WO2007032463A1 - Adhesive composition, adhesive sheet using same, and use of those - Google Patents

Abstract

Disclosed is an adhesive composition (I) characterized by containing a polyurethane polyurea resin (A) having a weight average molecular weight of 80,000-250,000 and an acid number of 3-25 mgKOH/g and an epoxy resin (B). The polyurethane polyurea resin (A) is obtained by reacting a urethane prepolymer (d) having an isocyanate group, a polyamino compound (e) and a monoamino compound (f) under the conditions stated below. The urethane prepolymer (d) having an isocyanate group is obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group. (i) The ratio between isocyanate groups of the urethane prepolymer (d) having an isocyanate group and amino groups of the polyamino compound (e) and the monoamino compound (f), namely amino groups/isocyanate groups is from 0.8/1 to 0.999/1 (molar ratio). (ii) The ratio of amino groups of the polyamino compound (e) in the 100 mol% of the total of the amino groups of the polyamide compound (e) and the amino groups of the monoamino compound (f) is 90.0-97.0 mol%.

Description

 Specification

 Adhesive composition, adhesive sheet using the same, and use thereof

 [0001] The present invention relates to an adhesive composition for a flexible printed wiring board using a polyimide film or the like as a base film on which a semiconductor integrated circuit (IC) or the like is mounted, and an adhesive sheet for a flexible printed wiring board. And various flexible printed wiring boards using the same, and a method for producing them.

 Specifically, adhesive composition, adhesive sheet, and cover film for fixing a reinforcing material such as metal, glass epoxy, or polyimide to the flexible printed wiring board are attached to the conductive circuit side of the flexible printed wiring board. The present invention relates to an adhesive composition, an adhesive composition suitable for further laminating flexible printed wiring boards, and an adhesive sheet, and further comprising an adhesive composition and a solder formed by laminating using the adhesive composition The present invention relates to various flexible printed wiring boards having excellent heat resistance.

 Background art

 [0002] A flexible printed wiring board, which has been used in an increased amount as a printed wiring board, has a conductive film provided on a base film by various methods.

 As a method for providing a conductive circuit, for example, a photosensitive etching resist layer is formed on a copper foil of a flexible copper-clad plate in which a copper foil is provided on a base film with or without an adhesive layer. By exposing through a mask film with a circuit pattern to cure only the exposed area, and then removing the unexposed area of the copper foil by etching, the remaining resist layer is peeled off, etc. Circuit can be formed. Alternatively, only a necessary circuit may be provided on the base film by means such as sputtering.

[0003] Generally, flexible printed wiring boards that have a conductive circuit on one surface, a conductive circuit on both sides, and a conductive circuit in the inside of those are used. . In addition, as the base film, a plastic film having insulating properties, flexibility, and heat resistance, for example, polyimide-polyethylene terephthalate (PET) is used. A film or the like is generally used, and an electrolytic copper foil or a rolled copper foil is generally used as the copper foil.

 Here, various adhesives are used for the flexible printed wiring board.

 For example,

 Adhesive to form a flexible copper-clad board by laminating a copper foil and a base film to form a conductive circuit,

 The conductive circuit of the flexible printed wiring board is provided, and the adhesive for attaching the reinforcing material to the part,

 An adhesive for attaching a cover film for covering the side of the flexible printed circuit board on which the conductive circuit is provided;

 In addition, an adhesive for laminating a plurality of flexible printed wiring boards and laminating a plurality of conductive circuit layers can be used.

 In the present specification, “a portion provided with a conductive circuit” is a surface of a flexible printed wiring board provided with a conductive circuit of a flexible printed wiring board. A circuit is formed on the surface on the same side as the surface on which the conductive circuit of the flexible printed wiring board is provided, which is the surface on the opposite side of the flexible printed wiring board. Including parts that are not.

 [0006] Further, as another use of the adhesive in the printed wiring board,

 Lightweight and thin adhesive · Adhesive for bonding the package substrate necessary for the manufacture of ball grid array (BGA), which is an excellent semiconductor package with low cost, to the reinforcing plate (stiffener) and heat sink (heat spreader) Or

 Examples thereof include an adhesive for affixing an electromagnetic shielding material or the like to the device casing.

[0007] Flexible printed wiring boards, which are increasingly used as wiring boards, have low strength and are susceptible to physical damage, so some of the wiring boards are reinforced with reinforcing materials and used with increased mechanical strength. Sometimes. For example, a reinforcing material is bonded to a portion where stress is concentrated, such as a terminal portion or a switch portion inserted into a socket.

[0008] Further, in order to protect the conductive circuit on the flexible printed wiring board, prevent oxidation, and improve the flexibility of the conductive circuit, the conductive circuit surface is generally held via an adhesive layer. Protective plastic film is coated. (This plastic film is also called “cover film”.)

 [0009] In addition, as electronic devices are increasingly becoming smaller and more dense, there is an increasing demand for multilayer printed wiring boards having a plurality of conductive circuit layers that can be efficiently wired in a narrow space. Therefore, there is an increasing demand for a printed wiring board in which a plurality of flexible printed wiring boards are laminated and a plurality of conductive circuits are laminated. Most of the interlayer adhesive materials used in current multilayer printed wiring boards are thermosetting resin prepregs in which a base material such as a glass cloth is impregnated with a thermosetting resin typified by an epoxy resin. However, in recent years, as multilayer printed wiring boards have become thinner and denser, there has been an increasing demand for layer-indirect bonding materials that do not use a substrate such as glass cloth, in order to make the interval between each printed wiring board extremely narrow. RU

 [0010] Polyimide films are often used for plastic films as base materials for the above-mentioned flexible printed wiring boards, cover films for surface protection, or BGA package substrates. In addition, reinforcing materials for flexible printed wiring boards, stiffeners used in BGA, heat spreaders, or electromagnetic wave shielding materials include glass epoxy plates, stainless steel plates (for example, SUS plates), metal materials, polyimide films, etc. Is often used.

 Therefore, polyimide film and glass epoxy board, polyimide film and metal plate, and polyimide films are used as adhesives used in these applications and adhesives for laminating and stacking flexible printed wiring boards. Good adhesion is required.

 [0011] A reinforcing material or cover film is attached to the flexible printed wiring board, or a printed wiring board in which a plurality of flexible printed wiring boards are laminated is manufactured. Electronic components are mounted on the board.

[0012] As a method of mounting electronic components on a wiring board, the entire wiring board including a solder part previously formed by printing or coating is heated to about 230 to 280 ° C by infrared reflow, etc., and the solder is melted to make electronic Many methods (solder reflow) are used to join parts to the wiring board. Also, attach a cover film so that a part of the conductive circuit of the printed wiring board is exposed, When the exposed conductive circuit portion is exposed to / contacted with molten solder, a dripping method is also employed.

 Therefore, in the adhesive used for the various applications described above, heat resistance to such an extent that foaming and peeling due to solder reflow does not occur, and further, foaming and peeling do not occur even when contacted with molten solder. High heat resistance is required.

 [0013] In addition, printed wiring boards are key components in the electronics field, where the market is rapidly expanding, and their manufacturing and processing bases are scattered throughout the country. Therefore, printed wiring boards and materials for producing them are desired to have excellent storage stability with little change in properties even after transportation and storage under various conditions.

 [0014] Currently, adhesives used in the above-mentioned applications related to the production of printed wiring boards include, for example, a mixture of an epoxy resin and an epoxy resin curing agent as a curing component to improve the peel strength. In order to impart flexibility, an epoxy resin composition containing a flexible component such as acrylonitrile butadiene rubber is widely used (see, for example, Patent Document 1). Such an epoxy resin composition has high heat resistance and good substrate adhesion, but the majority of the composition is occupied by epoxy resin and its curing agent. In many cases, it is in a sheeted state (B stage). Therefore, it needs to be stored at a low temperature, and has poor storage stability.

 [0015] Further, an acrylic resin composition in which an acrylic resin is used as a base polymer and an epoxy resin is blended as a curing component has been proposed (see, for example, Patent Document 2 and Patent Document 3). These contain functional groups that can be cross-linked with epoxy resin in acrylic resin, and since they do not use a hardener of epoxy resin, they have good storage stability and adhere well to metal materials. Although there is a problem, the adhesion to the polyimide film is still insufficient! /, And! /.

 [0016] Also, a method has been proposed in which saturated polyester resin is used in combination with a relatively reduced curing component to improve storage stability and adjust the degree of curing. (For example, see Patent Document 4 and Patent Document 5).

[0017] In addition, an adhesive composition comprising an epoxy adhesive as a main component and a urethane prepolymer and a diamine curing agent composed of a diol and a diisocyanate is excellent. Copper foil z It has been proposed to have polyimide adhesion and good solder heat resistance. This adhesive composition has the ability to react with both the epoxy resin and the urethane-based polymer as a curing agent, and to obtain good heat resistance. The functional group of the urethane-based polymer has the isocyanate group and the diamine-based curing agent. It is difficult to achieve both storage stability with high reactivity and solder heat resistance (see Patent Document 6).

[0018] Furthermore, an adhesive composition containing a resin containing a urethane bond and Z or urea bond in the main chain and a thermosetting resin is also known (Patent Document 7). However, a resin containing a urethane bond and Z or urea bond in the main chain disclosed in Patent Document 7 does not have a carboxyl group. Therefore, even if epoxy resin is used as the thermosetting resin, no reaction occurs between the two resins, so that it is inferior in terms of solder heat resistance. In particular, the solder heat resistance after humidification is significantly reduced.

Patent Document 1: Japanese Patent Laid-Open No. 4370996

 Patent Document 2: JP-A-9-316398

 Patent Document 3: Japanese Patent Laid-Open No. 2002-12841

 Patent Document 4: JP-A-6-330014

 Patent Document 5: Japanese Patent Laid-Open No. 2000-273430

 Patent Document 6: JP-A-8-32230

 Patent Document 7: Japanese Patent Laid-Open No. 10-178066

 Disclosure of the invention

 Problems to be solved by the invention

[0020] The present invention solves the problems of conventional adhesive compositions for flexible printed wiring boards and various constituent materials for printed wiring boards using the same, and provides polyimide film, conductive Adhesive composition that is excellent in adhesive strength to the electrical circuit and the reinforcing material, has good storage stability, and can obtain a cured layer having excellent solder heat resistance, and further uses the adhesive composition An object of the present invention is to provide various constituent materials for printed wiring boards.

 Means for solving the problem

[0021] The above object is achieved by the present invention by reacting a polyol compound (a), an organic diisocyanate (b), and a dioli compound (c) having a carboxyl group. The urethane prepolymer (d) having a group, the polyamino compound (e) and the monoamino compound (f) are reacted under the following conditions, and the weight average molecular weight force is 0000 to 250000, and the acid value is 3 to 25 mg KOHZg. This can be solved by an adhesive composition (I) comprising a polyurethane polyurethane resin (A) and an epoxy resin (B).

 (i) Ratio power of isocyanate group of urethane prepolymer (d) having isocyanate group and amino group of polyamino compound (e) and monoamino compound (f) Amino group Z isocyanate group = 0.8Zl to 0.9999Z1 Molar ratio),

 And,

(ii) a total of 100 mole% of the Amino group of the polyamino compound Amino groups and monoamino compounds of (e) (f), the proportion of Amino groups of the polyamino compound (e) is 90. 0-97. 0 mole _^0/0 .

 [0022] Further, in a preferred embodiment of the adhesive composition (I) of the present invention, a urethane prepolymer (d) having an isocyanate group (d) force a polyol compound (a) and a diol compound having a carboxyl group ( Ratio power of hydroxyl group of c) and isocyanate group of organic diisocyanate (b) Isocyanate group Z hydroxyl group = 1.05 Zl to l. 50 Z1 (molar ratio).

 [0023] Further, in a preferred embodiment of the adhesive composition (I) of the present invention, the polyurethane polyol resin (A) has an amine value of 0 to 1.5 mgKOHZg.

[0024] Further, in a preferred embodiment of the adhesive composition (I) of the present invention, the polyol compound (a) has a number average molecular weight of 1000 to 5000, and a urethane prepolymer (d ) Has a weight average molecular weight of 10,000 to 50,000.

[0025] Further, in a preferred embodiment of the adhesive composition (I) of the present invention, epoxy resin (B) 5 to: LOO with respect to 100 parts by weight of polyurethane polyurethane resin (A) Contains parts by weight.

[0026] Further, a preferred embodiment of the adhesive composition (I) of the present invention includes a filler (C), and in particular, 100 parts by weight of the polyurethane polyurethane resin (A). In contrast, filler (C) O. 1 ~: LO

Contains 0 parts by weight.

 [0027] The present invention also relates to an adhesive sheet having a curable adhesive layer (Π) made of the above-mentioned adhesive composition (I) on a peelable sheet.

[0028] In addition, according to a preferred embodiment of the adhesive sheet of the present invention, a curable adhesive layer (II ) On the other side.

 [0029] The present invention also relates to a reinforcing material with an adhesive layer for a flexible printed wiring board having a curable adhesive layer (層) formed from the above-mentioned adhesive composition (I) on the reinforcing material.

 [0030] Further, the present invention is provided with a conductive circuit of a flexible printed wiring board, and a part thereof is interposed with a cured adhesive layer (ΠΙ) formed from the above-mentioned adhesive composition (I). The present invention also relates to a flexible printed wiring board with a reinforcing material, wherein the reinforcing material is fixed.

 [0031] The present invention also relates to a method of manufacturing a flexible printed wiring board with a reinforcing material, wherein the reinforcing material is fixed to the flexible printed wiring board using the adhesive sheet.

 [0032] Further, the present invention provides a curable adhesive layer obtained by applying the above-mentioned adhesive composition (I) on a reinforcing material.

 (II) is provided, and then the curable adhesive layer (Π) is provided with the conductive circuit of the flexible printed wiring board, while being in contact with the part, and Z or in contact. It is related with the manufacturing method of the flexible printed wiring board with a reinforcing material characterized by heating after making it carry out.

 [0033] Further, the present invention provides an adhesive in which a curable adhesive layer (Π) made of the above-mentioned adhesive composition (I) is sandwiched between a plastic film that has not been subjected to a peeling treatment and a protective film. It relates to a plastic film with a layer.

 [0034] Further, the present invention provides a surface of the flexible printed wiring board having a conductive circuit on the surface thereof on the conductive circuit side with a cured adhesive layer (ΠΙ) formed from the above-mentioned adhesive composition (I). Further, the present invention relates to a flexible printed wiring board with a cover film, which is peeled and coated with a plastic film.

 [0035] In addition, the present invention provides a conductive film for a flexible printed wiring board having a conductive circuit on the surface by peeling off the protective film from the plastic film with the adhesive layer and exposing the exposed curable adhesive layer (Π). It is related with the manufacturing method of the flexible printed wiring board with a cover film characterized by heating, after making it contact and stick to the surface of a property circuit side, and Z or making it contact and sticking.

[0036] In the present invention, the above adhesive composition (I) is applied to one surface of a plastic film which has been peeled off to form a curable adhesive layer (Π). Then the curable adhesive Heat the adhesive layer (π) while the surface on the conductive circuit side of the flexible printed wiring board having the conductive circuit on the surface is in contact with and adhered, and Z or in contact with the surface. The present invention relates to a method for producing a flexible printed wiring board with a cover film.

 [0037] Further, the present invention provides the adhesive composition (I) as described above, which is applied to the surface of the flexible printed wiring board having a conductive circuit on the surface thereof on the side of the conductive circuit. And then heating the curable adhesive layer (II) while bringing it into contact with and adhering a plastic film that has not been subjected to release treatment, and Z or contacting and adhering. The present invention relates to a method for producing a flexible printed wiring board with a cover film.

 [0038] Further, the present invention provides a cured adhesive layer (III) formed from the above-mentioned adhesive composition (I).

 The surface of the first single-sided printed wiring board (1) having a conductive circuit only on one surface and the surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface The surface of the conductive circuit is stuck together, or

 One surface of the double-sided printed wiring board (2) having the conductive circuit on both sides is bonded to the surface on the conductive circuit side of the single-sided printed wiring board (1) having the conductive circuit only on one surface. Or

 The surface of the first single-sided printed wiring board (1) having a conductive circuit only on one surface and the surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface A conductive circuit is provided, and the surface is bonded together, or

 One side of a double-sided printed wiring board (2) having a conductive circuit on both sides and a one-sided printed wiring board (1) having a conductive circuit only on one side are provided with a conductive circuit. Is pasted, or

 One surface of the first double-sided printed wiring board (2) having conductive circuits on both sides is bonded to one surface of the second double-sided printed wiring board (2) having conductive circuits on both sides Force or

The conductive circuit of the first single-sided printed wiring board (1) having the conductive circuit only on one surface is provided, and the second single-sided pre-side having the conductive circuit only on the surface and one surface. The present invention relates to a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the conductive circuit of the printed wiring board (1) is provided and bonded to the surface.

 [0039] Further, the present invention is to peel off one peelable sheet from the above adhesive sheet and to expose the exposed curable adhesive layer (Π),

 Contact the conductive circuit side surface of the first single-sided printed wiring board (1) having the conductive circuit only on one surface, and then peel off the other peelable sheet,

 Adhering the exposed curable adhesive layer (II) to the conductive circuit side surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, and Z In addition, the present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, which are heated after contacting and sticking.

[0040] In the present invention, one peelable sheet is peeled from the above adhesive sheet, and the exposed curable adhesive layer (Π) is removed.

 Contact the conductive circuit side surface of the first single-sided printed wiring board (1) having the conductive circuit only on one surface, and then peel off the other peelable sheet,

 The exposed curable adhesive layer (II) is provided with a conductive circuit of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, and the surface is brought into contact with the adhesive circuit (II). And let Z or contact and stick, then heat,

 Or

 Remove one peelable sheet from the above adhesive sheet, and expose the exposed curable adhesive layer (Π)

 The first single-sided printed wiring board (1) having a conductive circuit only on one surface is provided with a conductive circuit, which is brought into contact with the surface, and then the other peelable sheet is peeled off with an exposed curing. While touching the surface of the conductive circuit side of the second single-sided printed wiring board (1) that has a conductive circuit only on one surface, the Z or contact The present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is performed after the attachment.

[0041] Further, the present invention peels one peelable sheet from the above adhesive sheet, and exposes the exposed curable adhesive layer (Π), Contact with the surface of the conductive circuit side of the single-sided printed wiring board (1) having a conductive circuit only on one surface, and then peel off the other peelable sheet,

After making one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides contact and stick to the exposed curable adhesive layer (Π), and Z or contact and sticking, Heating or

Or

Remove one peelable sheet from the above adhesive sheet and expose the exposed curable adhesive layer (層

)

Make contact with one surface of the double-sided printed wiring board (2) that has conductive circuits on both sides, then! Remove the other peelable sheet with

The exposed curable adhesive layer (II) is attached to the surface of the conductive circuit side of the single-sided printed wiring board (1) having a conductive circuit only on one surface, and Z or contact. The present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein the conductive circuit layer is heated after being adhered.

 In the present invention, one peelable sheet is peeled from the above adhesive sheet, and the exposed curable adhesive layer (Π) is removed.

A conductive circuit of a single-sided printed wiring board (1) having a conductive circuit only on one surface is provided, contacted with the surface, and then the other peelable sheet is peeled off,

After making one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides contact and stick to the exposed curable adhesive layer (Π), and Z or contact and sticking, Heating or

Or

Remove one peelable sheet from the above adhesive sheet and expose the exposed curable adhesive layer (層

)

Make contact with one surface of the double-sided printed wiring board (2) that has conductive circuits on both sides, then! Remove the other peelable sheet with

While adhering the surface of the single-sided printed wiring board (1), which has a conductive circuit only on one surface, to which the conductive circuit is not provided, in contact with the exposed curable adhesive layer (II), And a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein the heating is performed after z or contact and adhesion.

 [0043] Further, the present invention is to peel off one peelable sheet from the above adhesive sheet, and to expose the exposed curable adhesive layer (層),

 Contact with one surface of the first double-sided printed wiring board (2) having conductive circuits on both sides, and then peel off the other peelable sheet with

 Adhering to the exposed curable adhesive layer (II) with one surface of the second double-sided printed wiring board (2) having conductive circuits on both sides in contact with Z, or with contact with Z The present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is performed.

[0044] Further, the present invention is to peel off one peelable sheet from the above adhesive sheet, and to expose the exposed curable adhesive layer (層),

 The first single-sided printed wiring board (1) having a conductive circuit only on one surface is provided with a conductive circuit, which is brought into contact with the surface, and then the other peelable sheet is peeled off with an exposed curing. The conductive adhesive layer (II) is provided with the conductive circuit of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, while the surface is brought into contact with the adhesive circuit (II). And a method of manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, wherein Z is contacted or stuck and then heated.

[0045] Further, the present invention provides the above-mentioned adhesive composition (I),

 Apply to the surface on the conductive circuit side of the first single-sided printed wiring board (1) having a conductive circuit only on one surface to form a curable adhesive layer (Π),

 Next, the surface on the conductive circuit side of the second single-sided printed wiring board (1) having a conductive circuit only on one surface on the curable adhesive layer (II), or the second single-sided printed wiring board. A plurality of conductive circuit layers are provided, wherein the conductive circuit of (1) is provided, wherein the conductive circuit layer is heated while being brought into contact with the surface and Z or being brought into contact with the conductive circuit layer. The present invention relates to a method for manufacturing a laminated printed wiring board.

[0046] Further, the present invention provides the above-mentioned adhesive composition (I),

On the conductive circuit side of the single-sided printed wiring board (1) having a conductive circuit only on one surface Apply to the surface, form a curable adhesive layer (Π),

 Next, after making one surface of a double-sided printed wiring board (2) having a conductive circuit on both sides contact and sticking to the curable adhesive layer (層) and Z or making contact and sticking, Heating or

 Or

 The above-mentioned adhesive composition (I)

 Apply to one surface of double-sided printed wiring board (2) with conductive circuits on both sides to form a curable adhesive layer (Π)

 Next, the surface of the conductive circuit side of the single-sided printed wiring board (1) having the conductive circuit only on one surface is brought into contact with and adhered to the curable adhesive layer (II), and Z or contact. It is related with the manufacturing method of the flexible printed wiring board by which the several conductive circuit layer is laminated | stacked characterized by heating after making it touch and stick.

[0047] Further, the present invention provides the above-mentioned adhesive composition (I),

 Apply to one surface of double-sided printed wiring board (2) with conductive circuits on both sides to form a curable adhesive layer (Π)

 Then, the surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface, which is not provided with a conductive circuit, is brought into contact with and adhered to the curable adhesive layer (II), and The present invention relates to a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein the heating is performed after Z or contact and adhesion.

[0048] The present invention also provides the adhesive composition (I) described above,

 Apply to one surface of the first double-sided printed wiring board (2) with conductive circuits on both sides to form a curable adhesive layer (Π),

 Next, the surface of the second double-sided printed wiring board (2) having a conductive circuit on both sides is adhered to and adhered to the curable adhesive layer (II), and Z or contact is adhered. The present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is performed.

[0049] Further, the present invention provides the above-mentioned adhesive composition (I),

Conductive circuit of the first single-sided printed wiring board (1) having a conductive circuit only on one surface Is applied to the surface where is not provided, forming a curable adhesive layer (Π),

 Next, the surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface of the curable adhesive layer (II) or the second single-sided printed wiring board. (1) A plurality of conductive circuit layers are laminated, wherein the surface on which the conductive circuit of (1) is not provided is brought into contact and stuck, and is heated after Z or contact and stuck. The present invention relates to a method for producing a printed wiring board.

[0050] Further, the present invention provides the above-mentioned adhesive composition (I),

 A conductive circuit of a single-sided printed wiring board (1) having a conductive circuit only on one surface is provided! It is applied to a small ヽ surface to form a curable adhesive layer (Π),

 Next, after making one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides contact and sticking to the curable adhesive layer (Π) and Z or making contact and sticking, The present invention relates to a method for manufacturing a flexible printed wiring board in which a plurality of conductive circuit layers are laminated.

[0051] Further, the present invention provides a curable adhesive layer (Π) of the above adhesive sheet,

 Contact the conductive circuit side surface of the first single-sided printed wiring board (1) having a conductive circuit only on one surface, and then peel off the peelable sheet.

 On the exposed curable adhesive layer (II), the surface on the conductive circuit side of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, or the second single-sided printed wiring board (1) The conductive circuit is provided, and while the surface is brought into contact and Z is applied, and after Z is brought into contact and attached, heating is performed,

 Or

 The curable adhesive layer (Π) of the above adhesive sheet,

 A conductive circuit of the first single-sided printed wiring board (1) having a conductive circuit only on one surface is provided, which is brought into contact with the surface, and then the peelable sheet is peeled off with

Adhering the exposed curable adhesive layer (II) to the conductive circuit side surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, and Z In addition, the present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, which are heated after contacting and sticking. [0052] Further, the present invention provides a curable adhesive layer (Π) of the above adhesive sheet,

 Contact with the surface of the conductive circuit side of the single-sided printed wiring board (1) having the conductive circuit only on one surface, and then peel off the peelable sheet,

 After making one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides contact and stick to the exposed curable adhesive layer (Π), and Z or contact and sticking, Heating or

 Or

 The curable adhesive layer (Π) of the above adhesive sheet,

 Make contact with one surface of the double-sided printed wiring board (2) that has conductive circuits on both sides, then! Remove the peelable sheet with,

 The exposed curable adhesive layer (II) is attached to the surface of the conductive circuit side of the single-sided printed wiring board (1) having a conductive circuit only on one surface, and Z or contact. The present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein the conductive circuit layer is heated after being adhered.

[0053] Further, the present invention provides a curable adhesive layer (Π) of the above adhesive sheet,

 A conductive circuit of a single-sided printed wiring board (1) having a conductive circuit only on one surface is provided, which is brought into contact with the surface, and then the peelable sheet is peeled off,

 After making one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides contact and stick to the exposed curable adhesive layer (Π), and Z or contact and sticking, Heating or

 The curable adhesive layer (Π) of the above adhesive sheet,

 Make contact with one surface of the double-sided printed wiring board (2) that has conductive circuits on both sides, then! Remove the peelable sheet with,

 While the surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface not provided with the conductive circuit is brought into contact with and adhered to the exposed curable adhesive layer (II), and The present invention relates to a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein the heating is performed after Z or contact and adhesion.

[0054] Further, the present invention provides a curable adhesive layer (Π) of the above adhesive sheet, Make contact with one surface of the first double-sided printed wiring board (2) that has conductive circuits on both sides, and then peel off the peelable sheet with

 Adhering to the exposed curable adhesive layer (II) with one surface of the second double-sided printed wiring board (2) having conductive circuits on both sides in contact with Z, or with contact with Z The present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is performed.

[0055] Furthermore, the present invention provides a curable adhesive layer (Π) of the above adhesive sheet,

 A conductive circuit of the first single-sided printed wiring board (1) having a conductive circuit only on one surface is provided, which is brought into contact with the surface, and then the peelable sheet is peeled off with

 The exposed curable adhesive layer (II) is provided with a conductive circuit of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, and the surface is brought into contact with the adhesive circuit (II). In addition, the present invention relates to a method for manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, wherein the heating is performed after Z is contacted or pasted and then heated.

 The invention's effect

 [0056] The adhesive composition of the present invention is excellent in adhesive strength to polyimide films, conductive circuits, and reinforcing materials, has good storage stability, and can provide a cured layer having excellent soldering heat resistance. Therefore, it can be suitably used for laminating flexible printed wiring boards and mounting a cover film for protecting a reinforcing material and a conductive circuit. In addition, since the adhesive composition and the curable adhesive layer formed therefrom are excellent in storage stability, there is little change in properties even after the transportation and storage process under various conditions.

 In addition, the adhesive composition of the present invention can be stored at room temperature, such as an adhesive sheet using the same, a reinforcing agent with an adhesive layer for a flexible printed wiring board, or a cover film with an adhesive layer. Does not require low-temperature storage.

 Brief Description of Drawings

 FIG. 1 is a schematic cross-sectional view of a flexible printed wiring board to which a reinforcing material with an adhesive layer is attached.

FIG. 2 is a schematic cross-sectional view of a flexible printed wiring board covered with a cover film with an adhesive layer. FIG. 3 is a schematic cross-sectional view of a printed wiring board formed by laminating a plurality of conductive circuit layers.

 FIG. 4 is a schematic cross-sectional view of a single-sided printed wiring board (1).

 FIG. 5 is a schematic cross-sectional view of a double-sided printed wiring board (2).

 Explanation of symbols

[0058] 1: Base Finolem

 2: Conductive circuit

 3: Reinforcement material

 4: Cured adhesive layer (III)

 5: Flexible printed circuit board

 6: Plastic film (cover film)

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0059] First, the adhesive composition (I) of the present invention will be described.

 The polyurethane polyurethane resin (A) contained in the adhesive composition (I) is obtained by reacting the polyol compound (a), the organic diisocyanate (b), and the diolic compound (c) having a carboxyl group. It is obtained by reacting a urethane prepolymer (d) having an isocyanate group, a polyamino compound (e), and a monoamino compound (f).

 In the present specification, the “polyol compound (a)” is generally known as a polyol component constituting an ordinary polyurethane resin, and as a component (c) described later among the compounds described above. Compounds other than the carboxyl group-containing dioli compound used, for example, various polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene glycols other than the carboxyl group-containing dioli compound, or these Mixtures and the like can be used.

 [0061] Examples of polyether polyols include polymers or copolymers such as ethylene oxide, propylene oxide, or tetrahydrofuran.

[0062] Examples of polyester polyols include ethylene glycol, 1,2 propanediol, 1,3 propanediol, 1,3 butanediol, 1,4 butanediol, neopentyl glycol, pentanediol, 3-methyl-1, 5 Pentanediol, hexanediol, octanediol, 1,4-butylene diol, diethyleneglycol Saturated or unsaturated low molecular weight diols such as diethylene diol, triethylene glycol, dipropylene glycol or dimer diol and adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, To polyester polyols obtained by reacting dicarboxylic acids such as malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, or sebacic acid, or anhydrides thereof, to n-butyldaricidyl ether, or 2-ethyl It is obtained by reacting monocarboxylic acid glycidyl esters such as alkyl glycidyl ethers of xyl glycidyl ethers and glycidyl esters of versatic acid and anhydrides of the above dicarboxylic acids in the presence of hydroxyl-containing compounds such as alcohols. Polyester poly Lumpur compound, or a polyester polyol obtained by ring Esuterui 匕合 product by ring-opening polymerization.

[0063] Examples of polycarbonate polyols include:

 1) reaction product of diol or bisphenol and carbonate, or

 2) Reaction product obtained by reacting phosgene with diol or bisphenol in the presence of alkali

 Etc. can be used.

 [0064] Examples of the carbonate used in the case 1) include dimethyl carbonate, jetyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

[0065] Examples of the diol used in the above 1) or 2) include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2- Methyl-1,8 octanediol, 3,3,1 dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3 butanediol, 1,4 butanediol, 1,5 pentanediol, 1, 6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, 3,9bis (1, 1— Dimethyl-2-hydroxyethyl or 2, 2, 8, 10-te Examples include traoxospiro [5.5] undecane. [0066] The bisphenol used in the case of 1) or 2) is, for example, bisphenols such as bisphenol A and bisphenol F, and ethylene oxide or propylene oxide for these bisphenols. And a compound obtained by adding an alkylene oxide.

 [0067] Examples of the alkali used in the above case 2) include sodium hydroxide and lithium hydroxide.

 [0068] The number average molecular weight (Mn) of the polyol compound (a) is appropriately determined in consideration of the heat resistance, adhesive strength, solubility, etc. of the resulting polyurethane polyurethane resin (A). A force in the range of 0 to 5000 S is preferable, and more preferably, it is 1000 to 4000. When the Mn force is less than 1000, the number of urethane bonds in the polyurethane-polyurea resin (A) increases too much, and the flexibility of the polymer skeleton decreases and the adhesion to the polyimide film and conductive circuit tends to decrease. When Mn exceeds 5,000, the molecular weight between crosslink points tends to increase, and the solder heat resistance tends to decrease.

 [0069] The polyol compound (a) may be used alone or in combination of two or more. Further, within the range in which the adhesive performance of the polyurethane polyurethane resin (A) is not lost, a low molecular weight diol used as a part of the polyol compound (a), for example, a polyol compound used in the production of the polyol compound is not more than 00. Substantial amounts of various low molecular weight diols can be used instead.

 [0070] As the organic diisocyanate compound (b), for example, an aromatic diisocyanate, an aliphatic diisocyanate, an alicyclic isocyanate, or a mixture thereof can be used, and isophorone diisocyanate is particularly preferable. Better ,.

 Examples of the aromatic diisocyanate include 1,5 naphthylene diisocyanate, 4,4, -diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4 ' Monobenzil isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3 phenolic diisocyanate, 1,4 phenolic diisocyanate , Tolylene diisocyanate, xylylene diisocyanate and the like.

[0071] Examples of the aliphatic diisocyanate include butane 1,4-diisocyanate and hexane. Examples include methylene diisocyanate, 2, 2, 4 trimethylhexamethylene diisocyanate, and lysine diisocyanate.

 [0072] Examples of the alicyclic diisocyanate include, for example, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, norbornane diisocyanate methyl, bis (4 isocyanate cyclohexyl) methane, 1, 3 Bis (isocyanate methyl) cyclohexane, methylcyclohexane diisocyanate and the like.

 [0073] Examples of the diol compound (c) having a carboxyl group include dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolalkanoic acid such as dimethylolpentanoic acid, dihydroxysuccinic acid, or dihydroxybenzoic acid. Are listed. In particular, dimethylolpropionic acid or dimethylolbutanoic acid is preferred from the viewpoint of reactivity or solubility!

 [0074] The polyol compound (a), the organic diisocyanate (b), and the diol compound (c) having a carboxyl group are reacted to obtain a urethane prepolymer (d) having an isocyanate group. With respect to the total hydroxyl group of (a) and the diolic compound having a carboxyl group (c) and the isocyanate group of the organic diisocyanate (b), the ratio power of the isocyanate group Z hydroxyl group is in the range of 1.05Zl to l.50Z1. It is preferable to carry out the reaction within the range of 1.10Z1 ~: L. 45Z1. When the molar ratio of the isocyanate group Z hydroxyl group is less than 1.05Z1, the film formability may be reduced due to the small number of urea bonds contained in the polyurethane polyurethane resin (A). It is difficult to obtain a polyurethane polyurea resin having a weight average molecular weight necessary for exhibiting solder heat resistance.

Further, the ratio of the polyol compound (a) to the diol compound (c) having a carboxyl group is not particularly limited, but the molar ratio of the polyol compound (a) diol compound (c) having a Z carboxyl group is preferable. Is in the range of 95Z5 to 20Z80, more preferably in the range of 90Z10 to 35Ζ65. Polyol compound (a) If the molar ratio of the diol compound (c) having a Z carboxyl group exceeds 95Z5, the polyurethane polyurethane resin (A) and the epoxy resin (B) will be insufficiently crosslinked, resulting in reduced heat resistance. If it is less than 20Z80, the cross-linking between the polyurethane polyurethane resin (A) and the epoxy resin (B) becomes excessive, resulting in poor adhesion. There are things to do.

 [0075] The reaction can usually be performed at a temperature between room temperature and 150 ° C, and is preferably performed at a temperature between 60 and 120 ° C from the viewpoint of controlling the production time or side reaction.

 The weight average molecular weight of the obtained isocyanate group-containing urethane prepolymer (d) is preferably in the range of 1000 to 50000, more preferably 12000 to 40000. When M w is less than 10,000, it is difficult to obtain a polyurethane polyurea resin having a weight average molecular weight necessary for sufficient solder heat resistance to be exhibited. This is not preferable because the handling property is lowered due to the high viscosity.

The polyurethane polyurethane resin (A) is obtained by reacting a urethane prepolymer (d) having an isocyanate group, a polyamino compound (e), and a monoamino compound (f).

 The polyamino compound (e) functions as a chain extender, and includes, for example, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane. 4, 4'-diamin or norbornane diamine, 2- (2-aminoethylamino) ethanol, 2-hydroxyethylethylene diamine, 2-hydroxyethylpropylene diamine, di-2-hydroxyethylethylene diamine Alternatively, amines having a hydroxyl group such as di-2-hydroxypropylethylenediamine can also be used. Of these, isophorone diamine is preferably used.

 The monoamino compound (f) functions as a molecular weight modifier for polyurethane polyurethane resin, such as dialkylamines such as di-n-butylamine, dialkanolamines such as diethanolamine, ethanol or isopropyl alcohol, etc. Alcohols can be used.

[0077] The conditions for reacting the urethane prepolymer (d) having an isocyanate group, the polyamino compound (e), and the monoamino compound (f) are as follows: The free isocyanate group of the urethane prepolymer (d) Based on the amount, it is important that the total molar ratio of the amino groups of the polyamino compound (e) and the monoamino compound (f) is in the range of 0.8 to 0.999, preferably It is in the range of 85-0. When the total molar ratio of the amino groups is less than 0.8, the molecular weight of the polyurethane polyurethane resin cannot be increased sufficiently, and the solder heat resistance is not sufficient. When the total molar ratio is more than 0.999, the polyamino compound (e) And the monoamino compound (f) easily reacts with the epoxy resin in the adhesive composition, which is likely to remain unreacted, or exhibits catalytic activity, which decreases the storage stability of the adhesive composition, and is preferable. Absent.

[0078] Further Amino groups and monoamino compounds of the polyamino compound (e) out of the total 100 molar _^0/0 of the Amino group of (f), polyamino compounds Amino groups 90.0 mol% of (e) to 97. 0 mole ⁰ / a is important that _0, preferably 92.0 mole% to 96. range of 0 mol%. When the ratio of the amino group of the polyamino compound (e) is less than 90.0 mol%, it is difficult to obtain a polyurethane polyurea resin having a weight average molecular weight necessary for exhibiting sufficient solder heat resistance. If the ratio of the amino group of the polyamino compound (e) is more than 97.0 mol%, the viscosity of the adhesive composition is high and the handleability is lowered, and further, it remains unreacted as an amino compound. It is not preferable because it easily reacts directly with the epoxy resin in the adhesive composition, or exhibits catalytic activity and decreases the storage stability of the adhesive composition.

 [0079] The weight average molecular weight (Mw) of the polyurethane polyurethane resin (A) is important to be in the range of 80,000 to 250000, and preferably in the range of 90,000 to 200,000. When the weight average molecular weight is less than 80,000, the solder heat resistance is inferior, and when it exceeds 250000, the viscosity of the resin solution becomes high and the handling property is lowered, which is not preferable.

 [0080] The acid value of the polyurethane polyurethane resin (A) needs to be in the range of 3 to 25 mgKOHZg, preferably in the range of 7 to 20 mgKOH / g. The acid value is an acid value by a carboxy group and is based on the solid content of the polyurethane polyurethane resin (A). When the polyurethane polyurea resin (A) has an acid value of less than 3 mg KOH / g, the adhesive layer after curing due to insufficient crosslinking with the epoxy resin contained in the adhesive composition (I) The heat resistance of the solder is reduced and solder heat resistance is not exhibited. Also, when the acid value is larger than 25 mg KOHZg, it is excessively cross-linked with the epoxy resin contained in the adhesive composition (I), and the adherend, for example, a plastic film such as a polyimide film, a glass epoxy plate, or a metal The peel strength to the plate or the like decreases.

[0081] The amine value of the polyurethane polyurethane resin (A) is preferably in the range of 0 to 1.5 mgKOHZg, more preferably in the range of 0 to 1.2 mgKOHZg. Here, the amine value is necessary to neutralize the solid content lg of the polyurethane polyurethane resin (A). This is the number of mg of potassium hydroxide in the same mole as hydrochloric acid, and is proportional to the amount of unreacted polyamino compound (e) and monoamino compound (f) contained in the polyurethane polyurea resin. When the amine value is larger than 1.5 mg KOHZg, the unreacted polyamino compound (e) and the monoamino compound (f) react directly with the epoxy resin in the adhesive composition, or show catalytic activity. The storage stability of the adhesive composition is lowered, which is not preferable.

 The amine value is measured by the method shown below. That is, about 30 g of polyurethane polyurea resin solution is methanol / n-butanol Ztoluene = 40 mL / 20 mL / 40 mL (dissolved in a mixed solution, titrated with 0.1 N hydrochloric acid aqueous solution, and necessary for neutralization. Determine the amount of aqueous hydrochloric acid solution by converting the number of milligrams of potassium hydroxide in the same mole of hydrochloric acid and the same mole of hydrochloric acid in this aqueous hydrochloric acid solution to the lg of polyurethane polyurethane resin solids, and the ammine value (mg KOH / g).

 [0082] Further, when the urethane prepolymer (d) having an isocyanate group (d) is reacted with the polyamino compound (e) and the monoamino compound (f) (ureaization), the reaction temperature is appropriately adjusted to sufficiently promote urea formation. Can be made. In general, isocyanate groups and amino groups are said to react quantitatively even at a reaction temperature of about 50 ° C. from around room temperature. However, when obtaining polyurethane polyurethane resins having a weight average molecular weight specified by the present invention, It is preferable that urea formation proceeds sufficiently at a higher reaction temperature. Preferably 70 to: L00 ° C, more preferably 75 ° C to 95 ° C. When the reaction temperature is less than 70 ° C., the ureaization reaction is difficult to complete, and an unreacted amino compound decreases the storage stability of the adhesive composition, which is not preferable. If the temperature exceeds 100 ° C, the isocyanate group may react with a functional group other than the amino group, which is not preferable.

 [0083] When the polyurethane polyurethane resin (A) is synthesized, for example, an ester solvent, a ketone solvent, a glycol ether solvent, an aliphatic solvent, an aromatic solvent, an alcohol solvent, a carbonate solvent, or Water isotonicity A single selected compound or a combination of two or more can be used as a solvent.

 Examples of the ester solvent include ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, and ethyl lactate.

Examples of ketone solvents include acetone, methyl ethyl ketone, and methyl isobutyl keto. Benzene, diisoptyl ketone, diacetone alcohol, isophorone, or cyclohexanone.

 [0084] Examples of the glycol ether solvent include ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl butyl alcohol, diethylene glycol mono vinyl styrene, diethylene glycol mono vinyl ether. Nore etherenole, propylene glycol monomethenore etherenole, propylene glycol nole monoethylenole ether, or acetates of these monoethers, diethers such as diethylene glycol dimethyl ether, or diethylene glycol jetyl ether.

 [0085] Examples of the aliphatic solvent include n-heptane, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, and the like.

 Examples of the aromatic solvent include toluene and xylene.

 Examples of the alcohol solvent include methanol, ethanol, 1 propanol, 2-propanol, 1-butanol, and cyclohexanol.

 Examples of the carbonate-based solvent include dimethyl carbonate, ethylmethyl carbonate, or di-n-butyl carbonate.

 [0086] Of the various solvents described above, those having a hydroxyl group cannot be used for obtaining a urethane prepolymer (d) having an isocyanate group. However, when the urethane prepolymer (d) having an isocyanate group (d), the polyamino compound (e) and the monoamino compound (f) are reacted (ureaized), a solvent having a hydroxyl group can be appropriately used. This is because the reaction between the amino group and the isocyanate group is much faster than the reaction between the hydroxyl group and the isocyanate group. When a urea bond is formed by the reaction between a hydroxyl group and an isocyanate group, the hydrogen bond becomes stronger, and the viscosity of the reaction solution increases remarkably rapidly. If a solvent having a hydroxyl group is used during urea formation, the increase in hydrogen bonds can be mitigated.

[0087] The epoxy resin (B) contained in the adhesive composition (I) of the present invention is a compound having an epoxy group and may be liquid or solid. Although not particularly limited, those having an average of two or more epoxy groups in one molecule can be preferably used. As the epoxy resin (B), for example, glycidyl ether type epoxy resin, An epoxy resin such as a glycidinoleamine type epoxy resin, a glycidyl ester type epoxy resin, or a cyclic aliphatic (alicyclic type) epoxy resin can be used.

[0088] Examples of the glycidyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, and cresolol novolac. Type epoxy resin, phenol novolac type epoxy resin, _a naphthol novolac type epoxy resin, bisphenol A type novolac type epoxy resin, dicyclopentagen type epoxy resin, tetrabromobisphenol type A epoxy Examples thereof include rosin, brominated phenol novolac epoxy resin, tris (glycidyloxyphenyl) methane, and tetrakis (glycidyloxyphenyl) ethane.

 [0089] Examples of the glycidylamine-type epoxy resin include tetraglycidinoresinaminodiphenylmethane, triglycidylvalaminophenol, triglycidylmetaaminophenol, and tetraglycidinoremetaxylylenediamine. Can be mentioned.

[0090] Examples of the glycidyl ester type epoxy resin include diglycidyl phthalate, diglycidyl hexahydrophthalate, and diglycidyl tetrahydrophthalate.

 Examples of the cycloaliphatic (alicyclic type) epoxy resin include epoxy cyclohexyl methylol, epoxy cyclohexane power noroxylate, and bis (epoxycyclohexenole) adipate.

 As the epoxy resin (B), one kind of the above compounds can be used alone, or two or more kinds can be used in combination.

 Epoxy resin (B) includes bisphenol A type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, tris (glycidyloxyphenol-from the viewpoint of high adhesion and heat resistance. E) It is preferable to use methane or tetrakis (glycidyloxyphenyl) ethane.

[0091] The adhesive composition (I) of the present invention preferably contains 5 parts by weight of LOO of epoxy resin (B) to 100 parts by weight of polyurethane polyurethane resin (A). More preferably, it contains ˜90 parts by weight. Solder heat resistance when the amount of epoxy resin (B) is less than 5 parts by weight Is difficult to express. If the epoxy resin is more than 100 parts by weight of (B), the adhesion to plastic films such as polyimide films and conductive circuits tends to decrease.

[0092] The adhesive composition (I) used in the present invention includes a reaction between the polyurethane polyurethane resin (A) and the epoxy resin (B), and a reaction between the epoxy resins (B). In order to promote the curing, a curing accelerator and / or a curing agent can be contained. Examples of the curing accelerator for epoxy resin (B) include tertiary amine compounds, phosphine compounds, or imidazole compounds, and examples of curing agents include dicyandiamide, carboxylic acid hydrazide, and acid anhydrides. Can be used.

 [0093] The tertiary amine compound as a curing accelerator includes, for example, triethylamine, benzyldimethylamine, 1,8-diazabicyclo (5.4.0) undecene-7, or 1,5-diazabicyclo (4.3.0). ) Nonen 5 etc. Examples of the phosphine compound include triphenylphosphine and tributylphosphine. Examples of the imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ferro-4-methylimidazole, 2,4-dimethylimidazole, and 2-phenylimidazole. Furthermore, the potential for improving storage stability, such as a type in which an imidazole compound and an epoxy resin are reacted to make it insoluble in a solvent, or a type in which an imidazole compound is encapsulated in a microcapsule There are curing accelerators, and among these, latent curing accelerators are preferred.

 [0094] Examples of the carboxylic acid hydrazide as the hardener include succinic hydrazide and adipic hydrazide. Examples of the acid anhydride include hexahydrophthalic anhydride, trimellitic anhydride, and the like.

 As these curing accelerators or curing agents, the above compounds may be used alone or in combination of two or more, and the total content thereof is 0.100 parts by weight of epoxy resin (B). A range of 1 to 30 parts by weight is preferred.

 [0095] The adhesive composition (I) of the present invention may contain a filler (C) for the purposes of soldering heat resistance, improving thermal conductivity, or controlling the fluidity of the adhesive.

Examples of the filler (C) include silica, alumina, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, titanium oxide, zinc oxide, antimony trioxide, Examples thereof include inorganic fillers such as magnesium oxide, talc, montmorillonite, kaolin, and bentonite, and metal fillers such as aluminum, gold, silver, copper, and nickel. Of these, silica, alumina, or aluminum hydroxide is preferable from the viewpoint of dispersibility. In particular, hydrophobic silica obtained by modifying silanol groups on the silica surface with halogenated silane can reduce water absorption and is suitably used in the adhesive composition of the present invention.

 [0096] The blending amount of the filler (C) is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the polyurethane polyurethane resin (A), and is 0.2 to 50 parts by weight. It is more preferable.

 [0097] The adhesive composition (I) of the present invention includes a silane coupling agent, a heat stabilizer, a pigment, a dye, and a tackifier within a range that does not deteriorate the adhesive strength, heat resistance, and storage stability. Fats, plasticizers, ultraviolet absorbers, antifoaming agents, leveling regulators and the like can be blended.

 Further, by using a heat stabilizer in combination, it is possible to impart more excellent solder heat resistance. As a heat stabilizer, for example, a hindered phenol, phosphorus (phosphite), lactone, hydroxylamine, or thio-based one can be used. Particularly, a hindered phenol heat stabilizer is effective. It is.

 Next, the adhesive sheet of the present invention will be described.

 The adhesive sheet of the present invention is an adhesive having a curable adhesive layer (Π) composed of the adhesive composition (I) of the present invention, that is, an uncured adhesive layer (Π), on the peelable sheet. It is a sheet. The curable adhesive layer (Π) carried on the first peelable sheet may be further coated with another peelable sheet (second peelable sheet). Adhesive sheet made of 2 layer structure of peelable sheet Z curable adhesive layer (Π) or 1 layer peelable sheet Z curable adhesive layer (Π) Z of 3 layer structure of Z second peelable sheet There is something.

[0099] In either case of the first peelable sheet or the second peelable sheet, the peelable sheet may be a flexible printed wiring board substrate, a glass epoxy plate, a stainless steel plate (for example, a SUS plate) or the like. There is no particular limitation as long as the adhesive layer (か ら) can be peeled off from the adhesive layer when it is bonded to the body. Plastic film such as polyester, polyolefin, polyimide, or polyamide, dalasin paper, or polyethylene laminated fine paper, etc. In addition, a silicone or a release agent containing a fluorine compound coated with a release agent can be used. [0100] The adhesive layer (II) is formed on at least one surface of the peelable sheet by a conventionally known method such as knife coating, die coating, lip coating, ronore coating, curtain coating, no coating, gravure printing, flexographic printing, dip coating. After applying the adhesive composition (I) of the present invention by spray coating, spin coating or the like, the adhesive composition (I) is not cured, that is, usually at 40 to 150 ° C. for 20 seconds to 60 minutes. It is manufactured by drying under the following conditions.

 In addition, the dry film thickness of the curable adhesive layer (5) is preferably 5 μm to 500 μm in order to exhibit sufficient adhesion and solder heat resistance and from the viewpoint of ease of handling. More preferably, it is 10 μm to 100 μm.

 Next, the reinforcing material with an adhesive layer for flexible printed wiring boards and the flexible printed wiring board with reinforcing materials of the present invention will be described.

 The reinforcing material with an adhesive layer according to the present invention is obtained by forming a curable adhesive layer (Π) formed from the above-mentioned adhesive composition (I) of the present invention on a reinforcing material.

 For example, the adhesive composition (I) is applied onto the reinforcing material by the method exemplified in the above method for producing a peelable sheet, and this is dried under the condition that the adhesive composition (I) is not cured. It can be dried to form a curable adhesive layer ().

 [0102] The flexible printed wiring board used in the present invention is not particularly limited. For example, the flexible printed wiring board has a conductive circuit on one surface, has a conductive circuit on both surfaces, and further has conductivity inside the conductive circuit. Those having a circuit may be mentioned. Also, the base film of the flexible printed wiring board is not particularly limited, and suitable ones are plastic films having insulating properties, flexibility, and heat resistance, such as polyimide, polyethylene terephthalate (PET), and poly-phenylene sulfide. , Polyethersulfone, polyetheretherketone, aramid, polycarbonate, polyarylate, wholly aromatic polyamide, or a liquid crystal polymer represented by wholly aromatic polyester. As the copper foil, electrolytic copper foil or rolled copper foil can be used.

[0103] Examples of the reinforcing material include glass epoxy plates, metal plates such as aluminum or stainless steel (for example, SUS), and plate-like members such as polyimide plates. The thickness of the reinforcing material is preferably about 20 to 5000 μm as long as it can provide a reinforcing function for the flexible printed circuit board! [0104] The flexible printed wiring board with a reinforcing material of the present invention uses a glass epoxy board, a metal plate, or a flexible printed wiring board using the adhesive composition (I) of the present invention or the adhesive sheet of the present invention. A reinforcing material such as a polyimide plate is bonded and fixed by operations such as heat laminating, heat pressing, and Z or thermosetting alone or in combination.

 [0105] Fig. 1 is a cross-sectional view schematically showing a structure of one embodiment of a flexible printed wiring board with a reinforcing material of the present invention. That is, the flexible printed wiring board 10 with the reinforcing material includes the flexible printed wiring board 11 and the reinforcing material 12. The flexible printed wiring board 11 carries the conductive circuit 2 on the surface of one side of the insulating base film 1. The reinforcing material 12 is bonded and fixed to a part of the surface (back surface) 1 la opposite to the surface on which the conductive circuit 2 is supported of the base film 1 via the cured adhesive layer 4. The reinforcing material 12 can also be fixed to the entire back surface 1 la of the flexible printed wiring board 11.

 [0106] The flexible printed wiring board with a reinforcing material can be obtained by various methods.

 For example, after applying the adhesive composition (I) on the reinforcing material as described above and drying it to provide a curable adhesive layer (Π) to produce a reinforcing material with a curable adhesive layer, The curable adhesive layer (Π) of the reinforcing material with the adhesive layer and the portion of the flexible printed wiring board where the conductive circuit is not provided are heated while being in contact with each other, and after being adhered by being adhered, The curable adhesive layer (接着) can be cured by heating to obtain the flexible printed wiring board with a reinforcing material of the present invention.

 Alternatively, after the conductive circuit of the flexible printed wiring board is provided, the adhesive composition (I) is applied to the portion, and this is dried to provide the curable adhesive layer (、). The curable adhesive layer (Π) is heated while being in contact with the reinforcing material, or is heated after being brought into contact with the curable adhesive layer (Π) to cure the flexible print with the reinforcing material of the present invention. Get a circuit board.

 [0107] Further, the flexible printed wiring board with the reinforcing material can be obtained by using the adhesive sheet of the present invention.

That is, the curable adhesive layer (Π) of the adhesive sheet of the present invention having the curable adhesive layer (II) formed from the adhesive composition (I) on the peelable sheet is brought into contact with the reinforcing material. Next, peel off the peelable sheet with ヽ, and expose the exposed curable adhesive layer (Π) to the flexible printed circuit board. The conductive circuit is provided so that it can be heated while in contact with the part, or heated after being contacted,

 Or

 The curable adhesive layer (Π) of the adhesive sheet is brought into contact with the portion of the flexible printed wiring board where the conductive circuit is not provided, then the peelable sheet is peeled off, and the exposed curable adhesive layer (Π) is removed. It is possible to obtain the flexible printed wiring board with the reinforcing material of the present invention by heating while making contact with the reinforcing material or by heating after making it contact to cure the curable adhesive layer (硬化).

 [0108] Alternatively, from the adhesive sheet of the present invention in which the curable adhesive layer (II) formed from the adhesive composition (I) on the peelable sheet and another peelable sheet further laminated thereon One peelable sheet is peeled off, the exposed curable adhesive layer (Π) is brought into contact with the reinforcing material, the other peelable sheet is then peeled off, and the exposed curable adhesive layer (Π) is placed on the flexible print. Heat while in contact with the part of the circuit board where the conductive circuit is not provided, or heat it after making contact,

 Or

 One peelable sheet is peeled off from the adhesive sheet, and the exposed curable adhesive layer (Π) is provided with the conductive circuit of the flexible printed wiring board. The adhesive sheet is peeled off, and the exposed curable adhesive layer (Π) is heated while being brought into contact with the reinforcing material, or after being brought into contact, the curable adhesive layer (Π) is cured by heating. A flexible printed wiring board with a reinforcing material can also be obtained.

 The method for applying the adhesive composition (I) can be exemplified by the methods described in relation to the method for applying the adhesive sheet.

 [0109] In any of the above cases, when the reinforcing material is applied to the flexible printed wiring board, pressure can be applied after applying Z or the reinforcing material. More specifically, the flexible printed wiring board Z curable adhesive layer (Π) The laminate made of Z reinforcing material is passed between two heated rolls, or the laminate is hot pressed. In addition, the flexible printed wiring board and the reinforcing material can be bonded more firmly.

[0110] Further, after the flexible printed wiring board and the reinforcing material are bonded together, they are further heated and cured. Curing of the adhesive layer (π) can be further advanced.

 For example, by heating this curable adhesive layer (II) at 100 to 200 ° C. for about 30 minutes to 24 hours, the cured adhesive layer (III) can be obtained. The thickness of the cured adhesive layer (III) is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm.

 [Oil 1] The flexible printed wiring board with a reinforcing material obtained as described above is in a state in which the flexible printed wiring board and the reinforcing material are laminated via the cured adhesive layer (ΠΙ).

 Next, the plastic film with a curable adhesive layer and the flexible printed wiring board with a cover film of the present invention will be described.

 The plastic film with a curable adhesive layer of the present invention is preferably used for the production of a flexible printed wiring board with a cover film, and is peeled between the plastic film and the protective film. Inventive Adhesive Composition (I) A curable adhesive layer (i.e.) that is formed by a cover is sandwiched.

 [0113] The plastic film with a curable adhesive layer of the present invention is coated with the adhesive composition (I) on an unpeeled plastic film or a protective film by various methods, and dried to cure the plastic film. It can be obtained by forming an adhesive layer (Π) and superimposing a plastic film on the curable adhesive layer (Π) which has been treated with a protective film or peeled.

 As a method for applying the adhesive composition (I), the method exemplified above for the method for producing the peelable sheet can be used, and the curable adhesive layer (II) can be formed by drying in the same manner. It is formed.

 [0114] The plastic film is a cover film for covering the conductive circuit of the flexible printed wiring board. Examples of the plastic film that is not peeled off include plastic films such as polyester, polyolefin, polyimide, and polyamide, and a polyimide film is preferred.

[0115] Here, the protective film is for protecting the curable adhesive layer of the plastic film with the curable adhesive layer, and it may be peeled or not peeled. You can also. In other words, the protective film has a curable contact when the conductive circuit of the flexible printed wiring board is covered with a plastic film with a curable adhesive layer. As long as it can peel off the plastic film with an adhesive layer, various kinds of materials can be used even if they are not specially peeled off. For example, a plastic film such as polyester, polyolefin, polyimide, or polyamide coated with a release agent containing silicone or a fluorine compound can be used as the release treatment.

 [0116] The flexible printed wiring board with a cover film of the present invention is formed by curing the surface of the flexible printed wiring board having a conductive circuit on the surface thereof from the adhesive composition (I) of the present invention. It is peeled through the adhesive layer (ΠΙ) and covered with a new plastic film.

 [0117] Fig. 2 is a cross-sectional view schematically showing a structure of one embodiment of the flexible printed wiring board with a cover film of the present invention. In other words, the flexible printed wiring board 20 with the cover film is bonded and fixed to the plastic film (cover film) 6 on the surface of the flexible printed wiring board 5 that carries the conductive circuit 2 through the cured adhesive layer 4. Being! RU The flexible printed wiring board 5 carries the conductive circuit 2 on the surface of one side of the insulating base film 1 via the adhesive layer 4a.

 [0118] Such a flexible printed wiring board with a cover film can be obtained by various methods.

 For example, the protective film is peeled off from the plastic film with the curable adhesive layer of the present invention, and the exposed curable adhesive layer (Π) is electrically conductive on the flexible printed wiring board having a conductive circuit on the surface. The flexible printed wiring board with a cover film of the present invention can be obtained by heating while contacting the surface on the circuit side, or heating after contacting to cure the curable adhesive layer (II). it can.

 [0119] Further, the adhesive composition (I) of the present invention is applied to a plastic film that has not been subjected to a release treatment and dried to form a curable adhesive layer (Π), and then the curable adhesive layer. (Ii) is heated while being brought into contact with the surface of the flexible printed wiring board on the conductive circuit side, or heated after being brought into contact with the curable adhesive layer (II) to be cured. The flexible printed wiring board with a cover film of the invention can also be obtained.

[0120] Furthermore, an adhesive composition (I) is formed on the surface of the flexible printed wiring board on the conductive circuit side. After coating and drying to form a curable adhesive layer (Π), the curable adhesive layer (Π) is peeled off! Heated or brought into contact with the plastic film. The flexible printed wiring board with a cover film of the present invention can also be obtained by heating and then curing the curable adhesive layer (II).

 Examples of the method for applying the adhesive composition (I) include the methods described in connection with the method for applying the adhesive sheet.

 [0121] In any of the above cases, pressure can be applied when bonding the cover film and the surface of the flexible printed wiring board on the conductive circuit side, and after Z or bonding. More specifically, unexfoliated plastic film Z curable adhesive layer (

II) The cover film is more firmly attached to the flexible printed wiring board by passing the laminated body consisting of the flexible printed wiring board between two heated rolls or by hot pressing the laminated body. Can be attached.

 [0122] In addition, after the cover film is attached to the flexible printed wiring board, it can be further heated to further cure the curable adhesive layer (II).

 For example, the curable adhesive layer (II) can be obtained by heating the curable adhesive layer (II) at 100 to 200 ° C. for about 30 minutes to 24 hours. The thickness of the cured adhesive layer (III) is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm.

[0123] The flexible printed wiring board with a cover film obtained as described above is in a state where the cover film and the conductive circuit side of the flexible printed wiring board are bonded to each other via the cured adhesive layer (III). .

Next, a printed wiring board formed by laminating a plurality of conductive circuit layers of the present invention will be described.

 The printed wiring board used for constituting each layer of the printed wiring board formed by laminating a plurality of conductive circuit layers of the present invention has a conductive circuit only on one surface, both sides And those having a conductive circuit. In addition, it is preferable to use a flexible printed wiring board that uses a flexible plastic film as an insulating substrate in order to reduce the thickness and weight and to provide flexibility.

[0125] Next, with respect to the printed wiring board of the present invention in which a plurality of conductive circuit layers are laminated, This will be described with reference to FIGS. The printed wiring board of the present invention in which a plurality of conductive circuit layers are laminated is a printed wiring board having a conductive circuit on one surface of an insulating substrate, or a printed wiring having a conductive circuit on both surfaces of an insulating substrate. A plate is laminated using the adhesive composition (I). Fig. 4 shows a printed wiring board (hereinafter referred to as a single-sided printed wiring board) 41 having a conductive circuit 2 on one surface of a base film 1 as an insulating substrate, and Fig. 5 shows both of the base film 1 as an insulating substrate. 1 shows a printed wiring board (hereinafter, double-sided printed wiring board) 51 having conductive circuits 2 and 2 on its surface.

[0126] [1] in FIG. 3 shows that the surface of the first single-sided printed wiring board 41 on the conductive circuit side and the surface of the second single-sided printed wiring board 41 on the conductive circuit side are an adhesive composition. It schematically shows the state of being laminated and laminated via the hardened adhesive layer 4 formed from (I).

[0127] [2] in FIG. 3 is a curing in which one surface of the double-sided printed wiring board 51 and the surface of the single-sided printed wiring board 41 on the conductive circuit side are formed from the adhesive composition (I). A state in which the layers are bonded and laminated via the adhesive layer 4 is schematically shown.

 [0128] [3] in FIG. 3 shows that the surface on the conductive circuit side of the first single-sided printed wiring board 41 is bonded to the surface of the second single-sided printed wiring board 41 on which the conductive circuit is not provided. 1 schematically shows a state in which they are bonded and laminated via a cured adhesive layer 4 formed from the agent composition (I).

 [0129] In [4] of FIG. 3, the conductive circuit of one side of the double-sided printed wiring board 51 and the single-sided printed wiring board 41 is provided! / Cunning! FIG. 2 schematically shows a state in which the heel surface is bonded and laminated via a cured adhesive layer 4 formed from the adhesive composition (I).

 [0130] FIG. 3 [5] shows that one surface of the first double-sided printed wiring board 51 and one surface of the second double-sided printed wiring board 51 are formed from the adhesive composition (I). FIG. 2 schematically shows a state in which they are bonded and laminated through a cured adhesive layer 4 to be laminated.

[0131] [6] in FIG. 3 shows the surface of the first single-sided printed wiring board 41 that is not provided with the conductive circuit and the surface of the second single-sided printed wiring board 41 that is not provided with the conductive circuit. FIG. 2 schematically shows a state in which they are bonded and laminated via a cured adhesive layer 4 formed from the adhesive composition (I). In FIG. 3, depending on the type of printed wiring board to be laminated, there may or may not be an adhesive layer between the insulating substrate (base film) of each printed wiring board and the conductive circuit. A certain force In FIGS. 3 to 5, the illustration of the adhesive layer between the insulating substrate of the printed wiring board and the conductive circuit is omitted.

 [0132] The laminates of the embodiments of [1] to [6] in Fig. 3 may be laminated in any combination via the cured adhesive layer (III) to form a multilayer laminate. .

 [0133] A printed wiring board obtained by laminating a plurality of conductive circuit layers according to the present invention is a method using the adhesive sheet of the present invention, and a printed wiring board provided with the adhesive composition (I) for lamination. It can be obtained by various methods such as a coating method.

 [0134] First, the adhesive sheet of the present invention in which a curable adhesive layer (Π) made of the adhesive composition (I) is laminated on a peelable sheet and another peelable sheet is further laminated thereon is used. A method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated will be described.

 [0135] One peelable sheet is peeled off from the adhesive sheet, and the exposed curable adhesive layer (Π) is brought into contact with the surface on the conductive circuit side of the first single-sided printed wiring board 41, and then the other peelable sheet is peeled off. The adhesive sheet was peeled off, and the surface of the second single-sided printed wiring board 41 on the conductive circuit side was attached to the exposed curable adhesive layer (II) for attachment, and Z or contact was applied. Thereafter, by heating, a printed wiring board having a plurality of conductive circuit layers in the laminated state of [1] in FIG. 3 can be obtained.

[0136] The printed wiring board in which a plurality of conductive circuit layers in the laminated state of [2] in Fig. 3 is laminated is peeled off from the adhesive sheet, and one of the peelable sheets is peeled off, and the exposed curable adhesive layer (Π ) Is brought into contact with one surface of the double-sided printed wiring board 51, and then the other peelable sheet is peeled off, and the surface of the single-sided printed wiring board 41 on the conductive circuit side is exposed to the exposed curable adhesive layer (層). After making contact and sticking, and Z or making contact and sticking, it is heated, or one peelable sheet is peeled off from the adhesive sheet, and the exposed curable adhesive layer (II) is removed. Then, contact the surface of the single-sided printed wiring board 41 on the conductive circuit side, and then peel off the other peelable sheet, and then contact one surface of the double-sided printed wiring board 51 to the exposed curable adhesive layer (II). , And Z, or after contact and pasting, add heat It can be obtained by this fact.

 [0137] In the laminated state of [3] in Fig. 3, the printed wiring board in which a plurality of conductive circuit layers are laminated is peeled off one peelable sheet from the adhesive sheet, and the exposed curable adhesive layer (Π ) In contact with the surface of the first single-sided printed wiring board 41 on the side of the conductive circuit, and then peel off the other peelable sheet and apply the second single-sided printed layer to the exposed curable adhesive layer (II). While touching and pasting the surface of the wiring board 41 where the conductive circuit is not provided, and Z or contacting and pasting, heating,

 Alternatively, one peelable sheet is peeled off from the adhesive sheet, and the exposed curable adhesive layer (II) is brought into contact with the surface of the first single-sided printed wiring board 41 where the conductive circuit is not provided, and then Peel off the other peelable sheet and contact the surface of the conductive circuit side of the second single-sided printed wiring board 41 with the exposed curable adhesive layer (Π), and Z or contact It can be obtained by heating after sticking.

[0138] In the printed circuit board in which a plurality of conductive circuit layers in the laminated state of [4] in Fig. 3 are laminated, one peelable sheet is peeled off from the adhesive sheet, and the exposed curable adhesive layer (Π ) Is brought into contact with one surface of the double-sided printed wiring board 51, and then the other peelable sheet-like substrate is peeled off, and the conductive circuit of the single-sided printed wiring board 41 is placed on the exposed curable adhesive layer (Π). In this case, the surface is brought into contact and stuck, and after Z or brought into contact and stuck, it is heated,

 Alternatively, one peelable sheet is peeled off from the adhesive sheet, and the exposed curable adhesive layer (II) is brought into contact with the surface of the single-sided printed wiring board 41 where the conductive circuit is not provided, and then the other peelable sheet is peeled off. The adhesive sheet is peeled off, and one surface of the double-sided printed wiring board 51 is brought into contact with and adhered to the exposed curable adhesive layer (Π), and after Z is brought into contact with and adhered, heating is performed. Can be obtained.

[0139] The printed wiring board in which a plurality of conductive circuit layers in the laminated state of [5] in Fig. 3 is laminated is peeled off one release sheet from the adhesive sheet, and the exposed curable adhesive layer (Π ), No. Contact one surface of one double-sided printed wiring board 51, then peel off the other peelable sheet with, and expose one surface of second double-sided printed wiring board 51 to the exposed curable adhesive layer (II). It can be obtained by heating while making the surface contact and Z, or after contacting and sticking.

[0140] In the laminated state of [6] in FIG. 3, the printed wiring board in which a plurality of conductive circuit layers are laminated is peeled off one release sheet from the adhesive sheet, and the exposed curable adhesive layer (層) Is provided with the conductive circuit of the first single-sided printed wiring board 41, and is brought into contact with the surface, and then the other peelable sheet is peeled off, and the exposed curable adhesive layer (Π) The surface of the second single-sided printed wiring board 41 that is not provided with the conductive circuit can be obtained by heating it after making it contact and sticking, and Z or making it contact and sticking.

[0141] The printed wiring board having a plurality of conductive circuit layers in the laminated state shown in [1] to [6] in FIG. 3 is obtained by applying the adhesive composition (I) of the present invention on the printed wiring board. It can also be obtained by application.

 [0142] For example, the printed wiring board in which a plurality of conductive circuit layers in the stacked state of [1] in FIG. 3 is laminated is bonded to the surface of the first single-sided printed wiring board 41 on the conductive circuit side. The coating composition (I) is applied and dried to form a curable adhesive layer (Π). The curable adhesive layer (Π) is coated with the second single-sided printed wiring board 41 on the conductive circuit side. It can be obtained by heating with the surface being brought into contact and Z, or after being brought into contact with and stuck.

 [0143] The printed wiring board in which a plurality of conductive circuit layers in the laminated state of [2] in FIG. 3 is laminated is obtained by applying the adhesive composition (I) to one surface of the double-sided printed wiring board 51. And dry to form a curable adhesive layer (Π), and adhere to the curable adhesive layer (Π) with the conductive circuit side surface of the single-sided printed wiring board 41 in contact with and Z Or after contacting and sticking, heating,

Alternatively, the adhesive composition (I) is applied to the conductive circuit side of the single-sided printed wiring board 41 and dried to form a curable adhesive layer (Π), and the curable adhesive layer (Π) While touching and sticking one surface of the double-sided printed wiring board 51, and Z or touching and sticking, It can be obtained by burning heat.

 [0144] The printed wiring board in which a plurality of conductive circuit layers in the stacked state of [3] in FIG. 3 is laminated is formed on the surface of the first single-sided printed wiring board 41 on the side of the conductive circuit. (I) is applied and dried to form a curable adhesive layer (Π), and the conductive circuit of the second single-sided printed wiring board 41 is provided on the curable adhesive layer (Π). While touching and sticking the non-surface, and Z or touching and sticking, heating,

 Alternatively, the conductive circuit of the first single-sided printed wiring board 41 is provided, and the adhesive composition (I) is applied to the surface and dried to form a curable adhesive layer (Π). The surface of the conductive circuit side of the second single-sided printed wiring board 41 is brought into contact with the curable adhesive layer (Π) and stuck, and Z is brought into contact with and stuck, and then heated. Can be obtained.

 [0145] The printed wiring board in which a plurality of conductive circuit layers in the laminated state of [4] in FIG. 3 is laminated is obtained by applying the adhesive composition (I) to one surface of the double-sided printed wiring board 51. And drying, forming a curable adhesive layer (Π), and contacting the curable adhesive layer (Π) with the surface on which the conductive circuit of the single-sided printed wiring board 41 is not provided in contact with the curable adhesive layer (Π). , And Z, or after touching and sticking, heating,

 Alternatively, the adhesive composition (I) is applied to the surface of the single-sided printed wiring board 41 on which the conductive circuit is not provided, and dried to form a curable adhesive layer (Π), and the curable adhesive It can be obtained by heating the layer (II) with one surface of the double-sided printed wiring board 51 being brought into contact with the layer (II) and Z or being brought into contact with the layer and then heating.

[0146] The printed wiring board in which a plurality of conductive circuit layers in the laminated state of [5] in FIG. 3 is laminated on one surface of the first double-sided printed wiring board 51 is the adhesive composition (I) Applying and drying to form a curable adhesive layer (Π), with one surface of the second double-sided printed wiring board 51 in contact with the curable adhesive layer (Π) , And Z or after contacting and sticking, it can be obtained by applying heat. [0147] The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [6] in FIG. 3 is bonded to the surface of the first single-sided printed wiring board 41 where the conductive circuit is not provided. The coating composition (I) is applied and dried to form a curable adhesive layer (Π). The conductive circuit of the second single-sided printed wiring board 41 is provided on the curable adhesive layer (Π). It can be obtained by heating while touching the surface not touched and Z or touching and sticking.

 The method for applying the adhesive composition (I) can be exemplified by the methods described in relation to the method for applying the adhesive sheet.

[0148] Further, the printed wiring board having a plurality of conductive circuit layers has the curable adhesive layer (Π) made of the adhesive composition (I) on the peelable sheet, and the adhesive sheet of the present invention. It can be obtained by using.

 For example, a printed wiring board in which a plurality of conductive circuit layers in the laminated state shown in [1] of FIG. 3 are laminated is provided with a curable adhesive layer (上 の) on an adhesive sheet on a first side. The printed circuit board 41 is brought into contact with the surface of the conductive circuit side, and then the release sheet is peeled off. The exposed curable adhesive layer (Π) is exposed to the surface of the second single-sided printed circuit board 41 on the conductive circuit side. It can be obtained by contacting and sticking, and by heating after Z or contacting and sticking.

 [0149] The printed wiring board in which a plurality of conductive circuit layers in the laminated state of [2] in FIG. 3 are laminated is provided with a curable adhesive layer (Π) on the adhesive sheet, and a double-sided printed wiring board 51. Contact with one surface, then peel off the peelable sheet, and contact the surface of the conductive circuit side of the single-sided printed wiring board 41 to the exposed curable adhesive layer (Π), and Z Or after touching and sticking, heating,

Alternatively, the curable adhesive layer (Π) on the adhesive sheet is brought into contact with the conductive circuit side surface of the single-sided printed wiring board 41, and then the peelable sheet is peeled off to expose the exposed curable adhesive layer (II). In addition, it can be obtained by heating while making one surface of the double-sided printed wiring board 51 contact and sticking, and after Z or contacting and sticking. [0150] The printed wiring board in which a plurality of conductive circuit layers in the laminated state of [3] in FIG. 3 is laminated is a curable adhesive layer (Π) on the adhesive sheet, and the first single-sided printed wiring. Contact with the surface of the conductive circuit side of the board 41, then peel off the peelable sheet, and the exposed surface of the curable adhesive layer (II) where the conductive circuit of the second single-sided printed wiring board 41 is not provided While touching and sticking, Z or touching and sticking, heating,

 Alternatively, the adhesive layer (Π) on the adhesive sheet is brought into contact with the surface of the first single-sided printed wiring board 41 where the conductive circuit is not provided, and then the peelable sheet is peeled off to expose the hardened adhesive. The surface of the conductive circuit side of the second single-sided printed wiring board 41 is brought into contact with and adhered to the agent layer (Π), and Z is brought into contact with and adhered, and then heated. Can be obtained.

 [0151] The printed wiring board in which a plurality of conductive circuit layers in the laminated state of [4] in FIG. 3 is laminated is provided with an adhesive layer (Π) on the adhesive sheet and one side of the double-sided printed wiring board 51. Contact the surface, then peel off the peelable sheet, and contact the surface of the single-sided printed wiring board 41 that is not provided with the conductive circuit to the exposed curable adhesive layer (Π), and Z Or after contacting and sticking, heating,

 Alternatively, the adhesive layer (Π) on the adhesive sheet is brought into contact with the surface of the single-sided printed wiring board 41 where the conductive circuit is not provided, and then the peelable sheet is peeled off to expose the exposed curable adhesive layer ( In step (b), one surface of the double-sided printed wiring board 51 is brought into contact and stuck, and Z or is brought into contact and stuck, followed by heating.

[0152] The printed wiring board in which a plurality of conductive circuit layers in the laminated state of [5] in FIG. 3 is laminated is a curable adhesive layer (Π) on the adhesive sheet, and the first double-sided printed wiring While making contact with one surface of the board 51, then peeling off the peelable sheet, while making one surface of the second double-sided printed wiring board 51 contact and adhere to the exposed curable adhesive layer (II) , And Z or can be obtained by heating after contacting and sticking.

[0153] A printed wiring board in which a plurality of conductive circuit layers in the laminated state [6] in FIG. The curable adhesive layer (Π) on the adhesive sheet is brought into contact with the surface of the first single-sided printed wiring board 41 where the conductive circuit is not provided, and then the peelable sheet is peeled off to expose the hardenability. Heat the adhesive layer (Π) while contacting and pasting the surface of the second single-sided printed wiring board 41 that is not provided with the conductive circuit, and Z or contacting and pasting. It can be obtained by scooping.

In any of the above cases, pressure can be applied when each printed wiring board is bonded, and after Z or bonding. More specifically, the printed wiring board Z curable adhesive layer (II) The laminated body that also has Z printed wiring board force is passed between two heated rolls, or the laminated body is hot-pressed. Thus, it is possible to obtain a printed wiring board in which a plurality of conductive circuit layers are more firmly bonded and laminated.

 Further, after obtaining a printed wiring board obtained by laminating a plurality of conductive circuit layers, it can be further heated to further cure the curable adhesive layer (II).

 For example, by heating this curable adhesive layer (II) at 100 to 200 ° C. for about 30 minutes to 24 hours, the cured adhesive layer (III) can be obtained. The thickness of the cured adhesive layer (III) is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm.

 By setting the number of the printed wiring boards to be laminated to two or more, a large number of printed wiring boards are laminated through the cured adhesive layer (III).

 Example

 [0155] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the examples, parts and% mean parts by weight and% by weight, Mn means number average molecular weight, and Mw means weight average molecular weight.

 [0156] [Synthesis Example 1]

Polyester polyol obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol (Kuraray Co., Ltd.) was placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping device, and nitrogen introduction tube. “Kuraray polyol P-2011”, Mn = 2040] 195.2 parts, 6.67 parts dimethylolbutanoic acid, 40.7 parts isophorone diisocyanate, and 70.0 parts toluene, under nitrogen atmosphere React for 4 hours at 90 ° C, and add 250 parts of toluene to this. In addition, an isocyanate group-containing urethane prepolymer [Mw = 21,000, a polyol compound (a) and a hydroxyl group derived from a diol compound (c) having a carboxyl group, an isocyanate group derived from an organic diisocyanate (b) The molar ratio was 1.30].

 Next 【Iso, isophorone diamine 6. G n-Butanolamine 0. 59 咅 ^ 2—Prono Norole

112.5 parts and 184.5 parts of toluene Into a mixture of 54.5 parts of the above-mentioned urethane group-containing urethane prepolymer solution was added and reacted at 85 ° C. for 4 hours to obtain 63.0 parts of toluene. Diluted with 27.0 parts of 2-pronanol, polyurethane polyurethane resin [Mw = 110, 00 0, acid value = 10 lmg KOH / g, urethane prepolymer having isocyanate groups (d) Solution A-1 in which the molar ratio of the amino groups is 0.993, the ratio of the amino groups derived from the polyamino compound to the total amino groups is 94.0 mol%, the amine value is 0.85 mg ZKOH, and the solid content is about 25%. Obtained.

 [Synthesis Examples 2 to 5, 7 to 9, 13, and 16]

 Except that the raw materials shown in Table 1 were used, the reaction was carried out in the same manner as in Synthesis Example 1, and a polyurethane polyurea resin solution A— 2 to A— 5, A— 7 to A— 9, A— 13 and A — I got 16. The properties of the resulting polyurethane polyurethane resin were as shown in Table 2.

 [0158] [Synthesis Example 6]

 In the same reaction vessel as in Synthesis Example 1, terephthalic acid, adipic acid, 3-methyl-1,5-pentanediol and the resulting polyester polyol [Kuraray Co., Ltd. “Kuraray Polyol P — 2011”, Mn = 2040] 482 9 parts, 16.5 parts of dimethylolbutanoic acid, 100.6 parts of isophorone diisocyanate, and 70.0 parts of toluene were reacted at 90 ° C for 4 hours in a nitrogen atmosphere. Then, an isocyanate group-containing urethane prepolymer solution was obtained. The properties of the isocyanate group-containing urethane prepolymer obtained are shown in Table 2.

[Synthesis Example 10]

A reaction vessel similar to Synthesis Example 1 was charged with 13.30 parts of dimethylolbutanoic acid, 140.0 parts of isophorone diisocyanate, and 200.0 parts of toluene, and reacted at 90 ° C for 2 hours under a nitrogen atmosphere. And 120 parts of N, N-dimethylacetamide and isophorone diisocyanate added to the hydroxyl group of dimethylolbutanoic acid and isophorone diisocyanate. And a mixed solution was obtained.

 Next, isophorone diamine 74. G-n-butynoleamine 12. 56 咅 ^ 2-pronoanol In a mixture of 297 parts, isophorone diisocyanate was added to the hydroxyl group of the above dimethylolbutanoic acid. A mixed solution of the product and isophorone diisocyanate 426. 0 parts is slowly added, and the mixture is reacted at 50 ° C for 2 hours, followed by 70 ° C for 2 hours, and tonorene 63.0 0 ^^ 2-propanol Dilution with 27.0 parts gave a solution A-10 of a mixture of polyurethane polyurethane resin and polyurethane resin. The properties of the resulting mixture of rosin were as shown in Table 2. Since the solid content of A-10 was insoluble in tetrahydrofuran (THF), the weight average molecular weight was not measurable.

[0160] [Synthesis Example 11]

 In the same reaction vessel as in Synthesis Example 1, terephthalic acid, adipic acid, 3-methyl-1,5-pentanediol and the resulting polyester polyol [Kuraray Co., Ltd. “Kuraray Polyol P — 2011”, Mn = 2040] 7 parts, 5.96 parts of dimethylolbutanoic acid, 29.3 parts of isophorone diisocyanate, and 35.0 parts of toluene were reacted at 90 ° C for 10 hours in a nitrogen atmosphere. , 2—Prononol diluted with 55.0 parts to obtain a solution A-11 of polyurethane resin (Mw = 88,000, acid value = 10 OmgKOH / g, amine value 0 mgZKOH, solid content about 45%) Obtained.

[0161] [Synthesis Example 12]

 In the same reaction vessel as in Synthesis Example 1, terephthalic acid, adipic acid, 3-methyl-1,5-pentanediol and the resulting polyester polyol [Kuraray Co., Ltd. “Kuraray Polyol P — 2011”, Mn = 2040] 2 parts, 5.94 parts of dimethylolbutanoic acid, 29.8 parts of isophorone diisocyanate, and 35.0 parts of toluene were reacted at 90 ° C for 10 hours in a nitrogen atmosphere. , 2-Pronoanol 50.0 parts diluted with Polyurethane resin (Mw = 91, 000, acid value = 10. OmgKOH / g, amine value 0 mgZKOH, solid content approx. 45%) solution A-12 Obtained.

[0162] [Synthesis Example 14]

In the same reaction vessel as in Synthesis Example 1, terephthalic acid, adipic acid, 3-methyl-1,5-pentanediol and the resulting polyester polyol [Kuraray Co., Ltd. “Kuraray Polyol P — 2011 ”, Mn = 2040) 190. 1 part, dimethylolbutanoic acid 6.80 parts, isophorone diisocyanate 43.3 parts, and toluene 70.0 parts were charged in a nitrogen atmosphere at 90 ° C for 4 hours. Then, 250 parts of toluene was added thereto to obtain an isocyanate group-containing urethane prepolymer solution.

 Next, in the mixture of 7.96 parts of isophorone diamine, 0.91 part of di-n-butylamine, 112.5 parts of 2-propanol, and 184.5 parts of toluene, the above urethane group-containing urethane prepolymer solution 504. Add 1 part, react at 50 ° C for 2 hours, then react at 70 ° C for 2 hours, dilute with 63.0 parts toluene, 27.0 parts 2-pronanol, and polyurethane polyurethane A fat solution A-14 was obtained. The properties of the resulting polyurethane polyurethane resin were as shown in Table 2.

[0163] [Synthesis Example 15]

 A polyurethane polyurethane resin solution A-15 was obtained in the same manner as in Synthesis Example 14 except that the raw materials shown in Table 1 were used. The properties of the resulting polyurethane polyurethane resin were as shown in Table 2.

 [0164] The number average molecular weight (Mn) of the polyol compound and the weight average molecular weight (Mw) of the urethane prepolymer and the polyurethane polyurea resin are the number average molecular weight and the weight average molecular weight of polystyrene conversion determined by GPC measurement. The GPC measurement conditions are as follows.

 Equipment: Shodex GPC System—21 [made by Showa Denko Co., Ltd.]

 Column: A total of three columns, Shodex KF-802, KF-803L, KF-805L (Showa Denko Co., Ltd.) are used.

 Solvent: Tetrahydrofuran (THF)

 Flow rate: 1. OmL / mm

 Temperature: 40 ° C

 Sample concentration: 0.2% by weight

 Sample injection volume: 100 L

[0165] [Table 1]

Synthesis example 10: Mixture of polyurethane polyurea resin and polyurea resin Synthesis example 1 1, 1 2 _: Polyuretan tree

In Table 1, the abbreviations indicating the types of the polyol compound (a) have the following meanings.

P— 2011: Polyester polyol obtained from terephthalic acid, adipic acid and 3 methyl 1,5 pentanediol [Kuraray Co., Ltd. “Kuraray Polyol P— 2011”, Mn = 20 40]

 PTG 2000SN: Polyoxytetramethylene dalcole [Hodogaya Chemical Co., Ltd. “PTG-2000SN”, Mn = 2029]

 CD220: Polyhexamethylene carbonate diol (“Platacel CD220, Mn = 1965” manufactured by Daicel Chemical Industries, Ltd.)

[0167] [Table 2]

Synthesis example 10: Polyurethane polyurea resin and polyurea resin mixture Synthesis example 1 1, 12: Polyurethane resin

[Example 1]

 To 400 parts of polyurethane polyurethane resin solution A-1 obtained in Synthesis Example 1, tetrakis (glycidyloxyphenol) ethane [Japan Epoxy Resin Co., Ltd. “Epicoat 1031S”, epoxy equivalent = 180 parts by weight (220 to 220 gZeq) and 20 parts of a hydrophobic silica filler [Nipsil SS-50FJ] manufactured by Tosohichi Silica Co., Ltd. were mixed to obtain an adhesive composition.

 This adhesive composition was applied to a 75 μm thick polyimide film to a dry film thickness of 25 μm, dried at 80 ° C. for 2 minutes, and a curable adhesive layer (II) was laminated. A polyimide reinforcing material was produced.

 In addition, the adhesive composition was applied to a 25 μm-thick polyimide film (manufactured by Toray Industries, Inc., Kapton 100H) so that the dry film thickness was 25 μm, and dried at 80 ° C. for 2 min. A protective film (PET film peel-treated with silicone) was bonded to the surface of the coating to produce a cover film with a curable adhesive layer.

 Furthermore, the above adhesive composition is applied and dried on a polyester film which has been subjected to a release treatment so that the dry film thickness is 25 m, to form a curable adhesive layer (II), and another release treatment. The resulting polyester film was laminated to prepare an adhesive sheet in which the curable adhesive layer (Π) was sandwiched between the peelable sheet-like substrates.

[Examples 2-5, Comparative Examples 1-2, 5-12, 14-16]

 The adhesive composition and the curable adhesive layer (Π) were used in exactly the same manner as in Example 1 except that the types and amounts of polyurethane polyurethane resin, epoxy resin, and filler shown in Table 3 were used. ) With polyimide reinforcement, cover film with curable adhesive layer and adhesive sheet.

[0170] [Comparative Example 3]

Carboxyl group-containing tolyl butadiene rubber (Nippon Zeon Co., Ltd. “Nipol 1072JJ, bound acrylonitrile content 27.0%, mu-one viscosity 48) 100 parts, bisphenol A type epoxy resin (Japan epoxy resin) "Epicoat 828" manufactured by Co., Ltd., epoxy equivalent = 189 g Zeq] 200 parts, anhydrous silica filler ["Aerosil 300" manufactured by Nippon Aerosil Co., Ltd.], 2 parts, finely pulverized dicyandiamide [produced by Japan Epoxy Resin Co. “Epicure DICY7J” 1 4 parts, and imidazole-based curing accelerator (Ajinomoto Fine Techno Co., Ltd. “Amicure PN -40 "] 2 parts were mixed and dissolved in toluene to a solid content of 30% to prepare an adhesive composition. Using the obtained adhesive composition, a polyimide reinforcing material with a curable adhesive layer (付 き), a cover film with a curable adhesive layer, and an adhesive sheet were produced in exactly the same manner as in Example 1.

[0171] [Comparative Example 4]

 In the same reactor as in Synthesis Example 1, 95.0 parts of butyl acrylate, 5.0 parts of acrylic acid, 163.0 parts of ethyl acetate, and 0.06 part of 2,2, azobisisobutyoritol-tolyl are prepared. After the air in the reaction vessel was replaced with nitrogen gas, the reaction solution was heated to 80 ° C. and reacted for 9 hours in a nitrogen atmosphere with stirring. After completion of the reaction, 57 parts of toluene was added to obtain an acrylic resin solution having a solid content of 30.0%.

 In 133 parts of this acrylic resin solution, 10 parts of bisphenol A type epoxy resin “Epicoat 828”, 0.1 part of silica filler “Aerosil 300”, 0.7 part of finely ground dicyandiamide “Epiquia DICY7”, and imidazole An adhesive composition was obtained by blending 0.1 part of a system curing accelerator “Amicure PN-40”. Using the obtained adhesive composition, a polyimide reinforcing material with a curable adhesive layer (Π), a cover film with a curable adhesive layer, and an adhesive sheet were produced in the same manner as in Example 1.

[0172] [Comparative Example 5]

 20 parts of bisphenol A type epoxy resin (Epicoat 1001 manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent = 450-500 gZeq) to 167 parts of the urethane preforma resin solution obtained in Synthesis Example 6. 8 parts of diaminodiphenylsulfone [Wakayama Seika Kogyo "Seika Cure S"] and 30 parts of hydrophobic silica filler [Nipsil SS-50F] manufactured by Tosoh Silica Co., Ltd. A composition was prepared. Using the obtained adhesive composition, a polyimide reinforcing material with a curable adhesive layer (Π), a cover film with a curable adhesive layer, and an adhesive sheet were produced in exactly the same manner as in Example 1.

[Comparative Example 13]

To 400 parts of polyurethane polyurethane resin solution A-13 obtained in Synthesis Example 13, tetrakis (glycidyloxyphenol) ethane [Japan Epoxy Resin Co., Ltd. “Epico® 10313”, Epoxy equivalent = 180-220 ₈ 6) 10 parts, isophorone diamine 2.5 parts, And 20 parts of a hydrophobic silica filler (“Nipsil SS-50FJ” manufactured by Tosohichi Silica Co., Ltd.) were mixed to obtain an adhesive composition.

 This adhesive composition was applied to a 75 μm thick polyimide film to a dry film thickness of 25 μm, dried at 80 ° C. for 2 minutes, and a curable adhesive layer (II) was laminated. A polyimide reinforcing material was produced.

 In addition, the adhesive composition was applied to a 25 μm-thick polyimide film (manufactured by Toray Industries, Inc., Kapton 100H) so that the dry film thickness was 25 μm, and dried at 80 ° C. for 2 min. A protective film (PET film peel-treated with silicone) was bonded to the surface of the coating to produce a cover film with a curable adhesive layer.

 Furthermore, the above adhesive composition is applied and dried on a polyester film which has been subjected to a release treatment so that the dry film thickness is 25 m, to form a curable adhesive layer (II), and another release treatment. The resulting polyester film was laminated to prepare an adhesive sheet in which the curable adhesive layer (Π) was sandwiched between the peelable sheet-like substrates.

[0174] [Comparative Example 17]

 Except for using isocyanurate of hexamethylene diisocyanate (“Sumijour N3300” NCO% = 21.8%, manufactured by Sumika Bayer Urethane Co., Ltd.) instead of epoxy resin as the crosslinking agent In the same manner as in Example 1, an adhesive composition, a polyimide reinforcing material with a curable adhesive layer (II), a cover film with a curable adhesive layer, and an adhesive sheet were produced.

 [0175] [Comparative Example 18]

 Except for using alkylated melamine resin (“Cymel 303” manufactured by Mitsui Cytec Co., Ltd.) and curing catalyst (Catalyst 600 (0.5 phr against melamine resin)) as a crosslinking agent, instead of epoxy resin. In the same manner as in Example 1, an adhesive composition, a polyimide reinforcing material with a curable adhesive layer (Π), a cover film with a curable adhesive layer, and an adhesive sheet were prepared.

[Comparative Example 19]

Adhesive in exactly the same way as in Example 1 except that tris-2,4,6-(1-aziridyl) -1,3,5-triazine was used instead of epoxy resin as the crosslinking agent. Composition, cure A polyimide reinforcing material with a curable adhesive layer (π), a cover film with a curable adhesive layer, and an adhesive sheet were prepared.

 [0177] [Comparative Example 20]

 Except not using Epoxy Coat 1031S, which is an epoxy resin, exactly as in Example 1, adhesive composition, polyimide reinforcing material with curable adhesive layer (接着), cover film with curable adhesive layer, and An adhesive sheet was prepared.

[0178] [Table 3]

In Table 3, the abbreviations indicating the types of the crosslinking agents other than the epoxy resin (B), the filler (C), and the epoxy resin have the following meanings.

 EP1031S: Tetrakis (glycidyloxyphenyl) ethane, "Epicoat 1031S" manufactured by Japan Epoxy Resin Co., Ltd., Epoxy equivalent = 180-220g / eq

 EP152: Phenolic novolac type epoxy resin, Japan Epoxy Resin Co., Ltd. "Epi Coat 152", epoxy equivalent = 172 to 178 gZeq

 EP828: Bisphenol A type epoxy resin, "Epico 828" manufactured by Japan Epoxy Resin Co., Ltd., Epoxy equivalent = 189gZeq

 SS—50F: Hydrophobic silica filler, “Nipsil SS-50F” manufactured by Tosoh Silica Co., Ltd. R972: Hydrophobic silica filler, “AEROSIL R972” manufactured by Nippon Aerosil Co., Ltd. TAT: Trisou 2, 4, 6— (1 Ajirigi -Le) 1, 3, 5 Triadine

[0180] [Property evaluation]

 The following tests were conducted using the adhesive compositions obtained in Examples and Comparative Examples, a polyimide reinforcing material with a curable adhesive layer, a cover film with a curable adhesive layer, and an adhesive sheet.

 (1) Polyimide reinforcement with curable adhesive layer

 (1 1) Adhesive strength to polyimide film

 Bond the curable adhesive layer side of the polyimide reinforcing material with curable adhesive layer (II) and another polyimide film (film thickness 75 μm) using a thermal laminator with a roll temperature of 100 ° C. After that, heat press at 150 ° C, 1. OMPa, 2 min, and heat for 180 min in an electric oven at 150 ° C to obtain polyimide reinforcement Z cured adhesive layer (層) Ζ polyimide film stack. Produced. This laminate was cut to a width of 10 mm, and a 90 ° peel peel test was performed in an atmosphere with a relative humidity of 50% at 23 ° C and a pulling speed of 50 mmZmin to determine the adhesive strength (NZ cm).

[0181] (1 2) Adhesive strength to aluminum plate

After bonding the adhesive layer side of the polyimide reinforcement with curable adhesive layer (II) and the aluminum plate (thickness 100 μm, causticized) using a thermal laminator with a roll temperature of 100 ° C, Heat press at 150 ° C, 1. OMPa, 2min, 180 ° C in an electric oven at 150 ° C Heating for min, a laminate of polyimide reinforcing material Z cured adhesive layer (層) Ζ aluminum plate was produced. This laminate was cut to a width of 10 mm, and a 180 ° peel peel test was performed at a pulling speed of 50 mmZmin in an atmosphere of 23 ° C and 50% relative humidity to determine the adhesive strength (NZcm).

 [0182] (1 3) Adhesive strength after storage stability test

 A protective film (peeled PET film) is bonded to the curable adhesive layer of polyimide reinforcement with the above curable adhesive layer (層) and left in a constant temperature bath at 40 ° C for 30 days for protection. The film is peeled off, and the curable adhesive layer side and another polyimide film (film thickness 75 m) are bonded using a thermal laminator with a roll temperature of 100 ° C, then 150 ° C, 1.0 MPa, Heat-pressed for 2 minutes and heated in an electric oven at 150 ° C for 180 minutes to prepare a polyimide reinforcing material Z cured adhesive layer (ii) Z polyimide film laminate.

 This laminate was cut to a width of 10 mm, and a 90 ° peel peel test was performed at a pulling speed of 50 mmZmin in an atmosphere of 23 ° C and 50% relative humidity to determine the adhesive strength (NZcm) after the storage stability test. .

[0183] (1 4) Solder heat resistance after humidification

 Cut the laminate (measurement of adhesive strength to the aluminum plate) (polyimide reinforcement Z cured adhesive layer (III) laminate of Z aluminum plate) to a width of 10 mm and use purified water at 85 ° C for 3 hours. Immediately after immersion, the polyimide reinforcing material side was uniformly contacted with molten solder at 260 ° C for 1 minute. The appearance was visually observed, and the presence or absence of adhesion abnormality such as foaming, floating, and peeling of the adhesive layer was evaluated.

 ○: No adhesion abnormality.

 Δ: Some adhesion abnormality is observed.

 X: Abnormal adhesion.

 Table 4 shows the test results.

[0184] (2) Cover film with curable adhesive layer

 (2-1) Bond strength to roughened copper surface

Remove the protective film from the cover film with a curable adhesive layer, and use a thermal laminator with a roll temperature of 100 ° C on the matte surface of 35 μm thick electrolytic copper foil. Then, heat-pressing was performed under the conditions of 150 ° C, 1. OMPa, 2 min, and further heating for 180 min in an electric oven at 150 ° C to prepare an electrolytic copper foil with a cover film.

 Cut the above-mentioned electrolytic copper foil with cover film to a width of 10 mm, and perform an 1 80 ° peel peel test between the cover film and the electrolytic copper foil at 23 ° C and 50% relative humidity at a pulling speed of 50 mmZmin. Line! ヽ, bond strength (NZcm) was determined.

[0185] (2-2) Solder heat resistance after humidification

 The above-mentioned electrolytic copper foil with a cover film was cut to a width of 10 mm, immersed in purified water at 85 ° C for 3 hours, and immediately the cover film side was brought into contact with molten solder at 260 ° C for 1 minute. The appearance was visually observed and the presence or absence of adhesion abnormalities such as foaming, floating and peeling of the adhesive layer was observed.

 ○: No adhesion abnormality.

 Δ: Some adhesion abnormality is observed.

 X: Abnormal adhesion.

[0186] (2-3) Pattern embedding after storage stability test

 Cover film force with curable adhesive layer left in a constant temperature bath at 40 ° C for 30 days Flexible copper-clad laminate (line Z space 0.1 mm) with protective film removed and comb-shaped conductor pattern formed by subtractive method After laminating a curable adhesive layer using a thermal laminator with a roll temperature of 100 ° C, heat press at 150 ° C, 1.0MPa, 2min and heat in an electric oven at 150 ° C for 180min. Thus, a flexible copper clad laminate having a comb-shaped conductor pattern with a cover film was obtained. The filling property of the cover film adhesive layer into the comb-shaped conductor pattern portion was visually observed to check for the presence of voids.

 ○: No void.

 Δ: Slight voids are observed.

 X: Many voids are observed.

[0187] (2-4) Change in insulation resistance

A heat laminator with a roll temperature of 100 ° C is applied to a flexible copper-clad laminate (line Z space 0. lmm) with a comb-shaped conductor pattern peeled off by a subtractive method. Bond the curable adhesive layer using After that, heat press at 150 ° C, 1.0MPa, 2min, and heat for 180min in an electric oven at 150 ° C to obtain a flexible copper-clad laminate with comb-shaped conductor pattern with cover film It was. A flexible copper-clad laminate with a comb-shaped conductor pattern with a cover film was applied with a voltage of 24 V and lOOOHrs between the comb-shaped conductors in an atmosphere of 85 ° C. and 85% RH (relative humidity). We compared resistance values between comb-type conductors before and after voltage application in a humidified atmosphere.

 O: Ra / Rb≤10

 △: Ra / Rb> 10

 (Here, Ra represents a resistance value before voltage application, and Rb represents a resistance value after voltage application.)

 Table 5 shows the test results.

[0188] (3) Adhesive sheet

 (3-1) Bond strength to roughened copper surface

 Peel both peelable sheet-like substrates of the adhesive sheet (adhesive layer thickness 25 μm), and harden the adhesive layer with a 35 μm thick electrolytic copper foil matte surface and 50 μm thick It is sandwiched between polyimide films (Kapton 200EN), heat-laminated at a roll temperature of 100 ° C, hot-pressed at 150 ° C, 1.0 MPa, 2 min, and then heated in an electric oven at 150 ° C for 180 min. Thus, a laminated body comprising a mat surface Z-cured adhesive layer (m) Z polyimide film cover of the electrolytic copper foil was obtained.

 The laminate was cut to a width of 10 mm, and a 180 ° peel peel test was performed at a pulling speed of 50 mmZmin in an atmosphere with a relative humidity of 50% at 23 ° C. The bond strength (NZcm) was determined.

[0189] (3-2) Adhesive strength to copper glossy surface

Peel both peelable sheet-like substrates of the adhesive sheet (adhesive layer thickness 25 μm), and harden the adhesive layer with a glossy surface of 35 μm thick electrolytic copper foil and 50 μm thick It is sandwiched between polyimide films (Kapton 200EN), heat-laminated at a roll temperature of 100 ° C, then hot-pressed at 150 ° C, 1. OMPa, 2 min, and then heated in an electric oven at 150 ° C for 180 min. Glossy surface of electrolytic copper foil Z cured adhesive layer (III) Obtained.

 The laminate was cut to a width of 10 mm, and a 180 ° peel peel test was performed at a pulling speed of 50 mmZmin in an atmosphere with a relative humidity of 50% at 23 ° C. The bond strength (NZcm) was determined.

[0190] (3-3) Solder heat resistance after humidification

 Matte surface of the above electrolytic copper foil Z Curing adhesive layer (ΠΙ) A laminate made of Z polyimide film is cut to a width of 10 mm, immersed in purified water at 85 ° C for 3 hours, and immediately polyimide film The side was brought into contact with molten solder at 260 ° C for 1 minute. The appearance was visually observed, and the presence or absence of adhesion abnormality such as foaming, floating, and peeling of the adhesive layer was observed.

 ○: No adhesion abnormality.

 Δ: Some adhesion abnormality is observed.

 X: Abnormal adhesion.

[0191] (3-4) Pattern embedding after storage stability test

 A flexible comb-shaped conductor pattern is formed by peeling off both peelable sheet-like substrates of an adhesive sheet (adhesive layer thickness 25 μm) left in a constant temperature bath at 40 ° C for 30 days. After a curable adhesive layer is sandwiched between a copper-clad laminate (line Z space 0. lmm) and a polyimide film (Kapton 200EN) with a thickness of 50 μm and heat-laminated at a roll temperature of 100 ° C , 150 ° C, 1. OMPa, heat-pressed for 2 min and heated with 150 ° C electric oven for 180 min to obtain a flexible copper-clad laminate with a comb-shaped conductor pattern with polyimide film . The filling property of the adhesive layer into the comb-shaped conductor pattern was visually observed to check for the presence of voids.

 ○: No void.

 Δ: Slight voids are observed.

 X: Many voids are observed.

[0192] (3-5) Chemical resistance

The adhesive composition (I) obtained in each example and comparative example was applied to a tin plate so that the dry film thickness was 50 / zm, and cured by heating for 180 min in an electric oven at 150 ° C. The cured film was isolated by the mercury amalgam method. This cured film is applied with 10% NaOH aqueous solution, and The appearance after immersion in a 10% aqueous hydrochloric acid solution for 24 hours and the appearance after immersion in acetone for 3 hours were visually observed to evaluate whether there was swelling or dissolution.

 ○: No change.

 Δ: A slight change is observed.

 X: Obvious changes are observed.

 Table 6 shows the test results.

[Table 4]

[] []

[] Sffi0195 Industrial applicability

 The adhesive composition of the present invention can be suitably used for laminating flexible printed wiring boards and mounting cover films for protecting reinforcing materials and conductive circuits.

 As mentioned above, although this invention was demonstrated along the specific aspect, the deformation | transformation and improvement obvious to those skilled in the art are included in the scope of the present invention.

Claims

The scope of the claims  [1] A urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a polyol compound (c) having a carboxyl group, and a polyamino compound (e) And polyurethane resin (A) and epoxy resin (A) having a weight average molecular weight of 0000 to 250000 and an acid value of 3 to 25 mg KOH / g, obtained by reacting with a monoamino compound (f) under the following conditions: B) and an adhesive composition (1).  (i) Ratio power of isocyanate group of urethane prepolymer (d) having isocyanate group and amino group of polyamino compound (e) and monoamino compound (f) Amino group Z isocyanate group = 0.8Zl to 0.9999Z1 Molar ratio),  And,  (ii) The ratio of the amino group of the polyamino compound (e) is 90.0 to 97.0 mol% in the total of 100 mol% of the amino group of the polyamino compound (e) and the amino group of the monoamino compound (f). .  [2] Urethane prepolymer having an isocyanate group (d) force Ratio force between the hydroxyl group of the polyol compound (a) and the diol compound (c) having a ruboxyl group and the isocyanate group of the organic diisocyanate (b) Isocyanate group Z hydroxyl group The adhesive composition (I) according to claim 1, wherein the reaction is carried out in the range of = 1.05Zl to l.50Z1 (mol ratio). [3] The adhesive composition (1) according to claim 1 or 2, wherein the polyurethane polyol resin (A) has an amine value of 0 to 1.5 mgKOH / g.  [4] The number average molecular weight of the polyol compound (a) is 1,000 to 5,000, and the weight average molecular weight of the urethane prepolymer (d) is 10,000 to 50,000. The adhesive composition according to any one of (1)  [5] Polyurethane polyurethane resin (A) 100 parts by weight of epoxy resin (B) 5 to: L00 parts by weight, The resin composition according to any one of claims 1 to 4, Adhesive composition (1).  [6] The adhesive composition (1) according to any one of claims 1 to 5, comprising a filler (C). [7] Polyurethane polyurethane resin (A) 100 parts by weight of filler (C) 0.1 to: LOO parts by weight 7. The adhesive composition (I) according to claim 6, comprising: [8] An adhesive sheet having, on the peelable sheet, the curable adhesive layer (Π) having the adhesive composition (I) force according to any one of claims 1 to 7. [9] The adhesive sheet according to claim 8, further comprising another peelable sheet on the curable adhesive layer (接着).  [10] The adhesive layer for flexible printed wiring boards having the adhesive composition (I) force-formed curable adhesive layer ()) on the reinforcing material. With reinforcing material.  [11] A cured adhesive layer (ΠΙ) formed from the adhesive composition (I) according to any one of claims 1 to 7 on a portion of the flexible printed wiring board where the conductive circuit is not provided. ), A flexible printed wiring board with a reinforcing material, wherein the reinforcing material is fixed.  [12] A method for producing a flexible printed wiring board with a reinforcing material, wherein a reinforcing material is fixed to the flexible printed wiring board using the adhesive sheet according to claim 8 or 9. [13] On the reinforcing material, the adhesive composition (I) according to any one of claims 1 to 7 is applied, a curable adhesive layer (Π) is provided, and then the curable adhesive is provided. The adhesive layer (加熱) is heated while being brought into contact with and adhered to the portion of the flexible printed wiring board where the conductive circuit is not provided, and after being made to contact with Z or stuck and then heated. A method of manufacturing a flexible printed wiring board with a reinforcing material.  [14] A curable adhesive layer (II) comprising the adhesive composition (I) according to any one of V and Claims 1 to 7 between a plastic film not subjected to release treatment and a protective film. A plastic film with an adhesive layer.  [15] The cured adhesive formed from the adhesive composition (I) according to any one of claims 1 to 7, wherein the surface of the flexible printed wiring board having the conductive circuit on the surface thereof is on the conductive circuit side. A flexible printed wiring board with a cover film, which is covered with a plastic film which has not been subjected to a release treatment via a layer (III). [16] The plastic film with adhesive layer according to claim 14 may also be peeled off to remove the protective film. After sticking the curable adhesive layer (Π) that has been put out in contact with the surface of the flexible printed wiring board having the conductive circuit on the surface thereof on the side of the conductive circuit, and Z or in contact with it, A method for producing a flexible printed wiring board with a cover film, which comprises heating.  [17] The adhesive composition (I) according to any one of claims 1 to 7 is applied to one surface of a plastic film that has been subjected to a release treatment, and a curable adhesive layer (II Then, Z is applied to the curable adhesive layer (Π) while the surface of the flexible printed wiring board having the conductive circuit on the surface is brought into contact with and stuck to the curable adhesive layer (Π). A method for producing a flexible printed wiring board with a cover film, which is heated after being attached.  [18] The adhesive composition (I) according to any one of claims 1 to 7 is applied to the surface on the conductive circuit side of the flexible printed wiring board having the conductive circuit on the surface, and curable adhesion is performed. After forming the adhesive layer (Π) and then peeling off the curable adhesive layer (II) in the next step, the plastic film is brought into contact and stuck, and Z or is brought into contact and stuck The manufacturing method of the flexible printed wiring board with a cover film characterized by heating.  [19] Through the cured adhesive layer (III) formed from the adhesive composition (I) according to any one of claims 1 to 7,  The surface of the first single-sided printed wiring board (1) having a conductive circuit only on one surface and the surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface The surface of the conductive circuit is stuck together, or  One surface of the double-sided printed wiring board (2) having the conductive circuit on both sides is bonded to the surface on the conductive circuit side of the single-sided printed wiring board (1) having the conductive circuit only on one surface. Or  The surface of the first single-sided printed wiring board (1) having a conductive circuit only on one surface and the surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface A conductive circuit is provided, and the surface is bonded together, or There is provided a conductive circuit of one side of a double-sided printed wiring board (2) having a conductive circuit on both sides and a single-sided printed wiring board (1) having a conductive circuit only on one surface. The surface is stuck together, or  One surface of the first double-sided printed wiring board (2) having conductive circuits on both sides is bonded to one surface of the second double-sided printed wiring board (2) having conductive circuits on both sides Force or  The first single-sided printed wiring board (1) having the conductive circuit only on one surface is provided with the conductive circuit on the surface and the second single-sided print having the conductive circuit only on one surface. A printed wiring board formed by laminating a plurality of conductive circuit layers, wherein the conductive circuit of the wiring board (1) is provided and bonded to the surface. [20] One peelable sheet is peeled off from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (層) is removed.  Contact the conductive circuit side surface of the first single-sided printed wiring board (1) having the conductive circuit only on one surface, and then peel off the other peelable sheet,  Adhering the exposed curable adhesive layer (II) to the conductive circuit side surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, and Z Alternatively, a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, the method comprising heating after contacting and adhering. [21] One peelable sheet is peeled off from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (層) is removed.  Contact the conductive circuit side surface of the first single-sided printed wiring board (1) having the conductive circuit only on one surface, and then peel off the other peelable sheet,  The exposed curable adhesive layer (II) is provided with a conductive circuit of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, and the surface is brought into contact with the adhesive circuit (II). And let Z or contact and stick, then heat,  Or  One peelable sheet is peeled off from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (Π) is removed. A conductive circuit of the first single-sided printed wiring board (1) having a conductive circuit only on one surface is provided, which is brought into contact with the surface, and then the other peelable sheet is peeled off with Adhering the exposed curable adhesive layer (II) to the conductive circuit side surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, and Z Alternatively, a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, the method comprising heating after contacting and adhering. [22] One peelable sheet is peeled off from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (層) is removed.  Contact with the surface of the conductive circuit side of the single-sided printed wiring board (1) having a conductive circuit only on one surface, and then peel off the other peelable sheet,  After making one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides contact and stick to the exposed curable adhesive layer (Π), and Z or contact and sticking, Heating or  Or  One peelable sheet is peeled off from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (Π) is removed.  Make contact with one surface of the double-sided printed wiring board (2) that has conductive circuits on both sides, then! Remove the other peelable sheet with  The exposed curable adhesive layer (II) is attached to the surface of the conductive circuit side of the single-sided printed wiring board (1) having a conductive circuit only on one surface, and Z or contact. A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein the method comprises heating after sticking. [23] One peelable sheet is peeled off from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (層) is removed.  A conductive circuit of a single-sided printed wiring board (1) having a conductive circuit only on one surface is provided, contacted with the surface, and then the other peelable sheet is peeled off,  Double-sided printed wiring board with conductive circuit on both sides on exposed curable adhesive layer (Π) (2 ) While touching and sticking one surface of Z), or heating after Z or touching, Or One peelable sheet is peeled off from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (Π) is removed.  Make contact with one surface of the double-sided printed wiring board (2) that has conductive circuits on both sides, then! Remove the other peelable sheet with  While the surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface not provided with the conductive circuit is brought into contact with and adhered to the exposed curable adhesive layer (II), and A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein heating is performed after Z or contact and adhesion. [24] One peelable sheet is peeled off from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (層) is removed.  Contact with one surface of the first double-sided printed wiring board (2) having conductive circuits on both sides, and then peel off the other peelable sheet with  Adhering to the exposed curable adhesive layer (II) with one surface of the second double-sided printed wiring board (2) having conductive circuits on both sides in contact with Z, or with contact with Z A method for manufacturing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein heating is performed after the heating.  [25] One peelable sheet is peeled off from the adhesive sheet according to claim 9, and the exposed curable adhesive layer (層) is removed.  The first single-sided printed wiring board (1) having a conductive circuit only on one surface is provided with a conductive circuit, which is brought into contact with the surface, and then the other peelable sheet is peeled off with an exposed curing. The conductive adhesive layer (II) is provided with the conductive circuit of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, while the surface is brought into contact with the adhesive circuit (II). And a method of manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is performed after Z is brought into contact with and adhered. [26] The adhesive composition (I) according to any one of claims 1 to 7,  Apply to the surface on the conductive circuit side of the first single-sided printed wiring board (1) having a conductive circuit only on one surface to form a curable adhesive layer (Π), Next, a second piece having a conductive circuit only on one surface of the curable adhesive layer (II) The surface of the printed circuit board (1) on the side of the conductive circuit or the conductive circuit of the second single-sided printed circuit board (1) is provided. Alternatively, a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein heating is performed after contact and adhesion. [27] The adhesive composition (I) according to any one of claims 1 to 7,  It is applied to the surface of the single-sided printed wiring board (1) that has a conductive circuit only on one surface, on the conductive circuit side surface, and a curable adhesive layer (Π) is formed.  Next, after making one surface of a double-sided printed wiring board (2) having a conductive circuit on both sides contact and sticking to the curable adhesive layer (層) and Z or making contact and sticking, Heating or  Or  The adhesive composition (I) according to any one of claims 1 to 7,  Apply to one surface of double-sided printed wiring board (2) with conductive circuits on both sides to form a curable adhesive layer (Π)  Next, the surface of the conductive circuit side of the single-sided printed wiring board (1) having the conductive circuit only on one surface is brought into contact with and adhered to the curable adhesive layer (II), and Z or contact. A method for producing a flexible printed wiring board comprising a plurality of conductive circuit layers laminated, wherein the method comprises heating after touching and sticking. [28] The adhesive composition (I) according to any one of claims 1 to 7,  Apply to one surface of double-sided printed wiring board (2) with conductive circuits on both sides to form a curable adhesive layer (Π)  Then, the surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface, which is not provided with a conductive circuit, is brought into contact with and adhered to the curable adhesive layer (II), and A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein heating is performed after Z or contact and adhesion. [29] The adhesive composition (I) according to any one of claims 1 to 7, Apply to one surface of the first double-sided printed wiring board (2) with conductive circuits on both sides to form a curable adhesive layer (Π), Next, the surface of the second double-sided printed wiring board (2) having a conductive circuit on both sides is adhered to and adhered to the curable adhesive layer (II), and Z or contact is adhered. A method for manufacturing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein heating is performed after the heating.  [30] The adhesive composition (I) according to any one of claims 1 to 7,  It is applied to the surface of the first single-sided printed wiring board (1) having a conductive circuit only on one surface where no conductive circuit is provided, and a curable adhesive layer (層) is formed.  Next, the surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface of the curable adhesive layer (II) or the second single-sided printed wiring board. (1) A plurality of conductive circuit layers are laminated, wherein the surface on which the conductive circuit of (1) is not provided is brought into contact and stuck, and is heated after Z or contact and stuck. A method for producing a printed wiring board.  [31] The adhesive composition (I) according to any one of claims 1 to 7,  A conductive circuit of a single-sided printed wiring board (1) having a conductive circuit only on one surface is provided! It is applied to a small ヽ surface to form a curable adhesive layer (Π),  Next, after making one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides contact and sticking to the curable adhesive layer (Π) and Z or making contact and sticking, A method for producing a flexible printed wiring board comprising a plurality of conductive circuit layers laminated, wherein the method comprises heating. [32] The curable adhesive layer (Π) of the adhesive sheet according to claim 8,  Contact the conductive circuit side surface of the first single-sided printed wiring board (1) having a conductive circuit only on one surface, and then peel off the peelable sheet.  On the exposed curable adhesive layer (II), the surface on the conductive circuit side of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, or the second single-sided printed wiring board (1) The conductive circuit is provided, and while the surface is brought into contact and Z is applied, and after Z is brought into contact and attached, heating is performed,  Or The curable adhesive layer (Π) of the adhesive sheet according to claim 8, A conductive circuit of the first single-sided printed wiring board (1) having a conductive circuit only on one surface is provided, which is brought into contact with the surface, and then the peelable sheet is peeled off with  Adhering the exposed curable adhesive layer (II) to the conductive circuit side surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, and Z Alternatively, a method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, the method comprising heating after contacting and adhering.  [33] The curable adhesive layer (Π) of the adhesive sheet according to claim 8,  Contact with the surface of the conductive circuit side of the single-sided printed wiring board (1) having the conductive circuit only on one surface, and then peel off the peelable sheet,  After making one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides contact and stick to the exposed curable adhesive layer (Π), and Z or contact and sticking, Heating or  Or  The curable adhesive layer (Π) of the adhesive sheet according to claim 8,  Make contact with one surface of the double-sided printed wiring board (2) that has conductive circuits on both sides, then! Remove the peelable sheet with,  The exposed curable adhesive layer (II) is attached to the surface of the conductive circuit side of the single-sided printed wiring board (1) having a conductive circuit only on one surface, and Z or contact. A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein the method comprises heating after sticking. [34] The curable adhesive layer (Π) of the adhesive sheet according to claim 8,  A conductive circuit of a single-sided printed wiring board (1) having a conductive circuit only on one surface is provided, which is brought into contact with the surface, and then the peelable sheet is peeled off,  After making one surface of the double-sided printed wiring board (2) having a conductive circuit on both sides contact and stick to the exposed curable adhesive layer (Π), and Z or contact and sticking, Heating or  The curable adhesive layer (Π) of the adhesive sheet according to claim 8, Make contact with one surface of the double-sided printed wiring board (2) that has conductive circuits on both sides, then! , Remove the peelable sheet with  While the surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface not provided with the conductive circuit is brought into contact with and adhered to the exposed curable adhesive layer (II), and A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein heating is performed after Z or contact and adhesion.  [35] The curable adhesive layer (Π) of the adhesive sheet according to claim 8,  Make contact with one surface of the first double-sided printed wiring board (2) that has conductive circuits on both sides, and then peel off the peelable sheet with  Adhering to the exposed curable adhesive layer (II) with one surface of the second double-sided printed wiring board (2) having conductive circuits on both sides in contact with Z, or with contact with Z A method for manufacturing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein heating is performed after the heating. [36] The curable adhesive layer (Π) of the adhesive sheet according to claim 8,  A conductive circuit of the first single-sided printed wiring board (1) having a conductive circuit only on one surface is provided, which is brought into contact with the surface, and then the peelable sheet is peeled off with  The exposed curable adhesive layer (II) is provided with a conductive circuit of the second single-sided printed wiring board (1) having a conductive circuit only on one surface, and the surface is brought into contact with the adhesive circuit (II). A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein the heating is performed after Z and contact or pasting.