KR20150132195A - Resin composition and adhesive film, coverlay film, and interlayer adhesive using resin composition - Google Patents

Abstract

It has an excellent adhesive strength to a substrate material and exhibits electric characteristics in a high frequency range of 1 GHz or more in frequency, specifically, low dielectric constant (epsilon) and low dielectric loss tangent (tan delta) in a frequency range of 1 GHz or more, A resin composition which is less in shrinkage stress at a time and can be thermally cured at 180 or lower, and an adhesive film and a coverlay film produced using the resin composition. (A) a vinyl compound represented by the following general formula (1), (B) a polystyrene-poly (ethylene / butylene) block copolymer having a styrene content of 15 to 35%, (C) (D) an epoxy resin, (E) bismaleimide, (F) an exothermic peak measured by differential scanning calorimetry (DSC) of 100 to 100 (B) / (C) = 1.00 or more and 4.00 or less, wherein the mass ratio of (A + E) / (B + C) is 0.81 or more and 1.00 or less, (F) as a mass percentage with respect to the content of the component (A), 0.1 to 10 mass% of the component (D) with respect to the total mass of the components (A) to To 10% by mass.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a resin composition, and an adhesive film, a coverlay film, and an interlayer adhesive therefor,

The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition suitable for an adhesive film for electric or electronic use or a coverlay film for a printed wiring board.

The present invention also relates to an adhesive film and a coverlay film produced using the resin composition.

The present invention also relates to the use of the resin composition for interlayer adhesion of multilayer printed wiring.

2. Description of the Related Art In recent years, printed wiring boards used in electric and electronic devices have been progressing in size, weight, and high performance, and in particular, demand for additional multilayer, high density, thinness, light weight, high reliability, .

In addition, in response to a request for increasing the speed of the transmission signal in the printed wiring board in recent years, the frequency of the transmission signal is remarkably advanced. Thus, it is required that the material used for the printed wiring board is capable of reducing electric signal loss in a high frequency region, specifically, in a region of 1 GHz or more in frequency.

(Low permittivity (?), Low dielectric loss tangent (tan?)) In an interlayer adhesive used for a multilayer printed wiring board and an adhesive film used as a surface protective film (that is, a coverlay film) .

Patent Document 1 discloses a curable resin composition capable of imparting a cured product excellent in heat resistance, mechanical properties, chemical resistance and flame retardancy with a low dielectric constant and a low dielectric loss tangent and capable of curing at a low temperature and a curable film using the same, A cured product, and a film.

On the other hand, Patent Document 2 discloses a metal foil which forms a wiring of a flexible printed wiring board, an excellent adhesive strength to a substrate material of the flexible printed wiring board, an electrical characteristic in a high frequency region of 1 GHz or more, A coverlay film showing a low dielectric constant (epsilon) and a low dielectric loss tangent (tan delta) is proposed.

Patent Document 1: JP-A-2009-161725 Patent Document 2: JP-A No. 2011-68713

Stress may remain in the interlayer bonding portion due to shrinkage stress at the time of thermosetting at the time of interlayer bonding of the multilayer printed wiring board. When the stress deformation in the interlayer bonding portion becomes large, warpage occurs and the reliability of the via connection deteriorates.

In addition, even in an adhesive film used as a coverlay film of a flexible printed wiring board (FPC), warpage may occur due to shrinkage stress during thermal curing. If such warping occurs, the flexibility of the FPC to be originally obtained is impaired, making it difficult to use, for example, an FPC cable. On the other hand, such warpage is a problem even when used as a coverlay film of a rigid substrate on which thinning progresses.

In addition, when the multilayer printed wiring board is interlaminarly bonded or when the adhesive film used as the FPC cover film is thermally cured, the equipment and conditions generally used for manufacturing the substrate are applicable. When the adhesive is cooled from a high temperature of 200 ° C or higher, It is preferable to perform thermal curing at a lower temperature for reasons such as increasing the warping at the time of cooling. Concretely, it is preferable to perform thermosetting at 180 占 폚 or lower.

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems in the prior art, and it is an object of the present invention to provide an organic substrate material such as an epoxy resin, a phenol resin, a bismaleimide triazine resin, an inorganic substrate material such as a ceramic substrate or a silicon substrate, (?) And a low dielectric loss tangent (tan?) In a high frequency region of 1 GHz or more in frequency, specifically, in a region of 1 GHz or more in frequency, in addition to exhibiting an excellent adhesive strength to a substrate material of an FPC , A resin composition which has a low shrinkage stress upon thermal curing and can be thermally cured at 180 占 폚 or lower, an adhesive film produced using the resin composition, and a coverlay film.

In order to achieve the above object,

(A) a vinyl compound represented by the following general formula (1) and having a mass average molecular weight (Mw) of 500 to 4000,

_{(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).

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.

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 having a styrene content of 15 to 35%

(C) a polystyrene-poly (ethylene-ethylene / propylene) block copolymer having a styrene content of 25 to 40%

(D) an epoxy resin,

(E) bismaleimide,

(B) an organic peroxide having an exothermic peak measured by differential scanning calorimetry (DSC) of not less than 100 and not more than 180, wherein the mass ratio of (A + E) / (B + C) ) / (C) = 1.00 or more and 4.00 or less,

(D) in an amount of 1 to 10% by mass with respect to the total mass of the components (A) to (F)

Wherein the resin composition contains 0.1 to 10% by mass of the component (F) as a mass percentage with respect to the content of the component (A).

In the resin composition of the present invention, - (OXO) - of the component (A) is represented by the following structural formula (4) and - (YO) - of the component (A) It is preferable to have a structure represented by the following structural formula (6), or a structure represented by the following structural formula (5) and a structure represented by the following structural formula (6) at random.

In the resin composition of the present invention, it is preferable that the organic peroxide of component (F) is a peroxyester or a dialkyl peroxide.

In the resin composition of the present invention, it is preferable that the epoxy resin as the component (D) is at least one member selected from the group consisting of a biphenyl type epoxy resin in which no hydroxyl groups are present in the molecule, a fluorene type epoxy resin, and a naphthalene type epoxy resin .

Further, the present invention provides an adhesive film comprising the resin composition of the present invention.

The present invention also provides a multilayer printed wiring board using the resin composition of the present invention or the adhesive film of the present invention for interlayer bonding.

The substrate constituting the multilayered printed circuit board of the present invention is preferably a resin substrate comprising a vinyl compound represented by the above general formula (1) and a rubber and / or a thermoplastic elastomer as main components.

Further, the present invention provides a coverlay film comprising the resin composition of the present invention.

Further, the present invention provides a flexible printed wiring board having a coverlay film of the present invention.

Characterized in that the coverlay film of the present invention is used on the side of the wiring pattern of the resin substrate having the wiring with the wiring pattern formed on the main surface of the resin substrate having the liquid crystal polymer, polyimide and polyethylene naphthalate as main components A printed wiring board is provided.

The present invention also relates to a resin composition comprising a vinyl compound represented by the above general formula (1) and a wiring pattern side of a resin substrate having a wiring pattern formed with a wiring pattern on the main surface of a resin substrate containing rubber and / or thermoplastic elastomer as a main component, There is provided a flexible printed wiring board characterized in that a coverlay film of the present invention is used.

INDUSTRIAL APPLICABILITY The resin composition of the present invention has an excellent adhesive strength to a substrate material of an FPC such as a metal foil or an FPC such as a polyimide film which constitutes the wiring of the FPC and has excellent electric characteristics in a high frequency range, Low dielectric constant (epsilon) and low dielectric loss tangent (tan delta)), it is preferable as a coverlay film for FPC.

Further, since the resin composition of the present invention has an excellent adhesive strength to an organic substrate material such as an epoxy resin, a phenol resin, a bismaleimide triazine resin, and an inorganic substrate material such as a ceramic substrate or a silicon substrate, Is also preferable as an interlayer adhesive of a multilayered printed circuit board using the same.

In addition, since the resin composition of the present invention has appropriate fluidity and dimensional stability when bonded onto a substrate, it is excellent in workability when used as a coverlay film or when used as an interlayer adhesive for a multilayer printed wiring board, Further, the filling property of the circuit is not hindered.

Further, since the resin composition of the present invention has a low shrinkage stress at the time of thermal curing, the residual stress in the interlayer bonding portion is reduced when the resin composition is used as an interlayer adhesive of a multilayer printed wiring board. As a result, the occurrence of warping in the interlayer bonding portion is suppressed, so that the reliability of the via connection of the multilayer printed wiring board is improved.

In addition, when the resin composition of the present invention is used as a coverlay film of FPC, the occurrence of warping during thermal curing is suppressed. Therefore, the flexibility of the FPC is not hindered.

Further, since the resin composition of the present invention can be thermally cured at 180 ° C or lower, when used as an interlayer adhesive of a multilayer printed wiring board or when used as a coverlay film of an FPC, It is advantageous in that it can be applied to facilities and conditions and also has improved heat resistance such as warp reduction, dimensional stability, solder heat resistance, and improvement of peel strength.

Hereinafter, the resin composition of the present invention will be described in detail.

The resin composition of the present invention contains the following components (A) to (F) as essential components.

(A) a vinyl compound having a weight average molecular weight (Mw) of 500 to 4000 represented by the following general formula (1)

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).

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.

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).

(YO) - in the general formula (1) may have 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 that the structures shown are randomly arranged. Among them, - (Y-O) - is preferably a structure in which structures defined by the following structural formula (6) are arranged.

In the resin composition of the present invention, the component (A) is preferably an adhesive film and a coverlay film produced by using the resin composition, or an interlayer adhesive using the resin composition, wherein the thermosetting property, heat resistance, , That is, low dielectric constant (epsilon) and low dielectric loss tangent (tan delta) in the region of frequency 1 GHz or more.

In the resin composition of the present invention, among the vinyl compounds represented by the general formula (1), the mass average molecular weight (Mw) of 500 to 4000 is used as the component (A) for the following reasons.

If the mass average molecular weight (Mw) is less than 500, the flexibility of the adhesive film and the coverlay film produced using the resin composition becomes poor, and the film becomes brittle and fragile. In addition, since the melt viscosity is excessively lowered at the time of thermocompression bonding or heat curing, the uniformity of the film thickness of the adhesive film and the coverlay film produced using the resin composition may be deteriorated, or the resin composition may be used as an interlayer adhesive There is a possibility that the uniformity of the thickness of the interlayer bonding portion may be impaired.

On the other hand, when the mass average molecular weight (Mw) is more than 4000, solubility is lowered, which is a problem in preparation of the resin composition. Concretely, a long time mixing and dissolving in thermal toluene is required at the time of preparing a varnish diluted with a resin composition. In addition, when the varnish is returned to room temperature to produce a film, recrystallization starts and the storage stability of the varnish deteriorates. Further, since it is crystallized after film formation, it is difficult to maintain the shape of the film. Therefore, the adhesive film and the coverlay film produced by using the resin composition tend to be fragile. Further, a film of a thin film can not be produced. Further, the smoothness of the film surface is deteriorated.

As the component (A), among the vinyl compounds represented by the general formula (1), those having a mass average molecular weight (Mw) of 800 to 3500 are more preferable, and those having a weight average molecular weight (Mw) of 1000 to 3000 are more preferable.

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 is reacted with a compound represented by the following general formula (7) in the presence of an alkali catalyst such as sodium hydroxide, potassium carbonate, sodium ethoxide or the like, if necessary, benzyltri n-butylammonium bromide, 18- Crown-6-ether, or the like.

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

Component (B): A polystyrene-poly (ethylene / butylene) block copolymer having a styrene content of 15 to 35%

Component (C): A polystyrene-poly (ethylene-ethylene / propylene) block copolymer having a styrene content of 25 to 40%

In the resin composition of the present invention, the components (B) and (C) are excellent in electric characteristics (high dielectric constant) in the high frequency region of the adhesive film and the coverlay film produced by using the resin composition ) And low dielectric loss tangent (tan?)), Film properties and heat resistance. In addition, when the resin composition of the present invention is used as an interlayer adhesive, it contributes to excellent electrical properties (low dielectric constant (epsilon) and low dielectric loss tangent (tan delta) in the region of 1 GHz or more) and heat resistance at high frequencies.

Among these, the component (C) is superior in dielectric property to the component (B) and contributes to excellent electrical properties at a high frequency (low dielectric constant (epsilon) and low dielectric loss tangent (tan delta) do.

However, since the component (C) has a high modulus of elasticity (tensile modulus) of the thermosetting compound as compared with the component (B), when the component (C) is used alone, the shrinkage stress at the time of heat curing becomes high, ) Must be used in combination.

Therefore, in the resin composition of the present invention, the components (B) and (C) are used in a specific blending ratio described below.

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

(B) / (C) is less than 1.00, the desired adhesive strength is obtained, but since the modulus of elasticity of the thermosetting material increases, the shrinkage stress of the adhesive film and the coverlay film produced using the resin composition increases, And warpage is likely to occur. Further, when the resin composition is used as an interlayer adhesive, if the stress deformation in the interlayer bonding portion becomes large, warpage occurs and the reliability of the via connection deteriorates.

On the other hand, when the ratio of (B) / (C) is more than 4.00, the elastic modulus of the thermosetting agent is lowered, so that the occurrence of warpage in the adhesive film and the coverlay film produced using the resin composition, It is possible to suppress the occurrence of warping in the case of the above-mentioned method, but the desired bonding strength can not be obtained.

(B) / (C) = 1.00 or more and 4.00 or less, the modulus of elasticity of the thermosetting material is not increased and a desired adhesive strength is 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.

However, it is necessary to use the components (B) and (C) having a styrene content within the above specific range.

If the styrene content of the component (B) is less than 15%, there is a problem that compatibility with other components of the resin composition is poor.

On the other hand, when the styrene content of the component (B) is more than 35%, there is a problem that when the adhesive composition or the coverlay film is produced by using the resin composition, cracks are generated in the uncured film,

If the styrene content of the component (C) is less than 25%, there is a problem that compatibility with other components of the resin composition is poor.

On the other hand, when the styrene content of the component (C) is more than 40%, there is a problem that when the adhesive composition or the coverlay film is produced by using the resin composition, cracks are generated in the uncured film and film formation becomes difficult.

Component (D): Epoxy resin

In the resin composition of the present invention, the component (D) contributes to the thermosetting property and the adhesion property when the adhesive film and the coverlay film produced using the resin composition are used as the interlayer adhesive.

By using the component (D), the solubility of the component (E) in a low boiling point solvent such as toluene, methyl ethyl ketone, methyl isobutyl ketone or the like is improved.

In the resin composition of the present invention, the content of the component (D) is 1 to 10% by mass 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, problems such as an adhesive film and a coverlay film produced using the resin composition, and adhesiveness when the resin composition is used as an interlayer adhesive become insufficient have.

When the content of the component (D) is more than 10% by mass, the compatibility is deteriorated and a desired dielectric tangent (tan?) Value can not be obtained. In addition, the adhesive film and the coverlay film produced using the resin composition excessively flow out during thermal curing. In addition, since the proportion of the component (D) in the total components increases, the properties of the component (D) having a low heat resistance can be improved by using an adhesive film and a coverlay film produced using the resin composition, Affects the entire adhesive portion. Therefore, there is a possibility that heat resistance and curability of the adhesive film and coverlay film produced using the resin composition and the interlaminar bonding portion using the resin composition are lowered.

It is more preferable that the resin composition of the present invention contains 1 to 5% by mass of the component (D) based on the total mass of the components (A) to (E).

The epoxy resin used as the component (D) is not particularly limited, and examples thereof include novolak type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, fluorene type epoxy resins, naphthalene type epoxy resins Epoxy resins of various types can be used.

However, when the epoxy resin having the hydroxyl group in the molecule is used as the epoxy resin of the component (D), the dielectric constant of the resin composition increases due to the influence of the polarity of the hydroxyl group when the content of the epoxy resin increases.

For this reason, it is preferable to use the epoxy resin of the component (D) which does not contain a hydroxyl group in the molecule. Of the above epoxy resins, those corresponding to the above are biphenyl type epoxy resins, fluorene type epoxy resins and naphthalene type epoxy resins in which no hydroxyl groups are present in the molecule.

Use of an epoxy resin in which no hydroxyl group is present in these molecules can suppress an increase in the dielectric constant.

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.

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) can act with the vinyl compound of the component (A) to promote the heat curing of the adhesive layer of the coverlay film at a lower temperature.

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, the amount of the bismaleimide of the component (E) is preferably 0.1 to 3 equivalents, preferably 0.5 to 1.5 equivalents, more preferably 0.8 to 1.3 equivalents per equivalent of the vinyl group of the vinyl compound of the component (A) desirable.

In the resin composition 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 present invention, the mixing ratio of the thermosetting resin material and the thermoplastic resin material affects the physical properties of the resin composition. 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 from 1 to 10 mass%, based on the mass percentage with respect to the total mass of the components (A) (B), (C)) and the specific blending ratio described below, the component (D) can be used in an amount of from 0.01 to 10 parts by weight per 100 parts by weight of the resin composition of the present invention The effect on the physical properties can be neglected.

In the resin composition of the present invention, the mass ratio of the sum of the components (A) and (E) to the sum of the components (B) and (C) is set to (A + E) / (B + C) .

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, when (A + E) / (B + C) = 1.00, the elastic modulus of the thermosetting material increases, and therefore, the warpage in the adhesive film and the coverlay film produced using the resin composition, It is easy to cause warping in the bonding portion.

Component (F): An organic peroxide having an exothermic peak measured by differential scanning calorimetry (DSC) of 100 占 폚 or more and 180 占 폚 or less

In the resin composition of the present invention, the component (F) accelerates the reaction of the vinyl compound used as the component (A) and enables low-temperature curing at 180 ° C or lower. In addition, it exhibits an effect of improving heat resistance such as warp reduction, dimensional stability, solder heat resistance and the like, and improving peel strength.

The exothermic peak due to the DSC measurement in the present invention indicates that it is measured in the following order.

The exothermic peak is read out from the DSC curve obtained by raising the temperature by 5 DEG C / min with a differential scanning calorimeter. In the present invention, the temperature of the peak tower is defined as an exothermic peak of the object.

When the exothermic peak due to the DSC measurement is less than 100 占 폚, when the adhesive film or the coverlay film is formed from the resin composition, the reaction proceeds by thermal history and is cured. Therefore, the adhesive function is lost. Further, even when the resin composition of the present invention is used as an interlayer adhesive of a multilayered printed circuit board, varnish containing the resin composition must be applied, the solvent must be volatilized and dried, The adhesive function is lost by curing by thermal history.

When the exothermic peak by DSC measurement exceeds 180 DEG C, the heat curing time at 180 DEG C or less becomes longer.

In the present invention, it is more preferable that the exothermic peak by DSC measurement is 120 to 180 占 폚.

In the present invention, examples of the organic peroxide of component (F) include isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, para-chlorobenzoyl peroxide, di (3,5,5-trimethylhexanoyl) Diacyl peroxides such as oxides; Peroxiketration such as 2,2-di (4,4-di- (di-tert-butylperoxy) cyclohexyl) propane; Peroxydicarbonates such as di-3-methoxybutyl percarbonate and dicyclohexyl percarbonate; butyl perbenzoate, tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethylhexanoate, tert-butyl perisobutyrate, tert- butyl perpivalate, tert- butyl diperadipate, Butyl peroxybenzoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane. Peroxyesters; Ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; Di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, di-tert-hexyl peroxide, di- Dialkyl peroxides such as di (2-tert-butylperoxyisopropyl) benzene; Hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide, and p-mentha hydroperoxide can be used.

Of these, peroxyesters and dialkylperoxides are preferable, and tert-butylperoxybenzoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate and di (2- tert-butylperoxyisopropyl) benzene is particularly preferable because it has an exothermic peak of 120 to 180 ° C as measured by DSC and storage stability of the composition is good.

In the resin composition of the present invention, the content of the component (F) is 0.1 to 10% by mass with respect to the content of the component (A).

If the content of the component (F) is less than 0.1% by mass, the action of promoting the reaction of the vinyl compound used as the component (A) becomes insufficient. For this reason, thermal curing at 180 占 폚 or lower can not be achieved.

On the other hand, if the content of the component (F) is more than 10% by mass, the electric characteristics at high frequencies are deteriorated.

The content of the component (F) is more preferably 1 to 10% by mass in terms of the mass percentage with respect to the content of the component (A).

The resin composition of the present invention may contain a curing catalyst as the component (G) in addition to the above components (A) to (F). This curing catalyst functions as a curing catalyst for the epoxy resin of the component (D).

The curing catalyst used as the component (G) 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 amine curing catalysts include triazine compounds such as 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 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.

On the other hand, any one of the above curing catalysts may be used, or two or more of them may be used in combination. The effective amount of the curing catalyst depends on the type of curing catalyst. The effective amount of each type of curing catalyst is shown below.

In the case of the imidazole-based curing catalyst and the amine-based curing catalyst, the effective amount thereof is 0.01 to 5% by mass and more preferably 0.05 to 3% by mass with respect to the total mass of the total components of the resin composition.

In the case of phosphorus-containing curing catalysts, the effective amount thereof is 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total mass of the total components of the resin composition.

The resin composition of the present invention may contain other components as required. Specific examples of such components include a silane coupling agent, a defoaming agent, a flow control agent, a film forming auxiliary agent, and a dispersing agent.

The resin composition of the present invention can be produced by a conventional method. For example, the components (A) to (F) (in the case where the resin composition contains the component (G) or other optional components, further optional components thereof) are heated Mix with a vacuum mixing kneader.

The resin composition is dissolved in a predetermined solvent concentration so that the components (A) to (F) have a desired content ratio (if the resin composition contains the component (G) or any other component, , A predetermined amount of them are charged into a reaction kettle heated to 10 to 80 DEG C and the mixture is stirred for 3 to 30 hours while rotating at a revolution of 100 to 1000 rpm and then mixed and stirred under vacuum (1 Torr up to 30 Torr) for 30 to 60 minutes have.

The resin composition of the present invention has the following preferable characteristics.

In the resin composition of the present invention, the thermosetting material is excellent in electric characteristics at high frequency. Specifically, the thermosetting resin composition preferably has a dielectric constant (epsilon) at a frequency of 1 GHz or more of 3.0 or less, more preferably 2.5 or less. The dielectric loss tangent (tan?) In the region of 1 GHz or more is more preferably 0.01 or less, and more preferably 0.005 or less.

Since the dielectric constant (epsilon) and dielectric tangent (tan delta) in the region of the frequency of 1 GHz or more are in the above-mentioned range, the electric signal loss in the region of the frequency of 1 GHz or more can be reduced.

The resin composition of the present invention is preferably a thermoset material having a tensile modulus of 150 to 450 MPa because of its high bonding strength and reduced shrinkage stress upon thermal curing.

When the tensile modulus of elasticity is 450 MPa or less, the shrinkage stress at the time of thermosetting is reduced, and the following effects are exhibited.

When used as an interlayer adhesive of a multilayer printed wiring board, the stress remaining in the interlayer bonding portion is reduced. As a result, the occurrence of warping in the interlayer bonding portion is suppressed, so that the reliability of the via connection of the multilayer printed wiring board is improved.

In addition, when the resin composition of the present invention is used as a coverlay film of FPC, the occurrence of warping during thermal curing is suppressed. Therefore, the flexibility of the FPC is not hindered.

On the other hand, the resin composition of the present invention preferably has a warpage of thermosetting of 15 mm or less, more preferably 10 mm or less, in a film of 100 mm in length and 100 mm in order to be measured in the order described in the following Examples.

However, if the tensile modulus of the thermosetting resin is too low, the adhesive strength of the resin composition is lowered, and therefore, it is required to be 150 MPa or more.

In the resin composition of the present invention, it is more preferable that the thermo-hardened material has a tensile modulus of 200 to 400 MPa.

The resin composition of the present invention preferably has a minimum melt viscosity of 1,000 to 50,000 Pa · s at a temperature in the range of 100 to 180 ° C upon thermal curing.

When the lowest melt viscosity at the time of heat curing is within the above range, the flowability at the time of heat curing becomes appropriate, which is preferable. Concretely, since the fluidity is good at the time of thermocompression bonding of an adhesive film or a coverlay film produced by using the resin composition or when the resin composition is used as an interlayer adhesive, the fine pitch The filling property in the wiring pattern is improved.

Here, the lowest melt viscosity is the lowest value of the viscosity when the adhesive film is melted when the resin composition is heated.

If the minimum melt viscosity at a temperature range of 100 to 180 ° C is less than 1000 Pa · s, the fluidity at the time of thermal curing is too high, so that the film thickness of the adhesive film or the coverlay film, There is a possibility of change.

If the minimum melt viscosity at a temperature range of 100 to 180 占 폚 exceeds 50,000 Pa 占 퐏, the filling property in the fine pitch wiring pattern may become insufficient and the pressing pressure applied at the time of thermocompression bonding must be increased.

It is more preferable that the resin composition of the present invention has a minimum melt viscosity of 2000 to 20,000 Pa · s at a temperature range of 100 to 180 ° C.

The resin composition of the present invention preferably has a glass transition temperature of 160 DEG C or higher in view of heat resistance and long-term reliability of thermosetting resin.

The thermosetting resin composition of the present invention has sufficient adhesive strength. Concretely, the thermosetting resin composition preferably has a fill strength (180 degree fill) of 5 N / cm or more, more preferably 6 N / cm or more, for the copper foil screen measured in accordance with JIS C6471.

The fill strength (180 degree fill) of the polyimide film measured in accordance with JIS C6471 is preferably 5 N / cm or more, and more preferably 6 N / cm or more.

The adhesive film and the coverlay film of the present invention can be obtained by a known method from the resin composition of the present invention. For example, the resin composition of the present invention may be provided as a film having a support or a film peeled off from a support after the resin composition is diluted with a solvent to obtain a varnish, which is applied to at least one surface of the support and dried.

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 may be an amount conventionally used, but is preferably 20 to 90% by mass based on the solid content.

The support is appropriately selected depending on the desired form in the production method of the film and is not particularly limited, and examples thereof include metal foils such as copper and aluminum, and carrier films of resins such as polyester and polyethylene. When the adhesive film of the present invention is provided in the form of a film exfoliated from a support, it is preferable that the support is subjected to a release treatment with a silicone compound or the like.

The method of applying the varnish is not particularly limited, and for example, a slot die method, a gravure method, a doctor coater method, and the like are suitably selected depending on the desired film thickness and the like. Particularly, So that it is possible to design a thin one. The application is performed so that the thickness of the film formed after drying becomes a desired thickness. Such thickness can be derived from the solvent content by those skilled in the art.

The thickness of the adhesive film and the coverlay film of the present invention is appropriately designed based on the characteristics such as mechanical strength required depending on the application, and is generally 1 to 100 탆. When thinning is required, desirable.

The drying conditions are appropriately designed according to the type and amount of the solvent used in the varnish, the amount of varnish used, the thickness of the coating, and the like, and are not particularly limited, but can be, for example, 60 to 100 캜 and under atmospheric pressure.

The order of use of the adhesive film of the present invention is as follows.

The adhesive film of the present invention is placed on the surface to be adhered of one of the objects to be adhered using the adhesive film of the present invention and then the other adhered object is placed on the surface of the adhesive film do. Here, in the case of using an adhesive film having a support, the adhesive film is placed so that the exposed surface of the adhesive film comes into contact with the adherend surface of one of the objects, and the adhesive film is transferred onto the adherend surface. Here, the temperature at the time of transfer can be set at, for example, 130 占 폚.

Next, the support is peeled off at the time of transfer, and the other surface of the exposed adhesive film is placed so that the surface to be adhered is in contact with the exposed surface of the adhesive film. After the above steps are performed, they are thermocompression bonded at a predetermined temperature and for a predetermined time, and then they are heated and cured.

The temperature at the time of thermocompression bonding is preferably 100 to 180 占 폚. The time of thermocompression bonding is preferably 0.5 to 10 minutes.

The temperature of the heat curing is preferably 150 to 180 占 폚. The heat curing time is preferably 30 to 120 minutes.

On the other hand, instead of using a film made in advance, a procedure in which a varnish diluted with a solvent of the resin composition of the present invention is applied to the adhered surface of one of the objects to be adhered and then dried, .

The adhesive film of the present invention can also be used for interlayer adhesion of a multilayer printed wiring board. In this case, the object to be bonded is the substrate constituting each layer of the multilayer printed wiring board. On the other hand, as for the interlayer adhesion of the multilayered printed circuit board, a varnish obtained by diluting the resin composition of the present invention with a solvent may be used instead of a film which has been previously formed into a film.

In the multilayered printed circuit board laminated by using the adhesive film or the varnish of the present invention, the residual stress in the interlayer bonding portion is reduced. As a result, the occurrence of warping in the interlayer bonding portion is suppressed, so that the reliability of the via connection of the multilayer printed wiring board is improved. Further, the dimensional stability of the interlayer bonding portion is excellent.

The substrate constituting each layer of the multilayered printed circuit board is not particularly limited, and an organic substrate such as an epoxy resin, a phenol resin, a bismaleimide triazine resin, or an inorganic substrate such as a ceramic substrate or a silicon substrate can be used. A resin substrate suitable for the FPC of the present invention described later can also be used.

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

After the coverlay film of the present invention is disposed at a predetermined position of the resin substrate having the wiring with the wiring pattern formed on the main surface thereof, that is, at the position where the covering film is covered with the cover film on the side where the wiring pattern is formed, Followed by thermocompression at a predetermined temperature for a predetermined time.

The temperature at the time of pressure application during thermocompression bonding is preferably 100 to 180 占 폚. The pressing time is preferably 0.5 to 10 minutes.

The temperature of the heat curing is preferably 150 to 180 占 폚. The heat curing time is preferably 30 to 120 minutes.

In the coverlay film of the present invention, the occurrence of warping during thermal curing is suppressed.

The flexible printed wiring board (FPC) of the present invention is obtained by arranging the coverlay film of the present invention on the wiring pattern side of the resin substrate having the wiring with the wiring pattern formed on the main surface thereof, And the coverlay film are integrated with each other.

The resin substrate used for the FPC of the present invention is also preferably excellent in electric characteristics in a high frequency range, that is, low dielectric constant (?) And low dielectric loss tangent (tan?) In a frequency region of 1 GHz or more. As a specific example of such a resin substrate, a resin substrate containing a liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE), polyimide (PI), or polyethylene naphthalate (PEN) as a main component may 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) a resin substrate containing a rubber and / or a thermoplastic elastomer as a main component.

The vinyl compound represented by the above formula (1) of the component (a) is as described above for the resin composition 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 have the same constitution as the resin composition of the present invention, It is dielectric tangent. Therefore, for example, when combined with an interlayer adhesive or a coverlay film using the resin composition of the present invention, a printed board excellent in high-frequency characteristics can be obtained.

Further, since the resin composition has the same structure as the resin composition of the present invention, the adhesive strength between the resin composition of the present invention and the coverlay film is high.

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. Further, the compatibility with the component (a) is good, and the styrene content in the styrene-based thermoplastic elastomer is preferably 15 to 60 mass%, and more preferably 20 to 50 mass%. 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".

When the mass ratio of the components (B) and (C) is set to (B) / (C) = 1.00 or more with the components (B) and (C) of the resin composition of the present invention described above being used as the component When it is 4.00 or less, it does not increase the elastic modulus of the thermosetting material while contributing to excellent electric characteristics at high frequency, and is also excellent in adhesion with copper constituting the wiring pattern.

Further, addition of the component (D) of the resin composition of the present invention described above leads to improvement of the thermosetting property and improvement of the adhesion with copper constituting the wiring pattern, and the component (E) of the above- The addition leads to maintenance of dielectric properties, application of adhesive strength and high Tg (glass transition point).

The component (F) of the resin composition of the present invention described above may be added. Addition of the component (F) makes it possible to cure the resin substrate using the component (a) at a low temperature. This makes it possible to apply facilities and conditions generally used for manufacturing a substrate. In addition, it leads to improvement in heat resistance such as warp reduction, dimensional stability, solder heat resistance, and the like, and improvement in peel strength.

The specific examples of the resin substrate preferable for the FPC of the present invention include a silane coupling agent as the component (c) in addition to the above-mentioned components (a) and (b). The silane coupling agent of the component (c) contributes to adhesion between the resin substrate and the wiring pattern when transferring the wiring pattern to the resin substrate.

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.

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 (c). 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 inorganic compounds such as silica, alumina, titania, boron nitride, and 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 (c) 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 preferred for the FPC of the present invention may be formed by using inorganic fibers such as glass fibers and carbon fibers or organic fibers such as aramid fibers together with the filler described above 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 9 and Comparative Examples 1 to 12)

Sample preparation and measurement method

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 (B ')

Tuftec H1221: polystyrene-poly (ethylene / butylene) block copolymer (styrene content: 12%), manufactured by Asahi Kasei Corporation

Sephaton 8104: Polystyrene-poly (ethylene / butylene) block copolymer (styrene content: 60%), manufactured by Kuraray Co.,

Component (C)

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

Component (BC ')

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.

HP4032D: naphthalene type epoxy resin, manufactured by DIC Co., Ltd.

828EL: Bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation

Component (E)

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

Component (F)

Per butyl Z: tert-butyl peroxybenzoate, manufactured by Nichiyu Co., Ltd., exothermic peak 140 to 170 ° C

Per butyl P: di (2-tert-butylperoxyisopropyl) benzene, Nichiyu Co., exothermic peak 160 to 180 ° C

Perocta O: 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, manufactured by Nichiyu Corporation, exothermic peak 120 to 130 ° C

Component (F ')

Peroyl OPP: di (2-ethylhexyl) peroxydicarbonate, Nichiyu Co., exothermic peak 80 to 100 ° C

Nopmer BC-90: 2,3-dimethyl-2,3-diphenylbutane, Nichiyu Corporation, exothermic peak 200 ° C or higher

Component (G)

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

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

1B2PZ: 1-benzyl-2-phenylimidazole, manufactured by Shikoku Kasei Co., Ltd.

TPP-MK: tetraphenylphosphonium tetra-p-tolyl borate, manufactured by Hokuko Kagakuko Kogyo Co., Ltd.

Dielectric constant (?) And dielectric loss tangent (tan delta): The adhesive film was heated and cured at 180 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.

Tensile modulus: The adhesive film was heat-cured at 180 占 폚 and peeled 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 held on an autograph, set at a jig width of 170 mm, and measured up to a stroke of 5 mm at a tensile speed of 1 mm / min. The average value of N = 5 was taken as the measured value.

Amount of bending: Copper foil having a thickness of 18 탆 (copper foil CF-T8 manufactured by Fukuda Kinko Co., Ltd.) was cut to 100 ± 0.5 mm in length and the adhesive film cut in the same size was heat-cured while pressing the copper foil on one side with a press machine (180 DEG C, 60 min, 1 MPa). The support was peeled off, placed on a horizontal surface of a flat desk with its adhesive surface adhered down, and the amount of warpage due to curing shrinkage was measured. That is, the amount of warpage is the maximum value of the height from the horizontal plane of the desk to the open point of the film center.

Peel Strength (Cu): An adhesive film dried on a roughened surface of a copper foil (CF-T8, manufactured by Fukuda Kinko Corp., Hakuhoon Kogyo Co., Ltd., thickness 18 占 퐉) was hot-pressed and then heat cured Min., Heat curing: 180 DEG C x 1 hr), and the peel strength (180 degree peel) was measured according to JIS C6471. The adhesive film was cut from the copper foil surface with a width of 10 mm and peeled off with an autograph to measure the peel strength (180 degree peel).

Peel strength (PI): An adhesive film dried on a polyimide film (K100EN, manufactured by Toray DuPont Co., Ltd., 25 占 퐉) was hot-pressed and then heat cured (thermocompression bonding: 130 占 폚 for 3 minutes, heat curing: 180 占 폚 × 1 hr), and the peel strength (180 degree peel) was measured in accordance with JIS C6471. The adhesive film was cut 10 mm in width from the film side of the polyimide film and peeled off with an autograph to measure the peel strength (180 degree peel).

Dimensional stability (in conformity with JIS C6471): A copper foil was adhered to both sides of the adhesive film obtained by the above-described method by thermocompression bonding (180 DEG C, 60 minutes, 1 MPa) to obtain a sample of 200 mm x 250 mm. A hole having a diameter of 2 mm was drilled in four corners of the sample, and the interval between the vertical and the horizontal of the neighboring hole was measured. Next, the entire surface of the copper foil on the surface was etched and then subjected to a drying treatment at 80 DEG C for 30 minutes. The distance between the longitudinal and transverse sides of the neighboring holes was measured and the dimensional change ratio between the longitudinal and transverse directions was obtained from the change in the distance between the holes before and after the treatment. Further, heat treatment at 150 캜 for 30 minutes was carried out, and the same measurement as described above was carried out to determine the dimensional change ratio between the length and width. In the table, the average value of the rate of dimensional change between the vertical and horizontal directions is described.

Solder Heat Resistance (Solder Float Test): A copper foil was hot-pressed (180 DEG C, 60 minutes, 1 MPa) on both sides of the adhesive film obtained by the above-described method to prepare a sample of 50 mm x 50 mm. This was floated in a soldering bath at a temperature elevation from 290 ° C to 10 ° C for 30 seconds to evaluate the presence of solder. In the table, the temperature is 10 ° C lower than the temperature at which the buckling occurred.

On the other hand, evaluation of dimensional stability and solder heat resistance was not carried out on the composition which had a deflection amount of 15 mm or less and a result of which a result of peel strength of 5 N / cm or more could not be obtained.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Component (A) OPE2St-2200 30.4% 30.5% 32.1% 33.6% 30.4% 30.1% Component (B) Tuftec H1052 31.3% - 30.0% 28.7% 34.0% 36.2% Tuftec H1031 - 31.3% - - - - Component (B ') Tuftec H1221 - - - - - - Septon 8104 - - - - - - Component (C) Septon 4044 20.9% 20.9% 20.0% 19.2% 18.2% 15.6% Component (BC ') TR2003 - - - - - - Component (D) NC3000H 4.0% - - 3.9% 4.0% 5.0% HP4032D - 4.0% - - - - 828EL - - 3.9% - - - Component (E) BMI-70 12.3% 12.2% 12.9% 13.4% 12.3% 12.1% Component (F) Per butyl Z 1.0% 1.0% 1.0% 1.0% - 1.0% Per butyl P - - - - 1.0% - Per octa O - - - - - - Component (F ') PERRO IS OPP - - - - - - Nofmer BC-90 - - - - - - Component (G) C11ZCN 0.1% 0.1% - 0.1% - 0.1% 2E4MZ - - 0.1% - - - 1B2PZ - - - - 0.1% - TPP-MK - - - - - - (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 F / A (%) 3.3% 3.3% 3.1% 3.0% 3.3% 3.3% Deflection (mm) One One One 2 0 0 竜 (10 GHz) 2.33 2.32 2.33 2.35 2.33 2.33 tan? (10 GHz) 0.0036 0.0034 0.0031 0.0032 0.003 0.0033 Tensile modulus (MPa) 339 371 347 368 333 280 Peel strength (Cu) (N / cm) 8.1 9.1 8.5 8.7 9.3 9.4 Peel strength (PI) (N / cm) 7.3 8.2 7.9 8.1 8.2 9.1 Dimensional stability (etching)% 0.63 0.55 0.61 0.58 0.59 0.55 Dimensional stability 150 ℃ 30min 0.9 0.78 0.81 0.95 0.9 0.77 Solder float (30 sec) 320 320 320 320 320 320

Example 7 Example 8 Example 9 Component (A) OPE2St-2200 32.9% 31.1% 29.8% Component (B) Tuftec H1052 39.6% 32.0% 30.7% Tuftec H1031 - - - Component (B ') Tuftec H1221 - - - Septon 8104 - - - Component (C) Septon 4044 9.9% 21.3% 20.5% Component (BC ') TR2003 - - - Component (D) NC3000H 3.3% 2.0% 3.9% HP4032D - - - 828EL - - - Component (E) BMI-70 13.3% 12.5% 12.1% Component (F) Per butyl Z - - 2.9% Per butyl P 1.0% - - Per octa O - 1.0% - Component (F ') PERRO IS OPP - - - Nofmer BC-90 - - - Component (G) C11ZCN 0.1% 0.1% - 2E4MZ - - - 1B2PZ - - - TPP-MK - - 0.1% (A + E) / (B + C) 0.93 0.82 0.82 B / C 4.00 1.50 1.50 F / A (%) 3.0% 3.2% 9.8% Deflection (mm) 0 0 0 竜 (10 GHz) 2.32 2.32 2.33 tan? (10 GHz) 0.0039 0.0034 0.0048 Tensile modulus (MPa) 221 364 398 Peel strength (Cu) (N / cm) 8.2 8.1 9.3 Peel strength (PI) (N / cm) 7.9 8.1 8.8 Dimensional stability (etching)% 0.59 0.67 0.63 Dimensional stability 150 ℃ 30min 0.75 0.89 0.8 Solder float (30 sec) 320 320 310

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Component (A) OPE2St-2200 50.0% 48.9% 40.8% 27.8% 36.2% 35.3% Component (B) Tuftec H1052 - - 49.0% 33.6% 26.5% 23.8% Tuftec H1031 - - - - - - Component (B ') Tuftec H1221 - - - - - - Septon 8104 - - - - - - Component (C) Septon 4044 - 39.1% - 22.4% 17.7% 29.1% Component (BC ') TR2003 50.0% - - - - - Component (D) NC3000H - 2.0% 2.0% 4.0% 3.9% 3.6% HP4032D - - - - - - 828EL 5.0% - - - - - Component (E) BMI-70 - 9.8% 8.2% 11.1% 14.5% 7.1% Component (F) Per butyl Z - - - 1.0% 1.0% 1.0% Per butyl P - - - - - - Per octa O - - - - - - Component (F ') PERRO IS OPP - - - - - - Nofmer BC-90 - - - - - - Component (G) C11ZCN - 0.1% 0.1% 0.1% - 0.1% 2E4MZ - - - - 0.1% - 1B2PZ - - - - - - TPP-MK - - - - - - (A + E) / (B + C) - 1.50 1.00 0.70 1.15 0.80 B / C - - - 1.50 1.50 0.82 F / A (%) - - - 3.6% 2.7% - Deflection (mm) 23 31 0 2 18 20 竜 (10 GHz) 2.4 2.34 - 2.3 2.4 2.3 tan? (10 GHz) 0.002 0.0023 - 0.0034 0.003 0.0031 Tensile modulus (MPa) 780 1253.00 - 258.00 231.00 684.00 Peel strength (Cu) (N / cm) 7.5 10.2 1.3 4.5 9.5 7 Peel strength (PI) (N / cm) 6.5 10.1 1.5 3.4 8.5 6.5 Dimensional stability (etching)% 1.51 1.87 - - - - Dimensional stability 150 ℃ 30min 2.1 2.34 - - - - Solder float (30 sec) 290 310 - - - -

Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Component (A) OPE2St-2200 35.3% 30.4% 30.4% 30.4% 30.4% 30.4% Component (B) Tuftec H1052 45.0% 31.3% - - 31.3% 31.3% Tuftec H1031 - - - - - - Component (B ') Tuftec H1221 - - 31.3% - - - Septon 8104 - - - 31.3% - - Component (C) Septon 4044 7.9% 20.9% 20.9% 20.9% 20.9% 20.9% Component (BC ') TR2003 - - - - - - Component (D) NC3000H 3.6% 4.0% 4.0% 4.0% 4.0% 4.0% HP4032D - - - - - - 828EL - - - - - - Component (E) BMI-70 7.1% 12.3% 12.3% 12.3% 12.3% 12.3% Component (F) Per butyl Z 1.0% - 1.0% 1.0% - - Per butyl P - - - - - - Per octa O - - - - - - Component (F ') PERRO IS OPP - - - - - 1.0% Nofmer BC-90 - - - - 1.0% - Component (G) C11ZCN 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 2E4MZ - - - - - - 1B2PZ - - - - - - TPP-MK - - - - - - (A + E) / (B + C) 0.80 0.82 0.82 0.82 0.82 0.82 B / C 5.67 1.50 1.50 1.50 1.50 1.50 F / A (%) - 3.3% 3.3% 3.3% 3.3% 3.3% Deflection (mm) 0 3 One 16 3 3 竜 (10 GHz) 2.31 2.33 2.33 2.33 2.33 2.33 tan? (10 GHz) 0.0035 0.0024 0.0039 0.0033 0.0037 0.0037 Tensile modulus (MPa) 113.00 239.00 239.00 539.00 242.00 368.00 Peel strength (Cu) (N / cm) 2.5 8.1 5.1 8.1 8.1 Not measurable Peel strength (PI) (N / cm) 2.3 7.6 4.3 7.3 7.6 Not measurable Dimensional stability (etching)% - 1.15 1.15 1.35 1.21 - Dimensional stability 150 ℃ 30min - 1.43 1.43 1.84 1.51 - Solder float (30 sec) - 310 290 310 310 -

Examples 1 to 9 were excellent in both the amount of deflection and the electric characteristics (permittivity (?), Dielectric loss tangent (tan?)), Tensile elasticity, peel strength, dimensional stability and solder heat resistance. In Example 5 in which B / C was increased as compared with Example 1, the tensile elastic modulus could be lowered. In Example 6 in which B / C was larger than that in Example 5, the tensile elastic modulus 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 warping amount was large. In addition, dimensional stability and soldering heat resistance were poor.

In Comparative Example 2, which did not contain the component (B), the tensile modulus of elasticity was high and the amount of warpage was large. In addition, dimensional stability and soldering heat resistance were poor.

In Comparative Example 3 not containing the component (C), the peel strength was low.

In Comparative Example 4 in which the mass ratio of each component was less than (A + E) / (B + C) = 0.81, the peel strength was low.

In Comparative Example 5 in which the mass ratio of each component was (A + E) / (B + C) = 1.00, the amount of warpage was large.

In Comparative Example 6 in which the mass ratio (B) / (C) of components (B) and (C) was less than 1.00, the warping amount was large.

In Comparative Example 7 in which the mass ratio (B) / (C) of components (B) and (C) was more than 4.00, the peel strength was low.

In Comparative Example 8 not containing the component (F), the dimensional stability was poor.

In Comparative Example 9 using a polystyrene-poly (ethylene / butylene) block copolymer having a styrene content of less than 15% instead of the component (B), the PI strength was low. In addition, dimensional stability and soldering heat resistance were poor.

In Comparative Example 10 using a polystyrene-poly (ethylene / butylene) block copolymer having a styrene content of more than 35% instead of the component (B), the warpage was large. Also, dimensional stability was poor.

In Comparative Example 11 in which the exothermic peak of the component (F) was higher than 180 deg. C, the dimensional stability was poor.

In Comparative Example 12 in which the exothermic peak of the component (F) was lower than 100 占 폚, the peel strength could not be measured.

An FPC-based print comprising the components (a) and (b) as a main component Of the wiring board  Manufacturing method

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

Component (a): OPE2st: oligo (phenylene ether) (the vinyl compound of formula (1)) (Mn = 2200 ), manufactured by Mitsubishi Gas Kagaku Co., Ltd. Preparation 50.0 parts

Component (b): Polystyrene-polybutadiene block copolymer (TR2003, manufactured by JSR Corporation: mass average molecular weight: about 100,000, styrene content: 43% by mass) 50.0 parts

Component (c) 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 circumferential 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 the solvent toluene and the mixture was 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, followed by drying at 100 DEG C for 10 minutes, allowing to stand and cool, and peeling from the PET film to obtain a resin substrate for FPC. The thickness of the resin substrate was 30 mu m.

On both sides of the resin substrate obtained in the above procedure, the copper foils were stuck together with the roughened surface inward and thermally pressed (200 DEG C, 60 minutes, 1 MPa). The one surface or both surfaces of the copper foil subjected to thermocompression was etched to form a wiring pattern to produce a resin substrate having wiring. The coverlay film obtained in the above procedure was arranged so that the adhesive layers were opposed to each other on the wiring pattern side of the resin substrate having this wiring and the printed wiring board was prepared by heating and curing (180 DEG C, 60 min, 1 MPa) while thermocompression bonding with a press machine .

Insertion loss: A microstrip line designed to have an impedance of 50? On the resin substrate was prepared. As the coverlay film, the adhesive film was pasted with a vacuum press (180 占 폚 for 1 hour, 1 MPa, degree of vacuum <10 kPa) A test piece was prepared. Insertion loss (db) was measured using the prepared test piece under the following conditions.

Measuring instrument: E8363B (manufactured by Agilent Technologies)

Measuring frequency: 10MHz ~ 60GHz

Measuring points: 4000

Measuring probe: GSG250

Wiring length: 30mm, 50mm, 70mm

Wiring width: 130 ± 10㎛

The results are shown in the following table.

Wiring length Frequency (GHz) 30mm 50mm 70mm 5 -0.472938 -0.7987 -1.18823 10 -0.725895 -1.21986 -1.7662 20 -1.18862 -1.95858 -2.79156 30 -1.37431 -2.46625 -3.60955 40 -1.54586 -2.92485 -4.04599

From the results shown in Table 5, it can be seen that the resin substrate with a coverlay film manufactured using the resin composition of the present invention has an insertion loss of < 5 db, and therefore excellent in high-speed transmission.

Claims (12)

(A) a vinyl compound represented by the following general formula (1) and having a mass average molecular weight (Mw) of 500 to 4000,
[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 having a styrene content of 15 to 35%
(C) a polystyrene-poly (ethylene-ethylene / propylene) block copolymer having a styrene content of 25 to 40%
(D) an epoxy resin,
(E) bismaleimide
(F) an organic peroxide having an exothermic peak as measured by differential scanning calorimetry (DSC) of 100 占 폚 or more and 180 占 폚 or less, wherein the mass ratio of each component is (A + E) / (B + C) (B) / (C) = 1.00 or more and 4.00 or less,
(D) in an amount of 1 to 10% by mass with respect to the total mass of the components (A) to (F)
Wherein the component (F) is contained in an amount of 0.1 to 10% by mass with respect to the content of the component (A). The method according to claim 1,
- (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) or the following structural formula (6) Or a resin composition having a structure represented by the following structural formula (5) and a structure represented by the following structural formula (6) randomly arranged.
[Chemical Formula 4]

[Chemical Formula 5]

3. The method according to claim 1 or 2,
Wherein the organic peroxide of the component (F) is a peroxy ester or a dialkyl peroxide. 4. The method according to any one of claims 1 to 3,
Wherein the epoxy resin of the component (D) is at least one selected from the group consisting of biphenyl type epoxy resins, fluorene type epoxy resins and naphthalene type epoxy resins in which no hydroxyl groups are present in the molecule. An adhesive film comprising the resin composition according to any one of claims 1 to 4. A multilayer printed wiring board using the resin composition according to any one of claims 1 to 4 for interlayer adhesion. The multilayer printed wiring board using the adhesive film according to claim 5 for interlayer bonding. 8. The method of claim 7,
Wherein the substrate constituting the multilayered printed circuit board is a resin substrate comprising a vinyl compound represented by the following general formula (1) and a rubber and / or a thermoplastic elastomer as a main component.
(A) a vinyl compound represented by the following general formula (1)
[Chemical Formula 4]

_{(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 5]

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 6]

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 coverlay film comprising the resin composition according to any one of claims 1 to 4. A flexible printed wiring board having the coverlay film according to claim 9. Characterized in that the coverlay film according to claim 9 is used on the wiring pattern side of the resin substrate having the wiring with the wiring pattern formed on the main surface of the resin substrate comprising the liquid crystal polymer, polyimide and polyethylene naphthalate as main components A flexible printed wiring board. A method for producing a wiring board, comprising the steps of: forming a wiring pattern on a resin substrate having a wiring pattern formed on a main surface of a resin substrate comprising a vinyl compound represented by the following general formula (1) and a rubber and / or a thermoplastic elastomer as a main component; Ray film is used for the flexible printed wiring board.
(7)

_{(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 8]

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 9]

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.)