtain a copper-clad laminate 8.

[Example 48] Prepare double-sided copper-clad laminate (manufactured by NIPPON STEEL Chemical & Material, trade name: espanex FB12-25-00UEY) and use it on its single-sided copper foil The circuit processing is performed by etching to prepare the wiring board 1 on which the conductor circuit layer is formed. At the same time, the copper foil on one side of the double-sided copper-clad laminate (manufactured by NIPPON STEEL Chemical & Material, trade name: espanex FB12-25-00UEY) was etched and removed. ，制造铜装层板9。 Preparation of copper-clad laminate 9. The resin film 1 obtained in Example 13 was sandwiched between the surface of the wiring board 1 on the side of the conductor circuit layer and the surface of the copper-clad laminate 9 on the side of the insulating base material layer, and in the state of lamination, at a temperature Multilayer circuit substrate 1 was prepared by thermocompression bonding at 160°C and a pressure of 4.0 MPa for 120 minutes.

[Example 49] Liquid crystal polymer film (manufactured by Kuraray, trade name: CT-Z, thickness: 50 μm, CTE: 18 ppm/K, thermal deformation temperature: 300°C, dielectric constant: 3.40, dielectric loss) Tangent: 0.0022) As an insulating base material, a copper-clad laminate 10 with copper foil (electrolytic copper foil, thickness: 9 μm, surface roughness Rz: 2.0 μm) provided on both sides is used for the copper foil on one side The circuit processing is performed by etching to prepare the wiring board 2 on which the conductor circuit layer is formed. At the same time, the copper foil on one side of the copper-clad laminate 10 is etched away to prepare a copper-clad laminate 10'. The resin film 1 obtained in Example 13 was sandwiched between the surface of the wiring board 2 on the side of the conductor circuit layer and the surface of the copper-clad laminate 10' on the side of the insulating base material layer, and in the state of lamination, The multilayer circuit board 2 was prepared by thermocompression bonding at a temperature of 160°C and a pressure of 4.0 MPa for 120 minutes.

[Example 50] On the adhesive resin composition 1 side of the cover film 1'obtained in Example 41, a release PET film (manufactured by Dongshan Film Co., Ltd., trade name: HY-S05) was laminated in a contact manner, using a vacuum laminator Crimping was performed at a temperature of 160°C and a pressure of 0.8 MPa for 2 minutes. Thereafter, the adhesive resin composition 1 obtained in Example 13 was applied to the polyimide film side of the cover film 1'so that the thickness after drying became 25 μm, and the mixture was subjected to 15 minutes at 80°C. dry. Furthermore, on the adhesive resin composition 1 side after drying, a release PET film (manufactured by Dongshan Film Co., Ltd., trade name: HY-S05) was laminated in contact with each other, using a vacuum laminator at a temperature of 160°C and a pressure Compression bonding was carried out at 0.8 MPa for 2 minutes to prepare a polyimide adhesive laminate 1 having adhesive layers on both sides of the polyimide film.

In the above, the embodiment of the present invention has been described in detail for the purpose of illustration, but the present invention is not restricted by the above-described embodiment, and various modifications can be made.

no.

no

Claims (9)

A resin film characterized by containing polyimide as a resin component, wherein the polyimide is formed by reacting a tetracarboxylic anhydride component and a diamine component, and the diamine is relative to all diamine components The component contains a dimer diamine composition of 40 mol% or more. The dimer diamine composition is a dimer formed by replacing two terminal carboxylic acid groups of a dimer acid with a primary aminomethyl group or an amino group The diamine is the main component, and the resin film satisfies the following composition I and composition II: Composition I: calculated based on the following mathematical formula (i), and represents the constant temperature and humidity conditions of 23° C. and 50% RH The index of the dielectric characteristic at 10 GHz after the humidity adjustment is lowered for 24 hours, that is, the E ₁ value is 0.010 or less, E ₁ =√ε ₁ ×Tanδ ₁ ･･･ (i) In the mathematical formula (i), ε _{1 is} expressed as 23 The dielectric constant at 10 GHz measured by a separate dielectric resonator under constant temperature and humidity conditions of ℃ and 50%RH, that is, after 24 hours of humidity adjustment under normal conditions, Tanδ ₁ means constant temperature and constant temperature at 23℃ and 50%RH After adjusting the humidity for 24 hours under wet conditions, the dielectric loss tangent at 10 GHz measured by a separate dielectric resonator; Composition II: Calculated based on the following mathematical formula (ii), which means that after absorbing water at 23°C for 24 hours The index of the dielectric properties at 10 GHz is the E ₂ value, the ratio of the E ₂ value to the E ₁ value, that is, E ₂ /E ₁ is in the range of 3.0 to 1.0, E ₂ =√ε ₂ ×Tanδ ₂ ･･･ (ii) In the mathematical formula (ii), ε ₂ represents the dielectric constant at 10 GHz measured by a separate dielectric resonator after absorbing water at 23°C for 24 hours, Tan δ ₂ represents at 23°C After absorbing water for 24 hours, the dielectric loss tangent at 10 GHz was measured by a separate dielectric resonator. A cover film, characterized in that an adhesive layer and a cover film layer are laminated, wherein, The adhesive layer includes the resin film as described in item 1 of the patent application. A circuit board includes a base material, a wiring layer formed on the base material, and a cover film as described in item 2 of the patent application scope covering the wiring layer. A copper foil with resin, characterized in that an adhesive layer and a copper foil are laminated, wherein, The adhesive layer includes the resin film as described in item 1 of the patent application. A metal-clad laminate, characterized by having an insulating resin layer, an adhesive layer laminated on at least one side of the insulating resin layer, and being laminated on the substrate via the adhesive layer The metal layer of the insulating resin layer, wherein, The adhesive layer includes the resin film as described in item 1 of the patent application. A multilayer circuit board, characterized by comprising a laminate including a plurality of laminated insulating resin layers, and one or more conductor circuit layers embedded in the laminate, wherein, At least one layer of the plurality of insulating resin layers is formed of an adhesive layer having adhesiveness and covering the conductor circuit layer, The adhesive layer includes the resin film as described in item 1 of the patent application. A polyimide characterized by reacting a tetracarboxylic anhydride component and a diamine component, wherein the diamine component contains 40 mole% or more of a dimer dimer with respect to all diamine components An amine composition, the dimer diamine composition is mainly composed of a dimer diamine formed by replacing two terminal carboxylic acid groups of a dimer acid with a primary aminomethyl group or an amino group, Based on the area percentage of the chromatogram obtained by measuring the dimer diamine composition using colloidal permeation chromatography, the component c of the following components a to c is 2% or less; Component a: dimer diamine; Component b: a monoamine compound obtained by substituting the terminal carboxylic acid group of a monobasic acid compound having a carbon number in the range of 10 to 40 with a primary aminomethyl group or amino group; Component c: An amine compound obtained by substituting the terminal carboxylic acid group of the polyacid compound having a hydrocarbon group in the range of 41 to 80 with a primary aminomethyl group or an amino group, except for the dimer diamine. The polyimide as described in item 7 of the patent application range, which contains 50 mol% or more of 3,3',4,4'-diphenyl relative to the total amount of the tetracarboxylic anhydride component Ketone tetracarboxylic dianhydride. An adhesive resin composition characterized by comprising the following components A and B: Component A: Polyimide as described in item 8 of the patent application scope, and Component B: an amino compound having at least two primary amino groups as functional groups, and With respect to 3,3',4,4'-benzophenone tetracarboxylic dianhydride derived from 3,3',4,4'-benzophenone tetracarboxylic dianhydride in the A component The keto group of the residue is 1 mole, and the primary amino group contains the component B so that the total amount becomes 0.004 mole to 1.5 mole.