JP6747440B2 - Resin composition for film formation, sealing film using the same, sealing film with support, and semiconductor device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a film-forming resin composition, and particularly to a film-forming resin composition that has both excellent handleability and heat resistance. Further, the present invention enables application to sealing of semiconductor chips and embedding of a substrate on which electronic components are mounted, a sealing film using a resin composition for film formation, a sealing film with a support, and The present invention relates to a semiconductor device using these.

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

JP, 2004-327623, A

The film-shaped resin composition for sealing the semiconductor element can be produced, for example, by applying a resin varnish containing an organic solvent on a support and drying the resin varnish. In the film-shaped resin composition produced in this manner, the organic solvent is left to some extent to impart handleability in a semi-cured state.

However, when the film thickness increases, there is a problem that the volatile component (mainly the organic solvent) contained in the resin varnish is hard to volatilize, so that the volatile component cannot be sufficiently reduced. When the volatile component is not sufficiently reduced, defects such as voids are likely to occur when the semiconductor element or the like is sealed and the film-shaped resin composition is thermoset. Therefore, in the film-shaped resin composition for sealing the semiconductor element and the like, it is required that the volatile components are sufficiently reduced and the handleability is good. On the other hand, in the film-shaped resin composition for sealing a semiconductor element, the resin after curing 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 it is possible to form a sealing film that has good handleability even when the volatile component is reduced, and has sufficiently high heat resistance (high glass transition temperature). An object of the present invention is to provide a resin composition for film formation capable of forming a cured product, a sealing film, a sealing film with a support, and a semiconductor device using these.

In order to solve the above problems, as a result of the present inventors' investigation, as a result, 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 same. However, 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 findings.

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

According to the resin composition for film formation of the present invention, it is possible to obtain a sealing film which has good handleability even when the volatile component is reduced and which can form a cured product having a sufficiently high glass transition temperature.

The film-forming resin composition of the present invention may further contain a siloxane resin (D) having a phenolic hydroxyl group represented by the 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 the 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 film-forming resin composition of the present invention may further contain an inorganic filler (E).

The present invention also provides a sealing film using the resin composition for film formation according to the present invention.

The thickness of the sealing film of the present invention can be 30 to 250 μm.

The present invention also provides a support-equipped sealing film 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 by 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 sealing film which has favorable handleability, even if it reduces a volatile component, and can form the hardened|cured material which has a sufficiently high glass transition temperature, sealing film. It is possible to provide a sealing film with a support, and a semiconductor device using these.

FIG. 9 is a schematic cross-sectional view for explaining the embodiment of the method for manufacturing the semiconductor device. FIG. 9 is a schematic cross-sectional view for explaining the embodiment of the method for manufacturing the semiconductor device.

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

The resin composition for forming a film 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, it may include a component (B) and an oil gelling agent (C) (hereinafter, may be referred to as a component (C)).

According to the film-forming resin composition of the present embodiment, it is possible to obtain a sealing film which has good handleability even when the volatile component is reduced and which 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 speculate as follows. When a resin varnish made of a resin composition for film formation is applied to a support and dried to produce a sealing film, the resin composition on the side where the support is not provided is the resin on the side where the support is provided. Compared to the resin composition, it is easy to dry. Therefore, it is considered that drying of the resin composition on the side where the support is not provided progresses, and volatilization of volatile components (mainly organic solvent) in the resin composition on the side where the support is provided is prevented. To be In the resin composition of the present embodiment, by mixing 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 components of the resin composition on the holding side 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 gelated, and excessive tackiness caused by the liquid resin is suppressed. It is thought that you can do it.

In the present specification, the term "sealing film" refers to a film-shaped resin composition used for sealing or embedding semiconductor elements such as semiconductor chips and electronic components.

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

In the present specification, the epoxy resin which shows a liquid state at 25°C refers to an epoxy resin having a viscosity at 25°C measured by an E-type viscometer of 400 Pa·s or less.

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

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 it is a phenol novolac type cyanate resin, a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, Examples thereof include bisphenol F-type cyanate resin and tetramethylbisphenol F-type cyanate resin. These may be used alone or in combination of two or more. Among the above, 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 expansion, and low cost.

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

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. By adjusting the compounding amount of the component (B) to 25 parts by mass or more, the heat resistance, flame retardancy, and chemical resistance of the film-forming resin composition tend to improve. It becomes easy to secure the property.

The oil gelling agent of the component (C) can have a hydrocarbon group effective for oil solubility and a hydrogen-bonding functional group effective for self-assembly (hydroxy group, carboxy group, amino group, amide group, etc.). Examples of the oil gelling agent as the component (C) include hydroxystearic acid, particularly hydroxy fatty acid 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, compounds represented by the following general formulas (2) to (14), and the like can be given. 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-dibutylamide, 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 the 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 the 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 the 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 the 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 the 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 the 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 saturated hydrocarbon group having 1 to 20 carbon atoms and having at least one hydroxyl group in the molecular skeleton. ]

The blending amount of the component (C) is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 25 parts by mass, and more preferably 0.1 to 30 parts by mass based on 100 parts by mass of the total of the components (A) and (B). 5 to 20 parts by mass is more preferable, 1 to 10 parts by mass is particularly preferable, and 2 to 8 parts by mass is extremely preferable. When the blending amount of the component (C) is 0.1 part by mass or more, the resin can be sufficiently gelated, and when it is 30 parts by mass or less, the excellent heat resistance of the cyanate resin can be maintained.

A curing accelerator may be added to the film-forming resin composition of the present embodiment, if necessary. 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, and the like. 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 film-forming resin composition of the present 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 the 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 the component (D) is not particularly limited as long as it is a siloxane resin having a phenolic hydroxyl group at both ends of the structure represented by the general formula (1). As such a siloxane resin, for example, manufactured by Shin-Etsu Chemical Co., Ltd., product name X-22-1876 (hydroxyl value: 120 mgKOH/g), product name X-22-1875 (hydroxyl value: 60 mgKOH/g), product Name X-22-1821 (hydroxyl value: 30 mg KOH/g), trade name X-22-1822 (hydroxyl value: 20 mg KOH/g), trade name X-26-1064 (hydroxyl value: 25 mg KOH/g), Toray Dow The product name BY16-752A (hydroxyl group value: 30 mgKOH/g) and the product name BY16-799 (hydroxyl group value: 60 mgKOH/g) manufactured by Corning Co., Ltd. may be mentioned. These are commercially available from Shin-Etsu Chemical Co., Ltd. or Toray Dow Corning Co., Ltd. Of these, from the viewpoint of excellent heat resistance, low thermal expansion property, and solvent solubility, Shin-Etsu Chemical Co., Ltd. product name X-22-1876 (hydroxyl value: 120 mgKOH/g), product name X-22- 1875 (hydroxyl value: 60 mgKOH/g), trade name X-22-1821 (hydroxyl value: 30 mgKOH/g), manufactured by Toray Dow Corning, trade name BY16-752A (hydroxyl value: 30 mgKOH/g), trade name BY16-799 (hydroxyl value: 60 mg KOH/g) is preferred.

The blending amount of the component (D) is preferably 10 to 100 parts by mass, more preferably 20 to 90 parts by mass, and 30 to 80 parts by mass with respect to 100 parts by mass as the total of the components (A) and (B). Is more preferable. When the blending amount of the component (D) is 10 parts by mass or more, the cured product of the resin composition can have a sufficiently low elastic modulus and the stress relaxation property of the resin is improved. When the amount is 100 parts by mass or less, the excellent heat resistance of the cyanate resin can be maintained.

When the component (D) is blended, the compatibility between the resins can be improved by pre-reacting with the component (A) and the 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) is reacted with the iminocarbonation reaction and the triazine cyclization reaction. The reaction is carried out so that the reaction rate (sometimes referred to as the disappearance rate) of the component (B) by this reaction is 20 to 70%.

The reaction solvent that can be used in the pre-reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone Solvents, ethyl acetate, ester solvents such as γ-butyrolactone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, mesitylene, dimethylformamide, dimethylacetamide, nitrogen atom-containing solvents such as N-methylpyrrolidone, Examples thereof include a sulfur atom-containing solvent such as dimethyl sulfoxide. These may be used alone or in combination of two or more. Among the above, 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 are highly volatile and a residual solvent is less likely to remain during film formation.

In the etherification reaction of the component (A) and the component (D), a reaction catalyst can be used if 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-based catalyst such as triphenylphosphine because of its high reactivity with the components (A) and (D).

In the iminocarbonation reaction and the triazine cyclization reaction after the etherification reaction, an organic metal 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 may be used alone or in combination of two or more. Among the above, zinc naphthenate and copper naphthenate are preferable from the viewpoint of curability and solvent solubility.

In the iminocarbonation reaction and the triazine cyclization reaction, when the reaction rate is 20% or more, the resins are sufficiently compatible with each other, and when the reaction rate is 70% or less, the obtained resin is insoluble in the solvent. 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. A resin in which the component (A), the component (B), and the component (D) are uniformly dispersed by the reaction of the cyanate group to trimerize to form a triazine ring, which leads to a three-dimensional network structure. The composition is manufactured.

The reaction rate of the iminocarbonation reaction and the triazine cyclization reaction was determined from the disappearance rate of the peak area by comparing the peak area of the component (B) at the start of the reaction by GPC measurement with the peak area after the reaction for a predetermined time. To be

The film-forming resin composition of the present embodiment may include an inorganic filler (E) (hereinafter sometimes referred to as component (E)).

The inorganic filler of the 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 may be used alone or in combination of two or more.

Among the above, silica is particularly preferable in terms of dielectric properties, heat resistance, and low thermal expansion. Examples of silica include precipitated silica produced by a wet method and having a high water content, and dry silica produced by a dry method and containing almost no bound water. 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 preferable because of its low thermal expansion property and high fluidity when filled with a resin.

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

In the present embodiment, by combining and filling silica having different particle diameters, it is possible to further increase the filling rate and improve the filling rate while maintaining the fluidity.

The blending 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 (E) component and volatile components is 100 parts by mass) 10 to 300 parts by mass, and more preferably 50 to 250 parts by mass. By setting the compounding amount of the inorganic filler (E) within the above range, the moldability and low thermal expansion of the resin composition can be favorably maintained.

In order to improve the dispersibility of the inorganic filler (E) in the resin composition, the film-forming resin composition of the present embodiment has an epoxy silane type, a mercapto silane type, an amino silane type, a vinyl silane type, a styryl silane type. Coupling agents such as methacryloxysilane-based, acryloxysilane-based, titanate-based, and silicone oligomer can be added as appropriate.

Further, the film-forming resin composition according to the present embodiment may contain additives other than those described above within a range that does not impair the effects of the present invention. Examples of such additives include a surface conditioner, a flow conditioner, a pigment, and a release agent. Examples of the surface modifier include polyester-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, acrylic polymer and the like. By blending the surface modifier with the film-forming resin composition, the wettability of the film-forming resin composition to the support tends to be improved.

The sealing film of this embodiment is formed by using the resin composition for film formation according to this embodiment.

The sealing film of the present embodiment is, for example, a resin varnish obtained by dissolving or dispersing the above-mentioned components (A) to (C) and, if necessary, the components (D), (E) and other components in an organic solvent. Can be manufactured using.

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 in producing the resin varnish is not particularly limited, for example, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, alcohol solvents such as propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvent, ethyl acetate, ester solvent such as γ-butyrolactone, ether solvent such as tetrahydrofuran, aromatic solvent such as toluene, xylene and mesitylene, nitrogen atom such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone Examples of the solvent include a sulfur atom-containing solvent such as dimethyl sulfoxide. These may be used alone or in combination of two or more. Among the above, 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 are highly volatile and a residual solvent is less likely to remain during film formation.

The amount of the organic solvent used for producing the resin varnish is 100 parts by mass based on the total amount of the components (A) to (C), and optionally the components (D), (E) and other components. In this case, 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 amount of the organic solvent to be 8 parts by mass or more, the fluidity of the resin varnish can be easily ensured, and by setting it to be 50 parts by mass or less, the amount of the solvent that must be volatilized in forming a film can be reduced.

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

The support used is not particularly limited, for example, polyethylene film, polyolefin film such as polypropylene film, vinyl film such as polyvinyl chloride film, polyester film such as polyethylene terephthalate film, polycarbonate film, acetyl cellulose film. , Tetrafluoroethylene film, 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 also 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 on one side or both sides of the support is not particularly limited, but for example, a coating device such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, or a die coater 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 a method of blowing hot air. For example, a sealing film can be obtained by drying at 100 to 140° C. for 5 to 20 minutes.

The thickness of the sealing film of this embodiment is preferably 30 to 250 μm. In addition, a plurality of sealing films of this embodiment can be laminated to produce a sealing film having a thickness of more than 250 μm.

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. Is more preferable. Within such a range, problems such as film cracking can be prevented and good handleability can be obtained. Further, it is possible to prevent defects such as voids caused by volatilization of volatile components during heat curing.

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

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

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

The laminator to be used is not particularly limited, but examples thereof include roll type and balloon type laminators. Among these, from the viewpoint of embedding property, a balloon type that allows vacuum pressurization is preferable.

The laminating temperature is usually below the softening point of the film-shaped support. Further, the laminating temperature is preferably around the minimum melt viscosity of the sealing film. The pressure during lamination 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 0.3 to 1.0 MPa. preferable. The laminating time is also not particularly limited, but is preferably 20 to 600 seconds, more preferably 30 to 300 seconds, and further preferably 40 to 120 seconds.

Curing of the sealing film can be performed, for example, in the air or under an inert gas. The curing temperature is not particularly limited, but is preferably 80 to 280°C, more preferably 100 to 240°C, and further preferably 120 to 200°C. When the curing temperature is 80° C. or higher, the sealing film is sufficiently cured, and the occurrence of defects can be suppressed. When the curing temperature is 280° C. or lower, heat damage to other materials can be suppressed. The curing time is also 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, the sealing film is sufficiently cured and good production efficiency can be obtained. Moreover, a plurality of curing conditions may be combined.

In this embodiment, a semiconductor device can be obtained through the following steps of forming an insulating layer, forming a wiring pattern, ball mounting, and dicing.

First, an insulating layer 50 for a rewiring material is provided on the side of the molded encapsulation 100 separated from the substrate 30 where the semiconductor element 20 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 sealing molded product into individual pieces to obtain the semiconductor device 200.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Production Example 1: Preparation of thermosetting resin composition (A-1)>
Bisphenol F type epoxy resin (JER806 manufactured by Mitsubishi Chemical Co., Ltd.): 90.0 g and a general formula (1) were placed in a reaction vessel with a thermometer, a stirrer, and a reflux condenser that can heat and cool. A siloxane resin having a phenolic hydroxyl group represented by (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. Next, after cooling the reaction container to room temperature (25° C.), 120.0 g of phenol novolac type cyanate resin (PT-30, manufactured by Lonza Japan Co., Ltd.) was added. After raising the temperature of the reaction vessel to 110° C., 0.06 g of an 8 mass% mineral spirit solution of zinc naphthenate was added. Then, the reaction solution was reacted at the same temperature for 4 hours. Then, the reaction liquid was cooled to room temperature to obtain a solution of a thermosetting resin composition.

A small amount of this reaction solution was taken out and subjected to GPC measurement (in terms of polystyrene, eluent: tetrahydrofuran). The peak area of the phenol novolac type cyanate resin as a synthetic raw material that appears at an elution time of about 12.2 minutes was compared with the peak area of the phenol novolak type cyanate resin at the start of the reaction. It was 33%. From this, the reaction rate of the phenol novolak 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 forming 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. Then, the resin content was adjusted to 70 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>
Predetermined amounts of the components shown in Table 1 were 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 heated and dried at 120° C. for 15 minutes in a drying oven to obtain a resin composition for gelation evaluation.

<Production of sealing film with support>
Predetermined amounts of the components shown in Table 2 were dissolved and dispersed in methyl isobutyl ketone to prepare a resin varnish having a solid content of 80% by mass. A resin varnish made of the prepared resin composition for film formation is applied to one side of a polyethylene terephthalate film, and is heated and dried at 120° C. for 8 minutes in a drying oven to obtain a semi-cured sealing film with a support (sealing film). Thickness: 100 μm) was manufactured.

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

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

<Evaluation method>
(1) Gelation property of resin composition The screw tube containing the obtained resin composition for gelation evaluation was tilted at about 60° and left for 3 minutes, and the gelation property was evaluated based on whether or not the resin flowed. The results are shown in Table 1.
"A": No resin flow "B": Resin flow

(2) Measurement of Content of Volatile Components in Supporting Encapsulating Film The obtained supporting encapsulating film was cut into 5 cm square pieces, dried at 180° C. for 1 hour, and the mass change before and after drying was measured. By obtaining the content, the content of the volatile component on the basis of the total weight of the sealing film was obtained according to the following formula. The results are shown in Table 2.
Content of volatile components (mass %)=[(mass before drying−mass after drying)/(mass before drying−mass of support)]×100

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

As a tester, a bending tester (JIS type 1, cylindrical mandrel method, diameter 2 mm) made by Yoshimits Seiki Co., Ltd. was prepared. A test piece was obtained by cutting the support-attached sealing film into 5 cm square, and the support was placed on a bending tester to evaluate whether or not cracks were generated when the test piece was bent 180°. The results are shown in Table 2. When the bending resistance evaluation result 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 tackiness evaluation result is "B", the sealing film is inferior in handleability.

(5) Glass transition temperature (Tg) of cured resin
The encapsulating film part of the obtained encapsulating film with a support was scraped off, put in a predetermined amount in a Teflon (registered trademark) mold, and copper foil was placed on both sides of the encapsulating film so that the shiny side of the copper foil was in contact. The molding was carried out under heat and pressure at a pressure of 2 MPa for 60 minutes. After molding, the copper foil was peeled off to prepare a plate (thickness: 1 mm) of a cured product of the resin composition.

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

Table 1 shows the gelling properties of Examples 1 to 6 in which the oil gelling agent as the component (C) was blended and Comparative Examples 1 to 2 in which the oil gelling agent was not blended. By adding an oil gelling agent, thixotropy can be imparted to the composition, and even if the screw tube containing the varnish is tilted for 3 minutes and there is no fluidity, the shape can be maintained. From Table 1, it was shown that the gelation property can be imparted by the addition of the oil gelling agent (C).

Since the liquid epoxy resin of the component (A) is commonly used in Examples 7 to 8 and Comparative Examples 3 to 4 in Table 2, the content of volatile components is reduced even when the thickness of the sealing film is large. Can be made. When the content of the volatile component is reduced, the sealing film is likely to be cracked or cracked due to deformation, but from Examples 7 and 8 in Table 2, the content of the volatile component in the film is 0.6% by mass or less. However, it was confirmed that good flex resistance was exhibited. Furthermore, when a liquid resin is used, the sealing film is apt to have excessive tackiness due to the liquid resin, but from Examples 7 and 8 in Table 2, the tackiness is 100 μm which is good (no stickiness). It was confirmed that a thick film could be produced.

On the other hand, the sealing films of Comparative Examples 3 and 4 which did not contain the oil gelling agent (C) were good in the flex resistance of the film, but excessive tack occurred and the handleability was deteriorated.

The glass transition temperature (Tg) of the cured product of the sealing films of Examples 7 and 8 was 200° C. or higher. In general, the physical properties of an organic material are greatly impaired in a temperature range exceeding Tg. Therefore, the resin composition for forming a film according to the present invention, which can form a cured product having a high Tg, has good heat resistance. , Can get reliability.

As described above, according to the present invention, a film-forming resin composition, a sealing film, and a support which have good handleability even when the volatile component is reduced and can form a cured product having a sufficiently high glass transition temperature. It can be seen that an attached sealing film can be provided.

DESCRIPTION OF SYMBOLS 1... Support, 2... Sealing film, 2a... Cured material (sealing part), 10... Supporting sealing film, 20... Semiconductor element, 30... Substrate, 40... Temporary fixing material, 50... Insulating layer, 52... Insulating layer, 54... Wiring, 56... Ball, 60... Dicing cutter, 100... Sealing molded article, 200... Semiconductor device.

Claims (6)

Liquid epoxy resin (A), the cyanate resin (B), o Irugeru agent (C), and film-forming resin composition comprising a siloxane resin (D) having a phenolic hydroxyl group represented by the following general formula (1).

[In the 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 film-forming resin composition according to claim 1, further comprising an inorganic filler (E). A sealing film comprising the resin composition for film formation according to claim 1 or 2 . The sealing film according to claim 3 , which has a thickness of 30 to 250 µm. At least one sealing film support with the support is provided on the surface of the sealing film according to claim 3 or 4. A semiconductor device comprising the sealing film according to claim 3 or 4 , or a semiconductor element sealed by the sealing film of the sealing film with a support according to claim 5 .

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