KR20170084036A - Resin composition, and insulating film and semiconductor device using same - Google Patents

Abstract

(Epsilon) at a frequency of 1 to 10 GHz and a low dielectric constant (epsilon) at a frequency of 1 to 10 GHz in a high-frequency region, An insulating film showing dielectric tangent (tan delta), and a resin composition used for producing the insulating film. The composition of the present invention comprises (A) a thermosetting resin having a styrene group at the terminal and a phenylene ether skeleton, (B) a hydrogenated styrenic thermoplastic elastomer, and (C) a polytetrafluoroethylene filler, (C) relative to the total mass of the component (A) to the component (C) in an amount of 40 mass% or more and 80 mass% or less.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition,

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

2. Description of the Related Art In recent years, printed wiring boards used in electric and electronic devices have been progressing in size, weight, and high performance, and in particular, multilayer printed wiring boards are required to have higher multilayering, higher density, thinner, lighter weight, .

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

Patent Document 1 discloses a method of manufacturing a fluororesin substrate in which a metal conductor for wiring and a fluororesin such as PTFE which is a material of low dielectric constant (?) And low dielectric constant tangent (tan?) Are bonded by electron beam irradiation.

However, in order to bond a metal conductor for wiring and a fluororesin such as PTFE, it is necessary to heat to a temperature near the melting point of the fluororesin (in the case of PTFE, about 300 캜), and treatment at a high temperature is required. Further, since a treatment at a high temperature is required, toxic hydrofluoric acid may be generated by the decomposition of the fluororesin.

On the other hand, also in the case of an interlayer adhesive used for a multilayer printed wiring board and an adhesive film used as a surface protective film (i.e., a coverlay film) of a printed wiring board, excellent electric characteristics (low dielectric constant (?), Low dielectric loss tangent )).

The applicant of the present application, in the patent document 2, has an excellent adhesive strength to a substrate material of an FPC such as a metal foil or a polyimide film constituting the wiring of the FPC, and has an electric characteristic in a high frequency range of 1 to 10 GHz, And a coverlay film showing low dielectric constant (?) And low dielectric loss tangent (tan?) In the region of 1 to 10 GHz.

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

Japanese Laid-Open Patent Publication No. 2012-244056 Japanese Laid-Open Patent Publication No. 2011-68713

The requirements for electrical properties at high frequencies are becoming increasingly stringent, and dielectric constants in the frequency range of 1 to 10 GHz are required to be less than 2.30, and dielectric tangent (tan delta) in the frequency range of 1 to 10 GHz is required to be less than 0.0015.

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art described above and has an object to provide a semiconductor device having an excellent adhesive strength to a substrate material of an FPC such as a metal foil or a polyimide film constituting the wiring of the FPC, An insulating film exhibiting a low dielectric constant (?) And a low dielectric tangent (tan?) In a frequency range of 1 to 10 GHz, and a resin composition for use in the production of the insulating film.

(A) a thermosetting resin having a phenylene ether skeleton having a styrene group at the terminal thereof, (B) a hydrogenated styrenic thermoplastic elastomer, and (C) a polytetrafluoroethylene filler , And contains from 40% by mass to 80% by mass of the component (C) relative to the total mass of the components (A) to (C).

In the resin composition of the present invention, it is preferable that the average particle diameter of the polytetrafluoroethylene filler of the component (C) is 20 m or less.

(B-1) a styrene-based thermoplastic elastomer having a styrene content of 20% or more, and (B-2) a styrene-based thermoplastic elastomer having a styrene content of less than 20% And a styrene-based thermoplastic elastomer.

In the resin composition of the present invention, it is preferable to further include (D) a silane coupling agent containing a sulfur atom.

The present invention also provides an insulating film formed from the resin composition of the present invention.

Further, the present invention provides an insulating film with a support on which a layer of the resin composition of the present invention is formed on at least one surface of a support.

The present invention also provides an insulator with a support on which at least one surface of a support is provided with a layer of a cured product of the resin composition of the present invention.

The present invention also provides a flexible wiring board in which a layer of a cured product of the resin composition of the present invention is formed on the wiring pattern side of a resin-coated wiring board on which wiring patterns are formed on the main surface of the resin substrate.

Further, the present invention provides a flexible wiring board in which the insulating film of the present invention is adhered and cured on the wiring pattern side of the resin-coated wiring substrate on which the wiring pattern is formed on the main surface of the resin substrate.

The present invention also provides a flexible wiring board using a cured product of the resin composition of the present invention as a wiring board resin substrate on which wiring patterns are formed on a main surface.

The present invention also provides a flexible wiring board using a cured product of the insulating film of the present invention as a wiring board resin substrate on which wiring patterns are formed on a main surface.

The present invention also provides a semiconductor device using the resin composition of the present invention for interlayer bonding between substrates.

Further, the present invention provides a semiconductor device using the insulating film of the present invention for interlayer adhesion between substrates.

The insulating film formed from the resin composition of the present invention has an excellent adhesive strength to a substrate material of an FPC such as a metal foil or a polyimide film constituting the wiring of the FPC and has an electric characteristic in a high frequency region, (?) And low dielectric loss tangent (tan?) In the region of 10 GHz. Therefore, it is preferable for an adhesive film for electric or electronic use or a coverlay film for a printed wiring board. It is also preferable for interlayer adhesion between substrates of semiconductor devices. It can also be used as an FPC itself.

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 (C) as essential components.

(A) a thermosetting resin having a styrene group at the terminal and a phenylene ether skeleton

As the thermosetting resin having a styrene group at the terminal of the component (A) and having a phenylene ether skeleton (hereinafter referred to as " thermosetting resin of the component (A) " in the present specification), a compound represented by the following formula (1) .

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

In formula (2), R ₁ , R ₂ , R ₃ , R ₇ and R ₈ may be the same or different and are an alkyl group having 6 or less carbon atoms or a phenyl group. 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 each is a hydrogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

In the formula (1), - (Y-O) - is represented by the formula (4), and one kind of structure or two or more kinds 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 having 6 or less carbon atoms or a phenyl group. 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 each represent an integer of 0 to 100, at least one of which is not 0.

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

R ₁ , R ₂ , R ₃ , R ₇ , R ₈ , R ₁₇ and R ₁₈ are alkyl groups having up to 3 carbon atoms and R ₄ , R ₅ , R ₆ , R ₉ , It is preferable that R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₉ and R ₂₀ are each a hydrogen atom or an alkyl group having 3 or less carbon atoms, - (YO) - represented by the formula (4) is the formula (8) or the formula (9) or the formula (6) (8) and (9) are randomly arranged.

The method for producing the compound represented by the formula (1) is not particularly limited. For example, the terminal phenolic hydroxyl group of a bifunctional phenylene ether oligomer obtained by oxidatively coupling a bifunctional phenol compound and a monofunctional phenol compound is reacted with a vinylbenzyl ether . ≪ / RTI >

The number average molecular weight of the thermosetting resin of the component (A) is preferably in the range of 500 to 3,000, more preferably 1,000 to 2,500 in terms of polystyrene according to the GPC method. When the number average molecular weight is 500 or more, the resin composition of the present invention is hardly stuck to the coating film. When the number average molecular weight is 3,000 or less, deterioration of solubility in a solvent can be prevented. As the component (A), it is preferable to use one having a relative dielectric constant of 3.0 or less from the viewpoint of electric characteristics at a high frequency.

(B) a hydrogenated styrenic thermoplastic elastomer

The styrene-based thermoplastic elastomer of the component (B) refers to a thermoplastic elastomer containing styrene, an isomer thereof, or an analogue thereof. However, since the presence of an unsaturated bond in the molecule leads to an increase in dielectric tangent (tan delta), the component (B) that has been hydrogenated in the styrene series thermoplastic elastomer is used. That is, by using the hydrogenated styrenic thermoplastic elastomer, a dielectric loss tangent (tan?) As low as that obtained when no hydrogenation is obtained can be obtained.

Examples of the component (B) include polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene (SEEPS), polystyrene-poly (ethylene / propylene) block-polystyrene (SEPS), polystyrene- Block-polystyrene (SEBS).

The compounds exemplified herein may be used alone or in combination of two or more. However, in the case where the above-exemplified compounds are used singly or in combination of two or more thereof, it is preferable that the hydrogenated styrene-based thermoplastic elastomer of the component (B) includes those having different styrene ratios . Specifically, it preferably contains at least a styrene-based thermoplastic elastomer having a styrene content of at least 20% and (B-2) a styrene-based thermoplastic elastomer having a styrene content of less than 20%.

When only (B-1) is used as the component (B), the film produced using the resin composition tends to be easily cracked, and the workability may be deteriorated. On the other hand, in the case of using only (B-2), the film produced using the resin composition may become too soft and the workability may be deteriorated.

In addition, when (B-2) having a styrene content of less than 20% is used alone, the adhesive strength is improved because the number of rubber components is larger than when a styrene-based thermoplastic elastomer having a styrene content of about 20% is used alone. Therefore, from the viewpoint of improving the bonding strength, it is more preferable to use a styrene-based thermoplastic elastomer having a styrene content of less than 20% and a styrene content of less than 20% (B-1) are preferably used in combination so that the styrene content is adjusted to be about 20%.

The content ratio of (B-1) and (B-2) in the component (B) is not particularly limited, but the mass ratio of (B- 2) is preferably 20:80 to 80:20, more preferably 30:70 to 70:30, and even more preferably 40:60 to 60:40.

The component (A) and the component (B) are contained in an amount of 20 to 60 mass% with respect to the total mass of the components (A) to (C). The mass ratio of the component (A) to the component (B) is preferably from 5:95 to 95: 5, more preferably from 20:80 to 80:20, : 60 to 60:40.

When the amount of the component (B) is increased, the component (A) is relatively decreased, so that the resin composition of the present invention is liable to run out when cured. On the other hand, when the component (A) is increased, the component (B) relatively decreases, and therefore the moldability of the insulating film tends to deteriorate.

(C) a polytetrafluoroethylene (PTFE) filler

The polytetrafluoroethylene (PTFE) filler of the component (C) has an electric property at high frequency of the insulating film formed using the resin composition of the present invention, specifically, a low dielectric constant (?) At a frequency of 1 to 10 GHz, And low dielectric tangent (tan?).

As described above, PTFE is a material having a low dielectric constant (?) And a low dielectric tangent (tan?). However, in order to adhere the metal conductor for wiring and the fluororesin such as PTFE to the fluororesin substrate as described in Patent Document 1, it is necessary to heat to a temperature near the melting point of the fluororesin (in the case of PTFE, about 300 DEG C) Therefore, treatment at a high temperature is necessary. Further, since a treatment at a high temperature is required, toxic hydrofluoric acid may be generated by the decomposition of the fluororesin.

On the other hand, in the insulating film formed by using the resin composition of the present invention, the bonding strength between the substrate material of the FPC such as a metal foil and the polyimide film forming the wiring of the FPC and the insulating film is changed from the thermosetting resin of the component (A) (B), and the PTFE filler of the component (C) is contained in a predetermined amount as described below, whereby the electric characteristics of the insulating film at high frequency, specifically, the electric properties at a high frequency of 1 to 10 GHz, (?) and low dielectric loss tangent (tan?). Further, since the insulating film using the resin composition of the present invention can be bonded to the metal conductor for wiring at a temperature of about 200 캜, toxic hydrofluoric acid does not occur at the time of bonding.

The PTFE filler of the component (C) is contained in an amount of 40 to 80 mass% with respect to the total mass of the components (A) to (C). If the content of the component (C) is less than 40 mass% with respect to the total mass of the components (A) to (C), electric characteristics at a desired high frequency can not be obtained. If the content of the component (C) is more than 80 mass% with respect to the total mass of the components (A) to (C), film formation becomes difficult.

The content of the PTFE filler of the component (C) is preferably 45 to 75 mass%, more preferably 50 to 70 mass%, based on the total mass of the components (A) to (C).

Japanese Unexamined Patent Application Publication No. 2003-160725 discloses that the dielectric constant of the composition can be reduced by mixing a polyphenylene oxide (PPO) resin composition with a fluorine-based filler such as PTFE.

However, the PPO resin composition disclosed in Japanese Patent Application Laid-Open No. 2003-160725 is premised on being used as a prepreg by impregnation into glass fiber or the like, and from the viewpoints of moldability and impregnation with glass fibers, And the blending amount of the fluorine-based filler is 1 to 60 parts by mass with respect to 100 parts by mass of the resin component. When the upper limit of the amount of the fluorine-based filler is converted into the content of the component (C) in the present invention, it is about 37.5% by mass with respect to the total mass of the components (A) to (C) Is not obtained.

The PTFE filler of the component (C) preferably has an average particle diameter of 20 占 퐉 or less. When the average particle diameter is larger than 20 占 퐉, it is difficult to disperse uniformly in the resin composition, and there is a possibility that defects such as a stain pattern or a stripe pattern may occur when the film is made into a film.

Here, the shape of the PTFE filler is not particularly limited, and may be any shape such as spherical, irregular, and scaly. On the other hand, the average particle diameter of the PTFE filler in the present specification is a median diameter on a volume basis measured by laser diffraction after wet dispersion.

The average particle diameter of the PTFE filler of the component (C) is more preferably 0.01 to 20 占 퐉, and still more preferably 0.05 to 5 占 퐉.

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

(D) a silane coupling agent containing a sulfur atom

When a silane coupling agent containing a sulfur atom is contained as the component (D), the adhesive strength to the copper foil widely used as the wiring of the FPC, while maintaining the electrical characteristics at high frequency of the insulating film produced using the resin composition And the peeling risk after bonding can be reduced.

As the silane coupling agent containing a sulfur atom, a mercapto-based silane coupling agent, a sulfide-based silane coupling agent, or the like can be used.

Examples of the mercapto-based silane coupling agent include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 3-mercaptopropyltriethoxy Silane, and the like.

Examples of the sulfide-based silane coupling agent include bis (triethoxysilylpropyl) tetrasulfide, bis (trimethoxysilylpropyl) tetrasulfide, bis (methyldiethoxysilylpropyl) tetrasulfide, bis Bis (triethoxysilylpropyl) triesulfide, bis (triethoxypropyl) disulfide, and the like.

Among them, it is more preferable to use a sulfide-based silane coupling agent because the effect of improving the bonding strength with the copper foil widely used as an FPC wiring is great.

When a silane coupling agent containing a sulfur atom is contained as the component (D), the silane coupling agent containing the sulfur atom of the component (D) is used in an amount of 0.01 to 5.0 mass% based on the total mass of the components (A) %, More preferably 0.1 to 3.0 mass%, further preferably 0.2 to 1.0 mass%.

(Other compounding agent)

The resin composition of the present invention may further contain components other than the above components (A) to (D), if necessary. Specific examples of such components include a defoaming agent, a flow control agent, a film forming auxiliary agent, a dispersant, a silane coupling agent not containing a sulfur atom, an inorganic filler, and the like. For the purpose of improving electric characteristics at high frequencies, a fluorine resin other than PTFE or a hollow organic or inorganic filler may be added. The kind and blending amount of each compounding agent are the same as those in usual methods.

(Preparation of resin composition)

The resin composition of the present invention can be prepared by a conventional method. For example, in the presence or in the absence of a solvent, the components (A) to (C) (if the resin composition contains the component (D) or any other component, further optional components thereof) Mix by stirring mixer.

When the components (A) to (C) are dissolved in a predetermined solvent concentration (if the resin composition contains the component (D) or any other component, the components are further optionally dissolved therein) Is poured into a reaction kettle heated to 50 to 80 DEG C, and the mixture is stirred for 3 hours at atmospheric pressure while rotating at 100 to 1000 rpm.

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

The thermosetting resin composition of the present invention is excellent in electric characteristics at high frequency. Specifically, the thermosetting resin composition preferably has a dielectric constant (?) In a region of a frequency of 1 to 10 GHz of less than 2.30, more preferably less than 2.25. Further, the dielectric loss tangent (tan?) In the region of the frequency of 1 to 10 GHz is more preferably less than 0.0015, and more preferably less than 0.0010.

When the dielectric constant (epsilon) and the dielectric loss tangent (tan delta) in the frequency range of 1 to 10 GHz fall within the above-mentioned range, the electric signal loss in the high frequency region can be reduced.

The thermosetting resin composition of the present invention has sufficient adhesive strength. Specifically, the thermosetting resin composition preferably has a fill strength (180-degree fill) of 4 N / cm or more, more preferably 6 N / cm or more for a copper foil screen measured in accordance with JIS K6854-2 .

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 may be diluted with a solvent to obtain a varnish, which is then applied to at least one surface of the support and dried, and then the support may be provided as a support film or as a film peeled from the support.

Examples of usable solvents for the varnish include ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aromatic solvents such as toluene and xylene; Dimethylformamide, and 1-methyl 2-pyrrolidone. The amount of the solvent to be used is not particularly limited and may be an amount conventionally used, but is preferably 20 to 90 mass% based on the solid content.

It is also preferable to disperse the varnish in order to uniformly disperse the PTFE filler in the varnish. The dispersion method is not particularly limited, and examples thereof include a method using a dispersing device such as a ball mill, a bead mill, a jet mill, and a homogenizer.

The support is appropriately selected depending on the production method and application of the film, and is not particularly limited. Examples of the support include metal foil such as copper and aluminum, substrate made of polyimide, liquid crystal polymer, PTFE or the like, polyester, And a carrier film of a resin. When the insulating film of the present invention is provided in the form of a film peeled off from a support, it is preferable that the support is releasably treated with a silicone compound or the like.

By bonding the insulating film of the present invention to a metal foil which forms the wiring of an FPC, an insulating film with a metal foil, which is an insulating film with a support of the present invention, is obtained. Also, when a varnish diluted with a solvent of the resin composition of the present invention is applied to a metal foil of a wiring of an FPC and dried, an insulating film with a metal foil, which is an insulating film with a support of the present invention, is obtained.

Further, by bonding the insulating film of the present invention to a substrate made of a resin constituting a substrate of an FPC such as a polyimide film or a liquid crystal polymer film, an insulating film with a resin substrate, which is an insulating film with a support of the present invention, can be obtained. Further, even when the varnish diluted with the solvent of the resin composition of the present invention is applied to a substrate made of a resin constituting a substrate of an FPC such as a polyimide film or a liquid crystal polymer film and dried, A film is obtained.

The method of applying the varnish is not particularly limited, and for example, a slot die method, a gravure method, a doctor coater method, and the like can be mentioned, and the varnish can be appropriately selected depending on the desired film thickness and the like.

The thickness of the insulating film of the present invention is suitably designed on the basis of characteristics such as mechanical strength required depending on the application, but is generally 1 to 100 占 퐉. When thinning of the printed wiring board is required, Is more preferable.

The drying conditions are appropriately designed according to the type and amount of the solvent used in the varnish, the amount of varnish used, the thickness of the coating, and the like, and are not particularly limited. For example, the drying can be carried out at atmospheric pressure at 70 to 130 ° C.

When the insulating film of the present invention is used as an adhesive film for electric and electronic uses, the order of use is as follows.

The insulating film of the present invention is placed on the surface to be bonded of one of the objects to be adhered using the insulating film of the present invention and then the other surface of the object is placed so that the surface to be adhered is in contact with the exposed surface of the insulating film . Here, in the case of using an insulating film with a support, the insulating film is placed so that the exposed surface of the adhesive film comes into contact with the surface to be adhered to one of the objects, and the insulating film is pressed on the adhered surface. Here, the temperature at the time of pressure application may be, for example, 150 占 폚.

Then, the support is peeled off at the time of pressure application so that the other surface of the exposed insulating film is placed so that the surface to be adhered is in contact with the exposed surface of the insulating film. After the above steps are carried out, they are thermocompression-bonded at a predetermined temperature and for a predetermined time, and then cured by heating.

The temperature at the time of thermocompression bonding is preferably 150 to 220 占 폚. The time of thermocompression bonding is preferably 0.5 to 10 minutes.

The temperature of the heat curing is preferably 150 to 220 캜. The heat curing time is preferably 30 to 120 minutes.

On the other hand, instead of using a film made in advance, a varnish diluted with a solvent of the resin composition of the present invention is coated on the surface to be bonded of one of the objects to be adhered and dried, followed by placing the one object .

By the above procedure, the insulating film of the present invention is adhered to the metal foil of the FPC and cured to obtain the insulator with a metal foil which is the insulator with the support of the present invention.

In addition, by applying the varnish obtained by diluting the resin composition of the present invention with a solvent to the metal foil of the wiring of the FPC by the above procedure, and then forming a layer of the cured product of the resin composition on the metal foil, An insulator with a metal foil which is an insulator with a support of the invention is obtained.

The insulating film of the present invention is adhered to a substrate made of a resin constituting a substrate of an FPC such as a polyimide film or a liquid crystal polymer film and cured by the above procedure to obtain a resin- Is obtained.

A varnish diluted with a solvent of the resin composition of the present invention is applied to a plastic substrate such as a polyimide film or a liquid crystal polymer film, which is a substrate of an FPC. Thereafter, a layer made of a cured product of the resin composition The insulator with the resin base, which is the insulator with the support of the present invention, can be obtained.

When the insulating film of the present invention is used as a coverlay film, the order of use is as follows.

The insulating film of the present invention is disposed at a predetermined position of the wiring-attached resin substrate on which the wiring pattern is formed on the main surface, that is, the position where the insulating film on the side where the wiring pattern is formed is covered with the insulating film, Pressure bonding, thermocompression bonding, and heat curing. Here, the pressure application process and the thermocompression process may be omitted.

The temperature and time of pressure bonding, thermocompression bonding and heat curing are the same as those in the case of using as an adhesive film for electric / electronic use.

The flexible wiring board of the present invention is obtained by bonding the insulating film of the present invention to the wiring pattern side of the wiring-attached resin substrate on which the wiring pattern is formed on the main surface of the resin substrate such as a polyimide film or a liquid crystal polymer film, will be.

Further, the flexible wiring board of the present invention is formed by applying a varnish diluted with a solvent of the resin composition of the present invention to the wiring pattern side of the wiring-attached resin substrate on which the wiring pattern is formed on the main surface of the resin substrate such as a polyimide film or a liquid crystal polymer film And then a layer made of a cured product of the resin composition is formed on the metal foil.

The cured product of the resin composition or the insulating film of the present invention can be used for a flexible wiring board as a wiring board resin substrate on which a wiring pattern is formed on the main surface due to excellent electrical properties at high frequencies.

The insulating film of the present invention can also be used for interlayer adhesion between substrates of semiconductor devices. In this case, the object to be bonded becomes a plurality of substrates stacked in a plurality of layers constituting the semiconductor device. On the other hand, a varnish obtained by diluting the resin composition of the present invention with a solvent may be used instead of a film which has been previously formed into a film for interlayer adhesion between substrates of semiconductor devices.

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, a CCL (copper clad laminate) substrate, an inorganic substrate such as a ceramic substrate or a silicon substrate Can be used. Of course, the cured product of the resin composition or insulating film of the present invention may be used as a substrate.

Example

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

(Examples 1 to 14 and Comparative Examples 1 to 5)

Sample production and measurement methods

Each component was metered into a blend ratio (parts by mass) as shown in the following table, toluene was added, and the mixture was charged into a reaction kettle heated to 80 DEG C, and the mixture was subjected to atmospheric pressure mixing for 3 hours while rotating at a revolution of 150 rpm . Thereafter, the resin composition was dispersed in a wet atomizing apparatus (MN2-2000AR, manufactured by Yoshida Kagaku Kogyo Co., Ltd.).

The varnish containing the resin composition thus obtained was coated on one side of a support (PET film subjected to release treatment) and dried at 100 占 폚 to obtain an insulating film with a support (thickness 30 占 퐉).

The abbreviations in the tables indicate the following.

Component (A)

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

OPE1200: Oligophenylene ether (modified polyphenylene ether represented by the above formula (1) wherein - (OXO) - in the formula (1) is the formula (5) and - (YO) 8)) (Mn = 1200), manufactured by Mitsubishi Gas Chemical Co.,

Component (A ')

HP-7200: dicyclopentadiene type epoxy resin, manufactured by DIC Co., Ltd.

Component (B-1)

G1652: polystyrene-poly (ethylene / butylene) block-polystyrene (SEBS)), styrene content 30%, manufactured by Kleiton Polymer Japan Co.,

FG1901: polystyrene-poly (ethylene / butylene) block-polystyrene (SEBS)), styrene content 30%, maleic anhydride modified product, manufactured by Krayton Polymer Japan Co.,

G1642: polystyrene-poly (ethylene / butylene) block-polystyrene (SEBS)), styrene content 21%, manufactured by Kleiton Polymer Japan Co.,

SEPTON 4044: polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene (SEEPS), styrene content 32%, manufactured by Kuraray Co.,

Component (B-2)

G1657: polystyrene-poly (ethylene / butylene) block-polystyrene (SEBS)), styrene content 13%, manufactured by Kleiton Polymer Japan Co.,

FG1924: polystyrene-poly (ethylene / butylene) block-polystyrene (SEBS)), styrene content 13%, maleic anhydride modified product, manufactured by Kleiton Polymer Japan Co.,

Component (B ')

TR2003: Styrene-butadiene block copolymer (SBS), manufactured by JSR Corporation

Component (C)

LeBron L-2: PTFE filler, average particle diameter 3.5 mu m, manufactured by Daikin Industries, Ltd.

LeBron L-5: PTFE filler, average particle diameter 5 mu m, manufactured by Daikin Industries, Ltd.

 KTL450: PTFE filler, average particle diameter 22 占 퐉, manufactured by Kitamura Co., Ltd.

Component (D)

KBM803: mercapto-based silane coupling agent, 3-mercaptopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.

KBM846: a sulfide-based silane coupling agent, bis (triethoxysilylpropyl) tetrasulfide, manufactured by Shin-Etsu Chemical Co.,

Component (D ')

KBM1403: styryl silane coupling agent, p-styryltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.

Component (E)

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

Film state: The state of the insulating film when peeled from the support was visually observed. A case where cracking did not occur when peeling off from a support was evaluated as?, A case where cracking occurred partially was evaluated as?, A case where the appearance of the film was bad such as color unevenness and stripe pattern, and a case where filming was impossible was evaluated as?.

Dielectric constant (?) And dielectric tangent (tan?): The insulating film was heated and cured at 200 占 폚 to be peeled off from the support, and then the test piece (40 占 0.5 mm 占 100 占 2 mm) was cut out from the adhesive film and the thickness was measured. The dielectric constant (epsilon) and dielectric loss tangent (tan delta) of the specimen were measured by a cavity resonator perturbation method (10 GHz) with the length of 100 mm and the diameter of 2 mm or less. A case where the dielectric constant (?) Was less than 2.25 was evaluated as?, A case where the dielectric constant was less than 2.30 and a case where the dielectric constant (?) Was less than 2.30 was evaluated as? A case where the dielectric loss tangent (tan?) Was less than 0.0010 was rated as?, A case where the dielectric loss tangent was less than 0.0010 and less than 0.0015 was rated as?, And a case where the dielectric loss tangent was 0.0015 or more was evaluated as?.

Peel Strength: A copper foil (CF-T9FZSV, made by Fukuda Metal Bottom Kogyo Kogyo K.K., thickness 18 占 퐉) having roughened surfaces inward on both sides of the insulating film was laminated and thermocompressed by a press machine (200 占 폚, 60 min, 10 kgf). The test piece was cut to a width of 10 mm and peeled off with an autograph, and the peel strength (180 degrees peel) was measured according to JIS K6854-2. A case of 6 N / 10 mm or more was rated as?, A case of 6 N / 10 mm or less and 4 N / 10 mm or more was evaluated as?, And a case of less than 4 N / 10 mm was evaluated as x.

Examples 1 to 14 were excellent in electric characteristics (dielectric constant (?), Dielectric tangent (tan?)) And peak strength of high frequency. The differences between Examples 2 and 10 in Example 1 are as follows.

Example 2: Combined use of components (B-1) and (B-2).

Examples 3 and 4: Combined use of components (B-1) and (B-2). However, the type of SEBS of component (B-1) is different from that of Example 2. [

Example 5: Combined use of components (B-1) and (B-2). However, SEEPS is used as the component (B-1).

Examples 6 and 7: Combined use of components (B-1) and (B-2). The content of the component (C) is different from that of the second embodiment.

Examples 8 and 9: Combined use of components (B-1) and (B-2). The average particle diameter of the PTFE filler of the component (C) is different from that of the second embodiment.

Example 10: Combined use of components (B-1) and (B-2). Containing component (D).

Example 11: Combination of components (B-1) and (B-2). Containing component (D). The kind of the silane coupling agent of the component (D) is different from that of the tenth embodiment.

Example 12: Combined use of components (B-1) and (B-2). Containing component (D). The content of the silane coupling agent in the component (D) is different from that in the example 11.

Example 13: Combined use of components (B-1) and (B-2). Containing component (D). The type of the thermosetting resin of the component (A) is different from that of the twelfth embodiment.

Example 14: Combination of components (B-1) and (B-2). As the component (D '), a silane coupling agent not containing a sulfur atom is used.

In Comparative Example 1, which does not contain the component (C), electrical properties (permittivity (?), Dielectric tangent (tan?)) Of the high frequency were lowered.

In Comparative Example 2 in which the content of the component (C) was too small, the dielectric constant (?) Of the electric characteristics of the high frequency was lowered.

In Comparative Example 3 using SBS instead of the components (B-1) and (B-2), the dielectric tangent (tan?) Of the high-frequency electric characteristics dropped.

Comparative Example 4 containing no components (B-1) and (B-2) could not be made into a film.

In Comparative Example 5 using an epoxy resin (dicyclopentadiene type epoxy resin) instead of the component (A), the peel strength was low. In addition, the dielectric tangent (tan delta) of the high-frequency electric characteristics dropped.

Claims (13)

(A) a thermosetting resin having a styrene group at the terminal and a phenylene ether skeleton,
(B) a hydrogenated styrenic thermoplastic elastomer, and
(C) a polytetrafluoroethylene filler
, And contains from 40% by mass or more to 80% by mass or less of the component (C) based on the total mass of the components (A) to (C). The method according to claim 1,
Wherein the average particle diameter of the polytetrafluoroethylene filler of the component (C) is 20 占 퐉 or less. 3. The method according to claim 1 or 2,
The hydrogenated styrenic thermoplastic elastomer of the component (B)
(B-1) a styrene-based thermoplastic elastomer having a styrene content of 20% or more, and
(B-2) a styrene-based thermoplastic elastomer having a styrene content of less than 20%. 4. The method according to any one of claims 1 to 3,
(D) a silane coupling agent containing a sulfur atom. An insulating film formed from the resin composition of any one of claims 1 to 4. An insulating film with a support, wherein a layer made of the resin composition according to any one of claims 1 to 4 is formed on at least one surface of a support. An insulator having a support comprising a cured composition of the resin composition according to any one of claims 1 to 4 formed on at least one side of the support. A flexible wiring board in which a layer made of a cured product of the resin composition of any one of claims 1 to 4 is formed on a wiring pattern side of a wiring-attached resin substrate on which a wiring pattern is formed on a main surface of the resin substrate. A flexible wiring board comprising an insulating film according to claim 5 adhered to a wiring pattern side of a wiring board resin substrate on which a wiring pattern is formed on a main surface of a resin substrate and cured. A flexible wiring board using a cured resin composition according to any one of claims 1 to 4 as a wiring board resin substrate on which wiring patterns are formed on a main surface. A flexible wiring board using a cured product of the insulating film of claim 5 as a wiring board resin substrate on which wiring patterns are formed on a main surface. A semiconductor device using the resin composition according to any one of claims 1 to 4 for interlayer adhesion between substrates. A semiconductor device using the insulating film according to claim 5 for interlayer adhesion between substrates.