WO2021039687A1 - 樹脂組成物及び樹脂シート - Google Patents

樹脂組成物及び樹脂シート Download PDF

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WO2021039687A1
WO2021039687A1 PCT/JP2020/031768 JP2020031768W WO2021039687A1 WO 2021039687 A1 WO2021039687 A1 WO 2021039687A1 JP 2020031768 W JP2020031768 W JP 2020031768W WO 2021039687 A1 WO2021039687 A1 WO 2021039687A1
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Prior art keywords
resin composition
resin
component
ion trapping
trapping agent
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PCT/JP2020/031768
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English (en)
French (fr)
Japanese (ja)
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泰紀 柄澤
康貴 渡邉
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リンテック株式会社
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Priority to JP2021542870A priority Critical patent/JPWO2021039687A1/ja
Publication of WO2021039687A1 publication Critical patent/WO2021039687A1/ja

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02Monomers containing only one unsaturated aliphatic radical
    • C08F212/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36Amides or imides
    • C08F222/40Imides, e.g. cyclic imides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00Adhesives based on unspecified macromolecular compounds
    • C09J201/02Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35Heat-activated
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

  • the present invention relates to a resin composition and a resin sheet.
  • Patent Document 1 describes a maleimide compound, a compound having at least one of an allyl group and an epoxy group, an amine compound, and a radical generator containing at least one of an acetophenone derivative and a tetraphenylethane derivative.
  • the resin composition contained is disclosed.
  • An object of the present invention is to provide a resin composition and a resin sheet having excellent heat resistance and suppressed ion migration.
  • the resin composition according to one aspect of the present invention is a resin composition containing (A) a thermosetting component and (B) an ion trap agent, and the (A) thermosetting component is (A1). )
  • the maleimide resin is contained, and the total amount of ionic impurities contained in the extracted water of the cured product of the resin composition is 50 ⁇ S / cm or less in terms of electrical conductivity.
  • the ion trapping agent (B) may contain at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, antimony, and bismuth. preferable.
  • the (B) ion trapping agent is a binary ion trapping agent containing magnesium and aluminum, or a ternary ion trapping agent.
  • the ion trap agent (B) contains bismuth.
  • the ion trapping agent (B) is preferably a binary ion trapping agent containing zirconium or a ternary ion trapping agent.
  • the ion trapping agent (B) contains at least one element of magnesium and zirconium and at least one element of aluminum and bismuth. It is preferably a binary ion trapping agent or a ternary ion trapping agent.
  • the content of the ion trapping agent (B) is preferably 10% by mass or less based on the total solid content of the resin composition.
  • thermosetting component further contains (A2) an allyl resin.
  • the content of the (A1) maleimide resin in the (A) thermosetting component is based on the total solid content of the (A) thermosetting component. It is preferably 60% by mass or more.
  • thermosetting component (A) does not substantially contain an epoxy resin.
  • the resin composition according to one aspect of the present invention it is preferable that it is used for encapsulating a semiconductor element or for interposing it between the semiconductor element and another electronic component.
  • the resin composition according to one aspect of the present invention it is preferable that it is used for encapsulating a power semiconductor element or interposing it between the power semiconductor element and another electronic component.
  • a semiconductor device using any one or more of silicon carbide and gallium nitride is sealed, or any one or more of the silicon carbide and gallium nitride is used. It is preferably used for interposing between the used semiconductor element and other electronic components.
  • the resin sheet according to one aspect of the present invention is characterized by containing the resin composition according to one aspect of the present invention.
  • the resin composition according to this embodiment contains (A) a thermosetting component and (B) an ion trapping agent.
  • the (A) thermosetting component according to the present embodiment contains (A1) maleimide resin.
  • the total amount of ionic impurities contained in the extracted water of the cured product of the resin composition according to the present embodiment is 50 ⁇ S / cm or less in terms of electrical conductivity. From the viewpoint of further suppressing ion migration, the total amount of the ion impurities is preferably 40 ⁇ S / cm or less, and more preferably 35 ⁇ S / cm or less.
  • the curing conditions of the cured product of the resin composition are, for example, 4 hours at a temperature of 200 ° C.
  • the total amount of ionic impurities can be measured by the following method. That is, after preparing a sample having a thickness of 200 ⁇ m using the resin composition, 1.0 g of the measurement sample cured under the above curing conditions was measured and put into a Teflon (registered trademark) crucible. Next, 25 mL of ultrapure water was measured with a whole pipette, put into a crucible, protected with a metal jacket, and extracted under the conditions of a temperature of 121 ° C. for 24 hours to obtain extracted water. The electric conductivity of the obtained extracted water was measured using an electric conductivity measuring device (“CONDUCTIVITY METER B-173” manufactured by HORIBA, Ltd.).
  • thermosetting component (A) (hereinafter, may be simply referred to as “component (A)”) has a property of forming a three-dimensional network when heated and firmly adhering an adherend.
  • component (A) contains (A1) maleimide resin (hereinafter, may be simply referred to as “(A1) component”).
  • the (A1) maleimide resin in the present embodiment is not particularly limited as long as it is a maleimide resin containing two or more maleimide groups in one molecule.
  • the maleimide resin (A1) in the present embodiment preferably contains, for example, a benzene ring, and more preferably contains a structure in which a maleimide group is linked to the benzene ring. Further, the maleimide compound preferably includes two or more structures in which a maleimide group is linked to a benzene ring.
  • the (A1) maleimide resin in the present embodiment is a maleimide resin containing two or more maleimide groups and one or more biphenyl skeletons in one molecule (hereinafter, may be simply referred to as "biphenyl maleimide resin"). Is preferable.
  • the maleimide resin (A1) in the present embodiment is preferably represented by the following general formula (1) from the viewpoint of heat resistance and adhesiveness.
  • k is an integer of 1 or more, and the average value of k is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and 1 or more and 3 or less. It is more preferable to have.
  • m1 and m2 are independently integers of 1 or more and 6 or less, preferably 1 or more and 3 or less, and more preferably 1.
  • n1 and n2 are independently integers of 0 or more and 4 or less, preferably 0 or more and 2 or less, and more preferably 0.
  • R 1 and R 2 are independently alkyl groups having 1 to 6 carbon atoms, preferably alkyl groups having 1 to 3 carbon atoms, and more preferably methyl groups.
  • a plurality of R 1 may or different are identical to one another.
  • a plurality of R 2 is, or different are identical to one another.
  • maleimide resin represented by the general formula (1) in the present embodiment include compounds represented by the following general formula (2) or the following general formula (3).
  • k is the same as k in the general formula (1).
  • n1, n2, R 1 and R 2 are the same as n1, n2, R 1 and R 2 in the general formula (1).
  • Examples of the maleimide resin product represented by the general formula (3) include "MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd.
  • the maleimide resin (A1) in the present embodiment is preferably a maleimide resin containing two or more maleimide groups and two or more phenylene groups in one molecule. It is preferable to have a substituent on the phenylene group from the viewpoint of increasing the solubility in a solvent and improving the sheet formability. Examples of the substituent include an alkyl group such as a methyl group and an ethyl group, an alkylene group and the like. Further, the maleimide resin (A1) in the present embodiment is preferably a maleimide resin having an ether bond between the maleimide group and the phenylene group from the viewpoint of sheet formability.
  • the maleimide resin containing two or more maleimide groups and two or more phenylene groups in the one molecule is represented by, for example, the following general formula (4).
  • R 3 to R 6 are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms
  • L 1 is an alkylene group having 1 to 3 carbon atoms
  • L 2 and L 3 are independently alkylene groups having 1 or more and 2 or less carbon atoms or arylene groups having 6 or more and 10 or less carbon atoms
  • p and q are independently 0 or 1, respectively.
  • the total number of carbon atoms in L 1 , L 2 and L 3 is 3 or less.
  • the maleimide resin represented by the general formula (4) in the present embodiment is specifically represented by, for example, the following general formula (5) or the following general formula (6).
  • L 1 is an alkylene group having 1 or more carbon atoms and 3 or less carbon atoms.
  • R 3 to R 6 are independently hydrogen atoms or alkyl groups having 1 or more and 6 or less carbon atoms.
  • the maleimide resin (A1) in the present embodiment has two or more maleimide groups in one molecule from the viewpoint of flexibility and heat resistance, and has at least one pair of binding groups connecting the two maleimide groups.
  • a maleimide resin having four or more methylene groups in the main chain is preferable.
  • the bonding group linking the two maleimide groups preferably has 6 or more methylene groups in the main chain, and more preferably 8 or more methylene groups in the main chain, from the viewpoint of flexibility.
  • the bonding group linking the two maleimide groups preferably has one or more side chains from the viewpoint of flexibility.
  • this side chain include an alkyl group and an alkoxy group.
  • the side chains may be bonded to each other to form an alicyclic structure.
  • such a (A1) maleimide resin has the following characteristics when compared with other maleimide resins. That is, such (A1) maleimide resin is a liquid maleimide resin at a temperature of 25 ° C.
  • Such a (A1) maleimide resin is preferably represented by the following general formula (7) from the viewpoint of flexibility and heat resistance.
  • n is an integer of 0 or more, preferably an integer of 1 or more and 10 or less, and more preferably an integer of 1 or more and 5 or less.
  • the average value of n is preferably 0.5 or more and 5 or less, and more preferably 1 or more and 2 or less.
  • L 4 and L 5 are independently substituted or unsubstituted alkylene groups having 4 or more carbon atoms, and in this alkylene group, at least one -CH 2 -is -CH 2- O- or -O-. It may be replaced by CH 2-.
  • the alkylene group preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, and particularly preferably 10 or more and 30 or less carbon atoms.
  • the substituent is an alkyl group having 1 or more and 10 or less carbon atoms, or an alkoxy group having 1 or more and 10 or less carbon atoms. Further, these substituents may be bonded to each other to form an alicyclic structure.
  • X is independently, having 4 or more substituted or unsubstituted alkylene group having a carbon (at least one -CH 2 - including those replaced by - is -CH 2 -O- or -O-CH 2. ), And further preferably a divalent group having a phthalimide group.
  • the phthalimide group also includes a group derived from phthalimide. Specific examples of X include a group represented by the following structural formula (7-1) or the following general formula (7-2).
  • Y 1 and Y 2 are independently hydrogen, methyl or ethyl groups, and are preferably methyl groups.
  • the maleimide resin represented by the general formula (7) in the present embodiment is specifically represented by, for example, the following general formula (7-1-1) or the following general formula (7-2-1).
  • Compounds include.
  • n is an integer of 1 or more and 5 or less. The average value of n is 1 or more and 2 or less.
  • Examples of the maleimide resin product represented by the general formula (7-1-1) include Designer Molecules Inc. Examples include “BMI-1500” manufactured by the company. Examples of the maleimide resin product represented by the general formula (7-2-1) include Designer Molecules Inc. Examples include "BMI-1700" manufactured by the company.
  • Specific examples of the (A1) maleimide resin in the present embodiment include the maleimide resin and the screw (3) represented by the general formula (3) from the viewpoint of obtaining a cured product having high sheet formability and heat resistance.
  • -Ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, 4-methyl-1,3-phenylenebismaleimide, polyphenylmethanemaleimide, or 2,2-bis [4- (4-Maleimidephenoxy) phenyl] propane is preferable, and from the viewpoint of sheet formability, the maleimide resin represented by the general formula (3) or bis (3-ethyl-5-methyl-4-maleimide) is preferable.
  • Phenyl) methane is more preferable, and the maleimide resin represented by the general formula (3) is further preferable from the viewpoint of lowering the complex viscosity at a high temperature before curing of the resin sheet according to the present embodiment.
  • the maleimide resin (A1) in the present embodiment specifically, for example, from the viewpoint of flexibility and heat resistance, the maleimide resin represented by the general formula (7) is more preferable.
  • these maleimide resins can be used individually by 1 type or in combination of 2 or more types. Then, the maleimide resin represented by the general formula (3) and the maleimide resin represented by the general formula (7) may be used in combination.
  • the content of the component (A1) in the component (A) is based on the total amount of the solid content of the component (A) (that is, the amount of the non-volatile content of the component (A) excluding the solvent is 100% by mass. When), it is preferably 60% by mass or more, and more preferably 65% by mass or more. It is particularly preferable that it is 70% by mass or more. When the content of the component (A1) in the component (A) is in such a range, the heat resistance of the resin composition according to the present embodiment after curing can be improved.
  • thermosetting component contained in the resin composition in the present embodiment preferably further contains (A2) an allyl resin.
  • the (A2) allyl resin (hereinafter, may be simply referred to as “component (A2)”) is preferably liquid at room temperature. Since the thermosetting component (A) contains an allyl resin, it becomes easier to improve the peel strength of the resin sheet after curing while lowering the reaction temperature of the resin sheet according to the present embodiment.
  • the mass ratio (A1 / A2) of the maleimide resin as the component (A1) to the (A2) allyl resin is preferably 1.5 or more, and more preferably 3 or more.
  • the mass ratio (A1 / A2) is in the above range, the storage elastic modulus E'at 250 ° C. of the cured product of the resin sheet tends to increase.
  • the mass ratio (A1 / A2) is in the above range, the heat resistance of the resin sheet can be improved.
  • the mass ratio (A1 / A2) is within the above range, the complex viscosity ⁇ of the resin sheet is appropriately adjusted to ensure the fluidity of the resin sheet when applied to an adherend, and the resin sheet is cured. Later, further improvement in heat resistance is realized.
  • the mass ratio (A1 / A2) when the mass ratio (A1 / A2) is in the above range, bleeding out of the allyl resin from the resin sheet is also suppressed.
  • the upper limit of the mass ratio (A1 / A2) is not particularly limited.
  • the mass ratio (A1 / A2) may be 50 or less, and preferably 10 or less.
  • the (A2) allyl resin in the present embodiment is not particularly limited as long as it is a resin having an allyl group.
  • the (A2) allyl resin in the present embodiment is preferably, for example, an allyl resin containing two or more allyl groups in one molecule.
  • the allyl resin in the present embodiment is more preferably represented by the following general formula (8), the following general formula (9), or the following general formula (10).
  • R 7 and R 8 are each independently an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms, and preferably an alkyl group having 1 to 4 carbon atoms. More preferably, it is an alkyl group selected from the group consisting of a methyl group and an ethyl group.
  • n3 is 1 or more and 4 or less, preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less.
  • the ratio of the component having n3 of 1 is preferably 90 mol% or more.
  • the (A2) allyl resin in the present embodiment is specifically represented by, for example, diallyl bisphenol A (2,2-bis (3-allyl-4-hydroxyphenyl) propane), the general formula (9).
  • Examples thereof include an allylphenol resin and an allylphenol resin represented by the general formula (10). These allyl resins can be used alone or in combination of two or more.
  • the resin sheet according to the present embodiment when the resin composition contains a thermosetting resin, it is preferable that the resin sheet further contains a curing catalyst. As a result, the curing reaction of the thermosetting resin can be effectively advanced, and the resin sheet can be cured satisfactorily.
  • the curing catalyst include an imidazole-based curing catalyst, an amine-based curing catalyst, and a phosphorus-based 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 Examples thereof include -2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4,5-di (hydroxymethyl) imidazole.
  • 2-ethyl-4-methylimidazole it is preferable to use 2-ethyl-4-methylimidazole.
  • an imidazole compound having a triazine skeleton is used as the (F) adhesion-imparting agent described later, it also acts as a curing catalyst.
  • amine-based curing catalyst examples include tertiary amine compounds such as 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), triethylenediamine, benzyldimethylamine, and triethanolamine.
  • DBU 1,8-diazabicyclo [5,4,0] undecene-7
  • phosphorus-based curing catalyst examples include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine and the like.
  • the (A) thermosetting component of the present embodiment is a thermosetting resin other than the (A1) component, a curable resin other than the (A2) component, and a non-(A3) component as long as the object of the present invention is not impaired. It may contain a curing catalyst.
  • the thermosetting resin other than the component (A1) may be a thermosetting resin having high heat resistance, and examples thereof include epoxy resin, benzoxazine resin, cyanate resin, and melamine resin. These thermosetting resins can be used alone or in combination of two or more. However, from the viewpoint of high heat resistance, it is preferable that the (A) thermosetting component does not substantially contain an epoxy resin.
  • Examples of the curing catalyst other than the component (A3) include triazole-based compounds and thiazole-based compounds. These curing catalysts can be used alone or in combination of two or more.
  • a thermosetting resin other than the component (A1), a curing resin other than the component (A2), and a curing catalyst other than the component (A3) are used, the content thereof is based on the total solid content of the component (A). (That is, when the amount of the non-volatile content of the component (A) excluding the solvent is 100% by mass), it is preferably 10% by mass or less, and more preferably 5% by mass or less.
  • the content of the (A) thermosetting component in the resin composition is based on the total amount of the solid content of the resin composition (that is, the total amount of the non-volatile content of the resin composition excluding the solvent is 100% by mass).
  • it is preferably 2% by mass or more and 75% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and particularly preferably 10% by mass or more and 40% by mass or less.
  • the content of the thermosetting component (A) is within the above range, the handleability of the resin sheet, the sheet shape retention property, and the heat resistance of the resin composition are improved.
  • the (B) ion trapping agent (hereinafter, may be simply referred to as “component (B)”) has a property of trapping free ions.
  • Examples of the (B) ion trapping agent in the present embodiment include hydrotalcites, hydrous oxides of metal elements, and the like.
  • the ion trap agent (B) in the present embodiment preferably contains at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, antimony, and bismuth. Further, from the viewpoint of high ion trapping ability, the (B) ion trapping agent is preferably a binary ion trapping agent or a ternary ion trapping agent containing magnesium and aluminum.
  • the (B) ion trapping agent contains bismuth.
  • the (B) ion trapping agent is a binary ion trapping agent containing zirconium or a ternary ion trapping agent.
  • the (B) ion trapping agent contains at least one element of magnesium and zirconium, aluminum and A binary ion trapping agent or a ternary ion trapping agent containing at least one element of bismuth is preferable.
  • the content of the (B) ion trap agent in the resin composition is based on the total amount of the solid content of the resin composition (that is, the total amount of the non-volatile content of the resin composition excluding the solvent is 100% by mass). When), it is preferably 10% by mass or less, more preferably 0.1% by mass or more and 8% by mass or less, and further preferably 1% by mass or more and 5% by mass or less.
  • the resin composition preferably contains (C) binder component (hereinafter, may be simply referred to as “(C) component”) in addition to the component (A) and the component (B).
  • (C) component binder component
  • the (C) binder component of the present embodiment is a resin component other than the (A) component, and has a function of joining the (A) component or other components.
  • the binder component (C) is preferably a thermoplastic resin.
  • the component (C) may have a functional group as long as it has a function of bonding the component (A) or other components.
  • the (C) binder component when the (C) binder component has a functional group, even if the (C) binder component can be involved in the curing of the resin sheet by heat, in the present invention, the (C) binder component is (A) thermosetting. Distinguished from sex components.
  • the binder component (C) can be widely selected regardless of whether it is an aliphatic compound or an aromatic compound.
  • the binder component (C) is preferably at least one resin selected from the group consisting of, for example, phenoxy resin, acrylic resin, methacrylic resin, polyester resin, urethane resin, and polyamideimide resin, and is preferably from the viewpoint of heat resistance.
  • the polyester resin is preferably a totally aromatic polyester resin.
  • a rubber-modified polyamide-imide resin is preferable from the viewpoint of improving the flexibility of the resin sheet.
  • the binder component may be used alone or in combination of two or more.
  • the phenoxy resin includes a bisphenol A skeleton (hereinafter, bisphenol A may be referred to as "BisA”), a bisphenol F skeleton (hereinafter, bisphenol F may be referred to as "BisF”), a biphenyl skeleton, and a naphthalene skeleton.
  • BisA bisphenol A skeleton
  • BisF bisphenol F skeleton
  • a phenoxy resin having one or more skeletons selected from the above group is preferable, and a phenoxy resin having a bisphenol A skeleton and a bisphenol F skeleton is more preferable.
  • the weight average molecular weight (Mw) of the binder component is preferably 10,000 or more and 1 million or less, preferably 30,000 or more and 800,000 or less, from the viewpoint of facilitating the adjustment of the complex viscosity of the resin sheet to a desired range. It is more preferable that it is 50,000 or more and 100,000 or less.
  • the weight average molecular weight in the present specification is a standard polystyrene-equivalent value measured by the Gel Permeation Chromatography (GPC) method.
  • the content of the (C) binder component in the resin composition is based on the total amount of the solid content of the resin composition (that is, when the total amount of the non-volatile content of the resin composition excluding the solvent is 100% by mass). ), It is preferably 1.5% by mass or more and 50% by mass or less, more preferably 2% by mass or more and 30% by mass or less, and particularly preferably 2% by mass or more and 15% by mass or less.
  • the resin composition preferably contains (D) an inorganic filler (hereinafter, may be simply referred to as “component (D)”) in addition to the components (A) to (C).
  • component (D) an inorganic filler
  • the inorganic filler (D) include silica filler, alumina filler, and boron nitride filler. Among these, silica filler is preferable. Examples of the silica filler include molten silica and spherical silica.
  • the inorganic filler (D) can be used alone or in combination of two or more. Further, the inorganic filler (D) may be surface-treated.
  • the average particle size of the inorganic filler is not particularly limited.
  • the average particle size of the inorganic filler (D) is preferably 0.1 nm or more and 100 ⁇ m or less, and more preferably 10 nm or more and 10 ⁇ m or less, as a value obtained from a general particle size distribution meter.
  • the average particle size of the (D) inorganic filler is a value measured by a dynamic light scattering method using a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., product name “Nanotrack Wave-UT151”). To do.
  • the content of the (D) inorganic filler in the resin composition is 10% by mass based on the total solid content of the resin composition (that is, when the total amount of the non-volatile content of the resin composition excluding the solvent is 100% by mass). % Or more and 90% by mass or less, more preferably 20% by mass or more and 85% by mass or less, further preferably 40% by mass or more and 80% by mass or less, and 60% by mass or more and 80% by mass or less. Is particularly preferable.
  • the coefficient of linear expansion of the resin composition can be lowered, for example, the coefficient of linear expansion of the material to be sealed such as silicon carbide and the resin sheet. The difference can be reduced.
  • the resin composition preferably further contains (E) a coupling agent in addition to the components (A) to (D).
  • the coupling agent preferably has a functional group of the compound contained in the above-mentioned (A) thermosetting component or a group that reacts with the functional group of the binder component (C), and the (A) thermosetting component. It is more preferable to have a group that reacts with the functional group of the compound contained in.
  • the coupling agent may be used alone or in combination of two or more.
  • the content of the coupling agent as described above is 0.05 based on the total solid content of the resin composition (that is, when the total non-volatile content of the resin composition excluding the solvent is 100% by mass). It is preferably mass% or more and 5 mass% or less, more preferably 0.1 mass% or more and 3 mass% or less, and particularly preferably 0.2 mass% or more and 2 mass% or less.
  • the resin composition preferably further contains (F) an adhesion-imparting agent in addition to the components (A) to (E).
  • adhesion imparting agent include triazine compounds and the like.
  • the triazine compound may be an imidazole compound having a triazine skeleton.
  • Examples of the imidazole compound having a triazine skeleton include a compound represented by the following general formula (11).
  • R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 or more and 20 or less carbon atoms, a hydroxymethyl group, or a phenyl group, and have a hydrogen atom or 1 or more carbon atoms. It is preferably an alkyl group of 10 or less, and more preferably a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms.
  • R 13 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, or an allyl group, preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 3 carbon atoms. Is more preferable.
  • L 6 is an alkylene group having 1 or more and 5 or less carbon atoms, preferably an alkylene group having 2 or more and 4 or less carbon atoms, and more preferably an ethylene group.
  • imidazole compound having a triazine skeleton in the present embodiment examples include 2,4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl] -1,3,5-triazine, 2 , 4-Diamino-6- [2- (2-ethyl-4-methyl-1-imidazolyl) ethyl] -1,3,5-triazine, and 2,4-diamino-6- [2- (2-undecyl) -1-Imidazolyl) ethyl] -1,3,5-triazine and the like can be mentioned.
  • 2,4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl] -1,3,5-triazine 2,4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl] -1,3,5-triazine, from the viewpoint of the peel strength of the resin sheet and the reaction temperature.
  • 2,4-Diamino-6- [2- (2-ethyl-4-methyl-1-imidazolyl) ethyl] -1,3,5-triazine is preferred.
  • the content of the (F) adhesion-imparting agent in the resin composition is based on the total solid content of the resin composition (that is, the total non-volatile content of the resin composition excluding the solvent is 100% by mass).
  • it is preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.03% by mass or more and 3% by mass or less.
  • the peel strength of the resin composition after curing can be further improved.
  • (B) component, (C) component, (D) component, (E) component, and a resin composition containing only the (F) component a resin composition containing only the (F) component.
  • the component (A), the component (B), the component (C), the component (D), the component (E) and the component (F) and a resin composition containing a component other than the components (A) to (F).
  • the resin composition may further contain other components.
  • the other component is at least one selected from the group consisting of, for example, a cross-linking agent, a pigment, a dye, a defoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, a flame retardant, and an ion scavenger.
  • Ingredients include.
  • the resin composition may further contain a cross-linking agent in order to adjust the initial adhesiveness and cohesiveness of the resin sheet before curing.
  • the cross-linking agent include an organic multivalent isocyanate compound and an amino resin.
  • the cross-linking agent may be used alone or in combination of two or more.
  • organic polyvalent isocyanate compound examples include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimerics of these polyvalent isocyanate compounds, and Examples thereof include a terminal isocyanate urethane prepolymer obtained by reacting these polyvalent isocyanate compounds with a polyol compound. More specific examples of the organic polyvalent isocyanate compound include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylylene.
  • Isocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4 '-Diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysocyanate and the like can be mentioned.
  • the organic multivalent isocyanate compound may be used alone or in combination of two or more.
  • amino resin urea resin, melamine resin, guanamine resin, and their copolymer resin can be used.
  • the above-mentioned cross-linking agent is usually blended in a proportion of 0.01 parts by mass or more and 12 parts by mass or less, preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder component (C) described above. To.
  • the resin composition when the resin sheet is formed by coating, the resin composition preferably contains a solvent.
  • a solvent in addition to general solvents such as toluene, ethyl acetate and methyl ethyl ketone, cyclohexanone (boiling point: 155.6 ° C.), dimethylformamide (boiling point: 153.6 ° C.), dimethyl sulfoxide (boiling point: 189.0 ° C.), ethylene
  • high boiling point solvents such as glycol ethers (cellosolve) (boiling point: about 120 to 310 ° C.) and ortho-xylene (boiling point: 144.4 ° C.).
  • the resin sheet according to the present embodiment is formed from the above-mentioned resin composition according to the present embodiment.
  • the flexibility can be further improved while maintaining the heat resistance.
  • the present embodiment of the present embodiment from the viewpoint of the ability to follow the unevenness of the adherend to be attached when the resin sheet is used for sealing a semiconductor element or interposing between a semiconductor element and another electronic component. It is preferable that it comprises only the resin composition according to the above. That is, it is preferable that the resin sheet is not a composite material such as a combination of a resin composition and a fiber sheet, such as a prepreg.
  • the peel strength of the resin sheet according to the present embodiment after thermosetting is preferably 2.0 N / 10 mm or more, more preferably 3.0 N / 10 mm or more and 50 N / 10 mm or less, and 4.0 N / 10 mm. It is more preferably 40 N / 10 mm or less.
  • a component used in the resin composition is selected, and at least one selected from an allyl resin and an adhesion imparting agent is preferably blended in the resin composition.
  • the peel strength of the resin sheet according to the present embodiment after thermosetting is subjected to a peeling test at a peel angle of 90 degrees between the thermosetting resin sheet and the adherend by using the measurement method described later. Asked by doing. Specifically, a test piece was prepared as follows and a peeling test was performed.
  • the resin composition is in the form of a sheet, it is formed in advance in a shape suitable for the shape after the sealing step, so that it can be supplied as a sealing material having a certain degree of uniformity just by applying it. Further, if the resin composition is in the form of a sheet, it has no fluidity and is excellent in handleability.
  • the storage elastic modulus E'at 250 ° C. after the thermosetting of the resin sheet according to the present embodiment is preferably 150 MPa or more, preferably 300 MPa or more, from the viewpoint of improving the heat resistance of the cured product of the resin sheet. More preferably, it is more preferably 500 MPa or more.
  • the storage elastic modulus E'at 250 ° C. after thermosetting the resin sheet is a value measured for a test piece obtained by curing the resin sheet under the conditions of 200 ° C. for 4 hours.
  • the method for forming the resin composition into a sheet can be a conventionally known method for forming a sheet, and is not particularly limited.
  • the resin sheet according to the present embodiment may be a strip-shaped sheet or may be provided in a rolled-up state.
  • the resin sheet according to the present embodiment wound in a roll shape can be used by being unwound from the roll and cut into a desired size.
  • the thickness of the resin sheet according to the present embodiment is, for example, preferably 10 ⁇ m or more, and more preferably 20 ⁇ m or more. Further, the thickness is preferably 500 ⁇ m or less, more preferably 400 ⁇ m or less, and further preferably 300 ⁇ m or less.
  • the resin sheet according to this embodiment is preferably used for a semiconductor element. Specifically, the resin sheet according to the present embodiment is preferably used for sealing the semiconductor element. Further, the resin sheet according to the present embodiment is preferably used for interposing between the semiconductor element and other electronic components.
  • the semiconductor element is preferably a power semiconductor element. Since the resin sheet according to this embodiment has excellent heat resistance, it is intended to enclose a power semiconductor element that is expected to operate at a high temperature of 200 ° C. or higher, or to interpose it between the power semiconductor element and other electronic components. Can be used for.
  • the resin sheet according to the present embodiment is collectively applied to a plurality of semiconductor elements.
  • the resin composition is in the form of a sheet
  • a resin sheet is applied to a structure in which semiconductor elements are arranged in each gap of a frame provided with a plurality of gaps, and the frame and the semiconductor element are collectively combined. It can be used for sealing, so-called panel level packages.
  • the resin sheet according to the present embodiment is preferably used for encapsulating a semiconductor element using any one or more of silicon carbide and gallium nitride.
  • the resin sheet according to the present embodiment is preferably used for interposing between a semiconductor element using any one or more of silicon carbide and gallium nitride and other electronic components. Examples of other electronic components include a printed wiring board, a lead frame, and the like. Since the upper limit of the operating temperature of the silicon semiconductor element is about 175 ° C., it is preferable to use a semiconductor element using any one or more of silicon carbide and gallium nitride capable of high temperature operation for the power semiconductor element.
  • the resin sheet according to the present embodiment has excellent heat resistance, a semiconductor element using any one or more of silicon carbide and gallium nitride, which is expected to operate at a high temperature of 200 ° C. or higher, is sealed or silicon carbide is used. It can be used for interposing between a semiconductor device using any one or more of gallium nitride and gallium nitride and another electronic component.
  • thermosetting conditions Under the thermosetting conditions of the resin sheet according to the present embodiment, the heating temperature is preferably 50 ° C. or higher and 300 ° C. or lower, and preferably 100 ° C. or higher and 250 ° C. or lower. Under the thermosetting conditions of the resin sheet according to the present embodiment, the heating time is preferably 10 minutes or more and 10 hours or less, and more preferably 20 minutes or more and 7 hours or less. When the thermosetting condition of the resin sheet is within the above range, the thermosetting of the resin sheet can be realized.
  • FIG. 1 shows a schematic cross-sectional view of the laminated body 1 according to the present embodiment.
  • the laminate 1 of the present embodiment has a first release material 2, a second release material 4, and a resin sheet 3 provided between the first release material 2 and the second release material 4.
  • the resin sheet 3 is a resin sheet according to the present embodiment.
  • the first release material 2 and the second release material 4 have peelability, and there is a difference between the release force of the first release material 2 against the resin sheet 3 and the release force of the second release material 4 against the resin sheet 3. Is preferable.
  • the materials of the first release material 2 and the second release material 4 are not particularly limited.
  • the ratio (P2 / P1) of the peeling force P2 of the second peeling material 4 to the peeling force P1 of the first peeling material 2 is preferably 0.02 ⁇ P2 / P1 ⁇ 1 or 1 ⁇ P2 / P1 ⁇ 50. ..
  • the first release material 2 and the second release material 4 may be, for example, a member having a release property in the release material itself, a member having been subjected to a release treatment, a member having a release agent layer laminated, or the like. Good.
  • examples of the material of the first release material 2 and the second release material 4 include an olefin resin and a fluororesin. Be done.
  • the first release material 2 and the second release material 4 can be a release material including a release base material and a release agent layer formed by applying a release agent on the release base material. By using a release material having a release base material and a release agent layer, handling becomes easy. Further, the first release material 2 and the second release material 4 may have a release agent layer on only one side of the release base material, or may have a release agent layer on both sides of the release base material.
  • Examples of the peeling base material include a paper base material, a laminated paper obtained by laminating a thermoplastic resin such as polyethylene on the paper base material, and a plastic film.
  • Examples of the paper base material include glassine paper, coated paper, cast coated paper and the like.
  • Examples of the plastic film include polyester films (for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), and polyolefin films (for example, polypropylene, polyethylene, etc.). Of these, polyester film is preferable.
  • the release agent examples include a silicone-based release agent composed of a silicone resin; a long-chain alkyl group-containing compound-based release agent composed of a compound containing a long-chain alkyl group such as polyvinyl carbide and an alkylurea derivative; An alkyd resin-based release agent composed of a resin (for example, an immutable alkyd resin, a convertible alkyd resin, etc.); an olefin resin (for example, polyethylene (for example, high density polyethylene, low density polyethylene, and linear low density)).
  • a resin for example, an immutable alkyd resin, a convertible alkyd resin, etc.
  • an olefin resin for example, polyethylene (for example, high density polyethylene, low density polyethylene, and linear low density)).
  • Olefin resin-based release agent composed of (polyethylene, etc.), a propylene homopolymer having an isotactic structure or a syndiotactic structure, and a crystalline polypropylene resin such as a propylene- ⁇ -olefin copolymer); natural rubber , And a rubber-based release agent composed of rubber such as synthetic rubber (eg, butadiene rubber, isoprene rubber, styrene-butadiene rubber, methyl methacrylate-butadiene rubber, and acrylonitrile-butadiene rubber); and (meth) acrylic acid ester.
  • synthetic rubber eg, butadiene rubber, isoprene rubber, styrene-butadiene rubber, methyl methacrylate-butadiene rubber, and acrylonitrile-butadiene rubber
  • acrylic acid ester eg, butadiene rubber, isoprene rubber, styrene-butad
  • Examples thereof include various release agents such as an acrylic resin-based release agent composed of an acrylic resin such as a system copolymer, and these can be used alone or in combination of two or more. Of these, alkyd resin-based release agents are preferable.
  • an acrylic resin-based release agent composed of an acrylic resin such as a system copolymer
  • these can be used alone or in combination of two or more.
  • alkyd resin-based release agents are preferable.
  • a phenoxy resin or a polyamide-imide resin is used as the binder component (B) of the resin composition contained in the resin sheet 3
  • a general silicone-based release agent is used, the release material is unintentionally used as the resin sheet. Since there is a concern that the material 3 may be peeled off before use, it is preferable to use an alkyd resin-based release agent.
  • the thickness of the first release material 2 and the second release material 4 is not particularly limited. Usually, it is 1 ⁇ m or more and 500 ⁇ m or less, and preferably 3 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of the release agent layer is not particularly limited. When a solution containing a release agent is applied to form a release agent layer, the thickness of the release agent layer is preferably 0.01 ⁇ m or more and 3 ⁇ m or less, and more preferably 0.03 ⁇ m or more and 1 ⁇ m or less.
  • the manufacturing method of the laminated body 1 is not particularly limited.
  • the laminated body 1 is manufactured through the following steps. First, a resin composition containing a solvent is applied onto the first release material 2 to form a coating film. Next, this coating film is dried to form the resin sheet 3. Next, the laminated body 1 is obtained by laminating the resin sheet 3 and the second release material 4 at room temperature. In this case, when the types of the release materials of the first release material 2 and the second release material 4 are the same, the ratio of the release force P2 of the second release material 4 to the release force P1 of the first release material 2 (P2).
  • the resin sheet according to this embodiment can be suitably used for a power semiconductor element.
  • the semiconductor element is preferably a power semiconductor element.
  • the power semiconductor element is also expected to operate at a high temperature of 200 ° C. or higher. Heat resistance is required for materials used in semiconductor devices having power semiconductor devices. Since the resin sheet according to this embodiment has excellent heat resistance, it is suitably used for covering a power semiconductor element in a semiconductor device or for interposing it between a power semiconductor element and another component.
  • the resin sheet according to the present embodiment can be suitably used for a semiconductor device using any one or more of silicon carbide and gallium nitride.
  • the semiconductor element is preferably a semiconductor element using any one or more of silicon carbide and gallium nitride.
  • Semiconductor devices using any one or more of silicon carbide and gallium nitride have characteristics different from those of silicon semiconductor devices. Therefore, power semiconductor devices, high-power devices for base stations, sensors, detectors, Schottky barrier diodes, etc. It is preferably used in the above applications. In these applications, attention is also paid to the heat resistance of semiconductor devices using any one or more of silicon carbide and gallium nitride. Since the resin sheet of the present embodiment has excellent heat resistance, silicon carbide and gallium nitride are used. It is preferably used in combination with a semiconductor device using any one or more of the above.
  • the laminate having the first release material, the second release material, and the resin sheet provided between the first release material and the second release material has been described, but in addition, the resin sheet has been described. It may be a laminate having a release material on only one surface.
  • the resin sheet of the present invention also has other insulating materials for circuit boards (for example, hard printed wiring board materials, flexible wiring board materials, and materials. It can be used as an interlayer insulating material for a build-up substrate, etc.), an adhesive film for build-up, an adhesive, etc.
  • -Maleimide resin-1 Maleimide resin having a biphenyl group (maleimide resin represented by the general formula (3), "MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd.)
  • -Maleimide resin-2 Long-chain alkyl type maleimide resin (maleimide resin represented by the general formula (7-2-1), "BMI-1700” manufactured by Designer Molecules Inc.)
  • -Allyl resin Diallyl bisphenol A (“DABPA” manufactured by Daiwa Kasei Kogyo Co., Ltd.)
  • Phhenol resin Biphenyl type phenol novolac resin ("MEH-7851-H” manufactured by Meiwa Kasei Co., Ltd.)
  • Epoxy resin Mixed epoxy resin (Mitsubishi Chemical's "YL980” / Nippon Kayaku's "NC3000L” / DIC's "HP-6000" with a mass ratio of 5.64 / 5.64
  • Ion trap agent -Ion trapping agent-1: Zr, Mg, Al-based ion trapping agent ("IXEPLAS-A3" manufactured by Toagosei Co., Ltd.)
  • Ion trap agent-2 Mg, Al-based ion trap agent ("IXE-700F” manufactured by Toagosei Co., Ltd.)
  • Ion trap agent-3 Zr, Bi-based ion trap agent ("IXEPLAS-B1" manufactured by Toagosei Co., Ltd.)
  • Binder component Binder component: BisA / BisF mixed phenoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. "ZX-1356-2", weight average molecular weight 65,000)
  • Binder resin-2 BisA type phenoxy resin ("YX7200B35" manufactured by Mitsubishi Chemical Corporation)
  • the resin composition after drying and the second release material (polyethylene terephthalate film provided with a release layer formed from a silicone-based release agent, manufactured by Lintec Corporation, SP-PET382150, thickness 38 ⁇ m) )
  • the resin composition after drying and the second release material At room temperature to prepare a laminate in which the first release material, the resin sheet made of the resin composition, and the second release material are laminated in this order.
  • the obtained resin composition was applied onto a release material and dried at 90 ° C. for 1 minute and at 110 ° C. for 1 minute to prepare a resin sheet having a thickness of 25 ⁇ m. Eight of these resin sheets were laminated to have a thickness of 200 ⁇ m, and then peeled from the release material to prepare a sample. The sample was cured at a temperature of 200 ° C. under thermosetting conditions for 4 hours to prepare a sample for measurement. 1.0 g of this measurement sample was weighed and placed in a Teflon (registered trademark) crucible.
  • Electrode material Titanium (Ti) and Copper (Cu)
  • Electrode thickness (Ti / Cu): 30 nm / 100 nm
  • Electrode width and spacing (L / S): 80 ⁇ m / 20 ⁇ m
  • One surface of the resin sheet in the obtained laminate is bonded to this substrate by pressure-bonding under reduced pressure at a lamination temperature of 130 ° C.
  • the electrodes of this sample are connected to the electrodes in the device arranged in the PCT chamber (“TPC-411D” manufactured by Espec Co., Ltd .; conditions: temperature 130 ° C., humidity 85% RH, pressure 2 atm), and the potentiostat (Toho Giken)
  • TPC-411D manufactured by Espec Co., Ltd .
  • the potentiostat (Toho Giken) A voltage of 10 V was applied and the current value (unit: nA) after 168 hours had elapsed was measured using "PS-08" manufactured by the same company.
  • the results obtained are shown in Table 1. The smaller the current value, the more the ion migration is suppressed.
  • the second release material and the first release material of the resin sheet in the laminated body were peeled before being attached to the Si wafer and the copper plate, respectively.
  • the resin composition was cured under the thermosetting condition of 4 hours at a temperature of 200 ° C. to prepare a sample.
  • the copper foil was peeled off from the cured resin sheet under the conditions of a peeling speed of 50 mm / min and a peeling angle of 90 degrees using a tensile tester (“Autograph AG-IS” manufactured by Shimadzu Corporation).
  • the peel strength (unit: N / 10 mm) between the copper foil and the cured resin sheet was measured. The measurement was performed in an environment of 25 ° C. and a relative humidity of 50%. The results obtained are shown in Table 1.
  • Comparative Examples 1 and 3 differ from Example 1 and the like in that they do not contain an ion trap agent, but the results of the HAST test are inferior to those of Example 1 and the like, and it was found that ion migration cannot be sufficiently suppressed. Ion trap.
  • Comparative Example 2 uses an epoxy-based resin composition, it was found that the elastic modulus at 250 ° C. was low and the heat resistance was inferior as compared with Examples 1 to 4.

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WO2022210187A1 (ja) * 2021-03-31 2022-10-06 リンテック株式会社 樹脂シート
JP2023011147A (ja) * 2021-07-12 2023-01-24 信越化学工業株式会社 熱硬化性マレイミド樹脂組成物

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