KR20100107043A - Curable electromagnetic shielding adhesive film, method for producing the same, use of the same, method for producing electromagnetic shielding article, and electromagnetic shielding article - Google Patents

Abstract

A curable electromagnetic wave shielding adhesive film having a curable conductive polyurethane polyurethane urea adhesive layer (I) and a curable insulating polyurethane polyurethane urea resin composition layer (II), wherein the curable conductive polyurethane polyurethane urea adhesive layer (I) is a carboxyl group-containing diol Urethane prepolymer (a4) which has an isocyanate group in the terminal obtained by making polyol (a2) of the number average molecular weights 500-8000 and organic diisocyanate (a3) other than a compound (a1), a carboxyl group-containing diol compound react, and a polyamino compound (a5) 100 weights of the said polyurethane polyurea resin (A) and the said epoxy resin (B) containing the polyurethane polyurea resin (A) and the epoxy resin (B) which have two or more epoxy groups obtained by making it react. Conductive filler: 10 to 700 parts by weight based on parts, the curable insulating polyurethane polyurethane composition Urethane prepolymer which has an isocyanate group in the terminal obtained by making water layer (II) react the polyol (c2) and organic diisocyanate (c3) of number-average molecular weight 500-8000 other than a carboxyl group-containing diol compound (c1), a carboxyl group-containing diol compound ( A curable electromagnetic wave shielding adhesive film comprising c4), a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups. It starts.

Description

Curable electromagnetic shielding adhesive film, method for producing the same, method for use thereof, method for producing electromagnetic shielding and electromagnetic shielding {Curable electromagnetic shielding adhesive film, method for producing the same, use of the same, method for producing electromagnetic shielding article, and electromagnetic shielding article}

FIELD OF THE INVENTION The present invention is a curable electromagnetic wave shielding adhesive film which is adhered to a flexible printed wiring board that is repeatedly bent, and is suitably used for shielding electromagnetic noise generated in an electric circuit. The present invention relates to a method for manufacturing an electromagnetic shield and an electromagnetic shield.

Flexible printed wiring boards are flexible in that they are widely used to insert electronic circuits inside boxes of narrow and complicated structures in order to respond to the demand for further high performance and miniaturization of OA devices, communication devices, mobile phones, etc. in recent years. have. With the downsizing and high frequency of such electronic circuits, countermeasures against unnecessary electronic noise generated therein have become increasingly important. For this reason, the pasting of the electromagnetic wave shielding adhesive film which shields the electromagnetic noise generate | occur | produced in an electronic circuit to a flexible printed wiring board is performed conventionally.

In addition to electromagnetic shielding, this electromagnetic shielding adhesive film itself requires thinness and excellent flex resistance so as not to impair the flex resistance of the entire bonded flexible printed wiring board. Therefore, as an electromagnetic wave shielding adhesive film, what has a basic structure which provides a conductive layer on a thin base film is widely known.

As a conventional electromagnetic wave shielding adhesive film, the reinforcing shielding film which has a conductive adhesive layer and the shielding layer which becomes a metal thin film layer as needed on one side of a cover film, and an adhesive layer and a releasable reinforcement film are laminated | stacked sequentially on the other side is It is known (refer patent document 1).

Moreover, the shielding film which has a shielding layer which has a conductive adhesive layer and / or a metal thin film, and a base film which consists of aromatic polyamide resin is known (refer patent document 2).

Moreover, the shielding adhesive film which coats resin on one side of a separate film, forms a cover film, and provides the shielding layer which consists of a metal thin film layer and an adhesive bond layer on the surface of the said cover film is known (refer patent document 3).

And in the adhesive layer of the conventional electromagnetic wave shielding adhesive film, thermoplastic resins, such as a polystyrene type, a vinyl acetate type, polyester type, a polyethylene type, a polypropylene type, a polyamide type, a rubber type, an acryl type, a phenol type, an epoxy type, Thermosetting resins, such as urethane type, melamine type, and alkyd type, were used. However, the conventional adhesive layer does not have both bending resistance and heat resistance, and in particular, in order to use it for flexible printed wiring board applications, resistance to repeated bending is not perfect.

Patent Document 4 discloses that an electromagnetic wave shielding adhesive film using an adhesive composition containing a polyurethane polyurea resin having a carboxyl group, an epoxy resin having two or more epoxy groups, and a conductive filler is excellent in flex resistance and heat resistance. The contents are disclosed.

However, the electromagnetic wave shielding adhesive film disclosed in Patent Document 4 contains a polyphenylene sulfide (hereinafter sometimes abbreviated as PPS), a polyester resin having a carboxyl group and an epoxy resin having two or more epoxy groups. The film which hardened the curable film-like composition used was used as an insulating base film. With the electromagnetic wave shielding adhesive film using such a base film, it became impossible to respond to the stricter demand for flex resistance. Moreover, when the electromagnetic wave shielding adhesive film is stuck to a to-be-adhered body, and exposed under high temperature, high humidity, the new problem of electroconductivity will fall.

Patent Document 1: Japanese Unexamined Patent Publication No. 2003-298285

Patent Document 2: Japanese Patent Application Laid-Open No. 2004-273577

Patent Document 3: Japanese Patent Laid-Open No. 2004-95566

Patent Document 4: WO 2006-088127

EMBODIMENT OF THE INVENTION This invention is an electromagnetic wave shielding adhesive film used suitably for the use which adheres to a flexible printed wiring board, etc. and shields electromagnetic noise. After sticking to a flexible printed wiring board, in addition to sufficient electromagnetic wave shielding property, lead-free solder reflow is carried out. It has heat resistance that can withstand high temperatures and is excellent in flex resistance than before, and even when exposed to high temperature and high humidity (specifically, even through a pressure cracker test (hereinafter referred to as PCT)), the conductivity is lowered. An object of the present invention is to provide an electromagnetic wave shielding adhesive film.

In addition, in the present invention, the curable conductive adhesive layer hardly protrudes from the adhered region when heated to the adherend, and also when the substrate is heat-compressed to a circuit board having a step, the conductive polyurethane is formed in the stepped portion. It is an object of the present invention to provide an electromagnetic wave shielding adhesive film having sufficient concealability to a polyurea adhesive layer. Here, the reason why hiding property is requested | required is to conceal the conductive polyurethane polyurea adhesive layer which is a colored layer by the polyurethane polyurea insulating layer from the top. That is, although the polyurethane polyurea insulating layer after hardening which covers the conductive polyurethane polyurea adhesive layer after hardening needs to be rich in flexibility, if the softness is too rich before hardening or during hardening hardening, in a step part, hardening The polyurethane polyurea insulating layer of the process is excessively stretched, and the conductive polyurethane polyurea adhesive layer is exposed or made visible. Accordingly, the present invention is to provide an electromagnetic wave shielding adhesive film having abundant flexibility after curing, excellent in bending resistance, and having sufficient concealability to the conductive polyurethane polyurea adhesive layer in the stepped portion during adhesion. The purpose.

Moreover, this invention is a method of manufacturing the electromagnetic wave shielding adhesive film which has such excellent performance cheaply and stably, the method of using the electromagnetic wave shielding adhesive film, and the method of manufacturing an electromagnetic wave shield from the electromagnetic wave shielding adhesive film. And an electromagnetic wave shielding material obtained from the electromagnetic wave shielding adhesive film.

1st invention in this invention,

A curable electromagnetic wave shielding adhesive film which has a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II),

The curable conductive polyurethane polyurea adhesive layer (I) reacts a polyol (a2) having an average molecular weight of 500 to 8000 and an organic diisocyanate (a3) other than the diol compound (a1) having a carboxyl group, the carboxyl group-containing diol compound, Polyurethane polyurea resin (A) obtained by making the urethane prepolymer (a4) which has an isocyanate group in the terminal obtained, and the polyamino compound (a5) react, and the epoxy resin (B) which has two or more epoxy groups are contained, The said poly Conductive filler: 10 to 700 parts by weight based on 100 parts by weight of the total of the urethane polyurea resin (A) and the epoxy resin (B),

The said curable insulating polyurethane polyurea resin composition layer (II) reacts the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, the carboxyl group-containing diol compound. A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group with a terminal obtained by reacting a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups. It relates to a curable electromagnetic wave shielding adhesive film.

2nd invention,

As a curable electroconductive shielding adhesive film which has a curable conductive polyurethane polyurea adhesive layer (I) whose gel fraction is 30 to 90 weight%, and a curable insulating polyurethane polyurea resin composition layer (II),

The curable conductive polyurethane polyurea adhesive layer (I) is obtained by reacting a polyol (a2) having an average molecular weight of 500 to 8000 and an organic diisocyanate (a3) other than the diol compound (a1) having a carboxyl group, the carboxyl group-containing diol compound, and the like. Urethane prepolymer (a4) which has an isocyanate group at the terminal, Polyurethane polyurea resin (A) obtained by making polyamino compound (a5) react, Epoxy resin (B) which has two or more epoxy groups, and the said polyurethane polyurea The conductive filler: 10 to 700 parts by weight and the aziridine-based curing agent (E) are added to 1 mole of the carboxyl group in the polyurethane polyurea resin (A) based on 100 parts by weight in total of the resin (A) and the epoxy resin (B). It is formed with the curable conductive polyurethane polyurea adhesive agent containing an aziridinyl group in the range of 0.05-4 mol,

The said curable insulating polyurethane polyurea resin composition layer (II) reacts the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, the carboxyl group-containing diol compound. A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group with a terminal obtained by reacting a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups. It relates to a curable electromagnetic wave shielding adhesive film.

3rd invention,

A curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight, having a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II),

The curable conductive polyurethane polyurea adhesive layer (I) reacts a polyol (a2) having an average molecular weight of 500 to 8000 and an organic diisocyanate (a3) other than the diol compound (a1) having a carboxyl group, the carboxyl group-containing diol compound, Urethane prepolymer (a4) which has isocyanate group in the terminal obtained, Polyurethane polyurea resin (A) obtained by making polyamino compound (a5) react, Epoxy resin (B) which has two or more epoxy groups, and the said polyurethane poly 1 mol of carboxyl groups in the said polyurethane polyurea resin (A) of an electrically conductive filler: 10-700 weight part and an aziridine system hardener (E) with respect to a total of 100 weight part of a urea resin (A) and the said epoxy resin (B). It is formed with the curable conductive polyurethane polyurea adhesive agent containing an aziridinyl group in 0.05-4 mol with respect to,

The said curable insulating polyurethane polyurea resin composition layer (II) reacts the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, the carboxyl group-containing diol compound. Urethane prepolymer (c4) having an isocyanate group at the terminal to be obtained, and a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and an aziridine-based curing agent (F) is formed from a curable insulating polyurethane polyurethane urea resin composition having a film-forming ability, containing an aziridinyl group in a range of 0.05 to 4 moles per 1 mole of the carboxyl group in the polyurethane polyurea resin (C). It is related with the curable electromagnetic wave shielding adhesive film characterized by the above-mentioned.

4th invention,

As curable electroconductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II) whose gel fraction is 30 to 90 weight%,

The curable conductive polyurethane polyurea adhesive layer (I) reacts a polyol (a2) having an average molecular weight of 500 to 8000 and an organic diisocyanate (a3) other than the diol compound (a1) having a carboxyl group, the carboxyl group-containing diol compound, It contains the urethane prepolymer (a4) which has an isocyanate group in the terminal obtained, the polyurethane polyurea resin (A) obtained by making a polyamino compound (a5) react, the epoxy resin (B) which has two or more epoxy groups, and a conductive filler Conductive filler: 10 to 700 parts by weight based on 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B),

The said curable insulating polyurethane polyurea resin composition layer (II) reacts the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, the carboxyl group-containing diol compound. Urethane prepolymer (c4) having an isocyanate group at the terminal to be obtained, and a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups and an aziridine-based curing agent (E) is formed from curable insulating polyurethane polyurethane urea resin composition having a film-forming ability to contain an aziridinyl group in the range of 0.05 to 4 moles with respect to 1 mole of the carboxyl group in the polyurethane polyurea resin (C). It relates to a curable electromagnetic wave shielding adhesive film.

5th invention,

Curable conductive polyurethane polyurea adhesive layer (I) contains 3-200 weight part of epoxy resins (B) with respect to 100 weight part of polyurethane polyurea resins (A), and also curable insulating polyurethane polyurea resin composition Layer (II) contains 3-200 weight part of epoxy resins (D) with respect to 100 weight part of polyurethane polyurea resins (C), The curable electromagnetic wave shielding adhesion in any one of 1st-4th invention characterized by the above-mentioned. It is about sex film.

6th invention,

The peelable film 1 is laminated | stacked on the surface which curable electroconductive polyurethane polyurea adhesive bond layer I of curable insulating polyurethane polyurea resin composition layer (II) does not contact. The curable electromagnetic wave shielding adhesive film of this invention is related.

7th invention,

The peelable film 2 is laminated | stacked on the surface which the curable insulating polyurethane polyurea resin composition layer (II) of curable electroconductive polyurethane polyurea adhesive bond layer (I) does not contact. The curable electromagnetic wave shielding adhesive film of this invention is related.

8th invention,

On the surface which curable insulating polyurethane polyurea resin composition layer (II) does not contact curable conductive polyurethane polyurea adhesive bond layer (I), the peelable film (2) is laminated, and curable insulating poly The peelable film 1 is laminated | stacked on the surface of the urethane polyurea resin composition layer (II) which curable electroconductive polyurethane polyurea adhesive bond layer (I) does not contact, The curability of 5th invention characterized by the above-mentioned. An electromagnetic wave shielding adhesive film is related.

9th invention,

Terminal obtained by making polyol (c2) and organic diisocyanate (c3) of number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound react on one surface of the peelable film (1) Curable insulating polyurethane poly containing a polyurethane preurea resin (C4) obtained by reacting a urethane prepolymer (c4) having an isocyanate group with a polyamino compound (c5) and an epoxy resin (D) having two or more epoxy groups. Forming a urea resin composition layer (II),

Terminal obtained by making polyol (a2) and organic diisocyanate (a3) of number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound react on one surface of the peelable film (2) Urethane prepolymer (a4) having an isocyanate group, a polyurethane polyurea resin (A) obtained by reacting a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, and the polyurethane polyurea resin A step of forming a curable conductive polyurethane polyurethane urea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler based on 100 parts by weight of the total of (A) and the epoxy resin (B), and

Step of overlapping and combining the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II)

It relates to a method for producing a curable electromagnetic wave shielding adhesive film.

10th invention,

Terminal obtained by making polyol (c2) and organic diisocyanate (c3) of number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound react on one surface of the peelable film (1) Curable insulating polyurethane poly containing a polyurethane preurea resin (C4) obtained by reacting a urethane prepolymer (c4) having an isocyanate group with a polyamino compound (c5) and an epoxy resin (D) having two or more epoxy groups. Forming a urea resin composition layer (II),

On the said curable insulating polyurethane polyurea resin composition layer (II), the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which have a carboxyl group, the carboxyl group-containing diol compound Urethane prepolymer (a4) which has isocyanate group in the terminal obtained by making it react, Polyurethane polyurea resin (A) obtained by making polyamino compound (a5) react, Epoxy resin (B) which has two or more epoxy groups, and the said poly A step of forming a curable conductive polyurethane polyurethane urea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler with respect to a total of 100 parts by weight of the urethane polyurea resin (A) and the epoxy resin (B), and

Stacking the peelable film (2) on the curable conductive polyurethane polyurea adhesive layer (I), and

It relates to a method for producing a curable electromagnetic wave shielding adhesive film.

11th invention,

Terminal obtained by making polyol (a2) and organic diisocyanate (a3) of number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound react on one surface of the peelable film (2) Urethane prepolymer (a4) having an isocyanate group, a polyurethane polyurea resin (A) obtained by reacting a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, and the polyurethane polyurea resin A step of forming a curable conductive polyurethane polyurethane urea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler based on 100 parts by weight of the total of (A) and the epoxy resin (B),

On the said curable conductive polyurethane polyurea adhesive bond layer (I), the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which have a carboxyl group, the carboxyl group-containing diol compound are reacted. Curable insulating property containing the urethane prepolymer (c4) which has an isocyanate group in the terminal obtained by making it react, the polyurethane polyurea resin (C) obtained by making a polyamino compound (c5) react, and the epoxy resin (D) which has two or more epoxy groups Forming a polyurethane polyurea resin composition layer (II), and

Stacking the peelable film (1) on the curable insulating polyurethane polyurea resin composition layer (II), and

It relates to a method for producing a curable electromagnetic wave shielding adhesive film.

12th invention,

To the terminal obtained by making one surface of the peelable film 1 react the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound Curable insulating polyurethane polyurea containing the urethane prepolymer (c4) which has an isocyanate group, the polyurethane polyurea resin (C) obtained by making a polyamino compound (c5) react, and the epoxy resin (D) which has two or more epoxy groups. Forming a resin composition layer (II), and

Terminal obtained by making polyol (a2) and organic diisocyanate (a3) of number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound react on one surface of the peelable film (2) Urethane prepolymer (a4) having an isocyanate group, a polyurethane polyurea resin (A) obtained by reacting a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, and the polyurethane polyurea resin Conductive filler: 10 to 700 parts by weight and aziridine-based curing agent (E) based on 100 parts by weight of the total of (A) and the epoxy resin (B) with respect to 1 mole of the carboxyl group in the polyurethane polyurea resin (A). Curable conductive polyurethane polyurea adhesive having a gel fraction of 30 to 90% by weight from a curable conductive polyurethane polyurea adhesive containing an aziridinyl group in the range of 0.05 to 4 mol The step of forming the agent layer (I), and

Stacking and curing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II),

It relates to a method for producing a curable electromagnetic wave shielding adhesive film.

13th invention,

To the terminal obtained by making one surface of the peelable film 1 react the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound Curable insulating polyurethane polyurea containing the urethane prepolymer (c4) which has an isocyanate group, the polyurethane polyurea resin (C) obtained by making a polyamino compound (c5) react, and the epoxy resin (D) which has two or more epoxy groups. Process of forming resin composition layer (II),

On the said curable insulating polyurethane polyurea resin composition layer (II), the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which have a carboxyl group, the carboxyl group-containing diol compound Urethane prepolymer (a4) which has isocyanate group in the terminal obtained by making it react, Polyurethane polyurea resin (A) obtained by making polyamino compound (a5) react, Epoxy resin (B) which has two or more epoxy groups, and the said poly Conductive filler: 10 to 700 parts by weight and aziridine-based curing agent (E) with respect to a total of 100 parts by weight of the urethane polyurea resin (A) and the epoxy resin (B), and the carboxyl group in the polyurethane polyurea resin (A). Curable whose gel fraction is 30 to 90 weight% from the curable conductive polyurethane polyurea adhesive which contains an aziridinyl group in the range of 0.05-4 mol with respect to 1 mol. Forming a conductive polyurethane polyurea adhesive layer (I), and

Stacking the peelable film (2) on the curable conductive polyurethane polyurea adhesive layer (I), and

It relates to a method for producing a curable electromagnetic wave shielding adhesive film.

14th invention,

To the terminal obtained by making one surface of the peelable film 2 react with the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound The urethane prepolymer (a4) having an isocyanate group, the polyurethane polyurea resin (A) obtained by making a polyamino compound (a5) react, the epoxy resin (B) which has two or more epoxy groups, and the said polyurethane polyurea resin ( Conductive filler: 10 to 700 parts by weight and aziridine-based curing agent (E) based on 100 parts by weight of the total of A) and the epoxy resin (B) with respect to 1 mole of the carboxyl group in the polyurethane polyurea resin (A), Curable conductive polyurethane polyurea adhesive having a gel fraction of 30 to 90% by weight from the curable conductive polyurethane polyurea adhesive containing aziridinyl group in the range of 0.05 to 4 mol. The step of forming the layer (I),

On the said curable conductive polyurethane polyurea adhesive bond layer (I), the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which have a carboxyl group, the carboxyl group-containing diol compound are reacted. Curable insulating property containing the urethane prepolymer (c4) which has an isocyanate group in the terminal obtained by making it react, the polyurethane polyurea resin (C) obtained by making a polyamino compound (c5) react, and the epoxy resin (D) which has two or more epoxy groups Forming a polyurethane polyurea resin composition layer (II), and

Stacking the peelable film (1) on the curable insulating polyurethane polyurea resin composition layer (II), and

It relates to a method for producing a curable electromagnetic wave shielding adhesive film.

15th invention,

To the terminal obtained by making one surface of the peelable film 1 react the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound A urethane prepolymer (c4) having an isocyanate group, a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and an aziridine-based curing agent (F) The gel fraction is 30-90 from the curable insulating polyurethane polyurethane urea resin composition which has a film formation ability which contains an aziridinyl group in 0.05-4 mol with respect to 1 mol of carboxyl groups in the said polyurethane polyurea resin (C). Forming a curable insulating polyurethane polyurethane urea resin composition layer (II) that is% by weight,

To the terminal obtained by making one surface of the peelable film 2 react with the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound The urethane prepolymer (a4) having an isocyanate group, the polyurethane polyurea resin (A) obtained by making a polyamino compound (a5) react, the epoxy resin (B) which has two or more epoxy groups, and the said polyurethane polyurea resin ( Conductive filler: 10 to 700 parts by weight and aziridine-based curing agent (E) based on 100 parts by weight of the total of A) and the epoxy resin (B) with respect to 1 mole of the carboxyl group in the polyurethane polyurea resin (A), Curable conductive polyurethane polyurea adhesive having a gel fraction of 30 to 90% by weight from the curable conductive polyurethane polyurea adhesive containing aziridinyl group in the range of 0.05 to 4 mol. The step of forming the layer (I), and

Stacking and curing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II),

It relates to a method for producing a curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight.

16th invention,

To the terminal obtained by making one surface of the peelable film 1 react the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound A urethane prepolymer (c4) having an isocyanate group, a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and an aziridine-based curing agent (F) The gel fraction is 30-90 from the curable insulating polyurethane polyurethane urea resin composition which has a film formation ability which contains an aziridinyl group in 0.05-4 mol with respect to 1 mol of carboxyl groups in the said polyurethane polyurea resin (C). Forming a curable insulating polyurethane polyurethane urea resin composition layer (II) that is% by weight,

On the said curable insulating polyurethane polyurea resin composition layer (II), the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which have a carboxyl group, the carboxyl group-containing diol compound Urethane prepolymer (a4) which has isocyanate group in the terminal obtained by making it react, Polyurethane polyurea resin (A) obtained by making polyamino compound (a5) react, Epoxy resin (B) which has two or more epoxy groups, and the said poly Conductive filler: 10 to 700 parts by weight and aziridine-based curing agent (E) with respect to a total of 100 parts by weight of the urethane polyurea resin (A) and the epoxy resin (B), and the carboxyl group in the polyurethane polyurea resin (A). Curable whose gel fraction is 30 to 90 weight% from the curable conductive polyurethane polyurea adhesive which contains an aziridinyl group in the range of 0.05-4 mol with respect to 1 mol. Forming a conductive polyurethane polyurea adhesive layer (I), and

It relates to a method for producing a curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight, including the step of overlaying the peelable film 2 on the curable conductive polyurethane polyurea adhesive layer (I). .

17th invention,

To the terminal obtained by making one surface of the peelable film 2 react with the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound The urethane prepolymer (a4) having an isocyanate group, the polyurethane polyurea resin (A) obtained by making a polyamino compound (a5) react, the epoxy resin (B) which has two or more epoxy groups, and the said polyurethane polyurea resin ( Conductive filler: 10 to 700 parts by weight and aziridine-based curing agent (E) based on 100 parts by weight of the total of A) and the epoxy resin (B) with respect to 1 mole of the carboxyl group in the polyurethane polyurea resin (A), Curable conductive polyurethane polyurea adhesive having a gel fraction of 30 to 90% by weight from the curable conductive polyurethane polyurea adhesive containing aziridinyl group in the range of 0.05 to 4 mol. The step of forming the layer (I),

On the said curable conductive polyurethane polyurea adhesive bond layer (I), the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which have a carboxyl group, the carboxyl group-containing diol compound are reacted. Urethane prepolymer (c4) having an isocyanate group at the terminal to be obtained, and a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and an aziridine-based curing agent The gel fraction from the curable insulating polyurethane polyurethane urea resin composition having a film-forming ability, containing (F) aziridinyl group in the range of 0.05 to 4 moles per 1 mole of the carboxyl group in the polyurethane polyurea resin (C). Process of forming curable insulating polyurethane polyurethane urea resin composition layer (I) which is 30 to 90 weight%, and

Regarding the method for producing a curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight, including the step of overlaying the peelable film 1 on the curable insulating polyurethane polyurea resin composition layer (II). will be.

18th invention,

To the terminal obtained by making one surface of the peelable film 1 react the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound A urethane prepolymer (c4) having an isocyanate group, a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and an aziridine-based curing agent (E) The gel fraction is 30-90 from the curable insulating polyurethane polyurethane urea resin composition which has a film formation ability which contains an aziridinyl group in 0.05-4 mol with respect to 1 mol of carboxyl groups in the said polyurethane polyurea resin (C). Forming a curable insulating polyurethane polyurethane urea resin composition layer (II) that is% by weight,

To the terminal obtained by making one surface of the peelable film 2 react with the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound The urethane prepolymer (a4) having an isocyanate group, the polyurethane polyurea resin (A) obtained by making a polyamino compound (a5) react, the epoxy resin (B) which has two or more epoxy groups, and the said polyurethane polyurea resin ( A step of forming a curable conductive polyurethane polyurethane urea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler based on 100 parts by weight of the total of A) and the epoxy resin (B), and

Step of overlapping and combining the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II)

It relates to a method for producing a curable electromagnetic wave shielding adhesive film.

19th invention,

To the terminal obtained by making one surface of the peelable film 1 react the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound A urethane prepolymer (c4) having an isocyanate group, a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and an aziridine-based curing agent (E) The gel fraction is 30-90 from the curable insulating polyurethane polyurethane urea resin composition which has a film formation ability which contains an aziridinyl group in 0.05-4 mol with respect to 1 mol of carboxyl groups in the said polyurethane polyurea resin (C). Forming a curable insulating polyurethane polyurethane urea resin composition layer (II) that is% by weight,

On the said curable insulating polyurethane polyurea resin composition layer (II), the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which have a carboxyl group, the carboxyl group-containing diol compound Urethane prepolymer (a4) which has isocyanate group in the terminal obtained by making it react, Polyurethane polyurea resin (A) obtained by making polyamino compound (a5) react, Epoxy resin (B) which has two or more epoxy groups, and the said poly A step of forming a curable conductive polyurethane polyurethane urea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler with respect to a total of 100 parts by weight of the urethane polyurea resin (A) and the epoxy resin (B), and

Stacking the peelable film (2) on the curable conductive polyurethane polyurea adhesive layer (I), and

It relates to a method for producing a curable electromagnetic wave shielding adhesive film.

20th invention,

To the terminal obtained by making one surface of the peelable film 2 react with the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound The urethane prepolymer (a4) having an isocyanate group, the polyurethane polyurea resin (A) obtained by making a polyamino compound (a5) react, the epoxy resin (B) which has two or more epoxy groups, and the said polyurethane polyurea resin ( A step of forming a curable conductive polyurethane polyurethane urea adhesive layer (I) containing 10 to 700 parts by weight of the conductive filler with respect to 100 parts by weight of the total of A) and the epoxy resin (B),

On the said curable conductive polyurethane polyurea adhesive bond layer (I), the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which have a carboxyl group, the carboxyl group-containing diol compound are reacted. Urethane prepolymer (c4) having an isocyanate group at the terminal to be obtained, and a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups and an aziridine-based curing agent Gel fraction from the curable insulating polyurethane polyurethane urea resin composition which has (E) the film formation ability which contains an aziridinyl group in 0.05-4 mol with respect to 1 mol of carboxyl groups in the said polyurethane polyurea resin (C). Process of forming curable insulating polyurethane polyurea resin composition layer (II) which is 30 to 90 weight%, and

Stacking the peelable film (1) on the curable insulating polyurethane polyurea resin composition layer (II), and

It relates to a method for producing a curable electromagnetic wave shielding adhesive film.

21st invention,

The peelable film (2) of the curable electromagnetic wave shielding adhesive film of the eighth invention is peeled off, the exposed curable conductive polyurethane polyurea adhesive layer (I) is stacked on the adherend, heated, and the curable conductive polyurethane After hardening a polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II), the peelable film 1 is peeled off, The use method of the 8th curable electromagnetic wave shielding adhesive film characterized by the above-mentioned. It is about.

22nd invention,

The peelable film (2) of the curable electromagnetic wave shielding adhesive film of the eighth invention is peeled off, the exposed curable conductive polyurethane polyurea adhesive layer (I) is stacked on the adherend, and the peelable film (1) is peeled off. And then heating to cure the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II). 8. A method of using the eighth curable electromagnetic wave shielding adhesive film It is about.

23rd invention,

The exposed curable conductive polyurethane polyurethane urea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film of the sixth invention is laminated on the adherend, heated, and the curable conductive polyurethane polyurethane urea adhesive layer (I) and curable After hardening the insulating polyurethane polyurea resin composition layer (II), it is related with the manufacturing method of the electromagnetic shielding material characterized by peeling the peelable film (1).

24th invention,

The peelable film (2) of the curable electromagnetic wave shielding adhesive film of the seventh invention is peeled off, the exposed curable conductive polyurethane polyurea adhesive layer (I) is piled up on the adherend, heated, and the curable conductive polyurethane It relates to a method for producing an electromagnetic wave shield, wherein the polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are cured.

25th invention,

The peelable film (2) of the curable electromagnetic wave shielding adhesive film of the eighth invention is peeled off, the exposed curable conductive polyurethane polyurea adhesive layer (I) is stacked on the adherend, heated, and the curable conductive polyurethane The peelable film 1 is peeled after hardening a polyurea adhesive bond layer (I) and curable insulating polyurethane polyurea resin composition layer (II), and it is related with the manufacturing method of the electromagnetic wave shield.

26th invention,

The peelable film (2) of the curable electromagnetic wave shielding adhesive film of the eighth invention is peeled off, the exposed curable conductive polyurethane polyurea adhesive layer (I) is stacked on the adherend, and the peelable film (1) is peeled off. After heating, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are cured.

27th invention,

The electromagnetic wave shield obtained by the manufacturing method in any one of 23rd-26th invention.

It is preferable that the said curable conductive polyurethane polyurea adhesive bond layer (I) contains 3-200 weight part of epoxy resins (B) with respect to 100 weight part of polyurethane polyurea resins (A). Even if thin, the conductive adhesive layer I of such a composition exhibits sufficient cushioning property at the time of heating and crimping, and flows into the insulating film removal part on a grand circuit. Moreover, it has heat resistance which can fully endure lead-free solder reflow by heating and crimping | bonding. Moreover, it has the outstanding flex resistance and does not impair the flex resistance as a whole circuit board when stuck to a flexible printed wiring board.

The curable electromagnetic wave shielding adhesive film of the present invention can express excellent moisture heat resistance and bend resistance by having a curable conductive polyurethane polyurethane urea adhesive layer (I) and a curable insulating polyurethane polyurethane urea resin composition layer (II). . In particular, after affixing to a flexible printed wiring board, in addition to sufficient electromagnetic wave shielding property, it has heat resistance which can endure the high temperature of lead-free solder reflow, and it is excellent in bending resistance compared with the former, and even if exposed to high temperature, high humidity [specifically, Even through the pressure cracker test (hereinafter referred to as PCT)], the conductivity of the conductive polyurethane polyurea adhesive layer (I) does not decrease.

In addition, the curable electromagnetic wave shielding adhesive film of the present invention has a curable conductive polyurethane polyurethane urea adhesive layer (I) in a semi-cured state (gel fraction of 30 to 90% by weight), thereby making it possible Does not protrude excessively, and after hardening, flexible and excellent bending characteristics can be obtained.

In addition, the curable electromagnetic wave shielding adhesive film of the present invention has a curable insulating polyurethane polyurethane urea resin composition layer (II) in a semi-cured state (gel fraction of 30 to 90% by weight), thereby excessively during adhesion and curing. It can suppress the kidneys.

1 is an explanatory diagram of a pressure cracker test (PCT) resistance evaluation test method. FIG. 1 (1) is a schematic plan view of a flexible printed wiring board, in which circuits 2A and 2B are formed on a polyimide film 1 and through-holes are exposed so that a part of the circuit 2A is exposed. The cover film 3 which has (4) is laminated | stacked. FIG. 1 (2) is a cross sectional view taken along the line D-D 'of FIG. FIG.1 (3) is sectional drawing in the CC 'of FIG.1 (1). 1 (4) is curable electromagnetic wave shielding adhesion | attachment so that a part of circuits 2A and 2B may be exposed on the cover film 3 and circuit 2B shown to FIG. 1 (1)-FIG. 1 (3). It is a typical top view of the state which overlapped, crimped, and hardened | cured the sexual film 5. FIG. 1 (5) is sectional drawing in D-D 'of FIG. FIG.1 (6) is sectional drawing in the CC 'of FIG.1 (4).
Explanation of the sign
1: polyimide film
2: copper foil circuit
3: coverlay (adhesive layer not shown)
4: through hole
5: Hardened | cured material of curable electromagnetic wave shielding adhesive film
5a: cured layer of curable insulating polyurethane polyurea composition layer (II)
5b: Cured Layer of Curable Conductive Polyurethane Polyurea Adhesive Layer (I)

The curable electromagnetic wave shielding adhesive film of this invention has four aspects as a film structure.

First, the aspect 1 (hereinafter also referred to as the aspect 1 of the film) of the curable electromagnetic wave shielding adhesive film is a curable conductive polyurethane polyurethane urea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II). To have.

Curable conductive polyurethane polyurea adhesive layer (I) is a polyurethane polyurea resin (A), an epoxy resin (B) which has two or more epoxy groups, the said polyurethane polyurea resin (A), and the said epoxy resin ( It contains 10-700 weight part electroconductive filler with respect to a total of 100 weight part of B).

The said polyurethane polyurea resin (A) is produced by making the urethane prepolymer (a4) which has an isocyanate group at the terminal, and the polyamino compound (a5) react.

The urethane prepolymer (a4) is produced by reacting a diol compound (a1) having a carboxyl group, a polyol (a2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (a3). .

The adhesive resin composition containing a polyurethane polyurea resin (A) and an epoxy resin (B) disperse | distributes an electroconductive filler well, and exhibits sufficient adhesive force even if the electroconductive filler is contained, and also the electromagnetic wave shielding adhesive film and the There is little leakage of the adhesive layer at the time of thermocompression bonding of a complex. Therefore, excellent heat resistance and bending resistance that can withstand lead-free solder reflow can be obtained.

The polyurethane polyurea resin (A) contained in the curable conductive polyurethane urea adhesive layer (I) is a polyol (a2) having a number average molecular weight of 500 to 8000 other than a diol compound (a1) having a carboxyl group and a carboxyl group-containing diol compound. And a urethane prepolymer (a4) having an isocyanate group at the terminal obtained by reacting an organic diisocyanate (a3) and a polyamino compound (a5).

Examples of the diol compound (a1) having a carboxyl group include dimethylol alkanoic acid, such as dimethylol acetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, or dimethylolpentanoic acid, wherein alkanoic acid preferably has 2 to 8 carbon atoms. And dihydroxy aromatic carboxylic acids such as dihydroxysuccinic acid or dihydroxy benzoic acid (in which the aromatic carboxylic acid preferably has 7 to 11 carbon atoms) may be mentioned. Among them, dimethylolpropionic acid and dimethylolbutanoic acid are particularly preferable in terms of reactivity and solubility. The diol compound (a1) which has the said carboxyl group may be used independently, and may use two or more types together.

Polyol (a2) of the number average molecular weights 500-8000 other than a carboxyl group-containing diol compound is generally known as a polyol component which comprises a polyurethane resin, and is a polyol other than the diol compound (a1) which has a carboxyl group. Although the number average molecular weight (Mn) of the said polyol (a2) is suitably determined in consideration of heat resistance, adhesive strength, and / or solubility, etc. of the polyurethane polyurea resin (A) obtained, Preferably it is 1000-5000. When Mn is less than 500, the urethane bond in the polyurethane polyurea resin (A) obtained becomes too large, there exists a tendency for the flexibility of a polymer skeleton to fall and the adhesiveness to a flexible printed wiring board falls, and Mn becomes 8000 When it exceeds, the number in the polyurethane polyurea resin (A) of the carboxyl group derived from a diol compound (a1) will decrease. As a result, since the reaction point with an epoxy resin decreases, there exists a tendency for the solder reflow resistance of the electroconductive hardening adhesive bond layer obtained to fall.

As polyol (a2) of the number average molecular weights 500-8000 other than a carboxyl group-containing diol compound, various polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene glycol, etc. can be used.

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

Examples of the polyester polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, and 3-methyl-1,5- Saturated or unsaturated low molecular diols such as pentanediol, hexanediol, octanediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, or dimerdiol, adipic acid, phthalic acid, iso Polycarboxylic acids obtained by reacting dicarboxylic acids such as phthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, or sebacic acid, or anhydrides thereof Monocarboxylic acid glycidyl esters, such as alkyl glycidyl ethers, such as ester polyol, n-butylglycidyl ether, or 2-ethylhexyl glycidyl ether, and versatic acid glycidyl ester, and the said dica Alcohols of carboxylic acids By reacting in the presence of a hydroxyl group-containing compounds such as acids the polyester polyol, or a ring-opening a cyclic ester compound (開 環) there may be mentioned a polyester polyol obtained by polymerization.

As polycarbonate polyols, for example,

1) a reaction product of glycol or bisphenol and carbonate ester, or

2) A reaction product obtained by reacting phosgene with glycol or bisphenol in the presence of alkali may be used.

Examples of the glycol used for preparing the reaction product of 1) or 2) include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 1,9-nonanediol, neopentylglycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, 3,9-bis (1 , 1-dimethyl-2-hydroxyethyl, or 2,2,8,10-tetraoxose pyro [5.5] undecane.

Moreover, as bisphenol used for preparation of the reaction product of said 1) or 2), bisphenols, such as bisphenol A and bisphenol F, and alkylene oxides, such as ethylene oxide and a propylene oxide, were added to these bisphenols, for example. Compounds and the like.

Moreover, as carbonate ester used for preparation of the reaction product of said 1), dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. are mentioned, for example.

The various polyols illustrated as polyol (a2) of the number average molecular weights 500-8000 other than a carboxyl group-containing diol compound may be used independently, and may be used together two or more types.

Moreover, the polyol (a2) of the number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, the carboxyl group-containing diol compound, and organic within the range which the performance of the polyurethane polyurea resin (A) obtained is not lost. When making a diisocyanate (a3) react, you may use together low molecular diols (namely, diols with a number average molecular weight less than 500) other than a carboxyl group-containing diol compound. As low molecular diols which can be used together, various low molecular diols etc. which are used for manufacture of polyol (a2) of the number average molecular weights 500-8000 other than a carboxyl group-containing diol compound are mentioned, for example.

When synthesize | combining a urethane prepolymer (a4), the polyol (a2) of the number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound has the number average molecular weights 500-8000 other than a carboxyl group-containing diol compound. It is preferable to use in the ratio used as 0.1 mol-4.0 mol of diol compounds (a1) which have a carboxyl group with respect to 1 mol of 8000 polyols (a2), and it is more preferable to use it in the ratio used as 0.2 mol-3.0 mol. When the usage-amount of the carboxyl group-containing diol compound (a1) is less than 0.1 mol with respect to 1 mol of polyols (a2), there exists a tendency for the carboxyl group which can crosslink with an epoxy resin (B) to fall, and solder reflow resistance falls. Moreover, when more than 4.0 mol, there exists a tendency for adhesiveness to fall.

As organic diisocyanate (a3), aromatic diisocyanate, aliphatic diisocyanate, alicyclic isocyanate, or a mixture thereof can be used, but isophorone diisocyanate is particularly preferable.

As aromatic diisocyanate, it is 1, 5- naphthylene diisocyanate, 4,4'- diphenylmethane diisocyanate, 4,4'- diphenyl dimethylmethane diisocyanate, 4,4'- benzyl isocyanate, di, for example. Alkyl diphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, or xylylene diisocyanate.

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

Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexyl methane-4,4'-diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, Or methylcyclohexane diisocyanate.

The urethane prepolymer (a4) which has an isocyanate group at the terminal is obtained by making the diol compound (a1) which has a carboxyl group, the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than a carboxyl group-containing diol compound react Lose. Conditions for synthesizing the urethane prepolymer (a4) having an isocyanate group at the terminal are not particularly limited, except that the isocyanate group is excessive, but the ratio of the equivalent ratio of the isocyanate group / hydroxyl group is within the range of 1.2 / 1 to 3/1. In addition, it is preferable to make the diol compound (a1) which has a carboxyl group, the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than a carboxyl group-containing diol compound react. The reaction temperature is usually from room temperature to 120 ° C, but is preferably 60 to 100 ° C in terms of production time and side reaction control.

A polyurethane polyurea resin (A) is obtained by making the urethane prepolymer (a4) which has an isocyanate group in the terminal, and the polyamino compound (a5) react.

Examples of the polyamino compound (a5) include 2- (2) other than ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, or isophoronediamine and dicyclohexylmethane-4,4'-diamine. Amines having a hydroxyl group such as -aminoethylamino) ethanol, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, or di-2-hydroxypropylethylenediamine Can also be used. Especially, isophorone diamine is used suitably.

When synthesize | combining a polyurethane polyurea resin (A) by making the urethane prepolymer (a4) which has an isocyanate group at the terminal, and a polyamino compound (a5) react, a reaction terminator can be used together in order to adjust molecular weight. As the reaction terminator, dialkyl amines such as di-n-butylamine, dialkanolamines such as diethanolamine, and alcohols such as ethanol and isopropyl alcohol can be used.

The conditions at the time of reacting a urethane prepolymer (a4), a polyamino compound (a5), and the reaction terminator which have an isocyanate group at the terminal as needed are not specifically limited, The polyamino with respect to the isocyanate group which a urethane prepolymer (a4) has It is preferable that the equivalence ratio of the sum total of the amino group in a compound (a5) and a reaction terminator is in the range of 0.5-1.3. When the equivalent ratio is less than 0.5, the solder reflow resistance tends to be insufficient, and when more than 1.3, the polyamino compound (a5) and / or the reaction terminator is left unreacted, and odor tends to remain.

As a solvent used when synthesize | combining a polyurethane polyurea resin (A), aromatic solvents, such as benzene, toluene, xylene, alcohol solvents, such as methanol, ethanol, isopropanol, or n-butanol, acetone, methyl ethyl ketone, Or ester solvents such as ketone solvents such as methyl isobutyl ketone, ethyl acetate, or butyl acetate. These solvents can be used individually by 1 type or in mixture of 2 or more types.

It is preferable that the weight average molecular weight of the polyurethane polyurea resin (A) obtained is in the range of 5000-100000. When the weight average molecular weight is less than 5000, the solder reflow resistance tends to be inferior, and when it exceeds 100000, the adhesiveness tends to be lowered. Moreover, it is preferable that acid value is 3-25 mgKOH / g, and, as for a polyurethane polyurea resin (A), 7-20 mgKOH / g is more preferable. Moreover, although it can use also out of the said numerical range, compatibility of heat resistance and flexibility may become difficult.

In addition, the epoxy resin (B) contained in curable conductive polyurethane urea adhesive bond layer (I) is resin which has two or more epoxy groups, and may be liquid or solid may be sufficient as it.

Examples of the epoxy resin (B) include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, spiro ring type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, terpene type epoxy resins, and tris (glycis). Glycidyl amine type | mold epoxy resins, such as a dialkyloxy) methane or tetrakis (glycidyl oxyphenyl) ethane, tetraglycidyl diamino diphenylmethane, and tetrabrombisphenol A A type epoxy resin, a cresol novolak-type epoxy resin, a phenol novolak-type epoxy resin, the (alpha)-naphthol novolak-type epoxy resin, a brominated phenol novolak-type epoxy resin, etc. are mentioned. These epoxy resins can be used individually by 1 type or in combination of 2 or more type. It is preferable to use bisphenol-A epoxy resin, cresol novolak-type epoxy resin, or tetrakis (glycidyl oxyphenyl) ethane type epoxy resin among these in terms of high adhesiveness and heat resistance. It is preferable that epoxy equivalent (B) is 100-1500 g / eq, and it is more preferable that it is 150-700 g / eq. Although it can be used also outside the numerical range, there is a possibility that both heat resistance and flexibility are difficult.

In the curable conductive polyurethane polyurea adhesive layer (I) used in the present invention, the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) is in 100 parts by weight of the polyurethane polyurea resin (A). It is preferable that it is 3-200 weight part of epoxy resins (B), and it is more preferable that it is 5-100 weight part. When epoxy resin (B) is less than 3 weight part with respect to 100 weight part of polyurethane polyurea resins (A), there exists a tendency for solder reflow resistance to become low. On the other hand, when there are more epoxy resins (B) than 200 weight part, there exists a tendency for adhesiveness to fall.

The curable conductive polyurethane polyurea adhesive layer (I) has a phenolic resin, a silicone resin, a urea resin, an acrylic resin, a polyester resin, and a polyamide resin within a range that does not impair performance such as heat resistance and flex resistance. Or 1 type or more, such as polyimide resin.

The conductive filler contained in the curable conductive polyurethane polyurea adhesive layer provides conductivity to the adhesive layer. As the conductive filler, a metal filler, a carbon filler, or a mixture thereof is used.

As a metal filler, metal powders, such as silver, copper, or nickel, alloy powders, such as a solder, silver-plated copper powder, metal-plated glass fiber, a carbon filler, etc. are mentioned. Especially, the silver filler with high electrical conductivity is preferable, and the silver filler whose specific surface area is 0.5-2.5 m <2> / g which is easy to get a contact of fillers especially is preferable.

Examples of the shape of the conductive filler include spherical, flake, dendritic, fibrous, and the like.

The content of the conductive filler in the curable conductive polyurethane polyurea adhesive layer (I) varies depending on the degree of electromagnetic shielding effect required, but the total of the polyurethane polyurea resin (A) and the epoxy resin (B) is 100. It is preferable that it is 10-700 weight part and 50-500 weight part with respect to a weight part. When content of an electroconductive filler is less than 10 weight part, electroconductive fillers do not fully contact, and high electroconductivity is not obtained. Therefore, the electromagnetic shielding effect is likely to be insufficient. Moreover, even if content of an electrically conductive filler exceeds 700 weight part, the surface resistance value of a curable conductive polyurethane polyurea adhesive bond layer will not fall, conductivity will not only reach a saturation state, but also in the curable conductive polyurethane polyurea adhesive bond layer The quantity of an electroconductive filler becomes excessive, and the adhesiveness and adhesive force to the base film of curable electroconductive polyurethane polyurea adhesive bond layer (I) fall. It is preferable that the adhesive force of adhesive bond layer (I) is 1 N / cm or more of adhesive force with respect to a polyimide film. Although less than 1 N / cm can be used, there exists a possibility that the adhesiveness with a to-be-adhered body may be insufficient.

In the curable conductive polyurethane polyurea adhesive layer (I), for the purpose of promoting the reaction between the polyurethane polyurea resin (A) and the epoxy resin (B) and the reaction with the epoxy resin (B) alone, a curing accelerator and // Or a curing agent. As the curing accelerator of the epoxy resin (B), tertiary amine compounds, phosphine compounds, imidazole compounds and the like can be used. As the curing agent, dicyandiamide, carboxylic acid hydrazide, or acid anhydride can be used.

As the tertiary amine compound in the curing accelerator, triethylamine, benzyldimethylamine, 1,8-diazabicyclo (5.4.0) undecene-7, or 1,5-diazabicyclo (4.3.0) nonene- 5 etc. can be mentioned. Moreover, as a phosphine compound, a triphenyl phosphine, a tributyl phosphine, etc. are mentioned. As the imidazole compound, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2,4-dimethylimidazole, or 2-phenyl And imidazole compounds such as midazoles. Furthermore, potentials of improved storage stability, such as those in which an imidazole compound is reacted with an epoxy resin and insoluble in a solvent, or a type in which an imidazole compound is enclosed in a microcapsule, are used. Although a hardening accelerator can be mentioned, Among these, a latent hardening accelerator is preferable.

As carboxylic acid hydrazide as a hardening | curing agent, succinic acid hydrazide, adipic acid hydrazide, etc. are mentioned. Moreover, hexahydrophthalic anhydride, trimellitic anhydride, etc. are mentioned as an acid anhydride.

As these hardening accelerators or hardening | curing agents, you may use together 2 or more types, respectively, and the usage-amount is 0.1 with respect to 100 weight part of epoxy resins (B) in total (this also includes the case where only one of hardening accelerators or hardening agents is used). It is preferable that it is the range of -30 weight part.

In addition, a silane coupling agent, antioxidant, a pigment, a dye, a tackifying resin, and a plasticizer are contained in the curable conductive polyurethane polyurea adhesive layer within a range that does not deteriorate conductivity, adhesiveness and / or solder reflow resistance. You may add 1 type or more, such as a ultraviolet absorber, an antifoamer, a leveling regulator, a filler, or a flame retardant.

Next, the curable insulating polyurethane polyurea resin composition layer (II) used by this invention is demonstrated. The curable insulating polyurethane polyurea resin composition layer (II) plays a role of imparting mechanical strength to the curable electromagnetic wave shielding adhesive film. That is, even in an uncured state (before hardening), it has a function as a base material or a support | carrier, and corresponds to the base film in patent document 4, for example.

Curable insulating polyurethane polyurea resin composition layer (II) contains a polyurethane polyurea resin (C) and the epoxy resin (D) which has two or more epoxy groups.

The said polyurethane polyurea resin (C) is produced by making the urethane prepolymer (c4) which has an isocyanate group at the terminal, and the polyamino compound (c5) react.

The urethane prepolymer (c4) is produced by reacting a diol compound (c1) having a carboxyl group, a polyol (c2) having a number average molecular weight of 500 to 8000 other than the carboxyl group-containing diol compound, and an organic diisocyanate (c3). .

The adhesive resin composition layer (II) containing a polyurethane polyurea resin (C) and an epoxy resin (D) has little bleeding of the adhesive layer at the time of thermocompression bonding, and is excellent in heat resistance which can endure lead-free solder reflow. And bend resistance can be obtained.

As a polyurethane polyurea resin (C) contained in curable insulating polyurethane polyurea resin composition layer (II), the thing similar to the polyurethane polyurea resin (A) contained in curable conductive polyurethane polyurea adhesive layer (I) Can be mentioned.

Also about the epoxy resin (D) which has two or more epoxy groups, the same thing as the epoxy resin (B) which has two or more epoxy groups is mentioned.

The blending ratio of the epoxy resin (D) and the polyurethane polyurea resin (C) is also 100 parts by weight of the polyurethane polyurea resin (C) similarly to the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A). It is preferable that it is 3-200 weight part of epoxy resins (D) with respect to, and it is more preferable that it is 5-100 weight part.

In addition, like the curable conductive polyurethane polyurea adhesive layer (I), the curable insulating polyurethane polyurea resin composition layer (II) is a phenol-based resin or a silicone-based resin within a range that does not impair performance such as heat resistance and flex resistance. 1 type or more, such as urea resin, acrylic resin, polyester resin, polyamide resin, or polyimide resin, can be contained.

Moreover, also about the point which can contain a hardening accelerator and / or a hardening | curing agent for the purpose of promoting reaction of a polyurethane polyurea resin (C) and an epoxy resin (D), or reaction by an epoxy resin (D) alone, It is the same as that of the curable conductive polyurethane polyurea adhesive layer (I).

In addition, in the curable insulating polyurethane polyurea resin composition layer (II), similar to the case of the curable conductive polyurethane polyurea adhesive layer (I), silane is not deteriorated in adhesiveness and / or solder reflow resistance. You may add 1 type or more, such as a coupling agent, antioxidant, a pigment, dye, tackifying resin, a plasticizer, a ultraviolet absorber, an antifoamer, a leveling regulator, a filler, or a flame retardant.

In the aspect (1) of the film by this invention, the said curable conductive polyurethane polyurea adhesive layer (I) and the said curable insulating polyurethane polyurea resin composition layer (II) are the same except the presence or absence of a conductive filler. The composition may be a polyurethane polyurea resin composition having a composition, or may be a polyurethane polyurea resin composition having a different composition. The curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are both in the uncured (before curing) solidified dry state, and the curable conductive polyurethane polyurethane Even when only the urea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are formed as a film as a whole, a support or a carrier is not particularly required. It is also possible to save it in an attached state.

Next, the aspect 2 (hereinafter also referred to as the aspect 2 of the film) of the curable electromagnetic wave shielding adhesive film in the present invention will be described.

The aspect (2) of a film is flexible after hardening by having curable electroconductive polyurethane polyurea adhesive layer (I) containing an aziridine system hardening | curing agent (E), and curable insulating polyurethane polyurea resin composition layer (II). In addition, it exhibits an additional effect that the adhesive is not excessively protruded from the adhered area when heat-compression-bonded to the adherend while maintaining the effect that the bending property is excellent and the conductivity does not decrease even through PCT.

Specifically, the aspect 2 of the film has a curable electroconductive polyurethane polyurea adhesive layer (I) having a gel fraction of 30 to 90% by weight, and a curable electromagnetic wave having a curable insulating polyurethane polyurethane urea resin composition layer (II). It is a shielding adhesive film.

The curable conductive polyurethane polyurethane urea adhesive layer (I) having a gel fraction of 30 to 90% by weight is a polyol (a2) having a number average molecular weight of 500 to 8000 other than a diol compound (a1) having a carboxyl group, a carboxyl group-containing diol compound and an organic compound. Urethane prepolymer (a4) having an isocyanate group at the terminal obtained by making diisocyanate (a3) react, Polyurethane polyurea resin (A) obtained by making polyamino compound (a5) react, and epoxy resin which has two or more epoxy groups ( B), 10 to 700 parts by weight of an electrically conductive filler and an aziridine-based curing agent (E) based on 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B), the polyurethane polyurea resin An aziridinyl group is contained in 0.05-4 mol with respect to 1 mol of carboxyl groups in (A).

As a polyurethane polyurea resin (A) contained in curable electroconductive polyurethane polyurea adhesive bond layer (I), the thing similar to the polyurethane polyurea resin (A) demonstrated by the aspect (1) of a film is mentioned.

Moreover, also about the epoxy resin (B) which has two or more epoxy groups, the same thing as the epoxy resin (B) which has two or more epoxy groups demonstrated by the aspect (1) of a film is mentioned.

Moreover, the compounding ratio of an epoxy resin (B) and a polyurethane polyurea resin (A) is also a polyurethane similar to the compounding ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) demonstrated by the aspect (1) of a film. It is preferable that it is 3-200 weight part of epoxy resins (B) with respect to 100 weight part of polyurea resin (A), and it is more preferable that it is 5-100 weight part.

As an aziridine system hardening | curing agent (E) used for curable electroconductive polyurethane polyurea adhesive bond layer (I), it is preferable that it is a compound which has two or more aziridinyl groups. Specifically, trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), or N, N'-hexamethylene-1,6-bis (1-aziridinecarboxyamide), etc. are mentioned.

By using the aziridine-based curing agent (E), the high reactivity of the aziridinyl group and the carboxyl group in the polyurethane polyurea resin (A) can be used to make them semi-cured without requiring special aging. have. That is, by making both react and making the gel fraction of curable conductive polyurethane polyurea adhesive layer (I) into 30 to 90 weight%, it can reduce that the curable conductive adhesive layer protrudes from an adhesion area at the time of heat compression. . It is preferable that it is 50 to 85 weight%, and, as for the gel fraction of curable conductive polyurethane polyurea adhesive bond layer (I), it is more preferable that it is 60 to 80 weight%.

When the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is less than 30% by weight, that is, most of the polyurethane polyurea resin (A) remains unreacted, the adhesive vias in the hot pressing process Almost no reduction in the yield is expected. On the other hand, when the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) exceeds 90% by weight, most of the polyurethane urea resin (A) is already present with the aziridine-based curing agent (E) before reaching the heat-compression step. Since it has reacted and hardened | cured, it becomes difficult to ensure adhesiveness with a to-be-adhered body.

In order to obtain the curable conductive polyurethane polyurethane urea adhesive layer (I) having a gel fraction of 30 to 90% by weight, the aziridinyl group is in the range of 0.05 to 4 mol with respect to 1 mol of the carboxyl group in the polyurethane polyurea resin (A). It is important to contain an aziridine type hardening | curing agent (E), it is preferable to contain in 0.2-2 mol, and it is more preferable to contain in 0.4-1 mol.

When the aziridinyl group of an aziridine system hardening | curing agent (E) is less than 0.05 mol times with respect to 1 mol of carboxyl groups in a polyurethane polyurea resin (A), curable electroconductivity is the grade which reduces effectively the adhesiveness of the adhesive agent at the time of a heat-compression bonding process. When obtaining a polyurethane polyurea adhesive bond layer (I), hardening and crosslinking of a polyurethane polyurea resin (A) do not advance. On the other hand, when there are more than 4 mol of aziridinyl groups with respect to 1 mol of carboxyl groups, since reaction and hardening of a polyurethane polyurea resin (A) will advance excessively, curable electroconductive polyurethane polyurea at the time of a heat bonding process Adhesive layer (I) cannot fully wet a to-be-adhered body, reaction of a polyurethane polyurea resin (A) and an epoxy resin (B) cannot be expected, and adhesiveness with respect to a to-be-adhered body cannot be ensured.

In addition, the "gel fraction" used in this invention can be calculated | required as follows.

A wire mesh of 100 mesh is cut into a width of 30 mm and a length of 100 mm, and the weight W1 of the wire mesh is measured. Subsequently, the peelable film 2 is removed from the curable conductive polyurethane polyurea adhesive layer I formed on the peelable film 2, and the curable conductive polyurethane polyurea adhesive having a width of 10 mm and a length of 80 mm. The layer (I) is wrapped with the above-described wire mesh, and the weight (W2) of the test piece is measured as a test piece. The prepared test piece was immersed in methyl ethyl ketone (hereinafter referred to as MEK) and shaken at room temperature for 1 hour, then the test piece was taken out of MEK, dried at 150 ° C. for 10 minutes, and the weight (W3) of the dried test piece was measured. . Using the following formula [I], the weight (W) of the adhesive remaining in the wire mesh without dissolving is calculated as the gel fraction.

The curable electroconductive polyurethane polyurea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film of the aspect (2) of a film has heat resistance similarly to the curable electroconductive polyurethane polyurea adhesive layer (I) of the aspect (1) of a film. In the range which does not impair the performance, such as bending resistance, it contains 1 type or more, such as a phenol resin, silicone resin, urea resin, acrylic resin, polyester resin, polyamide resin, or polyimide resin, etc. You can.

Moreover, also about the point which can contain a hardening accelerator and / or a hardening | curing agent for the purpose of promoting reaction of a polyurethane polyurea resin (A) and an epoxy resin (B), or reaction by an epoxy resin (B) alone, It is the same as the case of curable electroconductive polyurethane polyurea adhesive bond layer (I) of the aspect (1) of a film.

In addition, in the curable electroconductive polyurethane polyurea adhesive layer I of the curable electromagnetic wave shielding adhesive film of the aspect 2 of a film, similarly to the curable electroconductive polyurethane polyurea adhesive layer I of the aspect 1 of a film, 1 type, such as a silane coupling agent, antioxidant, a pigment, dye, tackifying resin, a plasticizer, a ultraviolet absorber, an antifoamer, a leveling regulator, a filler, or a flame retardant, in the range which does not degrade adhesiveness and / or solder reflow resistance. Or more may be added.

On the other hand, curable insulating polyurethane polyurea resin composition layer (II) uses the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound. It contains the urethane prepolymer (c4) which has an isocyanate group in the terminal obtained by making it react, the polyurethane polyurea resin (C) obtained by making a polyamino compound (c5) react, and the epoxy resin (D) which has two or more epoxy groups, It is formed with the curable insulating polyurethane polyurea resin composition which has a film forming ability.

As a polyurethane polyurea resin (C) contained in curable insulating polyurethane polyurea resin composition layer (II), the thing similar to the polyurethane polyurea resin (A) contained in curable conductive polyurethane polyurea adhesive layer (I) Can be mentioned.

Also about the epoxy resin (D) which has two or more epoxy groups, the same thing as the epoxy resin (B) which has two or more epoxy groups is mentioned.

The blending ratio of the epoxy resin (D) and the polyurethane polyurea resin (C) is also 100 parts by weight of the polyurethane polyurea resin (C) similarly to the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A). It is preferable that it is 3-200 weight part of epoxy resins (D) with respect to, and it is more preferable that it is 5-100 weight part.

In addition, like the curable conductive polyurethane polyurea adhesive layer (I), the curable insulating polyurethane polyurea resin composition layer (II) is a phenol-based resin or a silicone-based resin within a range that does not impair performance such as heat resistance and flex resistance. 1 type or more, such as urea resin, acrylic resin, polyester resin, polyamide resin, or polyimide resin, can be contained.

Moreover, also about the point which can contain a hardening accelerator and / or a hardening | curing agent for the purpose of promoting reaction of a polyurethane polyurea resin (C) and an epoxy resin (D), or reaction by an epoxy resin (D) alone, It is the same as that of the curable conductive polyurethane polyurea adhesive layer (I).

In addition, in the curable insulating polyurethane polyurea resin composition layer (II), the silane coupling agent is in the range which does not deteriorate adhesiveness and solder reflow resistance similarly to the curable conductive polyurethane polyurea adhesive layer (I). You may add 1 type or more, such as antioxidant, a pigment, dye, tackifying resin, a plasticizer, a ultraviolet absorber, an antifoamer, a leveling regulator, a filler, or a flame retardant.

The aspect (2) of a film is flexible after hardening by having curable electroconductive polyurethane polyurea adhesive layer (I) containing an aziridine system hardening | curing agent (E), and curable insulating polyurethane polyurea resin composition layer (II). In addition, the bending property is excellent, and while maintaining the effect that the conductivity does not decrease even through PCT, additionally, the adhesive is not excessively protruded when hot-pressed to the adherend.

In the aspect (2) of the film by this invention, the said curable conductive polyurethane polyurea adhesive layer (I) and the said curable insulating polyurethane polyurea resin composition layer (II) are a conductive filler and an aziridine system hardening | curing agent (E) Except for the presence or absence of the present invention, a polyurethane polyurea resin composition having the same composition or a polyurethane polyurea resin composition having a different composition may be used. The curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are both in the uncured (before curing) solidified dry state, and the curable conductive polyurethane polyurethane Even when only the urea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are formed as a film as a whole, a support or a carrier is not particularly required. It is also possible to save it in an attached state.

Next, the aspect 3 (also called the aspect 3 of a film) of a curable electromagnetic wave shielding adhesive film is demonstrated.

Specifically, it is a curable electromagnetic wave shielding adhesive film which has curable electroconductive polyurethane polyurea adhesive bond layer (I) and curable insulating polyurethane polyurea resin composition layer (II), and the gel fraction as a whole is 30 to 90 weight%.

Curable electroconductive polyurethane polyurea adhesive bond layer (I) is obtained by making polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, the carboxyl group-containing diol compound react Urethane prepolymer (a4) which has an isocyanate group at the terminal, Polyurethane polyurea resin (A) obtained by making polyamino compound (a5) react, Epoxy resin (B) which has two or more epoxy groups, and the said polyurethane polyurea 10 to 700 parts by weight of the conductive filler and the aziridine-based curing agent (E) based on 100 parts by weight of the resin (A) and 100 parts by weight of the epoxy resin (B) per 1 mole of the carboxyl group in the polyurethane polyurea resin (A). And an aziridinyl group in the range of 0.05-4 mol.

As a polyurethane polyurea resin (A) contained in curable electroconductive polyurethane polyurea adhesive bond layer (I), the thing similar to the polyurethane polyurea resin (A) demonstrated by the aspect (1) of a film is mentioned.

Moreover, also about the epoxy resin (B) which has two or more epoxy groups, the same thing as the epoxy resin (B) which has two or more epoxy groups demonstrated by the aspect (1) of a film is mentioned.

In addition, the compounding ratio of an epoxy resin (B) and a polyurethane polyurea resin (A) is poly similarly to the compounding ratio of the epoxy resin (B) and polyurethane polyurea resin (A) demonstrated by the aspect (1) of a film. It is preferable that it is 3-200 weight part of epoxy resins (B) with respect to 100 weight part of urethane polyurea resins (A), and it is more preferable that it is 5-100 weight part.

About the aziridine system hardener (E), the same thing as the aziridine system hardener (E) demonstrated by the aspect (2) of a film can be used.

In addition, by using the aziridine-based curing agent (E), by utilizing the high reactivity of the aziridinyl group and the carboxyl group in the polyurethane polyurea resin (A), no special aging is required, and both are reacted to a semi-cured state. can do. That is, by making both react and making the gel fraction of curable conductive polyurethane polyurea adhesive layer (I) into 30 to 90 weight%, it can reduce that the curable conductive adhesive layer protrudes from an adhesion area at the time of heat compression. . It is preferable that it is 50 to 85 weight%, and, as for the gel fraction of curable conductive polyurethane polyurea adhesive bond layer (I), it is more preferable that it is 60 to 80 weight%.

When the gel fraction layer (I) of the curable conductive polyurethane polyurea adhesive is less than 30% by weight, that is, most of the polyurethane urea resin (A) remains unreacted, the adhesive in the hot pressing process is protruded. We can hardly expect the reduction. On the other hand, when the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) exceeds 90% by weight, most of the polyurethane urea resin (A) is already present with the aziridine-based curing agent (E) before reaching the heat-compression step. Since it has reacted and hardened | cured, it becomes difficult to ensure adhesiveness with a to-be-adhered body.

In order to obtain the curable conductive polyurethane polyurethane urea adhesive layer (I) having a gel fraction of 30 to 90% by weight, the aziridinyl group is in the range of 0.05 to 4 mol with respect to 1 mol of the carboxyl group in the polyurethane polyurea resin (A). It is important to contain an aziridine type hardening | curing agent (E), it is preferable to contain in 0.2-2 mol, and it is more preferable to contain in 0.4-1 mol.

When the aziridinyl group of an aziridine system hardening | curing agent (E) is less than 0.05 mol times with respect to 1 mol of carboxyl groups in a polyurethane polyurea resin (A), curable electroconductivity is the grade which reduces effectively the adhesiveness of the adhesive agent at the time of a heat-compression bonding process. When obtaining a polyurethane polyurea adhesive bond layer, hardening and crosslinking of a polyurethane polyurea resin (A) do not advance. On the other hand, when there are more than 4 mol of aziridinyl groups with respect to 1 mol of carboxyl groups, since reaction and hardening of a polyurethane polyurea resin (A) will advance excessively, curable electroconductive polyurethane polyurea at the time of a heat bonding process An adhesive bond layer cannot fully wet a to-be-adhered body, reaction of a polyurethane polyurea resin (A) and an epoxy resin (B) cannot be expected, and adhesiveness with respect to a to-be-adhered body cannot be secured.

The curable electroconductive polyurethane polyurea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film of the aspect 3 of a film has heat resistance similarly to the curable electroconductive polyurethane polyurea adhesive layer (I) of the aspect (1) of a film. In the range which does not impair the performance, such as bending resistance, it contains 1 type or more, such as a phenol resin, silicone resin, urea resin, acrylic resin, polyester resin, polyamide resin, or polyimide resin, etc. You can.

Moreover, also about the point which can contain a hardening accelerator and / or a hardening | curing agent for the purpose of promoting reaction of a polyurethane polyurea resin (A) and an epoxy resin (B), or reaction by an epoxy resin (B) alone, It is the same as the case of curable electroconductive polyurethane polyurea adhesive bond layer (I) of the aspect (1) of a film.

In addition, in the curable conductive polyurethane polyurea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film of the aspect 3 of a film, it is the same as the curable conductive polyurethane polyurea adhesive layer (I) of the aspect 1 of a film, 1 type, such as a silane coupling agent, antioxidant, a pigment, dye, tackifying resin, a plasticizer, a ultraviolet absorber, an antifoamer, a leveling regulator, a filler, or a flame retardant, in the range which does not degrade adhesiveness and / or solder reflow resistance. Or more may be added.

On the other hand, also in the aspect 3 of the film which concerns on this invention, the curable insulating polyurethane polyurea resin composition layer (II) gives a hardening electromagnetic wave shielding adhesive film the role which gives mechanical strength at the time of sticking and hardening. In charge of. That is, even in an uncured state (before hardening), it has a function as a base material or a support | carrier, and corresponds to the base film in patent document 4, for example.

Curable insulating polyurethane polyurea resin composition layer (II) is made to react the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, the carboxyl group-containing diol compound, Polyurethane polyurea resin (C) obtained by making the urethane prepolymer (c4) which has an isocyanate group in the terminal obtained react with a polyamino compound (c5), the epoxy resin (D) which has two or more epoxy groups, and an aziridine type hardening | curing agent (F) ) Is formed from a curable insulating polyurethane polyurethane urea resin composition having a film-forming ability, containing 1 aziridinyl group in the range of 0.05 to 4 mol with respect to 1 mol of the carboxyl group in the polyurethane polyurea resin (C).

Moreover, also about the point which can contain a hardening accelerator and / or a hardening | curing agent for the purpose of promoting reaction of a polyurethane polyurea resin (C) and an epoxy resin (D), or reaction by an epoxy resin (D) alone, It is the same as that of the curable conductive polyurethane polyurea adhesive layer (I).

In addition, in the curable insulating polyurethane polyurea resin composition layer (II), similar to the case of the curable conductive polyurethane polyurea adhesive layer (I), silane is not deteriorated in adhesiveness and / or solder reflow resistance. You may add 1 type or more, such as a coupling agent, antioxidant, a pigment, dye, tackifying resin, a plasticizer, a ultraviolet absorber, an antifoamer, a leveling regulator, a filler, or a flame retardant.

In the curable insulating polyurethane polyurea resin composition layer (II) of the aspect 3 of the film by this invention, an aziridine type hardening | curing agent (F) is with respect to 1 mol of carboxyl groups in the said polyurethane polyurea resin (C), It is preferable to contain an aziridinyl group in 0.2-2 mol, and it is more preferable to contain in 0.4-1 mol.

When the aziridinyl group of the aziridine-based curing agent (F) is less than 0.05 mole times with respect to 1 mol of the carboxyl group in the polyurethane polyurea resin (C), since most of the carboxylic acids in the polyurethane polyurea resin are unreacted, When heat-bonding to a circuit board, when curable insulating polyurethane polyurea resin composition layer (II) is extended | stretched excessively, the fall of a mechanical strength and concealment of the curable conductive polyurethane polyurea adhesive layer 1 in a step part are carried out. There is a risk of a lack of gender. On the other hand, when there are more than 4 mol of aziridinyl groups with respect to 1 mol of carboxyl groups, when the curable insulating polyurethane polyurea resin composition layer (II) is excessively suppressed, when manufacturing a curable electromagnetic wave shielding adhesive film, Adhesiveness of curable insulating polyurethane polyurea resin composition layer (II) and peelable film (1) and adhesiveness of curable insulating polyurethane polyurea resin composition layer (II) and curable conductive polyurethane polyurethane urea adhesive layer (I) There is a risk of deterioration.

As a polyurethane polyurea resin (C) contained in curable insulating polyurethane polyurea resin composition layer (II), the thing similar to the polyurethane polyurea resin (A) demonstrated by the aspect (1) of a film can be used.

Also about the epoxy resin (D) which has two or more epoxy groups, the thing similar to the epoxy resin (A) which has two or more epoxy groups demonstrated by the aspect (1) of a film is mentioned.

The blending ratio of the epoxy resin (D) and the polyurethane polyurea resin (C) is also similar to the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) described in the aspect (1) of the film. It is preferable that it is 3-200 weight part of epoxy resins (D) with respect to 100 weight part of urea resin (C), and it is more preferable that it is 5-100 weight part.

Similarly to the curable conductive polyurethane polyurea adhesive layer (I), the curable insulating polyurethane polyurea resin composition layer (II) has a phenol resin, a silicone resin, One or more types, such as urea resin, acrylic resin, polyester resin, polyamide resin, or polyimide resin, can be contained.

Moreover, also about the point which can contain a hardening accelerator and / or a hardening | curing agent for the purpose of promoting reaction of a polyurethane polyurea resin (C) and an epoxy resin (D), or reaction by an epoxy resin (D) alone, It is the same as that of the curable conductive polyurethane polyurea adhesive layer (I).

In addition, in the curable insulating polyurethane polyurea resin composition layer (II), the silane coupling agent is in the range which does not deteriorate adhesiveness and solder reflow resistance similarly to the curable conductive polyurethane polyurea adhesive layer (I). You may add 1 type or more, such as antioxidant, a pigment, dye, tackifying resin, a plasticizer, a ultraviolet absorber, an antifoamer, a leveling regulator, a filler, or a flame retardant.

The aspect 3 of a film has curable electroconductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II) as a constituent layer. The gel fraction of the curable electromagnetic wave shielding adhesive film is 30 to 90% by weight, preferably 50 to 85% by weight, more preferably 60 to 80% by weight.

Such a curable electromagnetic wave shielding adhesive film has a curable conductive polyurethane polyurethane urea adhesive layer (I) having a gel fraction of 30 to 90 wt%, and a curable insulating polyurethane polyurea resin composition layer having a gel fraction of 30 to 90 wt%. It is preferable to make (II) a structural layer, and it is preferable that it is respectively 50-85 weight%, and, as for the gel fraction of each layer, it is more preferable that it is 60-80 weight%.

That is, in the aspect 3 of the film by this invention, after hardening by using an aziridine system hardening | curing agent (E) and making the gel fraction of curable electroconductive polyurethane polyurea adhesive layer (I) into 30 to 90 weight%, In addition, it is flexible and excellent in bending property, and while maintaining the effect that electroconductivity does not fall even through PCT, the additional effect that an adhesive does not protrude excessively at the time of heat compression to a to-be-adhered body can be acquired. When the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is less than 30% by weight, that is, most of the polyurethane urea resin (A) remains unreacted, the adhesive of the adhesive in the hot pressing process Almost no reduction can be expected. On the other hand, when the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) exceeds 90% by weight, most of the polyurethane urea resin (A) is already present with the aziridine-based curing agent (E) before reaching the heat-compression step. Since it has reacted and hardened | cured, it becomes difficult to ensure adhesiveness with a to-be-adhered body.

In addition, in the aspect 3 of the film by this invention, it is curable by using the aziridine system hardening | curing agent (F) and making the gel fraction of curable insulating polyurethane polyurea resin composition layer (II) into 30 to 90 weight%. Excessive elongation of the curable insulating polyurethane polyurea resin composition layer at the time of heat-sealing an electromagnetic wave shielding adhesive film to a circuit board can be suppressed, and mechanical strength can be maintained. That is, when adhering to the stepped portion or the like of the circuit board, defects such as lack of concealability of the curable conductive polyurethane polyurethane urea adhesive layer due to excessive extension of the curable insulating polyurethane polyurethane urea resin composition layer (II) can be prevented.

If the gel fraction is less than 30% by weight, that is, most of the polyurethane urea resin (C) remains unreacted, the curable insulating polyurethane polyurethane urea resin composition layer (II) is excessively stretched when heat-bonded to the circuit board. Thereby, there exists a possibility of generating defects, such as the fall of a mechanical strength and the concealment lack of curable conductive polyurethane polyurea adhesive bond layer (I). On the other hand, when the gel fraction of curable insulating polyurethane polyurea resin composition layer (II) exceeds 90 weight%, the fluidity | liquidity of this curable insulating polyurethane polyurea resin composition layer (II) is suppressed excessively, and a manufacturing process There exists a possibility that adhesiveness with a peelable film and curable conductive polyurethane polyurea adhesive bond layer (I) may fall.

The aspect 3 of a film is curable conductive polyurethane polyurea adhesive layer (I) containing an aziridine system hardener (E), and curable insulating polyurethane polyurea resin composition layer (II) containing an aziridine system hardener (F). ), After curing, it is flexible and has excellent bending characteristics, and the adhesive does not protrude excessively when hot pressing to the adherend, while maintaining the effect that the conductivity does not decrease even through PCT. In this case, it is possible to exhibit flame resistance in which the conductive polyurethane polyurea adhesive layer is not exposed at the corner portions of the step.

In the aspect 3 of the film by this invention, the said curable conductive polyurethane polyurea adhesive layer (I) and the said curable insulating polyurethane polyurea resin composition layer (II) have the presence or absence of an electrically conductive filler, and an aziridine system hardening | curing agent ( Except for content of E), it is also possible to be a polyurethane polyurea resin composition of the same composition, or to be a polyurethane polyurea resin composition of a different composition. In addition, content of an aziridine system hardening | curing agent (E) may also differ from the said curable electroconductive polyurethane polyurea adhesive bond layer (I) and the said curable insulating polyurethane polyurea resin composition layer (II). The curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are both in the uncured (before curing) solidified dry state, and the curable conductive polyurethane polyurethane Even when only the urea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are formed as a film as a whole, a support or a carrier is not particularly required. It is also possible to save it in an attached state.

Next, the aspect 4 (hereinafter also referred to as the aspect 4 of the film) of the curable electromagnetic wave shielding adhesive film in the present invention will be described. Specifically, it is a curable electromagnetic wave shielding adhesive film which has curable electroconductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II) whose gel fraction is 30 to 90 weight%.

The curable conductive polyurethane polyurea adhesive layer (I) reacts a polyol (a2) having an average molecular weight of 500 to 8000 and an organic diisocyanate (a3) other than the diol compound (a1) having a carboxyl group, the carboxyl group-containing diol compound, It contains the urethane prepolymer (a4) which has an isocyanate group in the terminal obtained, the polyurethane polyurea resin (A) obtained by making a polyamino compound (a5) react, the epoxy resin (B) which has two or more epoxy groups, and a conductive filler And it contains electroconductive filler: 10-700 weight part with respect to a total of 100 weight part of the said polyurethane polyurea resin (A) and the said epoxy resin (B).

As a polyurethane polyurea resin (A) contained in curable electroconductive polyurethane polyurea adhesive bond layer (I), the thing similar to the polyurethane polyurea resin (A) demonstrated by the aspect (1) of a film is mentioned.

Moreover, also about the epoxy resin (B) which has two or more epoxy groups, the same thing as the epoxy resin (B) which has two or more epoxy groups demonstrated by the aspect (1) of a film is mentioned.

The blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) is also similar to the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) described in the aspect (1) of the film. It is preferable that it is 3-200 weight part of epoxy resins (B) with respect to 100 weight part of urea resin (A), and it is more preferable that it is 5-100 weight part.

In addition, the curable conductive polyurethane polyurea adhesive layer (I) includes a phenol resin, a silicone resin, a urea resin, an acrylic resin, a polyester resin, and a polyamide within a range that does not impair performance such as heat resistance and flex resistance. It can contain 1 type or more, such as type resin or polyimide type resin.

Moreover, also about the point which can contain a hardening accelerator and / or a hardening | curing agent for the purpose of promoting reaction of a polyurethane polyurea resin (C) and an epoxy resin (D), or reaction by an epoxy resin (D) alone, It is the same as that of the curable conductive polyurethane polyurea adhesive layer (I).

Moreover, a silane coupling agent, antioxidant, a pigment, dye, tackifying resin, a plasticizer, an ultraviolet absorber, is in the curable conductive polyurethane polyurea adhesive bond layer (I) in the range which does not degrade adhesiveness and solder reflow resistance. You may add 1 type or more, such as an antifoamer, a leveling regulator, a filler, or a flame retardant.

Next, the curable insulating polyurethane polyurea resin composition layer (II) whose gel fraction is 30 to 90 weight% is demonstrated.

Also in the aspect 4 of the film by this invention, curable insulating polyurethane polyurea resin composition layer (II) plays a role which provides the mechanical strength at the time of sticking and hardening to a curable electromagnetic wave shielding adhesive film. do. That is, even in an uncured state (before hardening), it has a function as a base material or a support | carrier, and corresponds to the base film in patent document 4, for example.

The curable insulating polyurethane polyurea resin composition layer (II) having a gel fraction of 30 to 90% by weight is a polyol (c2) having a number average molecular weight of 500 to 8000 other than a diol compound (c1) having a carboxyl group, a carboxyl group-containing diol compound, and Urethane prepolymer (c4) which has an isocyanate group in the terminal obtained by making organic diisocyanate (c3) react, Polyurethane polyurea resin (C) obtained by making polyamino compound (c5) react, and epoxy resin which has two or more epoxy groups Curable insulating polyurethane which has a film-forming ability which contains aziridinyl group in 0.05-4 mol with respect to 1 mol of carboxyl groups in said polyurethane polyurea resin (C) for (D) and an aziridine type hardening | curing agent (E). It is formed from a polyurea resin composition.

As a polyurethane polyurea resin (C) contained in curable insulating polyurethane polyurea resin composition layer (II), the thing similar to the polyurethane polyurea resin (A) demonstrated by the aspect (1) of a film is mentioned.

Also about the epoxy resin (D) which has two or more epoxy groups, the thing similar to the epoxy resin (A) which has two or more epoxy groups is mentioned.

The blending ratio of the epoxy resin (D) and the polyurethane polyurea resin (C) is also similar to the blending ratio of the epoxy resin (B) and the polyurethane polyurea resin (A) described in the aspect (1) of the film. It is preferable that it is 3-200 weight part of epoxy resins (D) with respect to 100 weight part of urea resin (C), and it is more preferable that it is 5-100 weight part.

In addition, the curable insulating polyurethane polyurea resin composition layer (II), like the curable conductive polyurethane polyurethane urea adhesive layer (I), has a phenolic resin and a silicone resin within a range that does not impair performance such as heat resistance and flex resistance. 1 type or more, such as urea resin, acrylic resin, polyester resin, polyamide resin, or polyimide resin, can be contained.

Moreover, also about the point which can contain a hardening accelerator and / or a hardening | curing agent for the purpose of promoting reaction of a polyurethane polyurea resin (C) and an epoxy resin (D), or reaction by an epoxy resin (D) alone, It is the same as that of the curable conductive polyurethane polyurea adhesive layer (I).

In addition, in the curable insulating polyurethane polyurea resin composition layer (II), the silane coupling agent is in the range which does not deteriorate adhesiveness and solder reflow resistance similarly to the curable conductive polyurethane polyurea adhesive layer (I). You may add 1 type or more, such as antioxidant, a pigment, dye, tackifying resin, a plasticizer, a ultraviolet absorber, an antifoamer, a leveling regulator, a filler, or a flame retardant.

The aziridine-based curing agent (E) will be described. By using the aziridine-based curing agent (E), high reactivity between the aziridinyl group and the carboxyl group in the polyurethane polyurea resin (C) is used, without requiring any special aging, and both are reacted to a semi-cured state. . That is, by making both react, the gel fraction of curable insulating polyurethane polyurea resin composition layer (II) can be 30-90 weight%. Thereby, excessive elongation of curable insulating polyurethane polyurea resin composition layer (II) at the time of heat-sealing an electromagnetic wave shielding adhesive film to a circuit board can be suppressed, and mechanical strength can be maintained. In addition, it is possible to prevent a defect such as lack of silver penability of the curable conductive polyurethane polyurea adhesive layer due to excessive extension of the curable insulating polyurethane polyurea resin composition layer (II) in the stepped portion of the circuit board and the like.

It is preferable that it is 50 to 85 weight%, and, as for the gel fraction of curable insulating polyurethane polyurea resin composition layer (II), it is more preferable that it is 60 to 80 weight%.

When the gel fraction of the curable insulating polyurethane polyurea resin composition layer (II) is less than 30% by weight, that is, the majority of the polyurethane polyurea resin (C) remains unreacted, the curable insulating property when heat-attached to a circuit board Excessive extension of polyurethane polyurea resin composition layer (II) produces the fall of mechanical strength and the defect of exposure of curable conductive polyurethane polyurea adhesive layer (I) in a step part. On the other hand, when the gel fraction of curable insulating polyurethane polyurea resin composition layer (II) exceeds 90 weight%, the fluidity of the curable insulating polyurethane polyurea resin composition layer (II) is suppressed excessively, and curable electromagnetic wave shielding property When producing the adhesive film, the adhesiveness of the curable insulating polyurethane polyurea resin composition layer (II) and the peelable film (1), and the curable insulating polyurethane polyurea resin composition layer (II) and the curable conductive polyurethane polyurethane The adhesiveness of adhesive bond layer (I) falls.

In order to obtain the curable insulating polyurethane polyurea resin composition layer (II) having a gel fraction of 30 to 90% by weight, the aziridinyl group is in the range of 0.05 to 4 mol to 1 mol of the carboxyl group in the polyurethane polyurea resin (C). It is important to contain an aziridine type hardening | curing agent (E), it is preferable to contain in the range of 0.2-2 mol, and it is more preferable to contain in the range of 0.4-1 mol.

When the aziridinyl group of the aziridine-based curing agent (E) is less than 0.05 mole relative to 1 mole of the carboxyl group in the polyurethane polyurea resin (C), since most of the carboxylic acids in the polyurethane polyurea resin are unreacted, the gel The fraction is less than 30%. On the other hand, when there are more aziridinyl groups per mole of carboxyl groups than 4 moles, since the aziridinyl group is excessively present, almost all of the carboxylic acids in the polyurethane polyurea resin (C) are aziridine-based curing agents (E). And the gel fraction exceeds 90%.

The aspect 4 of a film is flexible after hardening by having curable electroconductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II) containing an aziridine system hardening | curing agent (E). In addition, the bending property is excellent, and while maintaining the effect that the conductivity does not decrease even through PCT, additionally, the adhesive is not excessively protruded when hot-pressed to the adherend.

In the aspect 4 of the film by this invention, the said curable conductive polyurethane polyurea adhesive layer (I) and the said curable insulating polyurethane polyurea resin composition layer (II) are an electrically conductive filler and an aziridine type hardening | curing agent (E) Except the presence or absence, it is possible to use the polyurethane polyurea resin composition of the same composition, or to use the polyurethane resin composition of a different composition. The curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are both in the uncured (before curing) solidified dry state, and the curable conductive polyurethane polyurethane Even when only the urea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) form a film as a whole, a support or a carrier is not particularly required. It is also possible to preserve in a good state.

Next, the specific aspect of the manufacturing method of the aspect (1)-(4) of the curable electromagnetic wave shielding adhesive film of this invention is demonstrated.

First, according to the 1st manufacturing method of the aspect 1 of a film, one side of one peelable film (henceforth a peelable film 1) is a polyurethane polyurea resin (C) and an epoxy resin ( Coating and drying curable resin composition containing D), and forming curable insulating polyurethane polyurea resin composition layer (II),

Separately, the curable conductive resin composition containing a polyurethane polyurea resin (A), an epoxy resin (B), and an electrically conductive filler is coated on one surface of another peelable film (hereinafter, referred to as a peelable film 2). Dry to form a curable conductive polyurethane polyurea adhesive layer (I),

Subsequently, curable conductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II) are piled up together.

Or according to the 2nd manufacturing method of the aspect 1 of a film, the said curable resin composition is coated and dried to one surface of the peelable film 1, and curable insulating polyurethane polyurea resin composition layer (II) Forming,

The curable conductive polyurethane composition is coated and dried on the curable insulating polyurethane polyurea resin composition layer (II) to form a curable conductive polyurethane polyurethane urea adhesive layer (I), and the curable conductive polyurethane polyurea adhesive The peelable film 2 is superimposed on the layer I and joined.

Or according to the 3rd manufacturing method of the aspect 1 of a film, the said curable conductive resin composition is coated and dried to one surface of the peelable film 2, and the curable conductive polyurethane polyurethane urea adhesive layer (I) Forming,

The curable resin composition is coated and dried on the curable conductive polyurethane polyurea adhesive layer (I) to form a curable insulating polyurethane polyurea resin composition (II), and the curable insulating polyurethane polyurea resin composition layer The peelable film 1 is piled up on (II) and combined.

By the manufacturing method as illustrated, with respect to the aspect (1) of the curable electromagnetic wave shielding adhesive film of this invention, the peelable film (2) / curable conductive polyurethane polyurethane urea adhesive layer (I) / curable insulating polyurethane poly Curable electromagnetic wave shielding adhesive film of the laminated state called urea resin composition layer (II) / peelable film (1) / can be obtained.

Next, the peelable film used by this invention is demonstrated.

The peelable film 1 and the peelable film 2 can use the film which carried out the mold release process to single side | surface or both surfaces, the film which apply | coated the adhesive to single side | surface or both surfaces, etc. can be used.

Examples of the release film include polyethylene terephthalate, polyethylene naphthalate, polyvinyl fluoride, polyvinylidene fluoride, hard polyvinyl chloride, polyvinylidene chloride, nylon, polyimide, polystyrene, polyvinyl alcohol, and ethylene vinyl alcohol. Glass such as copolymer, polycarbonate, polyacrylonitrile, polybutene, soft polyvinyl chloride, polyvinylidene fluoride, polyethylene, polypropylene, polyurethane, ethylene vinyl acetate copolymer, or polyvinyl acetate Papers such as new paper, high-quality paper, kraft paper, or coated paper, various nonwoven fabrics, synthetic paper, metal foil, or a composite film combining them.

As a mold release treatment method, there exists a method of apply | coating a mold release agent to the single side | surface or both surfaces of a film, or physically matting.

As the release agent, hydrocarbon-based resins such as polyethylene or polypropylene, higher fatty acids or metal salts thereof, higher fatty acid soaps, waxes, animal and vegetable fats and oils, mica, talc, silicone surfactants, silicone oils, silicone resins, fluorine-based surfactants, fluorine resins, Or a fluorine-containing silicone resin.

As a coating method of a mold release agent, a conventionally well-known system, for example, a gravure coat system, a kiss coat system, a die coat system, a lip coat system, a comma coat system, a blade coat system, a roll coat system, a knife coat system, a spray coat system , Bar coat method, spin coat method, dip coat method, or the like.

As a method of providing the curable conductive polyurethane polyurethane urea adhesive layer (I) and the curable insulating polyurethane polyurethane urea resin composition layer (II), a conventionally known coating method, for example, a gravure coat method, a kiss coat method, a die coat It can be carried out by a method, a lip coat method, a comma coat method, a blade coat method, a roll coat method, a knife coat method, a spray coat method, a bar coat method, a spin coat method, or a dip coat method.

In addition, as mentioned later, since the peelable film 2 which coats curable conductive polyurethane polyurea adhesive bond layer (I) generally peels before hardening of curable conductive polyurethane polyurea adhesive bond layer (I), As long as it has peelability with the curable conductive polyurethane polyurea adhesive layer (I) in an uncured state, it is also possible to use a film (for example, a polyethylene film or a polyethylene terephthalate film) which has not been subjected to a peeling treatment in particular. In addition, since the peelable film 1 which coats curable insulating polyurethane polyurea resin composition layer (II) generally peels after hardening curable insulating polyurethane polyurea resin composition layer (II), after hardening As long as it has peelability with a polyurethane polyurea layer, it is also possible to use the film (for example, a polyethylene film or a polyethylene terephthalate film) which did not perform a peeling process in particular.

Next, the aspect 2 of a curable electromagnetic wave shielding adhesive film is demonstrated.

According to the 1st manufacturing method of the aspect 2 of a film, Curable which contains a polyurethane polyurea resin (C), an epoxy resin (D), and an aziridine system hardening | curing agent (E) in one surface of the peelable film 1 Coating and drying a resin composition to form curable insulating polyurethane polyurea resin composition layer (II),

Separately, one side of the peelable film 2 is coated and dried with a curable conductive resin composition containing a polyurethane polyurea resin (A), an epoxy resin (B), and a conductive filler to form a curable conductive polyurethane polyurethane urea adhesive. Form layer (I),

Subsequently, curable conductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II) are piled up together.

Or according to the manufacturing method of the aspect 2 of a film, the said curable resin composition is coated and dried on one surface of the peelable film 1, and the curable insulating polyurethane polyurethane urea resin composition layer (II) is formed, ,

The curable conductive polyurethane composition is coated and dried on the curable insulating polyurethane polyurea resin composition layer (II) to form a curable conductive polyurethane polyurethane urea adhesive layer (I), and the curable conductive polyurethane polyurea adhesive The peelable film 2 is superimposed on the layer I and joined.

Or according to the 3rd manufacturing method of the aspect 2 of a film, the said curable conductive resin composition is coated and dried to one surface of the peelable film 2, and the curable conductive polyurethane polyurea adhesive bond layer (I) Forming,

The curable resin composition is coated and dried on the curable conductive polyurethane polyurea adhesive layer (I) to form a curable insulating polyurethane polyurea resin composition layer (II), and the curable insulating polyurethane polyurea resin composition The peelable film 1 is piled up on the layer (II) and joined.

The curable conductive polyurethane polyurethane urea adhesive layer (I) or the curable insulating polyurethane polyurethane urea resin composition layer (30) to have a semi-cured state in which the gel fraction of the curable insulating polyurethane polyurea resin composition layer (II) is 30 to 90% by weight ( Drying conditions at the time of obtaining II), and the conditions which pile up and combine curable electroconductive polyurethane polyurea adhesive bond layer (I) and curable insulating polyurethane polyurea resin composition layer (II) can be selected.

For example, as a drying condition at the time of obtaining curable electroconductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II), a solvent fully volatilizes and a polyurethane polyurea resin ( It is preferable to heat-dry at 10 degreeC-about 5 minutes at 50 degreeC-150 degreeC on the conditions which can react the carboxylic acid of C) and an aziridine system hardening | curing agent (E), and heat 30 degreeC-3 minutes at 70 degreeC-120 degreeC It is more preferable to dry.

Moreover, since it is easy to maintain the hardening state of the curable insulating polyurethane polyurea resin composition layer (II) semi-hardened with the aziridine system hardening | curing agent (E), each curable conductive polyurethane polyurea adhesive agent formed separately. The method of laminating | stacking layer (I) and curable insulating polyurethane polyurea resin composition layer (II) together, and obtaining a curable electromagnetic wave shielding adhesive film is preferable. In this case, the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) have a temperature of 40 ° C to 120 ° C, a pressure of 0.1 to 5 MPa, and a time of 0.5 seconds to 60 It is preferable to superimpose and integrate in conditions of about a second.

By the manufacturing method as illustrated, with respect to the aspect (2) of the curable electromagnetic wave shielding adhesive film of this invention, the peelable film (2) / curable conductive polyurethane polyurea adhesive layer (I) / curable insulating polyurethane poly Curable electromagnetic wave shielding adhesive film of the laminated state called urea resin composition layer (II) / peelable film (1) / can be obtained.

Next, the aspect 3 of a curable electromagnetic wave shielding adhesive film is demonstrated.

According to the 1st manufacturing method of the aspect 3 of a film, For example, a polyurethane polyurea resin (C), an epoxy resin (D), and an aziridine system hardening | curing agent (F) are made to one side of the peelable film 1, for example. Coating and drying curable resin composition containing this, and forming curable insulating polyurethane polyurea resin composition layer (II),

Separately, a curable conductive resin composition containing a polyurethane polyurea resin (A), an epoxy resin (B), an aziridine-based curing agent (E), and a conductive filler is coated and dried on one surface of the peelable film 2, Forming a curable conductive polyurethane polyurea adhesive layer (I),

Subsequently, curable conductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II) are piled up together.

Or according to the 2nd manufacturing method of the aspect 3 of a film, the said curable resin composition is coated and dried to one surface of the peelable film 1, and curable insulating polyurethane polyurea resin composition layer (II) Forming,

The curable conductive polyurethane composition is coated and dried on the curable insulating polyurethane polyurea resin composition layer (II) to form a curable conductive polyurethane polyurethane urea adhesive layer (I), and the curable conductive polyurethane polyurea adhesive The peelable film 2 is superimposed on the layer I and joined.

Or according to the 3rd manufacturing method of the aspect 3 of a film, the said curable conductive resin composition is coated and dried to one surface of the peelable film 2, and the curable conductive polyurethane polyurethane urea adhesive layer (I) Forming,

The curable resin composition is coated and dried on the curable conductive polyurethane polyurea adhesive layer (I) to form a curable insulating polyurethane polyurea resin composition layer (II), and the curable insulating polyurethane polyurea resin composition The peelable film 1 was piled up on the layer (II), and it joined.

Curable conductive polyurethane polyurea adhesive layer (I), and curable conductive polyurethane polyurea adhesive layer (30) so that the gel fraction of curable insulating polyurethane polyurea resin composition layer (II) may be in the semi-cured state (30-90 weight%) ( Drying conditions at the time of obtaining I) and curable insulating polyurethane polyurea resin composition layer (II), and curable conductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II) are piled up and matched. Can select the condition. Moreover, drying conditions, hardening conditions, etc. can be performed on the conditions similar to the manufacturing method of the aspect 2 of a curable electromagnetic wave shielding adhesive film.

By the manufacturing method as illustrated, with respect to the aspect 3 of the curable electromagnetic wave shielding adhesive film of this invention, the peelable film 2 / curable conductive polyurethane polyurea adhesive layer (I) / curable insulating polyurethane poly Curable electromagnetic wave shielding adhesive film of the laminated state called urea resin composition layer (II) / peelable film (1) / can be obtained.

Next, the aspect 4 of a curable electromagnetic wave shielding adhesive film is demonstrated.

According to the 1st manufacturing method of the aspect 4 of a film, For example, the curable resin composition containing a polyurethane polyurea resin (C) and an epoxy resin (D) in one surface of the peelable film 1 is used. Coating and drying to form a curable insulating polyurethane polyurea resin composition layer (II),

Separately, a curable conductive resin composition containing a polyurethane polyurea resin (A), an epoxy resin (B), an aziridine-based curing agent (E), and a conductive filler is coated and dried on one surface of the peelable film 2, Forming a curable conductive polyurethane polyurea adhesive layer (I),

Subsequently, curable conductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II) are piled up together.

Or according to the 2nd manufacturing method of the aspect 4 of a film, the said curable resin composition is coated and dried to one side of the peelable film 1, and curable insulating polyurethane polyurea resin composition layer (II) Forming,

The curable conductive polyurethane composition is coated and dried on the curable insulating polyurethane polyurea resin composition layer (II) to form a curable conductive polyurethane polyurethane urea adhesive layer (I), and the curable conductive polyurethane polyurea adhesive The peelable film 2 is superimposed on the layer I and joined.

Or according to the 3rd manufacturing method of the aspect 4 of a film, the said curable conductive resin composition is coated and dried to one surface of the peelable film 2, and the curable conductive polyurethane polyurethane urea adhesive layer (I) Forming,

The curable resin composition is coated and dried on the curable conductive polyurethane polyurea adhesive layer (I) to form a curable insulating polyurethane polyurea resin composition layer (II), and the curable insulating polyurethane polyurea resin composition The peelable film 1 is piled up on the layer (II) and joined.

Curable conductive polyurethane polyurea adhesive layer (I) or curable insulating polyurethane polyurethane urea resin composition layer (II) such that the gel fraction of the curable conductive polyurethane polyurea adhesive layer (I) is in a semi-cured state of 30 to 90% by weight. The drying conditions at the time of obtaining ()), and the conditions which pile up and combine curable electroconductive polyurethane polyurea adhesive bond layer (I) and curable insulating polyurethane polyurea resin composition layer (II) can be selected. Moreover, drying conditions, hardening conditions, etc. can be performed on the conditions similar to the manufacturing method of the aspect 2 of a curable electromagnetic wave shielding adhesive film.

By the manufacturing method as illustrated, with respect to the aspect 4 of the curable electromagnetic wave shielding adhesive film of this invention, the peelable film 2 / curable electroconductive polyurethane polyurethane urea adhesive layer 1 / curable insulating polyurethane poly Curable electromagnetic wave shielding adhesive film of the laminated state called urea resin composition layer (II) / peelable film (1) / can be obtained.

Moreover, the specific aspect of the usage method of the curable electromagnetic wave shielding adhesive film of this invention is demonstrated.

The curable electromagnetic wave shielding adhesive film has a laminated state of a peelable film (2) / curable conductive polyurethane polyurea adhesive layer (I) / curable insulating polyurethane polyurea resin composition layer (II) / peelable film (1) / Although it is preferable to take, the peelable film 2 is removed from the curable electromagnetic wave shielding adhesive film, and the curable conductive polyurethane polyurea adhesive layer I is exposed. Polyurethane in curable electroconductive polyurethane polyurea adhesive layer (I) and curable insulating polyurethane polyurethane urea resin composition layer (II) by superimposing the curable electroconductive polyurethane polyurea adhesive layer (I) on a to-be-adhered body, and heating. Polyurea resin (A), an epoxy resin (B), polyurethane polyurea resin (C), and an epoxy resin (D) are made to react, and both layers (I) (II) are hardened. In the vicinity of the contact interface, the reaction between the polyurethane polyurea resin (A) and the epoxy resin (D) and the polyurethane polyurea resin (C) and the epoxy resin (B) may also occur. And after hardening of both layers (I) (II), by removing the peelable film 1, it becomes possible to shield a to-be-adhered body from an electromagnetic wave.

Moreover, the use aspect which heats and hardens the said both layers (I) (II) after peeling off the peelable film 1 after laminating | stacking and combining a curable electromagnetic wave shielding adhesive film with a to-be-adhered body is also preferable.

As a to-be-adhered body which can stick the curable electromagnetic wave shielding adhesive film of this invention, the flexible printed wiring board which repeatedly bends is mentioned as a representative example. Of course, it can also be applied to a rigid printed wiring board.

The electromagnetic wave shield manufactured by using the above-mentioned curable electromagnetic wave shielding adhesive film as a to-be-adhered body, for example using a printed wiring board, can be used suitably for articles, such as a mobile telephone and a digital camera, for example.

Example

Next, although an Example is shown and this invention is demonstrated in more detail, this invention is not limited by these. In an Example and a comparative example, what is represented by "part" and "%" shall mean "weight part" and "weight%", respectively.

In addition, the weight average molecular weight of the polyurethane polyurea resin described in the Example, and the number average molecular weight of the polyester resin are the weight average molecular weight of polystyrene conversion calculated | required by GPC measurement, and the number average molecular weight, The conditions of GPC measurement are It is as follows.

Device: Shodex GPC System-21 (made by Showa Denko)

Column: Shodex KF-802, KF-803L, KF-805L

A total of three of Showa Denko are used.

Solvent: Tetrahydrofuran

Flow rate: 1.0 mL / min

Temperature: 40 ℃

Sample concentration: 0.3 wt%

Sample injection volume: 100 μL

[Synthesis of Polyurethane Polyurea Resin (A), (C)]

Synthesis Example 1

A number average molecular weight (hereinafter referred to as "Mn") obtained from adipic acid, terephthalic acid and 3-methyl-1,5-pentanediol in a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, a dropping device, and a nitrogen inlet tube. 414 parts of diol of = 1006, 8 parts of dimethylol butanoic acid, 145 parts of isophorone diisocyanate, and 40 parts of toluene were added and reacted for 3 hours at 90 ° C under a nitrogen atmosphere. 300 parts of toluene were added to this and the solution of the urethane prepolymer which has an isocyanate group in the terminal was obtained. Next, 816 parts of the obtained urethane prepolymer was added to a mixture of 27 parts of isophorone diamine, 3 parts of di-n-butylamine, 342 parts of 2-propanol, and 576 parts of toluene, and reacted at 70 ° C for 3 hours, A solution of a polyurethane polyurea resin having a weight average molecular weight (hereinafter referred to as "Mw") = 54,000 and an acid value of 5 mgKOH / g was obtained. 144 parts of toluene and 72 parts of 2-propanol were added to this and the polyurethane polyurea resin solution (A-1) [or (C-1)] which is 30% of non volatile matter was obtained.

Synthesis Example 2

Diol 390 having Mn = 981 obtained from adipic acid, 3-methyl-1,5-pentanediol and 1,6-hexanecarbonate diol in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen inlet tube. 16 parts of dimethylol butanoic acid, 158 parts of isophorone diisocyanate, and 40 parts of toluene were added, and it was made to react at 90 degreeC under nitrogen atmosphere for 3 hours. 300 parts of toluene were added to this and the solution of the urethane prepolymer which has an isocyanate group in the terminal was obtained. Next, 814 parts of the obtained urethane prepolymer was added to 29 parts of isophorone diamine, 3 parts of di-n-butylamine, 342 parts of 2-propanol, and 576 parts of toluene, and reacted at 70 degreeC for 3 hours, A solution of polyurethane polyurea resin having Mw of 43,000 and an acid value of 10 mg KOH / g was obtained. 144 parts of toluene and 72 parts of 2-propanol were added to this and the polyurethane polyurea resin solution (A-2) [or (C-2)] which is 30% of non volatile matter was obtained.

Synthesis Example 3

In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen inlet tube, 352 parts of diol having Mn = 1002 obtained from adipic acid and 3-methyl-1,5-pentanediol, 32 parts of dimethylol butanoic acid, 176 parts of isophorone diisocyanate and 40 parts of toluene were added, and it was made to react at 90 degreeC under nitrogen atmosphere for 3 hours. 300 parts of toluene were added to this and the solution of the urethane prepolymer which has an isocyanate group in the terminal was obtained. Next, 810 parts of the obtained urethane prepolymer was added to 32 parts of isophorone diamine, 4 parts of di-n-butylamine, 342 parts of 2-propanol, and 576 parts of toluene, and reacted at 70 ° C for 3 hours, A solution of polyurethane polyurea resin having Mw of 35,000 and an acid value of 21 mgKOH / g was obtained. 144 parts of toluene and 72 parts of 2-propanol were added to this and the polyurethane polyurea resin solution (A-3) [or (C-3)] which is 30% of non volatile matter was obtained.

Synthesis Example 4

Diol 432 having Mn = 981 obtained from adipic acid, 3-methyl-1,5-pentanediol and 1,6-hexanecarbonate diol in a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, a dropping device, and a nitrogen inlet tube. To this, 137 parts of isophorone diisocyanate and 40 parts of toluene were added, and the mixture was reacted at 90 ° C. under nitrogen atmosphere for 3 hours. 300 parts of toluene were added to this and the solution of the urethane prepolymer which has an isocyanate group in the terminal was obtained. Next, 818 parts of the obtained urethane prepolymer was added to 25 parts of isophorone diamine, 3 parts of di-n-butylamine, 342 parts of 2-propanol, and 576 parts of toluene, and reacted at 70 ° C for 3 hours, A solution of polyurethane polyurea resin having a Mw of 48,000 and an acid value of 0 mg KOH / g was obtained. 144 parts of toluene and 72 parts of 2-propanol were added to this, and the polyurethane polyurea resin solution (A-4) [or (C-4)] which is 30% of non volatile matter was obtained.

[Synthesis of Polyester Resin (P-1)]

Synthesis Example 5

In a flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube and a reflux dehydrator, 184.4 parts of dimethyl terephthalate, 94.8 parts of neopentyl glycol, 94.2 parts of ethylene glycol, 54.7 parts of 2-methyl-1,3-propanediol and 0.035 zinc acetate Part was added. When the raw material could be melted by heating and stirred, the stirring was started, and the temperature was gradually raised from 170 ° C to 220 ° C over 3 hours while the methanol discharged out was removed out of the reaction system under normal pressure, and maintained at 220 ° C for 1 hour. . The internal temperature was once cooled to 170 ° C, and 92.6 parts of adipic acid, 65.8 parts of isophthalic acid, and 113.6 parts of 1,4-cyclohexanedicarboxylic acid were added, and the outflowing water was removed to the outside of the reaction system under normal pressure. The temperature was raised over time and further maintained at 240 ° C., and the reaction was continued until the acid value of the product became 15 mgKOH / g.

Next, the device was changed to a vacuum decompression device, 0.06 parts of tetrabutyl titanate was added, and the reaction was continued for 6 hours under a reduced pressure of 2 Torr at a temperature of 240 ° C, and then taken out into a container made of polyfluorinated ethylene resin.

The number average molecular weight of this resin was 18000, and the glass transition temperature was 27 degreeC.

Then, 100 parts of toluene was added and dissolved with respect to 100 parts of obtained polyester resins. Subsequently, 5 parts of ethylene glycol bistrimellitate dianhydride was added to each flask, and it was made to react at the temperature of 100 degreeC for 5 hours, and the solution of polyester resin of Mw = 24,000 and acid value 14 mgKOH / g was obtained. Toluene was added and diluted to this, and the solution (P-1) of the polyester resin which has a carboxyl group whose non volatile matter is 30% was obtained.

Example 1

20 parts of epoxy resins (B-1) were added with respect to 333 parts of polyurethane polyurea resin solutions (A-1), and the adhesive resin composition was obtained. To 353 parts of this adhesive resin composition, 180 parts of conductive fillers ("AgXF-301" manufactured by Fukuda Metal Foil Industry Co., Ltd.) were added, stirred, and mixed to 100 parts by weight of the total amount of the polyurethane polyurea resin and the epoxy resin (B-1). About curable conductive polyurethane polyurea adhesive agent containing 150 parts of conductive fillers was obtained.

Separately, 20 parts of epoxy resins (D-1) were added to 333 parts of polyurethane polyurea resin solution (C-1) to obtain an insulating resin composition (1).

Subsequently, a curable conductive polyurethane polyurethane urea adhesive was coated and dried on the peeling treated surface of the film subjected to the peeling treatment on one surface of the polyethylene terephthalate film having a thickness of 75 µm as the peelable film 2, and the dry film thickness was 8. A curable conductive polyurethane polyurea adhesive (I), which was μm, was formed.

Separately, the insulating resin composition was coated and dried on the peeling treated surface of the film subjected to the peeling treatment on one side of the polyethylene terephthalate film having a thickness of 50 µm as the peelable film 1, and the curable insulating property having a dry film thickness of 15 µm. Resin composition (II) was formed.

Curable electroconductive polyurethane polyurea adhesive layer (I) surface provided in the peelable film (2) and the curable insulating polyurethane polyurea resin composition layer (II) surface attached to the peelable film (1) are bonded together, and curable electromagnetic wave shielding property is carried out. An adhesive film was produced.

[Examples 2 to 13]

In the same manner as in Example 1, a curable conductive polyurethane polyurethane urea adhesive, and a curable insulating polyurethane polyurethane, using a polyurethane polyurea resin solution, an epoxy resin, and a conductive filler of the kind and amount shown in Tables 1 and 2 The resin composition was prepared and the curable electromagnetic wave shielding adhesive film was produced.

[Examples 14-28]

In the same manner as in Example 1, a curable conductive adhesive and a curable insulating resin composition were prepared by using a polyurethane polyurea resin solution, an epoxy resin, a conductive filler, and an aziridine-based curing agent of the types and amounts shown in Tables 3 and 4, A curable electromagnetic wave shielding adhesive film was produced.

[Examples 29-45]

In the same manner as in Example 1, a curable conductive polyurethane polyurethane urea adhesive, and a curable insulating polyurethane polyurethane, using a polyurethane polyurea resin solution, an epoxy resin, and a conductive filler of the kind and amount shown in Tables 5 and 6 The resin composition was prepared and the curable electromagnetic wave shielding adhesive film was produced.

[Examples 46-61]

In the same manner as in Example 1, a curable conductive adhesive and a curable insulating resin composition were prepared by using a polyurethane polyurea resin solution, an epoxy resin, a conductive filler, and an aziridine-based curing agent of the types and amounts shown in Tables 7 and 8. The curable electromagnetic wave shielding adhesive film was produced.

[Comparative Examples 1-7, and 11]

In the same manner as in Example 1, a curable conductive polyurethane polyurethane urea adhesive, and a curable insulating polyurethane polyurethane, using a polyurethane polyurea resin solution, an epoxy resin, and a conductive filler of the kinds and amounts shown in Tables 9 and 10 The resin composition was prepared and the electromagnetic wave shielding adhesive film was produced.

Comparative Example 8

Instead of the polyurethane polyurea resin solution (C-1) 333 parts, on the peeling process surface of the peelable film 1 using 333 parts of solutions (P-1) of the polyester resin which have a carboxyl group obtained by the synthesis example 5 An electromagnetic wave shielding adhesive film was produced in the same manner as in Example 1 except that the curable insulating resin composition layer (II) having a thickness of 15 μm was provided.

[Comparative Examples 9-10]

Except for using the polyphenylene sulfide film (comparative example 9) or the polyethylene terephthalate film (comparative example 10) instead of the curable insulating polyurethane polyurethane urea resin composition layer (II) used in Example 1, In the same manner, an electromagnetic wave shielding film was produced.

[Comparative Examples 12-20]

In the same manner as in Example 14, a curable conductive polyurethane polyurea adhesive and a curable insulating property using a polyurethane polyurea resin solution, an epoxy resin, a conductive filler, and an aziridine-based curing agent of the types and amounts shown in Tables 11 and 12 The polyurethane polyurea resin composition was prepared and the electromagnetic wave shielding adhesive film was produced.

Comparative Example 21

Instead of the polyurethane polyurea resin solution (C-1) 333 parts, on the peeling process surface of the peelable film 1 using 333 parts of solutions (P-1) of the polyester resin which have a carboxyl group obtained by the synthesis example 5 An electromagnetic wave shielding adhesive film was produced in the same manner as in Example 14 except that the curable insulating resin composition layer (II) having a thickness of 15 μm was provided.

[Comparative Examples 22 ~ 23]

Except having used the polyphenylene sulfide film (comparative example 22) or the polyethylene terephthalate film (comparative example 23) instead of the film-form curable insulating polyurethane polyurea resin composition layer (I) used in Example 14, Example It carried out similarly to 14, and produced the electromagnetic wave shielding film.

[Comparative Examples 24 ~ 31]

In the same manner as in Example 29, a conductive adhesive was prepared using a polyurethane polyurea resin solution, an epoxy resin, and a conductive filler of the kind and amount shown in Tables 13 and 14 to prepare an electromagnetic wave shielding adhesive film.

[Comparative Examples 32-33]

Instead of the polyurethane polyurea resin solution (C-1) 333 parts, using 333 parts of the solution (P-1) of the polyester resin having a carboxyl group obtained in Synthesis Example 5, in Comparative Example 32 without using an aziridine-based curing agent In Comparative Example 33, the same procedure as in Example 29 was carried out except that the curable insulating resin composition layer (II) having a thickness of 15 μm was provided on the release treatment surface of the release film 1 using an aziridine-based curing agent. An electromagnetic wave shielding adhesive film was produced.

[Comparative Examples 34 ~ 35]

Instead of the curable insulating polyurethane polyurea resin composition layer (II) used in Example 29, except that a polyphenylene sulfide film (Comparative Example 34) or a polyethylene terephthalate film (Comparative Example 35) was used, In the same manner, an electromagnetic wave shielding film was produced.

[Comparative Examples 36 ~ 44]

In the same manner as in Example 46, a curable conductive adhesive and a curable insulating resin composition were prepared by using a polyurethane polyurea resin solution, an epoxy resin, a conductive filler, and an aziridine-based curing agent of the kind and amount shown in Tables 15 and 16. The curable electromagnetic wave shielding adhesive film was produced.

[Comparative Examples 45-46]

Instead of the polyurethane polyurea resin solution (C-1) 333 parts, using 333 parts of the solution (P-1) of the polyester resin having a carboxyl group obtained in Synthesis Example 5, in Comparative Example 45 without using an aziridine-based curing agent In Comparative Example 46, in the same manner as in Example 46, except that the curable insulating resin composition layer (II) having a thickness of 15 μm was provided on the peeling treatment surface of the peelable film 1 using an aziridine-based curing agent. An electromagnetic wave shielding adhesive film was produced.

[Comparative Examples 47-48]

Instead of the curable insulating polyurethane polyurea resin composition layer (II) used in Example 46, except that a polyphenylene sulfide film (Comparative Example 47) or a polyethylene terephthalate film (Comparative Example 48) was used, In the same manner, an electromagnetic wave shielding film was produced.

With respect to the curable electromagnetic wave shielding adhesive film (or electromagnetic shielding film) with a peelable film obtained in each example and each comparative example, polyimide film adhesion, heat resistance, flex resistance, and pressure cracker (hereinafter PCT) resistance were It evaluated by the method. The results are shown in Tables 1 to 16.

(1) Evaluation of polyimide film adhesiveness

A curable electromagnetic wave shielding adhesive film (or electromagnetic wave shielding film) having a width of 10 mm and a length of 70 mm was prepared, the peelable film 2 was peeled off, and the polyimide film having a thickness of 50 μm on the exposed curable conductive adhesive layer. ("Katon 200EN" manufactured by Toray DuPont) was pressed under the conditions of 150 ° C, 1.0 MPa, and 30 min to cure the conductive adhesive layer (I) and the film-like insulating composition (II).

After crimping | bonding, for the reinforcement for a measurement, the peelable film 1 was removed and the said polyimide film carrier was made into the exposed cured film-like insulation layer using the polyurethane polyurea-type adhesive sheet, 150 It crimped | bonded on the conditions of ° C, 1 MPa, and 30 min.

At a temperature of 23 ° C. and a relative humidity of 50%, at a tensile rate of 50 mm / min, and at a peel angle of 90 °, the cured conductive adhesive layer and the polyimide film were peeled off, and the center value of the peeling force was determined as the polyimide film adhesive strength ( N / cm).

In addition, in the case of Comparative Examples 11 and 12, reinforcement for a measurement was not performed.

(2) evaluation of heat resistance

A curable electromagnetic wave shielding adhesive film (or electromagnetic wave shielding film) having a width of 10 mm and a length of 60 mm was prepared, the peelable film 2 was peeled off, and the exposed curable conductive adhesive layer I had a thickness of 50 μm. The polyimide film ("Katon 200EN" by Toray DuPont) was crimped under the conditions of 150 ° C, 1 MPa, and 30 min to cure the conductive adhesive layer (I) and the film-like insulating composition (II).

After the pressing, the peelable film 1 was removed and heat treated for 3 min in a 180 ° C. electric oven, followed by a 90 sec heat in an 280 ° C. electric oven. The appearance of the sample after the heat treatment was visually observed to evaluate the presence or absence of appearance defects such as foaming, lifting and / or peeling.

Each test was done 5 times, and it evaluated by the frequency | count of appearance defect generate | occur | producing.

○: No appearance defects

(Triangle | delta): Less than 2 occurrences of appearance defects

X: 3 or more appearance defect occurrences

(3) evaluation of bending resistance

Flexible printed wiring board (thickness) which peeled off peelable film 2 from curable electromagnetic wave shielding adhesive film (or electromagnetic wave shielding film) of 6mm in width, 120mm in length, and separately produced exposed curable conductive adhesive layer (I) On a 25 μm polyimide film, a circuit pattern made of copper foil having a thickness of 12 μm is formed, and on a cover film surface of a wiring board on which a cover film with a thickness of 40 μm with an adhesive is laminated on the circuit pattern. It crimped | bonded on the conditions of 150 degreeC, 1 MPa, and 30 min, and hardened | cured the conductive adhesive layer (I) and film-like insulating composition (II).

The peelable film 1 was removed, and the bend resistance was evaluated in accordance with the number of times until the circuit pattern was disconnected by applying to a MIT bending tester under conditions of a curvature radius of 0.38 mm, a load of 500 g, and a speed of 180 times / min. . Evaluation criteria are as follows.

○: 3000 times or more

△: more than 1500 times less than 3000 times

×: less than 1500 times

(4) Evaluation of PCT Resistance of Curable Electromagnetic Shielding Adhesive Film

Flexible printed wiring board (thickness) which peeled off peelable film 2 from curable electromagnetic wave shielding adhesive film (or electromagnetic wave shielding film) of 20 mm in width, 50 mm in length, and separately produced exposed curable conductive adhesive layer (I) Circuits 2A and 2B which are made of copper foil having a thickness of 18 μm and are not electrically connected are formed on the 12.5 μm polyimide film, and on the circuit 2A, a thickness of 37.5 μm, with adhesive, A wiring board on which a cover film having a 1.6 mm diameter through-hole is laminated) was pressed under conditions of 150 ° C., 1 MPa, and 30 min, and the conductive adhesive layer (I) and the film-like insulating composition (II) were cured ( See FIG. 1).

After crimping | compression-bonding, the peelable film 1 was removed and PCT (121 degreeC, 100) was used for the resistance value between 2A-2B shown to FIG. 1 (3) using 4 probe probes made from Mitsubishi Chemical Corporation "Lester" GP. % RH, and 2 atmospheres). Evaluation criteria are as follows.

○: less than 500 mΩ

△: 500 mΩ or more less than 1000 mΩ

×: 1000 mΩ or more

(5) Ductility test

A "small" polyimide film (A) having a thickness of 125 µm, a width of 20 mm, and a length of 30 mm, was approximately the center of a "large" polyimide film (B) having a width of 50 mm and a length of 50 mm. Put on.

A curable electromagnetic wave shielding adhesive film (or electromagnetic wave shielding film) having a width of 50 mm and a length of 60 mm was prepared, the peelable film 2 was removed, and the exposed curable conductive polyurethane polyurea adhesive layer (I) was used. It covers the whole surface of the said "large" polyimide film (B) including the whole "small" polyimide film (A), and crimped | bonded on conditions of 150 degreeC, 1 MPa, and 30min, and curable conductive polyurethane polyurea adhesive agent Layer (I) and curable insulating polyurethane polyurea resin composition layer (II) were cured.

After crimping | compression-bonding, the peelable film 1 is removed and each edge part of the said "small" polyimide film (A) sandwiched between the electromagnetic wave shielding film after hardening and the said "large" polyimide film (B) (by The projection part) was observed visually and with 50 times the microscope through the insulating layer of the electromagnetic wave shielding film after hardening, and the extent to which the electrically conductive adhesive bond layer after hardening of the projection part by step | steps was seen was evaluated.

(Circle): In neither the naked eye nor the microscope, a conductive adhesive layer could be seen.

(Triangle | delta): Although the electroconductive adhesive bond layer was not seen by the naked eye, the electroconductive adhesive bond layer was seen by the microscope.

X: The conductive adhesive layer looked into all of the naked eye and the microscope.

(6) Evaluation of the protruding property of the adhesive layer

Each curable conductive polyurethane polyurethane urea adhesive composition described in each example and each comparative example was coated on one surface of a polyimide film ("Katon 200EN" manufactured by Toray DuPont) having a thickness of 50 µm, and an electric oven was used. 20 minutes at 100 ° C. to form a curable conductive polyurethane polyurethane urea adhesive layer (I) having a dry film thickness of 8 μm, and punch a hole having a diameter of 5 mm using a punching machine to form the curable conductive polyurethane polyurethane urea adhesive layer ( It formed by penetrating I) and a polyimide film.

Separately, each curable insulating polyurethane polyurea resin composition described in each Example and each comparative example was coated on one surface of a polyimide film ("Katon 200EN" manufactured by Toray DuPont) having a thickness of 50 µm, and the electric oven It dried at 100 degreeC for 20 minutes using, and the curable insulating polyurethane polyurea composition layer (II) whose dry film thickness is 15 micrometers was formed.

Subsequently, the perforated curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) were overlapped, and crimped under conditions of 150 ° C, 1.0 MPa, and 30 min. After the crimping treatment, the hole portion of the conductive adhesive layer after curing was observed using a magnifying glass, and the amount of protruding of the conductive adhesive at the time of curing was measured. Evaluation criteria are as follows.

(Circle): The amount of bleeding of an electroconductive adhesive bond layer was less than 0.1 mm, ie, the diameter of the hole of the adhesive bond layer (I) after hardening exceeded 4.8 mm.

X: The amount of escape of the conductive adhesive layer was 0.1 mm or more, that is, the diameter of the hole of the adhesive layer I after hardening was 4.8 mm or less.

The symbols in each table are as follows.

B-1, D-1: Bisphenol A epoxy resin, "JER 828" made in Japan epoxy resin, Epoxy equivalent = 189 g / eq.

B-2, D-2: Bisphenol A epoxy resin, "JER 1002" made in Japan epoxy resin, Epoxy equivalent = 650 g / eq.

B-3, D-3: Tetrakis (glycidyloxyphenyl) ethane type epoxy resin, Japan epoxy resin agent "JER 1031", epoxy equivalent = 190 g / eq.

B-4, D-4: Monofunctional epoxy resin, "UVR-6216" made by Dow Chemical, Epoxy equivalent = 240 g / eq.

PPS: polyphenylene sulfide film.

PET: polyethylene terephthalate film.

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

Claims (27)

A curable electromagnetic wave shielding adhesive film which has a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II),
The curable conductive polyurethane polyurea adhesive layer (I) reacts a polyol (a2) having an average molecular weight of 500 to 8000 and an organic diisocyanate (a3) other than the diol compound (a1) having a carboxyl group, the carboxyl group-containing diol compound, Polyurethane polyurea resin (A) obtained by making the urethane prepolymer (a4) which has an isocyanate group in the terminal obtained, and the polyamino compound (a5) react, and the epoxy resin (B) which has two or more epoxy groups are contained, The said poly Conductive filler: 10 to 700 parts by weight based on 100 parts by weight of the total of the urethane polyurea resin (A) and the epoxy resin (B),
The said curable insulating polyurethane polyurea resin composition layer (II) reacts the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, the carboxyl group-containing diol compound. A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group with a terminal obtained by reacting a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups. Curable electromagnetic wave shielding adhesive film made into. As a curable electroconductive shielding adhesive film which has a curable conductive polyurethane polyurea adhesive layer (I) whose gel fraction is 30 to 90 weight%, and a curable insulating polyurethane polyurea resin composition layer (II),
The curable conductive polyurethane polyurea adhesive layer (I) is obtained by reacting a polyol (a2) having an average molecular weight of 500 to 8000 and an organic diisocyanate (a3) other than the diol compound (a1) having a carboxyl group, the carboxyl group-containing diol compound, and the like. Urethane prepolymer (a4) which has an isocyanate group at the terminal, Polyurethane polyurea resin (A) obtained by making polyamino compound (a5) react, Epoxy resin (B) which has two or more epoxy groups, and the said polyurethane polyurea The conductive filler: 10 to 700 parts by weight and the aziridine-based curing agent (E) are added to 1 mole of the carboxyl group in the polyurethane polyurea resin (A) based on 100 parts by weight in total of the resin (A) and the epoxy resin (B). It is formed with the curable conductive polyurethane polyurea adhesive agent containing an aziridinyl group in the range of 0.05-4 mol,
The said curable insulating polyurethane polyurea resin composition layer (II) reacts the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, the carboxyl group-containing diol compound. A polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (c4) having an isocyanate group with a terminal obtained by reacting a polyamino compound (c5), and an epoxy resin (D) having two or more epoxy groups. Curable electromagnetic wave shielding adhesive film made into. A curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight, having a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurea resin composition layer (II),
The curable conductive polyurethane polyurea adhesive layer (I) reacts a polyol (a2) having an average molecular weight of 500 to 8000 and an organic diisocyanate (a3) other than the diol compound (a1) having a carboxyl group, the carboxyl group-containing diol compound, Urethane prepolymer (a4) which has isocyanate group in the terminal obtained, Polyurethane polyurea resin (A) obtained by making polyamino compound (a5) react, Epoxy resin (B) which has two or more epoxy groups, and the said polyurethane poly 1 mol of carboxyl groups in the said polyurethane polyurea resin (A) of an electrically conductive filler: 10-700 weight part and an aziridine system hardener (E) with respect to a total of 100 weight part of a urea resin (A) and the said epoxy resin (B). It is formed with the curable conductive polyurethane polyurea adhesive agent containing an aziridinyl group in 0.05-4 mol with respect to,
The said curable insulating polyurethane polyurea resin composition layer (II) reacts the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, the carboxyl group-containing diol compound. Urethane prepolymer (c4) having an isocyanate group at the terminal to be obtained, and a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and an aziridine-based curing agent (F) is formed from a curable insulating polyurethane polyurethane urea resin composition having a film-forming ability, containing an aziridinyl group in a range of 0.05 to 4 moles per 1 mole of the carboxyl group in the polyurethane polyurea resin (C). Curable electromagnetic wave shielding adhesive film characterized by the above-mentioned. A curable electromagnetic wave shielding adhesive film which has a curable conductive polyurethane polyurea adhesive layer (I) and a curable insulating polyurethane polyurethane urea resin composition layer (II) having a gel fraction of 30 to 90% by weight,
The curable conductive polyurethane polyurea adhesive layer (I) reacts a polyol (a2) having an average molecular weight of 500 to 8000 and an organic diisocyanate (a3) other than the diol compound (a1) having a carboxyl group, the carboxyl group-containing diol compound, It contains the urethane prepolymer (a4) which has an isocyanate group in the terminal obtained, the polyurethane polyurea resin (A) obtained by making a polyamino compound (a5) react, the epoxy resin (B) which has two or more epoxy groups, and a conductive filler Conductive filler: 10 to 700 parts by weight based on 100 parts by weight of the total of the polyurethane polyurea resin (A) and the epoxy resin (B),
The said curable insulating polyurethane polyurea resin composition layer (II) reacts the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, the carboxyl group-containing diol compound. Urethane prepolymer (c4) having an isocyanate group at the terminal to be obtained, and a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and an aziridine-based curing agent (E) is formed from curable insulating polyurethane polyurethane urea resin composition having a film-forming ability to contain an aziridinyl group in the range of 0.05 to 4 moles with respect to 1 mole of the carboxyl group in the polyurethane polyurea resin (C). Curable electromagnetic wave shielding adhesive film made into. The method according to any one of claims 1 to 4,
Curable conductive polyurethane polyurea adhesive layer (I) contains 3-200 weight part of epoxy resins (B) with respect to 100 weight part of polyurethane polyurea resins (A), and also curable insulating polyurethane polyurea resin composition Layer (II) contains 3-200 weight part of epoxy resins (D) with respect to 100 weight part of polyurethane polyurea resins (C), The curable electromagnetic wave shielding adhesive film characterized by the above-mentioned. The method of claim 5,
Curable electromagnetic wave characterized in that the peelable film 1 is laminated on the surface of the curable insulating polyurethane polyurea resin composition layer (II) to which the curable conductive polyurethane polyurea adhesive layer (I) is not in contact. Shielding adhesive film. The method of claim 5,
Curable electromagnetic wave characterized in that the peelable film (2) is laminated on the surface of the curable conductive polyurethane polyurea adhesive layer (I) to which the curable insulating polyurethane polyurea resin composition layer (II) is not in contact. Shielding adhesive film. The method of claim 5,
On the surface which curable insulating polyurethane polyurea resin composition layer (II) does not contact curable conductive polyurethane polyurea adhesive bond layer (I), the peelable film (2) is laminated, and curable insulating poly Curable electromagnetic wave shielding adhesiveness characterized by the release film 1 being laminated on the surface of the urethane polyurea resin composition layer (II) to which the curable conductive polyurethane polyurea adhesive layer (I) is not in contact. film. Terminal obtained by making polyol (c2) and organic diisocyanate (c3) of number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound react on one surface of the peelable film (1) Curable insulating polyurethane poly containing a polyurethane preurea resin (C4) obtained by reacting a urethane prepolymer (c4) having an isocyanate group with a polyamino compound (c5) and an epoxy resin (D) having two or more epoxy groups. Forming a urea resin composition layer (II),
Terminal obtained by making polyol (a2) and organic diisocyanate (a3) of number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound react on one surface of the peelable film (2) Urethane prepolymer (a4) having an isocyanate group, a polyurethane polyurea resin (A) obtained by reacting a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, and the polyurethane polyurea resin A step of forming a curable conductive polyurethane polyurethane urea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler based on 100 parts by weight of the total of (A) and the epoxy resin (B), and
Step of overlapping and combining the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II)
A method of producing a curable electromagnetic wave shielding adhesive film comprising a. Terminal obtained by making polyol (c2) and organic diisocyanate (c3) of number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound react on one surface of the peelable film (1) Curable insulating polyurethane poly containing a polyurethane preurea resin (C4) obtained by reacting a urethane prepolymer (c4) having an isocyanate group with a polyamino compound (c5) and an epoxy resin (D) having two or more epoxy groups. Forming a urea resin composition layer (II),
On the said curable insulating polyurethane polyurea resin composition layer (II), the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which have a carboxyl group, the carboxyl group-containing diol compound Urethane prepolymer (a4) which has isocyanate group in the terminal obtained by making it react, Polyurethane polyurea resin (A) obtained by making polyamino compound (a5) react, Epoxy resin (B) which has two or more epoxy groups, and the said poly A step of forming a curable conductive polyurethane polyurethane urea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler with respect to a total of 100 parts by weight of the urethane polyurea resin (A) and the epoxy resin (B), and
Stacking the peelable film (2) on the curable conductive polyurethane polyurea adhesive layer (I), and
A method of producing a curable electromagnetic wave shielding adhesive film comprising a. Terminal obtained by making polyol (a2) and organic diisocyanate (a3) of number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound react on one surface of the peelable film (2) Urethane prepolymer (a4) having an isocyanate group, a polyurethane polyurea resin (A) obtained by reacting a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, and the polyurethane polyurea resin A step of forming a curable conductive polyurethane polyurethane urea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler based on 100 parts by weight of the total of (A) and the epoxy resin (B),
On the said curable conductive polyurethane polyurea adhesive bond layer (I), the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which have a carboxyl group, the carboxyl group-containing diol compound are reacted. Curable insulating property containing the urethane prepolymer (c4) which has an isocyanate group in the terminal obtained by making it react, the polyurethane polyurea resin (C) obtained by making a polyamino compound (c5) react, and the epoxy resin (D) which has two or more epoxy groups Forming a polyurethane polyurea resin composition layer (II), and
Stacking the peelable film (1) on the curable insulating polyurethane polyurea resin composition layer (II), and
A method of producing a curable electromagnetic wave shielding adhesive film comprising a. To the terminal obtained by making one surface of the peelable film 1 react the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound Curable insulating polyurethane polyurea containing the urethane prepolymer (c4) which has an isocyanate group, the polyurethane polyurea resin (C) obtained by making a polyamino compound (c5) react, and the epoxy resin (D) which has two or more epoxy groups. Forming a resin composition layer (II), and
Terminal obtained by making polyol (a2) and organic diisocyanate (a3) of number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound react on one surface of the peelable film (2) Urethane prepolymer (a4) having an isocyanate group, a polyurethane polyurea resin (A) obtained by reacting a polyamino compound (a5), an epoxy resin (B) having two or more epoxy groups, and the polyurethane polyurea resin Conductive filler: 10 to 700 parts by weight and aziridine-based curing agent (E) based on 100 parts by weight of the total of (A) and the epoxy resin (B) with respect to 1 mole of the carboxyl group in the polyurethane polyurea resin (A). Curable conductive polyurethane polyurea adhesive having a gel fraction of 30 to 90% by weight from a curable conductive polyurethane polyurea adhesive containing an aziridinyl group in the range of 0.05 to 4 mol The step of forming the agent layer (I), and
Stacking and curing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II),
A method of producing a curable electromagnetic wave shielding adhesive film comprising a. To the terminal obtained by making one surface of the peelable film 1 react the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound Curable insulating polyurethane polyurea containing the urethane prepolymer (c4) which has an isocyanate group, the polyurethane polyurea resin (C) obtained by making a polyamino compound (c5) react, and the epoxy resin (D) which has two or more epoxy groups. Process of forming resin composition layer (II),
On the said curable insulating polyurethane polyurea resin composition layer (II), the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which have a carboxyl group, the carboxyl group-containing diol compound Urethane prepolymer (a4) which has isocyanate group in the terminal obtained by making it react, Polyurethane polyurea resin (A) obtained by making polyamino compound (a5) react, Epoxy resin (B) which has two or more epoxy groups, and the said poly Conductive filler: 10 to 700 parts by weight and aziridine-based curing agent (E) with respect to a total of 100 parts by weight of the urethane polyurea resin (A) and the epoxy resin (B) in the carboxyl group in the polyurethane polyurea resin (A). Curable whose gel fraction is 30 to 90 weight% from the curable conductive polyurethane polyurea adhesive which contains an aziridinyl group in the range of 0.05-4 mol with respect to 1 mol. Forming a conductive polyurethane polyurea adhesive layer (I), and
Stacking the peelable film (2) on the curable conductive polyurethane polyurea adhesive layer (I), and
A method of producing a curable electromagnetic wave shielding adhesive film comprising a. To the terminal obtained by making one surface of the peelable film 2 react with the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound The urethane prepolymer (a4) having an isocyanate group, the polyurethane polyurea resin (A) obtained by making a polyamino compound (a5) react, the epoxy resin (B) which has two or more epoxy groups, and the said polyurethane polyurea resin ( Conductive filler: 10 to 700 parts by weight and aziridine-based curing agent (E) based on 100 parts by weight of the total of A) and the epoxy resin (B) with respect to 1 mole of the carboxyl group in the polyurethane polyurea resin (A), Curable conductive polyurethane polyurea adhesive having a gel fraction of 30 to 90% by weight from the curable conductive polyurethane polyurea adhesive containing aziridinyl group in the range of 0.05 to 4 mol. The step of forming the layer (I),
On the said curable conductive polyurethane polyurea adhesive bond layer (I), the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which have a carboxyl group, the carboxyl group-containing diol compound are reacted. Curable insulating property containing the urethane prepolymer (c4) which has an isocyanate group in the terminal obtained by making it react, the polyurethane polyurea resin (C) obtained by making a polyamino compound (c5) react, and the epoxy resin (D) which has two or more epoxy groups Forming a polyurethane polyurea resin composition layer (II), and
Stacking the peelable film (1) on the curable insulating polyurethane polyurea resin composition layer (II), and
A method of producing a curable electromagnetic wave shielding adhesive film comprising a. To the terminal obtained by making one surface of the peelable film 1 react the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound A urethane prepolymer (c4) having an isocyanate group, a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and an aziridine-based curing agent (F) The gel fraction is 30-90 from the curable insulating polyurethane polyurethane urea resin composition which has a film formation ability which contains an aziridinyl group in 0.05-4 mol with respect to 1 mol of carboxyl groups in the said polyurethane polyurea resin (C). Forming a curable insulating polyurethane polyurethane urea resin composition layer (II) that is% by weight,
To the terminal obtained by making one surface of the peelable film 2 react with the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound The urethane prepolymer (a4) having an isocyanate group, the polyurethane polyurea resin (A) obtained by making a polyamino compound (a5) react, the epoxy resin (B) which has two or more epoxy groups, and the said polyurethane polyurea resin ( Conductive filler: 10 to 700 parts by weight and aziridine-based curing agent (E) based on 100 parts by weight of the total of A) and the epoxy resin (B) with respect to 1 mole of the carboxyl group in the polyurethane polyurea resin (A), Curable conductive polyurethane polyurea adhesive having a gel fraction of 30 to 90% by weight from the curable conductive polyurethane polyurea adhesive containing aziridinyl group in the range of 0.05 to 4 mol. The step of forming the layer (I), and
Stacking and curing the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II),
A method of producing a curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight. To the terminal obtained by making one surface of the peelable film 1 react the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound A urethane prepolymer (c4) having an isocyanate group, a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and an aziridine-based curing agent (F) The gel fraction is 30-90 from the curable insulating polyurethane polyurethane urea resin composition which has a film formation ability which contains an aziridinyl group in 0.05-4 mol with respect to 1 mol of carboxyl groups in the said polyurethane polyurea resin (C). Forming a curable insulating polyurethane polyurethane urea resin composition layer (II) that is% by weight,
On the said curable insulating polyurethane polyurea resin composition layer (II), the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which have a carboxyl group, the carboxyl group-containing diol compound Urethane prepolymer (a4) which has isocyanate group in the terminal obtained by making it react, Polyurethane polyurea resin (A) obtained by making polyamino compound (a5) react, Epoxy resin (B) which has two or more epoxy groups, and the said poly Conductive filler: 10 to 700 parts by weight and aziridine-based curing agent (E) with respect to a total of 100 parts by weight of the urethane polyurea resin (A) and the epoxy resin (B), and the carboxyl group in the polyurethane polyurea resin (A). Curable which is 30 to 90 weight% of gel fraction which becomes curable electroconductive polyurethane polyurea adhesive agent containing aziridinyl group in the range of 0.05-4 mol with respect to 1 mol. Forming a conductive polyurethane polyurea adhesive layer (I), and
A method for producing a curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight, including the step of overlaying the peelable film (2) on the curable conductive polyurethane polyurea adhesive layer (I). To the terminal obtained by making one surface of the peelable film 2 react with the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound The urethane prepolymer (a4) having an isocyanate group, the polyurethane polyurea resin (A) obtained by making a polyamino compound (a5) react, the epoxy resin (B) which has two or more epoxy groups, and the said polyurethane polyurea resin ( Conductive filler: 10 to 700 parts by weight and aziridine-based curing agent (E) based on 100 parts by weight of the total of A) and the epoxy resin (B) with respect to 1 mole of the carboxyl group in the polyurethane polyurea resin (A), Curable conductive polyurethane polyurea adhesive having a gel fraction of 30 to 90% by weight from the curable conductive polyurethane polyurea adhesive containing aziridinyl group in the range of 0.05 to 4 mol. The step of forming the layer (I),
On the said curable conductive polyurethane polyurea adhesive bond layer (I), the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which have a carboxyl group, the carboxyl group-containing diol compound are reacted. Urethane prepolymer (c4) having an isocyanate group at the terminal to be obtained, and a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and an aziridine-based curing agent The gel fraction from the curable insulating polyurethane polyurethane urea resin composition having a film-forming ability, containing (F) aziridinyl group in the range of 0.05 to 4 moles per 1 mole of the carboxyl group in the polyurethane polyurea resin (C). Process of forming curable insulating polyurethane polyurethane urea resin composition layer (I) which is 30 to 90 weight%, and
A method for producing a curable electromagnetic wave shielding adhesive film having a gel fraction of 30 to 90% by weight, including the step of overlaying the peelable film (1) on the curable insulating polyurethane polyurea resin composition layer (II). To the terminal obtained by making one surface of the peelable film 1 react the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound A urethane prepolymer (c4) having an isocyanate group, a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and an aziridine-based curing agent (E) The gel fraction is 30-90 from the curable insulating polyurethane polyurethane urea resin composition which has a film formation ability which contains an aziridinyl group in 0.05-4 mol with respect to 1 mol of carboxyl groups in the said polyurethane polyurea resin (C). Forming a curable insulating polyurethane polyurethane urea resin composition layer (II) that is% by weight,
To the terminal obtained by making one surface of the peelable film 2 react with the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound The urethane prepolymer (a4) having an isocyanate group, the polyurethane polyurea resin (A) obtained by making a polyamino compound (a5) react, the epoxy resin (B) which has two or more epoxy groups, and the said polyurethane polyurea resin ( A step of forming a curable conductive polyurethane polyurethane urea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler based on 100 parts by weight of the total of A) and the epoxy resin (B), and
Step of overlapping and combining the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II)
A method of producing a curable electromagnetic wave shielding adhesive film comprising a. To the terminal obtained by making one surface of the peelable film 1 react the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which has a carboxyl group, and the carboxyl group-containing diol compound A urethane prepolymer (c4) having an isocyanate group, a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and an aziridine-based curing agent (E) The gel fraction is 30-90 from the curable insulating polyurethane polyurethane urea resin composition which has a film formation ability which contains an aziridinyl group in 0.05-4 mol with respect to 1 mol of carboxyl groups in the said polyurethane polyurea resin (C). Forming a curable insulating polyurethane polyurethane urea resin composition layer (II) that is% by weight,
On the said curable insulating polyurethane polyurea resin composition layer (II), the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which have a carboxyl group, the carboxyl group-containing diol compound Urethane prepolymer (a4) which has isocyanate group in the terminal obtained by making it react, Polyurethane polyurea resin (A) obtained by making polyamino compound (a5) react, Epoxy resin (B) which has two or more epoxy groups, and the said poly A step of forming a curable conductive polyurethane polyurethane urea adhesive layer (I) containing 10 to 700 parts by weight of a conductive filler with respect to a total of 100 parts by weight of the urethane polyurea resin (A) and the epoxy resin (B), and
Stacking the peelable film (2) on the curable conductive polyurethane polyurea adhesive layer (I), and
A method of producing a curable electromagnetic wave shielding adhesive film comprising a. To the terminal obtained by making one surface of the peelable film 2 react with the polyol (a2) and organic diisocyanate (a3) of the number average molecular weights 500-8000 other than the diol compound (a1) which has a carboxyl group, and the carboxyl group-containing diol compound The urethane prepolymer (a4) having an isocyanate group, the polyurethane polyurea resin (A) obtained by making a polyamino compound (a5) react, the epoxy resin (B) which has two or more epoxy groups, and the said polyurethane polyurea resin ( A step of forming a curable conductive polyurethane polyurethane urea adhesive layer (I) containing 10 to 700 parts by weight of the conductive filler with respect to 100 parts by weight of the total of A) and the epoxy resin (B),
On the said curable conductive polyurethane polyurea adhesive bond layer (I), the polyol (c2) and organic diisocyanate (c3) of the number average molecular weights 500-8000 other than the diol compound (c1) which have a carboxyl group, the carboxyl group-containing diol compound are reacted. Urethane prepolymer (c4) having an isocyanate group at the terminal to be obtained, and a polyurethane polyurea resin (C) obtained by reacting a polyamino compound (c5), an epoxy resin (D) having two or more epoxy groups, and an aziridine-based curing agent Gel fraction from the curable insulating polyurethane polyurethane urea resin composition which has (E) the film formation ability which contains an aziridinyl group in 0.05-4 mol with respect to 1 mol of carboxyl groups in the said polyurethane polyurea resin (C). Process of forming curable insulating polyurethane polyurea resin composition layer (II) which is 30 to 90 weight%, and
Stacking the peelable film (1) on the curable insulating polyurethane polyurea resin composition layer (II), and
A method of producing a curable electromagnetic wave shielding adhesive film comprising a. The peelable film 2 of the curable electromagnetic wave shielding adhesive film of Claim 8 is peeled off, the exposed curable conductive polyurethane polyurea adhesive layer (I) is piled up on a to-be-adhered body, it heats, and the said curable conductive polyurethane poly A method of using the curable electromagnetic wave shielding adhesive film of claim 8, wherein the peelable film (1) is peeled after the urea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II) are cured. The peelable film (2) of the curable electromagnetic wave shielding adhesive film of Claim 8 is peeled off, the exposed curable conductive polyurethane polyurea adhesive layer (I) is piled up on the adherend, and the peelable film (1) is peeled off. And heating to cure the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II). The exposed curable conductive polyurethane polyurethane urea adhesive layer (I) of the curable electromagnetic wave shielding adhesive film of claim 6 is piled up on an adherend to be heated, and the curable conductive polyurethane polyurethane urea adhesive layer (I) and the curable insulating property are combined. After hardening a polyurethane polyurea resin composition layer (II), the peelable film (1) is peeled off. The manufacturing method of the electromagnetic shielding material characterized by the above-mentioned. The peelable film (2) of the curable electromagnetic wave shielding adhesive film of Claim 7 is peeled off, the exposed curable conductive polyurethane polyurea adhesive layer (I) is overlaid on the adherend, heated, and the curable conductive polyurethane poly A method for producing an electromagnetic wave shield, comprising curing the urea adhesive layer (I) and the curable insulating polyurethane polyurea resin composition layer (II). The peelable film 2 of the curable electromagnetic wave shielding adhesive film of Claim 8 is peeled off, the exposed curable conductive polyurethane polyurea adhesive layer (I) is piled up on a to-be-adhered body, it heats, and the said curable conductive polyurethane poly A peeling film (1) is peeled after hardening a urea adhesive layer (I) and curable insulating polyurethane polyurea resin composition layer (II), The manufacturing method of the electromagnetic shielding material characterized by the above-mentioned. The peelable film (2) of the curable electromagnetic wave shielding adhesive film of Claim 8 is peeled off, the exposed curable conductive polyurethane polyurea adhesive layer (I) is piled up on the adherend, and the peelable film (1) is peeled off. And heating to cure the curable conductive polyurethane polyurea adhesive layer (I) and the curable insulating polyurethane polyurethane urea resin composition layer (II). The electromagnetic shielding body obtained by the manufacturing method of any one of Claims 23-26.

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