JP2019108491A - Heat-curable epoxy resin composition for hollow device-encapsulating film and heat-curable epoxy resin film for encapsulating hollow device - Google Patents

Abstract

To provide a heat-curable epoxy resin film for encapsulating a hollow device, having high hollow space-holding properties when encapsulating a hollow device, and a heat-curable epoxy resin composition for hollow device-encapsulating film.SOLUTION: The heat-curable epoxy resin composition for forming a hollow device-encapsulating film is provided that contains: an epoxy resin (A) which is liquid at 25°C and has two or more epoxy groups in one molecule; a phenolic curing agent (B) having one or more phenolic hydroxyl group in one molecule, and further having one or more polyimide skeleton in one molecule; a phenolic resin curing agent (C) which is solid at 25°C and has two or more phenolic hydroxyl groups and has no polyimide skeleton in one molecule; an inorganic filler (D); a curing accelerator (E); an adhesion auxiliary agent (F); and an organic solvent (G).SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting epoxy resin composition for a hollow device sealing film and a thermosetting epoxy resin film for sealing a hollow device.

  Typically, for production of an electronic device package, one or more electronic devices fixed to a substrate or the like via bumps or the like are sealed with a sealing resin, and the sealing body is used as an electronic device unit as necessary. The procedure of dicing to become a package of is adopted. As such a sealing resin, a tablet-type material is used as a material to be sealed by transfer molding, and a liquid or granular material is used as a material to be sealed by compression molding. In addition, it may seal with a laminate etc., and a film or sheet-like material may be used for these methods.

  In recent years, along with semiconductor packages, development of micro electronic devices called MEMS such as surface acoustic wave (SAW) filters, complementary metal oxide semiconductor (CMOS) sensors, and acceleration sensors has been advanced. The package in which these electronic devices are sealed generally has a hollow structure for securing propagation of surface acoustic waves, maintenance of an optical system, and mobility of a movable member of the electronic device. This hollow structure is often provided as an air gap between the substrate and the electronic device (element). At the time of sealing, it is necessary to seal while maintaining the hollow structure so as to secure the operation reliability of the movable member and the connection reliability of the element.

  As a method of resin sealing a hollow device having a hollow space between such a substrate and the adherend, for example, a technique of hollow molding a functional element using a gel-like curable resin sheet is examined. However, depending on the conditions, there are still problems such as foaming and resin flowing depending on the structure (Patent Document 1). Also, in view of the fact that the cost of the bump giving hollow space increases as its size decreases, and the demand for the expansion of the hollow space for complicating or compounding the movable member, the bump diameter will be increased in the future. It is expected that measures will be taken to expand the gap to around 100 μm. On the other hand, those which control flow by dilatancy-like action by adjusting the particle size and surface area of the inorganic filler to be filled, those which adjust the flow by increasing the melt viscosity during molding, and elastomers are added. Although what adjusts flow by making sea-island structure etc. is examined, in fact adjustment of detailed molding conditions etc. is necessary and it is poor in versatility, or it does not have satisfactory characteristics. It is a thing (patent documents 2-5).

JP, 2006-19714, A JP, 2014-209565, A JP, 2014-209566, A JP, 2014-209567, A JP, 2014-209568, A

  The present invention has been made in view of the above circumstances, and it is possible to form a thermosetting epoxy resin film for sealing a hollow device having high hollow space retention when sealing a hollow device, and a hollow device sealing capable of forming the film. It aims at providing a thermosetting epoxy resin composition for films.

In order to solve the above problems, according to the present invention, a thermosetting epoxy resin composition for film formation for sealing a hollow device is provided,
(A) An epoxy resin having two or more epoxy groups in one molecule and being liquid at 25 ° C.
(B) A phenolic curing agent having one or more phenolic hydroxyl groups in one molecule and further having one or more polyimide skeletons in one molecule,
(C) A phenolic resin-based curing agent which is solid at 25 ° C., having two or more phenolic hydroxyl groups in one molecule and having no polyimide skeleton,
(D) Inorganic filler,
(E) curing accelerator,
Provided is a thermosetting epoxy resin composition for a hollow device sealing film, which comprises (F) an adhesion promoter and (G) an organic solvent.

  With such a thermosetting epoxy resin composition, a film having high hollow space retention can be obtained when sealing a hollow device.

［式中、Ｚは４価の芳香族基であり、Ｙ^１は下記一般式（２）

（式中、Ｒ^１、Ｒ^２及びＲ^３は、炭素数１〜９のアルキル基、炭素数１〜１０のアルコキシ基、−ＣＯＯＲ（Ｒは炭素数１〜６のアルキル基を示す）で示されるアルコキシカルボニル基、または水素原子であり、相互に異なっていても同一でもよく；Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７は炭素数１〜９のアルキル基または水素原子であり、相互に異なっていても同一でもよく；Ｘは−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）（Ｃ_２Ｈ_５）−、または−Ｃ（ＣＦ_３）_２−を示し；ｎは１以上の整数である。）で表される芳香族ジアミン残基である］
で表される繰り返し単位を１種以上含有するものであることが好ましい。 In this case, the component (B) is represented by the following general formula (1)

[Wherein, Z is a tetravalent aromatic group, and Y ¹ is a group represented by the following general formula (2)

(Wherein, R ¹ , R ² and R ^{3 each} represents an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or -COOR (R represents an alkyl group having 1 to 6 carbon atoms) And R ⁴ , R ⁵ , R ⁶ and R ⁷ are each an alkyl group having 1 to 9 carbon atoms or a hydrogen atom, and they are different from each other may be the same or; X is _{-O -, - S -, -} SO 2 -, - C (CH 3) 2 -, - CH 2 -, - C (CH 3) (C 2 H 5) -, Or -C (CF ₃ ) _2- , wherein n is an integer of 1 or more.
It is preferable that it is a thing containing 1 or more types of repeating units represented by these.

  Thus, it is preferable that the component (B) contains one or more of the repeating units represented by the general formula (1), since the cured product has a sufficient crosslinking density. .

（式中、Ｚは前記と同じであり、Ｙ^２はシロキサンジアミン残基または非フェノール性芳香族ジアミン残基を示す。）
で表される繰り返し単位１種以上とからなるものであることが好ましい。 Furthermore, the repeating unit which comprises the said (B) component is 1 or more types of repeating units represented by the said General formula (1), and following General formula (3)

(Wherein Z is as defined above, and Y ² is a siloxane diamine residue or a nonphenolic aromatic diamine residue).
It is preferable that it consists of one or more types of repeating units represented by

  Thus, if it is a (B) component comprised from the repeating unit represented by the said General formula (1), and the repeating unit represented by the said General formula (3), the film property of a composition will be improved. Not only that, it becomes a film that can be sealed while holding the hollow space of the hollow device at the time of sealing while melting at high temperature. Moreover, if it is such (B) component, it can be easily diluted with an organic solvent, and since it can mix with an epoxy resin, it is preferable.

  Further, among all the repeating units constituting the component (B), 10 to 90 mol% of the repeating unit represented by the general formula (1) and 90 to 90 of the repeating unit represented by the general formula (3) It is preferable that it is 10 mol%.

  If it is such a component (B), the cured product has sufficient crosslinking density by the repeating unit represented by the said General formula (1) being 10 mol% or more, solvent resistance, adhesiveness And a cured product excellent in mechanical strength can be obtained. Moreover, when the repeating unit represented by the said General formula (1) is 90 mol% or less, modification | reformations, such as adhesive improvement to base materials, such as a board | substrate etc. and stress reduction of hardened | cured material, are fully performed. it can.

  Moreover, it is preferable that mass ratio (B) / (C) of the said (B) component and the said (C) component is 90/10-30/70.

  If the thermosetting epoxy resin composition satisfies this range, not only the handling of the film before curing is improved, but also a film excellent in storage stability and curability can be obtained.

Further, in the present invention, the thermosetting epoxy resin film for sealing a hollow device,
(A) An epoxy resin having two or more epoxy groups in one molecule and being liquid at 25 ° C.
(B) A phenolic curing agent having one or more phenolic hydroxyl groups in one molecule and further having one or more polyimide skeletons in one molecule,
(C) A phenolic resin-based curing agent which has two or more phenolic hydroxyl groups in one molecule and which is solid at 25 ° C. having no polyimide skeleton,
(D) Inorganic filler,
Provided is a thermosetting epoxy resin film for sealing a hollow device, which contains (E) a curing accelerator and (F) an adhesion assistant and does not contain an organic solvent.

  With such a thermosetting epoxy resin film for sealing a hollow device of the present invention, it is possible to suppress the penetration of resin into the hollow space, and to have high hollow space retention when sealing a hollow device Become.

［式中、Ｚは４価の芳香族基であり、Ｙ^１は下記一般式（２）

（式中、Ｒ^１、Ｒ^２及びＲ^３は、炭素数１〜９のアルキル基、炭素数１〜１０のアルコキシ基、−ＣＯＯＲ（Ｒは炭素数１〜６のアルキル基を示す）で示されるアルコキシカルボニル基、または水素原子であり、相互に異なっていても同一でもよく；Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７は炭素数１〜９のアルキル基または水素原子であり、相互に異なっていても同一でもよく；Ｘは−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）（Ｃ_２Ｈ_５）−、または−Ｃ（ＣＦ_３）_２−を示し；ｎは１以上の整数である。）で表される芳香族ジアミン残基である］
で表される繰り返し単位を１種以上含有するものであることが好ましい。 In this case, the component (B) is represented by the following general formula (1)

[Wherein, Z is a tetravalent aromatic group, and Y ¹ is a group represented by the following general formula (2)

(Wherein, R ¹ , R ² and R ^{3 each} represents an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or -COOR (R represents an alkyl group having 1 to 6 carbon atoms) And R ⁴ , R ⁵ , R ⁶ and R ⁷ are each an alkyl group having 1 to 9 carbon atoms or a hydrogen atom, and they are different from each other may be the same or; X is _{-O -, - S -, -} SO 2 -, - C (CH 3) 2 -, - CH 2 -, - C (CH 3) (C 2 H 5) -, Or -C (CF ₃ ) _2- , wherein n is an integer of 1 or more.
It is preferable that it is a thing containing 1 or more types of repeating units represented by these.

  Thus, it is preferable that the component (B) contains one or more of the repeating units represented by the general formula (1), since the cured product has a sufficient crosslinking density. .

（式中、Ｚは前記と同じであり、Ｙ^２はシロキサンジアミン残基または非フェノール性芳香族ジアミン残基を示す。）
で表される繰り返し単位１種以上とからなるものであることが好ましい。 Furthermore, the repeating unit which comprises the said (B) component is 1 or more types of repeating units represented by the said General formula (1), and following General formula (3)

(Wherein Z is as defined above, and Y ² is a siloxane diamine residue or a nonphenolic aromatic diamine residue).
It is preferable that it consists of one or more types of repeating units represented by

  Thus, as long as it is a component (B) composed of the repeating unit represented by the above general formula (1) and the repeating unit represented by the above general formula (3), it is possible to seal even while melting at high temperature It becomes a film which can be sealed while holding the hollow space of the hollow device at the time of stopping.

  Moreover, the repeating unit represented by the said General formula (1) is 10-90 mol% among all the repeating units which comprise the said (B) component, The repeating unit represented by the said General formula (3) is It is preferable that it is 90-10 mol%.

  If it is such a component (B), the cured product has sufficient crosslinking density by the repeating unit represented by the said General formula (1) being 10 mol% or more, solvent resistance, adhesiveness And a cured product excellent in mechanical strength can be obtained. Moreover, when the repeating unit represented by the said General formula (1) is 90 mol% or less, modification | reformations, such as adhesive improvement to base materials, such as a board | substrate etc. and stress reduction of hardened | cured material, are fully performed. it can.

  Moreover, it is preferable that mass ratio (B) / (C) of the said (B) component and the said (C) component is 90/10-30/70.

  If this range is satisfied, not only the handling property of the film before curing is improved, but also the film is excellent in storage stability and curability.

  Moreover, in this invention, the hollow device which is sealed by the said thermosetting epoxy resin film for hollow device sealing is provided.

  If it is a hollow device sealed by the thermosetting epoxy resin film for hollow device sealing of this invention like this, it will become the sealing body by which approach of resin to hollow space was suppressed.

  With the thermosetting epoxy resin composition for hollow device sealing film and the thermosetting epoxy resin film for hollow device sealing of the present invention, entry of the resin into the hollow space can be suppressed, and the hollow space is high. As it is possible to seal the hollow device while maintaining the accuracy, it is possible to ensure the operation reliability of the movable member and the connection reliability of the element.

  The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, a thermosetting epoxy resin film for sealing a hollow device manufactured from the thermosetting epoxy resin composition for a sealing film for a hollow device described below It has been found that the above object can be achieved, and the present invention has been completed. Hereafter, the thermosetting epoxy resin composition for hollow device sealing films of this invention and the thermosetting epoxy resin film for hollow device sealing are demonstrated in detail.

The thermosetting epoxy resin composition for a hollow device sealing film of the present invention contains the following (A) to (G).
(A) An epoxy resin having two or more epoxy groups in one molecule and being liquid at 25 ° C.
(B) A curing agent having one or more phenolic hydroxyl groups in one molecule and further having one or more polyimide skeletons in one molecule,
(C) A phenolic resin-based curing agent which has two or more phenolic hydroxyl groups in one molecule and which is solid at 25 ° C. having no polyimide skeleton,
(D) Inorganic filler,
(E) curing accelerator,
(F) adhesion assistant, and (G) organic solvent.
Each component will be described in detail below.

(A) Epoxy resin having two or more epoxy groups in one molecule and being liquid at 25 ° C. As component (A) used in the present invention, it has two or more epoxy groups in one molecule, 25 Use epoxy resin which is liquid at ° C. By being liquid at 25 ° C., the film of the present invention can be given flexibility or its brittleness can be improved.

  As such (A) component, as long as it has two or more epoxy groups in one molecule and is liquid at 25 ° C., those known as epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin Alicyclic epoxy resin having an ester skeleton, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type Epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin Butter, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like.

  The component (A) is liquid at 25 ° C., and preferably has a viscosity of 4.0 to 30 Pa · s measured by a rotational viscometer described in JIS K 7117-1: 1999, and more preferably And 10 to 20 Pa · s.

  The liquid epoxy resin of component (A) may be used alone or in combination of two or more. Among them, the liquid epoxy resin of the component (A) is a glycidyl amine epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a bisphenol AF epoxy resin from the viewpoint of heat resistance and adhesiveness. Is preferred.

  Moreover, you may use together a solid epoxy resin as needed for the thermosetting epoxy resin composition for hollow device sealing films of this invention.

(B) Phenolic curing agent having one or more phenolic hydroxyl groups in one molecule and further having one or more polyimide skeletons in one molecule In the present invention, one component (B) is contained in one molecule. A phenolic curing agent having the above-mentioned phenolic hydroxyl group and further having one or more polyimide skeletons in one molecule is used.

［式中、Ｚは４価の芳香族基、Ｙ^１は下記一般式（２）

（式中、Ｒ^１、Ｒ^２及びＲ^３は、炭素数１〜９のアルキル基、炭素数１〜１０のアルコキシ基、−ＣＯＯＲ（Ｒは炭素数１〜６のアルキル基を示す）で示されるアルコキシカルボニル基、または水素原子であり、相互に異なっていても同一でもよく；Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７は炭素数１〜９のアルキル基または水素原子であり、相互に異なっていても同一でもよく；Ｘは−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）（Ｃ_２Ｈ_５）−、または−Ｃ（ＣＦ_３）_２−を示し；ｎは１以上の整数である。）で表される芳香族ジアミン残基］で表される繰り返し単位を１種以上含有するものであることが好ましい。 Specifically, the component (B) has the following general formula (1)

[Wherein, Z is a tetravalent aromatic group, and Y ¹ is a group represented by the following general formula (2)

(Wherein, R ¹ , R ² and R ^{3 each} represents an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or -COOR (R represents an alkyl group having 1 to 6 carbon atoms) And R ⁴ , R ⁵ , R ⁶ and R ⁷ are each an alkyl group having 1 to 9 carbon atoms or a hydrogen atom, and they are different from each other may be the same or; X is _{-O -, - S -, -} SO 2 -, - C (CH 3) 2 -, - CH 2 -, - C (CH 3) (C 2 H 5) -, Or -C (CF ₃ ) ₂ -is shown; n is an integer of 1 or more. It is preferable that the aromatic diamine residue represented by .

（式中、Ｚは前記と同じであり、Ｙ^２はシロキサンジアミン残基または非フェノール性芳香族ジアミン残基を示す。）
で表される繰り返し単位１種以上とからなるものであることが好ましい。 Furthermore, the repeating unit which comprises (B) component is 1 or more types of repeating units represented by the said General formula (1), and following General formula (3)

(Wherein Z is as defined above, and Y ² is a siloxane diamine residue or a nonphenolic aromatic diamine residue).
It is preferable that it consists of one or more types of repeating units represented by

  Z in the general formula (1) and the general formula (3) is a tetravalent aromatic group, and more specifically, a tetravalent aromatic group which is an aromatic tetracarboxylic acid dianhydride residue It is. In the present invention, a tetravalent aromatic group means a group obtained by removing four hydrogen atoms from an aromatic compound having an aromatic ring. Examples of the aromatic tetracarboxylic acid dianhydride leading to such a tetravalent aromatic group include pyromellitic acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 3,3 ′. 4,4,4'-diphenyltetracarboxylic acid dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-diphenyltetracarboxylic acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride , 2,2-bis (3,4-dicarboxyphenyl) perfluoropropane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1 ′-(3,4-dicarboxy Phenyl Tetramethyldisiloxane dianhydride, and the like.

  Among others, a skeleton in which Z is derived from pyromellitic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) perfluoropropane dianhydride or bis (3,4-dicarboxyphenyl) sulfone dianhydride When it is a polyimide having a completely closed ring structure, it is preferable in that it is excellent in the solubility of the uncured product in a solvent. When Z contains a siloxane bond, it is preferable in terms of excellent adhesion to a substrate. Moreover, when Z has a biphenyl skeleton, the hardness of the cured product is improved, which is preferable.

Y ¹ in the general formula (1) is a divalent aromatic diamine residue having a phenolic hydroxyl group represented by the general formula (2). R ¹ , R ² and R ³ in the general formula (2) each represent a linear or branched alkyl group having 1 to 9 carbon atoms, preferably 1 to 4 carbon atoms, 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms Or an alkoxycarbonyl group represented by -COOR (R represents an alkyl group having 1 to 6 carbon atoms) or a hydrogen atom. The alkyl group in the alkoxy group may be linear or branched. R ¹ , R ² and R ³ may be different or identical to each other. Among these, when R ¹ , R ² and R ³ are alkyl groups, the water resistance of the polyimide is improved. In the case of an alkoxy group or an alkoxycarbonyl group, adhesion to a substrate is improved when the composition is used as a film for sealing. In particular, it is preferable that one or two of R ¹ , R ² and R ³ be a hydrogen atom and the rest be a methyl group.

In the above general formula (2), R ⁴ , R ⁵ , R ⁶ and R ^{7 each} represent a linear or branched alkyl group having 1 to 9 carbon atoms, preferably 1 to 4 carbon atoms, or a hydrogen atom, which are different from each other Or the same. Water resistance can be improved by introducing an alkyl group to R ⁴ , R ⁵ , R ⁶ and R ⁷ . From the viewpoint of keeping the reactivity of the amino group high, this alkyl group is preferably a methyl group.
In the general formula (2), X is -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) (C ₂ H ₅ )-, or -C _{(CF 3) 2} - a and may be the same or different. Among them, X is preferably -CH _2- because this facilitates the synthesis process of the diamine for introducing the aromatic diamine residue.

In the above general formula (3), Y ² is a siloxane diamine residue or a nonphenolic aromatic diamine residue. When Y ² is a non-phenolic aromatic diamine residue, the aromatic diamine for introducing Y ² is not particularly limited as long as it is non-phenolic. For example, phenylenediamines such as p-phenylenediamine and m-phenylenediamine, diphenylenediamines such as 4,4'-diphenylenediamine, 3,3'-diphenylenediamine and 3,4'-diphenylenediamine, Examples include various bis (aminophenyl) ethers, various bis (aminophenyloxy) benzenes, and various 2,2-bis (aminophenyloxyphenyl) propanes.

When Y ² is a siloxane diamine residue, a siloxane diamine residue represented by the following general formula (4) can be exemplified.

In the above general formula (4), W ¹ is an alkylene group having 1 to 6 carbon atoms, preferably 3 carbon atoms, and W ² has 1 to 10 carbon atoms, preferably 1 to 8 unsubstituted or hydrogen atoms as halogen atoms It is a monovalent hydrocarbon group substituted by an atom. Specific examples of W ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, Alkyl groups such as decyl group; alkenyl groups such as vinyl group, allyl group, propenyl group and butenyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and phenylethyl group; Examples thereof include halogen-substituted hydrocarbon groups in which a part or all of hydrogen atoms are substituted with halogen atoms such as fluorine, bromine, chlorine and the like, among which methyl group is preferable. u is an integer of 1 to 120, and particularly preferably an integer of 1 to 80. If u is 120 or less, the polyimide resin in the uncured material can be sufficiently dissolved in the solvent.

  By using a phenol-based curing agent having a polyimide skeleton having one or more kinds of repeating units represented by the general formula (1) and one or more repeating units represented by the general formula (3) As well as enhancing the film properties of the composition, it is possible to seal while holding the hollow space of the hollow device at the time of sealing while melting at high temperature. Furthermore, although it is polyimide by having this structure, it can be easily diluted with an organic solvent and can be mixed with an epoxy resin without using a high boiling point nitrogen-containing polar solvent such as N-methylpyrrolidone. It will be.

  The polyimide skeleton-containing phenol-based curing agent used in the present invention has 10 to 90% by mole of the repeating unit represented by the general formula (1), and 90 to 90 of the repeating unit represented by the general formula (3) It is preferable that it is 10 mol%. When the repeating unit represented by the above general formula (1) is 10 mol% or more, the cured product has a sufficient crosslinking density to obtain a cured product excellent in solvent resistance, adhesiveness, and mechanical strength. it can. When the repeating unit represented by the above general formula (1) is 90 mol% or less, modification such as adhesion to a substrate or reduction in stress of a cured product can be sufficiently performed.

  In addition, the weight average molecular weight of the polyimide skeleton-containing phenol-based curing agent (polyimide resin) in the present invention (GPC method, calculated using a standard polystyrene calibration curve) is preferably 5,000 to 150,000, and 20 And more preferably from 1,000 to 100,000. If the weight average molecular weight is 5,000 or more, the cured product can obtain mechanical strength, and if it is 150,000 or less, a carboxy group formed by hydrolysis of the terminal acid anhydride of the polyimide resin, Since the amount of terminal amino groups is a necessary and sufficient amount, the crosslinking density with the epoxy resin used as the component (A) is increased, and the solvent resistance of the curing agent having a polyimide skeleton is improved.

  Moreover, 300-3,000 are preferable and, as for the hydroxyl equivalent of the phenolic hydroxyl group of the said polyimide frame | skeleton containing phenol type hardening | curing agent, 500-2,500 are more preferable.

（式中、ｍは水酸基当量が３００〜３，０００を満たす数） As the component (B), for example, commercially available products such as GPI series (manufactured by Gunei Chemical Co., Ltd.) having a phenolimide skeleton represented by the following formula can be used.

(Wherein, m is a number satisfying the hydroxyl equivalent of 300 to 3,000)

  Moreover, it is preferable to dilute with a solvent and to use as a solution the polyimide frame | skeleton containing phenol type curing agent of (B) component. The solvent used for this solution is preferably a solvent having excellent compatibility, and is preferably an ether solvent such as tetrahydrofuran, anisole, diglyme, triglyme, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 2-octanone, acetophenone, etc. Examples thereof include ketone solvents, ester solvents such as butyl acetate, methyl benzoate, γ-butyrolactone, methyl 2-hydroxypropanoate, and aromatic hydrocarbon solvents such as toluene and xylene. Among these, cyclohexanone, methyl ethyl ketone, γ-butyrolactone and propylene glycol monomethyl ether acetate are more preferably used. When the component (B) is used as a solution, the solid content concentration is appropriately optimized depending on the properties of the component (B), but 10 to 60% by mass is preferable.

(C) A phenolic resin-based curing agent having two or more phenolic hydroxyl groups in one molecule and having no polyimide skeleton and being a solid at 25 ° C. As long as it has two or more phenolic hydroxyl groups in the molecule and is solid at 25 ° C. without having a polyimide skeleton, a known one used as a curing agent for epoxy resin can be used.

  As such a phenol resin-based curing agent, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, naphthol aralkyl resin, terpene modified phenolic resin, dicyclopentadiene modified phenolic resin and the like can be mentioned.

  The phenol resin-based curing agent is essential to be solid at 25 ° C., and the softening point measured by the method described in JIS K 6910: 2007 is preferably in the range of 55 to 125 ° C., more preferably 60. It is ~ 120 ° C. Within this range, the handling property at the time of molding into a film is improved, and it is preferable because it does not become brittle when formed into a film and the physical properties after curing such as the glass transition point also improve.

  These curing agents may be used alone or in combination regardless of the type.

With respect to the compounding amounts of the components (B) and (C), the equivalent ratio of the phenolic hydroxyl group in the component (B) to the phenolic hydroxyl group in the component (C) is 0 with respect to the epoxy group in the component (A). An amount of 0.5 to 2.0 is preferable, and an amount of 0.7 to 1.5 is more preferable. When the equivalent ratio satisfies this range, the curability, mechanical properties, reliability and the like do not decrease, which is preferable.

  As a ratio of (B) component and (C) component, it is preferable that (B) / (C) is 90/10-30/70 by mass ratio, More preferably, (B) / (C) = 85 / 15-40 / 60. If this range is satisfied, not only the handleability of the film before curing is improved, but also a film excellent in storage stability and curability can be obtained.

(D) Inorganic filler (D) The inorganic filler, which is the component (D), increases the strength before and after curing of the thermosetting epoxy resin film for sealing hollow devices of the present invention, and hollow spaces when sealing hollow devices. It is formulated to enhance retention. As an inorganic filler of (D) ingredient, what is usually blended with an epoxy resin composition and a silicone resin composition can be used. For example, silicas such as spherical silica, fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, glass fibers, glass particles and the like can be mentioned, and spherical silica is particularly preferable.

The average particle size and shape of the inorganic filler of component (D) are not particularly limited, but the average particle size is usually 0.5 to 40 μm, and particularly preferably spherical silica having an average particle size of 0.5 to 40 μm Be The average particle diameter is a value determined as a mass average value D _{50 (or} median diameter) in particle size distribution measurement by laser diffraction method.

  In addition, from the viewpoint of high fluidity of the composition to be obtained, inorganic fillers of a plurality of particle size ranges may be combined, and in such a case, fine particles of 0.1 to 3 μm, medium particles of 3 to 7 μm It is preferred to use spherical silica in the size range and in the coarse range of 10-40 μm in combination. It is preferable to use spherical silica having a larger average particle size for further fluidization.

  However, the films generally have a thickness of 150 μm or less. The maximum particle size of the inorganic filler is preferably about 1/3 of the thickness. Moreover, if it is silica having an average particle diameter of 10 μm or less, the composition of the present invention containing a solvent is varnished and there is no risk of settling when forming a film, so the film has an average particle diameter of 0.1 to 10 μm. It is preferable to use silica in a fine to medium particle size range.

  The inorganic filler of the component (D) is a coupling agent such as a silane coupling agent or a titanate coupling agent in order to strengthen the bonding strength with the resin components of the components (A), (B) and (C). You may mix | blend what was surface-treated beforehand.

  As such a coupling agent, for example, an epoxy function such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Amino-functional alkoxysilanes such as hydrophobic alkoxysilanes, N-.beta. (Aminoethyl)-. Gamma.-aminopropyltrimethoxysilane, .gamma.-aminopropyltriethoxysilane, N-phenyl-.gamma.-aminopropyltrimethoxysilane, etc. Is preferred. The amount of the coupling agent used for the surface treatment and the method for the surface treatment are not particularly limited, and may be carried out according to a conventional method.

  The loading amount of the inorganic filler of the component (D) is preferably 100 to 800 parts by mass, and particularly preferably 200 to 700 parts by mass with respect to 100 parts by mass of the total of the components (A), (B) and (C). If it is 100 parts by mass or more, sufficient strength can be obtained, and if it is 800 parts by mass or less, the film is excellent in flexibility, so there is no risk of breakage during handling. In addition, it is preferable to contain this inorganic filler in 30-85 mass% of the whole composition, especially 50-80 mass%.

(E) Curing accelerator As the curing accelerator for the component (E) used in the present invention, any curing accelerator may be used as long as it accelerates the curing reaction between the epoxy resin and the curing agent, for example, 1,8-diazabicyclo [5.4 .0] Amine compounds such as -7-undecene, organophosphorus compounds such as triphenylphosphine, tetraphenylphosphonium tetraborate salt, and imidazole compounds such as 2-methylimidazole, but are limited thereto It is not a thing. One or two or more of these curing accelerators can be used.

  The amount of the curing accelerator used is in the range of 0.05 to 5% by mass, particularly 0.1 to 3% by mass, based on the total of the components (A), (B) and (C). Is preferred. Within the above range, the balance between the heat resistance and the moisture resistance of the cured product of the epoxy resin composition is excellent, and the curing does not become too slow or too fast at the time of sealing.

(F) Adhesion assistant In the thermosetting epoxy resin composition for a hollow device sealing film of the present invention, an adhesion assistant is blended as a component (F). The bond strength between the resin components (A) to (C) and the inorganic filler (D) can be increased, or the adhesion between an organic substrate such as a BT substrate and a metal lead frame can be increased. As such an adhesion | attachment adjuvant, a silane coupling agent, a titanate coupling agent, etc. are mentioned. Among them, silane coupling agents are preferred. Specifically, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Epoxy functional alkoxysilane, Mercapto functional alkoxysilane such as γ-mercaptopropyltrimethoxysilane, Amine functionality such as γ-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane An alkoxysilane etc. are mentioned.

  The blending amount of the component (F) is preferably 0.1 to 8.0% by mass, particularly 0.5 to 6.0, with respect to the total of the components (A), (B) and (C). It is preferable to set it as mass%. When the content is 0.1% by mass or more, the adhesion to the substrate is excellent, and when the content is 8.0% by mass or less, generation of voids due to viscosity reduction does not occur.

(G) Organic solvent The organic solvent which is the component (G) in the present invention adjusts the viscosity of the epoxy resin composition to an appropriate range when producing a thermosetting epoxy resin film for sealing a hollow device described later. In order to As an example of an organic solvent, the thing similar to the solvent used when diluting the said (B) component is illustrated. Specifically, ether solvents such as tetrahydrofuran, anisole, diglyme and triglyme, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as 2-heptanone, 2-octanone and acetophenone, butyl acetate, methyl benzoate, γ- Examples thereof include ester solvents such as butyrolactone and methyl 2-hydroxypropanoate, and aromatic hydrocarbon solvents such as toluene and xylene. Among these, cyclohexanone, methyl ethyl ketone, γ-butyrolactone and propylene glycol monomethyl ether acetate are more preferably used.

  Moreover, it is preferable that solid content concentration in the thermosetting epoxy resin composition for hollow device sealing films of this invention is 10-60 mass%, More preferably, it is 20-40 mass%.

<Other additives>
The thermosetting epoxy resin composition for a hollow device sealing film of the present invention may further contain various additives as required. For example, additives such as organopolysiloxanes, silicone oils, thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, or light stabilizers, for the purpose of improving the properties of resins, and ion trap materials and coatings for the purpose of improving electrical properties Antifoaming agents, surfactants such as leveling agents, and other dyes, coloring agents such as dyes, pigments, thermal stabilizers, antioxidants, flame retardants, lubricants, etc. for the purpose of improving the workability at the time of work and the characteristics of the film It can be added and blended.

Thermosetting epoxy resin film and method for producing the same In the present invention, it is a thermosetting epoxy resin film for sealing a hollow device,
(A) An epoxy resin having two or more epoxy groups in one molecule and being liquid at 25 ° C.
(B) A phenolic curing agent having one or more phenolic hydroxyl groups in one molecule and further having one or more polyimide skeletons in one molecule,
(C) A phenolic resin-based curing agent which has two or more phenolic hydroxyl groups in one molecule and which is solid at 25 ° C. having no polyimide skeleton,
(D) Inorganic filler,
Provided is a thermosetting epoxy resin film for sealing a hollow device, which contains (E) a curing accelerator and (F) an adhesion assistant and does not contain an organic solvent.

  As a manufacturing method of the thermosetting epoxy resin film for hollow device sealing of the present invention, after blending the above-mentioned (A)-(G) ingredient and other arbitrary components by a predetermined composition ratio, and making it varnish state, It is possible to adopt a method of obtaining a film on a base substrate by coating on a suitable base substrate using a coater or the like and removing the solvent. As the base material, for example, a polyester film coated with a silicone resin or a fluororesin excellent in releasability, or a polyester film subjected to a release treatment such as embossing can be used. The solvent removal can be performed by heating at a predetermined temperature and time using, for example, a hot plate, a hot air heater, an infrared heater or the like. Here, if necessary, the base substrate may be removed, and only the thermosetting epoxy resin film for sealing a hollow device of the present invention may be used for sealing a hollow device, or in a laminate with the base substrate. And may be used to seal hollow devices.

  In the processing into a film, if heating is not sufficient when removing the solvent, the solvent may remain in the film to cause voids, which may cause peeling or cracking. Conversely, if the heating is excessive, the reaction between the epoxy resin and the curing agent may proceed, which may affect the flexibility or adhesiveness of the film. In addition, if the solvent is heated to the boiling point or more at once, such problems as void remaining in the film or on the surface of the film or non-uniform thickness of the film may occur. Therefore, when removing the solvent, it is desirable to raise the temperature stepwise from the temperature below the boiling point of the solvent for removal.

  The film thus obtained is characterized in that it contains no organic solvent. Here, "does not contain an organic solvent" means that it is substantially free of an organic solvent, that is, it is not intentionally added by a method such as impregnating a film after production with an organic solvent, It allows the presence of an organic solvent in the composition which slightly remains after the film production process. The residual amount is preferably 0.5% by mass or less in the film, and more preferably 2,000 ppm or less of the solvent volatile component generated at the time of curing.

Hollow Device Sealed by Thermosetting Epoxy Resin Film for Hollow Device Sealing According to the thermosetting epoxy resin film for hollow device sealing of the present invention, a hollow device can be sealed while holding a hollow space. it can. The hollow device of the present invention may be, for example, a SAW chip or the like, but is not particularly limited as long as it is an electronic device having a hollow space between it and the adherend. The distance between the adherend and the electronic device (the width of the hollow space) can be set as appropriate, but is generally 10 to 100 μm.

Method of using a thermosetting epoxy resin film for sealing a hollow device The thermosetting epoxy resin film for sealing a hollow device of the present invention can seal a hollow device by compression molding or lamination molding.

  For example, the hollow device of the present invention may be sealed by using a compression molding machine at a molding temperature of 110 to 190 ° C. and a molding time of 30 to 900 seconds, preferably 120 to 160 ° C. and a molding time of 120 to 600 seconds. By attaching the thermosetting epoxy resin film, the hollow device can be embedded and sealed in the thermosetting epoxy resin film for sealing a hollow device. Furthermore, post curing may be performed at 140 to 185 ° C. for 0.5 to 20 hours in any molding method.

  In addition, the thermosetting epoxy resin film for sealing a hollow device of the present invention is placed on a substrate on which a hollow device is mounted, and the sheet is melted for 30 to 240 minutes on a hot plate at 80 to 150 ° C. The hollow device can also be sealed as it follows the substrate.

  EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.

(Examples 1 to 5, Comparative Examples 1 to 5)
The composition (parts by mass) shown in Table 1 was mixed for 30 minutes in a gate mixer adjusted to 25 ° C. to obtain a target composition for a film. In addition, regarding the (B) component, the active ingredient amount was described as a mass part. The blending amount of the organic solvent described as the component (G) is the amount of cyclohexanone used to dissolve the curing agent of the component (B) in advance and the amount of the organic solvent added to dissolve the whole composition. Total amount of

（式中、ｎ１は上記エポキシ当量を満たす数）
（Ａ−１−２）：液状ビスフェノールＦ型エポキシ樹脂（三菱化学（株）製、商品名：ｊＥＲ−８０６、エポキシ当量１６５（下記式）、粘度：２．５Ｐａ・ｓ）

（式中、ｎ２は上記エポキシ当量を満たす数） The raw material used by the Example and the comparative example is shown below.
(A-1) Epoxy resin having two or more epoxy groups in one molecule and liquid at 25 ° C. (A-1-1): liquid bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, a product Name: jER-828, epoxy equivalent 190 (following formula), viscosity: 15 Pa · s)

(Wherein, n1 is a number satisfying the above epoxy equivalent)
(A-1-2): Liquid bisphenol F-type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: jER-806, epoxy equivalent 165 (following formula), viscosity: 2.5 Pa · s)

(Wherein n2 is a number satisfying the above epoxy equivalent)

（式中、ｎ３は上記エポキシ当量を満たす数） (A-2) Epoxy resin having two or more epoxy groups in one molecule and solid at 25 ° C. (A-2-1): Solid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, a product Name: jER-1001, epoxy equivalent 475, softening point 64 ° C (dry ball method)

(Wherein, n3 is a number satisfying the above epoxy equivalent)

（式中、ｎ４は上記水酸基当量を満たす数） (B) Phenolic curing agent (B-1) having one or more phenolic hydroxyl groups in one molecule and further having one or more polyimide skeletons in one molecule : a phenol imide skeleton represented by the following formula Polyimide skeleton-containing phenolic curing agent-1 (manufactured by Gunei Chemical Co., Ltd., trade name: GPI-HT, hydroxyl equivalent 545, active ingredient 30% by weight, cyclohexanone solution)
(B-2): Polyimide skeleton-containing phenolic curing agent 2 having a phenol imide skeleton represented by the following formula 2 (manufactured by Gunei Chemical Co., Ltd., trade name: GPI-LT, hydroxyl equivalent 870, active ingredient 35% by weight , Cyclohexanone solution)

(Wherein, n4 is a number satisfying the above hydroxyl equivalent)

(C-1) Phenolic resin-based curing agent (C-1-1) which has two or more phenolic hydroxyl groups in one molecule and does not have a polyimide skeleton and is solid at 25 ° C. (C-1-1): phenol novolac resin ( DIC Corporation product name: TD-2131, hydroxyl equivalent 110, softening point 78-82 ° C)

(C-2) Phenolic resin-based curing agent (C-2-1) which is liquid at 25 ° C. and has two or more phenolic hydroxyl groups in one molecule and does not have a polyimide skeleton (phenol resin Kasei Co., Ltd. product name: MEH-8000H, hydroxyl equivalent 141, liquid at 25 ° C., 2.5 Pa.s)

(D) Inorganic filler (D-1): fused spherical silica (average particle size 0.5 μm, manufactured by Admatex Co., Ltd., trade name: SO-25R)

(E) Hardening accelerator (E-1): 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Co., Ltd., trade name: 2PHZ)

(F) Adhesion assistant (F-1): Silane coupling agent: 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. product, trade name: KBM-803)

(G) Organic solvent (G-1): cyclohexanone

(H) Colorant (H-1): carbon black (manufactured by Mitsubishi Chemical Corporation, trade name: Mitsubishi carbon black # 3230 MJ)

  Subsequently, the above-mentioned thermosetting resin composition is applied to a polyethylene terephthalate film surface-treated with silicone for mold release, dried at 100 ° C. for 10 minutes to remove the solvent, and an 80 μm thick uncured state ( B-stage state) film.

[Handling property at room temperature]
When each film obtained in the B-stage state is bent 180 degrees, no cracks or tears are generated at all, and those which can be easily returned to the original state are "○", and even a few cracks or tears are generated. What was done was "x", and what was not able to be film-ized on a release film from the beginning was made into "xx."

[Shear minimum viscosity]
Each film of the obtained B-stage state was cut out to 10 mm square, and the measurement was performed using a dynamic viscoelasticity measuring device (U-PM make, rheometer MR-300). The measurement conditions were a measurement frequency of 1.0 Hz, a probe diameter of 8.0 mm, a measurement temperature of 80 ° C. to 180 ° C., a temperature rise rate of 5 ° C./minute, and a numerical value of the minimum viscosity was read. The same measurement was carried out for each film which was left at 25 ° C. for 336 hours.

[Glass transition temperature, thermal expansion coefficient]
Each film in the B-stage state obtained is cured under conditions of 180 ° C. for 2 hours, and elongation of the sample is carried out at a temperature rising rate of 5 ° C. per minute using a thermomechanical analyzer (TMA Q400 manufactured by TA Instruments) It measured and the glass transition temperature and the linear expansion coefficient of 50-100 degreeC were calculated | required.

[Evaluation of approachability to actual package hollow portion]
A SAW chip mounting substrate was produced in which a SAW chip of the following specification on which an aluminum comb electrode was formed was mounted on a glass substrate under the following bonding conditions. The gap width between the SAW chip and the glass substrate was 80 μm.

<SAW chip>
Chip size: 1.2 mm □ (thickness 150 μm)
Bump material: Lead-free solder (80 μm in height)
Number of bumps: 6 bumps Number of chips: 100 (10 × 10)

<Bonding condition>
Device: Panasonic Electric Works Ltd. Bonding conditions: 200 ° C., 3 N, 1 sec, ultrasonic output 2 W

Each hollow sealing sheet was attached to the obtained SAW chip mounting substrate by vacuum press under the following heating and pressurizing conditions.
<Paste conditions>
Temperature: 120 ° C., pressure: 5 MPa, degree of vacuum: 1.6 kPa, press time: 2 minutes

The hollow sealing resin film was thermally cured at 180 ° C. for 2 hours to obtain a sealed body. The amount of penetration of the resin into the hollow portion between the SAW chip and the glass substrate was measured from the glass substrate side by an electron microscope (trade name "Digital Microscope" manufactured by KEYENCE Corporation, 200 times). The amount of resin penetration was measured as the resin penetration amount by measuring the maximum reach distance of the resin which has entered the hollow portion from the end of the SAW chip after sealing. The case where the resin penetration amount was 20 μm or less was evaluated as “「 ”, the case where it exceeded 20 μm as“ × ”, and the case where the resin entered the entire surface as“ ×× ”.

  As shown in Table 1, the thermosetting epoxy resin films of Comparative Examples 1 and 2 can not suppress the penetration amount of the resin into the hollow portion, and the thermosetting epoxy resin film of Comparative Example 3 Peeling has occurred after molding, and the thermosetting epoxy resin film of Comparative Example 4 has tackiness even after curing. In Comparative Example 5, the composition could not be formed into a film. On the other hand, it was shown that the thermosetting epoxy resin film for hollow device sealing of the present invention has high hollow space retention when sealing a hollow device, and is useful as a sealing material for hollow devices ( Examples 1 to 5).

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has the substantially same constitution as the technical idea described in the claims of the present invention, and the same effects can be exhibited by any invention. Contained in the technical scope of

Claims (11)

A thermosetting epoxy resin composition for film formation for sealing a hollow device, comprising:
(A) An epoxy resin having two or more epoxy groups in one molecule and being liquid at 25 ° C.
(B) A phenolic curing agent having one or more phenolic hydroxyl groups in one molecule and further having one or more polyimide skeletons in one molecule,
(C) A phenolic resin-based curing agent which is solid at 25 ° C., having two or more phenolic hydroxyl groups in one molecule and having no polyimide skeleton,
(D) Inorganic filler,
(E) curing accelerator,
A thermosetting epoxy resin composition for a hollow device sealing film, comprising (F) an adhesion promoter and (G) an organic solvent. Said (B) component is the following general formula (1)

[Wherein, Z is a tetravalent aromatic group, and Y ¹ is a group represented by the following general formula (2)

(Wherein, R ¹ , R ² and R ^{3 each} represents an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or -COOR (R represents an alkyl group having 1 to 6 carbon atoms) And R ⁴ , R ⁵ , R ⁶ and R ⁷ are each an alkyl group having 1 to 9 carbon atoms or a hydrogen atom, and they are different from each other may be the same or; X is _{-O -, - S -, -} SO 2 -, - C (CH 3) 2 -, - CH 2 -, - C (CH 3) (C 2 H 5) -, Or -C (CF ₃ ) _2- , wherein n is an integer of 1 or more.
The thermosetting epoxy resin composition for a hollow device sealing film according to claim 1, which contains one or more of the repeating units represented by The repeating unit which comprises the said (B) component is 1 or more types of repeating units represented by the said General formula (1), and following General formula (3)

(Wherein Z is as defined above, and Y ² is a siloxane diamine residue or a nonphenolic aromatic diamine residue).
The thermosetting epoxy resin composition for a hollow device sealing film according to claim 2, comprising one or more kinds of repeating units represented by   10 to 90 mol% of the repeating unit represented by the general formula (1) and 90 to 10 mol of the repeating unit represented by the general formula (3) among all the repeating units constituting the component (B) %, The thermosetting epoxy resin composition for hollow device sealing films of Claim 3 characterized by the above-mentioned.   The mass ratio (B) / (C) of the said (B) component and the said (C) component is 90/10-30/70, It is any one of the Claims 1-4 characterized by the above-mentioned. Thermosetting epoxy resin composition for hollow device sealing films. A thermosetting epoxy resin film for sealing a hollow device,
(A) An epoxy resin having two or more epoxy groups in one molecule and being liquid at 25 ° C.
(B) A phenolic curing agent having one or more phenolic hydroxyl groups in one molecule and further having one or more polyimide skeletons in one molecule,
(C) A phenolic resin-based curing agent which has two or more phenolic hydroxyl groups in one molecule and which is solid at 25 ° C. having no polyimide skeleton,
(D) Inorganic filler,
A thermosetting epoxy resin film for sealing a hollow device, comprising (E) a curing accelerator, and (F) an adhesion assistant and containing no organic solvent. Said (B) component is the following general formula (1)

[Wherein, Z is a tetravalent aromatic group, and Y ¹ is a group represented by the following general formula (2)

(Wherein, R ¹ , R ² and R ^{3 each} represents an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or -COOR (R represents an alkyl group having 1 to 6 carbon atoms) And R ⁴ , R ⁵ , R ⁶ and R ⁷ are each an alkyl group having 1 to 9 carbon atoms or a hydrogen atom, and they are different from each other may be the same or; X is _{-O -, - S -, -} SO 2 -, - C (CH 3) 2 -, - CH 2 -, - C (CH 3) (C 2 H 5) -, Or -C (CF ₃ ) _2- , wherein n is an integer of 1 or more.
The thermosetting epoxy resin film for hollow device sealing according to claim 6, which contains one or more kinds of repeating units represented by The repeating unit which comprises the said (B) component is 1 or more types of repeating units represented by the said General formula (1), and following General formula (3)

(Wherein Z is as defined above, and Y ² is a siloxane diamine residue or a nonphenolic aromatic diamine residue).
8. The thermosetting epoxy resin film for sealing a hollow device according to claim 7, comprising one or more kinds of repeating units represented by   Among all repeating units constituting the component (B), the repeating unit represented by the general formula (1) is 10 to 90 mol%, and the repeating unit represented by the general formula (3) is 90 to 90 The thermosetting epoxy resin film for hollow device sealing according to claim 8, which is 10 mol%.   The weight ratio (B) / (C) of the said (B) component and the said (C) component is 90/10-30/70, The hollow as described in any one of Claims 6-9 characterized by the above-mentioned. Thermosetting epoxy resin film for device sealing. A hollow device sealed by the thermosetting epoxy resin film for sealing a hollow device according to any one of claims 6 to 10.