JP2019065110A - Resin sheet, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin sheet capable of forming a thick film of a resin composition layer and having excellent plating fixability in a cured layer obtained by curing the resin composition layer, and a method for producing the resin sheet. Kind Code: A1 A resin sheet 1 used for encapsulating an electronic component in a method for manufacturing a semiconductor device, the resin sheet 1 including a curable resin composition layer 11, and the resin composition layer 11 being cured. A resin sheet 1 formed from a resin composition containing a resin, a film-forming resin and an inorganic filler, wherein the film-forming resin contains a polyvinyl acetal resin. [Selection diagram] Figure 1

Description

  The present invention relates to a resin sheet used for sealing an electronic component in a method of manufacturing a semiconductor device, and a method of manufacturing the sheet.

  Conventionally, in a method of manufacturing a semiconductor device, an electronic component such as a semiconductor chip is sealed using a resin sheet provided with a curable resin composition layer. For example, after laminating a resin composition layer in the resin sheet on an electronic component provided on a substrate, the resin composition layer is cured to form a cured layer, thereby sealing the electronic component. (Patent Document 1). Here, the resin composition layer has a sufficient thickness in the resin sheet described above from the viewpoint of suppressing the formation of a void between the electronic component and the cured layer in the sealing, and thereby the resin composition It is required that the object layer well cover the periphery of the electronic component.

  In recent years, development of a substrate (hereinafter sometimes referred to as “component-embedded substrate”) in which an electronic component is incorporated is underway, and the resin sheet described above is used also in the production of such a component-embedded substrate. Sealing of electronic components may be performed. In this case, subsequent to the sealing of the electronic component, a hole penetrating the hardened layer is formed, and then a wire for electrically connecting the electronic component to the outside through the hole is formed.

  In the case of formation of the hole mentioned above, the residue (it may be hereafter mentioned "smear") of resin which comprises a cured layer may generate | occur | produce, and this smear may remain in a hole. If the wiring is formed with the smear remaining in the hole, a problem such as conduction failure of the wiring is likely to occur. Therefore, after the formation of the holes and before the formation of the wiring, a process of removing the generated smear (hereinafter, referred to as “desmear process”) is performed. As one of the methods of such a desmear process, the method of exposing the object of a process to alkaline solution exists. According to this method, the smear can be dissolved in an alkaline solution and removed.

JP, 2016-175972, A

  In the method of manufacturing the component-embedded substrate, following the desmearing process using the alkaline solution described above, the metal plating process is performed on the surface of the hardened layer as a part of the wiring formation process. Here, the resin sheet disclosed in Patent Document 1 has a problem that the plating is not sufficiently fixed to the cured layer formed by curing the resin composition layer in the plating process. If the fixing of the plating is insufficient, the wiring can not be formed well, and the quality of the component-embedded substrate obtained is degraded.

  The present invention has been made in view of such a situation, and it is possible to form a thick film of a resin composition layer, and it is excellent in the fixability of plating in a cured layer formed by curing the resin composition layer. It aims at providing a resin sheet and a method of manufacturing the resin sheet.

  In order to achieve the above object, first, the present invention is a resin sheet used for sealing an electronic component in a method of manufacturing a semiconductor device, wherein the resin sheet is provided with a curable resin composition layer The resin composition layer is formed of a resin composition containing a curable resin, a film-forming resin and an inorganic filler, and the film-forming resin contains a polyvinyl acetal resin. A resin sheet is provided (invention 1).

  In the resin sheet according to the invention (Invention 1), when the resin composition for forming the resin composition layer contains a polyvinyl acetal resin, the viscosity of the coating liquid of the resin composition becomes relatively high. Therefore, it becomes possible to form the resin composition layer which has sufficient thickness by coating of the said coating liquid. Furthermore, when the resin composition for forming the resin composition layer contains a polyvinyl acetal resin, the cured layer formed by curing the resin composition layer undergoes a desmear treatment using an alkaline solution, While the inorganic filler moderately detaches from the hardened layer, the matrix component present around the inorganic filler hardly dissolves in the alkaline solution. As a result, the surface of the hardened layer after desmearing has minute irregularities, and when plating is performed thereafter, the anchor effect of plating on the surface is exhibited well, and the fixing property of the plating in the hardened layer is It will be excellent.

  In the said invention (invention 1), it is preferable that the thickness of the said resin composition layer is 100 micrometers or more and 300 micrometers or less (invention 2).

  In the said invention (invention 1 and 2), it is preferable that the said resin composition layer consists of a single layer (invention 3).

  In the above inventions (Inventions 1 and 2), the resin composition layer is formed by laminating two or more unit resin composition layers, and the thickness of each of the unit resin composition layers is 100 μm or more. It is preferable that the

In the said invention (invention 1-4), it is preferable that the said inorganic filler is what was surface-treated by the surface treating agent whose minimum coverage area is less than 550 m < ² > / g (invention 5).

  In the above inventions (Inventions 1 to 5), the method of manufacturing the semiconductor device preferably includes the step of plating at least a part of the surface of a cured layer formed by curing the resin composition layer ( Invention 6).

  In the above inventions (Inventions 1 to 6), the method for manufacturing the semiconductor device preferably includes the step of bringing an alkaline solution into contact with at least a part of the surface of a cured layer formed by curing the resin composition layer (Invention 7).

  In the above inventions (Inventions 1 to 7), the semiconductor device is preferably a component built-in substrate (Invention 8).

  Second, the present invention is a method for producing a resin sheet used for sealing an electronic component in a method for producing a semiconductor device, wherein the resin sheet comprises a curable resin composition layer, and the resin composition The layer is formed of a resin composition containing a curable resin, a film-forming resin and an inorganic filler, and the film-forming resin contains a polyvinyl acetal resin, and the production method is the resin composition. A process for producing a resin sheet comprising the steps of applying a coating liquid of the above to form a coating film, and forming the resin composition layer by drying the coating film. Invention 9).

  In the said invention (invention 9), the said coating film is formed by one coating of the coating liquid of the said resin composition, and the single layer of said (invention 3) is dried by drying the said coating film. It is preferable to include forming the resin composition layer which consists of these, or forming the unit resin composition layer of the said (invention 4) (invention 10).

  In the said invention (invention 9 and 10), it is preferable that the coating liquid of the said resin composition contains the diluent whose boiling point is 130 degreeC or more (invention 11).

  The resin sheet of the present invention is capable of forming a thick film of the resin composition layer, and is excellent in the fixing property of the plating in the cured layer formed by curing the resin composition layer.

It is a sectional view of a resin sheet concerning one embodiment of the present invention. It is a photograph by the scanning electron microscope of the surface of the hardened layer concerning Example 1. FIG. It is a photograph by the scanning electron microscope of the surface of the hardened layer concerning comparative example 1. It is a photograph by the scanning electron microscope of the surface of the hardened layer concerning comparative example 2.

Hereinafter, embodiments of the present invention will be described.
[Resin sheet]
FIG. 1 shows a cross-sectional view of the resin sheet 1 according to the present embodiment. As shown in FIG. 1, the resin sheet 1 according to the present embodiment includes a resin composition layer 11 and a release sheet 12 laminated on at least one surface of the resin composition layer 11. In addition, another release sheet may be further laminated on the surface of the resin composition layer 11 opposite to the release sheet 12. However, the release sheet 12 and another release sheet may be omitted.

1. Resin Composition Layer In the resin sheet 1 according to the present embodiment, the resin composition layer 11 has curability. Here, having the curability means that the resin composition layer 11 can be cured by heating or the like. That is, the resin composition layer 11 is uncured in the state of constituting the resin sheet 1. The resin composition layer 11 is preferably thermosetting. As a result, even if it is difficult to cure the resin composition layer 11 by energy ray irradiation, because the resin composition layer 11 has a large thickness or contains a colorant. The resin composition layer 11 can be cured well.

  In the resin sheet 1 according to the present embodiment, the resin composition layer 11 is formed of a resin composition containing a curable resin, a film-forming resin and an inorganic filler. Furthermore, in the resin sheet 1 which concerns on this embodiment, the said resin composition contains polyvinyl acetal resin as a film forming resin.

(1) Curable resin In the resin sheet 1 which concerns on this embodiment, when a resin composition contains curable resin, it becomes possible to seal an electronic component strongly. Even in the case where it is difficult to irradiate the resin composition layer 11 with energy rays, as the curable resin, the thickness of the resin composition layer 11 is large or the resin composition layer 11 contains a colorant. From the viewpoint of being able to cure the resin composition layer 11 favorably, a thermosetting resin is preferred. The thermosetting resin is not particularly limited as long as the resin composition layer 11 can be cured, and, for example, a resin usually contained in a sealing material can be used. Specifically, epoxy resin, phenol resin, maleimide compound, melamine resin, urea resin, benzoxazine compound, acid anhydride compound, amine compound, active ester resin, cyanate ester resin and the like can be mentioned. The species can be used alone or in combination of two or more. Among these, it is preferable to use an epoxy resin, a phenol resin, or a mixture thereof, and it is preferable to use at least an epoxy resin. In addition, epoxy resin, those having a glycidyl group in a side chain such as acryl resin, and those having a high molecular weight epoxy group may also be involved in curing of the resin composition layer 11 because the epoxy group is reacted by heat. In the resin sheet 1 which concerns on this embodiment, what is a high molecular weight thing and has a function which forms the resin composition layer 11 in a sheet form is regarded as film forming resin. The weight average molecular weight of such a high molecular weight polymer is generally 25,000 or more.

  Epoxy resins generally have the property of being three-dimensional reticulated upon heating and forming a rigid cured product. As such an epoxy resin, various known epoxy resins can be used. Specifically, glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenyl novolac, cresol novolac; butanediol, polyethylene Glycidyl ethers of alcohols such as glycol and polypropylene glycol; Glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid and tetrahydrophthalic acid; Glycidyl type in which an active hydrogen bonded to a nitrogen atom such as aniline isocyanurate is substituted with a glycidyl group or Epoxy resins of the alkyl glycidyl type; vinylcyclohexane diepoxide, 3,4-epoxycyclohexylmethyl-3,4-dicyclohexanecarboxylate, 2- (3,4-epoxy So-called alicyclics in which an epoxy is introduced by, for example, oxidation of a carbon-carbon double bond in the molecule, such as cyclohexyl) -5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane, etc. Type epoxides can be mentioned. In addition, an epoxy resin having a biphenyl skeleton, a triphenylmethane skeleton, a dicyclohexadiene skeleton, a naphthalene skeleton and the like can also be used. These epoxy resins can be used singly or in combination of two or more. Among the epoxy resins described above, glycidyl ether of bisphenol A (bisphenol A type epoxy resin), epoxy resin having biphenyl skeleton (biphenyl type epoxy resin), epoxy resin having naphthalene skeleton (naphthalene type epoxy resin), or a combination thereof It is preferred to use.

  As a phenol resin, for example, bisphenol A, tetramethyl bisphenol A, diallyl bisphenol A, biphenol, bisphenol F, diallyl bisphenol F, triphenylmethane type phenol, tetrakis phenol, novolac type phenol, cresol novolac resin, biphenylaralkyl skeleton A phenol (biphenyl type phenol) etc. are mentioned, It is preferable to use a biphenyl type phenol among these. These phenolic resins can be used singly or in combination of two or more. In addition, when using an epoxy resin as a thermosetting resin, it is preferable to use a phenol resin together from a viewpoint of the reactivity with an epoxy resin etc.

  The content of the thermosetting resin in the resin composition is preferably 10% by mass or more, particularly preferably 15% by mass or more, and further preferably 20% by mass or more. In addition, the content is preferably 60% by mass or less, particularly preferably 50% by mass or less, and further preferably 40% by mass or less. When the content is 10% by mass or more, curing of the resin composition layer 11 becomes more sufficient, and the electronic component can be sealed more firmly. In addition, when the content is 60% by mass or less, curing of the resin composition layer 11 at an unintended stage can be further suppressed, and the storage stability becomes more excellent. In the case where the resin composition is diluted to form a coating liquid, and the coating and drying are performed to form a sheet, the content of the thermosetting resin in the resin composition is the amount of components volatilized in the drying step. The contents of the other components of the resin composition are the same, based on the amount excluding.

  An energy ray curable resin may be used as the curable resin. Examples of energy ray-curable resins include resins cured by ultraviolet light, and examples of resins cured by ultraviolet light include resins having a group having a reactive double bond such as an acryloyl group or methacryloyl group in the molecule. Can be mentioned. When using an energy ray-curable resin, the resin composition preferably further contains a photopolymerization initiator. In the resin sheet 1 according to the present embodiment, the resin composition may contain both a thermosetting resin and an energy ray curable resin.

(2) Film-Forming Resin In the resin sheet 1 according to the present embodiment, the resin composition containing the film-forming resin makes it easy to form the resin composition layer 11 into a sheet. Furthermore, in the resin sheet 1 which concerns on this embodiment, a resin composition contains polyvinyl acetal resin as a film forming resin. When the resin composition contains a polyvinyl acetal resin, the coating liquid of the resin composition has a relatively high viscosity, and by coating the coating liquid, a resin composition having a sufficient thickness. It becomes possible to form a layer.

  Furthermore, in the resin sheet 1 according to the present embodiment, when the resin composition contains a polyvinyl acetal resin, when performing a desmear treatment using an alkaline solution on a cured layer formed by curing the resin composition layer 11. The matrix component present around the inorganic filler in the hardened layer becomes difficult to elute in the alkaline solution. On the other hand, since the inorganic filler is properly desorbed from the hardened layer into the alkaline solution, the surface of the hardened layer is formed of fine voids formed by the desorbed inorganic filler and the remaining matrix. There will be irregularities. Subsequent to the desmearing treatment, the plating treatment is performed on the surface of the hardened layer having such minute irregularities, whereby the anchor effect of the plating on the surface is exhibited well, and the fixing property of the plating in the hardened layer is excellent. It will be As a result, it is possible to manufacture a semiconductor device in which the wiring is well fixed to the surface of the hardened layer.

  The polyvinyl acetal resin is limited as long as it imparts a desired viscosity to the coating solution of the resin composition and the cured layer formed by curing the resin composition layer has a desired resistance to an alkaline solution. For example, polyvinyl butyral obtained by reacting polyvinyl alcohol and butyraldehyde, polyvinyl formal obtained by reacting polyvinyl alcohol and formaldehyde, polyvinyl acetoacetal obtained by reacting polyvinyl alcohol and acetaldehyde, etc. These may be used alone or in combination of two or more. Among these, polyvinyl butyral is preferably used.

  The weight average molecular weight of the polyvinyl acetal resin is preferably 25,000 or more, and particularly preferably 50,000 or more. Further, the weight average molecular weight is preferably 600,000 or less, and particularly preferably 300,000 or less.

  In the resin sheet 1 which concerns on this embodiment, a resin composition may contain other film forming resin with polyvinyl acetal resin. Examples of other film-forming resins include phenoxy resins, olefin resins, polyester resins, polyurethane resins, polyester urethane resins, polyamide resins, polystyrene resins, polysiloxane resins, rubber resins, etc. These may be used alone or in combination of two or more. The weight average molecular weight of the other film-forming resin is preferably 25,000 or more, and particularly preferably 50,000 or more. Further, the weight average molecular weight is preferably 1,500,000 or less, and particularly preferably 800,000 or less.

  The phenoxy resin is not particularly limited, but, for example, bisphenol A type, bisphenol F type, bisphenol A / bisphenol F copolymer type, bisphenol S type, bisphenol acetophenone type, novolac type, fluorene type, dicyclopentadiene type, Examples thereof include norbornene type, naphthalene type, anthracene type, adamantane type, terpene type, trimethylcyclohexane type, biphenol type and biphenyl type. Among these, it is preferable to use a bisphenol A type phenoxy resin.

  Further, in the resin sheet 1 according to the present embodiment, it is preferable that the content of the film forming resin in the resin composition which is easily eluted from the cured layer formed by curing the resin composition layer 11 into the alkaline solution is small. In particular, it is preferable not to contain such a film-forming resin. Acrylic resin, polyester resin, and polyester urethane resin are mentioned as an example of the film-forming resin which is easy to elute from the said hardened layer in alkaline solution.

  The content of the polyvinyl acetal resin in the resin composition is preferably 4% by mass or more, particularly preferably 6% by mass or more, and further preferably 8% by mass or more. In addition, the content is preferably 40% by mass or less, particularly preferably 30% by mass or less, and further preferably 20% by mass or less. When the content is in the above range, it becomes easy to prepare a coating solution of a resin composition having a desired viscosity, and it becomes easy to form a thick film of the resin composition layer 11, and The resistance to the alkaline solution of the hardened layer formed by hardening becomes effectively high, and the fixing property of the plating to the hardened layer becomes more excellent.

  The content of all film-forming resins including polyvinyl acetal resin in the resin composition is preferably 1% by mass or more, particularly preferably 3% by mass or more, and further preferably 5% by mass It is preferable that it is more than. In addition, the content is preferably 30% by mass or less, particularly preferably 20% by mass or less, and further preferably 10% by mass or less. When the content is in the above range, it becomes easier to form the resin composition layer 11 in a sheet shape.

  The content of the polyvinyl acetal resin in the film-forming resin is preferably 75% by mass or more, particularly preferably 85% by mass or more, and further preferably 92% by mass or more. Moreover, it is preferable that content of polyvinyl acetal resin in film forming resin is 100 mass% or less.

(3) Inorganic Filler In the resin sheet 1 which concerns on this embodiment, when the resin composition contains an inorganic filler, the cured layer in which the resin composition layer 11 is hardened exhibits the outstanding mechanical strength. It becomes. Furthermore, when the hardened layer is subjected to a desmearing process using an alkaline solution, the inorganic filler is properly desorbed from the hardened layer, and as a result, the anchor effect of plating on the surface of the hardened layer as described above is good. The fixing property of the plating in the hardened layer is excellent.

  Examples of the inorganic filler include silica, alumina, glass, titanium oxide, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride Examples of the filler include aluminum borate, boron nitride, crystalline silica, amorphous silica, mullite, composite oxide such as cordierite, montmorillonite, smectite, etc. Or in combination of two or more. Among these, it is preferable to use a silica filler.

  The shape of the inorganic filler may be any of granular, needle-like, plate-like, indeterminate and the like, and among them, it is preferably spherical.

  The average particle diameter of the inorganic filler is preferably 0.01 μm or more, particularly preferably 0.1 μm or more, and further preferably 0.3 μm or more. The average particle diameter of the inorganic filler is preferably 3.0 μm or less, and particularly preferably 1.0 μm or less. When the average particle diameter of the inorganic filler is in the above range, the cured layer formed by curing of the resin composition layer 11 can easily exhibit mechanical strength effectively, and the inorganic filler can be in the alkaline solution from the cured layer. It becomes moderately easy to detach. In addition, let the average particle diameter of the inorganic filler in this specification be a value measured by the dynamic light scattering method using the particle size distribution measuring apparatus (made by Nikkiso Co., Ltd., product name "Nanotrac Wave-UT 151").

  The maximum particle size of the inorganic filler is preferably 0.05 μm or more, and more preferably 0.5 μm or more. Further, the maximum particle size is preferably 5 μm or less, and particularly preferably 3 μm or less. When the maximum particle size of the inorganic filler is in the above range, the inorganic filler can be easily filled in the hardened layer, and the hardened layer has more excellent mechanical strength. In addition, let the largest particle size of the inorganic filler in this specification be a value measured by a dynamic light scattering method using a particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., product name “Nanotrac Wave-UT 151”).

In the resin sheet 1 which concerns on this embodiment, it is preferable that the inorganic filler is surface-treated by the surface treating agent. As a result, the dispersibility and the filling property of the inorganic filler in the resin composition are improved, and when performing a desmear treatment using an alkaline solution on the cured layer formed by curing the resin composition layer 11, The filler is easily detached from the hardened layer appropriately. In particular, the minimum coverage area of the surface treatment agent is preferably less than 550 m ² / g, particularly preferably 520 m ² / g or less, and further preferably 450 m ² / g or less. Further, the minimum covering area of the surface treatment agent is preferably 100 m ² / g or more, particularly preferably 200 m ² / g or more, and further preferably 300 m ² / g or more. When the minimum covering area of the surface treatment agent is less than 550 m ² / g, detachment of the inorganic filler from the cured layer formed by curing the resin composition layer 11 is easily generated, and as a result, in the cured layer It becomes easy to obtain the excellent fixability of plating. In addition, when the minimum covering area of the surface treatment agent is 100 m ² / g or more, the dispersibility and the filling property of the inorganic filler in the resin composition become more excellent.

  An epoxysilane, a vinylsilane, etc. are mentioned as an example of the said surface treatment agent. Among these, epoxysilane is preferably used. Specific examples of the epoxysilane include, for example, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane etc. are mentioned. Among these, it is preferable to use 3-glycidoxypropyltrimethoxysilane from the viewpoint of effectively promoting the elimination of the inorganic filler.

  Specific examples of the vinylsilane include vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (2-methoxyethoxy) silane, and the like. Among these, it is preferable to use vinyltrimethoxysilane from the viewpoint of being able to effectively promote the detachment of the inorganic filler.

  The method for surface-treating the inorganic filler with a surface treatment agent is not particularly limited, and can be performed by a general method. For example, after a non-processed inorganic filler is stirred at normal temperature using a mixer and the surface treatment agent is sprayed thereto, the surface treatment can be performed by further stirring for a predetermined time. The stirring time after spraying is preferably, for example, 5 minutes or more and 15 minutes or less. In order to fix the surface treatment agent to the inorganic filler sufficiently, after the above operation, the inorganic filler may be removed from the mixer and left for a day or more, or a slight heat treatment may be performed. Moreover, in order to surface-treat uniformly, after spraying a surface treating agent, the organic solvent may be further added and the said stirring may be performed. As a mixer, a well-known thing can be used, For example, Blenders, such as V blender, a ribbon blender, a bubble cone blender, a Henschel mixer, mixers, such as a concrete mixer, a ball mill etc. are mentioned, Among these, using a mixer Is preferred.

  The content of the inorganic filler in the resin composition is preferably 40% by mass or more, particularly preferably 50% by mass or more, and further preferably 60% by mass or more. The content is preferably 90% by mass or less, particularly preferably 85% by mass or less, and further preferably 80% by mass or less. When the content of the inorganic filler is 40% by mass or more, a cured layer obtained by curing the resin composition layer 11 has better mechanical strength. In addition, when the content of the inorganic filler is 90% by mass or less, the resin composition layer 11 is easily cured, and a semiconductor device having better quality can be manufactured using the resin sheet 1 It becomes.

  When the inorganic filler is surface-treated with a surface treatment agent, the proportion of the inorganic filler surface-treated with the surface treatment agent is 70% by mass or more among the inorganic fillers contained in the resin composition. The content is preferably 85% by mass or more. When the ratio is in the above-mentioned range, it becomes possible to achieve both of effectively promoting the detachment of the inorganic filler from the hardened layer and the excellent mechanical strength of the hardened layer. .

(4) Curing catalyst In the resin sheet 1 which concerns on this embodiment, when a resin composition contains a thermosetting resin, it is preferable to further contain a curing catalyst. As a result, the curing reaction of the thermosetting resin can be effectively advanced, and the resin composition layer 11 can be favorably cured. Examples of curing catalysts include imidazole curing catalysts, amine curing catalysts, phosphorus curing catalysts and the like.

  Specific examples of the imidazole-based curing catalyst include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl 2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxymethyl) imidazole, etc. From the viewpoint of - It is preferred to use ethyl-4-methylimidazole.

  Specific examples of the amine curing catalyst include triazine compounds such as 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 1,8-diazabicyclo [5,4, 0] Undecene-7 (DBU), triethylenediamine, benzyldimethylamine, tertiary amine compounds such as triethanolamine and the like. Among these, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine is preferable.

  Further, specific examples of the phosphorus-based curing catalyst include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine and the like.

  The curing catalysts described above may be used alone or in combination of two or more.

  The content of the curing catalyst in the resin composition is preferably 0.01% by mass or more, particularly preferably 0.05% by mass or more, and further preferably 0.1% by mass or more preferable. The content is preferably 2.0% by mass or less, particularly preferably 1.5% by mass or less, and further preferably 1.0% by mass or less. When the content is in the above range, the resin composition layer 11 can be cured more favorably.

(5) Plastic solvent In resin sheet 1 concerning this embodiment, it is preferred that resin composition layer 11 contains a plastic solvent by content of 1.0 mass% or more. Thereby, the brittleness of the resin composition layer 11 is improved, and the resin composition layer 11 is less likely to collapse, and the occurrence of breakage or breakage in the resin composition layer 11 during storage, transport, use, etc. is suppressed. Be done. Furthermore, since the resin composition layer 11 has predetermined flexibility, the resin composition layer 11 can easily cover the periphery of the electronic component sufficiently, and a cured layer formed by curing the resin composition layer 11 and an electron The formation of an air gap between components can be well suppressed.

  The plastic solvent is not limited as long as it can sufficiently improve the brittleness of the resin composition layer 11. As described above, the resin composition layer 11 is preferably formed of a resin composition containing a thermosetting resin, and in this case, the resin composition layer 11 is used for sealing the electronic component. It can be cured by heating. Here, the plastic solvent is volatilized by heating, and thus is sufficiently removed from the formed hardened layer by the heating. The plastic solvent does not volatilize easily at normal temperature in order to suppress excessive release from the resin composition layer 11 at a stage prior to application to electronic parts such as storage and transport. Is preferred. Moreover, as described later, after the resin composition is diluted with a solvent to prepare a coating liquid, when the resin composition layer 11 is formed using the coating liquid, the above-mentioned plastic solvent is the above-mentioned plastic solvent. It is preferable that it is a solvent used to prepare a coating liquid.

  The plasticizing solvent preferably has a boiling point of 130 ° C. or more, and the plasticizing solvent preferably has a boiling point of 210 ° C. or less. Since the boiling point of the above-mentioned plastic solvent is 130 ° C or more, when drying the coating film formed by applying the coating liquid containing the plastic solvent concerned, the whole plastic solvent does not volatilize in the coating film, and appropriate The content of the plastic solvent in the resin composition layer 11 can be easily adjusted to the value described above. Furthermore, during storage or transport of the resin sheet 1, the release of the plastic solvent from the resin composition layer 11 can be effectively suppressed, and the content of the plastic solvent adjusted as described above is maintained for a long time It becomes easy to do. On the other hand, when the resin composition layer 11 is cured by heating because the boiling point of the plastic solvent is 210 ° C. or less, the plastic solvent is easily volatilized by the heating, so that the content of the plastic solvent in the hardened layer Is easy to lower enough.

  Specific examples of the plasticizing solvent include cyclohexanone (boiling point: 155.6 ° C.), dimethylformamide (boiling point: 153 ° C.), dimethyl sulfoxide (boiling point: 189.0 ° C.), ethers of ethylene glycol (cellosolve) (boiling point: And organic solvents such as ortho-xylene (boiling point: 144.4 ° C.) and the like.

(6) Other Components The resin composition in the present embodiment may further contain a plasticizer, a stabilizer, a tackifier, a colorant, a coupling agent, an antistatic agent, an antioxidant, and the like.

(7) Configuration of Resin Composition Layer The thickness of the resin composition layer 11 is preferably 100 μm or more, particularly preferably 105 μm or more, and further preferably 110 μm or more. In the resin sheet 1 according to the present embodiment, when the resin composition contains a polyvinyl acetal resin, the coating liquid of the resin composition has a relatively high viscosity, and once using the coating liquid. By coating, it becomes possible to form a sufficiently thick resin composition layer 11 of 100 μm or more. When the thickness of the resin composition layer 11 is 100 μm or more, the periphery of the electronic component can be effectively covered by the resin composition layer 11 when the electronic component is sealed using the resin sheet 1 It becomes possible to effectively suppress the formation of a void between the cured layer formed by curing the resin composition layer 11 and the electronic component. The upper limit of the thickness of the resin composition layer 11 is not particularly limited, but is preferably 300 μm or less, particularly preferably 250 μm or less, and further preferably 200 μm or less. When the resin composition layer 11 is formed by laminating two or more resin composition layers, the thickness of the above resin composition layer 11 is the thickness of all the resin composition layers 11. The total thickness of the

  In the resin sheet 1 according to the present embodiment, as described above, the coating liquid of the resin composition has a relatively high viscosity, and it is sufficient to be 100 μm or more by one coating using the coating liquid. It is possible to form a thick resin composition layer 11. In the resin sheet 1 which concerns on this embodiment, it is preferable that the resin composition layer 11 consists of a single layer. Here, "consists of a single layer" means that the resin composition layer 11 is not formed by laminating a plurality of unit resin composition layers, and is composed of a single unit resin composition layer It means that. In the resin sheet 1 according to the present embodiment, when the resin composition layer 11 is a single layer, productivity is excellent as compared to the case where the resin composition layer is formed by laminating a plurality of layers. It will be In addition, when a plurality of unit resin composition layers are laminated, there is a possibility that foreign matter or air bubbles may be caught during lamination, but such a phenomenon is caused by the resin composition layer 11 being formed of a single layer. It is possible to avoid the failure caused.

  Moreover, when forming the resin composition layer 11 by laminating | stacking the unit resin composition layer of two or more layers, it is preferable that the thickness of a unit resin composition layer is 100 micrometers or more in all. Thereby, since resin composition layer 11 with a total thickness of 200 μm or more can be obtained by laminating a small number of unit resin composition layers, productivity is excellent. The thickness of the unit resin composition layer is preferably 150 μm or less.

2. Release Sheet The resin sheet 1 according to the present embodiment may be provided with a release sheet 12. The configuration of the release sheet 12 is optional, and examples thereof include polyester films such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, and plastic films such as polyolefin films such as polypropylene and polyethylene. It is preferable that the peeling process is given to these peeling surfaces (surface which contact | connects the resin composition layer 11 of the resin sheet 1). As a release agent used for peeling process, release agents, such as a silicone type, fluorine type, a long chain alkyl type, are mentioned, for example.

  The thickness of the release sheet 12 is not particularly limited, but is usually 20 μm or more and 250 μm or less.

3. Physical Properties of Resin Sheet In the resin sheet 1 according to the present embodiment, a 30 μm thick layer formed by electroless copper plating and subsequent electrolytic copper plating on the cured layer formed by curing of the resin composition layer 11 It is preferable that the peeling strength at the time of peeling a copper plating layer from a hardening layer is 2 N / 10 mm or more, and it is preferable that it is especially 4 N / 10 mm or more. In the resin sheet 1 according to the present embodiment, the resin composition contains a polyvinyl acetal resin, and as a result, as described above, the fixing property of the plating to the cured layer formed by curing the resin composition layer 11 is excellent Become. Therefore, the high peel strength as described above can be achieved, and the swelling of the plating can be effectively suppressed. The upper limit of the peel strength is not particularly limited, but is preferably 15 N / 10 mm or less, and more preferably 12 N / 10 mm. The details of the method for measuring the peel strength are as described in the test examples described later.

4. Method of Manufacturing Resin Sheet The resin sheet 1 according to the present embodiment is preferably manufactured by forming the resin composition layer 11 by applying the coating liquid of the resin composition described above. If it is such a manufacturing method, when forming resin composition layer 11 which contains a trace amount of plastic solvent, dilution added to the above-mentioned coating liquid for dissolution, dispersion, dilution, etc. of a component which constitutes a resin composition It becomes easy to form the resin composition layer 11 without completely drying the agent, and it is easy to obtain the resin composition layer 11 containing such a plastic solvent in a small amount. In particular, the resin composition layer 11 consisting of a single layer is formed by applying a single coating solution of the resin composition described above (the resin composition layer 11 is formed by laminating a plurality of unit resin composition layers In this case, it is preferable to form and manufacture a unit resin composition layer. For example, a coating liquid containing the above-described resin composition, and optionally, a solvent or a dispersion medium is prepared, and the coating liquid is coated on the peeling surface of the release sheet 12 to form a coating film. The resin sheet 1 can be manufactured by drying the coating film. In the resin sheet 1 according to the present embodiment, when the resin composition contains a polyvinyl acetal resin, the above-described coating liquid has a relatively high viscosity, and the resin composition layer 11 (one coating) It becomes possible to form a thick film on the unit resin composition layer).

  The coating described above includes a knife coating method, a die coating method, a bar coating method, a gravure coating method, a blade coating method, a roll kiss coating method and the like, and in particular, the knife coating method is preferably used. According to these coating methods, it becomes easy to form the resin composition layer 11 having a sufficient thickness.

  When coating is performed by a knife coating method, the coating speed is preferably 0.3 m / min or more, and particularly preferably 0.5 m / min or more. Further, the speed is preferably 30 m / min or less, and particularly preferably 15 m / min or less. By setting it as such a coating speed, it becomes easy to form the resin composition layer 11 into a thick film.

  As conditions for drying the formed coating film, the drying temperature is preferably 40 ° C. or more, particularly preferably 45 ° C. or more. The drying temperature is preferably 150 ° C. or less, and particularly preferably 130 ° C. or less. The drying time is preferably 8 minutes or more, and more preferably 10 minutes or more. The drying time is preferably 20 minutes or less, and more preferably 15 minutes or less. The coating may be dried while changing the drying temperature. For example, the drying temperature is set to 50 ° C., 70 ° C., 90 ° C. and 100 ° C., with the drying time being about 3 minutes to 4 minutes for each temperature. It is preferable to sequentially raise and dry.

  As the above-mentioned diluent, those which can be adopted for the above-mentioned plastic solvent can be used, and as others, toluene (boiling point: 110.6 ° C.), ethyl acetate (boiling point: 77.1 ° C.), methyl ethyl ketone Organic solvents such as boiling point: 79.6 ° C.), isopropyl alcohol (boiling point: 82.6 ° C.) and the like can be mentioned. The diluent may be used in combination of two or more. The release sheet 12 may release as a process material, and may protect the resin composition layer 11 until it is used for sealing.

  Moreover, as a manufacturing method of the laminated body by which the peeling sheet was each laminated | stacked on both surfaces of the resin sheet 1, a coating liquid is coated on the peeling surface of one peeling sheet, a coating film is formed, and this is dried. After forming a laminate comprising the resin composition layer 11 and one release sheet, the surface of the resin composition layer 11 of the laminate opposite to the one release sheet is attached to the release surface of the other release sheet. Thus, the resin sheet 1 having a configuration of one release sheet / resin composition layer 11 / other release sheet can be obtained. In this case, at least one of the release sheets may be released as a process material, or the resin composition layer 11 may be protected until used for sealing.

  When the resin composition layer 11 is obtained by laminating a plurality of layers, the resin composition layer obtained by the above method is used as a unit resin composition layer, and a plurality of the resin composition layers are laminated to form a resin composition. The layer 11 may be obtained. In this case, there is an advantage that a thick resin composition layer 11 can be obtained by the amount of laminated unit resin composition layers.

5. Method of Using Resin Sheet The resin sheet 1 according to the present embodiment is used to seal an electronic component in a method of manufacturing a semiconductor device. For example, after laminating the resin composition layer 11 in the resin sheet 1 on an electronic component provided on a substrate or a temporary fixing material such as an adhesive sheet, the resin composition layer 11 is cured to form a cured layer. Thus, the electronic component can be sealed.

  The resin sheet 1 according to the present embodiment is preferably stored under refrigeration for substantially all or part of the period from production to use. Refrigerated storage can prevent the reaction of the curable resin contained in the resin composition layer 11 from proceeding. Moreover, when the resin composition layer 11 contains a trace amount of a plastic solvent, volatilization of the plastic solvent during storage can be suppressed. Cold storage is preferably performed at 15 ° C. or less, more preferably 0 to 12 ° C.

  When the resin composition contains a thermosetting resin, the curing described above is preferably performed by heating the resin composition layer 11. In this case, the temperature of the heat treatment is preferably 100 ° C. or higher, and more preferably 120 ° C. or higher. Further, the temperature is preferably 240 ° C. or less, and particularly preferably 200 ° C. or less. Further, the heat treatment time is preferably 15 minutes or more, and particularly preferably 20 minutes or more. Moreover, it is preferable to make the said time into 300 minutes or less, and it is preferable to set it as 100 minutes or less especially.

  Moreover, it is preferable to perform hardening of the resin composition layer 11 by the heating mentioned above in multiple steps by heat processing. The heating in this case is preferably performed in two or more separate steps, and in particular, a first heat treatment to be thermally cured at a temperature T1 and a second heat treatment to be thermally cured at a temperature T2 higher than the temperature T1. It is more preferable that the heat treatment be performed by a two-stage heating process. In this case, in the first heat treatment, the temperature T1 is preferably 100 ° C. or more and 130 ° C. or less, and the heat treatment time is preferably 15 minutes or more and 60 minutes or less. In the second heat treatment, the temperature T2 is preferably 150 ° C. or more and 220 ° C. or less, and the heat treatment time is preferably 30 minutes or more and 120 minutes or less.

When the resin composition contains an energy ray curable resin, curing of the resin composition layer 11 may be performed by irradiation of energy rays, for example, irradiation of ultraviolet rays. When ultraviolet light is irradiated, the conditions are usually an illuminance of about 50 to 500 mW / cm ² and an irradiation amount of about 100 to 2,500 mJ / cm ² . In this case, after the electronic component is laminated by the resin composition layer, a heating step for volatilizing the plastic solvent in the resin composition layer 11 may be performed before or after curing of the resin composition layer 11.

  When the resin sheet 1 which concerns on this embodiment equips only the single side | surface side of the resin composition layer 11 with the peeling sheet 12, the said peeling sheet 12 is a resin composition layer, after laminating the resin composition layer 11 on an electronic component. Peeling may be performed from the resin composition layer 11 before curing 11. Alternatively, after curing the resin composition layer 11, peeling may be performed from the formed curing layer. When the resin sheet 1 according to the present embodiment includes release sheets on both sides of the resin composition layer 11, one release sheet is released, and the exposed surface of the exposed resin composition layer 11 is laminated on the electronic component. The other release sheet may be released before or after curing of the resin composition layer 11.

  It is preferable that the manufacturing method of the semiconductor device mentioned above includes the process of making alkaline solution contact at least one part of the surface of the hardened layer formed by hardening | curing the resin composition layer 11. As shown in FIG. Preferably, the method of manufacturing a semiconductor device described above includes the step of plating at least a part of the surface of the cured layer formed by curing the resin composition layer 11.

  As an example of the manufacturing method including the step of contacting the alkaline solution described above and the step of performing the plating treatment described above, there is a method of manufacturing a component-embedded substrate as a semiconductor device. In the method for manufacturing a component-embedded substrate, for example, first, after laminating the resin composition layer 11 in the resin sheet 1 on the electronic component provided on the substrate, the resin composition layer 11 is cured to form a cured layer. Form Next, when the release sheet 12 is laminated on the cured layer, after the release sheet 12 is removed, the cured layer and the electronic component are viewed from the side of the cured layer opposite to the presence of the electronic component. And a hole that reaches the surface of the hardened layer on the side where the electronic component exists. Subsequently, in the step of bringing the alkaline solution into contact, the laminate of the hole-formed hardened layer, the electronic component, and the base material is brought into contact with the alkaline solution. By this treatment, the smear generated when the hole is formed is removed from the inside of the hole (desmear treatment). Subsequently, as a step of performing the above-described plating process, formation of a wiring is performed. Specifically, a plating process using a metal such as copper is performed on the surface of the hardened layer on which the holes are formed, the metal is embedded in the holes, and then an unnecessary portion of the plated metal is etched. It is possible to form the wiring as a remaining metal piece by removing it by the like. Thereafter, a multilayer substrate is formed on both surfaces of the hardened layer by a build-up method or the like to obtain a component-embedded substrate.

  In the resin sheet 1 according to the present embodiment, when the resin composition contains the polyvinyl acetal resin, in the case of performing the above-described step of contacting the alkaline solution, in the cured layer formed by curing the resin composition layer 11 The matrix components present around the inorganic filler become difficult to elute in the alkaline solution. On the other hand, since the inorganic filler is properly desorbed from the hardened layer into the alkaline solution, the surface of the hardened layer has fine unevenness due to the minute voids and the remaining matrix which are generated by the desorbed inorganic filler. It becomes. Furthermore, when the step of performing the plating process described above is performed following the step of bringing into contact with the alkaline solution, the anchor effect of plating is exhibited well on the surface of the hardened layer on which minute irregularities are formed. The fixability of the plating is excellent. As a result, it is possible to manufacture a semiconductor device in which the wiring is well fixed to the surface of the hardened layer.

  It will not specifically limit, if it is an electronic component generally made into the object of sealing as an example of the electronic component mentioned above, For example, a semiconductor chip, a capacitor | condenser, etc. are mentioned. Moreover, as a semiconductor device manufactured, a component built-in substrate, a semiconductor package, etc. are mentioned, It is preferable that it is especially a component built-in substrate.

  The embodiments described above are described to facilitate the understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents that fall within the technical scope of the present invention.

  Hereinafter, the present invention will be described in more detail by showing Examples and Test Examples, but the present invention is not limited to the following Test Examples and the like.

Example 1 and Comparative Examples 1 and 2
The components shown in Table 1 were mixed and diluted with methyl ethyl ketone to obtain a coating liquid of a resin composition having a solid content concentration shown in Table 1. Obtained by coating the above-mentioned coating liquid on a release surface of a release film (product name: “PET 38 AL-5 *” manufactured by Lintec Corporation, product name: “PET 38 AL-5 *”), one side of which was treated with silicone release, using a knife coater under the following conditions The resin coating layer was formed by drying the coated film under the following conditions. Thereafter, the release surface of the second release film (manufactured by Lintec Corporation, product name "SP-PET 381031") is laminated on the surface of the resin composition layer not in contact with the release film, and the resin composition layer and two sheets A resin sheet comprising the release sheet of In addition, as it mentions later, the inorganic filler is mix | blended in the coating liquid of a resin composition in the state disperse | distributed to the cyclohexanone as a dispersion medium. The said cyclohexanone remains in a resin sheet, even after formation of a resin sheet. Here, the compounding amount of the inorganic filler in Table 1 reflects only the content of the inorganic filler, and does not reflect the content of the cyclohexanone. Table 1 also shows the viscosities of the coating solution measured with a viscometer (manufactured by Anton Pearl Co., product name “Rheometer MCR302”).
<Coating conditions using a knife coater>
Coating speed: 0.6 m / min Coating gap: 700 μm
<Drying conditions>
Drying temperature: 50 ° C → 70 ° C → 90 ° C → 100 ° C
Drying time: 3 minutes 20 seconds for each temperature

Here, the details of the components shown in Table 1 are as follows.
[Thermosetting resin]
Bis A type epoxy resin: Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation, product name "YL 980")
Biphenyl type epoxy resin: Biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name "NC-3000-L")
Naphthalene type epoxy resin: Naphthalene type epoxy resin (manufactured by DIC, product name "HP-6000")
Biphenyl-type phenolic resin: Biphenyl-type phenolic resin (manufactured by Meiwa Chemical Co., Ltd., product name "MEHC-7851-SS")
[Film forming resin]
Polyvinyl acetal resin: Polyvinyl acetal resin (manufactured by Sekisui Chemical Co., Ltd., product name "BX-5", weight average molecular weight: 130,000)
Bis A type phenoxy resin: bisphenol A type phenoxy resin (Mitsubishi Chemical Co., Ltd., product name "YX7200B35", weight average molecular weight: 30,000)
Acrylic resin: Acrylic acid ester copolymer (manufactured by Nagase ChemteX, product name "SG-P3", weight average molecular weight: 130,000)
[Curing catalyst]
Imidazole-based thermosetting catalyst: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., product name "2E4MZ")
[Inorganic filler]
Epoxysilane-treated silica filler: silica filler (manufactured by Admatex, product name "SO-C2", average particle diameter: 0.5 μm, maximum particle diameter: 2 μm, shape: spherical), 3-glycidoxypropyltrimethoxy Surface-treated using silane (Shin-Etsu Chemical Co., Ltd., product name “KBM-403”, minimum coverage area: 330 m ² / g). In addition, it was mix | blended with the coating liquid of the resin composition in the dispersion state which made cyclohexanone the dispersion medium.

[Test Example 1] (Surface Observation)
After laminating the surface by the side of the resin composition layer in the resin sheet produced by the example and the comparative example on a copper bonded laminated board, the peeling sheet was peeled from the resin composition layer. Subsequently, the resin composition layer was cured by heating at 100 ° C. for 60 minutes and further heating at 170 ° C. for 60 minutes to form a cured layer. A sodium hydroxide solution containing potassium permanganate as an alkaline solution (product name “OPC-1200”, 35 ml of product name “OPC-1200” in 315 ml of water as an alkaline solution is used as a laminate of the obtained hardened layer and copper laminated plate) After dilution, potassium permanganate was further added to adjust the potassium permanganate concentration to 0.32 mol / L; hereinafter, it was immersed at 80 ° C. for 15 minutes in “alkaline solution (1)”. The surface of the measurement sample after the immersion is subjected to conditions of an acceleration voltage of 5 kV or 10 kV, an inclination angle of 45 degrees, and a magnification of 10000 using a scanning electron microscope (product name "S-4700" manufactured by Hitachi, Ltd.). I took a picture. The obtained photographs are shown in FIGS. Here, FIG. 2 shows a photograph according to Example 1, FIG. 3 shows a photograph according to Comparative Example 1, and FIG. 4 shows a photograph according to Comparative Example 2.

  According to the photographs shown in FIG. 2 and FIG. 3, on the surface of the cured layer of Example 1 and Comparative Example 1, there are a large number of cavities resulting from the detachment of the inorganic filler from the cured layer. From this, in the cured layer formed using the resin sheet of Example 1 and Comparative Example 1, when the treatment with the alkaline solution is performed, the inorganic filler is appropriately desorbed, while the periphery of the inorganic filler is filled. It can be seen that the matrix which had been used remains almost unchanged without dissolving out in the alkaline solution.

  On the other hand, according to the photograph shown in FIG. 4, on the surface of the cured layer of Comparative Example 2, while a large number of inorganic fillers are present, the above-mentioned matrix is hardly found. From this, it can be seen that in the cured layer formed using the resin sheet of Comparative Example 2, the above-described matrix was dissolved in the alkaline solution in the state where the inorganic filler was left.

Test Example 2 (Measurement of Thickness of Resin Composition Layer)
The thickness of the resin sheet produced in the example and the comparative example was measured using a constant pressure thickness measuring instrument (manufactured by Techlock, product name "PG-02J"), and the thickness of the release film was determined from the obtained measurement value. The thickness (μm) of the resin composition layer was calculated by subtracting the thickness. The results are shown in Table 1.

[Test Example 3] (Evaluation of peeling of plating)
The surface of the resin composition layer side of the resin sheet produced in the example and the comparative example is a vacuum laminator (Nikko Materials Co., Ltd.) on one side of a core material (product name "MCL-E-679FG" manufactured by Hitachi Chemical Co., Ltd.) It laminated on conditions of 90 degreeC and 0.3 Mpa using the product name "V130"), and peeled the peeling sheet from the resin composition layer after that. Subsequently, after heating at 100 ° C. for 60 minutes, the resin composition layer was thermally cured by further heating at 180 ° C. for 60 minutes. Thereby, the laminated body which consists of a core material and the hardened layer which a resin composition layer hardens | cures was obtained.

  The resulting laminate is mixed with a glycol ether solvent and ethylene glycol monobutyl ether at a ratio of 2: 1 in a swelling solution (Okuno Pharmaceutical Industry Co., Ltd., product name “OPC-1080 conditioner”) at 60 ° C. After being immersed for 5 minutes, desmearing was performed by immersing in the above-mentioned alkaline solution (1) as a roughening solution at 80 ° C. for 5 minutes.

  Subsequently, the above laminate is immersed in a palladium-tin colloid catalyst solution (manufactured by Okuno Pharmaceutical Industry Co., Ltd., product name “OPC 50 Inducer M”) at 40 ° C. for 6 minutes, and then an activation treatment solution (manufactured by Okuno Pharmaceutical Industries, Ltd.) Soak at room temperature for 5 minutes at room temperature, and then for 35 minutes at room temperature in an electroless copper plating solution (Okuno Seiyaku Kogyo Co., Ltd., product name "ATS Adkappa IW"). By immersion, electroless copper plating was performed on the laminate. Thus, a plated layer of copper with a thickness of 1 μm was formed. Thereafter, the laminate on which the plated layer was formed was subjected to an annealing treatment by being placed in an environment of 150 ° C. for 30 minutes.

After the above annealing treatment, the above laminate was subjected to conditions of current density 1 A / dm ^{2 in} an electrolytic solution (copper sulfate concentration: 200 g / L, sulfuric acid concentration: 50 g / L, chloride ion concentration: 50 mg / L). Electrolytic copper plating. Thereby, the final thickness of the plating layer became 30 μm. Subsequently, the laminate having the plated layer formed thereon was subjected to an annealing treatment by being placed in an environment of 190 ° C. for 60 minutes.

  The presence or absence of peeling of the plating layer from the hardened layer in the layered product in which the plating layer with a thickness of 30 micrometers was formed was checked visually. The results are shown in Table 1.

[Test Example 4] (Measurement of peel strength of plating)
In Test Example 3, the laminate in which the plating layer having a thickness of 30 μm was formed in Example 1 and Comparative Example 1 in which the peeling of the plating was evaluated as “absent” was cut to a width of 10 mm, and the universal type tensile test Using a machine (manufactured by Shimadzu Corporation, product name "Autograph AG-IS"), peel the plated layer on the side in contact with the hardened layer from the hardened layer under the conditions of peel angle 90 ° and peel speed 50 mm / min. The peel strength (N / 10 mm) at that time was measured. The results are shown in Table 1.

  As mentioned above, while the thickness of the resin composition layer was thick enough, the resin sheet obtained by the Example was excellent in the fixability of the plating in a hardened layer.

  The resin sheet according to the present invention can be suitably used for the production of a semiconductor device such as a component built-in substrate.

1 ... resin sheet 11 ... resin composition layer 12 ... release sheet

Claims (11)

A resin sheet used for sealing an electronic component in a method of manufacturing a semiconductor device,
The resin sheet comprises a curable resin composition layer,
The resin composition layer is formed of a resin composition containing a curable resin, a film-forming resin and an inorganic filler,
A resin sheet, wherein the film-forming resin contains a polyvinyl acetal resin.   The thickness of the said resin composition layer is 100 micrometers or more and 300 micrometers or less, The resin sheet of Claim 1 characterized by the above-mentioned.   The said resin composition layer consists of a single layer, The resin sheet of Claim 1 or 2 characterized by the above-mentioned. The resin composition layer is formed by laminating two or more unit resin composition layers,
The thickness of the said unit resin composition layer is 100 micrometers or more, The resin sheet of Claim 1 or 2 characterized by the above-mentioned. The resin sheet according to any one of claims 1 to 4, wherein the inorganic filler is surface-treated with a surface treatment agent having a minimum covering area of less than 550 m ² / g.   The method for manufacturing a semiconductor device according to any one of claims 1 to 5, further comprising the step of plating at least a part of the surface of a cured layer formed by curing the resin composition layer. The resin sheet as described in a term.   The method for manufacturing a semiconductor device according to any one of claims 1 to 6, further comprising the step of bringing an alkaline solution into contact with at least a part of the surface of a cured layer formed by curing the resin composition layer. The resin sheet as described in.   The resin sheet according to any one of claims 1 to 7, wherein the semiconductor device is a component built-in substrate. A method of manufacturing a resin sheet used for sealing an electronic component in a method of manufacturing a semiconductor device, comprising:
The resin sheet comprises a curable resin composition layer,
The resin composition layer is formed of a resin composition containing a curable resin, a film-forming resin and an inorganic filler,
The film-forming resin contains polyvinyl acetal resin,
The manufacturing method is characterized by comprising a step of applying a coating liquid of the resin composition to form a coating, and a step of forming the resin composition layer by drying the coating. Manufacturing method of resin sheet. The coating film is formed by a single application of a coating liquid of the resin composition,
Forming the resin composition layer consisting of the single layer according to claim 3 by drying the coating film, or including forming the unit resin composition layer according to claim 4 The manufacturing method of the resin sheet of Claim 9 characterized by the above-mentioned.   The coating liquid of the said resin composition contains the diluent whose boiling point is 130 degreeC or more, The manufacturing method of the resin sheet of Claim 9 or 10 characterized by the above-mentioned.