KR20150077429A - Coverlay film, flexible printed circuit board using the same, and menufacturing method for those - Google Patents

Abstract

The coverlay film of the present invention comprises (A) a specific vinyl compound, (B) a polystyrene-poly (ethylene / butylene) block copolymer, (C) a polystyrene-poly (ethylene-ethylene / propylene) ), (B) / (C) = 1 to 4, and the component (A), the epoxy resin and the bismaleimide (E) Wherein the adhesive layer containing 1 to 10 mass% of the component (D) based on the total mass of the components (A) to (E) has a melting point higher than the thermal curing temperature of the adhesive layer, Of 4 or less and a dielectric loss tangent of 0.02 or less.

Description

TECHNICAL FIELD [0001] The present invention relates to a coverlay film, a flexible printed wiring board using the coverlay film, and a method of manufacturing the same,

The present invention relates to a coverlay film. More particularly, it relates to a coverlay film for a flexible printed wiring board.

The present invention also relates to a flexible printed wiring board using the coverlay film.

Further, the present invention relates to the coverlay film and a manufacturing method of the flexible printed wiring board.

2. Description of the Related Art In recent years, the demand for high density, miniaturization, and thinness of electronic components used in electronic devices has been increasing, as electronic devices are rapidly progressing in performance, function, and size. As a result, further improvement of various physical properties such as heat resistance, mechanical strength, and electric characteristics has been required for the materials of electronic parts. For example, a printed wiring board on which semiconductor elements are mounted is required to have higher density, higher functionality, and higher performance.

In such a situation, the demand for a flexible printed wiring board (hereinafter referred to as FPC) capable of three-dimensional wiring and mounting in a narrow space is increasing. Generally, an FPC has a circuit pattern formed on a polyimide film excellent in heat resistance and flexibility, and its surface has a structure in which a cover layer having an adhesive layer, a so-called coverlay film is stuck.

The coverlay film of the FPC is required to have an excellent adhesive strength to a substrate material of an FPC such as a metal foil or a polyimide film that forms the wiring of the FPC. It is proposed in [3].

In recent years, since the high frequency of the transmission signal in the FPC is remarkably advanced, it is required that the material used for the FPC is capable of reducing electric signal loss in a high frequency range, specifically, in a frequency range of 1 to 10 GHz . For the coverlay film, it is also required to exhibit excellent electrical properties (low dielectric constant (epsilon), low dielectric loss tangent (tan delta)) in the high frequency range.

The applicant of the present application has found that in Patent Document 4, the inventors of the present invention have found that an adhesive sheet having excellent adhesive strength to a substrate material of an FPC such as a metal foil or a polyimide film constituting wirings of an FPC and having an electric characteristic in a high frequency range of 1 to 10 GHz, Discloses a coverlay film having low dielectric constant (?) And low dielectric loss tangent (tan?) In a frequency range of 1 to 10 GHz. This coverlay film is obtained by copolymerizing at least one of (a) a block copolymer of a vinyl compound (component (A)) having a specific structure, a polystyrene-poly (ethylene / butylene) block copolymer, and a polystyrene- B) component, an epoxy resin (component (C)), and a curing catalyst (component (D)).

1: Japanese Patent Application Laid-Open No. 2008-248141 2: Japanese Laid-Open Patent Publication No. 2006-169446 3: Japanese Unexamined Patent Publication No. 2005-248048 4: Japanese Laid-Open Patent Publication No. 2011-68713

In manufacturing the FPC, the connecting portion of the wiring of the FPC is plated. By forming fine holes in the coverlay film described in Patent Document 4, the resistance of the FPC in the cleaning process after the plating process, specifically, It has been found that a problem may arise in the resistance of the copper wiring of the FPC to the plating cleaning solution used in the process.

The coverlay film is placed at a predetermined position of the FPC, that is, at a position covered with the coverlay film, and then thermally compressed. The thermocompression bonding is performed by pressurizing the coverlay film onto the FPC and heating and curing the film while applying pressure. The coverlay film is thermally cured by heating and adhered to the FPC.

The coverlay film described in Patent Document 4 has a good filling property of a circuit when adhering to an FPC, but has a problem in that, due to the fluidity that brings about the filling property of the circuit, ), Fine concave portions corresponding to the convex portions are formed on the surface of the coverlay film. The cause of the fine protrusion on the surface of the press surface (press surface) is a fine protrusion mainly present on the surface of the release film. This release film is sandwiched between the cushioning material and the coverlay film upon thermal compression of the coverlay film, and the fine convex portion is mainly caused by a release agent applied to the surface of the release film.

The coverlay film is preliminarily made smaller in size as the connecting portion formed at the end portion of the wiring of the FPC. At the time of thermocompression bonding of the coverlay film, the film is deformed and thinned at the end portion of the coverlay film. If there is a fine convex portion at a position corresponding to the thinned portion of the coverlay film on the surface of the press surface, a concave portion may be formed in the coverlay film, and holes may be formed due to the concentration of charges during the plating process. If the plating cleaning solution penetrates through the hole through the cleaning process after the plating process, blackening (oxidation) or whitening (peeling) of the copper wiring of the FPC is caused, leading to lower reliability of the circuit.

Further, the coverlay film described in Patent Document 4 may cause deflection called curl in the FPC due to shrinkage and stress intensity at the time of thermal curing. When such curl occurs, the flexibility of the FPC to be originally required is impaired, making it difficult to use, for example, an FPC cable.

The present invention has been made in order to solve the problems of the prior art described above and has an excellent adhesive strength to a substrate material of an FPC such as a polyimide film and has an electric characteristic in a high frequency range of 1 to 10 GHz, The present invention aims to provide a coverlay film which exhibits a low dielectric constant (epsilon) and a low dielectric loss tangent (tan delta) in the region of 1 to 10 GHz and is plated with resistance to suppress the generation of curl upon thermal curing.

In order to achieve the above object,

(A) a vinyl compound represented by the following general formula (1)

[Chemical Formula 1]

_{(Wherein, R 1, R 2, R} 3, R 4, R 5, R 6, R 7 are, the same or different, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group -. (OXO) - Is represented by the following structural formula (2).

(2)

R ₈ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. R ₁₁ , R ₁₂ and R ₁₃ may be the same or different and are a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. - (YO) - is one kind of structure defined by the following structural formula (3), or two or more kinds of structures defined by the following structural formula (3) are randomly arranged.

(3)

R ₁₆ and R ₁₇ may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. R ₁₈ and R ₁₉ may be the same or different and are a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. Z is an organic group having 1 or more carbon atoms and may contain an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. a and b each represent an integer of 0 to 300, at least one of which is not zero. c and d represent an integer of 0 or 1.)

(B) a polystyrene-poly (ethylene / butylene) block copolymer,

(C) a polystyrene-poly (ethylene-ethylene / propylene) block copolymer,

(D) an epoxy resin,

(E) bismaleimide

(B) / (C) = 1.00 or more and 4.00 or less, and the mass ratio of each component is (A + E) / (B + C) = 0.81 or more and 1.00 or less. E), the adhesive layer containing 1 to 10% by mass of the above-mentioned component (D)

Wherein the adhesive layer is formed on one side of an organic film having a melting point higher than the thermal curing temperature of the adhesive layer and having a dielectric constant (?) Of 4.0 or less and a dielectric loss tangent (tan?) Of 0.02 or less in a frequency region of 1 to 10 GHz Thereby providing a coverlay film.

(OXO) - of the component (A) is represented by the following structural formula (4), - (YO) - of the component (A) is represented by the following structural formula (5) (6), or a structure in which the structure represented by the following structural formula (5) and the structure represented by the following structural formula (6) are randomly arranged.

[Chemical Formula 4]

[Chemical Formula 5]

In the coverlay film of the present invention, it is preferable that - (Y-O) - of the component (A) has a structure represented by the structural formula (6).

In the coverlay film of the present invention, it is preferable that the lowest melt viscosity of the adhesive layer in a temperature range of 150 to 200 DEG C is 2000 Pas to 10000 Pas.

The coverlay film of the present invention preferably has a dielectric constant (?) Of 3.5 or less and a dielectric loss tangent (tan?) Of 0.02 or less in a region of a frequency of 1 to 10 GHz after thermosetting of the adhesive layer.

The coverlay film of the present invention preferably has a dielectric constant (epsilon) of the adhesive layer of not more than 2.5 and a dielectric loss tangent (tan delta) of 0.004 or less in a region of frequency 1 to 10 GHz after thermosetting of the adhesive layer.

In the coverlay film of the present invention, it is preferable that the organic film is produced by using any one of liquid crystal polymer, polyimide, polyethylene naphthalate, and polytetrafluoroethylene.

Further, the present invention is characterized in that the coverlay film of the present invention is provided on the wiring pattern side of the resin substrate having the wiring pattern formed with the wiring pattern on the main surface of the resin substrate comprising the liquid crystal polymer, polyimide or polyethylene naphthalate as the main component, And a flexible printed wiring board characterized in that the resin substrate having the wiring and the coverlay film are integrated by thermocompression bonding.

The present invention also provides a resin substrate having a wiring pattern having a wiring pattern formed on the main surface of a resin substrate containing a vinyl compound represented by the general formula (1) and a rubber and / or a thermoplastic elastomer as a main component, There is provided a flexible printed wiring board characterized in that the coverlay film of the invention is arranged so that the adhesive layers are opposed to each other and the resin substrate having the wiring and the coverlay film are integrated by thermocompression bonding.

Further, the present invention is a method for producing a coverlay film in which an adhesive layer is formed on one surface of an organic film,

(A) a vinyl compound represented by the above general formula (1)

(B) a polystyrene-poly (ethylene / butylene) block copolymer,

(C) a polystyrene-poly (ethylene-ethylene / propylene) block copolymer,

(D) an epoxy resin,

(E) bismaleimide

(B) / (C) = 1.00 or more and 4.00 or less, and the mass ratio of each component is (A + E) / (B + C) = 0.81 or more and 1.00 or less. (D) is contained in an amount of 1 to 10% by mass, based on the total mass of the resin (A) and the resin (B)

By applying the composition on one side of an organic film having a melting point higher than the thermosetting temperature of the resin composition and having a dielectric constant (epsilon) of 4.0 or less and a dielectric loss tangent (tan delta) of 0.02 or less in a frequency range of 1 to 10 GHz, And an adhesive layer is formed on the surface of the cover layer film.

Further, the present invention is a method for producing a coverlay film in which an adhesive layer is formed on one surface of an organic film,

(A) a vinyl compound represented by the above general formula (1)

(B) a polystyrene-poly (ethylene / butylene) block copolymer,

(C) a polystyrene-poly (ethylene-ethylene / propylene) block copolymer,

(D) an epoxy resin,

(E) bismaleimide

(B) / (C) = 1.00 or more and 4.00 or less, and the mass ratio of each component is (A + E) / (B + C) = 0.81 or more and 1.00 or less. (D) in an amount of 1 to 10% by mass with respect to the total mass of the adhesive film (A) and the thermosetting resin composition , The adhesive layer is formed by sticking an organic film having a dielectric constant (?) Of 4.0 or less and a dielectric loss tangent (tan?) Of 0.02 or less in a region of a frequency of 1 to 10 GHz to provide.

The present invention also provides a method of manufacturing a resin substrate having a wiring pattern by forming a wiring pattern on the main surface of a resin substrate containing a liquid crystal polymer, polyimide, or polyethylene naphthalate as a main component,

And the coverlay film of the present invention is arranged so that the adhesive layer is opposed to the wiring pattern side of the resin substrate having the wiring and the coverlay film is integrated with the resin substrate having the wiring by thermocompression bonding. A manufacturing method of a printed wiring board is provided.

The present invention also provides a resin composition comprising a vinyl compound (a) represented by the general formula (1) and a wiring pattern formed on the main surface of a resin substrate containing rubber and / or thermoplastic elastomer (b) A substrate is manufactured,

And the coverlay film of the present invention is arranged so that the adhesive layer is opposed to the wiring pattern side of the resin substrate having the wiring and the coverlay film is integrated with the resin substrate having the wiring by thermocompression bonding. A manufacturing method of a printed wiring board is provided.

The coverlay film of the present invention has an excellent adhesive strength to a substrate material of an FPC such as a metal foil or a polyimide film constituting the wiring of the FPC and has excellent electric characteristics in a high frequency range, specifically, a frequency of 1 to 10 GHz (?) And low dielectric loss tangent (tan?) In the region of the FPC.

Further, since the coverlay film of the present invention is appropriate in amount to be leaked when bonded onto the substrate, the workability in bonding the coverlay film is excellent and the filling property of the circuit is not hindered .

In addition, since the coverlay film of the present invention is provided with plating resistance, it is possible to prevent penetration of the plating cleaning solution and thereby blackening the copper wiring of the FPC by the cleaning process after the plating process of the connecting portion of the FPC wiring Oxidation) and whitening (peeling) are prevented, and the reliability of the circuit is improved.

Further, in the coverlay film of the present invention, the occurrence of curling during thermal curing is suppressed, and the flexibility of the FPC is not impaired.

Hereinafter, the coverlay film of the present invention will be described in detail.

The coverlay film of the present invention is a two-layered coverlay film having an adhesive layer formed on one side of an organic film.

[Organic film]

The organic film in the coverlay film of the present invention has a function as a protective coating for imparting plating resistance to the coverlay film.

As described above, the coverlay film preferably has high fluidity at the time of thermocompression bonding with the FPC, in order to improve the filling property of the circuit when adhering to the FPC.

However, if the flowability of the coverlay film is high at the time of thermocompression bonding with an FPC, thinning occurs at the end of the coverlay film, and if there is a fine convex portion at a position corresponding to the thinned portion of the coverlay film on the surface of the press surface, A concave portion is formed in the coverlay film, and holes may be formed due to the concentration of charges during the plating process. If the plating cleaning solution penetrates through the hole through the cleaning process after the plating process, blackening (oxidation) or whitening (peeling) of the copper wiring of the FPC is caused, leading to lower reliability of the circuit.

INDUSTRIAL APPLICABILITY The coverlay film of the present invention can achieve the filling property of a circuit when adhering to an FPC in an adhesive layer having high fluidity at the time of thermocompression bonding with an FPC, .

For this reason, it is required that the organic film in the present invention does not have a recess formed in the adhesive layer leading to a defective plating process at the time of thermocompression bonding with an FPC.

To achieve this, an organic film having a melting point higher than the thermal curing temperature of the adhesive layer is used in the organic film of the present invention. For a resin having no melting point, for example, a resin having a glass transition temperature higher than the curing temperature of the adhesive layer is used. If the organic film has a melting point higher than the thermal curing temperature of the adhesive layer, no recess is formed in the adhesive layer during thermal compression bonding with the FPC, and formation of holes in the coverlay film is prevented. As a result, the plating resistance during the plating treatment is imparted.

On the other hand, as will be described later in detail, the adhesive layer has a thermosetting temperature of 180 to 210 deg.

As a required property of the coverlay film of the present invention, there is a low dielectric constant (?) And a low dielectric loss tangent (tan?) In a frequency range of 1 to 10 GHz. Specifically, it is required that the dielectric constant epsilon is 3.5 or less and the dielectric loss tangent (tan delta) is 0.02 or less in the region of frequency 1 to 10 GHz after adhesion with the FPC, that is, after heat curing of the adhesive layer.

Therefore, the organic film is required to have a low dielectric constant (?) And a low dielectric loss tangent (tan?) In a frequency range of 1 to 10 GHz. Specifically, it is required that the dielectric constant (?) Is 4.0 or less and the dielectric loss tangent (tan?) Is 0.02 or less in the frequency range of 1 to 10 GHz.

On the other hand, the adhesive layer is required to have a dielectric constant (?) Of not more than 2.5 and a dielectric loss tangent (tan?) Of not more than 0.004 after thermosetting of the adhesive layer in a frequency range of 1 to 10 GHz.

The organic film in the present invention is selected from those satisfying the conditions relating to the above-mentioned melting point and the conditions relating to the dielectric constant and dielectric tangent.

Specific examples of the organic film satisfying these are an organic film produced by using liquid crystal polymer (LCP) or polytetrafluoroethylene (PTFE). Since the LCP or PTFE has excellent electric characteristics in a high frequency region of 1 to 10 GHz in frequency, the organic film produced using LCP or PTFE has a dielectric constant (?) Of 3.0 or less in a frequency range of 1 to 10 GHz, (tan?) is 0.0030 or less.

As another specific example of the organic film satisfying these conditions, a film having a dielectric constant (epsilon) of 4.0 or less in a region of a frequency of 1 to 10 GHz manufactured using polyimide (PI) or polyethylene naphthalate (PEN) And an organic film having a tangent (tan?) Of 0.02 or less.

With respect to the organic film produced using these PIs and PENs, the dielectric constant (?) In the region of frequency 1 to 10 GHz is 4.0 or less and the dielectric loss tangent (tan?) Is 0.02 or less by appropriately selecting the grade of the film. Depending on the PI or PEN grades or the film thickness, the dielectric constant can be set to 3.0 or less and the dielectric loss tangent to 0.006 or less in the frequency range of 1 to 10 GHz.

Therefore, the thickness of the film is selected according to the material of the organic film to be used.

The thickness of the LCP or PTFE is not particularly limited, as described above, because the electrical characteristics of the high-frequency region are excellent. However, from the viewpoint of thinning the coverlay film, the thickness is preferably 1 to 100 μm, more preferably 1 to 50 Mu] m, more preferably from 1 to 30 mu m.

The thickness of the organic film produced using PI or PEN may vary depending on the grade, but is preferably 0.5 to 100 mu m, more preferably 0.5 to 50 mu m, further preferably 0.5 to 30 mu m Do.

In the case of a film produced using LCP, a film made of LCP such as? BECKA (registered trademark) manufactured by Kuraray Co., Ltd., and BaIAC manufactured by Nihon Gore Co., Ltd. can be used. In addition, there are commercially available products such as "VECTRA (registered trademark)" manufactured by Polyplastics Co., Ltd., "SIVERAS (registered trademark)" manufactured by Toray Co., Ltd., and "SUMIKA SUPER (Liquid Silicas Super) LCP" manufactured by Sumitomo Chemical Co., Of the LCP material may be used as a film with a desired thickness.

In the case of a film produced using PI, "Capton (registered trademark)" manufactured by Toray DuPont, "Genomex (registered trademark)" manufactured by Toyoboseki Corporation, "Yufilex (registered trademark) ) Manufactured by KANEKA CORPORATION, and Apical (registered trademark) manufactured by Kaneka Co., Ltd. can be used. Further, a PI material such as " Aurum (registered trademark) " manufactured by Mitsui Kagaku Co., Ltd. may be used as a film with a desired thickness.

In the case of a film produced using PEN, " Theonex (registered trademark) " manufactured by Teijin DuPont Films, Inc. can be used.

In the case of a film produced using PTFE, "Nitoflon (registered trademark)" manufactured by Nitto Denko Co., Ltd., "NAFLON (registered trademark)" manufactured by Nichia Corporation, "VALFLON (registered trademark) ) &Quot; can be used.

[Adhesive layer]

As described above, the coverlay film of the present invention is required to have high fluidity of the adhesive layer at the time of thermocompression bonding with the FPC in order to improve the filling property of the circuit when adhering to the FPC. As described later, the temperature of the coverlay film of the present invention at the time of pressure application is 100-150 占 폚, and the temperature at the time of heat curing is 150-210 占 폚. In the coverlay film of the present invention, it is preferable that the minimum melt viscosity of the adhesive layer in the temperature range of 150 to 210 DEG C is 2000 Pas to 10000 Pas. Here, the lowest melt viscosity is the lowest value of the viscosity when the adhesive layer is melted when the adhesive layer is heated.

As a required property of the coverlay film of the present invention, there is a low dielectric constant (?) And a low dielectric loss tangent (tan?) In a frequency range of 1 to 10 GHz. Specifically, it is required that the dielectric constant (epsilon) is 3.5 or less and the dielectric loss tangent (tan delta) is 0.02 or less in the region of frequency 1 to 10 GHz after adhesion with the FPC, that is, after heat curing of the adhesive layer.

Therefore, the adhesive layer in the present invention is required to have a dielectric constant (ε) of 2.5 or less and a dielectric loss tangent (tan δ) of 0.004 or less in a frequency region of 1 to 10 GHz.

The adhesive layer in the present invention contains the following components (A) to (E) as essential components in order to satisfy the conditions relating to the lowest melt viscosity and conditions relating to the dielectric constant and dielectric tangent.

(A) a vinyl compound represented by the following general formula (1)

[Chemical Formula 6]

In the general formula (1), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group. Among them, it is preferable that R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are hydrogen atoms.

In the formula, - (O-X-O) - is represented by the following structural formula (2).

(7)

In the structural formula (2), R ₈ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. Among them, R ₈ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ are preferably an alkyl group having 6 or less carbon atoms. Among them, R ₁₁ , R ₁₂ and R ₁₃ are preferably a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms.

In the general formula (1), - (Y-O) - is one kind of structure defined by the following structural formula (3), or two or more kinds of structures defined by the following structural formula (3) are randomly arranged.

[Chemical Formula 8]

In the structural formula (3), R ₁₆ and R ₁₇ may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. Among them, R ₁₆ and R ₁₇ are preferably an alkyl group having 6 or less carbon atoms.

R ₁₈ and R ₁₉ may be the same or different and are a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. Among them, it is preferable that R ₁₈ and R ₁₉ are a hydrogen atom or an alkyl group having 3 or less carbon atoms.

In the general formula (1), Z is an organic group having 1 or more carbon atoms and may contain an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. Among them, Z is preferably a methylene group.

a and b each represent an integer of 0 to 300, at least one of which is not zero.

c and d represent an integer of 0 or 1. Of these, c and d are preferably 1.

Among these, _{preferably, R 8, R 9, R} 10, R 14, R 15 is a C3-alkyl _{group, R 11, R 12, R} 13 or less is a hydrogen atom or an alkyl group having a carbon number of 3 or less, R _16, R ₁₇ Is an alkyl group having 3 or less carbon atoms, and R ₁₈ and R ₁₉ are hydrogen atoms.

Further, - (O-X-O) - in the general formula (1) is preferably represented by the following structural formula (4).

[Chemical Formula 9]

It is also preferable that - (YO) - in the general formula (1) is a structure represented by the following structural formula (5) or the following structural formula (6), or a structure represented by the following structural formula (5) It is preferable to have a structure in which structures are randomly arranged. Among them, - (Y-O) - is preferably a structure in which structures defined by the following structural formula (6) are arranged.

[Chemical formula 10]

In the coverlay film of the present invention, the component (A) has a low dielectric constant (?) And a low dielectric loss tangent (tan?) In the range of 1 to 10 GHz in the thermosetting property, heat resistance, .

The component (A) also functions as a compatibilizing agent for the components (B), (C), (D) and (E) described below.

The production method of the vinyl compound represented by the above general formula (1) is not particularly limited and may be produced by any method. For example, chloromethylstyrene can be reacted with a compound represented by the following general formula (7) in the presence of an alkali catalyst such as sodium hydroxide, potassium carbonate or sodium ethoxide, if necessary, benzyltri n-butylammonium bromide, 18- Crown-6-ether, or the like.

(11)

- (O-X-O) and - (Y-O) - in the general formula (7) are as described above for the general formula (1).

Component (B) Polystyrene-poly (ethylene / butylene) block copolymer

Component (C): Polystyrene-poly (ethylene-ethylene / propylene) block copolymer

In the coverlay film of the present invention, the components (B) and (C) are excellent in electric characteristics (low dielectric constant (epsilon) and low dielectric loss tangent (tan delta) in the region of frequency 1 to 10 GHz, It contributes to heat resistance.

Among them, the component (B) has high heat resistance because of high crystallinity of the poly (ethylene / butylene) portion and imparts heat resistance to the adhesive layer. On the other hand, since the crystallinity of the poly (ethylene-ethylene / propylene) portion is lower than the corresponding portion (poly (ethylene / butylene) portion) of the component (B) Is high.

For this reason, in the present invention, the components (B) and (C) in the adhesive layer are used in a specific blending ratio described below.

In the present invention, the mass ratio of the components (B) and (C) in the adhesive layer is (B) / (C) = 1.00 or more and 4.00 or less.

(B) / (C) = 1.00, the desired adhesive strength can be obtained, but the adhesive layer becomes highly elastic, and the stress at the time of curing is strong.

On the other hand, when the ratio (B) / (C) is more than 4.00, the adhesive layer can be made low-tacky, and curling can be suppressed, but desired adhesion strength can not be obtained.

It is more preferable that the mass ratio of the components (B) and (C) is (B) / (C) = 1.5 or more and 3.5 or less.

Component (D): Epoxy resin

In the coverlay film of the present invention, the component (D) contributes to the thermosetting property and adhesiveness of the adhesive layer of the coverlay film.

The adhesive layer of the coverlay film of the present invention contains 1 to 10% by mass of the component (D) with respect to the total mass of the components (A) to (E).

If the content of the component (D) is less than 1% by mass, the adhesiveness of the coverlay film becomes insufficient.

When the amount of the component (D) is more than 10% by mass, the compatibility tends to deteriorate and a desired dielectric tangent (tan?) Value can not be obtained. Further, the excess amount of the coverlay film exudes at the time of adhesion. Further, since the proportion of the component (D) in the total components increases, the property of the component (D) having an inferior heat resistance affects the entire adhesive layer of the coverlay film. Therefore, the heat resistance and curability of the adhesive layer of the coverlay film may be deteriorated.

It is more preferable that the coverlay film of the present invention contains 1 to 5% by mass of the component (D) with respect to the total mass of the components (A) to (E).

The epoxy resin to be used as the component (D) is not particularly limited, and various epoxy resins such as novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin and biphenyl type epoxy resin can be used.

A specific example of the novolak type epoxy resin is JER 152 (manufactured by Japan Epoxy Resin Co., Ltd.).

Specific examples of the bisphenol A type epoxy resin include JER 828 (manufactured by Japan Epoxy Resin Co., Ltd.).

Specific examples of the bisphenol F type epoxy resin include JER 806 (manufactured by Japan Epoxy Resin Co., Ltd.).

Specific examples of the biphenyl type epoxy resin include JER FX4000 (manufactured by Japan Epoxy Resin Co., Ltd.) and NC3000H (manufactured by Nippon Kayaku Co., Ltd.).

On the other hand, any one of the above epoxy resins may be used, or two or more epoxy resins may be used in combination.

Among the above epoxy resins, a bisphenol A type epoxy resin and a biphenyl type epoxy resin are preferable, and a biphenyl type epoxy resin is more preferable.

The number average molecular weight (Mn) of the epoxy resin used as the component (D) is preferably from 150 to 2500 because of the thermosetting property, the adhesiveness, and the mechanical properties after curing.

Component (E): Bismaleimide

In the coverlay film of the present invention, the bismaleimide of the component (E) acts with the vinyl compound of the component (A), and the heat curing of the adhesive layer of the coverlay film is carried out at a lower temperature Curing at < RTI ID = 0.0 > 150 C). ≪ / RTI >

In the present invention, the use of bismaleimide is preferable from the viewpoints of maintaining the dielectric properties, imparting the bonding strength, and high Tg (glass transition point).

The blending amount of the bismaleimide of the component (E) is preferably determined by the equivalent ratio to the vinyl group of the vinyl compound of the component (A). Specifically, it is preferable that the amount of the bismaleimide of the component (E) is 0.1 to 3 equivalents, preferably 0.5 to 1.5 equivalents, and 0.8 to 1.3 equivalents relative to 1 equivalent of the vinyl group of the vinyl compound of the component (A) desirable.

In the coverlay film of the present invention, the components (A) and (E) are thermosetting resin materials, and the components (B) and (C) are thermoplastic resin materials.

In the coverlay film of the present invention, the mixing ratio of the thermosetting resin material and the thermoplastic resin material affects the physical properties of the adhesive layer of the coverlay film. Therefore, the components (A) and (E) and (components (B) and (C)) are used in a specific mixing ratio described below.

On the other hand, the epoxy resin of the component (D) is also a thermosetting resin material. As described above, the content of the component (D) is preferably 1 to 10% by mass based on the total mass of the components (A) Therefore, when the component (D) is used in combination with the components (A) and (E) and (components (B) and (C) The effect can be ignored.

In the coverlay film of the present invention, the mass ratio of the content of the components (A) and (E) to the content of the components (B) and (C) is (A + E) / (B + C) = 0.81 or more and 1.00 or less .

If the mass ratio of each component is less than (A + E) / (B + C) = 0.81, desired adhesive strength can not be obtained.

On the other hand, if (A + E) / (B + C) = 1.00 is exceeded, the elasticity becomes high, and the stress at the time of curing is strong.

The adhesive layer of the coverlay film of the present invention may contain a curing catalyst as the component (F) in addition to the components (A) to (E). This curing catalyst functions as a curing catalyst for the epoxy resin of the component (D).

When the curing catalyst is contained as the component (F), it is preferably contained in an amount of 0.001 to 5 mass% with respect to the total mass of the components (A) to (F).

If the content of the component (F) is less than 0.001% by mass, the adhesive layer of the coverlay film can not be thermally cured in a short time, and thus the adhesive property becomes insufficient.

On the other hand, if the content of the component (F) exceeds 5% by mass, there is a problem that the curing catalyst is precipitated after the formation of the adhesive layer.

When the curing catalyst is contained as the component (F), it is more preferably contained in an amount of 0.01 to 3 mass% with respect to the total mass of the components (A) to (F).

The curing catalyst to be used as the component (F) is not particularly limited as long as it is a curing catalyst of an epoxy resin, and known curing catalysts can be used. For example, imidazole-based curing catalysts, amine-based curing catalysts, phosphorus-based curing catalysts, and the like.

Examples of the imidazole-based curing catalyst include 2-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-heptadecylimidazole, Imidazole compounds such as methylimidazole, 1-cyanoethyl-2-ethyl-4-imidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole. Among them, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole and 1-cyanoethyl-2-ethyl-4-imidazole are preferable.

Examples of the amine-based curing catalyst include triazine compounds such as 2,4-diamino-6-22'-methylimidazolyl- (1 ') 에틸 ethyl-s-triazine, and 1,8-diazabicyclo [ 5,4,0] undecene-7 (DBU), triethylenediamine, benzyldimethylamine, triethanolamine, and other tertiary amine compounds. Among them, 2,4-diamino-6? 2'-methylimidazolyl- (1 ')? Ethyl-s-triazine is preferable.

Examples of phosphorus-based curing catalysts include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, and tri (nonylphenyl) phosphine.

Among them, the imidazole-based curing catalyst is particularly preferable because it accelerates the low-temperature curing with only the organic component.

Further, the adhesive layer of the coverlay film of the present invention may contain other components as necessary. Specific examples of such components include flame retardants, modifiers, and fillers.

In order to improve adhesion to a substrate, a silane coupling agent having a hydroxyl group, an epoxy group, a vinyl group, a methyl group, an amino group, an isocyanate group, or the like may be contained as the silicon alkoxy oligomer and the functional group.

(Flame retardant)

As the flame retardant, known flame retardants such as phosphoric acid esters such as trimethyl phosphara, triphenyl phosphar, and tricresyl phosphapyr can be used.

When the flame retardant is contained, the content of the flame retardant is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass, and most preferably 10 to 100 parts by mass, relative to the total mass of the components (A) to (F) By mass to 50% by mass.

Next, the procedure for manufacturing the coverlay film of the present invention, that is, the procedure for forming the adhesive layer on one side of the organic film is shown.

For example, in the case where the components (A) to (E) of the above-mentioned adhesive layer (including the component (F) and other optional components in the presence of the solvent) ) Are mixed by a heated vacuum mixing kneader to obtain a resin composition containing these components.

Specifically, the component (A) to the component (E) are mixed so that the desired content ratio (when the component (F) or any other optional component is contained, And a predetermined amount is added to a reaction kettle heated to 10 to 80 DEG C and the mixture is subjected to atmospheric pressure mixing for 3 hours while rotating at a rotation number of 100 to 1000 rpm.

The varnish containing the resin composition thus obtained is applied to one side of the organic film and dried, whereby a coverlay film having an adhesive layer formed on one side of the organic film can be produced.

Examples of the solvent usable as the varnish include ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aromatic solvents such as toluene and xylene; And high boiling solvents such as dioctyl phthalate and dibutyl phthalate. The amount of the solvent to be used is not particularly limited and can be an amount conventionally used, but is preferably 20 to 90% by mass based on the solid content.

The method of applying the varnish is not particularly limited, and examples thereof include a slot die method, a micro gravure method, a doctor-putter method, and the like. The varnish may be appropriately selected according to the desired thickness of the adhesive layer, It is preferable in that the thickness of the light guide plate can be designed to be thin. The application is performed so that the thickness of the adhesive layer formed after drying becomes a desired thickness. Such thickness can be derived from the solvent content by those skilled in the art.

The drying conditions are appropriately designed according to the type and amount of the solvent used in the varnish, the amount of the varnish used, the thickness of the coating, and the like, and are not particularly limited, but can be, for example, 60 to 120 ° C and atmospheric pressure.

The thickness of the adhesive layer formed after drying is generally 1 to 100 占 퐉, and when thinning is required, it is preferably 1 to 30 占 퐉. In practice, the thickness of the adhesive layer is selected in accordance with the height of the wiring on the FPC to which the coverlay film is pasted.

Also, even if the varnish obtained in the above procedure is applied to at least one side of the support and dried, and then the adhesive film and the organic film peeled off from the support are press bonded together at 100 to 150 ° C, A coverlay film having an adhesive layer formed thereon can be produced.

The support is not particularly limited, and examples thereof include a metal foil such as copper and aluminum, and a carrier film of a resin such as polyester and polyethylene. The support is desirably subjected to release treatment with a silicone compound or the like.

The coverlay film of the present invention has preferable characteristics as a coverlay film for FPC as shown below.

The coverlay film of the present invention is excellent in electric characteristics at high frequency after heat curing. Specifically, the coverlay film after heat curing preferably has a dielectric constant (epsilon) in a range of frequency 1 to 10 GHz of 3.5 or less, more preferably 3.0 or less.

Further, the dielectric loss tangent (tan?) In the region of the frequency of 1 to 10 GHz is preferably 0.02 or less, more preferably 0.01 or less, and even more preferably 0.0075 or less.

By setting the dielectric constant (epsilon) and dielectric tangent (tan delta) in the range of the frequency of 1 to 10 GHz within the above range, it is possible to reduce the electric signal loss in the frequency range of 1 to 10 GHz.

In order to achieve these, the adhesive layer of the coverlay film of the present invention is required to have a dielectric constant (?) Of 2.5 or less and a dielectric loss tangent (tan?) Of 0.004 or less in the region of frequency 1 to 10 GHz.

On the other hand, the dielectric constant (epsilon) and dielectric tangent (tan delta) of the adhesive film shown in Examples described later correspond to the dielectric constant (epsilon) and dielectric tangent (tan delta) of the cured product of the adhesive layer.

The coverlay film of the present invention is preferably in a tensile modulus of 250 to 400 MPa after heat curing of the adhesive layer from the viewpoint of stress relaxation due to low carbonization.

In the coverlay film of the present invention, the adhesive layer preferably has a glass transition temperature of 190 to 250 DEG C from the viewpoints of heat resistance and long-term reliability.

In the coverlay film of the present invention, it is preferable that the curl of the adhesive layer measured in the order described in the following embodiments is D <15 mm or less.

Next, the procedure of using the coverlay film of the present invention is shown.

The coverlay film of the present invention is formed so that the adhesive layer of the coverlay film faces the predetermined position of the resin substrate having the wiring with the wiring pattern formed on the main surface thereof, Followed by thermocompression at a predetermined temperature and for a predetermined time.

The temperature at the time of pressure application during thermocompression bonding is preferably 100 to 150 占 폚. The pressing time is preferably 0.5 to 10 minutes.

The temperature of the heat curing is preferably 150 to 210 占 폚. The heat curing time is preferably 30 to 120 minutes.

A flexible printed wiring board (FPC) of the present invention is a flexible printed wiring board (FPC) in which a coverlay film of the present invention is disposed so as to face the wiring pattern side of a resin substrate having a wiring pattern formed on the main surface thereof, And a coverlay film.

The resin substrate used in the FPC of the present invention is also preferably excellent in electric characteristics in a high frequency range, that is, low in dielectric constant (?) And low dielectric loss tangent (tan?) In a frequency range of 1 to 10 GHz. As a specific example of such a resin substrate, a resin substrate comprising a liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE), polyimide (PI), and polyethylene naphthalate (PEN) as main components can be mentioned.

As another specific example of the resin substrate suitable for the FPC of the present invention,

(a) a vinyl compound represented by the following general formula (1), and

(b) rubber and / or thermoplastic elastomer,

As a main component.

[Chemical Formula 12]

The vinyl compound represented by the above formula (1) of the component (a) is as described above for the adhesive layer of the coverlay film of the present invention.

(a) a vinyl compound represented by the above general formula (1), and (b) a rubber and / or a thermoplastic elastomer as a main component, has the same structure as the coverlay film of the present invention, Low dielectric tangent. Therefore, by combining with the coverlay film of the present invention, an FPC excellent in high-frequency characteristics can be obtained.

Component (b): rubber and / or thermoplastic elastomer,

A specific example of the resin substrate suitable for the FPC of the present invention includes at least one of rubber and thermoplastic elastomer as the component (b). The resin substrate may contain both rubber and thermoplastic elastomer.

Examples of the rubber of the component (b) include styrene-butadiene rubber, butyl rubber, butadiene rubber, and acryl rubber. These rubbers may be used alone, or two or more rubbers may be used in combination.

On the other hand, examples of the thermoplastic elastomer include a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, and a polyester-based thermoplastic elastomer. The thermoplastic elastomer may be used alone or in combination of two or more.

As the component (b), a thermoplastic elastomer is preferable, and a styrene-based thermoplastic elastomer is particularly preferable because the resin substrate is excellent in flexibility.

Specific examples of the styrene-based thermoplastic elastomer include a styrene-butadiene block copolymer, a styrene-isoprene-styrene block copolymer, or a copolymer obtained by partially hydrogenating a double bond thereof. More specifically, styrene- Butene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-isoprene-styrene block copolymer (SIS) And the like. Of these, SBS and SEBS are preferable.

When a styrenic thermoplastic elastomer is used as the component (b), it is preferable that the mass average molecular weight is 20,000 to 250,000. The styrene-based thermoplastic elastomer preferably has a styrene content of 25 to 60% by mass, more preferably 30 to 50% by mass, in view of good compatibility with the component (a) and excellent transparency of the resin substrate %to be. On the other hand, the mass average molecular weight is a value obtained by GPC using a calibration curve by standard polystyrene.

Specific examples of the styrene-based thermoplastic elastomer include a styrene-butadiene block copolymer "JSR TR" series manufactured by JSR Corporation, and a series of styrene-isoprene block copolymer "JSR SIS".

A specific example of the resin substrate suitable for the FPC of the present invention is a resin substrate comprising a urethane prepolymer having two or more isocyanate groups or blocked isocyanate groups in one molecule as component (c) in addition to the components (a) and (b) . Such a urethane prepolymer comprises a polyol and a compound having at least two isocyanate groups or blocked isocyanate groups in at least one molecule.

The urethane prepolymer of component (c) contributes to the tackiness of the resin substrate and improves the tackiness of the resin substrate in the temperature range when transferring the wiring pattern to the resin substrate.

Specific examples of the polyol used as the raw material of the urethane prepolymer of the component (c) include polyolefin-based polyols obtained by hydrogenating polybutadiene polyol, polyisoprene polyol, polyisoprene polyol and the like, dimer acid polyol using dimer acid as a carboxylic acid component Ester polyol and the like.

Other specific examples of the polyol used as the raw material of the urethane prepolymer of the component (c) include bifunctional alcohols such as 1,4-butanediol, 1,6-hexanediol and ethylene glycol, trifunctional such as trimethylolpropane Alcohol.

These polyols may be used in combination of two or more.

The isocyanate group-containing compound used as a raw material for the urethane prepolymer of component (c) is not particularly limited as long as it contains two or more isocyanate groups or blocked isocyanate groups in one molecule in total. Specific examples of the compound having two or more isocyanate groups in one molecule include, for example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'- Hexyl methane diisocyanate, and the like. Of these, tolylene diisocyanate and isophorone diisocyanate are particularly preferable. Examples of the compound having a blocked isocyanate group include compounds blocked with a blocking agent such as alcohols, phenols, oximes and the like, the compounds having an isocyanate group as exemplified above.

The urethane prepolymer preferable as the component (c) is a urethane prepolymer containing at least 50 parts by mass of a urethane prepolymer obtained from polybutadiene polyol and 1,4-butanediol and tolylene diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate.

A specific example of the resin substrate suitable for the FPC of the present invention preferably contains a silane coupling agent as the component (d) in addition to the above components (a) to (c). The silane coupling agent of the component (d) contributes to adhesion between the resin substrate and the wiring pattern when transferring the wiring pattern to the resin substrate.

Specific examples of the silane coupling agent used as the component (d) include vinylsilane silane coupling agents, (meth) acryloxy silane based silane coupling agents, isocyanate silane based silane coupling agents, epoxy silane based silane coupling agents, Based silane coupling agent, a mercaptosilane-based silane coupling agent, a chloropropylsilane-based silane coupling agent, and oligomers of these silane coupling agents. Of these, preferred are (meth) acryloxysilane-based silane coupling agents and aminosilane-based silane coupling agents.

Examples of the vinylsilane-based silane coupling agent include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, di Trimethylolpropane, trimethylolpropane, trimethylolpropane, and the like.

Examples of the (meth) acryloxysilane-based silane coupling agent include? -Acryloxypropyltrimethoxysilane, 3- (trimethoxysilyl) propyl acrylate,? -Methacryloxypropyltrimethoxysilane, and the like .

Examples of the isocyanate silane-based silane coupling agent include 3- (triethoxysilyl) propyl isocyanate and the like.

Examples of the epoxy silane-based silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. .

Examples of the aminosilane-based silane coupling agent include N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, and the like.

Examples of the chloropropylsilane-based silane coupling agent include 3-chloropropyltrichlorosilane and the like.

Examples of the mercaptosilane-based silane coupling agent include (3-mercaptopropyl) triethoxysilane and (3-mercaptopropyl) trimethoxysilane.

Oligomers of these silane coupling agents can also be used as the component (d).

Among these, preferred are (meth) acryloxysilane-based silane coupling agents such as? -Acryloxypropyltrimethoxysilane, 3- (trimethoxysilyl) propyl acrylate and? -Methacryloxypropyltrimethoxysilane, Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) Aminosilane-based silane coupling agents such as methoxy silane and ethoxy silane.

In the specific examples of the resin substrate preferred for the FPC of the present invention, the mass ratio of the component (a) to the component (b) is preferably 3: 7 to 7: 3, more preferably 4: 6 to 6: Is more preferable.

When the urethane prepolymer is contained as the component (c), the mass ratio of the component (c) to the total amount of the components (a) and (b) is preferably 99: 1 To 40:60, more preferably from 97.5: 2.5 to 50:50, and even more preferably from 95: 5 to 60:40.

When the specific example of the resin substrate suitable for the FPC of the present invention contains a silane coupling agent as the component (d), the mass ratio of the component (d) to the total amount of the components (a) to (c) More preferably from 99.9: 0.1 to 95: 5, and even more preferably from 99.7: 0.3 to 98: 2.

Specific examples of the resin substrate suitable for the FPC of the present invention may include any components other than the above-mentioned components (a) to (d). Specific examples of such arbitrary components include fillers used for the purpose of improving the mechanical strength of the resin substrate. Specific examples of such fillers include metals such as silver, gold, and copper, metal compounds such as silica, alumina, titania, boron nitride, iron oxide, and organic fillers such as carbon.

When the filler is contained as an optional component, the mass ratio of the filler to the total amount of the components (a) to (d) is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2: 8, and more preferably from 7: 3 to 3: 7.

The resin substrate preferable for the FPC of the present invention may be a resin substrate in which inorganic fibers such as glass fibers or carbon fibers or organic fibers such as aramid fibers are used together with the above filler or in place of the above- And may be included for the purpose of improving the strength.

[Example]

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

(Examples 1 to 12 and Comparative Examples 1 to 9)

Sample preparation and measurement method (adhesive film only)

An adhesive film having the same composition as that of the adhesive layer of the coverlay film of the present invention was prepared, and the properties thereof were evaluated.

Each component was metered and compounded so as to have a blending ratio (mass%) as shown in the following table. The components were charged in a reaction kettle heated to 70 DEG C, and the mixture was subjected to atmospheric pressure mixing for 3 hours while rotating at a rotational speed of 300 rpm. When a curing agent is added, a curing agent is added after cooling.

The varnish containing the resin composition thus obtained was applied to one side of a support (PET film subjected to releasing treatment) and dried at 100 캜 to obtain an adhesive film having a support.

The abbreviations in the tables indicate the following.

Component (A)

OPE2200: Oligophenylene ether (vinyl compound represented by the above general formula (1)) (Mn = 2200), manufactured by Mitsubishi Gas Chemical Co.,

Component (B)

Tuftec H1052: a polystyrene-poly (ethylene / butylene) block copolymer (styrene content: 20%), manufactured by Asahi Kasei Corporation

Tuftec H1031: polystyrene-poly (ethylene / butylene) block copolymer (styrene content 30%), manufactured by Asahi Kasei Co.,

Component (C)

(Styrene content: 32%), manufactured by KURARAY CO., LTD.

Component (B ')

TR2003: polystyrene-polybutadiene block copolymer (styrene / butadiene = 43/57), manufactured by JSR Corporation

Component (D)

NC3000H: biphenyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd.

Component (E)

BMI-70: manufactured by Bismaleimide, K.I.Kasei Co., Ltd.

Component (F)

C11ZCN: 1-cyanoethyl-2-undecylimidazole, manufactured by Shikoku Kasei Co., Ltd.

2E4MZ: 2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei Co., Ltd.

TPP-MK: tetraphenylphosphonium tetra-p-tolyl borate, manufactured by Hokkogakukogyo Co., Ltd.

Compatibility: It was diluted with a solvent (toluene) at an appropriate concentration, applied to a peelable substrate, dried at 100 占 폚 for 10 minutes, and made to be a film having a thickness of 20 占 퐉. The state of the varnish diluted in the solvent and the state of the surface of the varnish film were observed to evaluate the compatibility. The varnish was visually judged whether or not there was turbidity, and the surface of the film was observed with a CCD camera (x100 magnification).

When the varnish had turbidity and the varnish had a film surface of 100 mu m or more on the surface of the varnish, or when the varnish could not be filmed, the varnish had turbidity, and the varnish had a film of 100 mu m The case where there was no stain on the surface of the varnish and the case where there was no turbidity on the varnish and the surface of the varnish was a film had no stain pattern of 100 占 퐉 or more was rated as?

Dielectric constant (?) And dielectric loss tangent (tan delta): The adhesive film was heat-cured at 200 占 폚 and peeled off from the support, and then a test piece (40 占 0.5 mm 占 100 占 2 mm) was cut out from the adhesive film, Respectively. The dielectric constant (ε) and dielectric loss tangent (tan δ) of the test piece were measured with a cavity resonator perturbation method (10 GHz) by rounding the test piece into a cylinder having a length of 100 mm and a diameter of 2 mm or less.

Glass transition point Tg: measured by dynamic viscoelasticity measurement (DMA). The adhesive film was heat-cured at 200 占 폚, peeled from the support, and then a test piece (10 占 0.5 mm 占 40 占 1 mm) was cut out from the adhesive film and the width and thickness of the test piece were measured. Thereafter, the measurement was carried out with DMS 6100 (3 ° C / min 25-300 ° C). The peak temperature of tanD was read to be Tg.

Cross-cut adhesive property: Copper foil-lacquered surface was adhered to one side of the adhesive film and thermocompression bonded (200 占 폚, 60 min, 10 kgf). After the support was peeled off, a tape was stuck on a scale of 100 when the sheath was placed in a lattice pattern at intervals of 1 mm on the adhesive film surface, and the tape was momentarily removed at an angle of 90 ° to the film surface. At that time, it was judged whether or not the film peeled off from the copper foil-lacquered surface. On the other hand, the results were judged according to the following criteria.

○: Among 100 scales, there is no scaling.

X: Among 100 scales, even scales with one exfoliation.

Tensile modulus: The adhesive film was heat-cured at 200 占 폚 and peeled off from the support. Five test pieces (25 占 0.5 mm 占 220 占 2 mm) were cut out from the adhesive film in the MD direction and the thickness was measured. The test piece was placed on an autograph, set at a jig width of 170 mm, and measured at a stretching speed of 1 mm / min to a stroke of 5 mm. The average value of N = 5 was taken as the measured value.

Curl evaluation: An LCP film (Beckstar (registered trademark) CT-Z (manufactured by Kuraray Co., Ltd.) having a thickness of 50 탆 was cut to a width of 50 ± 0.5 mm and an adhesive film cut in the same size was laminated on one side of the LCP film (200 DEG C, 60 min, 10 kgf). The support was peeled off and placed on a horizontal plane of a flat desk with the adhesive side of the adhesive film facing up, and the degree of curl was observed. The maximum height of the height of the test piece from the horizontal plane of the desk was defined as D, and the following criteria were used.

?: The specimen did not become cylindrical, and D = 15 mm.

?: The test piece did not become cylindrical, and 15 mm < D.

X: The test specimen became cylindrical.

Example
Example 2
Example 3
Example 4
Example 5
Example 6
Component (A)
OPE2St-2200
30.7%
30.5%
32.5%
34.0%
30.7%
30.4%
Component (B)
Tuftec H1052
31.6%
-
30.4%
29.1%
34.3%
36.5%
Tuftec H1031
-
31.3%
-
-
-
-
Component (C)
Septon 4044
21.1%
20.9%
20.3%
19.4%
18.4%
15.7%
Component (B ')
TR2003
-
-
-
-
-
-
Component (D)
NC3000H
4.0%
4.0%
4.0%
4.0%
4.0%
5.0%
Component (E)
BMI-70
12.4%
12.2%
13.0%
13.6%
12.4%
12.2%
Component (F)
C11ZCN
0.1%
0.1%
0.1%
0.1%
0.1%
0.1%
2E4MZ
-
-
-
-
-
-
TPP-MK
-
-
-
-
-
-
Sum
99.9%
99.0%
100.3%
100.3%
99.9%
99.9%
(A + E) / (B + C)
0.82
0.82
0.90
0.98
0.82
0.82
B / C
1.50
1.50
1.50
1.50
1.86
2.32
Solids
20.0%
18.0%
18.0%
18.0%
20.0%
18.0%
Compatibility
◎
○
◎
◎
◎
◎
curl
○
○
○
○
○
○
Cross-cut adhesive
○
○
○
○
○
○
? (10GH)
2.33
2.32
2.33
2.35
2.33
2.33
tan? (10 GHz)
0.0026
0.0024
0.0025
0.0028
0.003
0.0033
Tg (占 폚) (DMA)
-
232.9
232
229
-
234.4
Tensile modulus (MPa)
339.72
219.99
311.00
368.00
233.92
220.52

Example 7
Example 8
Example 9
Example 10
Example 11
Component (A)
OPE2St-2200
33.3%
31.4%
28.8%
30.7%
30.7%
Component (B)
Tuftec H1052
40.0%
32.3%
29.6%
31.6%
31.6%
Tuftec H1031
-
-
-
-
-
Component (C)
Septon 4044
10.0%
21.5%
19.8%
21.1%
21.1%
Component (B ')
TR2003
-
-
-
-
-
Component (D)
NC3000H
3.3%
2.0%
10.0%
4.0%
4.0%
Component (E)
BMI-70
13.4%
12.6%
11.6%
12.4%
12.4%
Component (F)
C11ZCN
0.1%
0.1%
0.3%
-
-
2E4MZ
-
-
-
0.1%
-
TPP-MK
-
-
-
-
0.1%
Sum
100.1%
99.9%
100.1%
99.9%
99.9%
(A + E) / (B + C)
0.93
0.82
0.82
0.82
0.82
B / C
0.93
0.82
0.82
0.82
0.82
Solids
20.0%
18.0%
19.0%
18.0%
18.0%
Compatibility
◎
◎
○
◎
○
curl
○
○
○
○
○
Cross-cut adhesive
○
○
○
○
○
? (10GH)
2.32
2.32
2.4
2.33
2.42
tan? (10 GHz)
0.0029
0.0021
0.0038
0.0028
0.0028
Tg (占 폚) (DMA)
224.3
-
-
-
233.5
Tensile modulus (MPa)
254.35
309.49
345.00
322.00
349.00

Comparative Example 1
Comparative Example 2
Comparative Example 3
Comparative Example 4
Comparative Example 5
Component (A)
OPE2St-2200
50.0%
48.9%
28.0%
36.7%
38.1%
Component (B)
Tuftec H1052
-
-
33.8%
26.9%
10.0%
Tuftec H1031
-
-
-
-
-
Component (C)
Septon 4044
-
39.1%
22.6%
18.0%
39.8%
Component (B ')
TR2003
50.0%
-
-
-
-
Component (D)
NC3000H
-
2.0%
4.0%
4.0%
3.0%
Component (E)
BMI-70
-
9.8%
11.2%
14.7%
9.0%
Component (F)
C11ZCN
-
0.1%
0.1%
0.1%
0.1%
2E4MZ
-
-
-
-
-
TPP-MK
-
-
-
-
-
Sum
100.0%
99.9%
99.7%
100.4%
100.0%
(A + E) / (B + C)
1.00
1.50
0.70
1.15
0.95
B / C
-
0.00
1.50
1.50
0.25
Solids
30.0%
15.0%
-
-
14.5%
Compatibility
○
○
○
×
-
curl
×
×
○
△
×
Cross-cut adhesive
○
○
×
○
○
? (10GH)
2.40
2.34
2.30
2.40
2.30
tan? (10 GHz)
0.0020
0.0023
0.0024
0.0030
0.0021
Tg (占 폚) (DMA)
185.0
232.8
228.0
231.0
235.2
Tensile modulus (MPa)
780.00
1253.12
118.00
433.00
833.00

Comparative Example 6
Comparative Example 7
Comparative Example 8
Comparative Example 9
Component (A)
OPE2St-2200
35.7%
35.7%
40.8%
27.1%
Component (B)
Tuftec H1052
24.1%
45.5%
49.0%
27.9%
Tuftec H1031
-
-
-
-
Component (C)
Septon 4044
29.4%
8.0%
-
18.6%
Component (B ')
TR2003
-
-
-
-
Component (D)
NC3000H
3.6%
3.6%
2.0%
15.0%
Component (E)
BMI-70
7.2%
7.2%
8.2%
11.0%
Component (F)
C11ZCN
0.1%
0.1%
0.1%
0.4%
2E4MZ
-
-
-
-
TPP-MK
-
-
-
-
Sum
100.1%
100.1%
100.1%
100.0%
(A + E) / (B + C)
0.80
0.80
1.00
0.82
B / C
0.82
5.67
-
1.50
Solids
-
-
-
20.0%
Compatibility
○
×
×
×
curl
×
○
-
○
Cross-cut adhesive
○
×
-
○
(10GH)
2.32
2.31
-
2.40
tan (10 GHz)
0.0021
0.0025
-
0.0045
Tg () (DMA)
236.0
200.0
-

Tensile modulus (MPa)
684.00
113.00
-
382.00

Examples 1 to 11 were excellent in compatibility, curl, cross-cut adhesion, electrical properties (dielectric constant (?), Dielectric loss tangent (tan?) And tensile elastic modulus in high frequency region) 10 was particularly excellent in compatibility. In Example 5 in which B / C was increased as compared with Example 1, the tensile elastic modulus could be lowered. Example 6 in which B / C was larger than Example 5 , The tensile modulus of elasticity could be lowered.

In Example 8 in which the content of the epoxy resin of the component (D) was smaller than that of Example 1, dielectric tangent (tan?) Could be lowered.

In Comparative Example 1 using a polystyrene-polybutadiene block copolymer as the thermoplastic elastomer instead of the components (B) and (C), the tensile elastic modulus was high and the curl deteriorated.

In Comparative Example 2 not containing the component (B), the tensile modulus of elasticity was increased and the curl was deteriorated.

In Comparative Example 3 in which the mass ratio of each component was less than (A + E) / (B + C) = 0.81, the crosscut adhesion was inferior.

In Comparative Example 4 in which the mass ratio of each component was (A + E) / (B + C) = 1.00, the compatibility was lowered, the tensile elastic modulus was increased, and the curl deteriorated.

In Comparative Examples 5 and 6, in which the mass ratio (B) / (C) of components (B) and (C) was less than 1.00, the tensile elastic modulus was high and the curl deteriorated.

In Comparative Example 7 in which the mass ratio (B) / (C) of components (B) and (C) was more than 4.00, the compatibility and the crosscut adhesion were inferior.

In Comparative Example 8 which did not contain the component (C), the compatibility was lowered and a flat film could not be obtained. Therefore, evaluation of curl and the like was not carried out.

In Comparative Example 9 in which the content of the epoxy resin in the component (D) was more than 6 parts by mass based on the component (A), the compatibility was lowered. Further, the dielectric tangent (tan?) Of the heat cured product of the adhesive film was more than 0.004.

Sample preparation and measurement method (a two layered coverlay film in which an adhesive layer is formed on one side of an organic film having a melting point higher than the thermal curing temperature of the adhesive layer).

The varnish containing the resin composition (Example 5) obtained in the same procedure as above was applied to one side of the organic film having a melting point higher than the thermal curing temperature of the resin composition and dried at 100 DEG C, A coverlay film having a two-layer structure was obtained.

As another method, an adhesive film (Example 5) having a support obtained in the same procedure as above was pressed at 120 DEG C onto one side of an organic film having a melting point higher than the thermal curing temperature of the adhesive film, A coverlay film having a two-layer structure in which an adhesive layer was formed on one side of the organic film was obtained.

On the other hand, as the organic film, BECSTAR (registered trademark) CT-Z (manufactured by Kuraray Co., Ltd.) and a thickness of 25 mu m were used as the LCP film. The melting point of the LCP film was 335 ° C. The thickness of the adhesive layer was set to 15 占 퐉 and 25 占 퐉.

The following two-layer structure of the coverlay film was evaluated.

The dielectric constant (?) And dielectric tangent (tan delta): The coverlay film having a two-layer structure was heated and cured at 200 占 폚, and a test piece (40 占 0.5 mm 占 100 占 2 mm) was cut out from the coverlay film of the two- The thickness was measured. The dielectric constant (ε) and dielectric loss tangent (tan δ) of the test piece were measured with a cavity resonator perturbation method (10 GHz) by rounding the test piece into a cylinder having a length of 100 mm and a diameter of 2 mm or less.

Peel Strength: A copper foil-lacquered surface was stuck to the adhesive layer of the coverlay film having a two-layer structure and thermally pressed (200 DEG C, 60 min, 10 kgf). The test piece was cut to a width of 10 mm and the copper foil was peeled off using an autograph to measure the peel strength. For the measurement results, the average value of each N = 5 was calculated.

Cross-cut adhesive property: A copper foil-lacquered surface was stuck to the adhesive layer of the coverlay film having a two-layer structure and thermocompression bonded (200 DEG C, 60 min, 10 kgf). A tape was stuck on a scale of 100 when the sheath was placed in a lattice pattern at intervals of 1 mm on the surface of the organic film (LCP film) of the coverlay film, and the tape was instantaneously I took it off. At that time, it was judged whether or not the organic film (LCP film) was peeled from the copper foil-lacquered surface.

In a coverlay film having a thickness of the adhesive layer of 15 mu m, the dielectric constant (?) Was 2.9 and the dielectric loss tangent (tan?) Was 0.0024. The peel strength was 6.58 N / cm. No peeling occurred in the crosscut adhesion evaluation.

In a coverlay film having an adhesive layer thickness of 25 占 퐉, the dielectric constant? And the dielectric tangent (tan?) Were 0.008 and 2.8, respectively. The peel strength was 6.77 N / cm. No peeling occurred in the crosscut adhesion evaluation.

From these results, it was confirmed that the coverlay film having a two-layer structure produced by changing the thickness of the adhesive layer was excellent in electrical characteristics (permittivity epsilon, dielectric tangent tan delta), peel strength and crosscut adhesion property in a high frequency region.

On the other hand, the dielectric constant (?) Of the LCP film alone was 3.2 and the dielectric loss tangent (tan?) Was 0.0022. The dielectric constant (?) Of the adhesive layer (adhesive film) alone (thickness of 25 占 퐉) was 2.3 and the dielectric loss tangent (tan?) Was 0.0030.

Further, a coverlay film having a two-layer structure was produced using the PI film as the organic film in the same procedure as above, and dielectric constant (?) And dielectric tangent (tan?) Were evaluated.

As the PI film, the following were used.

Genomax (registered trademark), manufactured by Toyoboseki Co., Ltd., having a thickness of 12.5 mu m

Capton (R) 100EN, manufactured by Toray &amp; DuPont Co., Ltd., having a thickness of 25 mu m

Capton (registered trademark) 300H, manufactured by Toray-DuPont Co., Ltd., thickness 77 mu m,

The results are as follows.

Genomax (registered trademark) alone

Permittivity (?): 3.6

Dielectric loss tangent (tan?): 0.0114

Two-layer coverlay film

Permittivity (?): 2.8

Dielectric tangent (tan?): 0.0059

Capton (R) 100EN alone

Permittivity (?): 3.3

Dielectric loss tangent (tan?): 0.0086

Two-layer coverlay film

Permittivity (?): 2.8

Dielectric tangent (tan?): 0.0059

Capton (R) 300H alone

Permittivity (?): 3.3

Dielectric loss tangent (tan?): 0.0144

Two-layer coverlay film

Permittivity (?): 3.0

Dielectric loss tangent (tan?): 0.0108

From these results, it was found that even in a coverlay film of a two-layer structure produced by using a different type of PI film as the organic film and changing the thickness of the adhesive layer, an excellent electrical characteristic (permittivity?, Dielectric loss tangent? .

A method for producing a printed wiring board based on an FPC having as a main component the components (a) and (b)

For the production of the resin substrate for FPC, a resin composition containing the following components was used.

Component (a): OPE2st: Oligophenylene ether (vinyl compound represented by the above general formula (1)) (Mn = 1200), 54.3 parts by Mitsubishi Gas Kagaku Co., Ltd.

Component (b): Polystyrene-polybutadiene block copolymer (TR2003, manufactured by JSR Corporation: mass average molecular weight: about 100,000, styrene content: 43 mass%) 36.2 parts

Component (c): Urethane prepolymer

600 g of toluene, 633.3 g of polyol ("Epol PIP-H", manufactured by Idemitsu Sekiyu Kagaku Co., Ltd., sp = 8.20), 33.3 g of 1,4-butanediol, After 233.3 g of isophorone diisocyanate was poured and uniformly dissolved, 0.06 g of triethylenediamine as a catalyst was added. The inside temperature of the flask was heated to 70 占 폚 to 80 占 폚, and the urethanization reaction was carried out for 7 hours. Thereafter, the resultant solution was cooled to obtain a toluene solution of a urethane prepolymer having a solid isocyanate content per solid content of 3.5% by mass. Part 9

Component (d): Silane coupling agent

0.5 part of? -acryloxypropyltrimethoxysilane ("KBM-5103", manufactured by Shin-Etsu Chemical Co., Ltd.)

Each of the above components was dry-mixed at a peripheral speed of 400 rpm using a three-one motor (BLW1200, manufactured by Shintokagaku Co., Ltd.) to prepare a resin composition. The resin composition was added to a solvent methyl ethyl ketone and heated and stirred to prepare a varnish (solid concentration of about 30% by mass). The varnish was coated on a supporting PET film (thickness: 50 mu m) with a gravure coater, and then dried at 100 DEG C for 10 minutes, left to cool, and peeled from the PET film to obtain a resin substrate for FPC. The thickness of the resin substrate was 30 mu m.

Copper foils were bonded to both surfaces of the resin substrate obtained in the above procedure with the roughened surface facing inward, and thermocompression bonded (200 占 폚, 60 min, 10 kgf). One side or both sides of the thermocompression-bonded copper foil was etched to form a wiring pattern and a resin substrate having wiring. A coverlay film having a two-layer structure obtained by the above procedure was disposed on the wiring pattern side of the resin substrate having this wiring so that the adhesive layers were opposed to each other and thermocompression-bonded (200 DEG C, 10 kgf) to produce a printed wiring board .

Claims (13)

(A) a vinyl compound represented by the following general formula (1)
[Chemical Formula 1]

_{(Wherein, R 1, R 2, R} 3, R 4, R 5, R 6, R 7 are, the same or different, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group -. (OXO) - Is represented by the following structural formula (2).
(2)

R ₈ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. R ₁₁ , R ₁₂ and R ₁₃ may be the same or different and are a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. - (YO) - is one kind of structure defined by the following structural formula (3), or two or more kinds of structures defined by the following structural formula (3) are randomly arranged.
(3)

R ₁₆ and R ₁₇ may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. R ₁₈ and R ₁₉ may be the same or different and are a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. Z is an organic group having 1 or more carbon atoms and may contain an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. a and b each represent an integer of 0 to 300, at least one of which is not zero. c and d represent an integer of 0 or 1.)
(B) a polystyrene-poly (ethylene / butylene) block copolymer,
(C) a polystyrene-poly (ethylene-ethylene / propylene) block copolymer,
(D) an epoxy resin,
(E) bismaleimide
(B) / (C) = 1.00 or more and 4.00 or less, and the mass ratio of each component is (A + E) / (B + C) = 0.81 or more and 1.00 or less. E), the adhesive layer containing 1 to 10% by mass of the above-mentioned component (D)
Wherein the adhesive layer is formed on one side of an organic film having a melting point higher than the thermal curing temperature of the adhesive layer and having a dielectric constant (?) Of 4.0 or less and a dielectric loss tangent (tan?) Of 0.02 or less in a frequency region of 1 to 10 GHz Coverlay film. The method according to claim 1,
The structure in which - (OXO) - of the component (A) is represented by the following structural formula (4) and - (YO) - of the component (A) is represented by the following structural formula (5) , A structure represented by the following structural formula (5) and a structure represented by the following structural formula (6) are randomly arranged.
[Chemical Formula 4]

[Chemical Formula 5]

3. The method of claim 2,
Wherein the - (YO) - of the component (A) has a structure represented by the structural formula (6). 4. The method according to any one of claims 1 to 3,
Wherein a minimum melt viscosity of the adhesive layer in a temperature range of 150 to 200 占 폚 is not less than 2000 Pa 占 퐏 and not more than 10,000 Pa 占 퐏. 5. The method according to any one of claims 1 to 4,
Wherein a dielectric constant (?) In a region of a frequency of 1 to 10 GHz after the heat curing of the adhesive layer is 3.5 or less and a dielectric loss tangent (tan?) Is 0.02 or less. 6. The method according to any one of claims 1 to 5,
Wherein the adhesive layer has a dielectric constant (?) Of 2.5 or less and a dielectric loss tangent (tan?) Of 0.004 or less in a region of a frequency of 1 to 10 GHz after thermosetting of the adhesive layer. 7. The method according to any one of claims 1 to 6,
Wherein the organic film is produced by using any one of a liquid crystal polymer, polyimide, polyethylene naphthalate, and polytetrafluoroethylene. The cover according to any one of claims 1 to 7, which is provided on a wiring pattern side of a resin substrate having a wiring pattern in which a wiring pattern is formed on a main surface of a resin substrate comprising a liquid crystal polymer, polyimide, and polyethylene naphthalate as a main component Wherein the resin film and the coverlay film are integrated with each other by thermocompression bonding. A vinyl compound (a) represented by the following general formula (1) and a wiring pattern side of a resin substrate having a wiring pattern in which a wiring pattern is formed on the main surface of a resin substrate containing a rubber and / or a thermoplastic elastomer (b) A coverlay film according to any one of claims 1 to 7, wherein the adhesive layer is disposed so as to face each other, and the resin substrate having the wiring and the coverlay film are integrated by thermocompression bonding. Wiring board.
[Chemical Formula 6]

_{(Wherein, R 1, R 2, R} 3, R 4, R 5, R 6, R 7 are, the same or different, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group -. (OXO) - Is represented by the following structural formula (2).
(7)

R ₈ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. R ₁₁ , R ₁₂ and R ₁₃ may be the same or different and are a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. - (YO) - is one kind of structure defined by the following structural formula (3), or two or more kinds of structures defined by the following structural formula (3) are randomly arranged.
[Chemical Formula 8]

R ₁₆ and R ₁₇ may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. R ₁₈ and R ₁₉ may be the same or different and are a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. Z is an organic group having 1 or more carbon atoms and may contain an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. a and b each represent an integer of 0 to 300, at least one of which is not zero. c and d represent an integer of 0 or 1.) A method for producing a coverlay film in which an adhesive layer is formed on one side of an organic film,
Wherein,
(A) a vinyl compound represented by the following general formula (1)
[Chemical Formula 9]

_{(Wherein, R 1, R 2, R} 3, R 4, R 5, R 6, R 7 are, the same or different, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group -. (OXO) - Is represented by the following structural formula (2).
[Chemical formula 10]

R ₈ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. R ₁₁ , R ₁₂ and R ₁₃ may be the same or different and are a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. - (YO) - is one kind of structure defined by the following structural formula (3), or two or more kinds of structures defined by the following structural formula (3) are randomly arranged.
(11)

R ₁₆ and R ₁₇ may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. R ₁₈ and R ₁₉ may be the same or different and are a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. Z is an organic group having 1 or more carbon atoms and may contain an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. a and b each represent an integer of 0 to 300, at least one of which is not zero. c and d represent an integer of 0 or 1.)
(B) a polystyrene-poly (ethylene / butylene) block copolymer,
(C) a polystyrene-poly (ethylene-ethylene / propylene) block copolymer,
(D) an epoxy resin,
(E) bismaleimide
(B) / (C) = 1.00 or more and 4.00 or less, and the mass ratio of each component is (A + E) / (B + C) = 0.81 or more and 1.00 or less. (D) is contained in an amount of 1 to 10% by mass, based on the total mass of the resin (A) and the resin (B)
Is formed by coating on one side of an organic film having a melting point higher than the thermosetting temperature of the resin composition and having a dielectric constant (?) Of 4.0 or less and a dielectric loss tangent (tan?) Of 0.02 or less in a frequency of 1 to 10 GHz Wherein the cover layer film has a thickness of from about 2 to about 10 .mu.m. A method for producing a coverlay film in which an adhesive layer is formed on one side of an organic film,
(A) a vinyl compound represented by the following general formula (1)
[Chemical Formula 12]

_{(Wherein, R 1, R 2, R} 3, R 4, R 5, R 6, R 7 are, the same or different, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group -. (OXO) - Is represented by the following structural formula (2).
[Chemical Formula 13]

R ₈ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. R ₁₁ , R ₁₂ and R ₁₃ may be the same or different and are a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. - (YO) - is one kind of structure defined by the following structural formula (3), or two or more kinds of structures defined by the following structural formula (3) are randomly arranged.
[Chemical Formula 14]

R ₁₆ and R ₁₇ may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. R ₁₈ and R ₁₉ may be the same or different and are a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. Z is an organic group having 1 or more carbon atoms and may contain an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. a and b each represent an integer of 0 to 300, at least one of which is not zero. c and d represent an integer of 0 or 1.)
(B) a polystyrene-poly (ethylene / butylene) block copolymer,
(C) a polystyrene-poly (ethylene-ethylene / propylene) block copolymer,
(D) an epoxy resin,
(E) bismaleimide
(B) / (C) = 1.00 or more and 4.00 or less, and the mass ratio of each component is (A + E) / (B + C) = 0.81 or more and 1.00 or less. (D) in an amount of 1 to 10% by mass with respect to the total mass of the adhesive film (A) and the thermosetting resin composition , And the adhesive layer is formed by sticking an organic film having a dielectric constant (?) Of 4.0 or less and a dielectric loss tangent (tan?) Of 0.02 or less in a region of a frequency of 1 to 10 GHz. A wiring pattern is formed on the main surface of a resin substrate composed mainly of a liquid crystal polymer, polyimide, and polyethylene naphthalate to produce a resin substrate having wiring,
The coverlay film according to any one of claims 1 to 7 is disposed on the wiring pattern side of the resin substrate having the wiring so that the adhesive layer is opposed to the resin substrate, And the coverlay film is integrated with the flexible printed wiring board. A resin substrate having wires is produced by forming a wiring pattern on the main surface of a resin substrate containing a vinyl compound represented by the following general formula (1) and a rubber and / or a thermoplastic elastomer as a main component,
The coverlay film according to any one of claims 1 to 7 is disposed on the wiring pattern side of the resin substrate having the wiring so that the adhesive layer is opposed to the resin substrate, And the coverlay film is integrated with the flexible printed wiring board.
[Chemical Formula 15]

_{(Wherein, R 1, R 2, R} 3, R 4, R 5, R 6, R 7 are, the same or different, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group -. (OXO) - Is represented by the following structural formula (2).
[Chemical Formula 16]

R ₈ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. R ₁₁ , R ₁₂ and R ₁₃ may be the same or different and are a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. - (YO) - is one kind of structure defined by the following structural formula (3), or two or more kinds of structures defined by the following structural formula (3) are randomly arranged.
[Chemical Formula 17]

R ₁₆ and R ₁₇ may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. R ₁₈ and R ₁₉ may be the same or different and are a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. Z is an organic group having 1 or more carbon atoms and may contain an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. a and b each represent an integer of 0 to 300, at least one of which is not zero. c and d represent an integer of 0 or 1.)