KR102323672B1 - Resin composition, and insulating film and semiconductor device using same - Google Patents

Abstract

It has excellent adhesive strength to the substrate material of FPC such as metal foil and polyimide film constituting the wiring of the FPC, and has excellent electrical properties in the high frequency region, specifically, in the frequency range of 1 to 10 GHz, low dielectric constant (e) and low dielectric constant Provision of an insulating film as a coverlay film showing tangent and having a good shelf life, and a resin composition contained in the insulating film. The resin composition comprises (A) a modified polyphenylene ether having ethylenically unsaturated groups at both terminals, (B) an epoxy resin, (C) a styrenic thermoplastic elastomer, (D) a compound having an imide group and an acrylate group in one molecule, And (E) A curing catalyst is contained, and 0.5-4 mass parts of said component (D) are contained with respect to a total of 100 mass parts of the said component (A) - a component (E).

Description

A resin composition, an insulating film and a semiconductor device using the same

<Cross Reference>

While this application claims the priority based on Japanese Patent Application "Patent Application No. 2014-215035" for which it applied on October 22, 2014, the content is taken in by reference.

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

In recent years, miniaturization, weight reduction, and high performance of printed wiring boards used in electric and electronic devices are progressing. In particular, additional high multilayering, high density, thinning, weight reduction, high reliability, and molding processability of the multilayer printed wiring board are required. Moreover, in recent years, the request|requirement for the speedup of the transmission signal processed by a printed wiring board is increasing. Accordingly, the high frequency of the transmission signal is progressing remarkably. Thereby, it is calculated|required by the material used for a printed wiring board that the electrical signal loss in a high frequency area|region, specifically, the area|region with a frequency of 1 GHz or more can be reduced. Interlayer adhesives used in multilayer printed wiring boards and adhesive films used as surface protective films (i.e., coverlay films) of printed wiring boards also exhibit excellent electrical properties (low dielectric constant (e), low dielectric tangent (tand)) in the high frequency region. is required

Patent Document 1 provides a cured product having low dielectric constant, low dielectric tangent and excellent heat resistance, mechanical properties, chemical resistance and flame retardancy, and also discloses a curable resin composition that can be cured at a low temperature. In addition, this document discloses a curable film using this curable resin composition, and a cured product and film obtained by curing them. On the other hand, in Patent Document 2, a metal foil constituting the wiring of a flexible printed wiring board (FPC) and a coverlay film having excellent adhesive strength to the substrate material of the flexible printed wiring board, and exhibiting excellent electrical properties in a high frequency region of 1 GHz or more This is 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 higher. Moreover, this coverlay film can be used also as an adhesive film for electrical and electronic use, and an interlayer adhesive of a multilayer printed wiring board.

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

The coverlay film described in Patent Document 2 exhibits excellent electrical properties in a high-frequency region after being heat-cured. Specifically, this film exhibits a dielectric constant of 3.0 or less, and further, 2.5 or less in a frequency range of 1 to 10 GHz. In addition, this film exhibits a dielectric tangent of 0.01 or less, and further, 0.0025 or less in the frequency range of 1 to 10 GHz.

In recent years, the demand for high-frequency characteristics has become more stringent. Specifically, the dielectric constant in the frequency range of 1 to 10 GHz is required to be 2.5 or less. Further, it is required that the dielectric tangent in the frequency range of 1 to 10 GHz be 0.0025 or less. The coverlay film of patent document 2 can satisfy this request|requirement. However, the film excellent in long-term storage property is calculated|required rather than this 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 the same document, heat curing of the coverlay film can be advanced at a lower temperature by using a maleimide-based curing agent (for example, the curing temperature of 200°C is usually set to 150°C). Among them, bismaleimide is particularly preferably used from the viewpoint of maintaining the dielectric properties of the coverlay film, imparting adhesion to the film, and high Tg (glass transition point) of the film. However, further, a film having a good shelf life and excellent appearance and pressure-adhesiveness of the film after long-term storage has been demanded.

It is an object of the present invention to provide a resin composition used for manufacturing an insulating film capable of solving the problems of the prior art. The insulating film containing this resin composition has excellent adhesive strength to the metal foil constituting the wiring of the FPC, and the substrate material of the FPC such as a polyimide film and a liquid crystal polymer. In addition, this insulating film exhibits excellent electrical properties in a high frequency region, specifically, a low dielectric constant (e) and a low dielectric tangent (tand) in a frequency range of 1 to 10 GHz. Moreover, the shelf life of this insulating film is favorable.

In order to achieve the above object, the resin composition of the present invention comprises (A) a modified polyphenylene ether having ethylenically unsaturated groups at both terminals, (B) an epoxy resin, (C) a styrenic thermoplastic elastomer, (D) in one molecule The compound and (E) curing catalyst which have an imide group and an acrylate group are contained, and 0.5-4 mass parts of said components (D) are contained with respect to a total of 100 mass parts of the said component (A) - a component (E).

The resin composition of this invention WHEREIN: Preferably, the epoxy resin of the said (B) component is an epoxy resin which has a naphthalene skeleton.

The resin composition of this invention WHEREIN: Preferably the curing catalyst of the said (E) component is an imidazole type curing catalyst.

Moreover, the resin composition of this invention WHEREIN: Preferably the curing catalyst of the said (E) component is an imidazole type curing catalyst which has a benzene ring.

The resin composition of this invention may contain (F) organic peroxide further.

In the resin composition of the present invention, the thermosetting product of the resin composition preferably has a dielectric constant (e) of 2.5 or less and a dielectric tangent (tand) of 0.0025 or less in a frequency range of 1 to 10 GHz. Moreover, the insulating film of this invention contains the resin composition of this invention.

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

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

The insulating film formed of the resin composition of the present invention has excellent adhesive strength to the metal foil forming the wiring of the FPC, and the substrate material of the FPC such as a polyimide film and a liquid crystal polymer film. In addition, this insulating film exhibits excellent electrical properties in a high frequency region, specifically, a low dielectric constant (e) and a low dielectric tangent (tand) in a frequency range of 1 to 10 GHz. Moreover, the shelf life of this insulating film is favorable. For this reason, crystallization of the components in a film does not occur easily even while this film is being stored for a long period of time. As a result, deterioration of the film appearance is unlikely to occur. In addition, deterioration of the physical properties of the film, specifically, a decrease in the pressure-adhesiveness of the film is unlikely to occur. For this reason, it is suitable for the adhesive film of an electric and electronic use, and the coverlay film of a printed wiring board. In addition, this insulating film is preferable as an interlayer adhesive between substrates of a semiconductor device.

Hereinafter, the resin composition of this invention is demonstrated in detail. The resin composition of this invention contains the component (A) - component (E) shown below at least.

(A) Modified polyphenylene ether having ethylenically unsaturated groups at both terminals

Examples of the ethylenically unsaturated group of the component (A), the modified polyphenylene ether having ethylenically unsaturated groups at both terminals, include an ethenyl group, an allyl group, a methallyl group, a propenyl group, a butenyl group, a hexenyl group and an octenyl group. alkenyl groups, such as cycloalkenyl groups, such as an alkenyl group, a cyclopentenyl group, and a cyclohexenyl group, and alkenylaryl groups, such as a vinylbenzyl group and a vinylnaphthyl group. Among these, a preferable example is a vinylbenzyl group. The two ethylenically unsaturated groups at both terminals may be the same or different.

The modified polyphenylene ether represented by the following formula (1) as the modified polyphenylene ether having ethylenically unsaturated groups at both terminals of the component (A) is preferable.

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

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

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 hydrogen atoms, or an alkyl group or phenyl group having 6 or less carbon atoms. -A- is a C20 or less linear, branched, or cyclic divalent hydrocarbon group.

In Formula (1), -(Y-O)- is represented by Formula (4). -(Y-O)- represents the same structure or different structures arranged at random.

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

In Formula (1), a and b represent the integer of 0-100 in which at least either one is not 0.

Examples of -A- in formula (3) include methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis(1-methylethylidene), 1, and divalent organic groups such as 3-phenylenebis(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) include R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₁₇ and R ₁₈ are an alkyl group having 3 or less carbon atoms, and R ₄ , R ₅ , R _{and compounds in which 6} , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₉ and R ₂₀ are a hydrogen atom or an alkyl group having 3 or less carbon atoms. In particular, preferably -(O-X-O)- of Formula (2) or Formula (3) represents Formula (5), Formula (6), or Formula (7), -( Y-O)- represents a structure represented by Formula (8) or Formula (9), or a structure represented by Formula (8) arranged at random and a structure represented by Formula (9).

The manufacturing method of the modified polyphenylene ether represented by Formula (1) is not specifically limited. For example, it can manufacture by vinylbenzyl etherification of the terminal phenolic hydroxyl group of a bifunctional phenylene ether oligomer. This bifunctional phenylene ether oligomer is obtained by oxidatively coupling a bifunctional phenol compound and a monofunctional phenol compound, for example.

The number average molecular weight of the modified polyphenylene ether having ethylenically unsaturated groups 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 GPC method. , more preferably in the range of 1,000 to 2,500. When a number average molecular weight is 500 or more and the resin composition of this invention is made into a coating-film shape, it is hard to stick a resin composition. Moreover, the solubility fall with respect to the solvent of a component (A) as a number average molecular weight is 4,500 or less can be suppressed.

The content of the modified polyphenylene ether having an ethylenically 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 in total with respect to 100 parts by mass in total of the components (A) to (E). Preferably it is 30-50 mass parts, More preferably, it is 35-45 mass parts. When there are too few components (A), not only the moldability of the insulating film containing the resin composition of this invention will deteriorate, but it will become difficult to obtain a desired high frequency characteristic. When component (A) is too large, the amounts of component (B) and component (C) are relatively reduced. For this reason, the adhesiveness of the insulating film containing the resin composition of this invention deteriorates. In addition, from the viewpoint of high-frequency characteristics, the 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 An epoxy resin, a glycidylamine type epoxy resin, a hydantoin type epoxy resin, and a naphthalene ring containing epoxy resin are mentioned. One of these epoxy resins may be used independently, and two or more may be mixed and used. Here, from the viewpoint of the moldability of the film, the epoxy resin of the component (B) is preferably liquid. Moreover, from a viewpoint of the adhesive improvement of the insulating film containing the resin composition of this invention, the epoxy resin of component (B), Preferably it has a naphthalene skeleton.

To [ content of the epoxy resin of component (B) ] a total of 100 mass parts of component (A) - component (E), Preferably 2-15 mass parts, More preferably, 4-12 mass parts, More preferably, It is 6-11 mass parts. When there are too few components (B), the adhesiveness of the insulating film containing the resin composition of this invention will deteriorate. When component (B) is too large, the amounts of component (A) and component (C) are relatively reduced. For this reason, the moldability and high frequency characteristic of the insulating film containing the resin composition of this invention deteriorate.

(C) Styrenic thermoplastic elastomer

The styrenic thermoplastic elastomer of component (C) refers to a thermoplastic elastomer containing styrene or a homologue or analog thereof. Examples of 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 may be mixed and used. The component (C) preferably contains SEEPS from the viewpoint of improving the adhesion strength of the metal foil constituting the wiring of the FPC and the FPC to the substrate material such as a polyimide film and a liquid crystal polymer. Content of SEEPS in a component (C) becomes like this. Preferably it is 10-70 mass %, More preferably, it is 10-50 mass %. In addition, from the viewpoint of heat resistance, component (C) preferably contains SEBS.

The content of the styrenic thermoplastic elastomer of the component (C) is preferably 30 to 70 parts by mass, more preferably 40 to 60 parts by mass, even more preferably 30 parts by mass to 100 parts by mass in total of the components (A) to (E). Preferably it is 45-55 mass parts. When there are too many components (C), a moldability will deteriorate. When there are too few components (C), adhesive strength will deteriorate, and moldability will also deteriorate further. In addition, the preferable dielectric constant of the component (C) used from a viewpoint of a high frequency characteristic is 3.0 or less.

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

(D) is a component which assists hardening of the insulating film formed using the resin composition of this invention. As mentioned above, bismaleimide is used for the coverlay film of patent document 2 as a hardening|curing agent of (E) component. In contrast, in the resin composition of the present invention, a compound having an imide group and an acrylate group in one molecule is used as the component (D). For this reason, compared with the insulating film using bismaleimide, crystallization of the component in a film does not occur easily while the insulating film formed using a resin composition is preserve|saved for a long period of time. For this reason, deterioration of a film external appearance is hard to occur. In addition, deterioration of the physical properties of the film, specifically, a decrease in the pressure-adhesiveness of the film is unlikely to occur. The pressure-adhesiveness of the film is not limited to the case where the insulating film is used as a coverlay film, but is a characteristic required even when used as an adhesive film for electrical and electronic applications and as an interlayer adhesive between substrates of semiconductor devices. A compound having an imide group and an acrylate group in one molecule used as the component (D) is bismaleic from the viewpoint of maintaining the dielectric properties of the insulating film, imparting adhesion to the insulating film, and high Tg (glass transition point) of the insulating film. It's not inferior to the mid.

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

Content of a component (D) is 0.5-4 mass parts with respect to a total of 100 mass parts of a component (A) - a component (E). When content of a component (D) is outside the said range, the adhesive strength of the insulating film containing the resin composition of this invention is inadequate. To [ content of a component (D) / 100 mass parts in total of a component (A) - a component (E)), Preferably it is 0.5-3.0 mass parts, More preferably, it is 0.5-2.5 mass parts.

(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, component (E) is a catalyst that accelerates the curing reaction of the epoxy resin of 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, and 2-ethyl-4- methylimidazole, 1-cyanoethyl-2-ethyl-4-imidazole, 2-phenylimidazole, 1-benzyl-2-phenylimidazole and 2-phenyl-4-methylimidazole; 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 curing catalyst include a triazine compound such as 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 1,8-diazabicyclo[ and tertiary amine compounds such as 5,4,0]undecene-7 (DBU), triethylenediamine, benzyldimethylamine, and triethanolamine. Among these, a preferable example is 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine. Further, examples of the phosphorus-based curing catalyst include triphenylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine and tri(nonylphenyl)phosphine. Among these, since moderate sclerosis|hardenability can be adjusted, an imidazole-type curing catalyst is used preferably. Moreover, since the imidazole type hardening catalyst which has a benzene ring can lengthen the shelf life of the insulating film formed using the resin composition of this invention, it is used more preferably. Examples of such an imidazole-based curing catalyst include 2-phenylimidazole, 1-benzyl-2-phenylimidazole, and 2-phenyl-4-methylimidazole. In particular, 1-benzyl-2-phenylimidazole is preferably used.

Content of component (E) is suitably selected according to the kind of curing catalyst used as component (E). When using an imidazole-type curing catalyst as component (E), with respect to 100 mass parts of epoxy resins of component (B), Preferably it is 0.01-20 mass parts, More preferably, it is 0.1-15 mass parts, More preferably, is 1 to 10 parts by mass. When there is too little content of a component (E), sclerosis|hardenability will deteriorate. On the other hand, when there is too much content of a component (E), the shelf life of an insulating film will deteriorate.

The resin composition of this invention may contain the component described below other than the said component (A) - component (E) as needed.

(F) organic peroxide

Examples of organic peroxides of component (F) include t-butylperoxybenzoate, t-butylperoxyisopropylcarbonate, t-butylperoxy-2-ethylhexylcarbonate, t-butylperoxyacetate, dicumylperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butylperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, methyl ethyl ketone peroxide, 2,5-dimethylhexyl -2,5-diperoxybenzoate, t-butyl hydroperoxide, p-menthane hydroperoxide, benzoyl peroxide, p-chlorobenzoyl peroxide, t-butylperoxyisobutyrate, hydroxyheptyl peroxide and cyclo Hexanone peroxide is mentioned. By adding the organic peroxide of the component (F), the curing reaction of the component (A) can be accelerated and the reactivity can be stabilized. Considering that the resin composition of the present invention is used as a film, the component (F) is preferably not activated in a temperature range of 60 to 120° C. in the drying process of film formation, and is activated in a temperature range higher than that is a compound. An example of such component (F) is t-butylperoxybenzoate.

(Other compounding agents)

The resin composition of this invention may contain components other than the said component (A) - component (F) further as needed. Specific examples of such a compoundable component include a silane coupling agent, an antifoaming agent, a flow regulator, a film forming aid, a dispersing agent, and inorganic particles. The type and amount of each compounding agent can be selected according to a conventional method.

In addition, it is not necessary to contain the component which exerts a bad influence on the high frequency characteristic of the insulating film containing the resin composition of this invention. Examples of such components include liquid rubber and flame retardants.

(Preparation of resin composition)

The resin composition of this invention can be manufactured by a conventional method. For example, in the presence of a solvent, the said component (A)-component (D) (when other arbitrary components are contained, these components further) are mixed with a hot mixing kneader. As for mixing conditions, the rotation speed of a kneader is 100-1000 rpm, mixing temperature is 80 degreeC, and mixing time is 3 hours, for example. After cooling the obtained mixture, further component (E) (component (F) when the resin composition includes component (F)) is further added to the mixture. Finally, the resin composition of the present invention can be obtained by stirring the mixture containing component (E) (and component (F)) at room temperature for 30 to 60 minutes.

The resin composition of this invention has the favorable characteristic shown below.

The thermosetting product of the resin composition of the present invention exhibits excellent electrical properties in a high-frequency region. Specifically, the dielectric constant (e) of the thermosetting material of the resin composition in a frequency range of 1 to 10 GHz is preferably 2.5 or less, more preferably 2.4 or less. Further, the dielectric tangent in the frequency range of 1 to 10 GHz is preferably 0.0025 or less, more preferably 0.0022 or less. When the dielectric constant (e) and dielectric tangent (tand) in the frequency range of 1 to 10 GHz are in the above ranges, it is possible to reduce the electrical signal loss in the frequency range of 1 to 10 GHz.

The thermosetting material of the resin composition of this invention has sufficient adhesive strength. The peeling strength (180 degree|times peel) with respect to the copper foil roughened surface specifically, measured based on JISK6854-2 of the thermosetting material of a resin composition becomes like this. Preferably it is 7 N/cm or more, More preferably, it is 8 N/cm or more. Moreover, the peeling strength (90 degree|times peel) with respect to the liquid crystal polymer film measured based on JISK6854-1 becomes like this. Preferably it is 6 N/cm or more, More preferably, it is 7 N/cm or more.

The insulating film of this invention can be obtained by a well-known method from the resin composition of this invention. For example, a varnish is prepared by diluting the resin composition of the present invention with a solvent. The resulting 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 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 point solvents such as dioctyl phthalate and dibutyl phthalate. The usage-amount of a solvent is not specifically limited. The amount of the solvent conventionally used can be used. A 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 used include metal foils such as copper and aluminum, and resin carrier films 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 a release treatment with a silicone compound or the like is preferably used.

The method of apply|coating a varnish is not specifically limited. Examples of the method that can be used include a slot die method, a gravure method, and a doctor coater method. Among these methods, an optimal method can be selected according to a desired film thickness or the like. In particular, the gravure method is preferably used in that the thickness of the film can be designed to be thin. Application is performed so that the thickness of the film formed after drying may become a desired thickness. Those skilled in the art can derive such thickness from solvent content.

The thickness of the insulating film of the present invention is appropriately designed based on characteristics such as mechanical strength required according to the use of the film. The thickness of the film is generally 1 to 100 µm. The thickness of the film when thinning is requested|required becomes like this. Preferably it is 1-30 micrometers.

Drying conditions are not particularly limited. Drying conditions are suitably set according to the kind and amount of the solvent used for a varnish, the usage-amount of a varnish, the thickness of application|coating, etc. For example, drying can be performed at 60-100 degreeC and atmospheric pressure.

The insulating film of the present invention has a good shelf life. Even while the insulating film is being stored for a long time, deterioration of the film appearance due to crystallization of the components in the film is unlikely to occur. Moreover, the fall of the press-adhesion property of the film measured in the procedure mentioned later does not occur easily also during this long-term storage.

The insulating film of this invention can be used as an adhesive film for electrical and electronic uses with the following procedure. The insulating film of this invention is mounted on the to-be-adhesive surface of one of the two objects to be adhere|attached using the insulation film of this invention. Then, the other target object is mounted on the film so that the to-be-adhered surface may contact|connect the exposed surface of an insulating film. Here, when using an insulating film with a support body, the insulating film is press-bonded on the adherend surface by placing the insulating film on the adherend surface so that the exposed surface of the insulating film is in contact with the adherend surface of one object. . Here, the temperature at the time of pressure bonding can be set to 130 degreeC, for example.

Next, the other target object is mounted on the insulating film surface exposed by peeling a support body after pressure bonding so that the to-be-adhered surface may contact with the exposed surface of an 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 cured by heat. Here, you may abbreviate|omit a thermocompression bonding process. The temperature at the time of thermocompression bonding becomes like this. Preferably it is 100-150 degreeC. The time for thermocompression bonding is preferably 0.5 to 10 minutes. The temperature of heat curing is preferably 150 to 200°C. The heat curing time is preferably 30 to 120 minutes. Here, instead of using a pre-filmed one, the varnish diluted with the resin composition of the present invention with a solvent is applied to the adherend surface of one of the adhered objects and dried, and then the one of the above-described objects is placed on the subsequent procedure may be carried out.

The insulating film of this invention can be used as a coverlay film with the following procedures. The coverlay film is arrange|positioned at the predetermined position of the resin substrate in which the wiring in which the wiring pattern was formed in the main surface of the insulating film of this invention is covered with the insulating film on the side where the wiring pattern was formed. After that, pressure bonding, thermocompression bonding, and heat curing can be performed at a predetermined temperature and a predetermined time. Here, you may abbreviate|omit a thermocompression bonding process. The temperature and time of pressure bonding, thermocompression bonding and heat curing are the same as in the case of using the adhesive film for electrical 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 above-described objects to be bonded become a plurality of laminated substrates constituting the semiconductor device. Moreover, instead of using what was previously filmed also as an interlayer adhesive agent between the board|substrates of a semiconductor device, you may use the varnish which diluted the resin composition of this invention with the solvent.

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

Example

Hereinafter, the present invention will be described in detail by way of Examples. However, the present invention is not limited thereto.

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

Sample preparation and measurement methods

It weighed and mix|blended each component so that it might become the compounding ratio (mass part) shown to the following table|surface. Thereafter, these components were put into a reaction kiln heated to 80°C. Subsequently, the charged components were mixed at a rotation speed of 250 rpm, atmospheric 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 obtained in this way is applied to one side of the support (PET film subjected to release treatment) and dried at 100 ° C. (80 ° C. when the organic peroxide of component (F) is included), whereby the support is The formed insulating film was obtained.

Here, the abbreviation|symbol in a table|surface shows the following, respectively.

Component (A)

OPE2200: oligophenylene ether (modified polyphenylene ether represented by formula (1) above (-(O-X-O)- in formula (1)) is formula (5), and -(Y- in formula (1) O) - is the formula (8)) (Mn = 2200), manufactured by Mitsubishi Gas Chemical Co., Ltd.

Component (B)

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

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

HP4032D: Naphthalene type epoxy resin, manufactured by DIC Corporation

Component (C)

Toughtech H1052: 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., Ltd.

Component (D)

M-140: imide acrylate (N-acryloyloxyethyl hexahydrophthalimide), manufactured by Toa Synthesis Co., Ltd.

Component (D')

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

M-5300: monoacrylate (ω-carboxy-polycaprolactone monoacrylate), Toa Synthesis Co., Ltd.

Component (E)

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

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

Component (F)

Perbutyl Z: tert-butyl peroxybenzoate, manufactured by Nichiyu Corporation

other ingredients

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

Dielectric constant (e), dielectric tangent (tand): The insulating film was heat-cured at 200°C (or 180°C when the organic peroxide of component (F) is included), and then peeled from the support. After that, the insulating film A test piece (40 ± 0.5 mm × 100 ± 2 mm) was cut out from the tube and the thickness was measured. The dielectric constant (e) and dielectric tangent (tand) of the cylindrically rounded test piece with a length of 100 mm and a diameter of 2 mm or less was measured in a cavity resonator. It was measured by the perturbation method (10 GHz).

Peeling strength (Cu): The copper foil (CF-T8, Fukuda Metal Foil Powder Industrial Co., Ltd. make, thickness 18 micrometers) which turned the roughened surface inside was pasted together on both surfaces of the insulating film peeled from the support body. Next, the insulating film was heat-cured using a press machine at 200°C, 60 min, and 10 kgf (when the organic peroxide of component (F) was included, 180°C, 60 min, and 10 kgf). This test piece was cut to a width of 10 mm. Peel strength (180 degree peel) was measured based on JISK6854-2 by peeling using an autograph.

Peel strength (LCP): A liquid crystal polymer (LCP) film (Vexstar CT-Z, manufactured by Kuraray Co., Ltd., 25 µm) was bonded to one side of the insulating film peeled from the support. Next, the FR4 board|substrate was bonded together to the other one side of an insulating film. Then, it heat-hardened at 200 degreeC, 60 min, and 10 kgf conditions (in the case of containing the organic peroxide of component (F), 180 degreeC, 60 min, and 10 kgf conditions). Then, based on JISK6854-1, peeling strength (90 degree|times peel) was measured by peeling using the autograph.

Adhesion property: The insulating film with the support formed in the above procedure was laminated on a liquid crystal polymer (LCP) film (Vexstar CT-Z, manufactured by Kuraray Co., Ltd., 25 μm) at 130° C. using a roll laminator. The support was peeled off after lamination. Then, the LCP film laminated with this insulating film was bent. When bending, evaluation of pressure-adhesiveness in the case where there is no peeling of films was shown with (circle). Evaluation in the case of peeling of films was shown by x. After production in the same procedure, the pressure-adhesiveness of the insulating film with the support body stored in an atmospheric atmosphere at room temperature for 3 months was also evaluated.

The high frequency electrical characteristics (dielectric constant (e), dielectric tangent (tand)), peeling strength, and pressure bonding property of the test pieces used in Examples 1-10 were all excellent. The difference between Example 1 and Examples 2-10 is as follows.

Example 2: Component (F) is not included.

Examples 3 and 4: Component (F) is not included. Moreover, content of a component (D) differs.

Examples 5 and 6: The type 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 type of the curing catalyst of the component (E) are different. Moreover, a silane coupling agent is added as another component.

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

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

Example 10: The kind of curing catalyst of component (E) is different. In addition, component (F) is not contained.

In Comparative Examples 1 and 2 in which bismaleimide was used instead of the imide acrylate of the component (D), the pressure-adhesiveness after 3 months was poor. In Comparative Example 1 with a high content of bismaleimide, the dielectric tangent was inferior among high-frequency electrical characteristics. In Comparative Example 3, in which a monoacrylate was used instead of the imide acrylate of component (D), the peel strength to the LCP film was low. In addition, the dielectric tangent (tand) was inferior among the electrical characteristics of high frequency. In Comparative Example 4, which does not contain component (D), the peel strength with respect to the LCP film was low. In the comparative example 5 with too much content of a component (D), the peeling strength with respect to an LCP film was low.

The following 1st - 6th resin compositions may be sufficient as the resin composition which concerns on embodiment of this invention.

The first resin composition comprises (A) a modified polyphenylene ether having ethylenically unsaturated groups at both terminals, (B) an epoxy resin, (C) a styrenic thermoplastic elastomer, (D) having an imide group and an acrylate group in one molecule A compound and (E) curing catalyst are contained, and 0.5-4 mass parts of said component (D) are contained with respect to a total of 100 mass parts of said component (A) - component (E), It is characterized by the above-mentioned.

The said 2nd resin composition is the said 1st resin composition whose epoxy resin of the said (B) component is an epoxy resin which has a naphthalene skeleton.

The said 3rd resin composition is the said 1st or 2nd resin composition whose curing catalyst of the said (E) component is an imidazole-type curing catalyst.

The said 4th resin composition is a resin composition in any one of said 1st - 3 whose curing catalyst of the said (E) component is an imidazole-type curing catalyst which has a benzene ring.

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

The sixth resin composition is any one of the first to fifth resin compositions, wherein the thermosetting product of 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 frequency region of 1 GHz or higher.

In addition, the insulator film which concerns on embodiment of this invention may be formed from the resin composition of any one of said 1st - 6th.

In addition, the semiconductor device which concerns on embodiment of this invention may be the following 1st or 2nd semiconductor device.

In the first semiconductor device, any of the above-mentioned resin compositions 1 to 6 is used for interlayer adhesion between substrates.

In the first semiconductor device, the insulating film is used for interlayer adhesion between substrates.

Claims (9)

(A) modified polyphenylene ether having ethylenically unsaturated groups at both terminals;
(B) an epoxy resin;
(C) a styrenic thermoplastic elastomer;
(D) a compound having an imide group and an acrylate group in one molecule, and
(E) contains a curing catalyst;
The resin composition containing 0.5-4 mass parts of said components (D) with respect to a total of 100 mass parts of the said component (A) - a component (E). The method of claim 1,
The resin composition in which the epoxy resin of the said (B) component is an epoxy resin which has a naphthalene skeleton. The method of claim 1,
The resin composition in which the curing catalyst of the said (E) component is an imidazole type curing catalyst. The method of claim 1,
The resin composition wherein the curing catalyst of the component (E) is an imidazole-based curing catalyst having a benzene ring. The method of claim 1,
A resin composition further comprising an organic peroxide. The method of claim 1,
A resin composition having 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 product of the resin composition has a frequency of 1 GHz or higher. The insulating film containing the resin composition of any one of Claims 1-6. A semiconductor device comprising the resin composition according to any one of claims 1 to 6 or a thermosetting product thereof as an interlayer adhesive between substrates. A semiconductor device comprising the insulating film of claim 7 or a thermosetting product thereof as an interlayer adhesive between substrates.