JPH11100504A - Perpendicular conductive sheet and preparation of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sheet in which conductive terminals arranged on a side of an insulating sheet and materials to be contacted are contacted by elevated temperature crimping by blending a polyimide resin obtained by reacting an amine component containing a silicon diamine and the like and an acid compo nent containing a tetracarboxylic acid dianhydride and the like, an epoxy com pound and an active hydrogen group-containing compound. SOLUTION: A silicon diamine is represented by the formula (R1 to R4 are each H or a hydrocarbon group having 6 or fewer carbon atoms; and k is 4-10). 5 to 100 pts.wt. of an epoxy compound having two epoxy groups in a molecule and 0.1 to 20 pts.wt. of a compound having an active hydrogen group capable of reacting with the epoxy compound are blended with 100 pts.wt. of a polyimide resin. Conductive terminals are arranged on the both sides of an insulating sheet facing each other and electrodes on a semiconductor device and connection terminals on substrate 5 are heated with a heat block to contact each other.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thickness direction conductive sheet capable of simultaneously and highly reliably electrically and mechanically connecting a plurality of electrode terminals of a semiconductor element and an electric / electronic component at the same time, and a sheet thereof. It relates to a manufacturing method.

[0002]

2. Description of the Related Art With the recent demand for higher functionality and lighter, thinner and smaller electronic equipment, high-density integration and high-density mounting of electronic components have been progressing. Semiconductor packages used in these electronic devices have been reduced in size and number of pins, and mounting substrates for mounting electronic components including the semiconductor packages have also been reduced in size. Further, in order to enhance the storability in electronic devices, a rigid-flex board, in which a rigid board and a flexible board are laminated and integrated and can be bent, has been used as a mounting board.

[0003] With the miniaturization of semiconductor packages,
Since the miniaturization of a package using a conventional lead frame has reached its limit, it has recently been proposed to mount a chip on a circuit board and use a BGA (Ball G
Rid Array) and CSP (Chip Scale)
A new package method of area mounting type such as “Package” has been proposed. In these semiconductor packages, a method of electrically connecting electrodes of a semiconductor chip to terminals of a substrate made of various materials such as plastics and ceramics, which is called a semiconductor package substrate having a function of a lead frame of a conventional semiconductor package. As a wire bonding method or TAB
(Tape Automated Bonding) method and FC (Flip Chip) method are known. Recently, BGA and CSP structures using FC connection method which is advantageous for miniaturization of semiconductor packages have been actively proposed. I have. In this FC connection method, generally, a connection bump is formed in advance on a semiconductor chip electrode, and the bump and the terminal on the substrate are aligned and connected by thermocompression bonding. The formation process is complicated and bump manufacturing costs are high, and it is necessary to fill the gap between the chip and the substrate with a resin called underfill to seal the connection part in order to obtain the moisture resistance reliability of the bump connection part. In addition, there is a problem that a process of filling and curing the underfill resin is required, so that the manufacturing process is complicated and the manufacturing cost is increased. Accordingly, a method of using an anisotropic conductive sheet as a connection material instead of a bump for electrical connection between a semiconductor chip and a substrate has been focused on and studied.

[0004] On the other hand, circuit boards are becoming finer and multi-layered due to the necessity of miniaturization. In particular, finer inter-layer connection circuits in multi-layering are important factors for miniaturization of mounting boards. It has become to. Conventionally known multilayer boards that perform interlayer connection with through vias have limitations on the drill diameter and the wiring design of each layer due to the through vias, which limits the miniaturization of the board. Therefore, recently, a build-up method in which an insulating resin layer is formed on a core substrate, and a circuit and a via are repeatedly formed on the insulating resin layer to obtain a multilayer board by laminating the insulating resin layer has attracted attention and various proposals have been made. With this build-up method, fine holes can be formed by laser method or photolithography method and conductors formed by plating, and fine and independent interlayer connection circuits can be obtained. It is advantageous. However, in this method, since a series of steps of forming one layer is repeated to perform multi-layering, the manufacturing cost increases due to the problem that the number of processing steps increases in proportion to the number of layers and the yield decreases. is there. Therefore, as a method of manufacturing a high-density wiring multilayer board with a reduced manufacturing cost, a method of using an anisotropic conductive sheet as an interlayer connection material and obtaining a multilayer board by laminating this with a double-sided board has been proposed and studied.

In the case of a rigid-flex board, which has recently been widely used as a mounting board, the conventional method of connecting a rigid board and a flexible board by through vias is the same as in the case of interlayer connection of a multilayer board. In this case, the use of an anisotropic conductive sheet as an interlayer connection material has been attempted to achieve high-density wiring and to reduce the size of the substrate.

The use of an anisotropic conductive sheet as an electrical connection material in the thickness direction as described above has been attracting more and more attention as an effective means for reducing the size of semiconductor packages and mounting substrates. Anisotropic conductive sheets have been proposed.

Conventionally, conductive fine particles are dispersed in a thermoplastic or thermosetting resin, and the resin flows during thermocompression bonding, so that the conductive fine particles sandwiched between the connection terminals make the electrical conduction in the thickness direction possible. Anisotropic conductive sheets for obtaining connection are well known, and include a liquid crystal display panel and a TCP (Tape Ca).
RRer Package). The anisotropic conductive sheet having the above structure is characterized in that it can be manufactured by a relatively simple process of dispersing conductive fine particles in a resin. Recently, a small through hole was drilled in a resin film using a drill or laser, and then the inside of the through hole was filled with a conductor by plating or conductive paste printing, and an adhesive layer was formed on the surface of the resin film. There has been proposed an anisotropic conductive sheet having such a structure, in which an adhesive layer flows at the time of thermocompression bonding, a conductor is exposed, and an electrical connection in a thickness direction is obtained by a conductor sandwiched between connection terminals. The anisotropic conductive sheet having the above structure is characterized in that the conductor can be arranged at an arbitrary position in the sheet surface.

[0008]

However, the anisotropic conductive sheet obtained as described above has the following problems. First, in the case of a structure in which conductive fine particles are dispersed in a thermoplastic or thermosetting resin, the terminals are narrow because electrical connection is obtained by the conductive fine particles that are stochastically present between the electrodes and the terminals. As the pitch becomes smaller, it is necessary to disperse the conductive fine particles more and more finely, thereby increasing the density of the fine particles and narrowing the distance between the fine particles, thereby deteriorating the electrical insulation property and the connection area between the fine particles and the terminals. There is a problem that the connection resistance increases due to the decrease. In addition, since the anisotropic conductive sheet having the above-described structure does not allow a connection point to be arbitrarily selected in the sheet plane, when used for interlayer connection of a multilayer board,
Circuits other than the terminals to be connected in advance must be covered with an insulating resin, and only the portion to be conducted must be subjected to pressure.In practice, an anisotropic conductive sheet having the above structure is arranged on the entire surface of the multilayer board. It is difficult to achieve conduction.

Next, a minute through hole is made in the resin film by a drill or a laser, and then the inside of the through hole is filled with a conductor by a method such as plating or conductive paste printing.
Furthermore, in the case of a structure in which an adhesive layer is formed on the surface of a resin film, as the terminals become narrower, fine drilling with high positional accuracy is required, and laser drilling becomes the mainstream. Lasers have problems such as low processing speed, low productivity, and high running cost. In addition, the formation of a conductor in a minute hole is generally performed by plating. However, as the hole diameter becomes smaller, uniform plating is more difficult, the height of the conductor tends to vary, and electrical connection cannot be performed at the time of terminal connection. Quality degradation.
Further, the number of processing steps is large and the cost is high.

Accordingly, the present invention has been made as a result of intensive studies in view of the above-mentioned problems of the conventional anisotropic conductive sheet, and has been developed for the connection between a semiconductor chip and a substrate and the interlayer connection of a multilayer board. Uses electrical and mechanical connection in the thickness direction, ensures reliable electrical connection even to narrow terminal pitches, and has electrical insulation with adjacent terminals. An object of the present invention is to provide a thickness direction conductive sheet which can be manufactured at low processing cost while maintaining high reliability.

[0011]

In order to achieve the above object, in the thickness direction conductive sheet of the present invention, (A) a mole of silicon diamine represented by the formula (1), 2,2-bis} 4- (4-aminophenoxy) phenyl} propane, 2,2-bis {4- (4-aminophenoxy) phenyl} hexafluoropropane, bis {4- (4-aminophenoxy) phenyl} ether, 1,3- Screw (3-
Aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 3,4′-diamino One or more diamines selected from diphenyl ether, 2,5-diamino-p-xylene, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane b mole and c mole of other diamine as an amine component, 4,4′-oxydiphthalic dianhydride, 3,
One or more tetracarboxylic dianhydrides selected from the group consisting of 3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride C mol of anhydride is used as an acid component, and 0.1 ≦ a / (a + b + c) ≦ 0.5, 0.05 ≦ b /
(A + b + c) ≦ 0.5, 0.9 ≦ c / (a + b + c)
100 parts by weight of a polyimide resin reacted at a ratio of ≦ 1.1, (B) 5 to 100 parts by weight of an epoxy compound having two epoxy groups in one molecule, and (C) a compound capable of reacting with the epoxy compound Terminals made of conductors are arranged on the surface of an insulating sheet containing 0.1 to 20 parts by weight of a compound having an active hydrogen group as an essential component. Is softened, the above-mentioned conductor sinks into the inside of the insulating sheet until it reaches the opposite surface, and conduction with the opposite surface of the insulating sheet is obtained, and at the same time, mechanical bonding with the connected object is performed. It is characterized by being performed.

[0012]

Embedded image (Wherein R ₁ , R ₂ , R ₃ , and R ₄ are a hydrogen atom or a monovalent aliphatic or aromatic hydrocarbon group having 6 or less carbon atoms, and R ₅ and R ₆ are a divalent group having 1 to 6 carbon atoms. An aliphatic or aromatic hydrocarbon group of k
(Integer between 4 and 10)

FIG. 1 is an example of a sectional view of a thickness direction conductive sheet of the present invention. FIG. 1 shows a cross-sectional structure of a thickness direction conductive sheet before performing heat compression bonding with a connected body. In FIG. 1, terminals made of a conductor are arranged on one surface of an insulating sheet. The resin constituting the insulating sheet softens during thermocompression bonding with the connected body,
Terminals made of a conductor arranged on the front surface sink into the insulating sheet and reach the opposite surface of the insulating sheet, so that the front and back can be electrically connected. At the time of thermocompression bonding with the connected body, the terminals arranged on the surface of the insulating sheet and the electric terminals of the connected body are aligned and crimped. By the thermocompression bonding, the terminals are electrically connected, and at the same time, the connection between the surface of the connected body without the electric terminals and the insulating sheet is performed.

The objects to be connected by the conductive sheet in the thickness direction of the present invention include a semiconductor element and a lead frame, a semiconductor element and a substrate, a semiconductor package and a mounting substrate, and chip parts used for surface mounting. Mounting board,
It can be widely used for devices that make electrical connections in the thickness direction, such as mounting substrates and mounting substrates, mounting substrates and flexible substrates, but because of the fine connection, electrical connection between the semiconductor element and the substrate It is particularly useful when used.

The conductor terminals of the conductive sheet in the thickness direction of the present invention may be arranged unevenly on only one surface of the insulating sheet as shown in FIG. 1, or may be arranged on both sides of the insulating sheet as shown in FIG. May be arranged so as to face the surface. In the case of the structure shown in FIG. 2, since the conductor terminals sink from both sides of the insulating sheet at the time of thermocompression bonding, if the height of the conductor terminals is half the thickness of the insulating sheet, the conduction between the front and back sides is reduced. Can be obtained. In such a configuration, it is necessary to precisely match the positions of the conductor terminals arranged on the front and back, but the height of the conductor terminals may be lower than when arranged on one side, so that the formation of the conductor terminals is easy. become. FIG. 3 shows an example in which the conductor terminals of the present invention are arranged on both sides of an insulating sheet so as not to face each other. In the case of the structure shown in FIG. 3, the distance between the conductor terminals for connection can be made wider than when all the connection terminals are arranged on one side of the insulating sheet, so that a narrower pitch of the connected terminals can be accommodated. it can.

Various characteristics are required for the insulating sheet in the thickness direction conductive sheet of the present invention. Not only high electrical insulation but also mechanical properties such as self-holding property and flexibility for holding handling of the sheet after processing the conductor terminal are required. Also, at the time of thermocompression bonding, the material constituting the connected body does not deteriorate, and the workability at low temperature and short time enables mass production in a short time. In this case, the conductor terminals move inside the sheet to the opposite side. It is necessary to have thermoplasticity as much as possible and a thermal elastic modulus so as not to move the conductor terminals in the plane direction of the sheet. After the thermocompression bonding, it is required to have adhesiveness to the object to be connected, heat resistance, and reliability such that the adhesive strength is not deteriorated even if moisture is absorbed after processing and migration of the conductive metal does not occur. In the present invention, (A) a polyimide resin (B) an epoxy resin (C) having a structure defined in the claims.
It has been found that by using a compound capable of reacting with an epoxy resin as an essential component, these characteristics, particularly, the moisture resistance reliability can be sufficiently satisfied.

The polyimide resin of the component (A) constituting the insulating sheet is characterized by containing a silicone component. This is because the polyimide structure realizes mechanical properties such as high heat resistance and flexibility, and the silicone structure in the molecule also realizes excellent properties such as workability at low temperature and short time, low water absorption and adhesion. There is a feature.

The silicone diamine represented by the formula (1) used in the present invention is α, ω-bis (3-aminopropyl) polydimethylsiloxane, etc., where k = 4-1.
5 is preferred, and a value of k in the range of 5 to 10 is particularly preferred in terms of glass transition temperature, adhesiveness, and heat resistance. When k is 3 or less, a high temperature or a long time is required for the bonding step. Conversely, when k is 16 or more, the compatibility of the silicone portion is reduced, and the properties of the entire sheet are reduced.

In the present invention, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis
{4- (4-aminophenoxy) phenyl} hexafluoropropane, bis {4- (4-aminophenoxy) phenyl} ether, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3- Aminophenoxy)
Benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 3,4′-diaminodiphenyl ether, 2,5-
One or more diamines selected from diamino-p-xylene and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane are also used. In the present invention, a diamine having another structure can be used in combination as long as the intended properties are not impaired. The content ratio of these diamines is 0.1 ≦ a /
(A + b + c) ≦ 0.5 and 0.5 ≦ b / (a + b +
c) Must be ≦ 0.9. a / (a + b + c)
If it is less than 0.1, workability at low temperature and short time will not be exhibited, and if it is more than 0.5, heat resistance and mechanical properties of the insulating sheet will be reduced. On the other hand, b / (a + b +
When c) is less than 0.5, the sheet formability in a solution state is reduced.

The tetracarboxylic dianhydride used in the present invention may be 4,4'-oxydiphthalic dianhydride, 3,3 'from the viewpoint of simultaneously forming a sheet in a solution, heat resistance and adhesiveness. , 4,4'-biphenyltetracarboxylic dianhydride or 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride as an essential component either alone or in combination of two or more Must be used. Among them, 4,4′-oxydiphthalic dianhydride alone, or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride Are preferably used in an abundance ratio of 50 to 90 mol% and 50 to 10 mol%, respectively. Further, an acid dianhydride having another structure can be used in combination with less than 20 mol% of the whole as long as the intended properties are not impaired.

The constituent molar ratio of these diamine and acid is 0.1.
9 ≦ (d + e) / (a + b + c + d + e) ≦ 1.1. More preferably, 0.975 ≦ d (d
+ E) / (a + b + c + d + e) ≦ 1.025. (D + e) / (a + b + c + d +
When e) is less than 0.9, the adhesive strength becomes weak because the molecular weight is low and brittle. On the other hand, when the ratio exceeds 1.1, unreacted carboxylic acid is undesirably decarbonated during heating, causing gas generation and foaming.

The reaction between the tetracarboxylic dianhydride and the diamine is carried out by a known method in an aprotic polar solvent. Aprotic polar solvents include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (D
MAC), N-methyl-2-pyrrolidone (NMP), γ
-Butyrolactone, tetrahydrofuran (THF), diglyme, cyclohexanone, 1,4-dioxane (1,4-DO) and the like. As the aprotic polar solvent, only one kind may be used, or two or more kinds may be used as a mixture. At this time, a non-polar solvent compatible with the aprotic polar solvent may be mixed and used. Aromatic hydrocarbons such as toluene, xylene, and solvent naphtha are often used. The proportion of the non-polar solvent in the mixed solvent is preferably 40% by weight or less. This is because if the amount of the nonpolar solvent is 40% by weight or more, the solvent power of the solvent may be reduced and polyamic acid may be precipitated. The reaction between the tetracarboxylic dianhydride and the diamine is carried out by dissolving the diamine component, which has been dried well, in the above-mentioned reaction solvent after dehydration and purification,
To this, a well-dried tetracarboxylic dianhydride having a ring closure of 98%, more preferably 99% or more is added to proceed the reaction.

The polyamic acid solution thus obtained is subsequently subjected to thermal dehydration cyclization in an organic solvent to give imidized polyimide. Since the water generated by the imidization reaction interferes with the ring closure reaction, an organic solvent incompatible with water is added to the system and azeotroped to form Dean-Stark (Dean-Stark).
k) Discharge out of the system using a device such as a pipe. Dichlorobenzene is known as an organic solvent that is not compatible with water, but the above-mentioned aromatic hydrocarbon is preferably used for electronics because a chlorine component may be mixed therein. Acetic anhydride, β-
It does not prevent the use of compounds such as picoline and pyridine.

In the present invention, the higher the degree of imide ring closure, the better the degree of imidization. If the rate of imidization is low, imidization occurs due to heat during use to generate water, which is not preferable. Therefore, 95% or more, more preferably 98% or more. Is preferably achieved.

The epoxy compound of the component (B) constituting the insulating sheet of the present invention is not particularly limited as long as it has two epoxy groups in one molecule. Are preferably those having good solubility. For example, bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether,
Examples thereof include tetramethylbiphenyl-type diglycidyl ether, biphenyl-type diglycidyl ether, and diphenylether-type diglycidyl ether.

The amount ratio of the epoxy compound is 5 to 100 parts by weight based on 100 parts by weight of the component (A) polyimide resin.
In particular, it is preferably in the range of 10 to 70 parts by weight. 5
If the amount is less than 10 parts by weight, the effect of adding an uncured epoxy compound to lower the softening temperature of the resin composition and increase the low-temperature processability is unlikely to be exhibited. If the amount exceeds 100 parts by weight, the heat resistance of the polyimide resin is impaired, which is not preferable.

The component (C) having an active hydrogen group capable of reacting with the epoxy compound used in the heat-resistant resin composition of the present invention is the same as the component (A) polyimide resin or the component (B) epoxy compound. It is preferable that the resin has good compatibility with the above and the solubility of the polyimide resin in the solvent. For example, resol, novolak, amino compound and the like can be mentioned. The mixing ratio of the component (C) is as follows.
The amount is 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight based on 00 parts by weight. If less than 0.1 parts by weight,
The reaction rate of the uncured epoxy compound becomes extremely low, and the effect desired in the present invention does not appear. Further, it is difficult to control the resin flow when the elastic modulus of the resin at a high temperature is low. If the amount is more than 20 parts by weight, a gel is likely to be formed in a resin solution state, whereby processability is impaired and heat resistance of the resin composition is impaired, which is not preferable. In the present invention, the coexistence of the thermosetting components of the components (B) and (C) with the polyimide resin of the component (A) allows the polyimide resin to exhibit flexibility and heat resistance as a thermoplastic adhesive film. It succeeded in significantly improving the humidity resistance reliability, which was its weak point. Although the detailed mechanism is currently being elucidated, it is considered that a reaction of a thermosetting component occurs at the time of the thermocompression bonding, and the properties after the compression are improved. Further, a curing accelerator for the epoxy resin, a coloring agent, an inorganic filler, various coupling agents, and the like may be added to these resin systems.

In the present invention, other components such as (B) and (C) can be added to the obtained polyimide solution as it is to process it as a solution. Further, the polyimide solution was put into a poor solvent to reprecipitate the polyimide resin to remove unreacted monomers, purified and dried, and then dried (B) and (C).
It can also be used after re-dissolving with other components.

As a method of forming the conductor terminal, a method of casting the above-mentioned resin solution on a metal foil, and then drying and forming a film to form a metal foil of a component, and a method of forming the above-mentioned resin solution A method in which a mask is applied to the surface of the insulating sheet formed by the above method and plating is performed, or a method in which the insulating sheet and the metal foil are laminated in advance and the metal foil is etched to form the same. One method of using the resin solution is to re-dissolve the reprecipitated solid polyimide resin in a low-boiling solvent, further reduce the drying temperature and heat history to the polyimide resin, and perform thermocompression bonding at a lower temperature. It can be possible. Usually, a rolled copper foil or an electrolytic copper foil is used as the metal foil, but the metal foil is not limited to these. The conductor terminals may be arranged in a lattice at an arbitrary pitch, or may be arranged so as to correspond to the terminals of the body to be connected, and may be selected according to the purpose. The height of the conductor terminal is preferably 0.7 to 1.5 times the thickness of the insulating sheet to be used. If the height is lower than 0.7 times the insulating sheet,
The conductor terminal does not reach the back surface of the insulating sheet at the time of thermocompression bonding, so that conduction between the front and back cannot be obtained. On the other hand, if it is higher than 1.5 times, the conductor terminal becomes a pillar when heat-pressed, a gap is formed between the connected body and the insulating sheet, and the sheet cannot be bonded, and the electrical reliability is reduced. A second conductor layer may be formed on the surface of the conductor terminal for the purpose of further improving electrical connection. As the method, for example, electrolytic plating or electroless plating is used, and for the conductor, for example, gold, tin,
Metals such as lead and indium can be used.

The method for connecting a body to be connected using the thickness direction conductive sheet of the present invention is as follows. First, the conductor terminal of the thickness direction conductive sheet of the present invention and the terminal of the body to be connected are aligned and overlapped. Then, the conductor terminals are sunk into the insulating sheet by heat and pressure bonding. Then, at the same time that the conductor terminal penetrates the insulating sheet, the terminal of the connected body and the conductor terminal are joined by thermocompression bonding, and the insulating sheet and the connected body are bonded. The temperature at the time of thermocompression bonding is set so that the conductor sheet formed on the surface of the insulating sheet is sufficiently softened and sinks into the inside of the insulating sheet by the pressure at the time of crimping. This temperature varies depending on the material of the insulating sheet to be used.
It can be performed at 00 to 400 ° C.

[0031]

【Example】

(Example 1) N-methyl-2-pyrrolidone (NMP) 2
68.2 g is vigorously stirred for 10 minutes while flowing nitrogen gas. Next, 78.9318 g (0.0270 mol) of 1,3-bis (3-aminophenoxy) benzene and 2,2
-Bis (4- (4-aminophenoxy) phenyl) propane 15.5994 g (0.0380 mol) and α, ω-
Bis (3-aminopropyl) polydimethylsiloxane 2
Charge 9.2950 g (average molecular weight 837, 0.0350 mol), heat the system to 60 ° C. and stir until uniform. After dissolving uniformly, the system was cooled to 5 ° C in an ice water bath,
4,4'-oxydiphthalic dianhydride 31.0222 g
(0.1000 mol) was added over 10 minutes while keeping the powdery state, and then stirring was continued for 5 hours. During this time the flask is 5
C. After that, remove the nitrogen gas inlet tube and cooler,
A Dean-Stark tube filled with xylene was attached to the flask, and 67.1 g of xylene was added to the polyamic acid solution formed in the system. The system was heated by replacing the ice water bath with an oil bath, and the generated water was removed from the system. After heating for 4 hours, no water was generated from the system. 100 g of the polyimide resin solution I obtained after cooling, 7 g of a tetramethylbiphenyl type epoxy compound (YX-4000H, manufactured by Yuka Shell Epoxy Co., Ltd.), and a resole resin (PR
-175, manufactured by Sumitomo Durez Co., Ltd.) was added to a glass flask and stirred at room temperature for 2 hours to prepare a heat-resistant resin solution II in which all additives were uniformly dissolved. This heat-resistant resin solution II was cast on a rolled copper foil having a thickness of 18 μm by a reverse roll coater and then dried to form a 15 μm-thick insulating layer sheet, thereby obtaining a polyimide sheet with a copper foil. The drying temperature was a maximum of 180 ° C. and the drying time was 15 minutes. As an adherend, a semiconductor element having electrodes for external connection around the circuit surface and a substrate having connection terminals at positions corresponding to the electrodes of the semiconductor element were prepared. The flexibility of laminating a dry film resist on the copper foil surface of the polyimide sheet with the copper foil and forming conductor terminals at positions corresponding to the electrodes of the semiconductor element by mask exposure, dry film development, etching and dry film peeling steps. A thick conductive sheet having thickness was obtained.
Conductor terminals of the thickness direction conductive sheet, electrodes of the semiconductor element,
And the corresponding terminals on the substrate are overlapped with each other at the same electrode terminal position.
/ Cm ² and sunk inside until the conductor terminal reached the opposite surface of the insulating sheet. The conductor terminal that reached the opposite surface of the insulating sheet was joined to the electrode of the semiconductor element and the connection terminal of the substrate, and electrical conduction was obtained.
The surface of the semiconductor element and the surface of the substrate were fixed by softening and bonding the insulating sheet. The shear strength at the connection surface was measured with a push-pull gauge and found to be 29 MPa, which was sufficient. In the fracture surface of the test piece, the adhesive resin layer was cohesively fractured, and no foaming was observed. Further, the obtained semiconductor device is placed in a thermo-hygrostat at a temperature of 85 ° C. and a relative humidity of 85% for 96 hours.
When the shear strength at the connection surface was measured in the same manner after standing for a period of time, no deterioration was observed at 34 MPa.

(Example 2) 265.8 g of N-methyl-2-pyrrolidone (NMP) was vigorously stirred for 10 minutes while flowing nitrogen gas. Next, 78.9318 g (0.0270 mol) of 1,3-bis (3-aminophenoxy) benzene and 15.9994 g (0.0380 mol) of 2,2-bis (4- (4-aminophenoxy) phenyl) propane And 29.2950 g of α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 837,
(0.0350 mol), and heat the system to 60 ° C. and stir until uniform. After homogeneous dissolution, the system was
C., and cooled to 20.5954 g (0.0700 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride 9 0.6669 g (0.0300 mol) was added in the form of a powder over 10 minutes, and then stirring was continued for 5 hours. During this time, the flask was kept at 5 ° C. Thereafter, the nitrogen gas inlet tube and the condenser were removed, a Dean-Stark tube filled with xylene was attached to the flask, and 66.4 g of xylene was added to the polyamic acid solution generated in the system.
The system was heated by replacing the ice water bath with an oil bath, and the generated water was removed from the system. After heating for 4 hours, no water was generated from the system. 100 g of polyimide resin solution B obtained after cooling, tetramethylbiphenyl type epoxy compound (YX-4000H, manufactured by Yuka Shell Epoxy Co., Ltd.)
, A resole resin (PR-175, manufactured by Sumitomo Durez Co., Ltd.) is added to a glass flask, and the mixture is stirred at room temperature for 2 hours so that all additives are uniformly dissolved. Solution II was prepared. This heat-resistant resin solution II was cast on a rolled copper foil having a thickness of 18 μm by a reverse roll coater and then dried to form a 15 μm-thick insulating layer sheet, thereby obtaining a polyimide sheet with a copper foil. The drying temperature was a maximum of 180 ° C. and the drying time was 15 minutes. As an adherend, a semiconductor element having electrodes for external connection around the circuit surface and a substrate having connection terminals at positions corresponding to the electrodes of the semiconductor element were prepared. Laminate a dry film resist on the copper foil surface of the polyimide sheet with copper foil, and form a conductor terminal at a position corresponding to the electrode of the semiconductor element by mask exposure, dry film development, etching and dry film peeling steps. A conductive sheet in the thickness direction was obtained. The conductor terminals of the thickness direction conductive sheet, the electrodes of the semiconductor element, and the corresponding terminals on the substrate are overlapped with each other at the same electrode terminal position, and then heated from the semiconductor element surface to 250 ° C. by a heat block. While the pressure was applied at a pressure of 10 kgf / cm ² , the conductor terminal was sunk inside until it reached the opposite surface of the insulating sheet.
At this time, generation of decomposition gas or the like was not observed from the insulating sheet. The conductor terminal that reached the opposite surface of the insulating sheet was joined to the electrode of the semiconductor element and the connection terminal of the substrate, and electrical conduction was obtained. The surface of the semiconductor element and the surface of the substrate were fixed by softening and bonding the insulating sheet. When the shear strength at the connection surface was measured with a push-pull gauge, it was 21MP.
a was enough. In the fracture surface of the test piece, the adhesive resin layer was cohesively fractured, and no foaming was observed. Further, the obtained semiconductor element is placed in a thermo-hygrostat at a temperature of 85 ° C.
When the shear strength at the connection surface was measured in the same manner after standing for 96 hours under the conditions of a relative humidity of 85% and the relative humidity was 85%, no deterioration was observed at 28 MPa.

Example 3 A heat-resistant resin solution II obtained by the method of Example 1 was applied to a polyester film (100 μm).
m thickness) and cast it with a bar coater.
After drying at 15 ° C. for 15 minutes, the polyester film was peeled off to obtain a flexible self-holding insulating sheet III having a thickness of 20 μm. 18 μm
A thick rolled copper foil was passed between two hot rolls at 140 ° C. and a linear pressure of 0.5 kgf / cm to be laminated to obtain an insulating sheet with a copper foil. As an adherend, a semiconductor element having electrodes for external connection in the periphery and a substrate having connection terminals at positions corresponding to the electrodes of the semiconductor element were prepared. Laminate a dry film resist on the copper foil surface of the insulating sheet with the copper foil, mask exposure, dry film development, etching, dry film peeling and electroless gold plating process, the conductor at the position corresponding to the electrode of the semiconductor element A thickness direction conductive sheet having terminals formed thereon was obtained.
Conductor terminals of this thickness direction conductive sheet, electrodes of the semiconductor element, and corresponding connection terminals on the substrate,
The positions of the respective electrode terminals were aligned and superimposed. Then, the conductor terminals which reached the opposite surface of the insulating sheet by applying a pressure of 10 kgf / cm ² from the semiconductor element surface to the opposite side of the insulating sheet while being heated to 250 ° by a heat block were connected to the electrodes of the semiconductor element and the connection terminals of the substrate. And electrical continuity was obtained. Further, the surface of the semiconductor element and the surface of the substrate were firmly fixed by the softening and bonding of the insulating sheet. When the shear strength at the connection surface was measured with a push-pull gauge, it was 20 MPa, which was sufficient. In the fracture surface of the test piece, the adhesive resin layer was cohesively fractured, and no foaming was observed. Further, after the obtained semiconductor device was left in a constant temperature and humidity chamber at a temperature of 85 ° C. and a relative humidity of 85% for 96 hours, the shear strength at the connection surface was measured in the same manner. I couldn't.

Example 4 A flexible four-layer board was manufactured using a conductive sheet in the thickness direction. First, the first layer and the second layer
The circuit of the layer is formed on the flexible substrate with double-sided electrolytic copper foil by drilling through holes, through-hole copper plating, dry film lamination, mask exposure, dry film development, etching, and dry film peeling to form a flexible circuit board IV. Obtained. Next, circuits of the third and fourth layers were formed in the same manner to obtain a flexible circuit board V. Connection terminals were provided on the second layer and the third layer at opposing positions. The first and fourth layers were coated with thermosetting polyimide as a solder resist and cured. Next, on both surfaces of the insulating sheet III obtained by the method of Example 3, 1
A 2 μm thick electrolytic copper foil was laminated to obtain an insulating sheet with double-sided copper foil. Laminating a dry film resist on the copper foil surface of the insulating sheet with copper foil, mask exposure,
By conducting the steps of dry film development, etching, dry film peeling, and electroless solder plating, the conductor terminals are opposed to both surfaces at positions corresponding to the connection terminals of the second and third layers of the flexible circuit boards IV and V. The formed thickness direction conductive sheet was obtained. The conductor terminals of this thickness direction conductive sheet and the connection terminals of the flexible circuit boards IV and V are aligned and laminated, and the conductor terminals are pressed at a pressure of 10 kgf / cm ² while being heated to 250 degrees by a hot press device. Submerged inside the insulating sheet. The conductor terminals arranged and formed so as to face both surfaces of the insulating sheet sink into the inside of the insulating sheet from the respective surfaces, and are joined to the facing conductor terminals inside the insulating sheet, and the second layer and the second layer. The three-layer connection terminals were also joined to obtain electrical continuity. Further, the second layer surface and the third layer surface of the flexible circuit board were fixed by the softening and bonding of the insulating sheet. When the 180-degree peel strength at the interface between the insulating sheet and the flexible circuit board was measured with a tensile tester (tensile speed: 50 mm / min), it was 2.2 kgf / cm, which was sufficient. In the fracture surface of the test piece, the adhesive resin layer was cohesively fractured, and no foaming was observed.

Comparative Example 1 In Example 1, α, ω−
Instead of bis (3-aminopropyl) polydimethylsiloxane having an average molecular weight of 837, an average molecular weight of 16
A polyimide sheet with a copper foil was obtained by the same operation using 58.4500 g (0.0350 mol) of 70.
However, in the thickness direction conductive sheet obtained after forming the conductor terminal, the insulating sheet portion was uneven and brittle, and the subsequent steps could not be performed.

Comparative Example 2 In Example 1, α, ω−
Bis (3-aminopropyl) polydimethylsiloxane having an average molecular weight of 24 instead of 837
8.6982 g (0.0350 mol) of 8.52
It was used and a polyimide sheet with a copper foil was obtained by the same operation. However, even after the conductor terminals are formed, even if the positions of the electrode terminals are adjusted and the connected body is heated and pressed under the same conditions,
The conductor terminal did not sink inside until it reached the opposite surface of the insulating sheet.

Comparative Example 3 In Example 1, 1, 3
-Bis (3-aminophenoxy) benzene was added at 11.69.
36 g (0.0400 mol) and 2,2-bis (4- (4
22.57-aminophenoxy) phenyl) propane
81 g (0.0550 mol) and 8.3500 g of α, ω-bis (3-aminopropyl) polydimethylsiloxane
(Average molecular weight: 837, 0.0050 mol), and a polyimide sheet with a copper foil was obtained by the same operation. However, as in Comparative Example 2, even after the conductor terminals are formed and the electrode terminals are aligned and heated and pressurized with the connected object under the same conditions, the conductor terminals sink inside until they reach the opposite surface of the insulating sheet. Did not.

Comparative Example 4 In Example 1, 1, 3
-Bis (3-aminophenoxy) benzene to 4.385
1 g (0.0150 mol) and 2,2-bis (4- (4-
Aminophenoxy) phenyl) propane is 10.262
8g (0.0150 mol) and 116.9000 of α, ω-bis (3-aminopropyl) polydimethylsiloxane
g (average molecular weight: 837, 0.0700 mol), and a polyimide sheet with a copper foil was obtained in the same manner. But,
In the thickness direction conductive sheet obtained after forming the conductor terminal, the insulating sheet part is brittle, and at the time of heating and pressing with the connected object,
The fluidity of the insulating sheet was large, and the conductor terminals flowed together with the insulating sheet.

Comparative Example 5 In Example 1, 100 g of the obtained polyimide resin solution B and 7 g of a tetramethylbiphenyl type epoxy compound (YX-4000H, manufactured by Yuka Shell Epoxy Co., Ltd.) were added to a glass flask. And
Stir at room temperature for 2 hours to prepare a resin solution in which all additives are uniformly dissolved, and add this to a heat-resistant resin solution.
The same operation was performed in the same manner as above except that II was used. Although the shear strength at the connection surface of the obtained semiconductor element was as large as 31 MPa immediately after heating and pressing, it was 9 MPa after standing for 96 hours at a temperature of 85 ° C. and a relative humidity of 85% in a thermo-hygrostat. It has been greatly reduced.

(Comparative Example 6) In Example 1, 100 g of the obtained polyimide resin solution B and a resole resin (PR-
175, manufactured by Sumitomo Durez Co., Ltd.) was added to a glass flask, and stirred at room temperature for 2 hours to prepare a resin solution in which all additives were uniformly dissolved. The same operation as described below was performed using the solution instead of the solution II. However, the shear strength at the connection surface of the obtained semiconductor element was as small as 13 MPa.

[0042]

According to the thickness direction conductive sheet of the present invention,
Compared to conventional anisotropic conductive sheets, electrical connections and mechanical connections in the thickness direction, such as connections between semiconductor chips and substrates, which are narrower in pitch, and interlayer connections between multilayer boards, are more reliable at lower cost and higher reliability. The electronic device can be downsized.

[Brief description of the drawings]

FIG. 1 is a thickness direction conductive sheet of the present invention in which conductive terminals are arranged on one surface of an insulating sheet.

FIG. 2 is a thickness direction conductive sheet of the present invention in which conductor terminals are arranged so as to face each other on both surfaces of an insulating sheet.

FIG. 3 is a thickness direction conductive sheet of the present invention in which conductor terminals are arranged so as not to face each other on both surfaces of an insulating sheet.

FIG. 4 shows an example of connection between a semiconductor element and a substrate using a sheet for connection in the thickness direction of the present invention.

[Explanation of symbols]

 1: Insulating sheet 2: Conductive terminal 3: Semiconductor element 4: Electrode of semiconductor element 5: Substrate 6: Connection terminal on substrate 7: Heat block

Claims (11)

[Claims] (A) Formula (1) (Wherein R ₁ , R ₂ , R ₃ , and R ₄ are a hydrogen atom or a monovalent aliphatic or aromatic hydrocarbon group having 6 or less carbon atoms, and R ₅ and R ₆ are a divalent group having 1 to 6 carbon atoms. An aliphatic or aromatic hydrocarbon group of k
Amol of silicon diamine represented by an integer of 4 to 10), 2,2-bis {4- (4-aminophenoxy) phenyl} propane, 2,2-bis {4- (4-aminophenoxy) phenyl} Hexafluoropropane, bis {4-
(4-aminophenoxy) phenyl} ether, 1,3
-Bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3
-Aminophenoxy) benzene, 3,4'-diaminodiphenyl ether, 2,5-diamino-p-xylene,
1,3-bis (3-aminopropyl) -1,1,3,3
One or two or more diamines selected from tetramethyldisiloxane and b moles of other diamines as an amine component, and 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4; D mol of one or more tetracarboxylic dianhydrides selected from the group of 4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride; E mol of another acid dianhydride is used as an acid component, and 0.1 ≦ a / (a +
b + c) ≦ 0.5, 0.5 ≦ b / (a + b + c) ≦ 0.
9, 0.8 ≦ d / (d + e) ≦ 1,0.9 ≦ (d + e)
/ (A + b + c + d + e) 100 parts by weight of a polyimide resin reacted at a ratio of 1.1, (B) 5 to 100 parts by weight of an epoxy compound having two epoxy groups in one molecule, and (C) the epoxy compound Independent terminals composed of conductors are arranged on one surface of an insulating sheet comprising, as an essential component, 0.1 to 20 parts by weight of a compound having an active hydrogen group capable of reacting with When the insulating sheet is softened at the time of heat compression bonding with
The conductor sinks until it reaches the opposite surface of the insulating sheet, and conduction between the opposite surface of the insulating sheet and the connected object is obtained through the conductor, and bonding with the connected object is performed at the same time. A thickness direction conductive sheet characterized by the above-mentioned. (A) a mole of a silicon diamine represented by the formula (1), 2,2-bis {4- (4-aminophenoxy) phenyl} propane, 2,2-bis {4- (4- Aminophenoxy) phenyl} hexafluoropropane,
Bis {4- (4-aminophenoxy) phenyl} ether, 1,3-bis (3-aminophenoxy) benzene,
1,4-bis (3-aminophenoxy) benzene, 1,
4-bis (4-aminophenoxy) benzene, 1,4-
Bis (3-aminophenoxy) benzene, 3,4′-diaminodiphenyl ether, 2,5-diamino-p-xylene, 1,3-bis (3-aminopropyl) -1,
One or two or more diamines selected from 1,3,3-tetramethyldisiloxane and b moles of other diamines are used as amine components, and 4,4′-oxydiphthalic dianhydride, One or more tetracarboxylic dianhydrides selected from the group consisting of 3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride D moles of anhydride,
Other acid dianhydride e mol as an acid component, and 0.1 ≤
a / (a + b + c) ≦ 0.5, 0.5 ≦ b / (a + b +
c) ≦ 0.9, 0.8 ≦ d / (d + e) ≦ 1, 0.9 ≦
100 parts by weight of a polyimide resin reacted at a ratio of (d + e) / (a + b + c + d + e) ≦ 1.1, and (B) an epoxy compound 5 to 10 having two epoxy groups in one molecule.
0 parts by weight and (C) 0.1 to 20 parts by weight of a compound having an active hydrogen group capable of reacting with the epoxy compound as an essential component. Are arranged facing each other, and when the insulating sheet is softened at the time of heating and press-bonding with the connected body, the above-described conductors are joined until the facing conductors are joined to each other in the insulating sheet. A thickness direction conductive sheet, wherein the thickness direction conductive sheet is sunk, and conduction is obtained between the opposite surface of the insulating sheet and the connected object through the conductor, and at the same time, adhesion to the connected object is performed. (A) a mole of silicon diamine represented by formula (1), 2,2-bis {4- (4-aminophenoxy) phenyl} propane, 2,2-bis {4- (4- Aminophenoxy) phenyl} hexafluoropropane,
Bis {4- (4-aminophenoxy) phenyl} ether, 1,3-bis (3-aminophenoxy) benzene,
1,4-bis (3-aminophenoxy) benzene, 1,
4-bis (4-aminophenoxy) benzene, 1,4-
Bis (3-aminophenoxy) benzene, 3,4′-diaminodiphenyl ether, 2,5-diamino-p-xylene, 1,3-bis (3-aminopropyl) -1,
One or two or more diamines selected from 1,3,3-tetramethyldisiloxane and b moles of other diamines are used as amine components, and 4,4′-oxydiphthalic dianhydride, One or more tetracarboxylic dianhydrides selected from the group consisting of 3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride D moles of anhydride,
Other acid dianhydride e mol as an acid component, and 0.1 ≤
a / (a + b + c) ≦ 0.5, 0.5 ≦ b / (a + b +
c) ≦ 0.9, 0.8 ≦ d / (d + e) ≦ 1, 0.9 ≦
100 parts by weight of a polyimide resin reacted at a ratio of (d + e) / (a + b + c + d + e) ≦ 1.1, and (B) an epoxy compound 5 to 10 having two epoxy groups in one molecule.
0 parts by weight and (C) 0.1 to 20 parts by weight of a compound having an active hydrogen group capable of reacting with the epoxy compound as an essential component. The terminals are arranged so as not to face each other, and when the insulating sheet is softened at the time of heating and press-bonding with the connected body, the conductor sinks until the conductor reaches the opposite surface of the insulating sheet. A conductive sheet in the thickness direction, wherein conduction between an opposite surface of the insulating sheet and a connected object is obtained through a conductor, and adhesion to the connected object is performed at the same time. 4. The thickness direction conductive sheet according to claim 1, wherein the thickness of the conductive terminal is in a range of 0.7 to 1.5 times the thickness of the insulating sheet. 5. The thickness direction conductive sheet according to claim 2, wherein the total thickness of the conductor terminals facing each other is in a range of 0.7 to 1.5 times the thickness of the insulating sheet. . 6. A mole of silicon diamine represented by the formula (1), 2,2-bis {4- (4-aminophenoxy) phenyl} propane, 2,2-bis {4- (4- Aminophenoxy) phenyl} hexafluoropropane,
Bis {4- (4-aminophenoxy) phenyl} ether, 1,3-bis (3-aminophenoxy) benzene,
1,4-bis (3-aminophenoxy) benzene, 1,
4-bis (4-aminophenoxy) benzene, 1,4-
Bis (3-aminophenoxy) benzene, 3,4′-diaminodiphenyl ether, 2,5-diamino-p-xylene, 1,3-bis (3-aminopropyl) -1,
One or two or more diamines selected from 1,3,3-tetramethyldisiloxane and b moles of other diamines are used as amine components, and 4,4′-oxydiphthalic dianhydride, One or more tetracarboxylic dianhydrides selected from the group consisting of 3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride D moles of anhydride,
Other acid dianhydride e mol as an acid component, and 0.1 ≤
a / (a + b + c) ≦ 0.5, 0.5 ≦ b / (a + b +
c) ≦ 0.9, 0.8 ≦ d / (d + e) ≦ 1, 0.9 ≦
100 parts by weight of a polyimide resin reacted at a ratio of (d + e) / (a + b + c + d + e) ≦ 1.1, and (B) an epoxy compound 5 to 10 having two epoxy groups in one molecule.
0 parts by weight and (C) a solution in which 0.1 to 20 parts by weight of a compound having an active hydrogen group capable of reacting with the epoxy compound is dissolved in an organic solvent as an essential component, and coated on a conductive foil; A step of forming an insulating sheet on the conductive foil by evaporating the solvent in the solution by heating, and a step of selectively etching only the conductive foil to form independent conductive terminals in a desired arrangement. The method for producing a conductive sheet in the thickness direction according to claim 1, wherein: (A) a mole of a silicon diamine represented by the formula (1), 2,2-bis {4- (4-aminophenoxy) phenyl} propane, 2,2-bis {4- (4- Aminophenoxy) phenyl} hexafluoropropane,
Bis {4- (4-aminophenoxy) phenyl} ether, 1,3-bis (3-aminophenoxy) benzene,
1,4-bis (3-aminophenoxy) benzene, 1,
4-bis (4-aminophenoxy) benzene, 1,4-
Bis (3-aminophenoxy) benzene, 3,4′-diaminodiphenyl ether, 2,5-diamino-p-xylene, 1,3-bis (3-aminopropyl) -1,
One or two or more diamines selected from 1,3,3-tetramethyldisiloxane and b moles of other diamines are used as amine components, and 4,4′-oxydiphthalic dianhydride, One or more tetracarboxylic dianhydrides selected from the group consisting of 3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride D moles of anhydride,
Other acid dianhydride e mol as an acid component, and 0.1 ≤
a / (a + b + c) ≦ 0.5, 0.5 ≦ b / (a + b +
c) ≦ 0.9, 0.8 ≦ d / (d + e) ≦ 1, 0.9 ≦
100 parts by weight of a polyimide resin reacted at a ratio of (d + e) / (a + b + c + d + e) ≦ 1.1, and (B) an epoxy compound 5 to 10 having two epoxy groups in one molecule.
A thin film conductor layer is formed on at least one insulating layer surface of an insulating sheet containing, as essential components, 0 parts by weight and (C) 0.1 to 20 parts by weight of a compound having an active hydrogen group capable of reacting with the epoxy compound. Forming, selectively electroplating the thin-film conductor layer to form conductor terminals in a desired arrangement, and etching and removing the thin-film conductor layer whose surface is not plated to electrically conduct the conductor terminals. 5. The method for producing a conductive sheet in the thickness direction according to claim 1, further comprising the step of: 8. (A) amol of silicon diamine represented by the formula (1), 2,2-bis {4- (4-aminophenoxy) phenyl} propane, 2,2-bis {4- (4- Aminophenoxy) phenyl} hexafluoropropane,
Bis {4- (4-aminophenoxy) phenyl} ether, 1,3-bis (3-aminophenoxy) benzene,
1,4-bis (3-aminophenoxy) benzene, 1,
4-bis (4-aminophenoxy) benzene, 1,4-
Bis (3-aminophenoxy) benzene, 3,4′-diaminodiphenyl ether, 2,5-diamino-p-xylene, 1,3-bis (3-aminopropyl) -1,
One or two or more diamines selected from 1,3,3-tetramethyldisiloxane and b moles of other diamines are used as amine components, and 4,4′-oxydiphthalic dianhydride, One or more tetracarboxylic dianhydrides selected from the group consisting of 3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride D moles of anhydride,
Other acid dianhydride e mol as an acid component, and 0.1 ≤
a / (a + b + c) ≦ 0.5, 0.5 ≦ b / (a + b +
c) ≦ 0.9, 0.8 ≦ d / (d + e) ≦ 1, 0.9 ≦
100 parts by weight of a polyimide resin reacted at a ratio of (d + e) / (a + b + c + d + e) ≦ 1.1, and (B) an epoxy compound 5 to 10 having two epoxy groups in one molecule.
Heat conductive foil on at least one insulating layer surface of an insulating sheet containing, as essential components, 0 parts by weight and (C) 0.1 to 20 parts by weight of a compound having an active hydrogen group capable of reacting with the epoxy compound. 5. The thickness according to claim 1, further comprising a step of forming a conductor layer by pressure bonding, and a step of selectively etching only the conductor layer to form independent conductor terminals in a desired arrangement. Manufacturing method of directional conductive sheet. 9. The method according to claim 6, wherein the sheet-like conductor is a rolled copper foil or an electrolytic copper foil. 10. A method for producing a thickness direction conductive sheet, comprising a step of forming a second conductor layer on a conductor surface of the thickness direction conductive sheet obtained by the production method according to claim 6, 7, or 8. 11. A method of manufacturing a thickness direction conductive sheet, comprising the step of heating and pressing a thickness direction conductive sheet obtained by the manufacturing method according to claim 6, and embedding conductor terminals in an insulating layer. Method.