TW201615677A - Resin composition, and insulating film and semiconductor device using same - Google Patents

Abstract

Provided are: an insulating film as a cover lay film, the insulating film having an excellent adhesive strength with respect to a metal foil which forms wiring of an FPC and with respect to an FPC substrate material such as a polyimide film or the like, exhibiting excellent electrical properties in a high-frequency range, specifically exhibiting a low permittivity (e) and a low dielectric tangent (tand) in a frequency range of 1 to 10 GHz, and having an excellent shelf life; and a resin composition contained in said insulating film. Said resin composition contains (A) modified polyphenylene ether having ethylenically unsaturated groups at both terminals thereof, (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 contains 0.5-4 parts by mass of the component (D) with respect to total 100 parts by mass of the components (A) to (E).

Description

Resin composition, and insulating film and semiconductor device using same

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

In recent years, printed wiring boards used in electrical and electronic equipment have been progressing toward miniaturization, weight reduction, and high performance. In particular, the multilayer printed wiring board is required to have a higher multilayer, higher density, thinner thickness, lighter weight, high reliability, and moldability. Moreover, recently, the demand for high-speed transmission signals processed by printed wiring boards has been increasing. Along with this, the frequency of the transmission signal is significantly increased. Accordingly, the material used for the printed wiring board is required to reduce the electric signal loss in a high frequency region, specifically, a region having a frequency of 1 GHz or more. The adhesive film used as the interlayer adhesive used for the multilayer printed wiring board and the surface protective film (that is, the cover film) of the printed wiring board is also required to exhibit excellent electrical characteristics (low dielectric constant (in the high frequency region). e), low dielectric tangent (tand).

Patent Document 1 discloses a curable resin composition which can be cured at a low temperature by imparting a cured product having a low dielectric constant and a low dielectric tangent, and excellent heat resistance, mechanical properties, chemical resistance, and flame retardancy. And, that A hardenable film using the curable resin composition and a cured product and a film obtained by curing the same are disclosed in the literature. On the other hand, Patent Document 2 proposes a cover film which has excellent adhesion strength to a metal foil constituting a wiring of a flexible printed wiring board (FPC) and a substrate material of the flexible printed wiring board, and A high frequency region having a frequency of 1 GHz or more exhibits excellent electrical characteristics. Specifically, the cover film exhibits a low dielectric constant (e) and a low dielectric tangent at a frequency of 1 GHz or more. Further, as the cover film, an interlayer film for electrical and electronic use and an interlayer adhesive for a multilayer printed wiring board can be used.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] International Publication No. 2008-18483

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-68713

The cover film described in Patent Document 2 exhibits excellent electrical characteristics in a high frequency region after heat curing. Specifically, the film exhibits a dielectric constant of 3.0 or less in a region of a frequency of 1 to 10 GHz, and further has a dielectric constant of 2.5 or less. Further, the film exhibits a dielectric tangent of 0.01 or less in a region of a frequency of 1 to 10 GHz and further a value of 0.0025 or less.

In recent years, the requirements for high frequency characteristics have become stricter. Specifically, the dielectric ratio of the region of frequency 1 to 10 GHz is required to be 2.5. under. Further, the dielectric tangent of the region of the frequency of 1 to 10 GHz is required to be 0.0025 or less. The cover film described in Patent Document 2 satisfies this requirement. However, a film which is superior in long-term storage property to the cover film is required.

Patent Document 2 discloses a maleic imine-based curing agent as a preferred example of a curing agent for the component (E) of the cover film. According to the same document, by using a maleic amide-based hardener, heat curing of the cover film can be carried out at a lower temperature (for example, a curing temperature of usually 200 ° C can be set to 150 ° C). Among them, bismaleimide is most suitable from the viewpoint of maintaining the dielectric properties of the cover film, imparting an adhesive force to the film, and a high Tg (glass transition temperature) of the film. However, a film having a good shelf life and excellent film appearance and temporary compressibility after long-term storage is required.

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition for use in the production of an insulating film which solves the above problems of the prior art. The insulating film containing the resin composition has excellent adhesion strength to the metal foil constituting the wiring of the FPC and the substrate material of the FPC such as a polyimide film or a liquid crystal polymer. Further, the insulating film exhibits excellent electrical characteristics 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. Further, the insulating film has a good shelf life.

In order to achieve the above object, the resin composition of the present invention contains (A) a modified polyphenylene ether having an ethylenically unsaturated group at both terminals, (B) an epoxy resin, and (C) a styrene-based thermoplastic elastomer, ( D) a compound having a quinone imine group and an acrylate group in one molecule, and (E) a curing catalyst, and containing 0.5 to 4 parts by mass based on 100 parts by mass of the total of the components (A) to (E) Ingredient (D).

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

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

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

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

In the resin composition of the present invention, the thermally cured product of the resin composition preferably has a dielectric constant (e) of 2.5 or less and a dielectric tangent of 0.0025 or less in a region of a frequency of 1 to 10 GHz. Further, the insulating film of the present disclosure contains the resin composition of the present disclosure.

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

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

The insulating film formed of the resin composition of the present invention has excellent adhesion strength to a metal foil for forming a wiring of an FPC, and a substrate material of an FPC such as a polyimide film or a liquid crystal polymer. And, that The insulating film exhibits excellent electrical characteristics 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. Further, the insulating film has a good shelf life. Therefore, the film does not easily cause crystallization of components in the film during storage for a long period of time. As a result, it is not easy to cause deterioration of the appearance of the film. Further, the physical properties of the film are less likely to be deteriorated, and specifically, the temporary compressive property of the film is less likely to be lowered. Therefore, it is suitable for an adhesive film for electrical and electronic use, and a cover film for a printed wiring board. Moreover, the insulating film can be preferably used as an interlayer adhesive between substrates of a semiconductor device.

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

(A) Modified polyphenylene ether having ethylenic unsaturation at both ends

Examples of the ethylenically unsaturated group possessed by the modified polyphenylene ether having an ethylenically unsaturated group at both ends of the component (A) are exemplified by a vinyl group, an allyl group, a metallyl group, and an acryl group. An alkenyl group such as a butenyl group, a hexenyl group or an octenyl group; a cycloalkenyl group such as a cyclopentenyl group and a cyclohexenyl group; and an alkenylaryl group such as a vinylbenzyl group or a vinylnaphthyl group. Among these, a preferred example is a vinyl benzyl group. The two ethylenically unsaturated groups at both ends may be the same or different.

Change of ethylenically unsaturated group at both ends of component (A) The polyphenylene ether 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 the formula (2), R1, R2, R3, R7 and R8 may be the same or different and are an alkyl group having 6 or less carbon atoms or a phenyl group. R4, R5 and R6 may be the same or different and are a hydrogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group.

In the formula (3), R9, R10, R11, R12, R13, R14, R15 and R16 may be the same or different and are 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 a carbon number of 20 or less.

In the formula (1), -(Y-O)- is represented by the formula (4). -(Y-O)- It refers to different configurations of the same structure or random arrangement.

In the formula (4), R17 and R18 are the same or different and are an alkyl group having 6 or less carbon atoms or a phenyl group. R19 and R20 are the same or different and are a hydrogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group.

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

Examples of -A- in the formula (3) are methylene, ethylene, 1-methylethylene, 1,1-propylene, 1,4-phenylene bis(1-methyl Ethylene), 1,3-phenylene bis(1-methylethylidene), cyclohexylene, phenylmethylene, naphthylmethylene, and 1-phenylethylene There is a foundation. However, -A- is not limited to these.

Preferable examples of the modified polyphenylene ether represented by the formula (1) include R1, R2, R3, R7, R8, R17 and R18 which are an alkyl group having 3 or less carbon atoms, and R4, R5, R6, R9 and R10. R11, R12, R13, R14, R15, R16, R19 and R20 are a hydrogen atom or a compound having an alkyl group having 3 or less carbon atoms. In particular, it is preferred that the formula (2) or the formula (3)-(OXO)- represents the formula (5), the formula (6), or the formula (7), and the formula (4)-( YO)- represents a structure represented by the formula (8 (or formula (9)), or a structure represented by the formula (8) and a structure represented by the formula (9).

The method for producing the modified polyphenylene ether represented by the formula (1) is not particularly limited. For example, it can be produced by subjecting a terminal phenolic hydroxyl group of a bifunctional phenyl ether oligomer to vinylbenzyl etherification. The bifunctional phenyl ether oligomer can be obtained, for example, by oxidative coupling of 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 ends of the component (A) is measured by a GPC method, preferably in the range of 500 to 4,500, more preferably in the range of 500 to 3,000. It is better for the range of 1000~2500. When the number average molecular weight is 500 or more, when the resin composition of the present invention is in the form of a coating film, the resin composition is less likely to be sticky. Further, when the number average molecular weight is 4,500 or less, the solubility of the component (A) in the solvent can be suppressed from being lowered.

The content of the modified polyphenylene ether having an ethylenically unsaturated group at both ends of the component (A) is preferably from 30 to 60 parts by mass, more preferably from 30 to 60 parts by mass, based on 100 parts by mass of the total of the components (A) to (E). It is 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, the moldability of the insulating film containing not only the resin composition of the present invention is deteriorated, and the desired high-frequency characteristics are not easily obtained. When the amount of the component (A) is too large, the amount of the component (B) and the component (C) is decreased. Therefore, the resin of the present disclosure is included The adhesion of the insulating film of the composition deteriorates. Further, from the viewpoint of high frequency characteristics, the specific component (A) has a specific dielectric constant of 3.0 or less.

(B) Epoxy resin

Examples of the epoxy resin of the component (B) are bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin, and decyl oxide type epoxy resin. , a biphenyl type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, a hydantoin type epoxy resin, and an epoxy resin containing a naphthalene ring. One type of these epoxy resins may be used alone or two or more types may be used in combination. Further, from the viewpoint of film formability, the epoxy resin of the component (B) is preferably liquid. Moreover, from the viewpoint of improving the adhesion of the insulating film containing 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 of the component (B) is preferably from 2 to 15 parts by mass, more preferably from 4 to 12 parts by mass, even more preferably 6 parts by mass based on 100 parts by mass of the total of the components (A) to (E). ~11 parts by mass. When the component (B) is too small, the adhesion of the insulating film containing the resin composition of the present invention deteriorates. When the amount of the component (B) is too large, the amount of the component (A) and the component (C) is decreased. Therefore, the moldability and high-frequency characteristics of the insulating film containing the resin composition of the present invention are deteriorated.

(C) Styrene thermoplastic elastomer

The styrene-based thermoplastic elastomer system of component (C) means benzene A thermoplastic elastomer of an alkene, a homolog or the like. Examples of the component (C) are 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 type of these thermoplastic elastomers may be used alone or two or more types may be used in combination. The component (C) preferably contains SEEPS 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 a polyimide film or a liquid crystal polymer. The content of SEEPS in the component (C) is preferably from 10 to 70% by mass, more preferably from 10 to 50% by mass. Further, the component (C) preferably contains SEBS from the viewpoint of heat resistance.

The content of the styrene-based thermoplastic elastomer of the component (C) is preferably from 30 to 70 parts by mass, more preferably from 40 to 60 parts by mass, per 100 parts by mass of the total of the components (A) to (E). It is preferably 45 to 55 parts by mass. When the component (C) is too much, the formability deteriorates. When the amount of the component (C) is too small, the strength is deteriorated, and the formability is also deteriorated. From the viewpoint of high frequency characteristics, the component (C) used preferably has a specific dielectric constant of 3.0 or less.

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

(D) is a component which assists in the hardening of the insulating film formed using the resin composition of the present disclosure. As described above, in the cover film described in Patent Document 2, bismaleimide is used as the curing agent of the component (E). In contrast, The resin composition of the present invention uses a compound having a quinone imine group and an acrylate group in one molecule as the component (D). Therefore, compared with the insulating film using bismaleimide, the insulating film formed using the resin composition is less likely to cause crystallization of components in the film during storage for a long period of time. Therefore, it is difficult to cause deterioration of the appearance of the film. Further, it is also less likely to cause deterioration of the physical properties of the film, and specifically, it is less likely to cause a decrease in temporary compressibility. The temporary crimpability of the film is not limited to the case where an insulating film is used as the cover film, and is also required when the film is used as an adhesive film for electrical and electronic use, and when an interlayer adhesive between substrates as a semiconductor device is used. The viewpoint of maintaining the dielectric properties of the insulating film, imparting an adhesive force to the insulating film, and high Tg (glass transition point) of the insulating film using a compound having a quinone imine group and an acrylate group in one molecule of the component (D) In comparison with Bismaleimide, it is not inferior.

An example of the component (D) is yttrium acrylate. Examples of quinone imine acrylates are N-propylene methoxyethyl hexahydrophthalene imine, N-propylene methoxyethyl-1,2,3,6-tetrahydrophthalene Amine, and N-propylene methoxyethyl-3,4,5,6-tetrahydrophthaleneimide. In particular, N-propylene methoxyethylhexahydrophthalamide is preferably used.

The content of the component (D) is 0.5 to 4 parts by mass based on 100 parts by mass of the total of the components (A) to (E). When the content of the component (D) is outside the above range, the insulating film containing the resin composition of the present invention has insufficient bonding strength. The content of the component (D) is preferably from 0.5 to 3.0 parts by mass, more preferably from 0.5 to 2.5 parts by mass, per 100 parts by mass of the total of the components (A) to (E).

(E) hardening catalyst

The hardening catalyst of the component (E) can promote the hardening of the insulating film formed using the resin composition of the present disclosure. More specifically, the component (E) is a catalyst for promoting the hardening 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. Imidazole hardening catalysts are exemplified by 2-methylimidazole, 2-undecylimidazole, 1-aminoethyl-2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4 -methylimidazole, 1-cyanoethyl-2-ethyl-4-imidazole, 2-phenylimidazole, 1-benzyl-2-phenylimidazole, and 2-phenyl-4-methylimidazole Imidazole compound. 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 are triazine compounds such as 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 1,8-di A tertiary amine compound such as azabicyclo[5.4.0]undecene-7 (DBU), triethylenediamine, benzyldimethylamine, and triethanolamine. Among them, a preferred example is 2,4-diamino-6-[2'-methylimidazolium-(1')]ethyl-s-triazine. Further, examples of the phosphorus-based curing catalyst are triphenylphosphine, tributylphosphine, tris(p-methylphenyl)phosphine, and tris(nonylphenyl)phosphine. Among these, an imidazole-based curing catalyst is preferably used in order to adjust the moderate hardenability. Further, the imidazole-based curing catalyst having a benzene ring can be extended by using the insulating film formed by using the resin composition of the present invention. Examples of the imidazole-based curing catalyst are 2-phenylimidazole, 1-benzyl-2-phenylimidazole, and 2-phenyl-4-methylimidazole. In particular, 1-benzyl-2-phenylimidazole is preferred.

The content of the component (E) is appropriately selected depending on the kind of the curing catalyst to be used as the component (E). When the imidazole-based curing catalyst is used as the component (E), it is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, even more preferably 1 part by mass based on 100 parts by mass of the epoxy resin of the component (B). ~10 parts by mass. When the content of the component (E) is too small, the hardenability is deteriorated. On the other hand, when the content of the component (E) is too large, the storage period of the insulating film is deteriorated.

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

(F) organic peroxide

Examples of the organic peroxide of the component (F) are t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, and tert-butylperoxy-2-ethyl. Hexyl carbonate, tert-butylperoxyacetate, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di- Tributyl peroxide, 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, tert-butyl hydroperoxide, p-menthane hydrogen peroxide, benzhydryl peroxide, p-chlorobenzylidene peroxide, tert-butyl Peroxyisobutyrate, hydroxyheptyl peroxide, and dichlorohexanone peroxide. By adding the organic peroxide of the component (F), the hardening reaction of the component (A) can be promoted, and the reactivity can be stabilized. Consider thinning the resin composition of the present disclosure When used, the component (F) is preferably a compound which is not activated in a temperature range of 60 to 120 ° C in the drying step of the thin film formation, and which is activated in a temperature region above it. An example of such a component (F) is exemplified by a tert-butylperoxybenzoate.

(other formulating agents)

The resin composition of the present invention may further contain components other than the above components (A) to (F) as needed. Specific examples of the components to be blended are decane coupling agents, antifoaming agents, flow regulating agents, film forming assistants, dispersing agents, and inorganic particles. The type and amount of each formulation can be selected according to the usual methods.

On the other hand, a component which adversely affects the high-frequency characteristics of the insulating film containing the resin composition of the present invention may not be contained. Examples of such components are listed as liquid rubber and flame retardant.

(modulation of resin composition)

The resin composition of the present disclosure can be produced by a conventional method. For example, in the presence of a solvent, the above components (A) to (D) are mixed by a heating and mixing kneader (including other components when other optional components are contained). The mixing conditions are, for example, a number of revolutions of the kneader of 100 to 1000 rpm, a mixing temperature of 80 ° C, and a mixing time of 3 hours. After cooling the obtained mixture, the component (E) (the resin composition contains the component (F) and the component (F) is further contained) is added to the mixture. Finally, 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 disclosure.

The resin composition of the present disclosure has the following good characteristics.

The thermally cured product of the resin composition of the present invention exhibits excellent electrical characteristics in a high frequency region. Specifically, the dielectric constant (e) of the thermally cured product of the resin composition in the region of the frequency of 1 to 10 GHz is preferably 2.5 or less, more preferably 2.4 or less. Further, the dielectric tangent 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 are in the above range, the electrical signal loss in the frequency range of 1 to 10 GHz can be reduced.

The thermally cured product of the resin composition of the present disclosure has sufficient bonding strength. Specifically, the peeling strength (180° peeling) of the roughened surface of the copper foil measured by the heat-cured material of the resin composition according to JIS K6854-2 is preferably 7 N/cm or more, more preferably 8 N/cm or more. Further, the peel strength (90° peeling) for the liquid crystal polymer film measured according to JIS K6854-1 is preferably 6 N/cm or more, more preferably 7 N/cm or more.

The insulating film of the present disclosure can be obtained by a conventional method from the resin composition of the present disclosure. For example, the resin composition of the present disclosure is diluted with a solvent to prepare a paint. The resulting paint is applied to at least one side of the support. The paint on the support is dried, whereby the insulating film of the present disclosure can be provided as a film with a support or a film peeled off from the support.

Examples of the solvent which can be used as the paint are 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 amount of the solvent to be used is not particularly limited. A solvent of the amount used in the past can be used. The preferred amount of the solvent is from 20 to 90% by mass based on the solid content.

The support is not particularly limited. A support having a desired form suitable for the method for producing a film can be appropriately selected. Examples of the support used are 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 peeled off from the support as a film, it is preferred to use a support which is subjected to mold release treatment with a polysiloxane or the like.

The method of applying the paint is not particularly limited. Examples of methods that can be used are the slit die method, the gravure method, and the blade coater method. In these ways, the most suitable mode can be selected depending on the desired film thickness. In particular, in order to design a thin film thickness, a gravure method is preferably used. The coating can be carried out in such a manner that the thickness of the film formed after drying becomes a desired thickness. This thickness can be derived from the solvent content by those skilled in the art.

The thickness of the insulating film of the present disclosure is appropriately designed based on characteristics such as mechanical strength required for the use of the film. The film thickness is generally from 1 to 100 μm. The film thickness at the time of film formation is preferably from 1 to 30 μm.

The drying conditions are not particularly limited. The drying conditions are appropriately set depending on the type and amount of the solvent used in the paint, the amount of the paint used, and the coating thickness. For example, drying can be carried out at 60 to 100 ° C under atmospheric pressure.

The insulating film of the present disclosure has a good shelf life. The insulating film is less likely to deteriorate in appearance of the film due to crystallization of components in the film even during storage for a long period of time. Moreover, in the long-term preservation, it is still not easy to cause later The temporary compressibility of the film measured in the order is lowered.

The insulating film of the present disclosure can be used as an adhesive film for electrical and electronic use by the following sequence. The insulating film of the present invention is placed on the succeeding surface of an object by using the insulating film of the present invention in the next two objects. Subsequently, another object is placed on the film in such a manner that it is brought into contact with the exposed face of the insulating film. Here, when the insulating film with the support is used, the insulating film is placed on the succeeding surface so that the exposed surface of the insulating film contacts the bonded surface of the object, thereby temporarily insulating the insulating film. Pressed on the surface to be pressed. Here, the temperature at the time of temporary pressing can be set to, for example, 130 °C.

Then, the surface of the insulating film exposed by peeling off the support after the temporary pressing is placed so that the contact surface of the other object comes into contact with the exposed surface of the insulating film. After the temporary pressing is performed in the order, heat pressing is performed for a specific time at a specific temperature. Subsequently, the film is heat-hardened. Further, the hot pressing step may be omitted. The temperature at the time of hot pressing is preferably from 100 to 150 °C. The hot pressing time is preferably 0.5 to 10 minutes. The temperature for heat hardening is preferably from 150 to 200 °C. The heat hardening time is preferably from 30 to 120 minutes. Further, instead of using a pre-film, a paint obtained by diluting the resin composition of the present invention in a solvent may be applied to the surface to be bonded of a subsequent object and dried, and then the substrate may be placed in the order after the object is placed. The person.

The insulating film of the present disclosure can be used as a cover film by the following procedure. The insulating film of the present invention is disposed at a specific position of the resin substrate on which the wiring pattern is formed on the main surface, that is, the cover film is disposed at a position covered with the insulating film on the side where the wiring pattern is formed. membrane. Subsequently, temporary pressing, hot pressing, and heat hardening can be performed at a specific temperature and at a specific time. Moreover, the hot pressing step can also be omitted. The temperature and time for the temporary pressing, the hot pressing, and the heat curing are the same as those for the above-mentioned film for electrical and electronic use.

The insulating film of the present disclosure can also be used as an interlayer adhesive between substrates of a semiconductor device. In this case, the object to be described next becomes a plurality of laminated substrates constituting the semiconductor device. Further, as the interlayer adhesive between the substrates of the semiconductor device, a paint obtained by diluting the resin composition of the present disclosure with a solvent may be used instead of the pre-filmer.

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

[Examples]

Hereinafter, the present disclosure will be described in detail by way of examples. However, the disclosure is not limited to the embodiments.

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

Sample preparation and determination method

Each component was metered in a blending ratio (parts by mass) as shown in the following table. Subsequently, the components were placed in a reaction vessel which had been warmed to 80 °C. Next, the components to be charged were mixed at a number of revolutions of 250 rpm and atmospheric pressure for 3 hours. However, the curing catalyst of the component (E) and the organic peroxide of the component (F) are added after cooling. a paint containing the resin composition thus obtained The material is coated on one side of a support (PET film subjected to release treatment), and dried at 100 ° C (80 ° C when the organic peroxide of the component (F) is contained) to obtain insulation with a support. film.

Also, the abbreviations in the table are shown below.

Ingredient (A)

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

Ingredient (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

Ingredient (C)

TUFTEC H1052: Polystyrene-poly(ethylene/propylene) 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.

Ingredient (D)

M-140: 醯imino acrylate (N-propylene methoxyethyl hexahydrophthalamide), manufactured by Toagosei Co., Ltd.

(ingredient (D’)

BMI-70: Bismaleimide, KI Chemical Co., Ltd.

M-5300: Monoacrylate (ω-carboxy-polycaprolactone monoacrylic acid) Ester), East Asia Synthetic Co., Ltd.

Ingredient (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.

Ingredient (F)

PERBUTYL Z: Tert-butylperoxybenzoate, manufactured by Nippon Oil Co., Ltd.

Other ingredients

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

Dielectric ratio (e), dielectric tangent: The insulating film was heat-hardened at 200 ° C (180 ° C in the case of the organic peroxide containing the component (F)), and then peeled off from the support. Subsequently, a test piece (40 ± 0.5 mm × 100 ± 2 mm) was cut out from the insulating film, and the thickness was measured. The dielectric constant (e) and dielectric tangent (t) of a test piece wound into a cylindrical shape of 100 mm in length and 2 mm in diameter or less were measured by a cavity resonator perturbation method (10 GHz).

Peeling strength (Cu): Copper foil (CF-T8, manufactured by Fukuda Metal Foil Powder Co., Ltd., thickness: 18 μm) was bonded to the inner side of the insulating film which was peeled off from the support. Next, the insulating film was heat-cured under the conditions of 200 ° C, 60 min, and 10 kgf (in the case of the organic peroxide containing the component (F) at 180 ° C, 60 min, and 10 kgf) using a press machine. The test piece was cut at a width of 10 mm. Peel strength was measured according to JIS K6854-2 using Autograph peeling (180 Degree peeling).

Peel strength (LCP): A liquid crystal polymer (LCP) film (VECSTAR CT-Z, manufactured by Kuraray Co., Ltd., 25 μm) was attached to one surface of an insulating film peeled off from a support. Next, the FR4 substrate was bonded to the other surface of the insulating film. Subsequently, it was heat-hardened under the conditions of 200 ° C, 60 min, and 10 kgf (the conditions of the organic peroxide containing the component (F) were 180 ° C, 60 min, and 10 kgf). Subsequently, peeling strength (90 degree peeling) was measured by Autograph peeling according to JIS K6854-1.

Temporary pressing property: an insulating film with a support prepared in the above-described order was laminated on a liquid crystal polymer (LCP) film (VECSTAR CT-Z, manufactured by Kuraray Co., Ltd., 25 μm) at 130 ° C in a roll laminator. on. After lamination, the support is peeled off. Subsequently, the LCP film laminated with the insulating film is bent. At the time of bending, the evaluation of the temporary crimping property when the films were not peeled off each other was indicated by ○. The evaluation when the films were peeled from each other is indicated by ×. The temporary compressibility of the insulating film with a support stored in a normal temperature atmosphere at 3 months after the production was also evaluated in the same order.

The test pieces used in Examples 1 to 10 were excellent in high-frequency electrical characteristics (dielectric ratio (e), dielectric tangent), peel strength, and temporary compressibility. The difference between Example 1 and Examples 2 to 10 is as follows.

Example 2: Free of ingredients (F)

Examples 3 and 4: Containing no component (F). And the content of the component (D) is different.

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). Further, a decane coupling agent was added as another component.

Example 7: The content of the component (D) and the type of the curing catalyst of the component (E) were different. Also, it does not contain the component (F). Further, a decane coupling agent was added as another component.

Example 8: The types of the curing catalyst of the component (E) were different. Further, a decane coupling agent was added as another component.

Example 9: The type of the epoxy resin of the component (B) and the type of the curing catalyst of the component (E) were different. Further, a decane coupling agent was added as another component.

Example 10: The type of the curing catalyst of the component (E) was different. Further, it does not contain the component (F).

In Comparative Examples 1 and 2 in which bis-iminide substituted for the component (D) of the bismuth imide was used, the temporary compressibility was poor after 3 months. In Comparative Example 1 in which the content of bismaleimide was high, the dielectric tangent was poor in high frequency electrical characteristics. In Comparative Example 3 in which a monoacrylate was used in place of the quinone imine acrylate of the component (D), the peel strength to the LCP film was low. Moreover, in the high frequency electrical characteristics, the dielectric tangent is poor. 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 excessive, the peel strength to the LCP film was low.

The resin composition of the embodiment of the present disclosure may be the following resin compositions of the first to sixth embodiments.

The resin composition of the first aspect is characterized by comprising (A) a modified polyphenylene ether having an ethylenically unsaturated group at both terminals, (B) an epoxy resin, and (C) a styrene-based thermoplastic elastomer, (D) a compound having a quinone imine group and an acrylate group in one molecule, and (E) a curing catalyst, and containing 0.5 to 4 parts by mass based on 100 parts by mass of the total of the components (A) to (E). The aforementioned component (D).

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

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

The resin composition of the fourth aspect is the resin composition of any one of the above-mentioned first to third aspects of the hardening catalyst of the component (E) having an imidazole-based curing catalyst of a benzene ring.

The resin composition of the fifth aspect is a resin composition according to any one of the above first to fourth aspects, which further comprises (F) an organic peroxide.

In the resin composition of the sixth aspect, the thermosetting material of the resin composition has a dielectric constant (e) of 2.5 or less in a region having a frequency of 1 GHz or more, and the first to fifth dielectrics having a dielectric tangent of 0.0025 or less. A resin composition of either.

Further, the insulator film of the embodiment of the present invention may be formed of the resin composition of any one of the above 1 to 6.

Further, the semiconductor device according to the embodiment of the present disclosure may be the semiconductor device according to the first or second aspect below.

In the first semiconductor device of the first aspect, the resin composition of any one of the above first to sixth is used in the interlayer between the substrates.

In the first semiconductor device described above, the insulating film is used in the interlayer between the substrates.

Claims (9)

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