KR20170071470A - Resin composition, and insulating film and semiconductor device using same - Google Patents

Abstract

(E) and a low dielectric constant (e) in an area of a frequency of 1 to 10 GHz, and has excellent adhesive strength to a substrate material of an FPC such as a metal foil and a polyimide film constituting the wiring of the FPC, Provided is an insulating film as a coverlay film which exhibits a tangent and has a good shelf life, and a resin composition contained in the insulating film. (B) an epoxy resin, (C) a styrenic thermoplastic elastomer, (D) a compound having an imide group and an acrylate group in one molecule, (D) a compound having an imide group and an acrylate group in one molecule, And (E) a curing catalyst, and contains 0.5 to 4 parts by mass of the above-mentioned component (D) relative to 100 parts by mass of the total of the components (A) to (E).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition and an insulating film and a semiconductor device using the resin composition.

<Cross reference>

The present application claims priority based on Japanese patent application "Patent Application No. 2014-215035" filed on October 22, 2014, together with its contents by reference.

The present invention relates to a resin composition and an insulating film and a semiconductor device using the resin composition.

In recent years, printed wiring boards used in electric and electronic devices have been made smaller, lighter, and have higher performance. Particularly, there is a demand for further multilayered, high-density, thin, lightweight, high reliability and molding processability of the multilayered printed circuit board. In addition, there is a growing demand for higher speed of transmission signals processed in printed wiring boards. As a result, the frequency of the transmission signal is significantly increased. Thus, it is required that the material used for the printed wiring board is capable of reducing electric signal loss in a high frequency range, specifically, in a frequency range of 1 GHz or more. (Low dielectric constant (e), low dielectric tangent (tand)) in the high-frequency region is also exhibited in the interlayer adhesive used in the multilayer printed wiring board and in the adhesive film used as the surface protective film of the printed wiring board Is required.

Patent Document 1 discloses a curable resin composition which can provide a cured product having a low dielectric constant, a low dielectric tangent, an excellent heat resistance, a mechanical property, a chemical resistance, and a flame retardancy and can be cured at a low temperature. In addition, this document discloses a curable film using the curable resin composition, and a cured product and a film obtained by curing the same. On the other hand, Patent Document 2 discloses a metal foil constituting a wiring of a flexible printed wiring board (FPC) and a coverlay film having excellent adhesive strength to a substrate material of the flexible printed wiring board and exhibiting excellent electric characteristics in a high frequency region of a frequency of 1 GHz or more Has been proposed. Specifically, the coverlay film exhibits a low dielectric constant (e) and a low dielectric tangent (tand) in a frequency region of 1 GHz or more. The coverlay film can also be used as an adhesive film for electric and electronic uses and as an interlayer adhesive for a multilayer printed wiring board.

International Publication No. WO 2008/18483 Japanese Laid-Open Patent Publication No. 2011-68713

The coverlay film described in Patent Document 2 exhibits excellent electrical properties in a high frequency region after heat curing. Specifically, the film exhibits a dielectric constant of 3.0 or less, more specifically 2.5 or less in the frequency range of 1 to 10 GHz. Further, this film exhibits a dielectric tangent (tand) of 0.01 or less, more preferably 0.0025 or less, in a frequency of 1 to 10 GHz.

In recent years, demands for high frequency characteristics have become more stringent. Concretely, it is required that the dielectric constant in the range of frequency 1 to 10 GHz is 2.5 or less. Further, it is required that the dielectric tangent (tand) in the range of frequency 1 to 10 GHz is 0.0025 or less. The coverlay film described in Patent Document 2 can satisfy this requirement. However, there is a demand for a film excellent in long-term preservability than the coverlay film.

Patent Document 2 discloses a maleimide-based curing agent as a preferable example of the curing agent which is the component (E) of the coverlay film. According to this document, by using a maleimide-based curing agent, the heat curing of the coverlay film can be proceeded at a lower temperature (for example, a curing temperature of 200 캜 is usually set at 150 캜). Among them, bismaleimide is particularly preferably used in view of maintaining the dielectric properties of the coverlay film, giving an adhesive force to the film, and high Tg (glass transition point) of the film. However, a film excellent in shelf life and excellent in external appearance and pressure-bonding property after long-term storage has been demanded.

An object of the present invention is to provide a resin composition for use in the production of an insulating film capable of solving the problems of the prior art described above. The insulating film containing the resin composition has excellent adhesive strength to a metal foil constituting the wiring of the FPC, and to a substrate material of an FPC such as a polyimide film and a liquid crystal polymer. Further, this insulating film exhibits excellent electrical characteristics in the high frequency range, specifically, low dielectric constant (e) and low dielectric tangent (tand) in the frequency range of 1 to 10 GHz. Further, the shelf life of the insulating film is good.

(B) an epoxy resin, (C) a styrenic thermoplastic elastomer, (D) a thermosetting resin composition containing, in one molecule, at least one compound selected from the group consisting of (A) a modified polyphenylene ether having an ethylenic unsaturated group at both terminals, A compound having an imide group and an acrylate group, and (E) a curing catalyst, and 0.5 to 4 parts by mass of the above-mentioned component (D) relative to 100 parts by mass of the total of the above components (A) to (E).

In the resin composition of the present invention, the epoxy resin of component (B) is preferably an epoxy resin having a naphthalene skeleton.

In the resin composition of the present invention, the curing catalyst of component (E) is preferably an imidazole-based curing catalyst.

In the resin composition of the present invention, the curing catalyst of component (E) is preferably an imidazole-based curing catalyst having a benzene ring.

The resin composition of the present invention may further contain (F) an organic peroxide.

The resin composition of the present invention has a dielectric constant (e) of not more than 2.5 and a dielectric tangent (tand) of not more than 0.0025 in a region where the thermosetting resin of the resin composition has a frequency of 1 to 10 GHz. Further, the insulating film of the present invention includes the resin composition of the present invention.

Further, the semiconductor device of the present invention includes the resin composition of the present invention or a thermosetting resin thereof as an interlayer adhesive between substrates.

Further, the semiconductor device of the present invention includes the insulating film of the present invention or thermosetting resin thereof as an interlayer adhesive between substrates.

The insulating film formed from the resin composition of the present invention has excellent adhesive strength to a metal foil forming the wiring of an FPC, and to a substrate material of an FPC such as a polyimide film and a liquid crystal polymer film. Further, this insulating film exhibits excellent electrical characteristics in the high frequency range, specifically, low dielectric constant (e) and low dielectric tangent (tand) in the frequency range of 1 to 10 GHz. Further, the shelf life of the insulating film is good. Therefore, crystallization of the components in the film is difficult to occur even when the film is stored for a long period of time. As a result, deterioration of the appearance of the film hardly occurs. Further, the physical properties of the film are deteriorated, and in particular, the pressure-bonding property of the film is hardly lowered. Therefore, it is preferable for an adhesive film for electric and electronic use and a coverlay film for printed wiring board. Further, this insulating film is preferable as an interlayer adhesive between substrates of a semiconductor device.

 Hereinafter, the resin composition of the present invention will be described in detail. The resin composition of the present invention contains at least the following components (A) to (E).

(A) a modified polyphenylene ether having an ethylenic unsaturated group at both terminals

Examples of the ethylenic unsaturated group contained in the modified polyphenylene ether having an ethylenic unsaturated group at both terminals of the component (A) include ethylenic, allyl, methallyl, propenyl, butenyl, A cycloalkenyl group such as an alkenyl group, a cyclopentenyl group and a cyclohexenyl group, and an alkenylaryl group such as a vinylbenzyl group and a vinylnaphthyl group. Of these, preferred examples are vinylbenzyl groups. The two ethylenic unsaturated groups at both terminals may be the same or different.

The modified polyphenylene ether having an ethylenic unsaturated group at both terminals of the component (A) is preferably a modified polyphenylene ether represented by the following formula (1).

In the formula (1), - (O-X-O) - is represented by the following formula (2) or (3).

In formula (2), R ₁ , R ₂ , R ₃ , R ₇ and R ₈ are the same or different alkyl groups having 6 or less carbon atoms or phenyl groups. R ₄ , R ₅ and R ₆ are the same or different hydrogen atoms, or an alkyl group having 6 or less carbon atoms or a phenyl group.

In formula (3), R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are the same or different and each represents a hydrogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. -A- is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

In the formula (1), - (Y-O) - is represented by the formula (4). - (Y-O) - have the same structure or represent different structures randomly arranged.

In the formula (4), R ₁₇ and R ₁₈ are the same or different alkyl groups having 6 or less carbon atoms or phenyl groups. R ₁₉ and R ₂₀ are the same or different hydrogen atoms, or an alkyl group having 6 or less carbon atoms or a phenyl group.

In formula (1), a and b each represent an integer of 0 to 100, at least one of which is not 0.

Examples of -A- in the formula (3) include methylene, ethylidene, 1-methylethylidene, 1, 1-propylidene, 1,4-phenylenebis (1-methylethylidene) And divalent organic groups such as 3-phenylene bis (1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene and 1-phenylethylidene. However, -A- is not limited to these.

Preferred examples of the modified polyphenylene ether represented by the formula (1) and the _{R 1, R 2, R 3} , R 7, R 8, R 17 and R ₁₈ an alkyl group of more than a carbon number of _{3, R 4, R 5,} R ₆ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₉ and R ₂₀ are hydrogen atoms or alkyl groups having 3 or less carbon atoms. Particularly preferably - (O-X-O) - in the formula (2) or (3) represents the formula (5), the formula (6), or the formula (7) Y-O) - represents a structure represented by formula (8) or (9), or a structure represented by formula (8) and a structure represented by formula (9).

The method for producing the modified polyphenylene ether expressed by the formula (1) is not particularly limited. For example, the terminal phenolic hydroxyl group of the bifunctional phenylene ether oligomer can be produced by vinylbenzyl etherification. This bifunctional phenylene ether oligomer is obtained, for example, by oxidatively coupling a bifunctional phenol compound and a monofunctional phenol compound.

The number average molecular weight of the modified polyphenylene ether having an ethylenically unsaturated group at both terminals of the component (A) is preferably in the range of 500 to 4,500, more preferably in the range of 500 to 3,000 in terms of polystyrene by the GPC method , More preferably in the range of 1,000 to 2,500. When the number average molecular weight is 500 or more, the resin composition is hardly stuck to the resin when the resin composition of the present invention is formed into a coating film. When the number average molecular weight is 4,500 or less, deterioration of the solubility of the component (A) in a solvent can be suppressed.

The content of the modified polyphenylene ether having an ethylenic unsaturated group at both terminals of the component (A) is preferably 30 to 60 parts by mass, more preferably 30 to 60 parts by mass with respect to 100 parts by mass of the total of the components (A) to (E) Is preferably 30 to 50 parts by mass, and more preferably 35 to 45 parts by mass. When the amount of the component (A) is too small, not only the moldability of the insulating film containing the resin composition of the present invention deteriorates but also the desired high frequency characteristics are hardly obtained. If the component (A) is too large, the amount of the component (B) and the component (C) is relatively reduced. For this reason, the adhesiveness of the insulating film containing the resin composition of the present invention is deteriorated. From the viewpoint of high-frequency characteristics, the relative dielectric constant of the preferable component (A) is 3.0 or less.

(B) Epoxy resin

Examples of the epoxy resin of the component (B) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin, siloxane type epoxy resin, biphenyl type epoxy resin, glycidyl ester type Epoxy resin, glycidylamine-type epoxy resin, hydantoin-type epoxy resin, and naphthalene ring-containing epoxy resin. One of these epoxy resins may be used alone, or two or more thereof may be used in combination. Here, from the viewpoint of the moldability of the film, the epoxy resin of the component (B) is preferably a liquid. Further, from the viewpoint of improving the adhesiveness of the insulating film comprising the resin composition of the present invention, the epoxy resin of the component (B) preferably has a naphthalene skeleton.

The content of the epoxy resin in the component (B) is preferably 2 to 15 parts by mass, more preferably 4 to 12 parts by mass, more preferably 4 to 12 parts by mass, relative to 100 parts by mass in total of the components (A) to 6 to 11 parts by mass. If the amount of the component (B) is too small, the adhesiveness of the insulating film comprising the resin composition of the present invention deteriorates. When the component (B) is too large, the amount of the component (A) and the component (C) is relatively reduced. As a result, the moldability and high-frequency characteristics of the insulating film containing the resin composition of the present invention are deteriorated.

(C) a styrene-based thermoplastic elastomer

The styrene-based thermoplastic elastomer of the component (C) refers to a thermoplastic elastomer containing styrene, an isomer thereof, or an analogue thereof. Examples of the component (C) include polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene (SEEPS), polystyrene-poly (ethylene / butylene) block-polystyrene (SEBS), styrene-butadiene block copolymer (SBS) Styrene-isoprene-styrene block copolymer (SIS) and polybutadiene (PB). One of these thermoplastic elastomers may be used alone, or two or more thereof may be used in combination. From the viewpoint of improving the bonding strength of the metal foil constituting the wiring of the FPC and the substrate material of the FPC such as the polyimide film and the liquid crystal polymer, the component (C) preferably includes SEEPS. The content of SEEPS in the component (C) is preferably from 10 to 70 mass%, more preferably from 10 to 50 mass%. Further, in view of heat resistance, component (C) preferably includes SEBS.

The content of the styrene-based thermoplastic elastomer of the component (C) is preferably 30 to 70 parts by mass, more preferably 40 to 60 parts by mass, further preferably 40 to 60 parts by mass, Is 45 to 55 parts by mass. If the component (C) is excessively large, the moldability is deteriorated. If the component (C) is too small, the bonding strength is deteriorated and further the moldability is deteriorated. From the viewpoint of high-frequency characteristics, the preferred relative dielectric constant of the component (C) used is 3.0 or less.

(D) a compound having an imide group and an acrylate group in one molecule

(D) is a component for assisting the curing of the insulating film formed using the resin composition of the present invention. As described above, bismaleimide is used as a curing agent for the component (E) in the coverlay film described in Patent Document 2. [ On the other hand, a compound having an imide group and an acrylate group in one molecule is used as the component (D) in the resin composition of the present invention. Therefore, as compared with an insulating film using bismaleimide, crystallization of components in the film is difficult to occur while an insulating film formed using the resin composition is stored for a long period of time. Therefore, deterioration of the film appearance is unlikely to occur. Further, the physical properties of the film are deteriorated, and in particular, the pressure-bonding property of the film is hardly lowered. The pressure-bonding property of the film is not limited to the case where the insulating film is used as a cover film, but is also a property required when used as an adhesive film for electric and electronic applications and as an interlayer adhesive between substrates of semiconductor devices. The compound having an imide group and an acrylate group in one molecule used as the component (D) can be also used in view of maintaining the dielectric property of the insulating film, giving the adhesive force to the insulating film and high Tg of the insulating film (glass transition point) There is no comparison to Mid.

An example of the component (D) is an imide acrylate. Examples of imide acrylates include N-acryloyloxyethylhexahydrophthalimide, N-acryloyloxyethyl-1,2,3,6-tetrahydrophthalimide and N-acryloyloxyethyl- 3,4,5,6-tetrahydrophthalimide. Particularly, N-acryloyloxyethylhexahydrophthalimide is preferably used.

The content of the component (D) is 0.5 to 4 parts by mass with respect to 100 parts by mass of the total of the components (A) to (E). If the content of the component (D) is out of the above range, the adhesive strength of the insulating film comprising the resin composition of the present invention is insufficient. The content of the component (D) is preferably 0.5 to 3.0 parts by mass, more preferably 0.5 to 2.5 parts by mass based on 100 parts by mass of the total of the components (A) to (E).

(E) Curing catalyst

The curing catalyst of component (E) promotes curing of the insulating film formed using the resin composition of the present invention. More specifically, the component (E) is a catalyst for promoting the curing reaction of the epoxy resin of the component (B). Examples of the component (E) include an imidazole-based curing catalyst, an amine-based curing catalyst and a phosphorus-based curing catalyst. Examples of the imidazole-based curing catalyst include 2-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-heptadecylimidazole, Methylimidazole, 1-cyanoethyl-2-ethyl-4-imidazole, 2-phenylimidazole, 1-benzyl-2-phenylimidazole and 2-phenyl- Imidazole compounds. Among them, preferred examples are 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole and 1-cyanoethyl-2-ethyl-4-imidazole. Examples of the amine-based curing catalyst include triazine compounds such as 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, and triazine compounds such as 1,8-diazabicyclo [ 5,4,0] undecene-7 (DBU), triethylenediamine, benzyldimethylamine, and triethanolamine. Among them, a preferable example is 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine. Examples of phosphorus-based curing catalysts include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine and tri (nonylphenyl) phosphine. Among them, an imidazole-based curing catalyst is preferably used since it is possible to adjust the appropriate curing properties. Further, an imidazole-based curing catalyst having a benzene ring is more preferably used since it can lengthen the shelf life of an insulating film formed using the resin composition of the present invention. Examples of such imidazole-based curing catalysts include 2-phenylimidazole, 1-benzyl-2-phenylimidazole and 2-phenyl-4-methylimidazole. Particularly, 1-benzyl-2-phenylimidazole is preferably used.

The content of the component (E) is appropriately selected depending on the kind of the curing catalyst used as the component (E). When the imidazole-based curing catalyst is used as the component (E), the amount is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, more preferably 0.1 to 15 parts by mass, relative to 100 parts by mass of the epoxy resin of the component (B) Is 1 to 10 parts by mass. If the content of the component (E) is too small, the curability is deteriorated. On the other hand, if the content of the component (E) is too large, the shelf life of the insulating film deteriorates.

The resin composition of the present invention may contain the components described below in addition to the components (A) to (E), if necessary.

(F) Organic peroxide

Examples of the organic peroxide of the component (F) include t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexylcarbonate, t-butyl peroxyacetate, dicumyl peroxide, Di (t-butylperoxy) hexane, di-t-butylperoxide, 2,5-dimethyl- 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, methyl ethyl ketone peroxide, 2,5- T-butyl peroxybenzoate, t-butyl peroxide, t-butyl peroxybenzoate, t-butyl hydroperoxide, p- menthol hydroperoxide, benzoyl peroxide, p-chlorobenzoyl peroxide, And hexanone peroxide. By adding the organic peroxide of the component (F), the curing reaction of the component (A) can be promoted and the reactivity can be stabilized. Considering the use of the resin composition of the present invention in the form of a film, the component (F) is preferably not activated at a temperature range of 60 to 120 캜 in the drying step of film formation, / RTI &gt; An example of such a component (F) is t-butyl peroxybenzoate.

(Other compounding agent)

The resin composition of the present invention may further contain components other than the above components (A) to (F), if necessary. Specific examples of such blendable components include silane coupling agents, defoaming agents, flow control agents, film forming assistants, dispersants and inorganic particles. The kind and blending amount of each compounding agent can be selected according to an ordinary method.

On the other hand, the insulating film containing the resin composition of the present invention may not contain a component that adversely affects the high-frequency characteristics. Examples of such components include liquid rubbers and flame retardants.

(Preparation of resin composition)

The resin composition of the present invention can be prepared by a conventional method. For example, in the presence of a solvent, the above-mentioned components (A) to (D) (in the case of containing any other optional components, these components) are mixed with a heated mixing kneader. For example, the number of revolutions of the kneader is 100 to 1000 rpm, the mixing temperature is 80 ° C, and the mixing time is 3 hours. After the obtained mixture is cooled, further component (E) (in addition, component (F) if the resin composition contains component (F)) is added to the mixture. Finally, the resin composition of the present invention can be obtained by stirring the mixture containing the component (E) (and the component (F)) at room temperature for 30 to 60 minutes.

The resin composition of the present invention has the following excellent properties.

The thermosetting resin composition of the present invention exhibits excellent electrical properties in the high frequency range. Specifically, the dielectric constant (e) of the thermosetting resin composition in the frequency range of 1 to 10 GHz is preferably 2.5 or less, and more preferably 2.4 or less. Further, the dielectric tangent (tand) in the region of the frequency of 1 to 10 GHz is preferably 0.0025 or less, more preferably 0.0022 or less. When the dielectric constant (e) and the dielectric tangent (tand) in the frequency range of 1 to 10 GHz fall within the above range, the electric signal loss in the frequency range of 1 to 10 GHz can be reduced.

The thermosetting resin composition of the present invention has a sufficient adhesive strength. Specifically, the fill strength (180 degree fill) of the thermosetting resin composition for a copper foil screen measured in accordance with JIS K6854-2 is preferably 7 N / cm or more, and more preferably 8 N / cm or more. The peel strength (90 degree fill) of the liquid crystal polymer film measured in accordance with JIS K6854-1 is preferably 6 N / cm or more, and more preferably 7 N / cm or more.

The insulating film of the present invention can be obtained from the resin composition of the present invention by a known method. For example, the resin composition of the present invention is diluted with a solvent to prepare a varnish. The obtained varnish is applied to at least one side of the support. By drying the varnish on the support, the insulating film of the present invention can be provided as a film on which the support is formed, or as a film peeled off from the support.

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. A conventionally used amount of a solvent may be used. The preferable amount of the solvent is 20 to 90 mass% with respect to the solid content.

The support is not particularly limited. A support having a desired shape suitable for the production method of the film can be appropriately selected. Examples of the support to be used include a metal foil such as copper and aluminum, and a carrier film made of resin such as polyester and polyethylene. When the insulating film of the present invention is provided as a film peeled off from a support, a support subjected to release treatment with a silicone compound or the like is preferably used.

The method of applying the varnish is not particularly limited. Examples of usable methods include a slot die method, a gravure method, and a doctor coater method. The optimum method can be selected from among these methods depending on the desired film thickness and the like. Particularly, a gravure method is preferably used in that the thickness of the film can be designed to be thin. Coating is performed so that the thickness of the film formed after drying becomes a desired thickness. Such thickness can be deduced from the solvent content if it is a person skilled in the art.

The thickness of the insulating film of the present invention is appropriately designed based on the characteristics such as the mechanical strength required depending on the use of the film. The thickness of the film is generally 1 to 100 mu m. The thickness of the film when thinning is required is preferably 1 to 30 mu m.

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

The insulating film of the present invention has good shelf life. The deterioration of the appearance of the film due to crystallization of the components in the film is hard to occur even while the insulating film is being stored for a long period of time. In addition, during this long-term storage, the pressure-bonding property of the film, which is measured in the following procedure, is hardly reduced.

The insulating film of the present invention can be used as an adhesive film for electric and electronic applications by the following procedure. The insulating film of the present invention is placed on the surface to be bonded of one of the two objects to be bonded using the insulating film of the present invention. Thereafter, the other one of the objects is placed on the film so that the surface to be adhered is in contact with the exposed surface of the insulating film. When an insulating film on which a support is formed is used, the insulating film is placed on the surface to be bonded such that the exposed surface of the insulating film comes into contact with the surface to be bonded of one of the objects, so that the insulating film is pressed on the surface to be bonded . Here, the temperature at the time of pressure application can be set at, for example, 130 deg.

Next, the support is peeled off after press-bonding, and the other object is placed on the exposed surface of the insulating film such that the surface to be adhered is in contact with the exposed surface of the insulating film. After performing pressure bonding in this order, thermocompression bonding is performed at a predetermined temperature for a predetermined time. Thereafter, the film is heat-cured. Here, the thermocompression bonding step may be omitted. The temperature at the time of thermocompression bonding is preferably 100 to 150 占 폚. The time of thermocompression bonding is preferably 0.5 to 10 minutes. The temperature of the heat curing is preferably 150 to 200 占 폚. The heat curing time is preferably 30 to 120 minutes. Here, instead of using a film which has been previously formed into a film, a varnish diluted with a solvent of the resin composition of the present invention is applied to the surface to be bonded of one of the objects to be adhered and dried, and then the above- .

The insulating film of the present invention can be used as a coverlay film by the following procedure. The cover film is disposed at a predetermined position of the resin substrate on which the wiring with the wiring pattern is formed on the main surface of the insulating film of the present invention, that is, the position where the wiring film is covered with the insulating film on the side where the wiring pattern is formed. Thereafter, pressure bonding, thermocompression bonding and heat curing can be performed at a predetermined temperature and for a predetermined time. Here, the thermocompression bonding step may be omitted. The temperature and time for pressure bonding, thermocompression bonding and heat curing are the same as those in the case of using as the adhesive film for the above electric and electronic uses.

The insulating film of the present invention can also be used as an interlayer adhesive between substrates of a semiconductor device. In this case, the object to be bonded becomes a plurality of stacked substrates constituting the semiconductor device. As an interlayer adhesive between the substrates of the semiconductor device, 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.

The substrate constituting the semiconductor device is not particularly limited. An organic substrate such as epoxy resin, phenol resin and bismaleimide triazine resin, an inorganic substrate such as CCL substrate, ceramic substrate and silicon substrate can be used.

Example

Hereinafter, the present invention will be described in detail with reference to Examples. However, the present invention is not limited to these.

(Examples 1 to 10 and Comparative Examples 1 to 5)

Sample preparation and measurement method

Each component was weighed and compounded so as to have a blending ratio (parts by mass) shown in the following table. These components were then added to a reaction kettle heated to 80 占 폚. Subsequently, the charged components were mixed at a revolution number of 250 rpmm, normal pressure, and 3 hours. However, the curing catalyst of component (E) and the organic peroxide of component (F) were added after cooling. The varnish containing the resin composition thus obtained was applied to one side of a support (PET film subjected to release treatment) and dried at 100 캜 (80 캜 when containing organic peroxide of component (F)), To obtain an insulating film formed.

Here, the weak symbols in the tables indicate the following.

Component (A)

OPE2200: Oligophenylene ether (modified polyphenylene ether represented by the above formula (1) (- (O-X-O) - in the formula (1) O) - is the formula (8)) (Mn = 2200), manufactured by Mitsubishi Gas Chemical Co.,

Component (B)

NC3000H: biphenyl type epoxy resin, manufactured by Nippon Yakusho KK

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

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

Component (C)

Polystyrene-poly (ethylene / butylene) block-polystyrene (SEBS) manufactured by Asahi Kasei Chemicals Co., Ltd.

SEPTON 4044: polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene (SEEPS), manufactured by Kuraray Co.,

Component (D)

M-140: imide acrylate (N-acryloyloxyethylhexahydrophthalimide), manufactured by Toa Gosei Co., Ltd.

Component (D ')

BMI-70: bismaleimide manufactured by K.I.Hwaseong Co., Ltd.

M-5300: monoacrylate (omega -carboxy-polycaprolactone monoacrylate), Toa Synthetic Co., Ltd.

Component (E)

2E4MZ: 2-ethyl-4-methylimidazole, manufactured by Shikoku Chemical Industry Co.,

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

Component (F)

Per butyl Z: tert-butyl peroxybenzoate, manufactured by Nichiyu Co., Ltd.

Other components

KBM403: silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.

The dielectric film (e) and the dielectric tangent (tand): The insulating film was heated and cured at 200 ° C (180 ° C in the case of containing the organic peroxide of component (F)) and then peeled off from the support. The dielectric constant (e) and the dielectric tangent (tand) of a test piece having a length of 100 mm and a diameter of 2 mm or less, which were rounded in a cylindrical shape, were cut from the cavity resonator And measured by the perturbation method (10 GHz).

Peel Strength (Cu): A copper foil (CF-T8, made by Fukuda Metal Bottom Kogyo Kogyo K.K., thickness 18 μm) having roughened surfaces inside was stuck on both sides of the insulation film peeled off from the support. Subsequently, the insulating film was heated and cured under the conditions of 200 DEG C, 60 min and 10 kgf (when the organic peroxide of component (F) was contained at 180 DEG C, 60 min and 10 kgf) using a press machine. This test piece was cut into a width of 10 mm. Peel strength (180 degree peel) was measured according to JIS K6854-2 by peeling using an autograph.

Peel strength (LCP): A liquid crystal polymer (LCP) film (BECKSTAR CT-Z, manufactured by Kuraray Co., Ltd., 25 mu m) was bonded to one side of the insulating film peeled off from the support. Then, the FR4 substrate was bonded to one of the other surfaces of the insulating film. Then, under the conditions of 200 DEG C, 60 min and 10 kgf (when the organic peroxide of component (F) was contained, the conditions were 180 DEG C, 60 min and 10 kgf). Thereafter, peel strength (90 degree peel) was measured by peeling using an autograph in accordance with JIS K6854-1.

Pressure-bonding: The insulating film on which the support prepared in the above procedure was formed was laminated on a liquid crystal polymer (LCP) film (BECKSTAR CT-Z, manufactured by Kuraray Co., Ltd., 25 탆) at 130 캜 using a roll laminator. After the lamination, the support was peeled off. Thereafter, the LCP film laminated with the insulating film was bent. Evaluation of the pressure-bonding property in the case where no peeling between the films was observed at the time of bending was evaluated as &amp; cir &amp; The evaluation when the films were peeled off was indicated by X. &lt; tb &gt; &lt; TABLE &gt; After the fabrication in the same order, the pressure-tightness of the insulating film on which the support was formed for 3 months was also evaluated.

The electrical properties (dielectric constant (e), dielectric tangent (tand)), fill strength and pressure bonding of the high frequency electrical properties of the test pieces used in Examples 1 to 10 were excellent. The differences between Example 1 and Examples 2 to 10 are as follows.

Example 2: Component (F) is not included.

Examples 3 and 4: Component (F) is not included. Further, the content of the component (D) is different.

Examples 5 and 6 differ in the kind of the epoxy resin of the component (B), the blending ratio of the thermoplastic elastomer of the component (C), the content of the component (D) and the kind of the curing catalyst of the component (E). In addition, a silane coupling agent is added as another component.

Example 7: The content of the component (D) and the kind of the curing catalyst of the component (E) are different. Further, the component (F) is not included. In addition, a silane coupling agent is added as another component.

Example 8: The kind of curing catalyst of component (E) is different. In addition, a silane coupling agent is added as another component.

Example 9: The kind of the epoxy resin of the component (B) and the kind of the curing catalyst of the component (E) are different. In addition, a silane coupling agent is added as another component.

Example 10: The kind of curing catalyst of component (E) is different. Further, the component (F) is not included.

In Comparative Examples 1 and 2 in which bismaleimide was used instead of the imide acrylate of the component (D), the pressure-bonding ability after 3 months was lost. In Comparative Example 1 in which the content of bismaleimide was high, the dielectric tangent of the high-frequency electric characteristics was disappeared. In Comparative Example 3 using monoacrylate instead of imide acrylate of the component (D), the peel strength to the LCP film was low. Also, the dielectric tangent was lost during the high frequency electrical characteristics. In Comparative Example 4 which did not contain the component (D), the peel strength to the LCP film was low. In Comparative Example 5 in which the content of the component (D) was excessively high, the peel strength to the LCP film was low.

The resin composition according to the embodiment of the present invention may be the following first to sixth resin compositions.

(B) an epoxy resin, (C) a styrenic thermoplastic elastomer, (D) a resin having an imide group and an acrylate group in one molecule, and (D) a modified polyphenylene ether having an ethylenic unsaturated group at both terminals, (D) in an amount of 0.5 to 4 parts by mass based on 100 parts by mass of the total of the components (A) to (E).

The second resin composition is the first resin composition wherein the epoxy resin of the component (B) is an epoxy resin having a naphthalene skeleton.

The third resin composition is the first or second resin composition wherein the curing catalyst of the component (E) is an imidazole-based curing catalyst.

The fourth resin composition is any one of the first to third resin compositions, wherein the curing catalyst of the component (E) is an imidazole-based curing catalyst having a benzene ring.

The fifth resin composition is any of the first to fourth resin compositions containing (F) an organic peroxide.

The sixth resin composition is any one of the first to fifth resin compositions wherein the dielectric constant (e) of the thermosetting resin composition in a frequency region of 1 GHz or more is 2.5 or less and the dielectric tangent (tand) is 0.0025 or less.

The insulator film according to the embodiment of the present invention may be formed of any one of the resin compositions of the first to sixth aspects.

The semiconductor device according to the embodiment of the present invention may be the following first or second semiconductor device.

In the first semiconductor device, any one of the first to sixth resin compositions is used for interlayer bonding between the substrates.

The first semiconductor device uses the insulating film for interlayer adhesion between the substrates.

Claims (9)

(A) a modified polyphenylene ether having ethylenic unsaturated groups at both terminals,
(B) an epoxy resin,
(C) a styrene-based thermoplastic elastomer,
(D) a compound having an imide group and an acrylate group in one molecule, and
(E) a curing catalyst,
And 0.5 to 4 parts by mass of the component (D), based on 100 parts by mass of the total of the components (A) to (E). The method according to claim 1,
Wherein the epoxy resin of the component (B) is an epoxy resin having a naphthalene skeleton. 3. The method according to claim 1 or 2,
Wherein the curing catalyst of component (E) is an imidazole-based curing catalyst. 4. The method according to any one of claims 1 to 3,
Wherein the curing catalyst of component (E) is an imidazole-based curing catalyst having a benzene ring. 5. The method according to any one of claims 1 to 4,
Further comprising an organic peroxide. 6. The method according to any one of claims 1 to 5,
Wherein the resin composition has a dielectric constant (e) of 2.5 or less and a dielectric tangent (tand) of 0.0025 or less in a region where the thermosetting resin has a frequency of 1 GHz or more. An insulating film comprising the resin composition of any one of claims 1 to 6. A semiconductor device comprising the resin composition of any one of claims 1 to 6 or a thermoset material thereof as an interlayer adhesive between substrates. A semiconductor device comprising the insulating film of claim 7 as an interlayer adhesive between substrates or a thermoset material thereof.