JP2007073737A - Printed wiring board having a plurality of conductive circuit layers - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printed wiring board laminating a plurality of conductive circuit layers and exhibiting good solder heat resistance, wherein an adhesive composition exhibiting excellent adhesion strength between a polyimide film used commonly as the substrate of a flexible printed wiring board and a conductive circuit surface, between the polyimide films, and between the conductive circuit surfaces, and also excellent storage stability, is employed. <P>SOLUTION: Urethane polymer (d) having a iosyanate group, obtained through reaction of a polyol compound (a), organic diisocynate (b), and a diol compound (c) having a carboxyl group, is made to react on a polyamino compound (e) to produce polyurethane poly urea resin (A) having an acid number of 3-25 mgKOH/g. A plurality of conductive circuit layers are laminated through a hardened adhesive layer (III) which is formed of an adhesive composition (I) containing the polyurethane poly urea resin (A), and epoxy resin (B), thereby obtaining a printed board. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a multilayer printed wiring board in which a plurality of conductive circuit layers are stacked on which a semiconductor integrated circuit (IC) or the like is mounted. In particular, the present invention relates to a multilayer printed wiring board in which a plurality of flexible printed wiring boards based on a plastic film such as polyimide or polyester are laminated, and a method for manufacturing the same.

In the process of producing a wiring board, various adhesives having excellent reliability, adhesive strength, heat resistance and the like are used. A printed wiring board, which is one of the wiring boards, is formed by providing a conductive circuit on a substrate by a printing method and is widely used.
Nowadays, as electronic devices are 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.
In order to mount an electronic component on a multilayer printed wiring board, the entire wiring board including a solder portion previously formed by printing or coating is heated to about 230 to 280 ° C. by infrared reflow or the like to melt the solder (solder reflow). The method is often adopted. In addition, a cover film is pasted so that a part of the conductive circuit of the multilayer printed wiring board is exposed or covered with a solder resist, and then the exposed conductive circuit part is contacted with molten solder The method of making it take is also taken.
Therefore, the adhesive layer used for the multilayer printed wiring board needs to have heat resistance that does not cause foaming / peeling due to solder reflow, and further, foaming / peeling etc. even when it comes into contact with molten solder. High heat resistance that does not occur is required.

  Multilayer printed wiring boards are a major component in the electronics field, where the market is growing rapidly, and their manufacturing and processing bases are scattered throughout the country. Therefore, a multilayer printed wiring board or a material used for manufacturing the multilayer printed wiring board is desired to have excellent storage stability with little property change even after transport and storage processes under various conditions.

  Most of the interlayer adhesive materials used in current multilayer printed wiring boards are thermosetting resin prepregs in which a glass cloth reinforcing material is impregnated with a thermosetting resin typified by an epoxy resin. However, in recent years, with the reduction in thickness and density of multilayer printed wiring boards, there is an increasing demand for interlayer adhesive materials that do not use reinforcing materials such as glass cloth in order to extremely narrow the interval between each printed wiring board to be laminated. .

  As an interlayer adhesive material that does not use such a reinforcing material, an adhesive composition that is molded into a sheet by adding an inorganic filler or the like to the adhesive composition used in the manufacture of a copper-clad laminate as required. Things are used. For example, an epoxy resin composition containing a flexible component such as acrylonitrile butadiene rubber is used in order to improve the peel strength using a mixture of an epoxy resin and an epoxy resin curing agent as a curing component (for example, Patent Document 1). Such an epoxy resin-based composition has high heat resistance and good substrate adhesion, but most of the composition is occupied by the epoxy resin and its curing agent, and the epoxy resin is in a semi-cured state (B stage) ) In many cases. Therefore, it needs to be stored at a low temperature, and has a problem of poor storage stability.

  Moreover, the acrylic resin type composition which mix | blended the epoxy resin as a hardening component using the acrylic resin for a base polymer is proposed (for example, refer patent document 2, patent document 3). These contain functional groups that can be cross-linked with epoxy resin in the acrylic resin, and since substantially no epoxy resin curing agent is used, a composition that has good storage stability and adheres well to metal materials is obtained. However, there is a problem that the solder heat resistance is not sufficient.

  In addition, a method of using a saturated polyester resin in combination for the purpose of relatively reducing the curing component contained in the adhesive composition, improving storage stability, and adjusting the degree of curing has been proposed, but solder heat resistance is reduced. (See Patent Documents 4 and 5).

  In addition, the main component of the adhesive composition is an epoxy resin, and an adhesive composition containing a urethane-based prepolymer composed of diol and diisocyanate and a diamine-based curing agent has excellent copper foil / polyimide adhesive strength, good It has been proposed to have solder heat resistance. In this adhesive composition, the diamine compound, which is a curing agent, reacts with both the epoxy resin and the urethane prepolymer to obtain good heat resistance, but the isocyanate group which is a functional group of the urethane prepolymer and the diamine curing agent It is highly reactive and it is difficult to achieve both storage stability and solder heat resistance (see Patent Document 6).

Furthermore, an adhesive composition containing a resin containing a urethane bond and / or a urea bond in the main chain and a thermosetting resin is disclosed (Patent Document 7). However, a resin containing a urethane bond and / or a urea bond in the main chain disclosed in Patent Document 7 does not have a functional group capable of crosslinking with an epoxy resin. Therefore, even if an epoxy resin is used as the thermosetting resin, no cross-linking occurs between the two resins, which is inferior in terms of solder heat resistance. In particular, the solder heat resistance after humidification is significantly reduced.
JP-A-4-370996 JP-A-9-316398 JP 2002-12841 A JP-A-6-330014 Japanese Unexamined Patent Publication No. 2000-273430 JP-A-8-32230 Japanese Patent Laid-Open No. 10-178066

  The present invention solves the problems of conventional interlayer adhesive materials, and is used as a polyimide film and a conductive circuit surface, a polyimide film and a polyimide film, and a conductive film, which are often used as a base material for flexible printed wiring boards. Provided is a printed wiring board in which a plurality of conductive circuit layers are laminated having a good soldering heat resistance, using an adhesive composition having excellent adhesive strength between conductive circuit surfaces and excellent in storage stability. With the goal.

The present invention comprises a urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group, and a polyamino compound (e). A cured adhesive layer formed from an adhesive composition (I) obtained by reacting and containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B) ( Through III)
Of the first single-sided printed wiring board (1) having the conductive circuit only on one surface and the second single-sided printed wiring board (1) having the conductive circuit only on one surface. The surface on the conductive circuit side is attached,
Whether the double-sided printed wiring board (2) having a conductive circuit on both sides and the conductive circuit side surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface are bonded together,
Of the first single-sided printed wiring board (1) having the conductive circuit only on one surface and the second single-sided printed wiring board (1) having the conductive circuit only on one surface. The surface where the conductive circuit is not provided is attached,
The double-sided printed wiring board (2) having a conductive circuit on both sides and the surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface are not attached,
Whether the first double-sided printed wiring board (2) having a conductive circuit on both sides and the second double-sided printed wiring board (2) having a conductive circuit on both sides are bonded together,
Or
A 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 second single-sided printed wiring board having a conductive circuit only on one surface ( It relates to a printed wiring board in which a plurality of conductive circuit layers are laminated to a surface on which a conductive circuit of 1) is not provided.

The present invention also provides a urethane prepolymer having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b), and a diol compound (c) having a carboxyl group between two peelable sheet-like substrates. Adhesive composition containing polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and epoxy resin (B) obtained by reacting polymer (d) with polyamino compound (e) One peelable sheet-like substrate is peeled from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II) formed from (I), and the exposed adhesive layer (II) is
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface on the conductive circuit side, and then the other peelable sheet-like substrate is peeled off,
After contacting and / or contacting the exposed adhesive layer (II) with the conductive circuit side surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface, The present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, which is characterized by heating.

The present invention also provides a urethane prepolymer having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b), and a diol compound (c) having a carboxyl group between two peelable sheet-like substrates. Adhesive composition containing polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and epoxy resin (B) obtained by reacting polymer (d) with polyamino compound (e) One peelable sheet-like substrate is peeled from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II) formed from (I), and the exposed adhesive layer (II) is
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface on the conductive circuit side, and then the other peelable sheet-like substrate is peeled off,
The exposed adhesive layer (II) is brought into contact with and / or brought into contact with the surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface where the conductive circuit is not provided. After heating or
Alternatively, one of the peelable sheet-like substrates is peeled off from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II) between two peelable sheet-like substrates, and the exposed adhesive layer (II) The
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface where the conductive circuit is not provided, and then the other peelable sheet-like substrate is peeled off,
After contacting and / or contacting the exposed adhesive layer (II) with the conductive circuit side surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface, The present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, which is characterized by heating.

The present invention also provides a urethane prepolymer having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b), and a diol compound (c) having a carboxyl group between two peelable sheet-like substrates. Adhesive composition containing polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and epoxy resin (B) obtained by reacting polymer (d) with polyamino compound (e) One peelable sheet-like substrate is peeled from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II) formed from (I), and the exposed adhesive layer (II) is
Contact the conductive circuit side surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface, and then peel off the other peelable sheet-like substrate,
The exposed adhesive layer (II) is heated while contacting and / or contacting the double-sided printed wiring board (2) having conductive circuits on both sides,
Alternatively, one of the peelable sheet-like substrates is peeled off from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II) between two peelable sheet-like substrates, and the exposed adhesive layer (II) The
Contact with a double-sided printed wiring board (2) having a conductive circuit on both sides, and then peel off the other peelable sheet-like substrate,
Heating the exposed adhesive layer (II) while contacting and / or contacting the surface on the conductive circuit side of the single-sided printed wiring board (1) having the conductive circuit only on one surface. And a method of manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated.

The present invention also provides a urethane prepolymer having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b), and a diol compound (c) having a carboxyl group between two peelable sheet-like substrates. Adhesive composition containing polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and epoxy resin (B) obtained by reacting polymer (d) with polyamino compound (e) One peelable sheet-like substrate is peeled from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II) formed from (I), and the exposed adhesive layer (II) is
Contact the surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface, where the conductive circuit is not provided, and then peel off the other peelable sheet-like substrate,
The exposed adhesive layer (II) is heated while contacting and / or contacting the double-sided printed wiring board (2) having conductive circuits on both sides,
Alternatively, one of the peelable sheet-like substrates is peeled off from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II) between two peelable sheet-like substrates, and the exposed adhesive layer (II) The
Contact with a double-sided printed wiring board (2) having a conductive circuit on both sides, and then peel off the other peelable sheet-like substrate,
After contacting and / or contacting the exposed adhesive layer (II) with the surface on which the conductive circuit of the single-sided printed wiring board (1) having the conductive circuit only on one surface is not provided, The present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, which is characterized by heating.

The present invention also provides a urethane prepolymer having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b), and a diol compound (c) having a carboxyl group between two peelable sheet-like substrates. Adhesive composition containing polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and epoxy resin (B) obtained by reacting polymer (d) with polyamino compound (e) One peelable sheet-like substrate is peeled from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II) formed from (I), and the exposed adhesive layer (II) is
Contact with the first double-sided printed wiring board (2) having a conductive circuit on both sides, and then peel off the other peelable sheet-like substrate,
The exposed adhesive layer (II) is heated while being in contact with and / or after contacting the second double-sided printed wiring board (2) having conductive circuits on both sides. The present invention relates to a method for manufacturing a printed wiring board in which conductive circuit layers are laminated.

The present invention also provides a urethane prepolymer having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b), and a diol compound (c) having a carboxyl group between two peelable sheet-like substrates. Adhesive composition containing polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and epoxy resin (B) obtained by reacting polymer (d) with polyamino compound (e) One peelable sheet-like substrate is peeled from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II) formed from (I), and the exposed adhesive layer (II) is
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface where the conductive circuit is not provided, and then the other peelable sheet-like substrate is peeled off,
The exposed adhesive layer (II) is brought into contact with and / or brought into contact with the surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface where the conductive circuit is not provided. Then, the present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated.

The present invention also provides a urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group, and a polyamino compound (e). And an adhesive composition (I) containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B).
Applying to the conductive circuit side surface of the first single-sided printed wiring board (1) having a conductive circuit only on one surface, forming an adhesive layer (II),
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 thereof on the adhesive layer (II), or the second single-sided printed wiring board (1 A printed circuit board having a plurality of laminated conductive circuit layers, wherein the surface is not contacted with a surface where the conductive circuit is not provided and / or is heated after contacting the surface. .

The present invention also provides a urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group, and a polyamino compound (e). And an adhesive composition (I) containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B).
Apply to the conductive circuit side surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface, and form the adhesive layer (II).
Next, the adhesive layer (II) is heated while contacting and / or contacting the double-sided printed wiring board (2) having conductive circuits on both sides,
Or
Applying the adhesive composition (I) to a double-sided printed wiring board (2) having a conductive circuit on both sides to form an adhesive layer (II),
Next, the adhesive layer (II) is heated after contacting and / or contacting the surface on the conductive circuit side of the single-sided printed wiring board (1) having the conductive circuit only on one surface. It is related with the manufacturing method of the flexible printed wiring board by which several electroconductive circuit layers are laminated | stacked characterized by these.

The present invention also relates to a urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group, and a polyamino compound (e). And an adhesive composition (I) containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B), and a conductive circuit on both sides. It is applied to the double-sided printed wiring board (2) that has the adhesive layer (II),
Next, after bringing the adhesive layer (II) into contact with and / or contacting the surface on which the conductive circuit of the single-sided printed wiring board (1) having the conductive circuit only on one surface is not provided, The present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, which is characterized by heating.

The present invention also provides a urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group, and a polyamino compound (e). And an adhesive composition (I) containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B).
It is applied to the first double-sided printed wiring board (2) having conductive circuits on both sides to form an adhesive layer (II),
Next, the adhesive layer (II) is heated while contacting and / or contacting the second double-sided printed wiring board (2) having conductive circuits on both sides, The present invention relates to a method for manufacturing a printed wiring board in which conductive circuit layers are laminated.

The present invention also provides a urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group, and a polyamino compound (e). And an adhesive composition (I) containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B).
Applying the first single-sided printed wiring board (1) having the conductive circuit only on one surface to the surface where the conductive circuit is not provided, forming the adhesive layer (II),
Next, a surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface on the adhesive layer (II) or the second single-sided printed wiring board (1). A method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein the surface on which the conductive circuit is not provided is brought into contact and / or is heated after contact. .

The present invention also provides a urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group, and a polyamino compound (e). And an adhesive composition (I) containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B).
It is applied to the surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface where no conductive circuit is provided, and an adhesive layer (II) is formed.
Next, the adhesive layer (II) is heated with the double-sided printed wiring board (2) having conductive circuits on both sides in contact with and / or after contact, and a plurality of conductive circuits The present invention relates to a method for manufacturing a flexible printed wiring board in which layers are laminated.

The present invention also provides a urethane prepolymer having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b), and a diol compound (c) having a carboxyl group on a peelable sheet-like substrate. An adhesive composition (I) obtained by reacting d) with a polyamino compound (e) and containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B) The adhesive layer (II) of the adhesive-carrying sheet (E) sheet-like adhesive composition provided with the adhesive layer (II) formed from
Contact with the surface on the conductive circuit side of the first single-sided printed wiring board (1) having a conductive circuit only on one surface, and then peel off the peelable sheet-like substrate,
On the exposed 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 Or) after contacting and / or contacting a surface not provided with a conductive circuit)
Alternatively, the adhesive layer (II) of the adhesive-carrying sheet (E) in which the adhesive layer (II) is provided on a peelable sheet-like substrate,
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface where the conductive circuit is not provided, and then the peelable sheet-like substrate is peeled off,
After contacting and / or contacting the exposed adhesive layer (II) with the conductive circuit side surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface, The present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, which is characterized by heating.

The present invention also provides a urethane prepolymer having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group on a peelable sheet-like substrate. An adhesive composition (I) obtained by reacting d) with a polyamino compound (e) and containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B) The adhesive layer (II) of the adhesive-carrying sheet (E) provided with the adhesive layer (II) formed from
Contact the conductive circuit side surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface, and then peel off the peelable sheet-like substrate.
The exposed adhesive layer (II) is heated while contacting and / or contacting the double-sided printed wiring board (2) having conductive circuits on both sides,
Alternatively, the adhesive layer (II) of the adhesive-carrying sheet (E) in which the adhesive layer (II) is provided on a peelable sheet-like substrate,
Contact with a double-sided printed wiring board (2) having a conductive circuit on both sides, then peel off the peelable sheet-like substrate,
Heating the exposed adhesive layer (II) while contacting and / or contacting the surface on the conductive circuit side of the single-sided printed wiring board (1) having the conductive circuit only on one surface. And a method of manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated.

The present invention also provides a urethane prepolymer having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group on a peelable sheet-like substrate. An adhesive composition (I) obtained by reacting d) with a polyamino compound (e) and containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B) The adhesive layer (II) of the adhesive-carrying sheet (E) provided with the adhesive layer (II) formed from
Contact with the surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface, which is not provided with the conductive circuit, and then peel off the peelable sheet-like substrate,
The exposed adhesive layer (II) is heated while contacting and / or contacting the double-sided printed wiring board (2) having conductive circuits on both sides,
Alternatively, the adhesive layer (II) of the adhesive-carrying sheet (E) in which the adhesive layer (II) is provided on a peelable sheet-like substrate,
Contact with a double-sided printed wiring board (2) having a conductive circuit on both sides, then peel off the peelable sheet-like substrate,
After contacting and / or contacting the exposed adhesive layer (II) with the surface on which the conductive circuit of the single-sided printed wiring board (1) having the conductive circuit only on one surface is not provided, The present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, which is characterized by heating.

Furthermore, the present invention provides a urethane prepolymer having an isocyanate group (d) obtained by reacting a polyol compound (a), an organic diisocyanate (b), and a diol compound (c) having a carboxyl group on a peelable sheet substrate. ) And a polyamino compound (e), and an adhesive composition (I) containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B) The adhesive layer (II) of the adhesive-carrying sheet (E) provided with the adhesive layer (II) formed from
Contact with the first double-sided printed wiring board (2) having a conductive circuit on both sides, and then peel off the peelable sheet-like substrate,
The exposed adhesive layer (II) is heated while being in contact with and / or after contacting the second double-sided printed wiring board (2) having conductive circuits on both sides. The present invention relates to a method for manufacturing a printed wiring board in which conductive circuit layers are laminated.

Furthermore, the present invention provides a urethane prepolymer having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b), and a diol compound having a carboxyl group (c) on a peelable sheet substrate ( An adhesive composition (I) obtained by reacting d) with a polyamino compound (e) and containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B) The adhesive layer (II) of the adhesive-carrying sheet (E) provided with the adhesive layer (II) formed from
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface where the conductive circuit is not provided, and then the peelable sheet-like substrate is peeled off,
The exposed adhesive layer (II) is brought into contact with and / or brought into contact with the surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface where the conductive circuit is not provided. Then, the present invention relates to a method for manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated.

  According to the present invention, the polyimide film and the conductive circuit surface that are often used as the base material of the flexible printed wiring board, the polyimide film and the polyimide film, and also the adhesive strength between the conductive circuit surfaces are excellent, and the storage stability is excellent. It has become possible to provide a printed wiring board comprising a plurality of conductive circuit layers laminated with a good soldering heat resistance, using the adhesive composition.

First, the adhesive composition (I) used for manufacturing the printed wiring board of the present invention in which a plurality of conductive circuit layers are laminated will be described.
The polyurethane polyurea resin (A) contained in the adhesive composition (I) is a urethane having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group. It is obtained by reacting the prepolymer (d), the polyamino compound (e), and a reaction terminator as necessary.

  The polyol compound (a) is a polyol component other than the diol compound (c) having a carboxyl group to be described later, and is generally known as a polyol component constituting a polyurethane resin. Various polyether polyols, polyester polyols, Polycarbonate polyols, polybutadiene glycols, or a mixture thereof can be used.

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

  Polyester polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1, Saturated and unsaturated low molecular weight diols such as 5-pentanediol, hexanediol, octanediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, dimer diol, and adipic acid, phthalic acid, isophthalate Obtained by reacting dicarboxylic acids such as acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, or their anhydrides Polyester polio N-butyl glycidyl ether, alkyl glycidyl ethers of 2-ethylhexyl glycidyl ether, monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester and anhydrides of the above dicarboxylic acids and the like Examples include polyester polyols obtained by reacting in the presence of a hydroxyl group-containing compound and polyester polyols obtained by ring-opening polymerization of a cyclic ester compound.

Examples of the polycarbonate polyol include 1) a reaction product of diol or bisphenol and a carbonate ester, and 2) a reaction product obtained by reacting diol or bisphenol with phosgene in the presence of an alkali.
Examples of the carbonic acid ester used in the case of 1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, and the like.
As the diol used in the above 1) and 2), ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1 , 8-octanediol, 3,3′-dimethylolheptane, 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, 3,9-bis (1,1-dimethyl) -2-Hyd Roxyethyl, 2,2,8,10-tetraoxospiro [5.5] undecane and the like can be mentioned.
Examples of the bisphenol used in the cases 1) and 2) include bisphenol A, bisphenol F, and bisphenols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to bisphenols.

The number average molecular weight (Mn) of the polyol compound (a) is appropriately determined in consideration of the heat resistance, adhesive strength, solubility and the like of the resulting polyurethane polyurea resin (A), but is usually in the range of 500 to 8000. Is more preferable, and 1000 to 5000 is more preferable. When Mn is less than 500, the number of urethane bonds in the polyurethane polyurea resin (A) increases too much, and the flexibility of the polymer skeleton tends to decrease and the adhesion to the polyimide film / conductive circuit tends to decrease. If it exceeds 8000, the molecular weight between cross-linking points increases, and the solder heat resistance tends to decrease.
The polyol compound (a) may be used alone or in combination of two or more. Furthermore, within the range in which the performance of the polyurethane polyurea resin (A) is not lost, various low-molecular diols used as a part of the polyol compound (a), for example, a molecular weight of about 400 or less used for the production of the polyol compound. Molecular diols can be used instead.

  As the organic diisocyanate compound (b), aromatic diisocyanate, aliphatic diisocyanate, alicyclic isocyanate, or a mixture thereof can be used, and isophorone diisocyanate is particularly preferable.

  Aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-benzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1 , 3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate and the like.

  Examples of the aliphatic diisocyanate include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.

  Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, norbornane diisocyanate methyl, bis (4-isocyanatocyclohexyl) methane, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, and the like. It is done.

  Examples of the diol compound (c) having a carboxyl group include dimethylol alkanoic acid such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid and dimethylolpentanoic acid, dihydroxysuccinic acid, and dihydroxybenzoic acid. In particular, dimethylolpropionic acid and dimethylolbutanoic acid are preferable from the viewpoint of reactivity and solubility.

The conditions for obtaining the urethane prepolymer (d) having an isocyanate group by reacting the polyol compound (a), the organic diisocyanate (b), and the diol compound (c) having a carboxyl group include an isocyanate group in excess. The equivalent ratio of isocyanate group / hydroxyl group is preferably in the range of 1.05 / 1 to 3/1. More preferably, it is 1.2 / 1 to 2/1. The reaction is usually carried out at a temperature between normal temperature and 150 ° C., and is preferably carried out between 60 ° C. and 120 ° C. from the viewpoints of production time and side reaction control.
The range of 1000-100000 is preferable and, as for the weight average molecular weight (Mw) of the urethane prepolymer (d) which has an isocyanate group obtained, it is more preferable that it is the range of 2000-80000. When Mw is less than 1000, the printed wiring board to be formed is inferior in soldering heat resistance, and when it exceeds 100,000, the viscosity of the adhesive composition is high and the handling property is lowered, which is not preferable.

The polyurethane polyurea resin (A) is obtained by reacting a urethane prepolymer (d) having an isocyanate group with a polyamino compound (e).
The polyamino compound (e) functions as a chain extender, and includes ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, norbornanediamine, 2 -(2-Aminoethylamino) ethanol, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxypropylethylenediamine and other amines having a hydroxyl group may also be used. it can. Of these, isophoronediamine is preferably used.

  In order to adjust the molecular weight of the resulting polyurethane polyurea resin (A) when reacting the urethane prepolymer (d) having an isocyanate group with the polyamino compound (e) to synthesize the polyurethane polyurea resin (A), a reaction terminator is used. Can be used in combination. As the reaction terminator, dialkylamines such as di-n-butylamine, dialkanolamines such as diethanolamine, and alcohols such as ethanol and isopropyl alcohol can be used.

The conditions for reacting the urethane prepolymer (d) having an isocyanate group, the polyamino compound (e), and the reaction terminator are not particularly limited, but 1 equivalent of a free isocyanate group at both ends of the urethane prepolymer. The total equivalent of amino groups in the polyamino compound (e) and the reaction terminator is preferably in the range of 0.5 to 1.3, and 50 to 100% of the total equivalents of amino groups is polyamino It is preferably derived from the compound (e). Furthermore, the total equivalent of amino groups is preferably in the range of 0.8 to 1.1, and 70 to 100% of it is preferably derived from the polyamino compound (e).
When the total equivalent of amino groups is less than 0.5, the molecular weight of the polyurethane urea resin (A) cannot be sufficiently increased, so that the solder heat resistance is not sufficient. When the amount exceeds 1.3, the polyamino compound (e) and the reaction terminator remain in a large amount unreacted and react directly with the epoxy resin in the adhesive composition, or exhibit catalytic activity and exhibit an adhesive composition. Reduces storage stability.
The weight average molecular weight of the polyurethane polyurea resin (A) is preferably in the range of 5,000 to 500,000. When the molecular weight is less than 5,000, the solder heat resistance is inferior, and when it exceeds 500,000, the viscosity of the adhesive composition is high and the handling property is lowered, which is not preferable.

  Further, the acid value of the polyurethane polyurea resin (A) needs to be 3 to 25 mg KOH / g, and preferably 7 to 20 mg KOH / g. In addition, an acid value is an acid value by a carboxyl group, and is with respect to solid content of a polyurethane polyurea resin (A). When the acid value of the polyurethane polyurea resin (A) is smaller than 3 mg KOH / g, the crosslinking with the epoxy resin contained in the adhesive composition becomes insufficient, the heat resistance is lowered, and the solder heat resistance is not exhibited. Moreover, when an acid value is larger than 25 mgKOH / g, it will bridge | crosslink with the epoxy resin contained in an adhesive composition too much, and the adhesive strength to the polyimide film and electroconductive circuit etc. which are adherends will fall.

When synthesizing the polyurethane polyurea resin (A), an ester solvent, a ketone solvent, a glycol ether solvent, an aliphatic solvent, an aromatic solvent, an alcohol solvent, a carbonate solvent, water or the like alone , Or two or more types can be used in combination.
Examples of ester solvents include ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, and ethyl lactate.
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone benzene, diisobutyl ketone, diacetone alcohol, isophorone, and cyclohexanone.

  Examples of glycol ether solvents include ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and these monoethers. Examples thereof include acetates and diethers such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether.

Examples of the aliphatic solvent include n-heptane, n-hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane.
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 solvent include dimethyl carbonate, ethyl methyl carbonate, di-n-butyl carbonate and the like.

  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 is reacted with the polyamino compound (e), 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, a hydrogen bond is generated, and the viscosity of the reaction solution is extremely rapidly increased due to the hydrogen bond. When a solvent having a hydroxyl group is used in the urea formation, the influence of the hydrogen bond can be alleviated.

In addition, the epoxy resin (B) contained in the adhesive composition (I) used in the present invention is a compound having an epoxy group, which may be liquid or solid and is particularly limited. Although it is not a thing, what has an average of two or more epoxy groups in 1 molecule is used.
As the epoxy resin (B), an epoxy resin such as a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, or a cyclic aliphatic (alicyclic type) epoxy resin can be used.

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, cresol novolac type epoxy resin, phenol novolac type epoxy resin, α-naphthol novolak type epoxy resin. Resin, bisphenol A type novolak type epoxy resin, dicyclopentadiene type epoxy resin, tetrabromobisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, tris (glycidyloxyphenyl) methane, tetrakis (glycidyloxyphenyl) ethane, etc. Can be mentioned.
Examples of the glycidylamine type epoxy resin include tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmetaaminophenol, and tetraglycidylmetaxylylenediamine.

Examples of the glycidyl ester type epoxy resin include diglycidyl phthalate, diglycidyl hexahydrophthalate, and diglycidyl tetrahydrophthalate.
Examples of the cycloaliphatic (alicyclic) epoxy resin include epoxycyclohexylmethyl-epoxycyclohexanecarboxylate, bis (epoxycyclohexyl) adipate, and the like.
An epoxy resin can be used individually by 1 type or in combination of 2 or more types.
As the epoxy resin (B), bisphenol A type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, tris (glycidyloxyphenyl) methane, tetrakis (glycidyloxyphenyl) from the viewpoint of high adhesion and heat resistance It is preferable to use ethane.

  The adhesive composition (I) used in the present invention preferably contains 3 to 200 parts by weight of the epoxy resin (B) with respect to 100 parts by weight of the polyurethane polyurea resin (A), and contains 5 to 100 parts by weight. More preferably. When the amount of the epoxy resin (B) is less than 3 parts by weight, the solder heat resistance is hardly exhibited. When the amount of the epoxy resin (B) is more than 200 parts by weight, the adhesion to the polyimide film and the conductive circuit tends to decrease.

  The adhesive composition (I) used in the present invention includes a curing accelerator and a curing agent for the purpose of promoting the reaction between the polyurethane polyurea resin (A) and the epoxy resin (B) and the reaction between the epoxy resins (B). Can be contained. As the curing accelerator for the epoxy resin (B), tertiary amine compounds, phosphine compounds, imidazole compounds and the like can be used, and as the curing agent, dicyandiamide, carboxylic acid hydrazide, acid anhydrides and the like can be used.

  Examples of the tertiary accelerator include triethylamine, benzyldimethylamine, 1,8-diazabicyclo (5.4.0) undecene-7, 1,5-diazabicyclo (4.3.0) nonene-5, and the like as the curing accelerator. It is done. Examples of the phosphine compound include triphenylphosphine and tributylphosphine. Examples of imidazole compounds include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2,4-dimethylimidazole, 2-phenylimidazole, and the like. A latent curing accelerator having improved storage stability such as a type in which an epoxy resin is reacted to insolubilize in a solvent or a type in which an imidazole compound is encapsulated in a microcapsule can be mentioned. Among these, a latent curing accelerator is preferable.

As the curing agent, examples of the carboxylic acid hydrazide include succinic acid hydrazide and adipic acid hydrazide. Examples of the acid anhydride include hexahydrophthalic anhydride and trimellitic anhydride.
Two or more kinds of these curing accelerators and curing agents may be used in combination, and the addition amount is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin (B).

In the adhesive composition (I) used in the present invention, a filler (C) can be added for the purposes of solder heat resistance, improvement in thermal conductivity, and flow control of the adhesive composition.
Examples of the filler (C) include silica, alumina, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, titanium oxide, zinc oxide, antimony trioxide, magnesium oxide, talc, montmorillonite, kaolin and bentonite. Examples include inorganic fillers, metal fillers such as aluminum, gold, silver, copper, and nickel. Among these, silica, alumina, and aluminum hydroxide are preferable from the viewpoint of dispersibility. In particular, hydrophobic silica obtained by modifying a silanol group on the silica surface with a halogenated silane can reduce the water absorption rate and is suitably used in the adhesive composition of the present invention.
The blending amount of the filler (C) is preferably 0.1 to 100 parts by weight and more preferably 0.2 to 50 parts by weight with respect to 100 parts by weight of the polyurethane polyurea resin (A).

The adhesive composition (I) used in the present invention includes a silane coupling agent, a heat stabilizer, a pigment, a dye, and a tackifying resin as long as the adhesiveness to a polyimide film and a conductive circuit and solder heat resistance are not deteriorated. , Plasticizers, ultraviolet absorbers, antifoaming agents, leveling regulators and the like can be blended.
By using a heat stabilizer in combination, it is possible to provide a roller with higher solder heat resistance. As the heat-resistant stabilizer, hindered phenol-based, phosphorus (phosphite) -based, lactone-based, hydroxylamine-based, sulfur-based, and the like can be used. In particular, a hindered phenol-based heat stabilizer is effective.

Next, the printed wiring board will be described.
The printed wiring board is obtained by forming a wiring pattern of a conductive circuit on an insulating substrate by a printing method and a chemical method such as plating or etching.
For example, a photosensitive etching resist layer is formed on a copper foil of a copper clad laminate in which a copper foil is provided on an insulating substrate with or without an adhesive layer, and exposed through a mask film having a circuit pattern. Then, only the exposed portion is cured, and then the copper foil in the unexposed portion is removed by etching, and then the remaining resist layer is peeled off, whereby a conductive circuit can be formed from the copper clad laminate.
Alternatively, only a necessary circuit may be provided on an insulating substrate by means such as sputtering or plating.
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 is one having a conductive circuit on one surface and conductive on both sides. Examples thereof include a circuit having a circuit, but it is preferable to use a flexible printed wiring board using a flexible plastic film as an insulating substrate in order to reduce the thickness and weight and to provide flexibility.

Next, the printed wiring board of the present invention in which a plurality of conductive circuit layers are laminated will be described with reference to the drawings. The printed wiring board of the present invention in which a plurality of conductive circuit layers are laminated includes a printed wiring board having a conductive circuit on one surface of an insulating substrate, and a printed wiring board having a conductive circuit on both surfaces of the insulating substrate. And laminated using the adhesive composition (I).
[1] in FIG. 1 indicates that the conductive circuit side surface of the first single-sided printed wiring board (1) and the conductive circuit side surface of the second single-sided printed wiring board (1) are adhesive compositions. FIG. 2 schematically shows a state in which they are bonded and laminated through a cured adhesive layer (III) formed from an object (I).

  [2] in FIG. 1 is a curing in which one surface of the double-sided printed wiring board (2) and the surface on the conductive circuit side of the single-sided printed wiring board (1) are formed from the adhesive composition (I). FIG. 2 schematically shows a state in which they are bonded and laminated through the adhesive layer (III).

  [3] in FIG. 1 includes a surface on the conductive circuit side of the first single-sided printed wiring board (1) and a surface on which the conductive circuit of the second single-sided printed wiring board (1) is not provided. FIG. 2 schematically shows a state in which they are bonded and laminated through a cured adhesive layer (III) formed from the adhesive composition (I).

  In [4] of FIG. 1, one side of the double-sided printed wiring board (2) and the side where the conductive circuit of the single-sided printed wiring board (1) is not provided are formed from the adhesive composition (I). FIG. 2 schematically shows a state where the laminated layers are laminated through the cured adhesive layer (III).

  [5] in FIG. 1 shows that one side of the first double-sided printed wiring board (2) and one side of the second double-sided printed wiring board (2) are formed from the adhesive composition (I). FIG. 2 schematically shows a state where the laminated layers are laminated through the cured adhesive layer (III).

[6] in FIG. 1 shows a surface on which the conductive circuit of the first single-sided printed wiring board (1) is not provided and a surface on which the conductive circuit of the second single-sided printed wiring board (1) is not provided. Are schematically shown in a state where they are bonded and laminated through the cured adhesive layer (III) formed from the adhesive composition (I).
In FIG. 1, depending on the type of printed wiring board to be laminated, there may be an adhesive layer between the insulating substrate of each printed wiring board and the conductive circuit. The illustration of the adhesive layer between the insulating substrate of the printed wiring board and the conductive circuit is omitted.

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

  A printed wiring board in which a plurality of conductive circuit layers of the present invention are laminated is a method using an adhesive-carrying sheet (D), and the adhesive composition (I) is applied on a printed wiring board for lamination. It can be obtained by various methods such as a method of using the adhesive-carrying sheet (E).

The adhesive-carrying sheet (D) used in the present invention comprises an adhesive layer (II) formed from the adhesive composition (I) between two peelable sheet-like substrates. It is.
The adhesive-carrying sheet (D) is obtained by applying the adhesive composition (I) to one peelable sheet-like substrate by various methods, drying it, and forming another adhesive layer on the formed adhesive layer (II). It can be obtained by superimposing sheet-like substrates.

The adhesive-carrying sheet (E) used in the present invention is obtained by providing an adhesive layer (II) formed from the adhesive composition (I) on a peelable sheet-like substrate.
The adhesive-carrying sheet (E) can be obtained by applying the adhesive composition (I) on the peelable sheet-like substrate by various methods and drying it.

  As a coating method of the adhesive composition (I), a conventionally known method, for example, comma coating, knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure printing, flexographic printing, dip coating, spraying. After applying the adhesive composition (I) by coating, spin coating or the like, the adhesive layer (II) can be obtained usually by drying at 40 to 150 ° C.

  As the peelable sheet-like substrate, polyester, polyolefin, polyimide, polyamide and other plastic films, and the surface of these plastic films coated with a release agent containing silicone or a fluorine compound, glassine paper, polyethylene laminated fine paper And the like, each of which is coated with a release agent containing silicone or a fluorine compound. In the present invention, “peelability” means that the adhesive layer (II) can be peeled off.

Next, the manufacturing method of the printed wiring board by which the some electroconductive circuit layer using the said adhesive agent carrying sheet (D) is laminated | stacked is demonstrated.
One peelable sheet-like substrate is peeled off from the adhesive-carrying sheet (D), and the exposed adhesive layer (II) is brought into contact with the surface on the conductive circuit side of the first single-sided printed wiring board (1), Next, the other peelable sheet-like substrate was peeled off, and the exposed adhesive layer (II) was brought into contact with and / or brought into contact with the conductive circuit side surface of the second single-sided printed wiring board (1). Thereafter, by heating, a printed wiring board having a plurality of conductive circuit layers in the stacked state of [1] in FIG. 1 can be obtained.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [2] in FIG.
One peelable sheet-like substrate is peeled off from the adhesive-carrying sheet (D), the exposed adhesive layer (II) is brought into contact with one surface of the double-sided printed wiring board (2), and then the other peelable sheet The substrate is peeled off and the exposed adhesive layer (II) is brought into contact with and / or brought into contact with the conductive circuit side surface of the single-sided printed wiring board (1).
Alternatively, one peelable sheet-like substrate is peeled off from the adhesive-carrying sheet (D), and the exposed adhesive layer (II) is brought into contact with the surface on the conductive circuit side of the single-sided printed wiring board (1), and then The other peelable sheet-like base material is peeled off, and the exposed adhesive layer (II) is heated by bringing one side of the double-sided printed wiring board (2) into contact and / or after making contact therewith. be able to.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [3] in FIG.
One peelable sheet-like substrate is peeled off from the adhesive-carrying sheet (D), and the exposed adhesive layer (II) is brought into contact with the surface on the conductive circuit side of the first single-sided printed wiring board (1), Next, the other peelable sheet-like substrate is peeled off, and the exposed adhesive layer (II) is brought into contact with the surface on which the conductive circuit of the second single-sided printed wiring board (1) is not provided, and / or After contact, heating,
Alternatively, one peelable sheet-like substrate is peeled from the adhesive-carrying sheet (D), and the exposed adhesive layer (II) is not provided with the conductive circuit of the second single-sided printed wiring board (1). Contacting the surface, then peeling off the other peelable sheet-like substrate, bringing the exposed adhesive layer (II) into contact with the conductive circuit side surface of the first single-sided printed wiring board (1), and It can be obtained by heating after contact.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [4] in FIG.
One peelable sheet-like substrate is peeled off from the adhesive-carrying sheet (D), the exposed adhesive layer (II) is brought into contact with one surface of the double-sided printed wiring board (2), and then the other peelable sheet The substrate is peeled off and the exposed adhesive layer (II) is brought into contact with and / or brought into contact with the surface on which the conductive circuit of the single-sided printed wiring board (1) is not provided.
Alternatively, one peelable sheet-like substrate is peeled off from the adhesive-carrying sheet (D), and the exposed adhesive layer (II) is brought into contact with the surface on which the conductive circuit of the single-sided printed wiring board (1) is not provided. Next, the other peelable sheet-like base material is peeled off, and the exposed adhesive layer (II) is heated while contacting and / or contacting one surface of the double-sided printed wiring board (2). It can be obtained by doing.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [5] in FIG.
One peelable sheet-like substrate is peeled off from the adhesive-carrying sheet (D), the exposed adhesive layer (II) is brought into contact with one surface of the first double-sided printed wiring board (2), and then the other By peeling off the peelable sheet-like base material and bringing the exposed adhesive layer (II) into contact with and / or contacting one surface of the second double-sided printed wiring board (2), by heating Obtainable.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [6] in FIG.
One peelable sheet-like substrate is peeled from the adhesive-carrying sheet (D), and the exposed adhesive layer (II) is removed from the surface on which the conductive circuit of the first single-sided printed wiring board (1) is not provided. Next, the other peelable sheet-like substrate is peeled off, and the exposed adhesive layer (II) is brought into contact with the surface on which the conductive circuit of the second single-sided printed wiring board (1) is not provided, And / or after contact, it can be obtained by heating.

The printed wiring board having a plurality of conductive circuit layers in the laminated state shown by [1] to [6] in FIG. 1 can also be obtained by applying the adhesive composition (I) onto the printed wiring board. Can do.
For example, the printed wiring board in which a plurality of conductive circuit layers in the stacked state [1] in FIG. 1 are stacked is bonded to the surface on the conductive circuit side of the first single-sided printed wiring board (1). The adhesive composition (I) is applied and dried to form an adhesive layer (II), and the conductive circuit side surface of the second single-sided printed wiring board (1) is formed on the adhesive layer (II). It can be obtained by heating with and / or after contacting.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [2] in FIG.
The adhesive composition (I) is applied to one surface of the double-sided printed wiring board (2), dried to form an adhesive layer (II), and the single-sided printed wiring board is formed on the adhesive layer (II). (1) The surface on the conductive circuit side is in contact and / or after being heated,
Alternatively, the adhesive composition (I) is applied to the conductive circuit side of the single-sided printed wiring board (1) and dried to form the adhesive layer (II). It can be obtained by heating while contacting and / or contacting one surface of the printed wiring board (2).

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [3] in FIG.
The adhesive composition (I) is applied to the surface on the conductive circuit side of the first single-sided printed wiring board (1) and dried to form an adhesive layer (II). The adhesive layer (II) In addition, the surface on which the conductive circuit of the second single-sided printed wiring board (1) is not provided is in contact with and / or after being heated,
Alternatively, the adhesive composition (I) is applied to the surface of the first single-sided printed wiring board (1) where the conductive circuit is not provided, and dried to form the adhesive layer (II). The agent layer (II) can be obtained by heating the surface of the second single-sided printed wiring board (1) on the conductive circuit side and / or after contacting it.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [4] in FIG.
The adhesive composition (I) is applied to one side of the double-sided printed wiring board (2), dried to form an adhesive layer (II), and the single-sided printed wiring board is formed on the adhesive layer (II). (1) The surface where the conductive circuit is not provided is brought into contact and / or after being heated,
Alternatively, the adhesive composition (I) is applied to the surface on which the conductive circuit of the single-sided printed wiring board (1) is not provided and dried to form the adhesive layer (II). II) can be obtained by heating one surface of the double-sided printed wiring board (2) in contact with and / or after contact.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [5] in FIG.
The adhesive composition (I) is applied to one surface of the first double-sided printed wiring board (2) and dried to form an adhesive layer (II). The two-sided printed wiring board (2) can be obtained by heating while contacting and / or contacting one surface of the two-sided printed wiring board (2).

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [6] in FIG.
The adhesive composition (I) is applied to the surface of the first single-sided printed wiring board (1) where no conductive circuit is provided, and dried to form an adhesive layer (II). (II) can be obtained by heating while contacting and / or contacting the surface of the second single-sided printed wiring board (1) where the conductive circuit is not provided.
In addition, as an application | coating method of adhesive composition (I), the method described when obtaining adhesive carrying | support sheet | seat (D) and adhesive carrying sheet | seat (E) can be illustrated similarly.

Furthermore, the printed wiring board in which a plurality of conductive circuit layers in the laminated state shown in [1] to [6] in FIG. 1 are laminated can also be obtained by using the adhesive-carrying sheet (E). Can do.
For example, the printed wiring board in which a plurality of conductive circuit layers in the laminated state shown in [1] in FIG. 1 is laminated has the adhesive layer (II) on the adhesive-carrying sheet (E) as The single-sided printed wiring board (1) is brought into contact with the surface on the conductive circuit side, and then the peelable sheet-like base material is peeled off. It can be obtained by heating while contacting and / or contacting the surface on the conductive circuit side.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [2] in FIG.
The adhesive layer (II) on the adhesive-carrying sheet (E) is brought into contact with one surface of the double-sided printed wiring board (2), and then the peelable sheet-like substrate is peeled off to expose the exposed adhesive layer (II) In addition, after contacting and / or contacting the surface on the conductive circuit side of the single-sided printed wiring board (1), heating,
Alternatively, the adhesive layer (II) on the adhesive-carrying sheet (E) is brought into contact with the conductive circuit side surface of the single-sided printed wiring board (1), and then the peelable sheet-like substrate is peeled off to expose the adhesive. It can be obtained by heating while contacting and / or contacting one surface of the double-sided printed wiring board (2) with the agent layer (II).

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [3] in FIG.
The adhesive layer (II) on the adhesive-carrying sheet (E) was brought into contact with the conductive circuit side surface of the first single-sided printed wiring board (1), and then the peelable sheet-like substrate was peeled off to be exposed. The adhesive layer (II) is heated while contacting and / or contacting the surface of the second single-sided printed wiring board (1) where the conductive circuit is not provided,
Alternatively, the adhesive layer (II) on the adhesive-carrying sheet (E) is brought into contact with the surface on which the conductive circuit of the first single-sided printed wiring board (1) is not provided, and then the peelable sheet-like substrate It is obtained by peeling off and heating the exposed adhesive layer (II) while contacting and / or contacting the surface on the conductive circuit side of the second single-sided printed wiring board (1). be able to.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [4] in FIG.
The adhesive layer (II) on the adhesive-carrying sheet (E) is brought into contact with one surface of the double-sided printed wiring board (2), then the peelable sheet-like substrate is peeled off, and the exposed adhesive layer (II) In addition, the surface on which the conductive circuit of the single-sided printed wiring board (1) is not provided is brought into contact with and / or after being heated,
Alternatively, the adhesive layer (II) on the adhesive-carrying sheet (E) is brought into contact with the surface on which the conductive circuit of the single-sided printed wiring board (1) is not provided, and then the peelable sheet-like substrate is peeled off, It can be obtained by heating the exposed adhesive layer (II) while bringing one side of the double-sided printed wiring board (2) into contact and / or after contacting it.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [5] in FIG.
The adhesive layer (II) on the adhesive-carrying sheet (E) is brought into contact with one surface of the first double-sided printed wiring board (2), and then the peelable sheet-like substrate is peeled off to expose the adhesive layer (II) can be obtained by heating while contacting and / or contacting one surface of the second double-sided printed wiring board (2).

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [6] in FIG.
The adhesive layer (II) on the adhesive-carrying sheet (E) is brought into contact with the surface on which the conductive circuit of the first single-sided printed wiring board (1) is not provided, and then the peelable sheet-like substrate is peeled off Obtained by heating the exposed adhesive layer (II) while contacting and / or contacting the surface of the second single-sided printed wiring board (1) where the conductive circuit is not provided. Can do.

In any of the above cases, pressure can be applied when the printed wiring board is bonded and / or after bonding. More specifically, a laminated body composed of a printed wiring board / adhesive layer (II) / printed wiring board is passed between two heated rolls, or the laminated body is hot-pressed. It is possible to obtain a printed wiring board in which conductive circuit layers are more firmly bonded and laminated.
Moreover, after obtaining the printed wiring board by which several electroconductive circuit layers are laminated | stacked, it can heat further and can also harden | cure the adhesive bond layer (II) further.
For example, by heating the adhesive layer (II) at 100 to 200 ° C. for about 30 minutes to 24 hours, the cured adhesive layer (III) can be obtained. The film 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 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).

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, respectively.
[Synthesis Example 1]
Polyester polyol (made by Kuraray Co., Ltd.) obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube. Kuraray polyol P-2011 ", Mn = 2040) 195.2 parts, 6.67 parts dimethylolbutanoic acid, 40.7 parts isophorone diisocyanate, 70.0 parts toluene, and reacted at 90 ° C for 4 hours in a nitrogen atmosphere. To this was added 250 parts of toluene to obtain a urethane prepolymer solution having an isocyanate group with Mw = 21,000.
Next, the urethane prepolymer solution 506.3 having the above isocyanate group in a mixture of 6.08 parts of isophoronediamine, 0.59 parts of di-n-butylamine, 112.5 parts of 2-propanol, and 184.5 parts of toluene. A polyurethane polyurea resin solution A-1 having Mw = 110,000, acid value = 10.1 mg KOH / g, and solid content of about 25% was obtained.

[Synthesis Example 2]
In a reaction vessel similar to Synthesis Example 1, 195.0 parts of polyoxytetramethylene glycol (“PTG-2000SN”, Mn = 2029, manufactured by Hodogaya Chemical Co., Ltd.), 6.70 parts of dimethylolbutanoic acid, 40 of isophorone diisocyanate 8 parts and 70.0 parts of toluene were reacted in a nitrogen atmosphere at 90 ° C. for 4 hours, and 250 parts of toluene was added thereto to obtain a urethane prepolymer solution having an isocyanate group with Mw = 22,000.
Next, the urethane prepolymer solution 506. containing the above isocyanate group in a mixture of 6.11 parts of isophoronediamine, 0.59 parts of di-n-butylamine, 112.5 parts of 2-propanol, and 184.5 parts of toluene. 3 parts were added and reacted at 85 ° C. for 4 hours to obtain a polyurethane polyurea resin solution A-2 having Mw = 105,000, acid value = 10.2 mgKOH / g, and solid content of about 25%.

[Synthesis Example 3]
In a reaction vessel similar to that in Synthesis Example 1, 193.6 parts of polyhexamethylene carbonate diol ("Placcel CD220" manufactured by Daicel Chemical Industries, Ltd., Mn = 1965), 6.87 parts of dimethylolbutanoic acid, 41. 9 parts and 70.0 parts of toluene were charged and reacted at 90 ° C. for 4 hours under a nitrogen atmosphere, and 250 parts of toluene was added thereto to obtain a urethane prepolymer solution containing Mw = 20,000 and containing an isocyanate group.
Next, a urethane prepolymer solution 506.1 containing the above isocyanate in a mixture of 6.26 parts of isophoronediamine, 0.61 part of di-n-butylamine, 112.5 parts of 2-propanol, and 184.5 parts of toluene. A polyurethane polyurea resin solution A-3 having Mw = 88,000, acid value = 10.4 mgKOH / g, and solid content of about 25% was obtained.

[Synthesis Example 4]
In the same reaction vessel as in Synthesis Example 1, polyester polyol obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol (“Kuraray Polyol P-2011”, Mn = 2040) 209 manufactured by Kuraray Co., Ltd. .4 parts, 1.69 parts of dimethylolbutanoic acid, 32.9 parts of isophorone diisocyanate, and 70.0 parts of toluene were reacted in a nitrogen atmosphere at 90 ° C. for 4 hours. To this, 250 parts of toluene was added, and Mw = 23. 1,000, urethane prepolymer solution having an isocyanate group was obtained.
Next, a urethane prepolymer solution having the above isocyanate group in a mixture of 4.93 parts of isophoronediamine, 0.48 parts of di-n-butylamine, 112.5 parts of 2-propanol, and 184.5 parts of toluene 6 parts were added and reacted at 85 ° C. for 4 hours to obtain a polyurethane polyurea resin solution A-4 having Mw = 120,000, acid value = 2.6 mgKOH / g, and solid content of about 25%.

[Synthesis Example 5]
In a reaction vessel similar to Synthesis Example 1, polyester polyol obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol ("Kuraray Polyol P-2011" manufactured by Kuraray Co., Ltd., Mn = 2040) 155 0.0 part, 20.9 parts of dimethylolbutanoic acid, 62.7 parts of isophorone diisocyanate, and 70.0 parts of toluene were reacted in a nitrogen atmosphere at 90 ° C. for 4 hours, 250 parts of toluene was added thereto, and Mw = 19 1,000, urethane prepolymer solution having an isocyanate group was obtained.
Next, in a mixture of 9.38 parts of isophoronediamine, 0.91 part of di-n-butylamine, 112.5 parts of 2-propanol, and 184.5 parts of toluene, the urethane prepolymer solution having the above isocyanate group 502. 7 parts were added and reacted at 85 ° C. for 4 hours to obtain a polyurethane polyurea resin solution A-5 having Mw = 94,000, acid value = 31.7 mgKOH / g, and solid content of about 25%.

[Synthesis Example 6]
In the same reaction vessel as in Synthesis Example 1, polyester polyol obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol (“Kuraray Polyol P-2011” manufactured by Kuraray Co., Ltd., 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 in a nitrogen atmosphere at 90 ° C. for 4 hours, 330 parts of toluene was added thereto, and Mw = 21 1,000, urethane prepolymer solution having an isocyanate group was obtained.

In addition, the weight average molecular weight of polyurethane polyurea resin is the weight average molecular weight of polystyrene conversion calculated | required by GPC measurement, and GPC measurement conditions are as follows.
Apparatus: Shodex GPC System-21 (manufactured by Showa Denko KK)
Column: A total of 3 columns, Shodex KF-802, KF-803L, KF-805L (manufactured by Showa Denko Co., Ltd.), are connected and used.
Solvent: Tetrahydrofuran Flow rate: 1.0 ml / min
Temperature: 40 ° C
Sample concentration: 0.2% by weight
Sample injection volume: 100 μl

[Example 1]
Tetrakis (glycidyloxyphenyl) ethane (“Epicoat 1031S” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent = 180 to 220 g / eq) with respect to 400 parts of the polyurethane polyurea resin solution A-1 obtained in Synthesis Example 1 10 parts and 20 parts of hydrophobic silica filler (“Nippil SS-50F” manufactured by Tosoh Silica Co., Ltd.) were mixed to obtain an adhesive composition.
This adhesive composition is coated and dried on a polyester film that has been peel-treated so that the dry film thickness is 25 μm, and an adhesive layer (II) is formed, and another peel-treated polyester film is laminated. Thus, an adhesive-carrying sheet (D) in which the adhesive layer (II) was sandwiched between peelable sheet-like substrates was produced.

[Examples 2-5 and Comparative Examples 1-2]
Adhesive composition and adhesion in exactly the same manner as in Example 1 except that the type and amount of polyurethane polyurea resin (A) solution, epoxy resin (B), and filler (C) shown in Table 1 were used. An agent carrying sheet (D) was produced.

Abbreviations in Table 1 are shown below.
EP828: Bisphenol A type epoxy resin (“Epicoat 828” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent = 189 g / eq)
EP152: phenol novolac type epoxy resin ("Epicoat 152" manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent = 172 to 178 g / eq)
1031S: Tetrakis (glycidyloxyphenyl) ethane (“Epicoat 1031S” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent = 180 to 220 g / eq)
SS-50F: Hydrophobic silica filler (“Nippil SS-50F” manufactured by Tosoh Silica Co., Ltd.)
R972: Hydrophobic silica filler (“AEROSIL R972” manufactured by Nippon Aerosil Co., Ltd.)

[Comparative Example 3]
Carboxyl group-containing nitrile butadiene rubber (“Nipol 1072J” manufactured by Nippon Zeon Co., Ltd., bound acrylonitrile amount 27.0%, Mooney viscosity 48) 100 parts, bisphenol A type epoxy resin “Epicoat 828” 200 parts, anhydrous silica filler “Aerosil” 2 parts of 300 ", 14 parts of finely pulverized dicyandiamide" Epicure DICY7 "and 2 parts of imidazole curing accelerator" Amicure PN-40 "were dissolved in toluene so that the solid content was 30%, and the adhesive composition A product was made. Using the obtained adhesive composition, an adhesive-carrying sheet (D) was produced in exactly the same manner as in Example 1.

[Comparative Example 4]
In a reactor similar to Synthesis Example 1, 95.0 parts of butyl acrylate, 5.0 parts of acrylic acid, 163.0 parts of ethyl acetate, 0.06 part of 2,2′-azobisisobutyronitrile were charged. 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 pulverized dicyandiamide “Epicure DICY7”, and imidazole curing accelerator 0.1 part of “Amicure PN-40” was blended to obtain an adhesive composition. Using the obtained adhesive composition, an adhesive-carrying sheet (D) was produced in exactly the same manner as in Example 1.

[Comparative Example 5]
With respect to 167 parts of the urethane prepolymer resin obtained in Synthesis Example 6, 20 parts of bisphenol A type epoxy resin (“Epicoat 1001” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent = 450 to 500 g / eq) and diamino An adhesive composition was prepared by mixing 8 parts of diphenylsulfone (“Seika Cure-S” manufactured by Wakayama Seika Kogyo Co., Ltd.) and 30 parts of hydrophobic silica filler (“Nipsil SS-50F” manufactured by Tosoh Silica Co., Ltd.). Using the obtained adhesive composition, an adhesive-carrying sheet (D) was produced in exactly the same manner as in Example 1.

Using the adhesive-carrying sheets (D) obtained in the examples and comparative examples, the adhesive strength to the copper mating surface, the adhesive strength to the copper glossy surface, the solder heat resistance after humidification, and the pattern embedding property after the storage stability test The chemical resistance was evaluated by the following method. The results are shown in Table 2.
(1) Adhesive strength to copper mating surface Both peelable sheet-like substrates of adhesive-carrying sheet (D) (adhesive layer thickness 25 μm) are peeled off, and the adhesive layer is a 35 μm thick electrolytic copper foil mat The film is sandwiched between a surface and a polyimide film (Kapton 200EN) having a thickness of 50 μm, heat-laminated at a roll temperature of 100 ° C., then hot-pressed under conditions of 150 ° C., 1.0 MPa, 2 min, and further in an electric oven at 150 ° C. Heated for 180 min to obtain a laminate comprising electrolytic copper foil mat surface / cured adhesive layer (III) / polyimide film.
This laminate was cut into a width of 10 mm, and a 180 ° peel peel test was performed at an elongation rate of 50 mm / min in an atmosphere of 23 ° C. and 50% relative humidity, to determine the adhesive strength (N / cm).

(2) Adhesive strength to copper glossy surface Both peelable sheet-like substrates of the adhesive-carrying sheet (D) (adhesive layer thickness 25 μm) are peeled off, and the 35 μm thick electrolytic copper foil glossy surface and 50 μm thick After being sandwiched between polyimide films (Kapton 200EN) and thermally laminated at a roll temperature of 100 ° C., heat-pressed under the conditions of 150 ° C., 1.0 MPa, 2 min, and further heated for 180 min in an electric oven at 150 ° C., A laminate comprising the glossy surface of the electrolytic copper foil / cured adhesive layer (III) / polyimide film was obtained.
This laminate was cut into a width of 10 mm, and a 180 ° peel peel test was performed at an elongation rate of 50 mm / min in an atmosphere of 23 ° C. and 50% relative humidity, to determine the adhesive strength (N / cm).

(3) Solder heat resistance after humidification The laminated body consisting of the above-mentioned electrolytic copper foil mat surface / cured adhesive layer (III) / polyimide film is cut to a width of 10 mm, and purified water at 85 ° C. for 3 hours. Immersed, the polyimide film side was immediately brought into contact with 260 ° C. molten solder 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: Adhesion abnormality occurred.

(4) Pattern embedding after storage stability test Both peelable sheet-like substrates of the adhesive-carrying sheet (D) (thickness of adhesive layer 25 μm) left in a constant temperature bath at 40 ° C. for 30 days are peeled off, It was sandwiched between a flexible copper-clad laminate (line / space 0.1 mm) on which a comb-shaped conductor pattern was formed by a subtractive method and a polyimide film (Kapton 200EN) having a thickness of 50 μm, and heat laminated at a roll temperature of 100 ° C. Then, it heat-pressed on the conditions of 150 degreeC, 1.0 MPa, and 2 minutes, and heated for 180 minutes with 150 degreeC electric oven, and obtained the flexible copper clad laminated board with a comb-shaped conductor pattern with a polyimide film. The filling property of the 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.
(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 μm, and heated in an electric oven at 150 ° C. for 180 minutes. After curing, the cured film was isolated by the mercury amalgam method. This cured film was visually observed for appearance after being immersed in a 10% NaOH aqueous solution and a 10% hydrochloric acid aqueous solution for 24 hours and after being immersed in acetone for 3 hours to evaluate whether there was swelling or dissolution.
○: No change.
Δ: A slight change is observed.

Schematic sectional view of the printed wiring board of the present invention in which a plurality of conductive circuit layers are laminated Schematic cross-sectional view of single-sided printed wiring board (1) Schematic sectional view of double-sided printed wiring board (2)

Explanation of symbols

1: Insulated substrate of printed wiring board 2: Conductive circuit 3: Cured adhesive layer (III) formed from adhesive composition (I)

Claims (18)

Obtained by reacting a urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group with a polyamino compound (e). Through a cured adhesive layer (III) formed from an adhesive composition (I) containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B) And
Of the first single-sided printed wiring board (1) having the conductive circuit only on one surface and the second single-sided printed wiring board (1) having the conductive circuit only on one surface. The surface on the conductive circuit side is attached,
Whether the double-sided printed wiring board (2) having a conductive circuit on both sides and the conductive circuit side surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface are bonded together,
Of the first single-sided printed wiring board (1) having the conductive circuit only on one surface and the second single-sided printed wiring board (1) having the conductive circuit only on one surface. The surface where the conductive circuit is not provided is attached,
The double-sided printed wiring board (2) having a conductive circuit on both sides and the surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface are not attached,
Whether the first double-sided printed wiring board (2) having a conductive circuit on both sides and the second double-sided printed wiring board (2) having a conductive circuit on both sides are bonded together,
Or
A 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 second single-sided printed wiring board having a conductive circuit only on one surface ( 1) A printed wiring board formed by laminating a plurality of conductive circuit layers, which is bonded to a surface on which a conductive circuit is not provided. A urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group between two peelable sheet-like substrates; It is formed from an adhesive composition (I) obtained by reacting a polyamino compound (e) and containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B). One peelable sheet-like substrate is peeled from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II), and the exposed adhesive layer (II) is removed.
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface on the conductive circuit side, and then the other peelable sheet-like substrate is peeled off,
After contacting and / or contacting the exposed adhesive layer (II) with the conductive circuit side surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface, A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein heating is performed. A urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group between two peelable sheet-like substrates; It is formed from an adhesive composition (I) obtained by reacting a polyamino compound (e) and containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B). One peelable sheet-like substrate is peeled from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II), and the exposed adhesive layer (II) is removed.
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface on the conductive circuit side, and then the other peelable sheet-like substrate is peeled off,
The exposed adhesive layer (II) is brought into contact with and / or brought into contact with the surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface where the conductive circuit is not provided. After heating or
Alternatively, one of the peelable sheet-like substrates is peeled off from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II) between two peelable sheet-like substrates, and the exposed adhesive layer (II) The
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface where the conductive circuit is not provided, and then the other peelable sheet-like substrate is peeled off,
After contacting and / or contacting the exposed adhesive layer (II) with the conductive circuit side surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface, A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein heating is performed. A urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group between two peelable sheet-like substrates; It is formed from an adhesive composition (I) obtained by reacting a polyamino compound (e) and containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B). One peelable sheet-like substrate is peeled from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II), and the exposed adhesive layer (II) is removed.
Contact the conductive circuit side surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface, and then peel off the other peelable sheet-like substrate,
The exposed adhesive layer (II) is heated while contacting and / or contacting the double-sided printed wiring board (2) having conductive circuits on both sides,
Alternatively, one of the peelable sheet-like substrates is peeled off from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II) between two peelable sheet-like substrates, and the exposed adhesive layer (II) The
Contact with a double-sided printed wiring board (2) having a conductive circuit on both sides, and then peel off the other peelable sheet-like substrate,
Heating the exposed adhesive layer (II) while contacting and / or contacting the conductive circuit side surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface. A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated. A urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group between two peelable sheet-like substrates; It is formed from an adhesive composition (I) obtained by reacting a polyamino compound (e) and containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B). One peelable sheet-like substrate is peeled from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II), and the exposed adhesive layer (II) is removed.
Contact the surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface, where the conductive circuit is not provided, and then peel off the other peelable sheet-like substrate,
The exposed adhesive layer (II) is heated while contacting and / or contacting the double-sided printed wiring board (2) having conductive circuits on both sides,
Alternatively, one of the peelable sheet-like substrates is peeled off from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II) between two peelable sheet-like substrates, and the exposed adhesive layer (II) The
Contact with a double-sided printed wiring board (2) having a conductive circuit on both sides, and then peel off the other peelable sheet-like substrate,
After contacting and / or contacting the exposed adhesive layer (II) with the surface on which the conductive circuit of the single-sided printed wiring board (1) having the conductive circuit only on one surface is not provided, A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein heating is performed. A urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group between two peelable sheet-like substrates; It is formed from an adhesive composition (I) obtained by reacting a polyamino compound (e) and containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B). One peelable sheet-like substrate is peeled from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II), and the exposed adhesive layer (II) is removed.
Contact with the first double-sided printed wiring board (2) having a conductive circuit on both sides, and then peel off the other peelable sheet-like substrate,
The exposed adhesive layer (II) is heated while contacting and / or contacting the second double-sided printed wiring board (2) having conductive circuits on both sides, A method for producing a printed wiring board in which conductive circuit layers are laminated. A urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group between two peelable sheet-like substrates; It is formed from an adhesive composition (I) obtained by reacting a polyamino compound (e) and containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B). One peelable sheet-like substrate is peeled from the adhesive-carrying sheet (D) formed by sandwiching the adhesive layer (II), and the exposed adhesive layer (II) is removed.
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface where the conductive circuit is not provided, and then the other peelable sheet-like substrate is peeled off,
The exposed adhesive layer (II) is brought into contact with and / or brought into contact with the surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface, where the conductive circuit is not provided. And then heating the printed wiring board, wherein a plurality of conductive circuit layers are laminated. Obtained by reacting a urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group with a polyamino compound (e). An adhesive composition (I) containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B),
Applying to the conductive circuit side surface of the first single-sided printed wiring board (1) having a conductive circuit only on one surface, forming an adhesive layer (II),
Next, the surface on the conductive circuit side of the second single-sided printed wiring board (1) having the conductive circuit only on one surface, or the above-mentioned surface on the adhesive layer (II) or the second single-sided printed wiring board (1). A method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein the surface on which the conductive circuit is not provided is heated in contact with and / or after contact. Obtained by reacting a urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group with a polyamino compound (e). An adhesive composition (I) containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B),
Apply to the conductive circuit side surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface, and form the adhesive layer (II).
Next, the adhesive layer (II) is heated while contacting and / or contacting the double-sided printed wiring board (2) having conductive circuits on both sides,
Or
Applying the adhesive composition (I) to a double-sided printed wiring board (2) having a conductive circuit on both sides to form an adhesive layer (II),
Next, the adhesive layer (II) is heated after contacting and / or contacting the surface on the conductive circuit side of the single-sided printed wiring board (1) having the conductive circuit only on one surface. A method for producing a flexible printed wiring board comprising a plurality of conductive circuit layers laminated. Obtained by reacting a urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group with a polyamino compound (e). A double-sided printed wiring board having a conductive circuit on both sides of an adhesive composition (I) containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B) ( 2) Apply to form an adhesive layer (II),
Next, after bringing the adhesive layer (II) into contact with and / or contacting the surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface, where the conductive circuit is not provided, A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein heating is performed. Obtained by reacting a urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group with a polyamino compound (e). An adhesive composition (I) containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B),
It is applied to the first double-sided printed wiring board (2) having conductive circuits on both sides to form an adhesive layer (II),
Next, the adhesive layer (II) is heated while contacting and / or contacting the second double-sided printed wiring board (2) having conductive circuits on both sides, A method for producing a printed wiring board in which conductive circuit layers are laminated. Obtained by reacting a urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group with a polyamino compound (e). An adhesive composition (I) containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B),
Applying the first single-sided printed wiring board (1) having the conductive circuit only on one surface to the surface where the conductive circuit is not provided, forming the adhesive layer (II),
Next, a surface of the second single-sided printed wiring board (1) having a conductive circuit only on one surface on the adhesive layer (II) or the second single-sided printed wiring board (1). A method for producing a printed wiring board in which a plurality of conductive circuit layers are laminated, wherein the surface on which the conductive circuit is not provided is heated while being brought into contact and / or after being brought into contact. Obtained by reacting a urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group with a polyamino compound (e). An adhesive composition (I) containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B),
It is applied to the surface of the single-sided printed wiring board (1) having a conductive circuit only on one surface where no conductive circuit is provided, and an adhesive layer (II) is formed.
Next, the adhesive layer (II) is heated with the double-sided printed wiring board (2) having conductive circuits on both sides in contact with and / or after contact, and a plurality of conductive circuits The manufacturing method of the flexible printed wiring board by which a layer is laminated | stacked. A urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group on a peelable sheet-like substrate, and a polyamino compound Adhesion formed from an adhesive composition (I) obtained by reacting (e) and containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B) The adhesive layer (II) of the adhesive-carrying sheet (E) sheet-like adhesive composition provided with the adhesive layer (II),
Contact with the surface on the conductive circuit side of the first single-sided printed wiring board (1) having a conductive circuit only on one surface, and then peel off the peelable sheet-like substrate,
On the exposed 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 Or) after contacting and / or contacting a surface not provided with a conductive circuit)
Alternatively, the adhesive layer (II) of the adhesive-carrying sheet (E) in which the adhesive layer (II) is provided on a peelable sheet-like substrate,
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface where the conductive circuit is not provided, and then the peelable sheet-like substrate is peeled off,
After contacting and / or contacting the exposed adhesive layer (II) with the conductive circuit side surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface, A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein heating is performed. A urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group on a peelable sheet-like substrate, and a polyamino compound Adhesion formed from an adhesive composition (I) obtained by reacting (e) and containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B) The adhesive layer (II) of the adhesive-carrying sheet (E) provided with the adhesive layer (II),
Contact the conductive circuit side surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface, and then peel off the peelable sheet-like substrate.
The exposed adhesive layer (II) is heated while contacting and / or contacting the double-sided printed wiring board (2) having conductive circuits on both sides,
Alternatively, the adhesive layer (II) of the adhesive-carrying sheet (E) in which the adhesive layer (II) is provided on a peelable sheet-like substrate,
Contact with a double-sided printed wiring board (2) having a conductive circuit on both sides, then peel off the peelable sheet-like substrate,
Heating the exposed adhesive layer (II) while contacting and / or contacting the conductive circuit side surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface. A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated. A urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group on a peelable sheet-like substrate, and a polyamino compound Adhesion formed from an adhesive composition (I) obtained by reacting (e) and containing a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B) The adhesive layer (II) of the adhesive-carrying sheet (E) provided with the adhesive layer (II),
Contact with the surface of the single-sided printed wiring board (1) having the conductive circuit only on one surface, which is not provided with the conductive circuit, and then peel off the peelable sheet-like substrate,
The exposed adhesive layer (II) is heated while contacting and / or contacting the double-sided printed wiring board (2) having conductive circuits on both sides,
Alternatively, the adhesive layer (II) of the adhesive-carrying sheet (E) in which the adhesive layer (II) is provided on a peelable sheet-like substrate,
Contact with a double-sided printed wiring board (2) having a conductive circuit on both sides, then peel off the peelable sheet-like substrate,
After contacting and / or contacting the exposed adhesive layer (II) with the surface on which the conductive circuit of the single-sided printed wiring board (1) having the conductive circuit only on one surface is not provided, A method for producing a printed wiring board comprising a plurality of conductive circuit layers laminated, wherein heating is performed. A urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group on a peelable sheet substrate, and a polyamino compound ( An adhesive formed from an adhesive composition (I) obtained by reacting e) with a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B) The adhesive layer (II) of the adhesive-carrying sheet (E) provided with the layer (II),
Contact with the first double-sided printed wiring board (2) having a conductive circuit on both sides, and then peel off the peelable sheet-like substrate,
The exposed adhesive layer (II) is heated while contacting and / or contacting the second double-sided printed wiring board (2) having conductive circuits on both sides, A method for producing a printed wiring board in which conductive circuit layers are laminated. A urethane prepolymer (d) having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group on a peelable sheet substrate, and a polyamino compound ( An adhesive formed from an adhesive composition (I) obtained by reacting e) with a polyurethane polyurea resin (A) having an acid value of 3 to 25 mg KOH / g and an epoxy resin (B) The adhesive layer (II) of the adhesive-carrying sheet (E) provided with the layer (II),
The first single-sided printed wiring board (1) having a conductive circuit only on one surface is brought into contact with the surface where the conductive circuit is not provided, and then the peelable sheet-like substrate is peeled off,
The exposed adhesive layer (II) is brought into contact with and / or brought into contact with the surface of the second single-sided printed wiring board (1) having the conductive circuit only on one surface, where the conductive circuit is not provided. And then heating the printed wiring board, wherein a plurality of conductive circuit layers are laminated.

Images