JPWO2016204183A1 - Film forming resin composition, sealing film using the same, sealing film with support, and semiconductor device - Google Patents

Abstract

The purpose of the present invention is to provide a film-forming resin composition that can form a sealing film with good handleability even when volatile components are reduced, and can form a cured product having sufficiently high heat resistance (high glass transition temperature). A film-forming resin composition comprising a liquid epoxy resin (A), a cyanate resin (B), and an oil gelling agent (C) is provided.

Description

  The present invention relates to a film-forming resin composition, and more particularly to a film-forming resin composition having both excellent handling properties and heat resistance. Furthermore, the present invention provides a sealing film using a resin composition for film formation, a sealing film with a support, which can be applied to sealing of semiconductor chips and embedding of substrates on which electronic components are mounted. The present invention relates to a semiconductor device using these.

  Sealing of a semiconductor element such as a semiconductor chip is usually performed by molding using a solid or liquid resin composition (sealing material). In recent years, in order to more easily encapsulate semiconductor elements, it has been proposed to encapsulate a plurality of semiconductor elements mounted on a substrate at once using a film-like resin composition (Patent Document 1). ).

JP 2004-327623 A

  A film-like resin composition for sealing a semiconductor element can be produced, for example, by applying and drying a resin varnish containing an organic solvent on a support. In the film-shaped resin composition manufactured in this way, the handleability in the semi-cured state is imparted by leaving the organic solvent to some extent.

  However, when the film thickness increases, the volatile components (mainly organic solvents) contained in the resin varnish are difficult to volatilize, and thus there is a problem that the volatile components cannot be reduced sufficiently. When the volatile components are not sufficiently reduced, defects such as voids are likely to occur when the semiconductor element or the like is sealed and the film-like resin composition is thermally cured. Therefore, the film-like resin composition for sealing a semiconductor element or the like is required to have a sufficiently reduced volatile component and good handleability. On the other hand, in a film-shaped resin composition for sealing a semiconductor element, the cured resin is required to have a sufficiently high glass transition temperature from the viewpoint of heat resistance and reliability.

  The present invention has been made in view of such circumstances, and can form a sealing film with good handleability even when volatile components are reduced, and has sufficiently high heat resistance (high glass transition temperature). It aims at providing the resin composition for film formation which can form hardened | cured material, a sealing film, the sealing film with a support body, and a semiconductor device using these.

  As a result of investigations by the present inventors to solve the above problems, a resin composition containing a liquid epoxy resin, a cyanate resin, and an oil gelling agent reduces volatile components in a film formed using the resin composition. Even so, it has been found that a cured product having good handleability and a sufficiently high glass transition temperature (high heat resistance) can be formed, and the present invention has been completed based on such knowledge.

  That is, this invention provides the resin composition for film formation containing a liquid epoxy resin (A), cyanate resin (B), and an oil gelling agent (C).

  According to the film-forming resin composition of the present invention, it is possible to obtain a sealing film that can form a cured product that has good handleability even when the volatile components are reduced and has a sufficiently high glass transition temperature.

  The resin composition for film formation of this invention can further contain the siloxane resin (D) which has the phenolic hydroxyl group shown by following General formula (1).

［一般式（１）中、Ｒは各々独立に炭素数１〜５のアルキレン基であり、ｍは５〜１００の整数である。］

[In General Formula (1), each R is independently an alkylene group having 1 to 5 carbon atoms, and m is an integer of 5 to 100. ]

  The resin composition for film formation of the present invention can further contain an inorganic filler (E).

  The present invention also provides a sealing film using the film-forming resin composition according to the present invention.

  The thickness of the sealing film of this invention can be 30-250 micrometers.

  The present invention also provides a sealing film with a support in which a support is provided on at least one surface of the sealing film according to the present invention.

  The present invention also provides a semiconductor device comprising a semiconductor element sealed with the sealing film according to the present invention or the sealing film of the sealing film with a support according to the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition for film formation which can form the hardened | cured material which can form the sealing film which has favorable handleability even if it reduces a volatile component, and has a sufficiently high glass transition temperature, and a sealing film Further, it is possible to provide a sealing film with a support and a semiconductor device using these.

It is a schematic cross section for explaining one embodiment of a manufacturing method of a semiconductor device. It is a schematic cross section for explaining one embodiment of a manufacturing method of a semiconductor device.

  Hereinafter, embodiments of the present invention will be described in detail.

  The film-forming resin composition of the present embodiment (hereinafter sometimes referred to as a resin composition) includes a liquid epoxy resin (A) (hereinafter sometimes referred to as a component (A)), a cyanate resin (B) ( Hereinafter, the component (B) may be referred to), and the oil gelling agent (C) (hereinafter may be referred to as component (C)).

  According to the film-forming resin composition of the present embodiment, it is possible to obtain a sealing film that has good handleability even when the volatile components are reduced and can form a cured product having a sufficiently high glass transition temperature. .

  The reason why the resin composition for film formation of the present embodiment can sufficiently reduce the volatile components is not necessarily clear, but the present inventors presume as follows. When a sealing film is produced by applying a resin varnish composed of a film-forming resin composition to a support and drying it, the resin composition on the side where the support is not provided is on the side where the support is provided. Compared to the resin composition, drying is easy to proceed. Therefore, it is considered that the drying of the resin composition on the side where the support is not provided advances and the volatilization of volatile components (mainly organic solvents) in the resin composition on the side where the support is provided is prevented. It is done. In the resin composition of the present embodiment, by blending the liquid epoxy resin (A), excessive drying of the resin composition on the side where the support is not provided can be suppressed, and the support is provided. It is considered that the volatile component of the resin composition on the side of the surface can be sufficiently volatilized. Further, by blending the oil gelling agent (C), the resin composition comprising the liquid epoxy resin (A) and the cyanate resin (B) is gelled, and excessive tack caused by the liquid resin is suppressed. It is thought that you can.

  In addition, in this specification, a sealing film means the film-form resin composition used in order to seal or embed semiconductor elements, such as a semiconductor chip, and electronic components.

  The liquid epoxy resin of component (A) is not particularly limited as long as it is liquid at 25 ° C., and examples thereof include bisphenol A, bisphenol F, biphenyl, novolac, dicyclopentadiene, and many Examples include functional phenol-based, naphthalene-based, aralkyl-modified, alicyclic and alcohol-based glycidyl ethers, glycidyl amine-based, and glycidyl ester-based resins. These can be used alone or in combination of two or more. Among these, bisphenol F type epoxy resin is preferable from the viewpoint of imparting handleability.

  In this specification, the epoxy resin which is liquid at 25 ° C. refers to one having a viscosity at 25 ° C. of 400 Pa · s or less as measured with an E-type viscometer.

  The compounding amount of the component (A) in the film-forming resin composition is based on the total amount of the components that form the cured product from the viewpoint of imparting good flexibility to the sealing film (inorganic substances such as the component (E) and volatilization. Based on the total amount of the components excluding the components), it is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, and still more preferably 20 to 70% by mass.

  The cyanate resin of the component (B) is not particularly limited as long as it is a compound having at least two cyanato groups in one molecule, and is a phenol novolac type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, Examples thereof include bisphenol F type cyanate resin and tetramethylbisphenol F type cyanate resin. These can be used alone or in combination of two or more. Among these, bisphenol A type cyanate resin and phenol novolac type cyanate resin are preferable from the viewpoints of dielectric properties, heat resistance, flame retardancy, low thermal expansibility, and low cost.

  Examples of commercially available cyanate resins include bisphenol A type cyanate resin (Lonza Japan Co., Ltd .; trade name Primaset BADCy), phenol novolac type cyanate resin (Lonza Japan Co., Ltd .; trade name Primaset PT-30), and the like.

  The blending amount of the component (B) is preferably 25 to 400 parts by mass, more preferably 50 to 250 parts by mass, and 60 to 150 parts by mass with respect to 100 parts by mass of the component (A). More preferably. When the blending amount of the component (B) is 25 parts by mass or more, the heat resistance, flame retardancy, and chemical resistance of the film-forming resin composition tend to be improved. It becomes easy to be secured.

  The oil gelling agent of component (C) can have a hydrocarbon group effective for oil solubility and a hydrogen bonding functional group (hydroxy group, carboxy group, amino group, amide group, etc.) effective for self-assembly. As the oil gelling agent of component (C), hydroxystearic acid, particularly hydroxy fatty acids such as 12-hydroxystearic acid, n-lauroyl-L-glutamic acid-α, γ-dibutylamide, di-p-methylbenzylidene sorbitol gluci Tol, 1,3: 2,4-bis-O-benzylidene-D-glucitol, 1,3: 2,4-bis-O- (4-methylbenzylidene) -D-sorbitol, bis (2-ethylhexanoato ) Hydroxyaluminum, and compounds represented by the following general formulas (2) to (14). These may be used alone or in combination of two or more. Among these, at least one of 12-hydroxystearic acid, n-lauroyl-L-glutamic acid-α, γ-dibutyramide, and 1,3: 2,4-bis-O-benzylidene-D-glucitol is more preferable. .

［一般式（２）中、ｎ１は３〜１０の整数、ｎ２は２〜６の整数、Ｒ^１は炭素数１〜２０の飽和炭化水素基、Ｘ^１は硫黄原子又は酸素原子である。］

[In General Formula (2), n1 is an integer of 3 to 10, n2 is an integer of 2 to 6, R ¹ is a saturated hydrocarbon group having 1 to 20 carbon atoms, and X ¹ is a sulfur atom or an oxygen atom. ]

［一般式（３）中、Ｒ^２は炭素数１〜２０の飽和炭化水素基、Ｙ^１は結合手（単結合）又はベンゼン環（フェニレン基）である。］

[In General Formula (3), R ² is a saturated hydrocarbon group having 1 to 20 carbon atoms, and Y ¹ is a bond (single bond) or a benzene ring (phenylene group). ]

［一般式（４）中、Ｒ^３は炭素数１〜２０の飽和炭化水素基、Ｙ^２は結合手又はベンゼン環である。］

[In General Formula (4), R ³ is a saturated hydrocarbon group having 1 to 20 carbon atoms, and Y ² is a bond or a benzene ring. ]

［一般式（５）中、Ｒ^４は炭素数１〜２０の飽和炭化水素基である。］

[In the general formula (5), ^{R 4} is a saturated hydrocarbon group having 1 to 20 carbon atoms. ]

［一般式（７）中、Ｒ^５及びＲ^６は、それぞれ独立に炭素数１〜２０の飽和炭化水素基である。］

[In General Formula (7), R ⁵ and R ⁶ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms. ]

［一般式（８）中、Ｒ^７は、炭素数１〜２０の飽和炭化水素基である。］

In General formula (8), ^{R 7} is a saturated hydrocarbon group having 1 to 20 carbon atoms. ]

［一般式（９）中、Ｒ^８は、炭素数１〜２０の飽和炭化水素基である。］

In General Formula (9), ^{R 8} is a saturated hydrocarbon group having 1 to 20 carbon atoms. ]

［一般式（１０）中、Ｐｈは、フェニル基を示す。］

[In General Formula (10), Ph represents a phenyl group. ]

［一般式（１１）中、Ｒ^９及びＲ^１０は、それぞれ独立に炭素数１〜２０の飽和炭化水素基である。］

[In General Formula (11), R ⁹ and R ¹⁰ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms. ]

［一般式（１４）中、Ｒ^１１は、２価の炭素数１〜１０の飽和炭化水素基であり、Ｒ^１２及びＲ^１３は、それぞれ独立に炭素数１〜２０の飽和炭化水素基である。Ｒ^１２及びＲ^１３の上記飽和炭化水素基は、分子骨格中に少なくとも１つの水酸基を有する炭素数１〜２０の飽和炭化水素基であってもよい。］

[In General Formula (14), R ¹¹ is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and R ¹² and R ¹³ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms. . The saturated hydrocarbon group for R ¹² and R ¹³ may be a C 1-20 saturated hydrocarbon group having at least one hydroxyl group in the molecular skeleton. ]

  0.1-30 mass parts is preferable with respect to 100 mass parts of sum totals of a component (A) and a component (B), and, as for the compounding quantity of a component (C), 0.3-25 mass parts is more preferable. 5-20 mass parts is further more preferable, it is especially preferable that it is 1-10 mass parts, and it is very preferable that it is 2-8 mass parts. When the compounding amount of the component (C) is 0.1 parts by mass or more, the resin can be sufficiently gelled, and when it is 30 parts by mass or less, the excellent heat resistance of the cyanate resin can be maintained.

  You may mix | blend a hardening accelerator with the resin composition for film formation of this embodiment as needed. Examples of the curing accelerator include monofunctional phenols such as p- (α-cumyl) phenol, mono (α-methylbenzyl) phenol, and di (α-methylbenzyl) phenol, zinc naphthenate, copper naphthenate, Examples thereof include organic metal salts such as cobalt naphthenate and tin octylate, amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. These may be used alone or in combination of two or more.

  The resin composition for film formation of this embodiment may include a siloxane resin (D) having a phenolic hydroxyl group represented by the general formula (1) (hereinafter sometimes referred to as component (D)).

［一般式（１）中、Ｒは各々独立に炭素数１〜５のアルキレン基であり、ｍは５〜１００の整数である。］

[In General Formula (1), each R is independently an alkylene group having 1 to 5 carbon atoms, and m is an integer of 5 to 100. ]

  The siloxane resin of component (D) is not particularly limited as long as it is a siloxane resin containing phenolic hydroxyl groups at both ends of the structure represented by the general formula (1). As such siloxane resin, for example, trade name X-22-1876 (hydroxyl value: 120 mgKOH / g), trade name X-22-1875 (hydroxyl value: 60 mgKOH / g), manufactured by Shin-Etsu Chemical Co., Ltd., product Name X-22-1821 (hydroxyl value: 30 mgKOH / g), trade name X-22-1822 (hydroxyl value: 20 mgKOH / g), trade name X26-1064 (hydroxyl value: 25 mgKOH / g), Toray Dow Product name BY16-752A (hydroxyl value: 30 mgKOH / g), product name BY16-799 (hydroxyl value: 60 mgKOH / g), manufactured by Corning Corporation. These are commercially available from Shin-Etsu Chemical Co., Ltd. or Toray Dow Corning Co., Ltd. Among these, Shin-Etsu Chemical Co., Ltd., trade name X-22-1876 (hydroxyl value: 120 mgKOH / g), trade name X-22-from the point which is excellent in heat resistance, low thermal expansibility, and solvent solubility. 1875 (hydroxyl value: 60 mgKOH / g), trade name X-22-1821 (hydroxyl value: 30 mgKOH / g), manufactured by Toray Dow Corning Co., Ltd., trade name BY16-752A (hydroxyl value: 30 mgKOH / g), trade name BY16-799 (hydroxyl value: 60 mgKOH / g) is preferable.

  The blending amount of the component (D) is preferably 10 to 100 parts by weight, more preferably 20 to 90 parts by weight, and more preferably 30 to 80 parts by weight with respect to 100 parts by weight of the sum of the component (A) and the component (B). Is more preferable. When the blending amount of component (D) is 10 parts by mass or more, the cured product of the resin composition can be sufficiently reduced in elastic modulus, and the stress relaxation property of the resin is improved. The outstanding heat resistance which cyanate resin has as it is 100 mass parts or less can be hold | maintained.

  When mix | blending a component (D), the compatibility of resin can be improved by making it pre-react with a component (A) and a component (B). That is, after the component (A) and the component (D) are etherified in an organic solvent at 80 to 120 ° C., the component (B), the imino carbonate reaction, and the triazine cyclization reaction are allowed to proceed. The reaction is carried out so that the reaction rate of component (B) due to this reaction (sometimes referred to as the disappearance rate) is 20 to 70%.

  The reaction solvent that can be used for the pre-reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Solvents, ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, And sulfur atom-containing solvents such as dimethyl sulfoxide. These can be used alone or in combination of two or more. Among these, cyclohexanone, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, and toluene are preferable, and methyl ethyl ketone, methyl isobutyl ketone, and toluene are more preferable because they have high volatility and hardly leave a residual solvent during film production.

  In the etherification reaction of component (A) and component (D), a reaction catalyst can be used as necessary. Examples of the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus-based catalysts such as triphenylphosphine. These may be used alone or in combination of two or more. Among these, it is preferable to use a phosphorus catalyst such as triphenylphosphine from the viewpoint of high reactivity with the component (A) and the component (D).

  In the iminocarbonation reaction and the triazine cyclization reaction after the etherification reaction, an organometallic salt can be used as a reaction catalyst. Examples of the organic metal salt include zinc naphthenate, manganese naphthenate, copper naphthenate, cobalt naphthenate, tin octylate, and cobalt octylate. These can be used alone or in combination of two or more. Among these, zinc naphthenate and copper naphthenate are preferable from the viewpoints of curability and solvent solubility.

  In the imino carbonate reaction and the triazine cyclization reaction, if the reaction rate is 20% or more, the resin is sufficiently compatible, and if the reaction rate is 70% or less, the resulting resin is insoluble in the solvent. It can be avoided.

  The iminocarbonation reaction is a reaction in which an iminocarbonate bond (—O— (C═NH) —O—) is generated by the addition reaction of a hydroxyl group and a cyanate group, and the triazine cyclization reaction is a cyanate group. Is a reaction to form a triazine ring by trimerization. In addition, a three-dimensional network structure is formed by a reaction in which the cyanate group is trimerized to form a triazine ring, whereby the component (A), the component (B), and the component (D) are uniformly dispersed. A composition is produced.

  The reaction rate of the imino carbonate reaction and the triazine cyclization reaction is obtained from the peak area disappearance rate by comparing the peak area of the component (B) at the start of the reaction with the peak area after the reaction for a predetermined time by GPC measurement. It is done.

  The resin composition for film formation of the present embodiment may contain an inorganic filler (E) (hereinafter sometimes referred to as component (E)).

  The inorganic filler of component (E) is not particularly limited, but silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide , Titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, and potassium titanate. These can be used alone or in combination of two or more.

  Among these, silica is particularly preferable from the viewpoints of dielectric properties, heat resistance, and low thermal expansion. Examples of the silica include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water or the like. Examples of the dry process silica include crushed silica, fumed silica, and fused spherical silica depending on the production method. Of these, fused spherical silica is preferred because of its low thermal expansibility and high fluidity when filled in a resin.

  When using fused spherical silica as the component (E), the average particle size is preferably 0.1 to 10 μm, and more preferably 0.3 to 8 μm. By setting the average particle size of the fused spherical silica to 0.1 μm or more, the fluidity when the resin is highly filled can be kept good, and by setting the average particle size to 10 μm or less, the mixing probability of coarse particles is reduced and coarse particles It is possible to suppress the occurrence of defects due to this. Here, the average particle diameter is a particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle diameter is obtained with the total volume of the particles being 100%, and the particle size using the laser diffraction scattering method. It can be measured with a distribution measuring device or the like.

  In this embodiment, by combining and packing silica having different particle diameters, further high packing can be achieved, and the packing rate can be improved while maintaining fluidity.

  The compounding amount of the component (E) is 100 parts by mass when the total amount of the components forming the cured product in the resin composition for film formation is 100 parts by mass (the total amount of the components excluding inorganic substances such as the component (E) and volatile components is 100 parts by mass 10 to 300 parts by mass, and more preferably 50 to 250 parts by mass. By making the compounding quantity of an inorganic filler (E) into the said range, the moldability and low thermal expansibility of a resin composition can be kept favorable.

  In the resin composition for film formation of this embodiment, in order to improve the dispersibility of the inorganic filler (E) in the resin composition, epoxy silane, mercapto silane, amino silane, vinyl silane, styryl silane Coupling agents such as methacryloxysilane, acryloxysilane, titanate, and silicone oligomer can be added as appropriate.

  Moreover, additives other than the above can be blended with the film-forming resin composition according to the present embodiment as long as the effects of the present invention are not impaired. Examples of such additives include surface conditioners, flow conditioners, pigments, mold release agents, and the like. Examples of the surface conditioner include polyester-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, and an acrylic polymer. There exists a tendency for the wettability to the support body of the resin composition for film formation to improve by mix | blending a surface conditioning agent with the resin composition for film formation.

  The sealing film of this embodiment uses the film-forming resin composition according to this embodiment.

  The sealing film of this embodiment is, for example, a resin varnish in which the components (A) to (C) described above and, if necessary, the components (D), (E) and other components are dissolved or dispersed in an organic solvent. Can be used.

  The resin varnish can be produced by blending the components (A) to (C) and, if necessary, the components (D), (E) and other components with an organic solvent.

  The organic solvent used for producing the resin varnish is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate and γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atoms such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone Examples thereof include a solvent containing a sulfur atom-containing solvent such as dimethylsulfoxide. These can be used alone or in combination of two or more. Among these, cyclohexanone, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, and toluene are preferable, and methyl ethyl ketone, methyl isobutyl ketone, and toluene are more preferable from the viewpoint of high volatility and difficulty in remaining a residual solvent during film production.

  The blending amount of the organic solvent in producing the resin varnish is 100 parts by mass of the sum of the components (A) to (C) and the components (D) and (E) and other components blended as necessary. 8 to 50 parts by mass is preferable, 9 to 45 parts by mass is more preferable, and 10 to 40 parts by mass is particularly preferable. By setting the blending amount of the organic solvent to 8 parts by mass or more, the fluidity of the resin varnish is easily secured, and by setting it to 50 parts by mass or less, the amount of solvent that must be volatilized in film formation can be reduced.

  The resin varnish thus produced can be applied to one or both sides of the support and then dried by heating to obtain a sealing film.

  Although it does not specifically limit as a support body to be used, For example, Polyolefin films, such as a polyethylene film and a polypropylene film, Vinyl films, such as a polyvinyl chloride film, Polyester films, such as a polyethylene terephthalate film, A polycarbonate film, An acetylcellulose film , Tetrafluoroethylene films, and metal foils such as copper foil and aluminum foil. Among these, it is preferable to use a polyester film in terms of price and heat resistance.

  The thickness of the support is not particularly limited, but is preferably 10 to 200 μm, and more preferably 20 to 150 μm, for example.

  The method for applying the resin varnish to one or both sides of the support is not particularly limited, but for example, a coating device such as a comma coater, bar coater, kiss coater, roll coater, gravure coater, die coater or the like is used. be able to.

  The method of heating and drying the resin varnish applied to the support is not particularly limited, and examples thereof include hot air blowing. For example, the sealing film can be obtained by drying at 100 to 140 ° C. for 5 to 20 minutes.

  It is preferable that the thickness of the sealing film of this embodiment is 30-250 micrometers. Moreover, the sealing film exceeding 250 micrometers can also be manufactured by laminating | stacking several sealing films of this embodiment.

  The content of volatile components (mainly organic solvents) in the sealing film is preferably 0.2 to 1.6% by mass, and 0.3 to 1% by mass based on the total mass of the sealing film. It is more preferable. By setting it as such a range, malfunctions, such as a film crack, can be prevented and favorable handleability is obtained. Further, it is possible to prevent defects such as voids accompanying volatilization of volatile components during thermosetting.

  The sealing film with a support of the present embodiment is one in which a support is provided on at least one surface of the sealing film of the present embodiment. As a support body, the support body used when manufacturing the above-mentioned sealing film can be used.

  The semiconductor device of the present embodiment includes a semiconductor element sealed with the sealing film of the present embodiment. The sealing film with a support of this embodiment can also be used for sealing the semiconductor element with the sealing film.

  1 and 2 are schematic cross-sectional views for explaining an embodiment of a method for manufacturing a semiconductor device. In the method according to the present embodiment, the support 1 and the sealing film 2 provided on the support 1 are provided on the semiconductor element 20 to be embedded arranged side by side on the substrate 30 having the temporary fixing material 40. The process of embedding the semiconductor element 20 in the sealing film 2 by making the sealing film 10 with a support provided opposite and pressing the sealing film 2 on the semiconductor element 20 under heating (FIGS. 1A and 1B) ) And a step of curing the sealing film in which the semiconductor element is embedded (FIG. 1C). In the present embodiment, a sealing molded product in which the semiconductor element 20 is embedded in the cured product 2a obtained by thermosetting the sealing film is obtained by a laminating method, but even if the sealing molded product is obtained by a compression mold, Good.

  Although it does not specifically limit as a laminator to be used, Laminators, such as a roll type and a balloon type, are mentioned. Among these, from the viewpoint of embeddability, a balloon type capable of vacuum pressurization is preferable.

  The laminating temperature is usually performed below the softening point of the film-like support. Furthermore, the laminating temperature is preferably near the minimum melt viscosity of the sealing film. The pressure at the time of laminating varies depending on the size and density of the semiconductor element or electronic component to be embedded, but is preferably in the range of 0.2 to 1.5 MPa, more preferably in the range of 0.3 to 1.0 MPa. preferable. The laminating time is not particularly limited, but is preferably 20 to 600 seconds, more preferably 30 to 300 seconds, and still more preferably 40 to 120 seconds.

  Curing of the sealing film can be performed, for example, in the air or under an inert gas. Although it does not specifically limit as hardening temperature, 80-280 degreeC is preferable, 100-240 degreeC is more preferable, 120-200 degreeC is still more preferable. If the curing temperature is 80 ° C. or higher, the curing of the sealing film proceeds sufficiently and the occurrence of defects can be suppressed. When the curing temperature is 280 ° C. or lower, the occurrence of heat damage to other materials can be suppressed. The curing time is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 300 minutes, and further preferably 60 to 240 minutes. When the curing time is within these ranges, curing of the sealing film proceeds sufficiently, and good production efficiency is obtained. A plurality of curing conditions may be combined.

  In the present embodiment, a semiconductor device can be obtained through the following insulating layer formation, wiring pattern formation, ball mounting, and dicing steps.

  First, the insulating layer 50 for the rewiring material is provided on the side where the semiconductor element 20 of the sealing molded product 100 peeled from the substrate 30 is exposed (FIGS. 2A and 2B). Next, after forming a wiring pattern on the insulating layer 50, ball mounting is performed to form the insulating layer 52, the wiring 54, and the ball 56.

  Next, the dicing cutter 60 separates the sealed molded product into the semiconductor device 200.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

<Production Example 1: Production of thermosetting resin composition (A-1)>
In a reaction vessel having a thermometer, a stirrer, and a reflux condenser with a capacity of 500 ml that can be heated and cooled, bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., JER806): 90.0 g and general formula (1) A siloxane resin having a phenolic hydroxyl group represented by the formula (X-22-1876, manufactured by Shin-Etsu Chemical Co., Ltd.): 90.0 g, methyl isobutyl ketone: 120.0 g, and triphenylphosphine: 1.45 g were added. The reaction vessel was heated to 90 ° C. and stirred at the same temperature for 4 hours to complete the etherification reaction. Subsequently, after cooling a reaction container to room temperature (25 degreeC), phenol novolak-type cyanate resin (Lonza Japan Co., Ltd. product, PT-30): 120.0g was injected | thrown-in. After raising the temperature of the reaction vessel to 110 ° C., 0.06 g of an 8% by mass mineral spirit solution of zinc naphthenate was added. And the reaction liquid was made to react at the same temperature for 4 hours. Thereafter, the reaction solution was cooled to room temperature to obtain a thermosetting resin composition solution.

A small amount of this reaction solution was taken out and subjected to GPC measurement (polystyrene conversion, eluent: tetrahydrofuran). The peak area of the phenol novolac cyanate resin, which is a synthetic raw material that appears at around 12.2 minutes, is compared with the peak area of the phenol novolac cyanate resin at the start of the reaction. 33%. From this, the reaction rate of the phenol novolac type cyanate resin was 33%. Furthermore, when a small amount of the reaction solution was taken out and FT-IR measurement was performed by a thin film formation method, a peak appearing in the vicinity of a wave number of 1560 cm ^{−1 of the} triazine ring produced by the polymerization reaction could be confirmed. It was also possible to confirm a peak appeared in the vicinity of isocyanurate and wave number 1670 cm ^-1 and 1740 cm ^-1 of the oxazolidinone produced by the insertion reaction of the epoxy groups respectively. Thereafter, the resin content was adjusted to 70% by mass by adding a predetermined amount of methyl isobutyl ketone to obtain a thermosetting resin composition (A-1).

<Preparation of resin composition for gelation evaluation>
A predetermined amount of each component shown in Table 1 was dissolved in methyl isobutyl ketone to prepare a resin varnish having a solid content of 70% by mass. The adjusted resin varnish was added to a 2 ml screw tube and dried by heating in a drying furnace at 120 ° C. for 15 minutes to obtain a resin composition for gelation evaluation.

<Preparation of sealing film with support>
A predetermined amount of each component shown in Table 2 was dissolved and dispersed in methyl isobutyl ketone to prepare a resin varnish having a solid content of 80% by mass. A resin varnish composed of the prepared resin composition for film formation is applied to one side of a polyethylene terephthalate film, and is heat-dried at 120 ° C. for 8 minutes in a drying furnace, so that the sealing film with a support in a semi-cured state (sealing film) Thickness: 100 μm).

The following ingredients were used as blending components in the table.
(1) Liquid epoxy resin JER806: Bisphenol F type epoxy resin (Mitsubishi Chemical Corporation, JER806, trade name)
(2) Cyanate resin PT-30: Phenol novolac type cyanate resin (Lonza Japan Co., Ltd., Primeset PT-30, trade name)
(3) Oil gelling agent gelol D: 1,3: 2,4-bis-O-benzylidene-D-glucitol (manufactured by Shin Nippon Chemical Co., Ltd., Gelol D, trade name)
HSA: 12-hydroxystearic acid (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
NGB: n-lauroyl-L-glutamic acid-α, γ-dibutyramide (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)

(4) Organic metal salt zinc naphthenate: zinc naphthenate 8% by mass mineral spirit solution (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
(5) Phenol compound p- (α-cumyl) phenol: p- (α-cumyl) phenol (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.)
(6) Surface conditioner BYK-310: Polyester-modified polydimethylsiloxane (trade name, manufactured by BYK)
(7) Inorganic filler spherical silica: spherical silica Average particle size 0.5 μm (manufactured by Admatechs, SC-2500-SXJ, trade name)

<Evaluation method>
(1) Gelation property of resin composition The screw tube containing the obtained resin composition for gelation property evaluation was tilted by about 60 ° and left for 3 minutes, and the gelation property was evaluated from the presence or absence of resin flow. The results are shown in Table 1.
“A”: no resin flow “B”: resin flow

(2) Measurement of content of volatile component of sealing film with support The obtained sealing film with support is cut into 5 cm square, dried at 180 ° C. for 1 hour, and the mass change before and after drying is measured. By calculating | requiring, according to the following formula, content of the volatile component in the total mass reference | standard of a sealing film was calculated | required. The results are shown in Table 2.
Volatile component content (mass%) = [(mass before drying−mass after drying) / (mass before drying−mass of support)] × 100

(3) Bending resistance of sealing film The bending resistance of the obtained sealing film with support was evaluated by the following procedure using a bending tester (JIS type 1, cylindrical mandrel method).

  A bending tester (JIS type 1, cylindrical mandrel method, diameter 2 mm) manufactured by Yoshimitsu Seiki Co., Ltd. was prepared as a testing machine. A test piece obtained by cutting the sealing film with a support into 5 cm square was used as a test piece, and the support was applied to a bending tester to evaluate the presence or absence of cracks when the test piece was bent 180 °. The results are shown in Table 2. When the evaluation result of the bending resistance is “B”, the sealing film is inferior in handleability.

(4) Tackiness of sealing film A finger was pressed against the obtained sealing film with a support, and when the sealing film stuck to the finger, it was evaluated as "B", and when not sticking, it was evaluated as "A". . The results are shown in Table 2. When the evaluation result of tackiness is “B”, the sealing film is inferior in handleability.

(5) Glass transition temperature (Tg) of cured resin
The sealing film portion of the obtained sealing film with support is scraped off, put in a predetermined amount in a Teflon (registered trademark) formwork, and placed on both sides of the copper foil so that the glossy surface of the copper foil is in contact with it, 240 Heat pressing was performed under the press conditions of 2 ° C. for 60 minutes. After molding, the copper foil was peeled off to produce a cured plate (thickness: 1 mm) of the resin composition.

  Tan δ of the obtained cured plate was measured with a dynamic viscoelasticity measuring apparatus (Rheogel-E4000, manufactured by UBM Co., Ltd.) (tensile mode, frequency 10 Hz, temperature increase rate 5 ° C./min). The maximum value of tan δ was taken as the glass transition temperature. The results are shown in Table 2.

  Table 1 shows gelling properties of Examples 1 to 6 in which the oil gelling agent of component (C) was blended and Comparative Examples 1 and 2 in which no oil gelling agent was blended. By blending an oil gelling agent, thixotropy can be imparted to the composition, and even after 3 minutes have passed after the varnished screw tube is tilted, there is no fluidity and the shape can be maintained. From Table 1, it was shown that the gelling property can be imparted by blending the oil gelling agent (C).

  In Examples 7 to 8 and Comparative Examples 3 to 4 in Table 2, since the liquid epoxy resin of the component (A) is commonly used, even when the sealing film is thick, the content of volatile components is reduced. Can be made. When the content of volatile components is decreased, cracks or cracks due to deformation are likely to occur in the sealing film. From Examples 7 and 8 in Table 2, the content of volatile components in the film is 0.6% by mass or less. However, it was confirmed that the film exhibits good bending resistance. Furthermore, when a liquid resin is used, the sealing film tends to cause excessive tack due to the liquid resin, but from Examples 7 and 8 in Table 2, tackiness is also good (no stickiness) 100 μm. It was confirmed that a thick film could be produced.

  On the other hand, the sealing films of Comparative Examples 3 and 4 that did not contain the oil gelling agent (C) had good film bending resistance, but excessive tack occurred and handling properties deteriorated.

  As for the sealing film of Example 7, 8, the glass transition temperature (Tg) of hardened | cured material was 200 degreeC or more. In general, since organic materials are greatly impaired in physical properties in a temperature range exceeding Tg, the film-forming resin composition according to the present invention capable of forming a cured product having a high Tg has good heat resistance. , Can get reliability.

  As mentioned above, according to this invention, even if it reduces a volatile component, the handleability is favorable, and the resin composition for film formation which can form the hardened | cured material which has a sufficiently high glass transition temperature, a sealing film, and a support body It turns out that an attached sealing film can be provided.

  DESCRIPTION OF SYMBOLS 1 ... Support body, 2 ... Sealing film, 2a ... Hardened | cured material (sealing part), 10 ... Sealing film with a support body, 20 ... Semiconductor element, 30 ... Board | substrate, 40 ... Temporary fixing material, 50 ... Insulating layer, 52 ... Insulating layer, 54 ... Wiring, 56 ... Ball, 60 ... Dicing cutter, 100 ... Sealed molding, 200 ... Semiconductor device.

Claims (7)

  A film-forming resin composition comprising a liquid epoxy resin (A), a cyanate resin (B), and an oil gelling agent (C). Furthermore, the resin composition for film formation of Claim 1 containing the siloxane resin (D) which has the phenolic hydroxyl group shown by following General formula (1).

[In General Formula (1), each R is independently an alkylene group having 1 to 5 carbon atoms, and m is an integer of 5 to 100. ]   The resin composition for film formation according to claim 1 or 2, further comprising an inorganic filler (E).   The sealing film which uses the resin composition for film formation of any one of Claims 1-3.   The sealing film of Claim 4 whose thickness is 30-250 micrometers.   The sealing film with a support body in which the support body was provided in the at least 1 surface of the sealing film of Claim 4 or 5.   A semiconductor device provided with the semiconductor element sealed by the said sealing film of the sealing film of Claim 4 or 5, or the sealing film with a support body of Claim 6.

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