WO2019188255A1 - Resin sheet and method for producing same - Google Patents

Resin sheet and method for producing same Download PDF

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Publication number
WO2019188255A1
WO2019188255A1 PCT/JP2019/010018 JP2019010018W WO2019188255A1 WO 2019188255 A1 WO2019188255 A1 WO 2019188255A1 JP 2019010018 W JP2019010018 W JP 2019010018W WO 2019188255 A1 WO2019188255 A1 WO 2019188255A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
resin
resin sheet
composition layer
less
Prior art date
Application number
PCT/JP2019/010018
Other languages
French (fr)
Japanese (ja)
Inventor
康貴 渡邉
裕介 根津
貴志 杉野
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to KR1020207024355A priority Critical patent/KR20200135310A/en
Priority to CN201980022521.8A priority patent/CN111918931A/en
Priority to JP2020509851A priority patent/JPWO2019188255A1/en
Publication of WO2019188255A1 publication Critical patent/WO2019188255A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

  • the present invention relates to a resin sheet used for sealing electronic components and a method for manufacturing the same.
  • an electronic component such as a semiconductor chip is sealed with a curable resin composition.
  • the electronic component is sealed by curing the resin composition.
  • a semiconductor device obtained by sealing an electronic component as described above may be exposed to high temperatures due to heat generation during use. Therefore, the hardened
  • Patent Document 1 discloses a resin composition containing a predetermined epoxy resin, a curing agent and a phosphate ester. In addition, the said resin composition is assumed that the electronic component is sealed by transfer molding.
  • the above-described resin composition for sealing an electronic component is formed into a sheet shape to form a resin sheet.
  • the resin composition hardly flows during sealing, thereby suppressing the occurrence of unevenness due to the flow and the movement of the electronic component.
  • the resin composition disclosed in Patent Document 1 seals electronic components by transfer molding and cannot be molded well into a sheet shape. Therefore, a resin sheet having good flame retardancy cannot be produced using the resin composition disclosed in Patent Document 1.
  • a cured product obtained by curing the resin composition has good adhesion to the electronic component and a substrate that supports the electronic component. It is required to have. In particular, even when a force that shears the cured product and the target that is in contact with the cured product is applied, the cured product has sufficient adhesive force to prevent the cured product from peeling from the target. Is required. In particular, such adhesive strength is required to be sufficiently maintained even after the obtained semiconductor device is subjected to a reliability test (such as a wet heat test).
  • Patent Document 1 Although the resin composition disclosed in Patent Document 1 is disclosed in the example of Cited Document 1 that the occurrence of cracks can be suppressed to some extent when the cured product is subjected to a reflow treatment under predetermined conditions, it has been described above. Adhesive strength sufficient to counter such shear forces cannot be achieved.
  • This invention is made
  • the present invention is a resin sheet used for sealing an electronic component, the resin sheet comprising a thermosetting resin, a thermoplastic resin, an inorganic filler, Provided is a resin sheet comprising a resin composition layer formed from a resin composition containing a flame retardant, wherein the flame retardant is an aromatic condensed phosphate ester that is liquid at room temperature (Invention 1). ).
  • the resin composition layer is formed from a resin composition containing an aromatic condensed phosphate ester that is liquid at room temperature as a flame retardant, whereby the resin composition A cured product obtained by curing the physical layer has excellent flame retardancy. Furthermore, the aromatic condensed phosphate ester that is liquid at room temperature exhibits good compatibility with other components contained in the resin composition, and thereby the cured layer formed by curing the resin composition layer has high uniformity. Thus, the cured product has excellent adhesive force with respect to an object with which the cured product is in contact.
  • the aromatic condensed phosphate ester has the following formula (1): (In the formula (1), n represents an integer of 1 or more and 5 or less, R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 2 represents a hydrogen atom or 1 carbon atom. Represents an alkyl group of ⁇ 5.) And the following formula (2) (In the formula (2), Ar represents a divalent aromatic hydrocarbon, and R 3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) It is preferable that at least 1 type of the compound represented by these is included (invention 2).
  • the aromatic condensed phosphate ester preferably has a viscosity at 25 ° C. of 5000 mPa ⁇ s or more and 30000 mPa ⁇ s or less (Invention 3).
  • the content of the flame retardant in the resin composition is preferably 0.5% by mass or more and 5.0% by mass or less (Invention 4).
  • the present invention is a method for producing the resin sheet (Invention 1 to 5), wherein a coating liquid containing the resin composition layer is applied onto a predetermined release sheet, whereby the resin composition layer
  • the manufacturing method of the resin sheet characterized by providing the process of forming is provided (invention 6).
  • the resin sheet of the present invention can form a cured product having excellent flame retardancy and excellent adhesive force. Moreover, according to the manufacturing method of this invention, such a resin sheet can be manufactured.
  • the resin sheet according to the present embodiment is used for sealing electronic components, and is formed from a resin composition containing a thermosetting resin, a thermoplastic resin, an inorganic filler, and a flame retardant.
  • a resin composition layer is provided.
  • the flame retardant is an aromatic condensed phosphate ester that is liquid at room temperature.
  • the resin composition in the present embodiment can be cured by heating because it contains a thermosetting resin.
  • the cured layer formed by curing the resin composition layer contains the above-described inorganic filler, and the formed cured layer exhibits good heat resistance and mechanical strength. Accordingly, the electronic component can be satisfactorily sealed by using the resin sheet according to the present embodiment.
  • the resin composition in this embodiment can maintain the sheet-like shape of the resin composition layer favorably by containing a thermoplastic resin. Therefore, the resin sheet in the present embodiment is excellent in handleability, and when using the resin sheet according to the present embodiment, the resin sheet is laminated on the electronic component without performing transfer molding. Sealing can be performed by a simpler operation.
  • the resin composition in the present embodiment contains an aromatic condensed phosphate ester that is liquid at room temperature as a flame retardant, so that the semiconductor device manufactured using the resin sheet according to the present embodiment generates heat during use. Even if the semiconductor device is placed in a high temperature environment, the formed hardened layer is difficult to burn and exhibits excellent flame retardancy.
  • the aromatic condensed phosphate ester flame retardant which is liquid at room temperature exhibits excellent compatibility with other components such as thermoplastic resins and thermosetting resins contained in the resin composition. Therefore, in the resin composition layer in the present embodiment, each component is uniformly mixed without aggregating the constituent components, and by curing the resin composition layer, a highly uniform cured layer is obtained. Can be formed. As a result, the adhesive force between the cured layer and the target that the cured layer contacts is improved, and the cured product is described above even when a force that shears the cured product and the target is applied. Peeling from the object is suppressed.
  • the resin composition in the present embodiment contains a thermoplastic resin
  • the flame retardant described above can exhibit excellent compatibility with the thermoplastic resin
  • the resin composition is a predetermined one.
  • the viscosity when the resin composition layer is heated for curing the resin composition layer, it becomes difficult for the flame retardant to bleed out from the resin composition layer. For this reason, a decrease in flame retardancy due to a decrease in the content of the flame retardant in the resin composition layer is suppressed, and an adverse effect on the semiconductor device due to the bleed-out flame retardant is also suppressed.
  • thermosetting resin is not particularly limited as long as the resin composition layer can be cured.
  • a resin usually contained in a sealing material is used. can do.
  • epoxy resin, phenol resin, melamine resin, urea resin, polyester resin, urethane resin, acrylic resin, polyimide resin, benzoxazine resin, phenoxy resin, acid anhydride compound, amine compound, naphthol resin, activity Examples include ester resins, benzoxazine resins, cyanate ester resins, and the like. These may 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.
  • Epoxy resins generally have the property of forming a three-dimensional network when heated and forming a hardened product.
  • 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; Alkyl glycidyl type epoxy resin; vinylcyclohexane diepoxide, 3,4-epoxycyclohexylmethyl-3,4-dicyclohexanecarboxylate, 2- (3,4-epoxy I) Cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-d
  • an epoxy resin having a biphenyl skeleton, a triphenylmethane skeleton, a dicyclohexadiene skeleton, a naphthalene skeleton, or the like can also be used. These epoxy resins can be used alone or in combination of two or more.
  • glycidyl ether of bisphenol A bisphenol A type epoxy resin
  • epoxy resin having a biphenyl skeleton bisphenol A type epoxy resin
  • epoxy resin having a naphthalene skeleton naphthalene type epoxy resin
  • phenol resin examples include bisphenol A, tetramethyl bisphenol A, diallyl bisphenol A, biphenol, bisphenol F, diallyl bisphenol F, triphenylmethane phenol, tetrakisphenol, novolac phenol, cresol novolac resin, and biphenyl aralkyl skeleton.
  • Phenol (biphenyl type phenol) and the like can be mentioned, and among these, it is preferable to use biphenyl type phenol.
  • These phenol resins can be used individually by 1 type or in combination of 2 or more types.
  • an epoxy resin as curable resin it is preferable to use a phenol resin together from the viewpoint of reactivity with the epoxy resin.
  • 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. Further, 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, the resin composition layer is more sufficiently cured, and the electronic component can be more firmly sealed. Further, when the content is 60% by mass or less, curing at an unintended stage of the resin composition layer can be further suppressed, and the storage stability becomes more excellent.
  • thermoplastic resin is not particularly limited as long as it is suitable for forming the resin composition into a sheet.
  • thermoplastic resins include phenoxy resins, polyvinyl acetal resins, olefin resins, polyester resins, polyurethane resins, polyester urethane resins, amide resins, styrene resins, silane resins, rubber resins, etc. These may be used alone or in combination of two or more.
  • the phenoxy resin is not particularly limited.
  • 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 include norbornene type, naphthalene type, anthracene type, adamantane type, terpene type, trimethylcyclohexane type, biphenol type, and biphenyl type.
  • bisphenol A type phenoxy resin is preferably used.
  • the content of the thermoplastic 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 or more. Further, 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 into a sheet shape.
  • the inorganic filler is not particularly limited as long as a desired mechanical strength can be imparted to a cured layer formed by curing the resin composition layer.
  • 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 include fillers made of aluminum oxide borate whisker, boron nitride, crystalline silica, amorphous silica, mullite, cordierite, and other composite oxides, montmorillonite, smectite, etc., and these can be used alone. Alternatively, two or more kinds can be used in combination. Among these, it is preferable to use a silica filler.
  • the shape of the inorganic filler may be any of a granular shape, a needle shape, a plate shape, an indeterminate shape, etc., but among these, a spherical shape is preferable.
  • the average particle size of the inorganic filler is preferably 0.01 ⁇ m or more, particularly preferably 0.1 ⁇ m or more, and more preferably 0.3 ⁇ m or more.
  • the average particle size of the inorganic filler is preferably 3.0 ⁇ m or less, and particularly preferably 1.0 ⁇ m or less.
  • the average particle size of the inorganic filler in the present specification is a value measured by a dynamic light scattering method. For example, a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., product name “Nanotrack Wave-UT151”) is used. Can be measured.
  • the maximum particle size of the inorganic filler is preferably 0.05 ⁇ m or more, and particularly preferably 0.5 ⁇ m or more.
  • the maximum particle size is preferably 5 ⁇ m or less, particularly preferably 3 ⁇ m or less.
  • the maximum particle size of the inorganic filler in the present specification is a value measured by a dynamic light scattering method.
  • the particle size distribution measuring device manufactured by Nikkiso Co., Ltd., product name “Nanotrack Wave-UT151” is used. Can be measured.
  • the inorganic filler is surface-treated with the surface treating agent.
  • the dispersibility and filling property of the inorganic filler in the resin composition are improved.
  • the minimum coating area of the surface treatment agent is preferably less than 550 m 2 / g, particularly preferably 520 m 2 / g or less, and more preferably 450 m 2 / g or less.
  • 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 more preferably 300 m 2 / g or more.
  • Examples of the surface treatment agent include epoxy silane and vinyl silane. Among these, it is preferable to use epoxysilane.
  • Specific examples of the epoxy silane include, for example, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Of these, 3-glycidoxypropyltrimethoxysilane is preferably used.
  • vinyl silane examples include vinyl triacetoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl trichloro silane, vinyl tris (2-methoxy ethoxy) silane, and the like. Among these, it is preferable to use vinyltrimethoxysilane.
  • the method for surface-treating the inorganic filler with the surface treatment agent is not particularly limited, and can be performed by a general method.
  • the untreated inorganic filler can be stirred at room temperature using a mixer, and after the surface treatment agent is sprayed thereon, the surface treatment can be performed by further stirring for a predetermined time.
  • the stirring time after spraying is preferably 5 minutes or more and 15 minutes or less, for example.
  • the inorganic filler may be taken out from the mixer and allowed to stand for one day or longer, or a slight heat treatment may be performed.
  • a mixer a well-known thing can be used, for example, blenders, such as a V blender, a ribbon blender, a bubble cone blender, a Henschel mixer, a mixer, such as a concrete mixer, a ball mill etc., Among these, a mixer is used. Is preferred.
  • the content of the inorganic filler in the resin composition is preferably 65% by mass or more, particularly preferably 70% by mass or more, and more preferably 72% by mass or more. Further, the content is preferably 95% by mass or less, particularly preferably 90% by mass or less, and further preferably 80% by mass or less.
  • the content of the inorganic filler is 65% by mass or more, the cured layer formed by curing the resin composition layer has better mechanical strength. Further, when the content of the inorganic filler is 95% by mass or less, the resin composition layer is easily cured, and it becomes possible to manufacture a semiconductor device having better quality by using the resin sheet. .
  • the flame retardant in the present embodiment is an aromatic condensed phosphate ester that is liquid at room temperature.
  • “normal temperature” usually means a temperature of 20 ° C. or higher and 30 ° C. or lower
  • “liquid at normal temperature” means that a flame retardant is dissolved in a solvent or mixed with a solvent under such a temperature environment. Without mentioning, it means that the flame retardant is in a liquid state or a fluid state.
  • the melting point of the aromatic condensed phosphate ester in the present embodiment is preferably 5 ° C. or less, particularly preferably ⁇ 5 ° C. or less, and further preferably ⁇ 15 ° C. or less.
  • the aromatic condensed phosphorus is used at the temperature when the resin sheet according to the present embodiment is stored and used, and at the temperature when the resin composition layer in the present embodiment is cured.
  • the acid ester can be maintained in a liquid state. This makes it easy to maintain good compatibility between the flame retardant and other components, and as a result, the cured layer formed by curing the resin composition layer in the present embodiment is more excellent for electronic components and substrates. It has an adhesive strength.
  • the lower limit of the melting point is not particularly limited, and is preferably, for example, ⁇ 50 ° C. or higher, particularly preferably ⁇ 40 ° C. or higher, and more preferably ⁇ 30 ° C. or higher.
  • the viscosity at 25 ° C. of the aromatic condensed phosphate ester in this embodiment is preferably 30000 mPa ⁇ s or less, particularly preferably 25000 mPa ⁇ s or less, and more preferably 20000 mPa ⁇ s or less.
  • the viscosity is 30000 mPa ⁇ s or less, it becomes easy to maintain good compatibility between the flame retardant and other components, and as a result, a cured layer formed by curing the resin composition layer in the present embodiment, It has better adhesion to electronic components and substrates.
  • the lower limit of the said viscosity does not specifically limit about the lower limit of the said viscosity, For example, it is preferable that it is 5000 mPa * s or more, It is especially preferable that it is 8000 mPa * s or more, Furthermore, it is preferable that it is 10000 mPa * s or more.
  • the vapor pressure at 25 ° C. of the aromatic condensed phosphate ester in the present embodiment is preferably 1.0 ⁇ 10 ⁇ 5 kPa or less, particularly preferably 5.0 ⁇ 10 ⁇ 6 kPa or less. Is preferably 1.0 ⁇ 10 ⁇ 6 kPa or less.
  • the vapor pressure is 1.0 ⁇ 10 ⁇ 5 kPa or less
  • the temperature at which the resin sheet according to the present embodiment is stored and used, and the resin composition layer in the present embodiment is cured.
  • the aromatic condensed phosphate ester becomes difficult to volatilize, and the bleedout of the flame retardant from the resin composition layer is effectively suppressed.
  • the reduction in flame retardancy due to such bleed-out is effectively suppressed, and the occurrence of adverse effects on the semiconductor device due to the flared-out flame retardant is also effectively suppressed.
  • n represents a positive integer
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Represents a group.
  • the compound represented by these is mentioned.
  • the compounds may be used alone, or in, n, at least one of R 1 and R 2 may be used in combination of two or more different compounds.
  • N in the above formula (1) is preferably 1 or more and 5 or less.
  • Preferred examples of the compound represented by the above formula (1) include compounds in which R 1 is all a hydrogen atom and R 2 is an alkyl group having 1 carbon atom (—CH 3 ), that is, Formula (3) (In formula (3), n represents a positive integer.)
  • the compound represented by these is mentioned.
  • the said compound may be used individually by 1 type, or may be used combining 2 or more types of compounds from which n differs.
  • N in the above formula (3) is preferably 1 or more and 5 or less.
  • the compound represented by the above formula (3) is superior in compatibility with other components in the resin composition, a cured layer obtained by curing the resin composition layer in this embodiment is an electronic component or It has better adhesion to the substrate.
  • the following formula (2) (In the formula (2), Ar represents a divalent aromatic hydrocarbon, and R 3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)
  • the compound represented by these is mentioned.
  • the said compound may be used individually by 1 type, or may be used combining 2 or more types of compounds from which R ⁇ 3 > differs.
  • aromatic hydrocarbon in the above formula (2) examples include benzene, naphthalene, anthracene, fluorene, phenanthrene and the like.
  • the content of the flame retardant in the resin composition is preferably 0.5% by mass or more, particularly preferably 1.0% by mass or more, and more preferably 2% by mass or more. Further, the content is preferably 10% by mass or less, particularly preferably 7% by mass or less, and further preferably 5% by mass or less.
  • the content of the flame retardant is 0.5% by mass or more
  • the cured layer obtained by curing the resin composition layer in the present embodiment easily exhibits excellent flame retardancy.
  • aggregation of the flame retardant in a resin composition layer can be effectively suppressed because content of a flame retardant is 10 mass% or less, As a result, a hardening layer is with respect to an electronic component or a board
  • the resin composition further contains a curing catalyst.
  • a curing catalyst examples include an imidazole curing catalyst, an amine curing catalyst, and a phosphorus curing catalyst.
  • imidazole-based curing catalyst examples 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 perspective of sex It is preferred to use 2-ethyl-4-methylimidazole.
  • the amine-based curing catalyst include triazine compounds such as 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 1,8-diazabicyclo [5,4, 0] tertiary amine compounds such as undecene-7 (DBU), triethylenediamine, benzyldimethylamine, triethanolamine and the like.
  • DBU undecene-7
  • 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine is preferable.
  • phosphorus curing catalyst examples include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, and the like.
  • the above-mentioned curing catalyst 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 more preferably 0.1% by mass or more. preferable. Further, 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 can be cured more favorably.
  • the resin composition in this embodiment may further contain a coloring material.
  • the resin composition contains a coloring material
  • the cured layer formed by curing the resin composition layer in the present embodiment is colored, and the concealability of the electronic component sealed by the cured layer is improved. At the same time, it is easy to perform laser marking on the cured layer.
  • the coloring material is not particularly limited as long as it can color the cured layer, and those generally used as pigments and dyes can be used.
  • the coloring material preferably has excellent insulating properties and is also excellent in the effect of blocking electromagnetic waves that induce malfunctions, and such a coloring material comprises an aliphatic hydrocarbon group for all carbon atoms. It is preferable to use a carbon-based material, an insulating metal compound, or the like in which the proportion of carbon atoms to be exceeded exceeds 3% by mass.
  • the carbon-based material described above is a carbon-based pigment from the viewpoint of being excellent in concealability, laser marking property, and insulation and easily achieving an effect of blocking electromagnetic waves that induce malfunction. *
  • Examples of the carbon-based material in which the proportion of carbon atoms constituting the aliphatic hydrocarbon group with respect to all carbon atoms exceeds 3% by mass include carbon filler, coke, charcoal, diamond, etc.
  • a carbon filler is preferable.
  • a carbon filler is an amorphous carbon substance having a structure in which conjugated systems of carbon atoms are mainly linked, but having a structure in which the conjugation of the carbon atoms is appropriately cut off by an aliphatic hydrocarbon group.
  • the coloring materials described above may be used alone or in combination of two or more.
  • the content of the coloring material in the resin composition is preferably 0.5% by mass or more, and particularly preferably 1.0% by mass or more.
  • the content is preferably 5% by mass or less, and particularly preferably 3% by mass or less.
  • the resin composition in the present embodiment may further contain a plasticizer, a stabilizer, a tackifier, a coupling agent, an antistatic agent, an antioxidant, and the like.
  • the thickness of the resin composition layer in the present embodiment is preferably 20 ⁇ m or more, particularly preferably 50 ⁇ m or more, and more preferably 100 ⁇ m or more.
  • the thickness of the resin composition layer is 1000 ⁇ m or less, preferably 500 ⁇ m or less, and particularly preferably 300 ⁇ m or less.
  • the thickness of the resin composition layer is 20 ⁇ m or more, the resin composition layer has excellent embedding properties with respect to electronic components.
  • the thickness of the resin composition layer is 1000 ⁇ m or less, it is easy to reduce the size and thin the semiconductor device manufactured using the resin sheet according to the present embodiment.
  • the resin sheet according to the present embodiment may include a release sheet laminated on at least one surface of the resin composition layer.
  • the configuration of the release sheet is arbitrary, and examples thereof include plastic films such as polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. It is preferable that a peeling treatment is performed on these peeling surfaces (surfaces in contact with the resin composition layer of the resin sheet).
  • the release agent used for the release treatment include silicone-based, fluorine-based, long-chain alkyl-based, alkyd-based, olefin-based, and rubber-based release agents.
  • the resin composition layer is laminated on a silicon mirror wafer, and the resin composition layer is cured to form a cured layer.
  • the shear adhesive strength of the layer to the above-mentioned wafer is preferably 30 N / 5 mm ⁇ or more, particularly preferably 35 N / 5 mm ⁇ or more, and more preferably 40 N / 5 mm ⁇ or more.
  • the resin composition in the present embodiment contains an aromatic condensed phosphate ester that is liquid at room temperature as a flame retardant, and the component is excellent in compatibility with other components contained in the resin composition. Thus, the obtained cured layer can easily achieve the above-described shear adhesive force.
  • the resin sheet according to the present embodiment makes it easy to form a cured layer having an excellent adhesive force with respect to the electronic component and the substrate that supports the electronic component.
  • the upper limit value of the shear adhesive force described above is not particularly limited. For example, it is preferably 140 N / 5 mm ⁇ or less, particularly preferably 120 N / 5 mm ⁇ or less, and more preferably 100 N / 5 mm ⁇ or less. It is preferable that Moreover, the shear adhesive force mentioned above is a shear adhesive force measured before putting a hardened layer on the wet heat conditions mentioned later. Further, the above-mentioned shear adhesive strength is measured in accordance with MIL-STD-883J (METHOD 20199.9), and details of the measuring method are as described later.
  • the resin composition layer is laminated on a silicon mirror wafer, and the cured body and the wafer are cured with respect to the cured layer obtained by curing the resin composition layer.
  • the shear adhesive strength to the above-mentioned wafer measured after being placed under a moist heat condition of 168 hours in an environment of 85 ° C. and a relative humidity of 85%, is preferably 25 N / 5 mm ⁇ or more, particularly 30 N / 5 mm ⁇ . It is preferable that it is above, and it is more preferable that it is 35N / 5mm ⁇ or more.
  • the obtained cured layer can easily achieve the above-described shear adhesive force. And when the hardened layer obtained achieves the above-mentioned shear adhesive force after wet heat conditions, the semiconductor device manufactured using the resin sheet according to the present embodiment has excellent heat resistance.
  • the upper limit value of the shear adhesive strength after the wet heat condition is not particularly limited, and is preferably, for example, 120 N / 5 mm ⁇ or less, particularly preferably 100 N / 5 mm ⁇ or less, and more preferably 80 N / 5 mm. It is preferable that it is below. Further, the above-mentioned shear adhesive strength after wet heat conditions is measured in accordance with MIL-STD-883J (METHOD 20199.9), and the details of the measurement method are as described later.
  • N / 5 mm ⁇ which is a unit representing the above-described shear adhesive force, means a force (N) per area of 5 mm ⁇ 5 mm.
  • Method for Producing Resin Sheet The method for producing a resin sheet according to the present embodiment is not particularly limited.
  • the method described above is performed by applying a coating liquid containing the above-described resin composition layer on a predetermined release sheet.
  • a method including a step of forming a resin composition layer hereinafter, sometimes referred to as “first manufacturing method” or a step of forming the resin composition layer by extruding the above-described resin composition.
  • first manufacturing method a step of forming a resin composition layer
  • second production method Method for producing a resin composition layer by extruding the above-described resin composition.
  • the resin sheet according to the present embodiment is preferably manufactured by the first manufacturing method among the methods described above.
  • the coating liquid used in the first production method is not particularly limited in its properties as long as it can be applied, and may contain a component for forming the resin composition layer as a solute. It may be contained as a dispersoid.
  • the solvent include organic solvents such as cyclohexanone, toluene, ethyl acetate, methyl ethyl ketone, acetone, and xylene.
  • a coating method of the coating liquid for example, a resin composition and, if desired, a coating liquid further containing a solvent or a dispersion medium are prepared, and a die coater or curtain is formed on the release surface of the release sheet.
  • a resin sheet can be produced by applying the coating solution with a coater, spray coater, slit coater, knife coater or the like to form a coating film and drying the coating film.
  • the said peeling sheet may peel as process material, and may protect the resin composition layer until it uses a resin sheet. Moreover, after laminating the resin composition layer on the electronic component, it may be peeled off from the resin composition layer before curing the resin composition layer, or the cured formed after curing the resin composition layer The layer may be peeled off.
  • the first manufacturing method may be performed after the step of forming the resin composition layer on the release sheet as described above, on the surface of the formed resin composition layer opposite to the release sheet described above.
  • a step of attaching the release sheet may be provided.
  • the resin sheet which has the structure of one release sheet / resin composition layer / other release sheet can be obtained.
  • at least one of the release sheets may be peeled off as a process material, or the resin composition layer may be protected until it is used for sealing.
  • the resin sheet according to the present embodiment is used for sealing electronic components.
  • the resin sheet according to the present embodiment is preferably used for sealing an electronic component in a method for manufacturing a semiconductor device, and further used for sealing an electronic component in a semiconductor mounting process of the method for manufacturing a semiconductor device. It is preferable.
  • the resin sheet according to this embodiment is used for sealing an electronic component, for example, the resin composition layer in the resin sheet with respect to the electronic component provided on a temporary fixing material such as a substrate or an adhesive sheet. After laminating
  • the resin composition layer is formed from a resin composition containing an aromatic condensed phosphate ester that is liquid at room temperature as a flame retardant.
  • a cured product obtained by curing is excellent in flame retardancy.
  • the aromatic condensed phosphate ester that is liquid at room temperature exhibits excellent compatibility with other components contained in the resin composition, and the resulting cured product is excellent for the object that the cured product contacts. Adhesive strength can be demonstrated. As a result, a semiconductor device having excellent performance can be manufactured using the resin sheet according to the present embodiment.
  • the above-described curing is preferably performed by heating the resin composition layer.
  • the heating temperature is preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher. Further, the temperature is preferably 240 ° C. or lower, and particularly preferably 200 ° C. or lower.
  • the heating time is preferably 15 minutes or more, and particularly preferably 20 minutes or more. In addition, the time is preferably 300 minutes or less, particularly preferably 100 minutes or less.
  • the above-described curing of the resin composition layer by heating is performed stepwise by a plurality of heat treatments.
  • the heating in this case is preferably performed in two or more times.
  • the temperature T1 is preferably 100 ° C. or higher and 130 ° C. or lower
  • the heat treatment time is preferably 15 minutes or longer and 60 minutes or shorter.
  • the temperature T2 is preferably 150 ° C. or higher and 220 ° C. or lower
  • the heat treatment time is preferably 30 minutes or longer and 120 minutes or shorter.
  • the release sheet is laminated on the electronic component and then cured before the resin composition layer is cured. You may peel from a resin composition layer, or after hardening a resin composition layer, you may peel from the formed cured layer.
  • the resin sheet according to this embodiment includes release sheets on both sides of the resin composition layer, one release sheet is peeled off, and the exposed surface of the exposed resin composition layer is laminated on the electronic component, and the other About a peeling sheet, you may peel in either before and after hardening of a resin composition layer.
  • Examples of the electronic components described above are not particularly limited as long as they are electronic components that are generally sealed, and examples thereof include semiconductor chips. Further, examples of the semiconductor device to be manufactured include a component built-in substrate, a semiconductor package, and the like, and a component built-in substrate is particularly preferable.
  • Examples 1 to 3 and Comparative Examples 1 to 3 The components shown in Table 1 were mixed and diluted with cyclohexanone to obtain a resin composition coating solution having a solid content concentration of 58% by mass.
  • the coating solution was applied at a coating speed of 2.0 m / min on the release surface of a release film (product name “SP-PET 382150”, manufactured by Lintec Co., Ltd.) on which one side was subjected to silicone release treatment, using a knife coater.
  • the obtained coating film was dried by heating in an oven at 50 ° C. for 1 minute, 70 ° C. for 1 minute, 90 ° C. for 1 minute, and 100 ° C. for 1 minute, and a resin composition having a thickness of 50 ⁇ m.
  • a resin sheet comprising a layer and a release film was obtained.
  • test piece was cured by heating in order at 100 ° C. for 30 minutes and at 190 ° C. for 2 hours to obtain a test piece for combustion test.
  • the obtained laminated body was made into a 10 mm square silicon mirror wafer under the conditions of 150 ° C., 300 gf and 3 seconds.
  • EDB65 product name “EDB65”
  • the resin composition layer was cured by sequentially heating the obtained sample at 100 ° C. for 30 minutes and at 190 ° C. for 2 hours to obtain a test piece for measuring shear adhesive force.
  • the resin sheet according to the present invention can be suitably used for sealing electronic components in a semiconductor mounting process.

Abstract

A resin sheet which is used for sealing of an electronic component, and which is provided with a resin composition layer that is formed from a resin composition which contains a thermosetting resin, a thermoplastic resin, an inorganic filler, and a flame retardant that is composed of an aromatic condensed phosphoric acid ester which is in a liquid state at room temperature. This resin sheet is able to form a cured product which has excellent flame retardancy and excellent adhesive power.

Description

樹脂シートおよびその製造方法Resin sheet and manufacturing method thereof
　本発明は、電子部品の封止に使用される樹脂シートおよびその製造方法に関する。 The present invention relates to a resin sheet used for sealing electronic components and a method for manufacturing the same.
　従来、半導体装置の製造方法における半導体実装工程では、硬化性の樹脂組成物によって、半導体チップといった電子部品を封止することが行われている。例えば、基板上に設けられた電子部品を樹脂組成物で覆った後、当該樹脂組成物を硬化させることで電子部品の封止が行われる。 Conventionally, in a semiconductor mounting process in a manufacturing method of a semiconductor device, an electronic component such as a semiconductor chip is sealed with a curable resin composition. For example, after covering an electronic component provided on a substrate with a resin composition, the electronic component is sealed by curing the resin composition.
　上述のように電子部品を封止することで得られる半導体装置は、使用時に発熱するなどして高温に曝されることがある。そのため、上述した樹脂組成物が硬化してなる硬化物には、高温に曝された場合であっても燃焼し難い難燃性が求められる。 A semiconductor device obtained by sealing an electronic component as described above may be exposed to high temperatures due to heat generation during use. Therefore, the hardened | cured material formed by hardening | curing the resin composition mentioned above is calculated | required the flame retardance which is hard to burn even when it is a case where it is exposed to high temperature.
　このような難燃性を達成することを目的とした樹脂組成物の例として、特許文献１には、所定のエポキシ樹脂、硬化剤およびリン酸エステルを含有する樹脂組成物が開示されている。なお、当該樹脂組成物は、トランスファー成形により電子部品を封止することが想定されたものである。 As an example of a resin composition aiming at achieving such flame retardancy, Patent Document 1 discloses a resin composition containing a predetermined epoxy resin, a curing agent and a phosphate ester. In addition, the said resin composition is assumed that the electronic component is sealed by transfer molding.
特開２０１１－２４６５４５号公報JP 2011-246545 A
　ところで、電子部品を封止するための上述した樹脂組成物は、シート状に成形され、樹脂シートとすることが行われている。このような樹脂シートでは、封止の際に樹脂組成物の流動が生じ難く、それにより、当該流動に起因するムラの発生が抑制されるとともに、電子部品の移動が抑制される。しかしながら、特許文献１に開示される樹脂組成物は、トランスファー成形によって電子部品を封止するものとなっており、シート状に良好に成形することができない。そのため、特許文献１に開示される樹脂組成物を用いて、良好な難燃性を有する樹脂シートを製造することはできない。 Incidentally, the above-described resin composition for sealing an electronic component is formed into a sheet shape to form a resin sheet. In such a resin sheet, the resin composition hardly flows during sealing, thereby suppressing the occurrence of unevenness due to the flow and the movement of the electronic component. However, the resin composition disclosed in Patent Document 1 seals electronic components by transfer molding and cannot be molded well into a sheet shape. Therefore, a resin sheet having good flame retardancy cannot be produced using the resin composition disclosed in Patent Document 1.
　また、樹脂組成物を用いて電子部品を封止してなる半導体装置では、樹脂組成物が硬化してなる硬化物が、電子部品や当該電子部品を支持する基板等に対して良好な密着性を有することが求められる。特に、当該硬化物と、当該硬化物とが接する対象とをせん断するような力が印加された場合であっても、硬化物が上述した対象から剥離することを抑制する十分な接着力を有することが求められる。特に、このような接着力は、得られる半導体装置を信頼性試験（湿熱試験等）に供した後においても十分に維持されることが求められる。しかしながら、特許文献１に開示される樹脂組成物は、その硬化物を所定の条件でリフロー処理した場合にクラックの発生をある程度抑制できることが引用文献１の実施例に開示されているものの、上述したようなせん断力に対抗できる十分な接着力を達成することはできない。 Further, in a semiconductor device in which an electronic component is sealed using a resin composition, a cured product obtained by curing the resin composition has good adhesion to the electronic component and a substrate that supports the electronic component. It is required to have. In particular, even when a force that shears the cured product and the target that is in contact with the cured product is applied, the cured product has sufficient adhesive force to prevent the cured product from peeling from the target. Is required. In particular, such adhesive strength is required to be sufficiently maintained even after the obtained semiconductor device is subjected to a reliability test (such as a wet heat test). However, although the resin composition disclosed in Patent Document 1 is disclosed in the example of Cited Document 1 that the occurrence of cracks can be suppressed to some extent when the cured product is subjected to a reflow treatment under predetermined conditions, it has been described above. Adhesive strength sufficient to counter such shear forces cannot be achieved.
　本発明は、このような実状に鑑みてなされたものであり、優れた難燃性および優れた接着力を有する硬化物を形成することができる樹脂シート、および当該樹脂シートの製造方法を提供することを目的とする。 This invention is made | formed in view of such an actual condition, and provides the resin sheet which can form the hardened | cured material which has the outstanding flame retardance and the outstanding adhesive force, and the manufacturing method of the said resin sheet. For the purpose.
　上記目的を達成するために、第１に本発明は、電子部品の封止に使用される樹脂シートであって、前記樹脂シートが、熱硬化性樹脂と、熱可塑性樹脂と、無機フィラーと、難燃剤とを含有する樹脂組成物から形成された樹脂組成物層を備え、前記難燃剤が、常温で液体の芳香族縮合リン酸エステルであることを特徴とする樹脂シートを提供する（発明１）。 In order to achieve the above object, first, the present invention is a resin sheet used for sealing an electronic component, the resin sheet comprising a thermosetting resin, a thermoplastic resin, an inorganic filler, Provided is a resin sheet comprising a resin composition layer formed from a resin composition containing a flame retardant, wherein the flame retardant is an aromatic condensed phosphate ester that is liquid at room temperature (Invention 1). ).
　上記発明（発明１）に係る樹脂シートでは、樹脂組成物層が、常温で液体の芳香族縮合リン酸エステルを難燃剤として含有する樹脂組成物から形成されたものであることにより、当該樹脂組成物層を硬化してなる硬化物が優れた難燃性を有するものとなる。さらに、常温で液体の芳香族縮合リン酸エステルは、樹脂組成物に含有されるその他の成分と良好な相溶性を示し、これにより、樹脂組成物層を硬化してなる硬化層が高い均一性を有するものとなり、当該硬化物が、当該硬化物が接する対象に対して優れた接着力を有するものとなる。 In the resin sheet according to the invention (Invention 1), the resin composition layer is formed from a resin composition containing an aromatic condensed phosphate ester that is liquid at room temperature as a flame retardant, whereby the resin composition A cured product obtained by curing the physical layer has excellent flame retardancy. Furthermore, the aromatic condensed phosphate ester that is liquid at room temperature exhibits good compatibility with other components contained in the resin composition, and thereby the cured layer formed by curing the resin composition layer has high uniformity. Thus, the cured product has excellent adhesive force with respect to an object with which the cured product is in contact.
　上記発明（発明１）において、前記芳香族縮合リン酸エステルは、以下の式（１）
Figure JPOXMLDOC01-appb-C000003
（式（１）中、ｎは、１以上、５以下の整数を表し、Ｒ１は、水素原子または炭素数が１～３のアルキル基を表し、Ｒ２は、水素原子または炭素数が１～５のアルキル基を表す。）
で表される化合物、および以下の式（２）
Figure JPOXMLDOC01-appb-C000004
（式（２）中、Ａｒは、２価の芳香族炭化水素を表し、Ｒ３は、水素原子または炭素数が１～５のアルキル基を表す。）
で表される化合物の少なくとも１種を含むことが好ましい（発明２）。 In the above invention (Invention 1), the aromatic condensed phosphate ester has the following formula (1):
Figure JPOXMLDOC01-appb-C000003
(In the formula (1), n represents an integer of 1 or more and 5 or less, R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 2 represents a hydrogen atom or 1 carbon atom. Represents an alkyl group of ˜5.)
And the following formula (2)
Figure JPOXMLDOC01-appb-C000004
(In the formula (2), Ar represents a divalent aromatic hydrocarbon, and R 3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)
It is preferable that at least 1 type of the compound represented by these is included (invention 2).
　上記発明（発明１，２）において、前記芳香族縮合リン酸エステルの２５℃における粘度は、５０００ｍＰａ・ｓ以上、３００００ｍＰａ・ｓ以下であることが好ましい（発明３）。 In the inventions (Inventions 1 and 2), the aromatic condensed phosphate ester preferably has a viscosity at 25 ° C. of 5000 mPa · s or more and 30000 mPa · s or less (Invention 3).
　上記発明（発明１～３）において、前記樹脂組成物中における前記難燃剤の含有量は、０．５質量％以上、５．０質量％以下であることが好ましい（発明４）。 In the above inventions (Inventions 1 to 3), the content of the flame retardant in the resin composition is preferably 0.5% by mass or more and 5.0% by mass or less (Invention 4).
　上記発明（発明１～４）においては、半導体実装工程における電子部品の封止に用いられることが好ましい（発明５）。 In the above inventions (Inventions 1 to 4), it is preferably used for sealing electronic components in a semiconductor mounting process (Invention 5).
　第２に本発明は、前記樹脂シート（発明１～５）の製造方法であって、前記樹脂組成物層を含有する塗布液を所定の剥離シート上に塗布することで、前記樹脂組成物層を形成する工程を備えることを特徴とする樹脂シートの製造方法を提供する（発明６）。 Second, the present invention is a method for producing the resin sheet (Invention 1 to 5), wherein a coating liquid containing the resin composition layer is applied onto a predetermined release sheet, whereby the resin composition layer The manufacturing method of the resin sheet characterized by providing the process of forming is provided (invention 6).
　本発明の樹脂シートは、優れた難燃性および優れた接着力を有する硬化物を形成することができる。また、本発明の製造方法によれば、そのような樹脂シートを製造することができる。 The resin sheet of the present invention can form a cured product having excellent flame retardancy and excellent adhesive force. Moreover, according to the manufacturing method of this invention, such a resin sheet can be manufactured.
　以下、本発明の実施形態について説明する。
〔樹脂シート〕
　本実施形態に係る樹脂シートは、電子部品の封止に使用されるものであり、熱硬化性樹脂と、熱可塑性樹脂と、無機フィラーと、難燃剤とを含有する樹脂組成物から形成された樹脂組成物層を備える。そして、当該難燃剤は、常温で液体の芳香族縮合リン酸エステルである。 Hereinafter, embodiments of the present invention will be described.
[Resin sheet]
The resin sheet according to the present embodiment is used for sealing electronic components, and is formed from a resin composition containing a thermosetting resin, a thermoplastic resin, an inorganic filler, and a flame retardant. A resin composition layer is provided. The flame retardant is an aromatic condensed phosphate ester that is liquid at room temperature.
　本実施形態における樹脂組成物は、熱硬化性樹脂を含有していることにより、加熱によって硬化することができる。そして、樹脂組成物層が硬化してなる硬化層には、上述した無機フィラーが含有されるものとなり、形成された硬化層は良好な耐熱性および機械的強度を発揮するものとなる。これらにより、本実施形態に係る樹脂シートを使用することで、電子部品を良好に封止することが可能となる。 The resin composition in the present embodiment can be cured by heating because it contains a thermosetting resin. The cured layer formed by curing the resin composition layer contains the above-described inorganic filler, and the formed cured layer exhibits good heat resistance and mechanical strength. Accordingly, the electronic component can be satisfactorily sealed by using the resin sheet according to the present embodiment.
　また、本実施形態における樹脂組成物は、熱可塑性樹脂を含有することにより、樹脂組成物層がシート状の形状を良好に維持することができる。このため、本実施形態における樹脂シートが取り扱い性に優れたものとなるとともに、本実施形態に係る樹脂シートを使用する際に、トランスファー成形を行うことなく、電子部品に樹脂シートを積層するという、より簡便な操作によって封止を行うことが可能となる。 Moreover, the resin composition in this embodiment can maintain the sheet-like shape of the resin composition layer favorably by containing a thermoplastic resin. Therefore, the resin sheet in the present embodiment is excellent in handleability, and when using the resin sheet according to the present embodiment, the resin sheet is laminated on the electronic component without performing transfer molding. Sealing can be performed by a simpler operation.
　そして、本実施形態における樹脂組成物が、常温で液体の芳香族縮合リン酸エステルを難燃剤として含むことにより、本実施形態に係る樹脂シートを用いて製造された半導体装置が使用に伴って発熱したり、当該半導体装置が高温環境下に置かれた場合であっても、形成される硬化層が燃焼し難いものとなり、優れた難燃性を発揮するものとなる。 The resin composition in the present embodiment contains an aromatic condensed phosphate ester that is liquid at room temperature as a flame retardant, so that the semiconductor device manufactured using the resin sheet according to the present embodiment generates heat during use. Even if the semiconductor device is placed in a high temperature environment, the formed hardened layer is difficult to burn and exhibits excellent flame retardancy.
　また、常温で液体の芳香族縮合リン酸エステルの難燃剤は、樹脂組成物中に含有される熱可塑性樹脂や熱硬化性樹脂といったその他の成分との間で優れた相溶性を示す。そのため、本実施形態における樹脂組成物層では、構成する成分が凝集したりすることなく各成分が均一に混合されたものとなり、当該樹脂組成物層を硬化することで、均一性の高い硬化層を形成することができる。その結果、当該硬化層と当該硬化層が接触する対象との接着力が向上し、当該硬化物と当該対象とをせん断するような力が印加された場合であっても、硬化物が上述した対象から剥離することが抑制される。 Moreover, the aromatic condensed phosphate ester flame retardant which is liquid at room temperature exhibits excellent compatibility with other components such as thermoplastic resins and thermosetting resins contained in the resin composition. Therefore, in the resin composition layer in the present embodiment, each component is uniformly mixed without aggregating the constituent components, and by curing the resin composition layer, a highly uniform cured layer is obtained. Can be formed. As a result, the adhesive force between the cured layer and the target that the cured layer contacts is improved, and the cured product is described above even when a force that shears the cured product and the target is applied. Peeling from the object is suppressed.
　さらに、本実施形態における樹脂組成物が熱可塑性樹脂を含有しており、上述した難燃剤が当該熱可塑性樹脂に対して優れた相溶性を発揮できるものであり、さらには樹脂組成物が所定の粘度を有するものであることにより、樹脂組成物層の硬化のために当該樹脂組成物層を加熱した際に、難燃剤が樹脂組成物層からブリードアウトし難くなる。そのため、樹脂組成物層中における難燃剤の含有量の減少に起因した難燃性の低下が抑制されるとともに、ブリードアウトした難燃剤による半導体装置への悪影響の発生も抑制される。 Furthermore, the resin composition in the present embodiment contains a thermoplastic resin, the flame retardant described above can exhibit excellent compatibility with the thermoplastic resin, and the resin composition is a predetermined one. By having the viscosity, when the resin composition layer is heated for curing the resin composition layer, it becomes difficult for the flame retardant to bleed out from the resin composition layer. For this reason, a decrease in flame retardancy due to a decrease in the content of the flame retardant in the resin composition layer is suppressed, and an adverse effect on the semiconductor device due to the bleed-out flame retardant is also suppressed.
１．樹脂組成物層
（１）熱硬化性樹脂
　熱硬化性樹脂としては、樹脂組成物層の硬化を可能とするものであれば特に限定されず、例えば、封止材に通常含有される樹脂を使用することができる。具体的には、エポキシ樹脂、フェノール樹脂、メラミン樹脂、尿素樹脂、ポリエステル樹脂、ウレタン樹脂、アクリル樹脂、ポリイミド樹脂、ベンゾオキサジン樹脂、フェノキシ樹脂、酸無水物化合物、アミン系化合物、ナフトール系樹脂、活性エステル系樹脂、ベンゾオキサジン系樹脂、シアネートエステル系樹脂等が挙げられ、これらは１種を単独でまたは２種以上を組み合わせて用いることができる。これらの中でも、エポキシ樹脂、フェノール樹脂、またはそれらの混合物を使用することが好ましい。 1. Resin composition layer (1) Thermosetting resin The thermosetting resin is not particularly limited as long as the resin composition layer can be cured. For example, a resin usually contained in a sealing material is used. can do. Specifically, epoxy resin, phenol resin, melamine resin, urea resin, polyester resin, urethane resin, acrylic resin, polyimide resin, benzoxazine resin, phenoxy resin, acid anhydride compound, amine compound, naphthol resin, activity Examples include ester resins, benzoxazine resins, cyanate ester resins, and the like. These may 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.
　エポキシ樹脂は、一般的に、加熱を受けると三次元網状化し、強固な硬化物を形成する性質を有する。このようなエポキシ樹脂としては、公知の種々のエポキシ樹脂が用いることができ、具体的には、ビスフェノールＡ、ビスフェノールＦ、レゾルシノール、フェニルノボラック、クレゾールノボラック等のフェノール類のグリシジルエーテル；ブタンジオール、ポリエチレングリコール、ポリプロピレングリコール等のアルコール類のグリシジルエーテル；フタル酸、イソフタル酸、テトラヒドロフタル酸等のカルボン酸のグリシジルエーテル；アニリンイソシアヌレート等の窒素原子に結合した活性水素をグリシジル基で置換したグリシジル型もしくはアルキルグリシジル型のエポキシ樹脂；ビニルシクロヘキサンジエポキシド、３，４－エポキシシクロヘキシルメチル－３，４－ジシクロヘキサンカルボキシレート、２－（３，４－エポキシ）シクロヘキシル－５，５－スピロ（３，４－エポキシ）シクロヘキサン－ｍ－ジオキサン等のように、分子内の炭素－炭素二重結合を例えば酸化することによりエポキシが導入された、いわゆる脂環型エポキシドを挙げることができる。その他、ビフェニル骨格、トリフェニルメタン骨格、ジシクロヘキサジエン骨格、ナフタレン骨格等を有するエポキシ樹脂を用いることもできる。これらエポキシ樹脂は、１種を単独で、または２種以上を組み合わせて用いることができる。上述したエポキシ樹脂の中でも、ビスフェノールＡのグリシジルエーテル（ビスフェノールＡ型エポキシ樹脂）、ビフェニル骨格を有するエポキシ樹脂（ビフェニル型エポキシ樹脂）、ナフタレン骨格を有するエポキシ樹脂（ナフタレン型エポキシ樹脂）またはこれらの組み合わせを使用することが好ましい。 Epoxy resins generally have the property of forming a three-dimensional network when heated and forming a hardened 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; Alkyl glycidyl type epoxy resin; vinylcyclohexane diepoxide, 3,4-epoxycyclohexylmethyl-3,4-dicyclohexanecarboxylate, 2- (3,4-epoxy I) Cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane or the like, a so-called alicyclic ring in which an epoxy is introduced by, for example, oxidizing a carbon-carbon double bond in the molecule. Mention may be made of type epoxides. In addition, an epoxy resin having a biphenyl skeleton, a triphenylmethane skeleton, a dicyclohexadiene skeleton, a naphthalene skeleton, or the like can also be used. These epoxy resins can be used alone or in combination of two or more. Among the above-mentioned epoxy resins, glycidyl ether of bisphenol A (bisphenol A type epoxy resin), epoxy resin having a biphenyl skeleton (biphenyl type epoxy resin), epoxy resin having a naphthalene skeleton (naphthalene type epoxy resin), or a combination thereof It is preferable to use it.
　フェノール樹脂としては、例えば、ビスフェノールＡ、テトラメチルビスフェノールＡ、ジアリルビスフェノールＡ、ビフェノール、ビスフェノールＦ、ジアリルビスフェノールＦ、トリフェニルメタン型フェノール、テトラキスフェノール、ノボラック型フェノール、クレゾールノボラック樹脂、ビフェニルアラルキル骨格を有するフェノール（ビフェニル型フェノール）等が挙げられ、これらの中でも、ビフェニル型フェノールを使用することが好ましい。これらのフェノール樹脂は、１種を単独でまたは２種以上を組み合わせて用いることができる。なお、硬化性樹脂としてエポキシ樹脂を使用する場合には、エポキシ樹脂との反応性等の観点から、フェノール樹脂を併用することが好ましい。 Examples of the phenol resin include bisphenol A, tetramethyl bisphenol A, diallyl bisphenol A, biphenol, bisphenol F, diallyl bisphenol F, triphenylmethane phenol, tetrakisphenol, novolac phenol, cresol novolac resin, and biphenyl aralkyl skeleton. Phenol (biphenyl type phenol) and the like can be mentioned, and among these, it is preferable to use biphenyl type phenol. These phenol resins can be used individually by 1 type or in combination of 2 or more types. In addition, when using an epoxy resin as curable resin, it is preferable to use a phenol resin together from the viewpoint of reactivity with the epoxy resin.
　樹脂組成物中における熱硬化性樹脂の含有量は、１０質量％以上であることが好ましく、特に１５質量％以上であることが好ましく、さらには２０質量％以上であることが好ましい。また、当該含有量は、６０質量％以下であることが好ましく、特に５０質量％以下であることが好ましく、さらには４０質量％以下であることが好ましい。当該含有量が１０質量％以上であることで、樹脂組成物層の硬化がより十分なものとなり、電子部品をより強固に封止することができる。また、当該含有量が６０質量％以下であることで、樹脂組成物層の意図しない段階での硬化をより抑制することができ、保存安定性がより優れたものとなる。 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. Further, 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, the resin composition layer is more sufficiently cured, and the electronic component can be more firmly sealed. Further, when the content is 60% by mass or less, curing at an unintended stage of the resin composition layer can be further suppressed, and the storage stability becomes more excellent.
（２）熱可塑性樹脂
　熱可塑性樹脂としては、樹脂組成物をシート状に形成するのに適したものである限り、特に限定されない。熱可塑性樹脂の例としては、フェノキシ系樹脂、ポリビニルアセタール樹脂、オレフィン系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂、ポリエステルウレタン系樹脂、アミド系樹脂、スチレン系樹脂、シラン系樹脂、ゴム系樹脂等が挙げられ、これらは、１種を単独で、または２種以上を組み合わせて用いることができる。 (2) Thermoplastic resin The thermoplastic resin is not particularly limited as long as it is suitable for forming the resin composition into a sheet. Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, olefin resins, polyester resins, polyurethane resins, polyester urethane resins, amide resins, styrene resins, silane resins, rubber resins, etc. These may be used alone or in combination of two or more.
　上記フェノキシ系樹脂としては、特に限定されないものの、例えば、ビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＡ／ビスフェノールＦ共重合型、ビスフェノールＳ型、ビスフェノールアセトフェノン型、ノボラック型、フルオレン型、ジシクロペンタジエン型、ノルボルネン型、ナフタレン型、アントラセン型、アダマンタン型、テルペン型、トリメチルシクロヘキサン型、ビフェノール型、ビフェニル型等が例示され、これらの中でもビスフェノールＡ型フェノキシ樹脂を使用することが好ましい。 The phenoxy resin is not particularly limited. 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 include norbornene type, naphthalene type, anthracene type, adamantane type, terpene type, trimethylcyclohexane type, biphenol type, and biphenyl type. Among these, bisphenol A type phenoxy resin is preferably used.
　樹脂組成物中における熱可塑性樹脂の含有量は、１質量％以上であることが好ましく、特に３質量％以上であることが好ましく、さらには５質量％以上であることが好ましい。また、当該含有量は、３０質量％以下であることが好ましく、特に２０質量％以下であることが好ましく、さらには１０質量％以下であることが好ましい。当該含有量が上記範囲であることで、樹脂組成物層をシート状に形成することがより容易となる。 The content of the thermoplastic 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 or more. Further, 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 into a sheet shape.
（３）無機フィラー
　無機フィラーとしては、樹脂組成物層を硬化してなる硬化層に対して、所望の機械的強度を付与できるものである限り、特に限定されない。無機フィラーとしては、例えば、シリカ、アルミナ、ガラス、酸化チタン、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム、酸化カルシウム、酸化マグネシウム、酸化アルミニウム、窒化アルミニウム、ほう酸アルミウイスカ、窒化ほう素、結晶性シリカ、非晶性シリカ、ムライト、コージェライト等の複合酸化物、モンモリロナイト、スメクタイト等を材料とするフィラーを例示することができ、これらは１種を単独でまたは２種以上を組み合わせて用いることができる。これらの中でもシリカフィラーを使用することが好ましい。 (3) Inorganic filler The inorganic filler is not particularly limited as long as a desired mechanical strength can be imparted to a cured layer formed by curing the resin composition layer. 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 include fillers made of aluminum oxide borate whisker, boron nitride, crystalline silica, amorphous silica, mullite, cordierite, and other composite oxides, montmorillonite, smectite, etc., and these can be used alone. Alternatively, two or more kinds can be used in combination. Among these, it is preferable to use a silica filler.
　無機フィラーの形状は、粒状、針状、板状、不定型等の何れでもよいものの、これらの中でも球状であることが好ましい。 The shape of the inorganic filler may be any of a granular shape, a needle shape, a plate shape, an indeterminate shape, etc., but among these, a spherical shape is preferable.
　上記無機フィラーの平均粒径は、０．０１μｍ以上であることが好ましく、特に０．１μｍ以上であることが好ましく、さらには０．３μｍ以上であることが好ましい。また、上記無機フィラーの平均粒径は、３．０μｍ以下であることが好ましく、特に１．０μｍ以下であることが好ましい。無機フィラーの平均粒径が上記範囲であることにより、樹脂組成物層が硬化されてなる硬化層が機械的強度を効果的に発揮し易くなる。なお、本明細書における無機フィラーの平均粒径は、動的光散乱法により測定した値であり、例えば粒度分布測定装置（日機装社製，製品名「ナノトラックＷａｖｅ－ＵＴ１５１」）を使用して測定することができる。 The average particle size of the inorganic filler is preferably 0.01 μm or more, particularly preferably 0.1 μm or more, and more preferably 0.3 μm or more. The average particle size 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 obtained by curing the resin composition layer easily exhibits the mechanical strength effectively. The average particle size of the inorganic filler in the present specification is a value measured by a dynamic light scattering method. For example, a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., product name “Nanotrack Wave-UT151”) is used. Can be measured.
　また、上記無機フィラーの最大粒径は、０．０５μｍ以上であることが好ましく、特に０．５μｍ以上であることが好ましい。また、当該最大粒径は、５μｍ以下であることが好ましく、特に３μｍ以下であることが好ましい。無機フィラーの最大粒径が上記範囲であることで、硬化層中に無機フィラーを充填し易くなり、硬化層がより優れた機械的強度を有するものとなる。なお、本明細書における無機フィラーの最大粒径は、動的光散乱法により測定した値であり、例えば粒度分布測定装置（日機装社製，製品名「ナノトラックＷａｖｅ－ＵＴ１５１」）を使用して測定することができる。 The maximum particle size of the inorganic filler is preferably 0.05 μm or more, and particularly preferably 0.5 μm or more. The maximum particle size is preferably 5 μm or less, particularly preferably 3 μm or less. When the maximum particle size of the inorganic filler is in the above range, the cured layer can be easily filled with the inorganic filler, and the cured layer has better mechanical strength. The maximum particle size of the inorganic filler in the present specification is a value measured by a dynamic light scattering method. For example, the particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., product name “Nanotrack Wave-UT151”) is used. Can be measured.
　本実施形態に係る樹脂シートでは、無機フィラーが表面処理剤により表面処理されていることが好ましい。これにより、樹脂組成物中における無機フィラーの分散性や充填性が改善される。特に、当該表面処理剤の最小被覆面積は、５５０ｍ２／ｇ未満であることが好ましく、特に５２０ｍ２／ｇ以下であることが好ましく、さらには４５０ｍ２／ｇ以下であることが好ましい。また、表面処理剤の最小被覆面積は、１００ｍ２／ｇ以上であることが好ましく、特に２００ｍ２／ｇ以上であることが好ましく、さらには３００ｍ２／ｇ以上であることが好ましい。表面処理剤の最小被覆面積が上記範囲であることで、樹脂組成物中における無機フィラーの分散性や充填性がより優れたものとなる。 In the resin sheet which concerns on this embodiment, it is preferable that the inorganic filler is surface-treated with the surface treating agent. Thereby, the dispersibility and filling property of the inorganic filler in the resin composition are improved. In particular, the minimum coating area of the surface treatment agent is preferably less than 550 m 2 / g, particularly preferably 520 m 2 / g or less, and more 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 more preferably 300 m 2 / g or more. When the minimum coating area of the surface treatment agent is within the above range, the dispersibility and filling properties of the inorganic filler in the resin composition are further improved.
　上記表面処理剤の例としては、エポキシシラン、ビニルシラン等が挙げられる。これらの中でも、エポキシシランを使用することが好ましい。エポキシシランの具体例としては、例えば３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、２－（３，４エポキシシクロヘキシル）エチルトリメトキシシラン等が挙げられる。これらの中でも、３－グリシドキシプロピルトリメトキシシランを使用することが好ましい。 Examples of the surface treatment agent include epoxy silane and vinyl silane. Among these, it is preferable to use epoxysilane. Specific examples of the epoxy silane include, for example, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Of these, 3-glycidoxypropyltrimethoxysilane is preferably used.
　上記ビニルシランの具体例としては、例えばビニルトリアセトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリクロルシラン、ビニルトリス（２－メトキシエトキシ）シラン等が挙げられる。これらの中でも、ビニルトリメトキシシランを使用することが好ましい。 Specific examples of the vinyl silane include vinyl triacetoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl trichloro silane, vinyl tris (2-methoxy ethoxy) silane, and the like. Among these, it is preferable to use vinyltrimethoxysilane.
　無機フィラーを表面処理剤で表面処理する方法は、特に限定されず、一般的な方法により行うことができる。例えば、混合機を用いて未処理の無機フィラーを常温にて撹拌し、そこへ表面処理剤を噴霧した後、さらに所定時間撹拌することで表面処理することができる。噴霧後の撹拌時間は、例えば５分以上、１５分以下であることが好ましい。なお、表面処理剤を無機フィラーに十分に定着させるために、上記の操作後、混合機から無機フィラーを取り出して１日以上放置してもよく、また、軽微な加熱処理を行なってもよい。また、均一に表面処理を行うために、表面処理剤の噴霧した後、有機溶媒をさらに添加して、上記撹拌を行ってもよい。混合機としては、公知のものを使用でき、例えば、Ｖブレンダー、リボンブレンダー、バブルコーンブレンダー等のブレンダー、ヘンシェルミキサー、コンクリートミキサー等のミキサー、ボールミル等が挙げられ、これらの中でもミキサーを使用することが好ましい。 The method for surface-treating the inorganic filler with the surface treatment agent is not particularly limited, and can be performed by a general method. For example, the untreated inorganic filler can be stirred at room temperature using a mixer, and after the surface treatment agent is sprayed thereon, the surface treatment can be performed by further stirring for a predetermined time. The stirring time after spraying is preferably 5 minutes or more and 15 minutes or less, for example. In order to sufficiently fix the surface treatment agent to the inorganic filler, after the above operation, the inorganic filler may be taken out from the mixer and allowed to stand for one day or longer, or a slight heat treatment may be performed. Moreover, in order to perform a surface treatment uniformly, after spraying a surface treating agent, you may further add an organic solvent and perform said stirring. As a mixer, a well-known thing can be used, for example, blenders, such as a V blender, a ribbon blender, a bubble cone blender, a Henschel mixer, a mixer, such as a concrete mixer, a ball mill etc., Among these, a mixer is used. Is preferred.
　樹脂組成物中における、無機フィラーの含有量は、６５質量％以上であることが好ましく、特に７０質量％以上であることが好ましく、さらには７２質量％以上であることが好ましい。また、当該含有量は、９５質量％以下であることが好ましく、特に９０質量％以下であることが好ましく、さらには８０質量％以下であることが好ましい。無機フィラーの含有量が６５質量％以上であることで、樹脂組成物層を硬化してなる硬化層がより良好な機械的強度を有するものとなる。また、無機フィラーの含有量が９５質量％以下であることで、樹脂組成物層が硬化し易いものとなり、樹脂シートを使用してより良好な品質を有する半導体装置を製造することが可能となる。 The content of the inorganic filler in the resin composition is preferably 65% by mass or more, particularly preferably 70% by mass or more, and more preferably 72% by mass or more. Further, the content is preferably 95% by mass or less, particularly preferably 90% by mass or less, and further preferably 80% by mass or less. When the content of the inorganic filler is 65% by mass or more, the cured layer formed by curing the resin composition layer has better mechanical strength. Further, when the content of the inorganic filler is 95% by mass or less, the resin composition layer is easily cured, and it becomes possible to manufacture a semiconductor device having better quality by using the resin sheet. .
（４）難燃剤
　本実施形態における難燃剤は、常温で液体の芳香族縮合リン酸エステルである。ここで、「常温」とは、通常２０℃以上、３０℃以下の温度をいい、「常温で液体」とは、そのような温度環境下において、難燃剤を溶剤に溶解したり溶剤と混合することなく、難燃剤単独で液体の状態または流動性を有する状態であることをいう。 (4) Flame retardant The flame retardant in the present embodiment is an aromatic condensed phosphate ester that is liquid at room temperature. Here, “normal temperature” usually means a temperature of 20 ° C. or higher and 30 ° C. or lower, and “liquid at normal temperature” means that a flame retardant is dissolved in a solvent or mixed with a solvent under such a temperature environment. Without mentioning, it means that the flame retardant is in a liquid state or a fluid state.
　本実施形態における芳香族縮合リン酸エステルの融点は、５℃以下であることが好ましく、特に－５℃以下であることが好ましく、さらには－１５℃以下であることが好ましい。当該融点が５℃以下であることで、本実施形態に係る樹脂シートが保管および使用される際の温度、並びに本実施形態における樹脂組成物層が硬化される際の温度において、芳香族縮合リン酸エステルが液体の状態を良好に維持することが可能となる。これにより、難燃剤とその他の成分との相溶性を良好に維持し易くなり、その結果、本実施形態における樹脂組成物層を硬化してなる硬化層が、電子部品や基板に対してより優れた接着力を有するものとなる。なお、上記融点の下限値については特に限定されず、例えば、－５０℃以上であることが好ましく、特に－４０℃以上であることが好ましく、さらには－３０℃以上であることが好ましい。 The melting point of the aromatic condensed phosphate ester in the present embodiment is preferably 5 ° C. or less, particularly preferably −5 ° C. or less, and further preferably −15 ° C. or less. When the melting point is 5 ° C. or lower, the aromatic condensed phosphorus is used at the temperature when the resin sheet according to the present embodiment is stored and used, and at the temperature when the resin composition layer in the present embodiment is cured. The acid ester can be maintained in a liquid state. This makes it easy to maintain good compatibility between the flame retardant and other components, and as a result, the cured layer formed by curing the resin composition layer in the present embodiment is more excellent for electronic components and substrates. It has an adhesive strength. The lower limit of the melting point is not particularly limited, and is preferably, for example, −50 ° C. or higher, particularly preferably −40 ° C. or higher, and more preferably −30 ° C. or higher.
　本実施形態における芳香族縮合リン酸エステルの２５℃における粘度は、３００００ｍＰａ・ｓ以下であることが好ましく、特に２５０００ｍＰａ・ｓ以下であることが好ましく、さらには２００００ｍＰａ・ｓ以下であることが好ましい。当該粘度が３００００ｍＰａ・ｓ以下であることで、難燃剤とその他の成分との相溶性を良好に維持し易くなり、その結果、本実施形態における樹脂組成物層を硬化してなる硬化層が、電子部品や基板に対してより優れた接着力を有するものとなる。なお、上記粘度の下限値については特に限定されず、例えば、５０００ｍＰａ・ｓ以上であることが好ましく、特に８０００ｍＰａ・ｓ以上であることが好ましく、さらには１００００ｍＰａ・ｓ以上であることが好ましい。 The viscosity at 25 ° C. of the aromatic condensed phosphate ester in this embodiment is preferably 30000 mPa · s or less, particularly preferably 25000 mPa · s or less, and more preferably 20000 mPa · s or less. When the viscosity is 30000 mPa · s or less, it becomes easy to maintain good compatibility between the flame retardant and other components, and as a result, a cured layer formed by curing the resin composition layer in the present embodiment, It has better adhesion to electronic components and substrates. In addition, it does not specifically limit about the lower limit of the said viscosity, For example, it is preferable that it is 5000 mPa * s or more, It is especially preferable that it is 8000 mPa * s or more, Furthermore, it is preferable that it is 10000 mPa * s or more.
　本実施形態における芳香族縮合リン酸エステルの２５℃における蒸気圧は、１．０×１０－５ｋＰａ以下であることが好ましく、特に５．０×１０－６ｋＰａ以下であることが好ましく、さらには１．０×１０－６ｋＰａ以下であることが好ましい。上述した蒸気圧が１．０×１０－５ｋＰａ以下であることで、本実施形態に係る樹脂シートが保管および使用される際の温度、並びに本実施形態における樹脂組成物層が硬化される際の温度において、芳香族縮合リン酸エステルが揮発し難いものとなり、樹脂組成物層からの難燃剤のブリードアウトが効果的に抑制される。これにより、このようなブリードアウトに起因した難燃性の低下が効果的に抑制されるとともに、ブリードアウトした難燃剤による、半導体装置への悪影響の発生も効果的に抑制される。 The vapor pressure at 25 ° C. of the aromatic condensed phosphate ester in the present embodiment is preferably 1.0 × 10 −5 kPa or less, particularly preferably 5.0 × 10 −6 kPa or less. Is preferably 1.0 × 10 −6 kPa or less. When the vapor pressure is 1.0 × 10 −5 kPa or less, the temperature at which the resin sheet according to the present embodiment is stored and used, and the resin composition layer in the present embodiment is cured. At this temperature, the aromatic condensed phosphate ester becomes difficult to volatilize, and the bleedout of the flame retardant from the resin composition layer is effectively suppressed. As a result, the reduction in flame retardancy due to such bleed-out is effectively suppressed, and the occurrence of adverse effects on the semiconductor device due to the flared-out flame retardant is also effectively suppressed.
　本実施形態における芳香族縮合リン酸エステルの好ましい例としては、以下の式（１）
Figure JPOXMLDOC01-appb-C000005
（式（１）中、ｎは、正の整数を表し、Ｒ１は、水素原子または炭素数が１～３のアルキル基を表し、Ｒ２は、水素原子または炭素数が１～５のアルキル基を表す。）
で表される化合物が挙げられる。当該化合物は、１種を単独で使用してもよく、あるいは、ｎ、Ｒ１およびＲ２の少なくとも１つが異なる２種以上の化合物を組み合わせて使用してもよい。 As a preferable example of the aromatic condensed phosphate ester in the present embodiment, the following formula (1):
Figure JPOXMLDOC01-appb-C000005
(In the formula (1), n represents a positive integer, R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Represents a group.)
The compound represented by these is mentioned. The compounds may be used alone, or in, n, at least one of R 1 and R 2 may be used in combination of two or more different compounds.
　上記式（１）におけるｎは、１以上、５以下であることが好ましい。 N in the above formula (1) is preferably 1 or more and 5 or less.
　上記式（１）で表される化合物の好ましい例としては、Ｒ１が全て水素原子であるとともに、およびＲ２が、炭素数が１のアルキル基（－ＣＨ３）である化合物、すなわち以下の式（３）
Figure JPOXMLDOC01-appb-C000006
（式（３）中、ｎは正の整数を表す。）
で表される化合物が挙げられる。なお、当該化合物は、１種を単独で使用してもよく、あるいは、ｎが異なる２種以上の化合物を組み合わせて使用してもよい。上記式（３）におけるｎは、１以上、５以下であることが好ましい。上記式（３）で表される化合物を使用することで、優れた難燃性を達成し易いものとなる。また、上記式（３）で表される化合物は、樹脂組成物中におけるその他の成分との相溶性により優れるため、本実施形態における樹脂組成物層を硬化してなる硬化層が、電子部品や基板に対してより優れた接着力を有するものとなる。 Preferred examples of the compound represented by the above formula (1) include compounds in which R 1 is all a hydrogen atom and R 2 is an alkyl group having 1 carbon atom (—CH 3 ), that is, Formula (3)
Figure JPOXMLDOC01-appb-C000006
(In formula (3), n represents a positive integer.)
The compound represented by these is mentioned. In addition, the said compound may be used individually by 1 type, or may be used combining 2 or more types of compounds from which n differs. N in the above formula (3) is preferably 1 or more and 5 or less. By using the compound represented by the above formula (3), excellent flame retardancy can be easily achieved. In addition, since the compound represented by the above formula (3) is superior in compatibility with other components in the resin composition, a cured layer obtained by curing the resin composition layer in this embodiment is an electronic component or It has better adhesion to the substrate.
　上述した式（３）で表される化合物としては、市販されるものを使用することができ、その例としては、ＡＤＥＫＡ社製の製品名「ＦＰ－６００」、大八化学社製の製品名「ＣＲ－７４１」等が挙げられる。 As the compound represented by the above formula (3), commercially available compounds can be used. Examples thereof include the product name “FP-600” manufactured by ADEKA and the product name manufactured by Daihachi Chemical. “CR-741” and the like.
　本実施形態における芳香族縮合リン酸エステルの別の好ましい例としては、以下の式（２）
Figure JPOXMLDOC01-appb-C000007
（式（２）中、Ａｒは、２価の芳香族炭化水素を表し、Ｒ３は、水素原子または炭素数が１～５のアルキル基を表す。）
で表される化合物が挙げられる。当該化合物は、１種を単独で使用してもよく、あるいは、Ｒ３が異なる２種以上の化合物を組み合わせて使用してもよい。 As another preferable example of the aromatic condensed phosphate ester in the present embodiment, the following formula (2):
Figure JPOXMLDOC01-appb-C000007
(In the formula (2), Ar represents a divalent aromatic hydrocarbon, and R 3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)
The compound represented by these is mentioned. The said compound may be used individually by 1 type, or may be used combining 2 or more types of compounds from which R < 3 > differs.
　上記式（２）における芳香族炭化水素の例としては、ベンゼン、ナフタレン、アントラセン、フルオレン、フェナントレン等が挙げられる。 Examples of the aromatic hydrocarbon in the above formula (2) include benzene, naphthalene, anthracene, fluorene, phenanthrene and the like.
　上記式（２）で表される化合物の好ましい例としては、Ａｒが、メタ位で２置換されたベンゼン環を表し、Ｒ３が全て水素原子である化合物、すなわち以下の式（４）
Figure JPOXMLDOC01-appb-C000008
で表される化合物が挙げられる。 As a preferable example of the compound represented by the above formula (2), a compound in which Ar represents a benzene ring disubstituted at the meta position and R 3 is all hydrogen atoms, that is, the following formula (4)
Figure JPOXMLDOC01-appb-C000008
The compound represented by these is mentioned.
　上述した式（４）で表される化合物としては、市販されるものを使用することができ、その例としては、大八化学社製の製品名「ＣＲ－７３３Ｓ」等が挙げられる。 As the compound represented by the above formula (4), commercially available compounds can be used, and examples thereof include a product name “CR-733S” manufactured by Daihachi Chemical Co., Ltd.
　樹脂組成物中における難燃剤の含有量は、０．５質量％以上であることが好ましく、特に１．０質量％以上であることが好ましく、さらには、２質量％以上であることが好ましい。また、当該含有量は、１０質量％以下であることが好ましく、特に７質量％以下であることが好ましく、さらには５質量％以下であることが好ましい。難燃剤の含有量が０．５質量％以上であることで、本実施形態における樹脂組成物層を硬化してなる硬化層が優れた難燃性を発揮し易いものとなる。また、難燃剤の含有量が１０質量％以下であることで、樹脂組成物層中における難燃剤の凝集を効果的に抑制することができ、その結果、硬化層が電子部品や基板に対してより優れた接着力を有するものとなる。 The content of the flame retardant in the resin composition is preferably 0.5% by mass or more, particularly preferably 1.0% by mass or more, and more preferably 2% by mass or more. Further, the content is preferably 10% by mass or less, particularly preferably 7% by mass or less, and further preferably 5% by mass or less. When the content of the flame retardant is 0.5% by mass or more, the cured layer obtained by curing the resin composition layer in the present embodiment easily exhibits excellent flame retardancy. Moreover, aggregation of the flame retardant in a resin composition layer can be effectively suppressed because content of a flame retardant is 10 mass% or less, As a result, a hardening layer is with respect to an electronic component or a board | substrate. It has more excellent adhesive force.
（５）硬化触媒
　本実施形態に係る樹脂シートでは、樹脂組成物が、硬化触媒をさらに含有することが好ましい。これにより、熱硬化性樹脂の硬化反応を効果的に進行させることが可能となり、樹脂組成物層を良好に硬化することが可能となる。硬化触媒の例としては、イミダゾール系硬化触媒、アミン系硬化触媒、リン系硬化触媒等が挙げられる。 (5) Curing catalyst In the resin sheet which concerns on this embodiment, it is preferable that the resin composition further contains a curing catalyst. Thereby, it becomes possible to advance the hardening reaction of a thermosetting resin effectively, and it becomes possible to cure | harden a resin composition layer favorably. Examples of the curing catalyst include an imidazole curing catalyst, an amine curing catalyst, and a phosphorus curing catalyst.
　イミダゾール系硬化触媒の具体例としては、２－メチルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、２－エチル－４－メチルイミダゾール、１－ベンジル－２－メチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾール、１，２－ジメチルイミダゾール、１－シアノエチル－２－メチルイミダゾール、１－シアノエチル－２－エチル－４－メチルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、２－フェニル－４，５－ジ（ヒドロキシメチル）イミダゾールなどが挙げられ、反応性の観点から、２－エチル－４－メチルイミダゾールを使用することが好ましい。 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 perspective of sex It is preferred to use 2-ethyl-4-methylimidazole.
　アミン系硬化触媒の具体例としては、２，４－ジアミノ－６－〔２’－メチルイミダゾリル－（１’）〕エチル－ｓ－トリアジン等のトリアジン化合物、１，８－ジアザビシクロ［５，４，０］ウンデセン－７（ＤＢＵ）、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン等の第三級アミン化合物が挙げられる。中でも、２，４－ジアミノ－６－〔２’－メチルイミダゾリル－（１’）〕エチル－ｓ－トリアジンが好ましい。 Specific examples of the amine-based curing catalyst include triazine compounds such as 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 1,8-diazabicyclo [5,4, 0] tertiary amine compounds such as undecene-7 (DBU), triethylenediamine, benzyldimethylamine, triethanolamine and the like. Among them, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine is preferable.
　また、リン系硬化触媒の具体例としては、トリフェニルホスフィン、トリブチルホスフィン、トリ（ｐ－メチルフェニル）ホスフィン、トリ（ノニルフェニル）ホスフィン等が挙げられる。 Specific examples of the phosphorus curing catalyst include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, and the like.
　上述した硬化触媒は、１種を単独で使用してもよく、２種以上を併用してもよい。 The above-mentioned curing catalyst may be used alone or in combination of two or more.
　樹脂組成物中における硬化触媒の含有量は、０．０１質量％以上であることが好ましく、特に０．０５質量％以上であることが好ましく、さらには、０．１質量％以上であることが好ましい。また、当該含有量は、２．０質量％以下であることが好ましく、特に１．５質量％以下であることが好ましく、さらには１．０質量％以下であることが好ましい。当該含有量が上記範囲であることで、樹脂組成物をより良好に硬化することが可能となる。 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 more preferably 0.1% by mass or more. preferable. Further, 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 can be cured more favorably.
（６）着色材料
　本実施形態における樹脂組成物は、着色材料をさらに含有していてもよい。樹脂組成物が着色材料を含有することにより、本実施形態における樹脂組成物層を硬化してなる硬化層が着色されたものとなり、当該硬化層によって封止される電子部品の隠蔽性が向上するとともに、当該硬化層に対してレーザーマーキングを行い易くなる。 (6) Coloring material The resin composition in this embodiment may further contain a coloring material. When the resin composition contains a coloring material, the cured layer formed by curing the resin composition layer in the present embodiment is colored, and the concealability of the electronic component sealed by the cured layer is improved. At the same time, it is easy to perform laser marking on the cured layer.
　上記着色材料としては、硬化層を着色できるものであれば特に限定されず、顔料や染料として一般的に使用されるものを使用することができる。特に、上記着色材料としては、絶縁性に優れるとともに、誤作動を誘発する電磁波を遮断する効果にも優れるものが好ましく、このような着色材料としては、全炭素原子に対する脂肪族炭化水素基を構成する炭素原子の割合が３質量％を超える炭素系材料、絶縁性の金属化合物等を使用することが好ましい。なお、隠蔽性、レーザーマーキング性および絶縁性に優れるとともに、誤作動を誘発する電磁波を遮断する効果を達成し易いという観点から、上述した炭素系材料は、炭素系顔料であることが好ましい。　　　 The coloring material is not particularly limited as long as it can color the cured layer, and those generally used as pigments and dyes can be used. In particular, the coloring material preferably has excellent insulating properties and is also excellent in the effect of blocking electromagnetic waves that induce malfunctions, and such a coloring material comprises an aliphatic hydrocarbon group for all carbon atoms. It is preferable to use a carbon-based material, an insulating metal compound, or the like in which the proportion of carbon atoms to be exceeded exceeds 3% by mass. In addition, it is preferable that the carbon-based material described above is a carbon-based pigment from the viewpoint of being excellent in concealability, laser marking property, and insulation and easily achieving an effect of blocking electromagnetic waves that induce malfunction. *
　全炭素原子に対する脂肪族炭化水素基を構成する炭素原子の割合が３質量％を超える炭素系材料の例としては、カーボンフィラー、コークス、木炭、ダイヤモンド等が挙げられ、これらの中でも、本実施形態に係る樹脂シートが前述した効果を達成し易い観点から、カーボンフィラーが好ましい。カーボンフィラーとは、主として炭素原子の共役系が連なった構造を有するものの、当該炭素原子の共役が脂肪族炭化水素基によって適度に断ち切られた構造を有する、アモルファス炭素物質である。　　　 Examples of the carbon-based material in which the proportion of carbon atoms constituting the aliphatic hydrocarbon group with respect to all carbon atoms exceeds 3% by mass include carbon filler, coke, charcoal, diamond, etc. Among these, the present embodiment From the viewpoint that the resin sheet according to the above easily achieves the effects described above, a carbon filler is preferable. A carbon filler is an amorphous carbon substance having a structure in which conjugated systems of carbon atoms are mainly linked, but having a structure in which the conjugation of the carbon atoms is appropriately cut off by an aliphatic hydrocarbon group. *
　以上説明した着色材料は、１種を単独で使用してもよく、または２種以上を組み合わせて使用してもよい。 The coloring materials described above may be used alone or in combination of two or more.
　樹脂組成物中における着色材料の含有量は、０．５質量％以上であることが好ましく、特に１．０質量％以上であることが好ましい。また、当該含有量は、５質量％以下であることが好ましく、特に３質量％以下であることが好ましい。当該含有量が０．５質量％以上であることで、前述したような、優れた隠蔽性、誤作動を誘発する電磁波の遮断、優れた絶縁性および優れたレーザーマーキング性の効果を効果的に得ることができる。また、当該含有量が５質量％以下であることで、樹脂組成物中におけるその他の成分の含有量を確保し易いものとなり、所望の性質を有する樹脂組成物層を形成し易いものとなる。 The content of the coloring material in the resin composition is preferably 0.5% by mass or more, and particularly preferably 1.0% by mass or more. The content is preferably 5% by mass or less, and particularly preferably 3% by mass or less. When the content is 0.5% by mass or more, the above-described excellent concealing properties, blocking of electromagnetic waves that induce malfunction, excellent insulating properties, and excellent laser marking properties are effectively obtained. Obtainable. Moreover, it becomes easy to ensure the content of the other component in a resin composition because the said content is 5 mass% or less, and it becomes easy to form the resin composition layer which has a desired property.
（７）その他の成分
　本実施形態における樹脂組成物は、さらに、可塑剤、安定剤、粘着付与剤、カップリング剤、帯電防止剤、酸化防止剤等を含有してもよい。 (7) Other components The resin composition in the present embodiment may further contain a plasticizer, a stabilizer, a tackifier, a coupling agent, an antistatic agent, an antioxidant, and the like.
（８）樹脂組成物層の厚さ
　本実施形態における樹脂組成物層の厚さは、２０μｍ以上であることが好ましく、特に５０μｍ以上であることが好ましく、さらには１００μｍ以上であることが好ましい。一方、樹脂組成物層の厚さは、１０００μｍ以下であり、５００μｍ以下であることが好ましく、特に３００μｍ以下であることが好ましい。樹脂組成物層の厚さが２０μｍ以上であることで、電子部品に対する埋め込み性に優れたものとなる。また、樹脂組成物層の厚さが１０００μｍ以下であることで、本実施形態に係る樹脂シートを用いて製造される半導体装置の小型化・薄膜化が容易となる。 (8) Thickness of the resin composition layer The thickness of the resin composition layer in the present embodiment is preferably 20 μm or more, particularly preferably 50 μm or more, and more preferably 100 μm or more. On the other hand, the thickness of the resin composition layer is 1000 μm or less, preferably 500 μm or less, and particularly preferably 300 μm or less. When the thickness of the resin composition layer is 20 μm or more, the resin composition layer has excellent embedding properties with respect to electronic components. Moreover, since the thickness of the resin composition layer is 1000 μm or less, it is easy to reduce the size and thin the semiconductor device manufactured using the resin sheet according to the present embodiment.
２．剥離シート
　本実施形態に係る樹脂シートは、樹脂組成物層の少なくとも一方の面に積層された剥離シートを備えていてもよい。剥離シートの構成は任意であり、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム、ポリプロピレン、ポリエチレン等のポリオレフィンフィルムなどのプラスチックフィルムが挙げられる。これらの剥離面（樹脂シートの樹脂組成物層と接する面）には、剥離処理が施されていることが好ましい。剥離処理に使用される剥離剤としては、例えば、シリコーン系、フッ素系、長鎖アルキル系、アルキッド系、オレフィン系、ゴム系等の剥離剤が挙げられる。 2. Release sheet The resin sheet according to the present embodiment may include a release sheet laminated on at least one surface of the resin composition layer. The configuration of the release sheet is arbitrary, and examples thereof include plastic films such as polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. It is preferable that a peeling treatment is performed on these peeling surfaces (surfaces in contact with the resin composition layer of the resin sheet). Examples of the release agent used for the release treatment include silicone-based, fluorine-based, long-chain alkyl-based, alkyd-based, olefin-based, and rubber-based release agents.
　剥離シートの厚さについては特に制限はないが、通常２０μｍ以上、２５０μｍ以下である。 Although there is no restriction | limiting in particular about the thickness of a peeling sheet, Usually, they are 20 micrometers or more and 250 micrometers or less.
３．本実施形態に係る樹脂シートの物性
　本実施形態に係る樹脂シートでは、樹脂組成物層をシリコン製のミラーウエハに積層し、当該樹脂組成物層を硬化させて硬化層とした場合に、当該硬化層における上述のウエハに対するせん断接着力が、３０Ｎ／５ｍｍ□以上であることが好ましく、特に３５Ｎ／５ｍｍ□以上であることが好ましく、さらには４０Ｎ／５ｍｍ□以上であることが好ましい。本実施形態における樹脂組成物が、難燃剤として常温で液体の芳香族縮合リン酸エステルを含有し、当該成分が樹脂組成物中に含まれるその他の成分との相溶性に優れるものであることにより、得られる硬化層が上述したせん断接着力を達成し易いものとなる。そして、上述したせん断接着力を達成することにより、本実施形態に係る樹脂シートによって、電子部品や当該電子部品を支持する基板に対して優れた接着力を有する硬化層を形成し易いものとなる。なお、上述したせん断接着力の上限値についは、特に限定されず、例えば、１４０Ｎ／５ｍｍ□以下であることが好ましく、特に１２０Ｎ／５ｍｍ□以下であることが好ましく、さらには１００Ｎ／５ｍｍ□以下であることが好ましい。また、上述したせん断接着力は、硬化層を後述する湿熱条件下に置く前に測定されたせん断接着力である。また、上述したせん断接着力は、ＭＩＬ－ＳＴＤ－８８３Ｊ（ＭＥＴＨＯＤ　２０１９．９）に準拠して測定されるものであり、その測定方法の詳細は後述する通りである。 3. Physical properties of the resin sheet according to the present embodiment In the resin sheet according to the present embodiment, the resin composition layer is laminated on a silicon mirror wafer, and the resin composition layer is cured to form a cured layer. The shear adhesive strength of the layer to the above-mentioned wafer is preferably 30 N / 5 mm □ or more, particularly preferably 35 N / 5 mm □ or more, and more preferably 40 N / 5 mm □ or more. The resin composition in the present embodiment contains an aromatic condensed phosphate ester that is liquid at room temperature as a flame retardant, and the component is excellent in compatibility with other components contained in the resin composition. Thus, the obtained cured layer can easily achieve the above-described shear adhesive force. And by achieving the above-mentioned shear adhesive force, the resin sheet according to the present embodiment makes it easy to form a cured layer having an excellent adhesive force with respect to the electronic component and the substrate that supports the electronic component. . The upper limit value of the shear adhesive force described above is not particularly limited. For example, it is preferably 140 N / 5 mm □ or less, particularly preferably 120 N / 5 mm □ or less, and more preferably 100 N / 5 mm □ or less. It is preferable that Moreover, the shear adhesive force mentioned above is a shear adhesive force measured before putting a hardened layer on the wet heat conditions mentioned later. Further, the above-mentioned shear adhesive strength is measured in accordance with MIL-STD-883J (METHOD 20199.9), and details of the measuring method are as described later.
　また、本実施形態に係る樹脂シートでは、樹脂組成物層をシリコン製のミラーウエハに積層し、当該樹脂組成物層を硬化させた硬化層について、当該硬化層と当該ウエハとの積層体を温度８５℃、相対湿度８５％の環境下に１６８時間という湿熱条件下に置いた後に測定される、上述のウエハに対するせん断接着力が、２５Ｎ／５ｍｍ□以上であることが好ましく、特に３０Ｎ／５ｍｍ□以上であることが好ましく、さらには３５Ｎ／５ｍｍ□以上であることが好ましい。本実施形態における樹脂シートによれば、このような湿熱条件下に置かれた後においても、得られる硬化層が上述したせん断接着力を達成し易いものとなる。そして、得られる硬化層が、湿熱条件後において上述したせん断接着力を達成することにより、本実施形態に係る樹脂シートを用いて製造された半導体装置が優れた耐熱性を有するものとなる。なお、湿熱条件後のせん断接着力の上限値についは、特に限定されず、例えば、１２０Ｎ／５ｍｍ□以下であることが好ましく、特に１００Ｎ／５ｍｍ□以下であることが好ましく、さらには８０Ｎ／５ｍｍ□以下であることが好ましい。また、上述した湿熱条件後のせん断接着力は、ＭＩＬ－ＳＴＤ－８８３Ｊ（ＭＥＴＨＯＤ　２０１９．９）に準拠して測定されるものであり、その測定方法の詳細は後述する通りである。 Further, in the resin sheet according to the present embodiment, the resin composition layer is laminated on a silicon mirror wafer, and the cured body and the wafer are cured with respect to the cured layer obtained by curing the resin composition layer. It is preferable that the shear adhesive strength to the above-mentioned wafer, measured after being placed under a moist heat condition of 168 hours in an environment of 85 ° C. and a relative humidity of 85%, is preferably 25 N / 5 mm □ or more, particularly 30 N / 5 mm □. It is preferable that it is above, and it is more preferable that it is 35N / 5mm □ or more. According to the resin sheet in the present embodiment, even after being placed under such wet heat conditions, the obtained cured layer can easily achieve the above-described shear adhesive force. And when the hardened layer obtained achieves the above-mentioned shear adhesive force after wet heat conditions, the semiconductor device manufactured using the resin sheet according to the present embodiment has excellent heat resistance. Incidentally, the upper limit value of the shear adhesive strength after the wet heat condition is not particularly limited, and is preferably, for example, 120 N / 5 mm □ or less, particularly preferably 100 N / 5 mm □ or less, and more preferably 80 N / 5 mm. It is preferable that it is below. Further, the above-mentioned shear adhesive strength after wet heat conditions is measured in accordance with MIL-STD-883J (METHOD 20199.9), and the details of the measurement method are as described later.
　なお、本明細書において、上述したせん断接着力を表す単位である「Ｎ／５ｍｍ□」は、５ｍｍ×５ｍｍの面積当たりの力（Ｎ）を意味するものとする。 In the present specification, “N / 5 mm □”, which is a unit representing the above-described shear adhesive force, means a force (N) per area of 5 mm × 5 mm.
４．樹脂シートの製造方法
　本実施形態に係る樹脂シートの製造方法としては、特に限定されず、例えば、前述した樹脂組成物層を含有する塗布液を所定の剥離シート上に塗布することで、前述した樹脂組成物層を形成する工程を備える方法（以下、「第１の製造方法」という場合がある。）や、前述した樹脂組成物を押出成形して、樹脂組成物層を形成する工程を備える方法（以下、「第２の製造方法」という場合がある。）等が挙げられる。 4). Method for Producing Resin Sheet The method for producing a resin sheet according to the present embodiment is not particularly limited. For example, the method described above is performed by applying a coating liquid containing the above-described resin composition layer on a predetermined release sheet. A method including a step of forming a resin composition layer (hereinafter, sometimes referred to as “first manufacturing method”) or a step of forming the resin composition layer by extruding the above-described resin composition. Method (hereinafter may be referred to as “second production method”).
　特に、本実施形態に係る樹脂シートは、上述した方法のうち、第１の製造方法により製造することが好ましい。第１の製造方法に使用される塗布液は、塗布を行うことが可能であればその性状は特に限定されず、樹脂組成物層を形成するための成分を溶質として含有する場合もあれば、分散質として含有する場合もある。上記溶媒の例としては、シクロヘキサノン、トルエン、酢酸エチル、メチルエチルケトン、アセトン、キシレン等の有機溶媒等が挙げられる。 In particular, the resin sheet according to the present embodiment is preferably manufactured by the first manufacturing method among the methods described above. The coating liquid used in the first production method is not particularly limited in its properties as long as it can be applied, and may contain a component for forming the resin composition layer as a solute. It may be contained as a dispersoid. Examples of the solvent include organic solvents such as cyclohexanone, toluene, ethyl acetate, methyl ethyl ketone, acetone, and xylene.
　第１の製造方法において、塗布液の塗布方法としては、例えば、樹脂組成物、および所望によりさらに溶媒または分散媒を含有する塗布液を調製し、剥離シートの剥離面上に、ダイコーター、カーテンコーター、スプレーコーター、スリットコーター、ナイフコーター等によりその塗布液を塗布して塗膜を形成し、当該塗膜を乾燥させることにより樹脂シートを製造することができる。 In the first manufacturing method, as a coating method of the coating liquid, for example, a resin composition and, if desired, a coating liquid further containing a solvent or a dispersion medium are prepared, and a die coater or curtain is formed on the release surface of the release sheet. A resin sheet can be produced by applying the coating solution with a coater, spray coater, slit coater, knife coater or the like to form a coating film and drying the coating film.
　第１の製造方法における剥離シートとしては、前述したものを使用することができる。また、当該剥離シートは工程材料として剥離してもよいし、樹脂シートを使用するまでの間、樹脂組成物層を保護していてもよい。また、樹脂組成物層を電子部品に積層した後、樹脂組成物層を硬化させる前に樹脂組成物層から剥離してもよく、または、樹脂組成物層を硬化させた後、形成された硬化層から剥離してもよい。 As the release sheet in the first production method, those described above can be used. Moreover, the said peeling sheet may peel as process material, and may protect the resin composition layer until it uses a resin sheet. Moreover, after laminating the resin composition layer on the electronic component, it may be peeled off from the resin composition layer before curing the resin composition layer, or the cured formed after curing the resin composition layer The layer may be peeled off.
　また、第１の製造方法は、上述したような、剥離シート上に樹脂組成物層を形成する工程の後に、形成された樹脂組成物層における上述した剥離シートとは反対側の面に、他の剥離シートを貼付する工程を備えてもよい。これにより、一の剥離シート／樹脂組成物層／他の剥離シートという構成を有する樹脂シートを得ることができる。この場合、剥離シートの少なくとも一方は工程材料として剥離してもよいし、封止に使用するまでの間、樹脂組成物層を保護していてもよい。 In addition, the first manufacturing method may be performed after the step of forming the resin composition layer on the release sheet as described above, on the surface of the formed resin composition layer opposite to the release sheet described above. A step of attaching the release sheet may be provided. Thereby, the resin sheet which has the structure of one release sheet / resin composition layer / other release sheet can be obtained. In this case, at least one of the release sheets may be peeled off as a process material, or the resin composition layer may be protected until it is used for sealing.
５．樹脂シートの使用方法
　本実施形態に係る樹脂シートは、電子部品の封止に使用されるものである。特に、本実施形態に係る樹脂シートは、半導体装置の製造方法における電子部品の封止に使用されることが好ましく、さらには半導体装置の製造方法の半導体実装工程における電子部品の封止に使用されることが好ましい。本実施形態に係る樹脂シートを電子部品の封止に使用する際には、例えば、基板上や、粘着シートといった仮固定材上に設けられた電子部品に対して、樹脂シートにおける樹脂組成物層を積層した後、樹脂組成物層を硬化させて硬化層を形成することで、電子部品の封止を行うことができる。 5. Usage of Resin Sheet The resin sheet according to the present embodiment is used for sealing electronic components. In particular, the resin sheet according to the present embodiment is preferably used for sealing an electronic component in a method for manufacturing a semiconductor device, and further used for sealing an electronic component in a semiconductor mounting process of the method for manufacturing a semiconductor device. It is preferable. When the resin sheet according to this embodiment is used for sealing an electronic component, for example, the resin composition layer in the resin sheet with respect to the electronic component provided on a temporary fixing material such as a substrate or an adhesive sheet. After laminating | stacking, an electronic component can be sealed by hardening a resin composition layer and forming a hardened layer.
　本実施形態に係る樹脂シートでは、樹脂組成物層が、難燃剤として、常温で液体の芳香族縮合リン酸エステルを含有する樹脂組成物から形成されたものであることにより、当該樹脂組成物層を硬化してなる硬化物が優れた難燃性を有するものとなる。さらに、常温で液体の芳香族縮合リン酸エステルは、樹脂組成物に含有されるその他の成分と良好な相溶性を示すことにより、得られる硬化物が、当該硬化物が接する対象に対して優れた接着力を発揮することができる。その結果、本実施形態に係る樹脂シートを用いて、優れた性能を有する半導体装置を製造することができる。 In the resin sheet according to the present embodiment, the resin composition layer is formed from a resin composition containing an aromatic condensed phosphate ester that is liquid at room temperature as a flame retardant. A cured product obtained by curing is excellent in flame retardancy. Furthermore, the aromatic condensed phosphate ester that is liquid at room temperature exhibits excellent compatibility with other components contained in the resin composition, and the resulting cured product is excellent for the object that the cured product contacts. Adhesive strength can be demonstrated. As a result, a semiconductor device having excellent performance can be manufactured using the resin sheet according to the present embodiment.
　上述した硬化は、樹脂組成物層を加熱することによって行うことが好ましい。この場合、加熱の温度は、１００℃以上とすることが好ましく、特に１２０℃以上とすることが好ましい。また、当該温度は、２４０℃以下とすることが好ましく、特に２００℃以下とすることが好ましい。また、上記加熱の時間は、１５分間以上とすることが好ましく、特に２０分間以上とすることが好ましい。また、当該時間は、３００分間以下とすることが好ましく、特に１００分間以下とすることが好ましい。 The above-described curing is preferably performed by heating the resin composition layer. In this case, the heating temperature is preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher. Further, the temperature is preferably 240 ° C. or lower, and particularly preferably 200 ° C. or lower. The heating time is preferably 15 minutes or more, and particularly preferably 20 minutes or more. In addition, the time is preferably 300 minutes or less, particularly preferably 100 minutes or less.
　また、上述した加熱による樹脂組成物層の硬化は、複数回の加熱処理により段階的に行うことが好ましい。この場合の加熱は、２回以上に分けて行うことが好ましく、特に、温度Ｔ１で熱硬化させる第１の加熱処理と、温度Ｔ１よりも高い温度Ｔ２にて熱硬化させる第２の加熱処理とによる、２段階の加熱の処理により行われることがより好ましい。この場合、第１の加熱処理では、温度Ｔ１が１００℃以上、１３０℃以下であることが好ましく、加熱処理の時間は１５分以上、６０分以下であることが好ましい。また、第２の加熱処理では、温度Ｔ２が、１５０℃以上、２２０℃以下であることが好ましく、加熱処理の時間は３０分以上、１２０分以下であることが好ましい。 Moreover, it is preferable that the above-described curing of the resin composition layer by heating is performed stepwise by a plurality of heat treatments. The heating in this case is preferably performed in two or more times. In particular, a first heat treatment for thermosetting at a temperature T1 and a second heat treatment for thermosetting at a temperature T2 higher than the temperature T1. More preferably, it is carried out by a two-stage heating process. In this case, in the first heat treatment, the temperature T1 is preferably 100 ° C. or higher and 130 ° C. or lower, and the heat treatment time is preferably 15 minutes or longer and 60 minutes or shorter. In the second heat treatment, the temperature T2 is preferably 150 ° C. or higher and 220 ° C. or lower, and the heat treatment time is preferably 30 minutes or longer and 120 minutes or shorter.
　本実施形態に係る樹脂シートが、樹脂組成物層の片面側のみに剥離シートを備える場合、当該剥離シートは、樹脂組成物層を電子部品に積層した後、樹脂組成物層を硬化させる前に樹脂組成物層から剥離してもよく、あるいは、樹脂組成物層を硬化させた後、形成された硬化層から剥離してもよい。本実施形態に係る樹脂シートが、樹脂組成物層の両面側に剥離シートを備える場合、一の剥離シートを剥離して、露出した樹脂組成物層の露出面を電子部品に積層し、他の剥離シートについては、樹脂組成物層の硬化の前後のいずれかにおいて剥離してよい。 When the resin sheet according to the present embodiment includes a release sheet only on one side of the resin composition layer, the release sheet is laminated on the electronic component and then cured before the resin composition layer is cured. You may peel from a resin composition layer, or after hardening a resin composition layer, you may peel from the formed cured layer. When the resin sheet according to this embodiment includes release sheets on both sides of the resin composition layer, one release sheet is peeled off, and the exposed surface of the exposed resin composition layer is laminated on the electronic component, and the other About a peeling sheet, you may peel in either before and after hardening of a resin composition layer.
　上述した電子部品の例としては、一般的に封止の対象となる電子部品であれば特に限定されず、例えば、半導体チップ等が挙げられる。また、製造される半導体装置としては、部品内蔵基板、半導体パッケージ等が挙げられ、特に部品内蔵基板であることが好ましい。 Examples of the electronic components described above are not particularly limited as long as they are electronic components that are generally sealed, and examples thereof include semiconductor chips. Further, examples of the semiconductor device to be manufactured include a component built-in substrate, a semiconductor package, and the like, and a component built-in substrate is particularly preferable.
　以上説明した実施形態は、本発明の理解を容易にするために記載されたものであって、本発明を限定するために記載されたものではない。したがって、上記実施形態に開示された各要素は、本発明の技術的範囲に属する全ての設計変更や均等物をも含む趣旨である。 The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.
　以下、実施例および試験例等を示すことにより本発明をさらに詳細に説明するが、本発明は下記の試験例等に何ら限定されるものではない。 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.
〔実施例１～３および比較例１～３〕
　表１に示す構成成分を混合し、シクロヘキサノンにて希釈して、固形分濃度が５８質量％である樹脂組成物の塗布液を得た。当該塗布液を、片面がシリコーン剥離処理された剥離フィルム（リンテック社製，製品名「ＳＰ－ＰＥＴ３８２１５０」）の剥離面上にナイフコーターを用いて、塗工速度２．０ｍ／ｍｉｎで塗布し、得られた塗膜をオーブンにて５０℃で１分間、７０℃で１分間、９０℃で１分間および１００℃で１分間の条件で順に加熱することで乾燥させ、厚さ５０μｍの樹脂組成物層と剥離フィルムとからなる樹脂シートを得た。 [Examples 1 to 3 and Comparative Examples 1 to 3]
The components shown in Table 1 were mixed and diluted with cyclohexanone to obtain a resin composition coating solution having a solid content concentration of 58% by mass. The coating solution was applied at a coating speed of 2.0 m / min on the release surface of a release film (product name “SP-PET 382150”, manufactured by Lintec Co., Ltd.) on which one side was subjected to silicone release treatment, using a knife coater. The obtained coating film was dried by heating in an oven at 50 ° C. for 1 minute, 70 ° C. for 1 minute, 90 ° C. for 1 minute, and 100 ° C. for 1 minute, and a resin composition having a thickness of 50 μm. A resin sheet comprising a layer and a release film was obtained.
　ここで、表１に示す構成成分の詳細は以下の通りである。
［熱可塑性樹脂］
　ＢｉｓＡ型フェノキシ樹脂：ビスフェノールＡ型フェノキシ樹脂（三菱化学社製，製品名「ｊＥＲ１２５６」）
［熱硬化性樹脂］
　ＢｉｓＡ型エポキシ樹脂：ビスフェノールＡ型エポキシ樹脂（三菱化学社製，製品名「ｊＥＲ８２８」）
　ビフェニル型エポキシ樹脂：ビフェニル型エポキシ樹脂（日本化薬社製，製品名「ＮＣ－３０００－Ｌ」）
　ナフタレン型エポキシ樹脂：ナフタレン型エポキシ樹脂（ＤＩＣ社製，製品名「ＨＰ－６０００」）
　ビフェニル型フェノール樹脂：ビフェニル型フェノール樹脂（明和化成社製，製品名「ＭＥＨＣ－７８５１－ＳＳ」）
［硬化触媒］
　イミダゾール系熱硬化触媒：２－エチル－４－メチルイミダゾール（四国化成社製，製品名「２Ｅ４ＭＺ」）
［無機フィラー］
　エポキシシラン処理シリカフィラー：シリカフィラー（アドマテックス社製，製品名「ＳＯ－Ｃ２」，平均粒径：０．５μｍ，最大粒径：２μｍ，形状：球状）を、３－グリシドキシプロピルトリメトキシシラン（信越化学社製，製品名「ＫＢＭ－４０３」，最小被覆面積：３３０ｍ２／ｇ）を用いて表面処理したもの
［着色材料］
　カーボンフィラー：カーボンフィラー（コスモ石油社製，製品名「ＣＣＦ－Ｒ０１Ｌ」，形状：不定形，平均粒径：１μｍ，全炭素原子に対する脂肪族炭化水素基を構成する炭素原子の割合：５％）
［難燃剤］
　液状芳香族縮合リン酸エステル（ＦＰ－６００）：前述した式（１）で表される化合物（式中、Ｒ１およびＲ２は全て水素原子を表す。）の混合物（ＡＤＥＫＡ社製，製品名「ＦＰ－６００」，常温で液体，２５℃における粘度：１８０００～２００００ｍＰａ・ｓ，２５℃における蒸気圧：１．２×１０－６ｋＰａ未満）
　液状芳香族縮合リン酸エステル（ＣＲ－７４１）：ビスフェノールＡビス（ジフェニルホスフェート）（大八化学社製，製品名「ＣＲ－７４１」，常温で液体）
　リン酸エステルトリアジン系化合物塩：リン酸エステルトリアジン系化合物塩（日産化学工業社製，製品名「ＰＨＯＳＭＥＬ　２００－ＦＩＮＥ」，常温で固体）
　有機リン酸金属塩：有機リン酸金属塩（クラリアントケミカルズ社製，製品名「Ｅｘｏｌｉｔ　ＯＰ　９３５」，常温で固体） Here, the detail of the component shown in Table 1 is as follows.
[Thermoplastic resin]
BisA type phenoxy resin: Bisphenol A type phenoxy resin (product name “jER1256” manufactured by Mitsubishi Chemical Corporation)
[Thermosetting resin]
BisA type epoxy resin: bisphenol A type epoxy resin (product name “jER828” manufactured by Mitsubishi Chemical Corporation)
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 (Maywa Kasei Co., Ltd., product name "MEHC-7785-SS")
[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 Admatechs, product name “SO-C2”, average particle size: 0.5 μm, maximum particle size: 2 μm, shape: spherical) was added to 3-glycidoxypropyltrimethoxy Surface treatment with silane (Shin-Etsu Chemical Co., Ltd., product name “KBM-403”, minimum coating area: 330 m 2 / g) [coloring material]
Carbon filler: Carbon filler (manufactured by Cosmo Oil Co., Ltd., product name “CCF-R01L”, shape: amorphous, average particle size: 1 μm, ratio of carbon atoms constituting aliphatic hydrocarbon groups to all carbon atoms: 5%)
[Flame retardants]
Liquid aromatic condensed phosphate ester (FP-600): mixture of compounds represented by formula (1) described above (wherein R 1 and R 2 all represent hydrogen atoms) (product name, manufactured by ADEKA) “FP-600”, liquid at room temperature, viscosity at 25 ° C .: 18000 to 20000 mPa · s, vapor pressure at 25 ° C .: less than 1.2 × 10 −6 kPa)
Liquid aromatic condensed phosphate ester (CR-741): bisphenol A bis (diphenyl phosphate) (manufactured by Daihachi Chemical Co., Ltd., product name “CR-741”, liquid at room temperature)
Phosphate triazine compound salt: Phosphate ester triazine compound salt (manufactured by Nissan Chemical Industries, Ltd., product name “PHOSMEL 200-FINE”, solid at room temperature)
Organophosphate metal salt: Organophosphate metal salt (manufactured by Clariant Chemicals, product name “Exolit OP 935”, solid at room temperature)
〔試験例１〕（難燃性の評価）
　実施例および比較例で作製した樹脂シートにおける樹脂組成物層を積層することで、０．１５ｍｍの厚さの樹脂組成物層の積層体を作製した後、当該積層体を裁断することで、長さ１２５ｍｍ、幅１３ｍｍの試験片を得た。 [Test Example 1] (Evaluation of flame retardancy)
By laminating the resin composition layers in the resin sheets produced in Examples and Comparative Examples, a laminate of a resin composition layer having a thickness of 0.15 mm was produced, and then the laminate was cut to obtain a long A test piece having a thickness of 125 mm and a width of 13 mm was obtained.
　次いで、当該試験片を、１００℃で３０分間、および１９０℃で２時間の条件で順に加熱することで硬化し、燃焼試験用試験片とした。 Next, the test piece was cured by heating in order at 100 ° C. for 30 minutes and at 190 ° C. for 2 hours to obtain a test piece for combustion test.
　得られた燃焼試験用試験片について、ＵＬ９４規格に基づく難燃性試験を行い、以下の基準に基づいて、難燃性を評価した。
　〇：ＵＬ９４規格の難燃レベルＶ－０を満たした。
　×：ＵＬ９４規格の難燃レベルＶ－０を満たさなかった。 About the obtained test piece for combustion tests, the flame retardance test based on UL94 specification was done, and the flame retardance was evaluated based on the following references | standards.
A: The flame retardant level V-0 of UL94 standard was satisfied.
X: The flame resistance level V-0 of UL94 standard was not satisfied.
〔試験例２〕（せん断接着力の測定）
　実施例および比較例で製造した樹脂シートにおける樹脂組成物層側の面を、真空ラミネーター（ニッコー・マテリアルズ社製，製品名「Ｖ１３０」）を用いて、９０℃、０．３ＭＰａおよび３０秒間の条件で、シリコン製のミラーウエハ（直径：８インチ，厚さ：３５０μｍ）のミラー面に真空ラミネートした。さらに、ダイサー（ディスコ社製，製品名「ＤＦＤ６３６２」）を用いて、５ｍｍ×５ｍｍのサイズにダイシングすることで、５ｍｍ角の樹脂組成物層と５ｍｍ角のチップとの積層体を得た。 [Test Example 2] (Measurement of shear adhesive strength)
The surface of the resin composition layer side of the resin sheets produced in the examples and comparative examples is 90 ° C., 0.3 MPa, and 30 seconds using a vacuum laminator (Nikko Materials, product name “V130”). Under conditions, vacuum lamination was performed on the mirror surface of a silicon mirror wafer (diameter: 8 inches, thickness: 350 μm). Further, a dicer (manufactured by Disco Corporation, product name “DFD6362”) was diced into a size of 5 mm × 5 mm to obtain a laminate of a 5 mm square resin composition layer and a 5 mm square chip.
　続いて、得られた積層体を、マニュアルボンダー（ノードソン・アドバンスト・テクノロジー社製，製品名「ＥＤＢ６５」）を用いて、１５０℃、３００ｇｆおよび３秒間の条件で、１０ｍｍ角のシリコン製のミラーウエハ（厚さ：３５０μｍ）のほぼ中央にマニュアルボンディングすることで、チップと、５ｍｍ角の樹脂組成物層と、ウエハとが順に積層されてなるサンプルを得た。 Subsequently, using the manual bonder (manufactured by Nordson Advanced Technology Co., Ltd., product name “EDB65”), the obtained laminated body was made into a 10 mm square silicon mirror wafer under the conditions of 150 ° C., 300 gf and 3 seconds. By manual bonding at approximately the center of (thickness: 350 μm), a sample in which a chip, a 5 mm square resin composition layer, and a wafer were sequentially laminated was obtained.
　次に、得られたサンプルを、１００℃で３０分間、１９０℃で２時間の条件で順に加熱することで樹脂組成物層を硬化し、せん断接着力測定用試験片とした。 Next, the resin composition layer was cured by sequentially heating the obtained sample at 100 ° C. for 30 minutes and at 190 ° C. for 2 hours to obtain a test piece for measuring shear adhesive force.
　得られたせん断接着力測定用試験片について、ＭＩＬ－ＳＴＤ－８８３Ｊ（ＭＥＴＨＯＤ　２０１９．９）に準拠して、ボンドテスター（ノードソン・アドバンスト・テクノロジー社製，製品名「ＤＡＧＥ４０００」）を用いて、せん断接着力を測定した。具体的には、上述したせん断接着力測定用試験片を２５０℃で３０秒間加熱した後、ボンドテスターの測定端子をチップの側面に当てた。次に、ウエハを固定しながら、当該測定端子によって、チップと硬化物との界面に平行な方向に力をチップに印加し、硬化物からチップが剥がれるまで印加する力を増大した。そして、硬化物からチップが剥がれたときの力（Ｎ／５ｍｍ□）を記録した。この力を、硬化直後のせん断接着力（Ｎ／５ｍｍ□）とした。結果を表１に示す。 About the obtained test piece for shear adhesive strength measurement, using a bond tester (manufactured by Nordson Advanced Technology, product name “DAGE4000”) in accordance with MIL-STD-883J (METHOD 20199.9) The adhesive force was measured. Specifically, after the above-mentioned test piece for measuring the shear adhesive force was heated at 250 ° C. for 30 seconds, the measurement terminal of the bond tester was applied to the side surface of the chip. Next, while fixing the wafer, a force was applied to the chip in a direction parallel to the interface between the chip and the cured product by the measurement terminal, and the force applied until the chip was peeled off from the cured product was increased. And the force (N / 5mm □) when the chip was peeled from the cured product was recorded. This force was defined as a shear adhesive force (N / 5 mm □) immediately after curing. The results are shown in Table 1.
　さらに、上記と同様に作製したせん断接着力測定用試験片を、温度８５℃、相対湿度８５％の環境下で１６８時間という湿熱条件に置いた後、上記と同様にして、せん断接着力を測定した。得られた測定結果を、湿熱条件後のせん断接着力（Ｎ／５ｍｍ□）とした。結果を表１に示す。 Further, after the test piece for measuring shear adhesion force prepared in the same manner as described above was placed in a moist heat condition of 168 hours in an environment of a temperature of 85 ° C. and a relative humidity of 85%, the shear adhesion force was measured in the same manner as described above. did. The obtained measurement result was defined as shear adhesive strength (N / 5 mm □) after wet heat conditions. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　表１に示されるように、実施例の樹脂シートは、難燃性に優れていることがわかった。また、実施例の樹脂シートは、硬化直後および湿熱条件後において、十分なせん断接着力を有するものであった。 As shown in Table 1, it was found that the resin sheets of the examples were excellent in flame retardancy. Moreover, the resin sheet of an Example had sufficient shearing adhesive force immediately after hardening and after wet heat conditions.
　本発明に係る樹脂シートは、半導体実装工程における電子部品の封止に好適に使用することができる。 The resin sheet according to the present invention can be suitably used for sealing electronic components in a semiconductor mounting process.

Claims (6)

  1. 　電子部品の封止に使用される樹脂シートであって、
    　前記樹脂シートが、熱硬化性樹脂と、熱可塑性樹脂と、無機フィラーと、難燃剤とを含有する樹脂組成物から形成された樹脂組成物層を備え、
    　前記難燃剤が、常温で液体の芳香族縮合リン酸エステルである
    ことを特徴とする樹脂シート。     A resin sheet used for sealing electronic components,
    The resin sheet includes a resin composition layer formed from a resin composition containing a thermosetting resin, a thermoplastic resin, an inorganic filler, and a flame retardant,
    The resin sheet, wherein the flame retardant is an aromatic condensed phosphate ester that is liquid at room temperature.
  2. 　前記芳香族縮合リン酸エステルは、以下の式（１）
    Figure JPOXMLDOC01-appb-C000001
    （式（１）中、ｎは、１以上、５以下の整数を表し、Ｒ１は、水素原子または炭素数が１～３のアルキル基を表し、Ｒ２は、水素原子または炭素数が１～５のアルキル基を表す。）
    で表される化合物、および以下の式（２）
    Figure JPOXMLDOC01-appb-C000002
    （式（２）中、Ａｒは、２価の芳香族炭化水素を表し、Ｒ３は、水素原子または炭素数が１～５のアルキル基を表す。）
    で表される化合物の少なくとも１種を含むことを特徴とする請求項１に記載の樹脂シート。     The aromatic condensed phosphate ester has the following formula (1):
    Figure JPOXMLDOC01-appb-C000001
    (In the formula (1), n represents an integer of 1 or more and 5 or less, R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 2 represents a hydrogen atom or 1 carbon atom. Represents an alkyl group of ˜5.)
    And the following formula (2)
    Figure JPOXMLDOC01-appb-C000002
    (In the formula (2), Ar represents a divalent aromatic hydrocarbon, and R 3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)
    The resin sheet according to claim 1, comprising at least one compound represented by the formula:
  3. 　前記芳香族縮合リン酸エステルの２５℃における粘度は、５０００ｍＰａ・ｓ以上、３００００ｍＰａ・ｓ以下であることを特徴とする請求項１または２に記載の樹脂シート。 The resin sheet according to claim 1 or 2, wherein the viscosity of the aromatic condensed phosphate ester at 25 ° C is 5000 mPa · s or more and 30000 mPa · s or less.
  4. 　前記樹脂組成物中における前記難燃剤の含有量は、０．５質量％以上、５．０質量％以下であることを特徴とする請求項１～３のいずれか１項に記載の樹脂シート。 The resin sheet according to any one of claims 1 to 3, wherein the content of the flame retardant in the resin composition is 0.5 mass% or more and 5.0 mass% or less.
  5. 　半導体実装工程における電子部品の封止に用いられることを特徴とする請求項１～４のいずれか１項に記載の樹脂シート。 The resin sheet according to any one of claims 1 to 4, which is used for sealing an electronic component in a semiconductor mounting process.
  6. 　請求項１～５のいずれか１項に記載の樹脂シートの製造方法であって、
    　前記樹脂組成物層を含有する塗布液を所定の剥離シート上に塗布することで、前記樹脂組成物層を形成する工程を備える
    ことを特徴とする樹脂シートの製造方法。     A method for producing a resin sheet according to any one of claims 1 to 5,
    A method for producing a resin sheet, comprising a step of forming the resin composition layer by applying a coating liquid containing the resin composition layer on a predetermined release sheet.
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