JP6458985B2 - Resin composition, insulating film using the same, and semiconductor device - Google Patents

Description

The present invention relates to a resin composition, an insulating film using the same, and a semiconductor device.
The insulating film of the present invention is suitable for an adhesive film for electrical / electronic applications or a coverlay film for printed wiring boards.
The semiconductor device of the present invention uses the resin composition of the present invention or the insulating film of the present invention for interlayer adhesion between substrates.

In recent years, printed wiring boards used in electrical and electronic equipment have been reduced in size, weight, and performance, especially for multilayer printed wiring boards. Thinning, lightening, high reliability, moldability, etc. are required.
In addition, with the recent demand for higher speed transmission signals in printed wiring boards, the frequency of transmission signals has increased significantly. Thereby, it is required that the material used for the printed wiring board can reduce electric signal loss in a high frequency region, specifically, in a region having a frequency of 1 GHz or more.
Excellent electrical properties in the high frequency range (low dielectric constant (ε), low) are also used for interlayer adhesives used in multilayer printed wiring boards and adhesive films used as surface protective films (ie, coverlay films) for printed wiring boards. It is required to show a dielectric loss tangent (tan δ)).

Patent Document 1 provides a curable resin composition that has a low dielectric constant, a low dielectric loss tangent, and has excellent heat resistance, mechanical properties, chemical resistance, and flame retardancy, and can be cured at low temperature. Curable films, cured products obtained by curing these films, and films are disclosed.
On the other hand, Patent Document 2 discloses a high-frequency region having excellent adhesive strength with respect to a metal foil forming a flexible printed wiring board (FPC) and a substrate material of the flexible printed wiring board, and having a frequency of 1 GHz or more. In particular, a coverlay film has been proposed that exhibits a low dielectric constant (ε) and a low dielectric loss tangent (tan δ) in a region of a frequency of 1 GHz or higher. This coverlay film can also be used for adhesive films for electrical and electronic applications and interlayer adhesion of multilayer printed wiring boards.

International Publication No. 2008-18484 JP 2011-68713 A

  The coverlay film described in Patent Document 2 is excellent in electrical characteristics at high frequencies after heat curing, and the dielectric constant in the frequency range of 1 to 10 GHz is 3.0 or less, and further 2.5 or less. Can do. Further, the dielectric loss tangent (tan δ) in the frequency region of 1 to 10 GHz can be set to 0.01 or less, and further to 0.0025 or less.

The demand for high-frequency characteristics is becoming more and more demanding. The dielectric constant in the frequency range of 1 to 10 GHz is required to be 2.5 or less, and the dielectric loss tangent (tan δ) in the frequency range of 1 to 10 GHz is 0. .0025 or less.
Although the coverlay film described in Patent Document 2 can satisfy this requirement, it has become clear that there is a problem in terms of long-term storage.

In the coverlay film described in Patent Document 2, as the curing agent for the component (E), the heat curing of the coverlay film is allowed to proceed at a lower temperature (for example, what is usually cured at 200 ° C. is cured at 150 ° C.). In view of the above, maleimide-based curing agents are preferred, and among them, bismaleimide is preferred from the viewpoints of maintaining dielectric properties, imparting adhesive strength, and increasing Tg (glass transition point).
However, when bismaleimide is used as the curing agent for component (E), crystallization occurs in the film during long-term storage, and the appearance of the film deteriorates.
Also, when using the coverlay film, the film with the substrate is temporarily pressure-bonded on the FPC, and then the substrate is peeled off and then heated and cured. During long-term storage, the bismaleimide crystallizes over time. As it progresses, the provisional pressure-bonding property deteriorates, which causes a problem.

  In order to solve the above-described problems of the prior art, the present invention has excellent adhesive strength for FPC substrate materials such as metal foil, polyimide film, liquid crystal polymer, etc., which form FPC wiring, and in a high frequency region. Insulating film exhibiting low dielectric constant (ε) and low dielectric loss tangent (tan δ) in a frequency range of 1 to 10 GHz, and having a good shelf life, and the insulation It aims at providing the resin composition used for manufacture of a film.

In order to achieve the above object, the present invention provides:
(A) a modified polyphenylene ether having an ethylenically unsaturated group at both ends;
(B) epoxy resin,
(C) styrenic thermoplastic elastomer,
(D) a compound having an imide group and an acrylate group in one molecule, and
(E) A curing catalyst is contained, 30 to 50 parts by mass of component (A), 2 to 15 parts by mass of component (B), and 100 parts by mass of component (A) to component (E) in total. A resin composition comprising 40 to 60 parts by mass of (C) and 0.5 to 4 parts by mass of the component (D) is provided.

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

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

In the resin composition of the present invention, the thermoset of the resin composition has a dielectric constant (ε) of 2.5 or less and a dielectric loss tangent (tan δ) of 0.0025 or less in a frequency range of 1 to 10 GHz. More preferably.
Moreover, this invention provides the insulating film formed from the resin composition of this invention.

  The present invention also provides a semiconductor device in which the resin composition of the present invention is used for interlayer adhesion between substrates.

  The present invention also provides a semiconductor device in which the insulating film of the present invention is used for interlayer adhesion between substrates.

  The insulating film formed from the resin composition of the present invention has excellent adhesive strength for FPC substrate materials such as metal foil, polyimide film, liquid crystal polymer film, etc. that form FPC wiring, and has a high frequency range. Electrical characteristics, specifically, a low dielectric constant (ε) and a low dielectric loss tangent (tan δ) in a frequency range of 1 to 10 GHz. In addition, the shelf life is good, and even during long-term storage, the components in the film are less likely to crystallize. Decline is unlikely to occur. Therefore, it is suitable for an adhesive film for electrical / electronic applications and a coverlay film for printed wiring boards. Further, it is suitable for interlayer adhesion 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 the following components (A) to (E) as essential components.

(A) Modified polyphenylene ether having an ethylenically unsaturated group at both ends As the ethylenically unsaturated group in the modified polyphenylene ether having an ethylenically unsaturated group at both ends of the component (A), an ethenyl group, an allyl group, Alkenyl groups such as methallyl group, propenyl group, butenyl group, hexenyl group, and octenyl group; cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group; and alkenyl aryl groups such as vinylbenzyl group and vinylnaphthyl group. A benzyl group is preferred. The two ethylenically unsaturated groups at both ends may be the same functional group or different functional groups.

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

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

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

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

In Formula (1),-(YO)-is represented by General Formula (4), and one type of structure or two or more types of structures are randomly arranged.

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

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

  Examples of -A- in formula (3) include methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis (1-methylethylidene), 1,3-phenylenebis (1- Examples thereof include, but are not limited to, divalent organic groups such as methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethylidene.

As the modified polyphenylene ether represented by the formula (1), R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₁₇ and R ₁₈ are alkyl groups having 3 or less carbon atoms, and R ₄ , R ₅ , R ₆ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₉ , R ₂₀ are preferably hydrogen atoms or alkyl groups having 3 or less carbon atoms, particularly -(O-X-O)-represented by the general formula (2) or the general formula (3) is the general formula (5), the general formula (6), or the general formula (7). It is more preferable that — (YO) — represented by 4) is the formula (8) or the formula (9), or a structure in which the formula (8) and the formula (9) are randomly arranged. .

  The production method of the modified polyphenylene ether represented by the formula (1) is not particularly limited. For example, the terminal phenol of a bifunctional phenylene ether oligomer obtained by oxidative coupling of a bifunctional phenol compound and a monofunctional phenol compound. It can be produced by converting a functional hydroxyl group into vinylbenzyl ether.

  The number average molecular weight of the modified polyphenylene ether having an ethylenically unsaturated group at both ends 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, it is the range of 1000-2500. If the number average molecular weight is 500 or more, it is difficult to stick when the resin composition of the present invention is formed into a coating, and if it is 4500 or less, a decrease in solubility in a solvent can be prevented.

The modified polyphenylene ether having an ethylenically unsaturated group at both ends of the component (A) is preferably contained in an amount of 30 to 60 parts by mass with respect to 100 parts by mass in total of the components (A) to (E). More preferably, 50 parts by mass are contained, and still more preferably 35-45 parts by mass.
When there are too few components (A), the moldability of the insulating film formed using the resin composition of this invention will deteriorate, and it will become difficult to obtain a desired high frequency characteristic. When there are too many components (A), since the quantity of a component (B) and a component (C) will reduce relatively, the adhesiveness of the insulating film formed using the resin composition of this invention will deteriorate. Moreover, as a component (A), it is preferable to use a thing with a dielectric constant of 3.0 or less from a viewpoint of a high frequency characteristic.

(B) Epoxy resin As the epoxy resin of component (B), for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin, siloxane type epoxy resin, biphenyl type epoxy resin Glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, and naphthalene ring-containing epoxy resin. In the epoxy resin composition, the compounds exemplified here may be used alone or in combination of two or more. In addition, it is preferable that the epoxy resin of a component (B) is liquid from a viewpoint of the moldability of a film.
Moreover, since the epoxy resin of a component (B) is an epoxy resin which has a naphthalene skeleton, since the adhesiveness of the insulating film formed using the resin composition of this invention improves, it is preferable.

The component (B) epoxy resin is preferably contained in an amount of 2 to 15 parts by weight, more preferably 4 to 12 parts by weight, based on a total of 100 parts by weight of the components (A) to (E). More preferably, it is contained in 11 parts by mass.
When there are too few components (B), the adhesiveness of the insulating film formed using the resin composition of this invention will deteriorate. If the amount of the component (B) is too large, the amount of the component (A) and the component (C) is relatively reduced, so that the moldability of the insulating film formed using the resin composition of the present invention is deteriorated. The high frequency characteristic of the insulating film formed using the resin composition of this invention deteriorates.

(C) Styrenic thermoplastic elastomer The styrene thermoplastic elastomer of the component (C) refers to a thermoplastic elastomer containing styrene, a homologue 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), and styrene-butadiene block copolymer (SBS). ), Styrene-isoprene-styrene block copolymer (SIS), and polybutadiene (PB). The compounds exemplified here may be used alone or in combination of two or more. From the viewpoint of improving the adhesive strength of the FPC substrate material such as a metal foil, a polyimide film, or a liquid crystal polymer that forms an FPC wiring, the component (C) preferably contains SEEPS. The amount of SEEPS in the component (C) is preferably 10 to 70% by mass, and more preferably 10 to 50% by mass. Moreover, it is preferable that a component (C) contains SEBS from a heat resistant viewpoint.

The styrene-based thermoplastic elastomer of component (C) is preferably contained in an amount of 30 to 70 parts by mass, more preferably 40 to 60 parts by mass with respect to 100 parts by mass in total of components (A) to (E). Preferably, 45 to 55 parts by mass are contained.
When there are too many components (C), a moldability will deteriorate. When there are too few components (C), adhesive strength will deteriorate and also a moldability will also deteriorate. Moreover, as a component (C), it is preferable to use a thing with a dielectric constant of 3.0 or less from a viewpoint of a high frequency characteristic.

(D) Compound having an imide group and an acrylate group in one molecule Component (D) is a component that assists in curing an insulating film formed using the resin composition of the present invention. As described above, in the coverlay film described in Patent Document 2, since bismaleimide is used as the curing agent for the component (E), crystallization occurs in the film during long-term storage, and the appearance of the film deteriorates. In addition, since the crystallization of bismaleimide progresses with time in the film, there is a problem because the temporary press bonding property is lowered when the coverlay film is used.
On the other hand, since the resin composition of the present invention uses a compound having an imide group and an acrylate group in one molecule as the component (D), a long-term insulating film formed using the resin composition is used. During storage, the components in the film are hardly crystallized, and the appearance of the film is deteriorated, the physical properties of the film are deteriorated, specifically, the temporary press bonding property of the film is hardly deteriorated. Temporary pressure bonding of the film is required not only when the insulating film is used as a coverlay film, but also when used as an adhesive film for electrical and electronic applications or when used for interlayer adhesion between substrates of semiconductor devices. It is a characteristic.
A compound having an imide group and an acrylate group in one molecule used as the component (D) is comparable to bismaleimide in terms of maintaining dielectric properties, imparting adhesive force, and increasing Tg (glass transition point). .

  Examples of the component (D) include imide acrylate. Examples of the imide acrylate include N-acryloyloxyethyl hexahydrophthalimide, N-acryloyloxyethyl-1,2,3,6-tetrahydrophthalimide, and N-acryloyloxyethyl-3,4,5,6-tetrahydrophthalimide. In particular, N-acryloyloxyethyl hexahydrophthalimide is preferred.

Content of a component (D) is 0.5-4 mass parts with respect to a total of 100 mass parts of a component (A) -component (E). When content of a component (D) is outside said range, the insulating film formed using the resin composition of this invention cannot obtain desired adhesive strength.
The content of the component (D) is preferably 0.5 to 3.0 parts by mass, and 0.5 to 2.5 parts by mass with respect to a total of 100 parts by mass of the components (A) to (E). It is more preferable that

(E) Curing catalyst The curing catalyst of component (E) accelerates the curing of the insulating film formed by using the resin composition of the present invention, more specifically, the curing reaction of the epoxy resin of component (B). It is a catalyst.
Examples of the component (E) include an imidazole curing catalyst, an amine curing catalyst, and a phosphorus curing catalyst. Examples of imidazole-based curing catalysts include 2-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl. Examples include imidazole compounds such as -4-imidazole, 2-phenylimidazole, 1-benzyl-2-phenylimidazole, and 2-phenyl-4-methylimidazole. Of these, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-ethyl-4-imidazole are preferable. Examples of amine-based curing catalysts include triazine compounds such as 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 1,8-diazabicyclo [5,4,0] undecene. And tertiary amine compounds such as -7 (DBU), triethylenediamine, benzyldimethylamine, and triethanolamine. Among these, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine is preferable. Examples of the phosphorus curing catalyst include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, and tri (nonylphenyl) phosphine. Among these, an imidazole-based curing catalyst is preferable because it can be adjusted with appropriate curability. Furthermore, an imidazole-based curing catalyst having a benzene ring is more preferable because the shelf life of an insulating film formed using the resin composition of the present invention can be increased. Examples of such an imidazole-based curing catalyst include 2-phenylimidazole, 1-benzyl-2-phenylimidazole, and 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole is particularly preferable.

Content of a component (E) is suitably selected according to the kind of curing catalyst used as a component (E). When using an imidazole-type curing catalyst as a component (E), it is preferable that it is 0.01-20 mass parts with respect to 100 mass parts of epoxy resins of a component (B), and is 0.1-15 mass parts. More preferably, the amount 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), there exists a problem which the shelf life of an insulating film deteriorates.

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

(F) Organic peroxide Examples of the organic peroxide of component (F) include t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate, and t-butyl. Peroxyacetate, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl 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, t-butyl hydroperoxide, p-me Nthane hydroperoxide, benzoyl peroxide, p-chlorobenzoyl peroxide, t-butyl peroxyisobutyrate, hydroxyheptyl peroxide, dichlorohexanone peroxide and the like. By adding the organic peroxide of component (F), the curing reaction of component (A) can be promoted, and the reactivity can be stabilized.
Considering that the resin composition of the present invention is used in the form of a film, the component (F) is not activated in the temperature range of 60 to 120 ° C. in the drying step of film formation, and is active in a temperature range higher than that. It is preferable that Examples of such component (F) include t-butyl peroxybenzoate.

(Other ingredients)
The resin material composition of this invention may further contain components other than the said component (A)-component (F) as needed. Specific examples of such components include silane coupling agents, antifoaming agents, flow control agents, film forming aids, dispersants, inorganic particles, and the like. The type and amount of each compounding agent are as usual.

  On the other hand, it is preferable not to contain a component that adversely affects the high-frequency characteristics of the insulating film formed using the resin composition of the present invention. Examples of such components include liquid rubber and flame retardant.

(Preparation of resin composition)
The resin composition of the present invention can be produced by a conventional method. For example, in the presence of a solvent, the above components (A) to (D) (if any other optional components are included, these optional components are further mixed) by a heat mixing kneader (rotation speed: 100 to 1000 rpm, 80 ° C. 3 hours).
After cooling this, component (E) (or further component (F) when the resin composition contains component (F)) can be added and stirred at room temperature for 30 to 60 minutes.

  The resin composition of the present invention has suitable characteristics shown below.

As for the resin composition of this invention, the thermosetting material is excellent in the electrical property in a high frequency. Specifically, the thermosetting product of the resin composition preferably has a dielectric constant (ε) of 2.5 or less, more preferably 2.4 or less in a frequency range of 1 to 10 GHz. Further, the dielectric loss tangent (tan δ) in the frequency region of 1 to 10 GHz is more preferably 0.0025 or less, and more preferably 0.0022 or less.
When the dielectric constant (ε) and the dielectric loss tangent (tan δ) in the frequency range of 1 to 10 GHz are in the above ranges, the electric signal loss in the frequency range of 1 to 10 GHz can be reduced.

In the resin composition of the present invention, the thermosetting product of the resin composition of the present invention has sufficient adhesive strength. Specifically, the thermoset of the resin composition preferably has a peel strength (180 degree peel) with respect to the roughened copper foil surface measured according to JIS K6854-2 of 7 N / cm or more, more preferably. 8 N / cm or more.
Moreover, it is preferable that the peel strength (90 degree | times peel) with respect to the liquid crystal polymer film measured based on JISK6854-1 is 6 N / cm or more, More preferably, it is 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 obtain a varnish, which is applied to at least one side of a support and dried, and then provided as a film with a support or a film peeled from the support. be able to.

  Examples of the solvent that can be used as the varnish include ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; high-boiling solvents such as dioctyl phthalate and dibutyl phthalate. Although the usage-amount of a solvent is not specifically limited, Although it can be set as the quantity conventionally used, Preferably, it is 20-90 mass% with respect to solid content.

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

  The method for applying the varnish is not particularly limited, and examples thereof include a slot die method, a gravure method, a doctor coater method, and the like, which are appropriately selected according to a desired film thickness and the like. This is preferable because it can be designed to be thin. Application | coating is performed so that the thickness of the film formed after drying may turn into desired thickness. Such a thickness can be derived from the solvent content by those skilled in the art.

  The thickness of the insulating film of the present invention is appropriately designed based on properties such as mechanical strength required according to the application, but is generally 1 to 100 μm, and 1 to 30 μm when thinning is required. Preferably there is.

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

The insulating film of the present invention has a good shelf life, and the appearance of the film is hardly deteriorated due to crystallization of components in the film even during long-term storage.
Further, even during long-term storage, the temporary press-bonding property of the film, which is measured by the procedure described later, is unlikely to decrease.

When the insulating film of the present invention is used as an adhesive film for electrical / electronic applications, the procedure for use is as follows.
Among the objects to be bonded using the insulating film of the present invention, after mounting the insulating film of the present invention on the bonded surface of one target object, the bonded surface of the other object is exposed of the insulating film. Place it in contact with the surface. Here, when using an insulating film with a support, place the insulating film so that the exposed surface of the insulating film is in contact with the adherend surface of one object, and temporarily press the insulating film onto the adherend surface. To do. Here, the temperature at the time of temporary pressure bonding can be set to 130 ° C., for example.
Next, the other object is placed on the surface of the insulating film exposed by peeling off the support after temporary pressure bonding so that the surface to be bonded is in contact with the exposed surface of the insulating film. After performing these procedures, thermocompression bonding is performed for a predetermined temperature and for a predetermined time, and then heat-cured. The thermocompression bonding process may be omitted.
The temperature during thermocompression bonding is preferably 100 to 150 ° C. The time for thermocompression bonding is preferably 0.5 to 10 minutes.
The temperature for heat curing is preferably 150 to 200 ° C. The heat curing time is preferably 30 to 120 minutes.
Instead of using a pre-filmed one, the varnish obtained by diluting the resin composition of the present invention with a solvent is applied to the adherend surface of one object to be bonded and dried, and then the one object described above is used. You may implement the procedure which mounts an object.

When the insulating film of the present invention is used as a coverlay film, the usage procedure is as follows.
The cover lay film is disposed at a predetermined position on the resin substrate with wiring having a wiring pattern formed on the main surface, that is, at a position where the insulating film of the present invention is covered with the insulating film on the side on which the wiring pattern is formed. After that, temporary pressing, thermocompression bonding, and heat curing may be performed for a predetermined temperature and a predetermined time. The thermocompression bonding process may be omitted. The temperature and time for temporary pressure bonding, thermocompression bonding, and heat curing are the same as in the case of using as an adhesive film for the electrical / electronic applications.

  The insulating film of the present invention can be used for interlayer adhesion between substrates of a semiconductor device. In this case, the above-described object to be bonded becomes a plurality of substrates that are stacked in a plurality of layers that constitute the semiconductor device. For interlayer adhesion 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 using a film formed in advance.

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

(Examples 1-10, Comparative Examples 1-5)
Sample preparation and measurement method Each component was metered and blended so as to have the blending ratio (parts by mass) shown in the following table, and then charged into a reaction kettle heated to 80 ° C., while rotating at a rotational speed of 250 rpm. Normal pressure mixing was performed for 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 is applied to one side of a support (PET film which has been subjected to a release treatment), and 100 ° C. (80 ° C. in the case of containing an organic peroxide of component (F)). ) To obtain an insulating film with a support.
In addition, the symbol in a table | surface represents the following, respectively.
Ingredient (A)
OPE2200: oligophenylene ether (modified polyphenylene ether represented by the above general formula (1) (-(O—X—O) — in the formula (1) is the general formula (5), and − in the formula (1) (YO)-is the formula (8)) (Mn = 2200), manufactured by Mitsubishi Gas Chemical Company, Inc.
Ingredient (B)
NC3000H: biphenyl type epoxy resin, Nippon Kayaku Co., Ltd. 828: bisphenol A type epoxy resin, Mitsubishi Chemical Corporation HP4032D: naphthalene type epoxy resin, manufactured by DIC Corporation
Ingredient (C)
Tuftec H1052: Polystyrene-poly (ethylene / butylene) block-polystyrene (SEBS)), Septon 4044 manufactured by Asahi Kasei Chemicals Corporation: Polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene (SEEPS), manufactured by Kuraray Co., Ltd.
Ingredient (D)
M-140: Imido acrylate (N-acryloyloxyethyl hexahydrophthalimide), manufactured by Toagosei Co., Ltd.
Ingredient (D ')
BMI-70: Bismaleimide, manufactured by Kay Kasei Co., Ltd. M-5300: Monoacrylate (ω-carboxy-polycaprolactone monoacrylate), Toagosei Co., Ltd.
Ingredient (E)
2E4MZ: 2-ethyl-4-methylimidazole, manufactured by Shikoku Chemicals Co., Ltd. 1B2PZ: 1-benzyl-2-phenylimidazole, manufactured by Shikoku Chemicals Co., Ltd.
Ingredient (F)
Perbutyl Z: tert-butyl peroxybenzoate, manufactured by NOF Corporation
Other components KBM403: Silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.

Dielectric constant (ε), dielectric loss tangent (tan δ): The insulating film is heated and cured at 200 ° C. ((180 ° C. when the organic peroxide of component (F) is included)), peeled from the support, and then the insulating film A test piece (40 ± 0.5 mm × 100 ± 2 mm) was cut out from the film, and the thickness was measured. The test piece was rolled into a cylindrical shape having a length of 100 mm and a diameter of 2 mm or less, and a dielectric constant (ε) and a dielectric loss tangent (tan δ) were measured by a cavity resonator perturbation method (10 GHz).
Peel strength (Cu): A copper foil (CF-T8, manufactured by Fukuda Metal Foil Co., Ltd., thickness 18 μm) with the roughened surface inside is bonded to both sides of the insulating film peeled off from the support, and pressed. It was heat-cured with a machine (200 ° C., 60 min, 10 kgf, 180 ° C., 60 min, 10 kgf when containing an organic peroxide of component (F)). This test piece was cut to a width of 10 mm, peeled off by an autograph, and peel strength (180 degree peel) was measured according to JIS K6854-2.
Peel strength (LCP): A liquid crystal polymer (LCP) film (Bexter CT-Z, manufactured by Kuraray Co., Ltd., 25 μm) is bonded to one side of an insulating film peeled off from a support, and an FR4 substrate is attached to the other side of the insulating film. After being cured by heating and curing at 200 ° C., 60 min, 10 kgf (180 ° C., 60 min, 10 kgf if component (F) organic peroxide is included), it is peeled off by an autograph in accordance with JIS K6854-1. The peel strength (90 degree peel) was measured.
Temporary pressure bonding property: The insulating film with a support produced by the above procedure was laminated on a liquid crystal polymer (LCP) film (Bexter CT-Z, manufactured by Kuraray Co., Ltd., 25 μm) at 130 ° C. with a roll laminator. After lamination, the support was peeled off, and then the LCP film laminated with this insulating film was folded. When the film was folded, the case where there was no peeling between the films was rated as “◯”, and the case where there was peeling between the films was marked as “X”. The same procedure was performed on an insulating film with a support that was stored in a room temperature air atmosphere for 3 months after the production.

Examples 1 to 10 were excellent in high-frequency electrical characteristics (dielectric constant (ε), dielectric loss tangent (tan δ)), peel strength, and temporary press bonding properties. The differences between Example 1 and Example 2-10 are as follows.
Example 2: It does not contain a component (F).
Examples 3 and 4: The component (D) content is different, not including the component (F).
Examples 5 and 6: Different types of epoxy resins as component (B), different blending ratios of thermoplastic elastomer as component (C), different contents of component (D), curing catalyst as component (E) A silane coupling agent is added as another component of different types.
Example 7: The content of the component (D) is different, the type of the curing catalyst of the component (E) is different, the component (F) is not included, and a silane coupling agent is added as the other component.
Example 8: A silane coupling agent is added as another component in which the type of the curing catalyst of component (E) is different.
Example 9: Different types of epoxy resin as component (B), different types of curing catalyst as component (E), and silane coupling agent added as other components.
Example 10: The type of the curing catalyst of the component (E) is different, and the component (F) is not included.
In Comparative Examples 1 and 2 using bismaleimide instead of the imide acrylate of component (D), the temporary press bonding property after 3 months was inferior. Comparative Example 1 having a high bismaleimide content was inferior in dielectric loss tangent (tan δ) among high-frequency electrical characteristics.
In Comparative Example 3 using monoacrylate instead of the imide acrylate of component (D), the peel strength against the LCP film was low. Moreover, the dielectric loss tangent (tan δ) is inferior among the high frequency electrical characteristics. The temporary press bonding property after 3 months was inferior.
The comparative example 4 which does not contain a component (D) had low peel strength with respect to an LCP film.
In Comparative Example 5 in which the content of the component (D) is too large, the peel strength with respect to the LCP film was low.

Claims (9)

(A) a modified polyphenylene ether having an ethylenically unsaturated group at both ends;
(B) epoxy resin,
(C) styrenic thermoplastic elastomer,
(D) a compound having an imide group and an acrylate group in one molecule, and
(E) A curing catalyst is contained, 30 to 50 parts by mass of component (A), 2 to 15 parts by mass of component (B), and 100 parts by mass of component (A) to component (E) in total. 40 to 60 parts by mass of (C) and 0.5 to 4 parts by mass of the component (D).   The resin composition according to claim 1, wherein the epoxy resin as the component (B) is an epoxy resin having a naphthalene skeleton.   The resin composition according to claim 1 or 2, wherein the curing catalyst of the component (E) is an imidazole curing catalyst.   The resin composition according to any one of claims 1 to 3, wherein the curing catalyst of the component (E) is an imidazole curing catalyst having a benzene ring.   Furthermore, the resin composition in any one of Claims 1-4 containing (F) organic peroxide.   The thermosetting product of the resin composition has a dielectric constant (ε) of 2.5 or less and a dielectric loss tangent (tan δ) of 0.0025 or less in a frequency region of 1 GHz or more. A resin composition according to claim 1.   The insulating film formed from the resin composition in any one of Claims 1-6.   A semiconductor device in which the resin composition according to claim 1 is used for interlayer adhesion between substrates.   A semiconductor device in which the insulating film according to claim 7 is used for interlayer adhesion between substrates.