WO2022270316A1 - Composition de résine, produit durci, feuille de résine, substrat de circuit et boîtier de puce semi-conductrice - Google Patents

Composition de résine, produit durci, feuille de résine, substrat de circuit et boîtier de puce semi-conductrice Download PDF

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WO2022270316A1
WO2022270316A1 PCT/JP2022/023158 JP2022023158W WO2022270316A1 WO 2022270316 A1 WO2022270316 A1 WO 2022270316A1 JP 2022023158 W JP2022023158 W JP 2022023158W WO 2022270316 A1 WO2022270316 A1 WO 2022270316A1
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resin composition
resin
mass
semiconductor chip
epoxy resin
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PCT/JP2022/023158
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English (en)
Japanese (ja)
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啓之 阪内
成 佐々木
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味の素株式会社
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Priority to JP2023529821A priority Critical patent/JPWO2022270316A1/ja
Priority to KR1020237044186A priority patent/KR20240023049A/ko
Priority to CN202280043646.0A priority patent/CN117500886A/zh
Publication of WO2022270316A1 publication Critical patent/WO2022270316A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the present invention relates to resin compositions. Furthermore, it relates to a cured product, a resin sheet, a circuit board, and a semiconductor chip package obtained using the resin composition.
  • Patent Document 1 A resin composition is used to form such an insulating layer.
  • the resin composition is required to suppress warpage that occurs when forming the insulating layer.
  • an object of the present invention is preferably a resin composition that provides a cured product in which the occurrence of warpage is suppressed and at least has a stable viscosity life;
  • An object of the present invention is to provide a resin sheet, a circuit board, and a semiconductor chip package using the composition.
  • the present inventors have made extensive studies to solve the above problems. As a result, the present inventor found that a resin composition containing (A) a curable resin and (B) an inorganic filler, wherein the average particle diameter of the inorganic filler is within a specific range, the inorganic
  • the above problems can be solved by setting the crystalline silica content in the filler within a specific range, and have completed the present invention.
  • the adhesiveness to the substrate for example, the adhesiveness to the polyimide resin
  • the present invention includes the following.
  • the average particle diameter of the (B) inorganic filler is in the range of 0.5 ⁇ m to 12 ⁇ m, and the inorganic filler A resin composition having a crystalline silica content of 0% by mass or more and less than 2.1% by mass.
  • the described resin composition [5] The resin composition according to any one of [1] to [4], wherein the crystalline silica content is calculated based on an X-ray diffraction pattern obtained by X-ray diffraction measurement. [6] The resin composition according to [5], wherein the crystalline silica content is calculated by Rietveld analysis of an X-ray diffraction pattern. [7] The resin composition according to any one of [1] to [6], which is used for forming a resin composition layer having a thickness of 50 ⁇ m or more.
  • a semiconductor chip package comprising a semiconductor chip sealed with the resin composition according to any one of [1] to [8].
  • a method for manufacturing a semiconductor chip package comprising: A resin composition containing (A) a curable resin and (B) an inorganic filler, wherein the average particle diameter of the (B) inorganic filler is in the range of 0.5 ⁇ m to 12 ⁇ m, and the inorganic filler
  • a method for manufacturing a semiconductor chip package comprising curing a resin composition having a crystalline silica content in the range of 0% by mass or more and less than 2.1% by mass.
  • the present invention it is possible to provide a resin composition with a stable viscosity life; a resin sheet, a circuit board, and a semiconductor chip package using the resin composition.
  • FIG. 1 is a cross-sectional view schematically showing the configuration of a fan-out type WLP as an example of a semiconductor chip package according to one embodiment of the present invention.
  • the resin composition of the present invention is a resin composition containing (A) a curable resin and (B) an inorganic filler, wherein the average particle size of the (B) inorganic filler is in the range of 0.5 ⁇ m to 12 ⁇ m. and wherein the content of crystalline silica in the inorganic filler is in the range of 0% by mass or more and less than 2.1% by mass.
  • the present invention provides a resin composition with a stable viscosity life; a resin sheet, a circuit board, and a semiconductor chip package using the resin composition. At least it has the effect of being able to. Other effects produced by the present invention can be grasped by those skilled in the art by referring to the specification and drawings.
  • the resin composition of the present invention contains (A) a curable resin and (B) an inorganic filler.
  • the resin composition of the present invention contains, in addition to components (A) and (B), for example, (C) a curing agent, (D) other additives, and a solvent, as long as the above effects are not excessively inhibited. You can stay.
  • the resin composition of the present invention contains (A) a curable resin.
  • a curable resin one or more resins selected from thermosetting resins, photocurable resins, and radically polymerizable resins can be used.
  • a radically polymerizable resin is a resin in which radical polymerization proceeds by heat or light, optionally in the presence of a polymerization initiator, and may be classified as a thermosetting resin or a photocurable resin.
  • (A) component may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
  • thermosetting resins examples include epoxy resins, epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, polyimide resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, silicone resins, phenoxy resins, and the like. is mentioned.
  • the curable resin comprises an epoxy resin.
  • the resin composition contains a thermosetting resin, it preferably contains (C) a curing agent, and more preferably contains a curing accelerator described later.
  • Epoxy resin refers to a resin having an epoxy group.
  • epoxy resins include bixylenol type epoxy resin, bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; bisphenol AF type epoxy resin; dicyclopentadiene type epoxy resin; Glycidylamine type epoxy resin; Glycidyl ester type epoxy resin; Cresol novolac type epoxy resin; Biphenyl type epoxy resin; Linear aliphatic epoxy resin; Epoxy resin having a butadiene structure; Alicyclic epoxy resin having a skeleton; heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexane type epoxy resin; cyclohexanedimethanol type epoxy resin; trimethylol type epoxy resin; Epoxy resins containing a condensed ring skeleton such as epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene
  • the epoxy resin may contain an epoxy resin containing an aromatic structure.
  • Aromatic structures are chemical structures generally defined as aromatic and also include polycyclic aromatic and heteroaromatic rings.
  • Examples of epoxy resins containing an aromatic structure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol novolak type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bixylenol type epoxy resin, glycidylamine type epoxy having an aromatic structure Resin, glycidyl ester type epoxy resin having aromatic structure, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having aromatic structure, epoxy resin having butadiene structure having aromatic structure
  • epoxy resins containing an aromatic structure it is preferable to include an epoxy resin containing a condensed ring structure from the viewpoint of obtaining a cured product with excellent heat resistance.
  • the condensed ring in the epoxy resin containing a condensed ring structure include naphthalene ring, anthracene ring, phenanthrene ring and the like, and naphthalene ring is particularly preferred. Therefore, the epoxy resin preferably contains a naphthalene-type epoxy resin containing a naphthalene ring structure.
  • the amount of the naphthalene-type epoxy resin is preferably 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, and preferably 50% by mass or less based on the total amount of the epoxy resin of 100% by mass. , more preferably 40% by mass or less, and still more preferably 30% by mass or less.
  • the epoxy resin may contain a glycidylamine type epoxy resin from the viewpoint of improving the heat resistance and metal adhesion of the cured product.
  • the epoxy resin may contain an epoxy resin having a butadiene structure.
  • the resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the epoxy resin.
  • the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass with respect to 100% by mass of the non-volatile component of the epoxy resin. % or more.
  • Epoxy resins include liquid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resins”). ).
  • the resin composition of the present embodiment may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a liquid epoxy resin and a solid epoxy resin in combination. Although it may be contained, it is preferable to contain at least a liquid epoxy resin.
  • the resin composition of the present invention contains only a liquid epoxy resin as the curable resin.
  • the resin composition of the present invention may contain a combination of a liquid epoxy resin and a solid epoxy resin as a curable resin, or may contain only a liquid epoxy resin.
  • a liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.
  • liquid epoxy resins examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, ester skeleton.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, alicyclic epoxy resin having ester skeleton, epoxy resin having butadiene structure, alkyleneoxy skeleton and butadiene skeleton containing epoxy
  • resins fluorene structure-containing epoxy resins, and dicyclopentadiene type epoxy resins.
  • liquid epoxy resins include "HP4032”, “HP4032D”, and “HP4032SS” (naphthalene type epoxy resins) manufactured by DIC; “828US”, “828EL”, “jER828EL”, and “825" manufactured by Mitsubishi Chemical Corporation; ”, “Epikote 828EL” (bisphenol A type epoxy resin); “jER807” and “1750” (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “jER152” manufactured by Mitsubishi Chemical Corporation (phenol novolac type epoxy resin); “630", “630LSD”, “604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “ED-523T” (glycirrol type epoxy resin) manufactured by ADEKA; “EP-3950L” manufactured by ADEKA; “EP-3980S” (glycidylamine type epoxy resin); “EP-4088S” (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX1059” manufactured by Nippon Steel Chemical & Materials (bis
  • the solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.
  • Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin.
  • solid epoxy resins include “HP4032H” (naphthalene-type epoxy resin) manufactured by DIC; “HP-4700” and “HP-4710” (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; “N-690” (cresol novolac type epoxy resin) manufactured by DIC Corporation; “N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200”, “HP-7200HH”, “HP -7200H” (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", “EXA-7311-G3", “EXA-7311-G4", "EXA-7311-G4S”, "HP6000” ( Naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd.
  • the amount of the liquid epoxy resin is not particularly limited, it is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more, based on the total amount of the epoxy resin of 100% by mass. More preferably 90% by mass or more, particularly preferably 100% by mass.
  • the epoxy equivalent of the epoxy resin is preferably 50 g/eq. ⁇ 5000g/eq. , more preferably 50 g/eq. ⁇ 3000g/eq. , more preferably 80 g/eq. ⁇ 2000g/eq. , even more preferably 110 g/eq. ⁇ 1000 g/eq. is.
  • Epoxy equivalent weight is the mass of resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.
  • the weight average molecular weight (Mw) of the epoxy resin is preferably 100-5000, more preferably 200-3000, and even more preferably 400-1500.
  • the weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
  • the amount of the curable resin is not particularly limited, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, and particularly preferably It is 1.5% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, and particularly preferably 35% by mass or less.
  • the resin composition of the present invention contains (B) an inorganic filler.
  • a cured product of a resin composition containing (B) an inorganic filler usually tends to be prevented from warping.
  • the cured product of the resin composition containing (B) the inorganic filler can generally have a small coefficient of thermal expansion.
  • An inorganic compound is used as the inorganic filler.
  • inorganic fillers include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, hydroxide
  • silica and alumina are preferred, and silica is particularly preferred.
  • examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica.
  • silica spherical silica is preferable.
  • the inorganic filler may be used singly or in combination of two or more.
  • the inorganic filler may be treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility.
  • a surface treatment agent examples include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, A titanate-based coupling agent and the like can be mentioned.
  • one type of surface treatment agent may be used alone, or two or more types may be used in combination.
  • Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry Co., Ltd. "KBE903” (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. “KBE903” (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.
  • KBM573 N-phenyl-3- aminopropyltrimethoxysilane
  • Shin-Etsu Chemical Co., Ltd. "KBM103” (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.
  • KBM-4803 long-chain epoxy type silane coupling agent
  • KBM-7103 (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
  • the degree of surface treatment with a surface treatment agent is preferably within a specific range.
  • 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2-5 parts by mass of a surface treatment agent, and is surface-treated with 0.2-3 parts by mass. preferably 0.3 parts by mass to 2 parts by mass of the surface treatment.
  • the degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler.
  • the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and more preferably 0.2 mg/m 2 from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable.
  • it is preferably 1 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, and even more preferably 0.5 mg/m 2 or less.
  • the amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.
  • EMIA-320V manufactured by Horiba Ltd.
  • the (B) inorganic filler contained in the resin composition of the present invention has an average particle diameter in the range of 0.5 ⁇ m to 12 ⁇ m and a crystalline silica content of 0% by mass or more and 2.1% by mass. % (hereinafter also referred to as “highly amorphous small diameter inorganic filler”).
  • the resin composition of the present invention may contain two or more specific inorganic fillers, but at least one of them is preferably silica.
  • the resin composition of the present invention may contain an inorganic filler other than the highly amorphous small-diameter inorganic filler as long as the intended effect of the present invention is not impaired. It is preferable not to contain inorganic fillers other than.
  • the highly amorphous small-diameter inorganic filler has an average particle size within the range of 0.5 ⁇ m to 12 ⁇ m. Since the highly amorphous small-diameter inorganic filler has such a small average particle diameter, it is possible to increase the degree of filling in the resin composition.
  • the lower limit of the average particle size of the inorganic filler is more than 0.5 ⁇ m, 0.6 ⁇ m or more, 0.7 ⁇ m or more, 0.8 ⁇ m or more, 0.9 ⁇ m or more, or 1.5 ⁇ m or more, as long as the intended effect of the present invention is not impaired. It may be 0 ⁇ m or more.
  • the upper limit of the average particle size of the inorganic filler may be less than 12 ⁇ m, 10 ⁇ m or less, 8 ⁇ m or less, 6 ⁇ m or less, 5 ⁇ m or less, or 4.5 ⁇ m or less, as long as the desired effect of the present invention is not impaired, which will be described later.
  • the upper limit of the average particle size of the inorganic filler is preferably 10 ⁇ m or less, more preferably less than 10 ⁇ m, even more preferably 9 ⁇ m or less, and 8 ⁇ m or less. is particularly preferred.
  • the average particle size of component (B) can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring apparatus, and the median diameter can be used as the average particle size for measurement.
  • a measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial bottle and dispersing them with ultrasonic waves for 10 minutes.
  • the measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, and the volume-based particle size distribution of the inorganic filler (B) is measured by the flow cell method.
  • the average particle size can be calculated as the median size from the size distribution.
  • Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.
  • the specific surface area of the inorganic filler is preferably 1 m 2 /g or more, more preferably 1.5 m 2 /g or more, still more preferably 2 m 2 /g or more, and particularly preferably 2.5 m 2 /g or more. be. Although there is no particular upper limit, it is preferably 60 m 2 /g or less, 50 m 2 /g or less, or 40 m 2 /g or less.
  • the specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method and calculating the specific surface area using the BET multipoint method. .
  • the highly amorphous small-diameter inorganic filler has a crystalline silica content of 0% by mass or more and less than 2.1% by mass. Since the highly amorphous small-diameter inorganic filler has such a low crystalline silica content, it is possible to achieve the desired effect of the present invention. And, as is clear from the exemplification in the Examples section below, the lower the crystalline silica content, preferably the more the detection limit is exceeded and the closer to the detection limit, the more stable the viscosity life tends to be. The intended effects of the invention can be obtained more remarkably. In addition, the higher the filling degree of the inorganic filler, the more the stability of the viscosity life usually tends to decrease. Can be higher than normal.
  • the crystalline silica content is 2.0% by mass or less, 1.9% by mass or less, 1.8% by mass or less, 1.7% by mass or less, Or it is preferably 1.6% by mass or less, 1.5% by mass or less, 1.4% by mass or less, 1.3% by mass or less, 1.2% by mass or less, 1.1% by mass or less, or 1 0% by mass or less, 0.9% by mass or less, 0.8% by mass or less, 0.7% by mass or less, 0.6% by mass or less, 0.5% by mass or less, 0.4% by mass or less Even more preferably, it is 0.3 mass % or less, 0.2 mass % or less, or 0.1 mass % or less.
  • the content of crystalline silica is particularly preferably below the detection limit, and may be 0% by mass.
  • the crystalline silica content is preferably more than 0% by mass, more preferably 0.01. % by mass or more, more preferably 0.02% by mass or more, 0.03% by mass or more, 0.04% by mass or more, 0.05% by mass or more, 0.06% by mass or more, and 0.07% by mass % or more, or 0.08% by mass or more. Therefore, it is preferred in embodiments where the crystalline silica content is in the range of greater than 0 wt% and less than 2.1 wt%.
  • the crystalline silica content is calculated based on the X-ray diffraction pattern obtained by X-ray diffraction measurement.
  • the X-ray diffraction measurement may be carried out using a commercially available X-ray diffraction analysis device, for example, the Rigaku X-ray diffraction device “SmartLab (registered trademark)”.
  • the conditions for the X-ray diffraction measurement are not limited as long as crystalline silica can be detected, and the X-ray source, output, diffraction angle measurement range, scanning speed, etc. are appropriately set.
  • the crystalline silica content is calculated by Rietveld analysis of the X-ray diffraction pattern.
  • dedicated software attached to the X-ray diffraction analysis device for example, the qualitative analysis program PDXL attached to the X-ray diffraction device "SmartLab (registered trademark)" manufactured by Rigaku Corporation can be used.
  • Such dedicated software contains information about crystalline silica (usually ⁇ -quartz or cristobalite) and amorphous silica (amorphous silica). According to the Rietveld analysis, even if the content of crystalline silica is 0.01% by mass, the crystalline silica content can be calculated, which is preferable.
  • the crystalline silica content may be calculated by a method other than the method described above. However, if the numerical value of the crystalline silica content calculated by such a method is significantly different from the numerical value of the crystalline silica content calculated by the method described above (preferably Rietveld analysis), such a method is adopted. shouldn't.
  • the peak intensity of crystalline silica and the peak intensity (integrated value) of amorphous silica may be calculated, and the X-ray diffraction pattern of a highly amorphous small-diameter inorganic filler with a known crystalline silica content is used as a calibration curve, and the crystalline silica content in an inorganic filler with an unknown crystalline silica content is A rate may be calculated.
  • the inorganic fillers A, B, C, D, E, and F described in Production Examples 1 to 4 in the Examples section below, or modifications thereof (for example, surface treatment agents of which the type has been changed, or which has not undergone surface treatment) can be used.
  • the method for producing the highly amorphous small-diameter inorganic filler is not limited.
  • a crystalline inorganic filler such as crystalline silica (for example, crystalline silica disclosed in JP-A-2015-211086) can be used as a raw material for the highly amorphous small-diameter inorganic filler.
  • the heating temperature and heating time in the melting step in the melting method can be changed within the range of 500 ° C. to 1100 ° C. and 1 to 12 hours.
  • the density of the obtained fused silica is 2.4 g /
  • the heating temperature and heating time are adjusted so that the thickness is cm 3 or less (see Japanese Patent No. 6814906).
  • the highly amorphous small-diameter inorganic filler may be an amorphous inorganic filler containing no crystalline component, such as amorphous silica, as a raw material.
  • silica with a low crystalline silica content (hereinafter also referred to as "highly amorphous small-diameter silica") was found to tend to be obtained regardless of the type of silica. Then, whether or not the crystalline silica content in the obtained inorganic filler is within the above-described range can be easily confirmed by calculating the crystalline silica content by the above-described method. If the crystalline silica content is not within the above range, the initial crystalline silica content may be obtained by, for example, increasing the number of melting steps.
  • the amount of the highly amorphous small-diameter inorganic filler relative to 100% by mass of the non-volatile component in the resin composition is not particularly limited, but from the viewpoint of obtaining a cured product with suppressed warpage, it is 30% by mass. % or more, preferably 40% by mass or more, more preferably 50% by mass or more, more preferably more than 50% by mass, and 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, or 80% by mass % or more.
  • the amount of the highly amorphous small-diameter inorganic filler is not particularly limited, but is 96% by mass or less, 95% by mass or less, or 94% by mass or less relative to 100% by mass of the nonvolatile components in the resin composition. It can be 93% by mass or less.
  • a cured product of a resin composition containing a highly amorphous small-diameter inorganic filler in such an amount is suppressed from warping.
  • the cured product of the resin composition containing the highly amorphous small-diameter inorganic filler in such a range can effectively reduce the coefficient of thermal expansion.
  • the amount of the highly amorphous small-diameter inorganic filler relative to 100% by volume of the non-volatile component in the resin composition is not particularly limited, but from the viewpoint of obtaining a cured product with suppressed warpage, it is 50% by volume. % or more, preferably 55 vol% or more, more preferably 60 vol% or more, still more preferably 65 vol% or more, and may be 66 vol% or more, 67 vol% or more, or 68 vol% or more.
  • the amount of the highly amorphous small-diameter inorganic filler is 95% by volume or less, 90% by volume or less, 85% by volume or less, relative to 100% by volume of the nonvolatile components in the resin composition. It can be vol % or less or 83 vol % or less.
  • a cured product of a resin composition containing a highly amorphous small-diameter inorganic filler in such a range can effectively reduce the coefficient of thermal expansion.
  • the resin composition of the present invention preferably contains (C) a curing agent.
  • (C) Curing agent usually has the function of reacting with (A) curable resin to cure the resin composition.
  • the curing agent (C) includes active ester curing agents, phenol curing agents, benzoxazine curing agents, acid anhydride curing agents, amine curing agents, and cyanate ester curing agents. Among these, in one embodiment, at least one selected from the group consisting of acid anhydride-based curing agents, amine-based curing agents, and phenol-based curing agents is used as (C) the curing agent.
  • an acid anhydride-based curing agent an amine-based curing agent, or a phenol-based curing agent
  • warpage of the cured product can generally be suppressed.
  • One type of curing agent may be used alone, or two or more types may be used in combination.
  • the curing agent (C) one or more selected from liquid curing agents and solid curing agents can be used, and liquid curing agents are preferably used.
  • the curing agent comprises a liquid curing agent.
  • the curing agent comprises a solid curing agent.
  • “Liquid curing agent” refers to a curing agent that is liquid at a temperature of 20°C
  • solid curing agent refers to a curing agent that is solid at a temperature of 20°C.
  • Acid anhydride-based curing agents include, for example, curing agents having one or more acid anhydride groups in one molecule, and curing agents having two or more acid anhydride groups in one molecule. preferable.
  • Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylnazic.
  • Examples of commercially available acid anhydride curing agents include “HNA-100”, “MH-700”, “MTA-15”, “DDSA” and “OSA” manufactured by Shin Nippon Rika; “YH-306” and “YH-307” manufactured by Hitachi Chemical; “HN-2200” and “HN-5500” manufactured by Hitachi Chemical;
  • Amine curing agents include, for example, curing agents having one or more, preferably two or more amino groups in one molecule. Specific examples thereof include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred. Amine-based curing agents are preferably primary amines or secondary amines, more preferably primary amines. Specific examples of amine-based curing agents include 4,4′-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 3,3′.
  • amine-based curing agents may be used, for example, "SEIKACURE-S” manufactured by Seika, “KAYABOND C-200S”, “KAYABOND C-100” and “Kayahard AA” manufactured by Nippon Kayaku. , “Kayahard AB”, “Kayahard AS”, Mitsubishi Chemical “Epicure W”, Sumitomo Seika “DTDA”, and the like.
  • Phenolic curing agents include curing agents having one or more, preferably two or more, hydroxyl groups bonded to aromatic rings such as benzene rings and naphthalene rings in one molecule. Among them, a compound having a hydroxyl group bonded to a benzene ring is preferred. From the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolac structure is preferred. Furthermore, from the viewpoint of adhesion, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable. In particular, a triazine skeleton-containing phenol novolak curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion.
  • phenol-based curing agents include “MEH-7700”, “MEH-7810", “MEH-7851”, and “MEH-8000H” manufactured by Meiwa Kasei; CBN", “GPH”; DIC's "TD-2090”, “TD-2090-60M”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018”, “ LA-3018-50P”, “EXB-9500”, “HPC-9500”, “KA-1160”, “KA-1163”, “KA-1165”; GDP-6115H", “ELPC75”; and "2,2-diallylbisphenol A” manufactured by Sigma-Aldrich.
  • the active group equivalent of the curing agent is preferably 50 g/eq. ⁇ 3000g/eq. , more preferably 100 g/eq. ⁇ 1000g/eq. , more preferably 100 g/eq. ⁇ 500 g/eq. , particularly preferably 100 g/eq. ⁇ 300 g/eq. is.
  • Active group equivalents represent the mass of curing agent per equivalent of active groups.
  • the amount of the (C) curing agent is preferably determined according to the number of active groups of the (A) curable resin.
  • the number of active groups of the (C) curing agent is preferably 0.1 or more, more preferably 0.3 or more, and still more preferably 0.5 or more when the number of reactive groups of the (A) curable resin is 1. Yes, preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.0 or less.
  • the number of reactive groups of the curable resin means the sum of all the values obtained by dividing the mass of the non-volatile component of the curable resin present in the resin composition by the reactive group equivalent.
  • the number of active groups of the (C) curing agent represents the sum of all the values obtained by dividing the mass of the non-volatile component of the (C) curing agent present in the resin composition by the active group equivalent.
  • the mass ratio of the component (C) to the component (A) is preferably in the range of 1:0.01 to 1:10. Such mass ratio is more preferably in the range of 1:0.05 to 1:9, more preferably in the range of 1:0.1 to 1:8.
  • the amount of the curing agent (C) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass, based on 100% by mass of the non-volatile components in the resin composition. or more, preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.
  • the resin composition of the present invention may further contain (D) other additives.
  • a first example of other additives includes a curing accelerator, a silane coupling agent, a radical polymerizable compound, a radical polymerization initiator, a polyether skeleton-containing compound having a reactive functional group, and a high molecular weight component.
  • the resin composition of the present invention may further contain a curing accelerator as an optional component.
  • the curing accelerator can efficiently adjust the curing time of the resin composition.
  • curing accelerators examples include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. Among them, imidazole-based curing accelerators are preferred.
  • the curing accelerator may be used alone or in combination of two or more.
  • Phosphorus-based curing accelerators include, for example, rephenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.
  • amine curing accelerators examples include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1, 8-diazabicyclo(5,4,0)-undecene, 1,8-diazabicyclo[5,4,0]undecene-7,4-dimethylaminopyridine, 2,4,6-tris(dimethylaminomethyl)phenol and the like 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.
  • DMAP 4-dimethylaminopyridine
  • benzyldimethylamine 2,4,6-tris(dimethylaminomethyl)phenol
  • 1, 8-diazabicyclo(5,4,0)-undecene 1,8-diazabicyclo[5,4,0]undecene-7
  • imidazole curing accelerators examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-d
  • imidazole-based curing accelerator a commercially available product may be used. —CN”, “Cl1Z-CNS”, “Cl1Z-A”, “2MZ-OK”, “2MA-OK”, “2MA-OK-PW”, “2PHZ” and the like.
  • Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and
  • metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin.
  • organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate.
  • organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate;
  • organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
  • the amount of the curing accelerator is 0% by mass or more, and is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0. 05% by mass or more, particularly preferably 0.1% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.
  • the resin composition of the present invention may further contain a silane coupling agent as an optional component.
  • a silane coupling agent used as the surface treatment agent for the inorganic filler
  • the inorganic filler treated with the surface treatment agent is classified as the component (B) described above.
  • Silane coupling agents include, for example, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents.
  • an epoxysilane-based coupling agent containing an epoxy group and a mercaptosilane-based coupling agent containing a mercapto group are preferable, and an epoxysilane-based coupling agent is particularly preferable.
  • a silane coupling agent may be used individually by 1 type, and may be used in combination of 2 or more types. In one embodiment, as an optional component, one type of silane coupling agent is included.
  • the resin composition of the present invention preferably contains a plurality of types of silane coupling agents, and the silane coupling agent used as the surface treatment agent of component (B) and the silane coupling agent used as the optional component It is preferable to include a plurality of types of silane coupling agents in combination with the above.
  • silane coupling agent for example, a commercially available product may be used.
  • examples of commercially available silane coupling agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBE903” (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.
  • KBM573 N-phenyl-3-aminopropyltrimethoxysilane
  • KBM103 phenyltrimethoxysilane
  • Shin-Etsu Chemical Co., Ltd. Long-chain epoxy type silane coupling agent
  • KBM manufactured by Shin-Etsu Chemical Co., Ltd.
  • the amount of the silane coupling agent is 0% by mass or more, preferably 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass with respect to 100% by mass of non-volatile components in the resin composition. or more, preferably 10% by mass or less, 5% by mass or less, or 3% by mass or less.
  • the amount of the silane coupling agent is 0% by mass or more, preferably 0.01% by mass or more, 0.1% by mass or more, or 0.2% by mass with respect to 100% by mass of the resin component in the resin composition. or more, preferably 15% by mass or less, 10% by mass or less, or 5% by mass or less.
  • the resin composition of the present invention may further contain a radically polymerizable compound as an optional component. Radically polymerizable compounds may be classified as component (A).
  • a compound having an ethylenically unsaturated bond can be used as the radically polymerizable compound.
  • radically polymerizable compounds include vinyl groups, allyl groups, 1-butenyl groups, 2-butenyl groups, acryloyl groups, methacryloyl groups, fumaroyl groups, maleoyl groups, vinylphenyl groups, styryl groups, cinnamoyl groups and Compounds having a radically polymerizable group such as a maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) can be mentioned.
  • the radically polymerizable compound may be used singly or in combination of two or more.
  • radically polymerizable compounds include (meth)acrylic radically polymerizable compounds having one or more acryloyl groups and/or methacryloyl groups; a styrene radically polymerizable compound having a vinyl group; an allyl radically polymerizable compound having one or two or more allyl groups; a maleimide radically polymerizable compound having one or two or more maleimide groups; mentioned.
  • (meth)acrylic radically polymerizable compounds are preferred.
  • the radically polymerizable compound preferably contains a polyalkylene oxide structure.
  • a radically polymerizable compound containing a polyalkylene oxide structure By using a radically polymerizable compound containing a polyalkylene oxide structure, the flexibility of the cured product of the resin composition can be enhanced.
  • a polyalkylene oxide structure can be represented by Formula (1): —(R f O) n —.
  • n usually represents an integer of 2 or more.
  • the integer n is preferably 4 or more, more preferably 9 or more, still more preferably 11 or more, and usually 101 or less, preferably 90 or less, more preferably 68 or less, and still more preferably 65 or less.
  • each R f independently represents an optionally substituted alkylene group.
  • the number of carbon atoms in the alkylene group is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, and particularly preferably is 2.
  • substituents that the alkylene group may have include a halogen atom, —OH, an alkoxy group, a primary or secondary amino group, an aryl group, —NH 2 , —CN, —COOH, —C(O ) H, —NO 2 , and the like. However, it is preferable that the alkyl group does not have a substituent.
  • Specific examples of polyalkylene oxide structures include polyethylene oxide structures, polypropylene oxide structures, poly n-butylene oxide structures, poly(ethylene oxide-co-propylene oxide) structures, poly(ethylene oxide-ran-propylene oxide) structures, poly(ethylene oxide -alt-propylene oxide) and poly(ethylene oxide-block-propylene oxide) structures.
  • the number of polyalkylene oxide structures contained in one molecule of the radically polymerizable compound may be one, or two or more.
  • the number of polyalkylene oxide structures contained in one molecule of the radically polymerizable compound is preferably 2 or more, more preferably 4 or more, still more preferably 9 or more, particularly preferably 11 or more, and preferably 101 or less, more preferably is 90 or less, more preferably 68 or less, and particularly preferably 65 or less.
  • those polyalkylene oxide structures may be the same or different.
  • Examples of commercially available radically polymerizable compounds containing a polyalkylene oxide structure include monofunctional acrylates “AM-90G”, “AM-130G” and “AMP-20GY” manufactured by Shin-Nakamura Chemical Co., Ltd.; bifunctional acrylates; "A-1000", “A-B1206PE”, “A-BPE-20”, “A-BPE-30”; monofunctional methacrylates “M-20G”, “M-40G”, “M-90G”, “ M-130G”, “M-230G”; and bifunctional methacrylates "23G", “BPE-900", "BPE-1300N", “1206PE".
  • the ethylenically unsaturated bond equivalent of the radically polymerizable compound is preferably 20 g/eq. ⁇ 3000g/eq. , more preferably 50 g/eq. ⁇ 2500 g/eq. , more preferably 70 g/eq. ⁇ 2000 g/eq. , particularly preferably 90 g/eq. ⁇ 1500 g/eq. is.
  • the ethylenically unsaturated bond equivalent represents the mass of the radically polymerizable compound per equivalent of ethylenically unsaturated bond.
  • the weight average molecular weight (Mw) of the radically polymerizable compound is preferably 150 or more, more preferably 250 or more, still more preferably 400 or more, preferably 40000 or less, more preferably 10000 or less, still more preferably 5000 or less, especially Preferably it is 3000 or less.
  • the amount of the radically polymerizable compound is 0% by mass or more, preferably 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass with respect to 100% by mass of the non-volatile components in the resin composition. or more, preferably 15% by mass or less, 10% by mass or less, or 8% by mass or less.
  • the amount of the radical polymerizable compound is 0% by mass or more, preferably 0.01% by mass or more, 0.1% by mass or more, or 0.2% by mass with respect to 100% by mass of the resin component in the resin composition. or more, preferably 25% by mass or less, 20% by mass or less, or 15% by mass or less.
  • the resin composition of the present invention may further contain a radical polymerization initiator as an optional component.
  • a radical polymerization initiator a thermal polymerization initiator that generates free radicals when heated is preferred.
  • the resin composition contains a radical polymerizable compound, the resin composition usually contains a radical polymerization initiator.
  • the radical polymerization initiator may be used alone or in combination of two or more.
  • radical polymerization initiators examples include peroxide-based radical polymerization initiators and azo-based radical polymerization initiators. Among them, a peroxide-based radical polymerization initiator is preferable.
  • peroxide-based radical polymerization initiators include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; tert-butyl cumyl peroxide, di-tert-butyl peroxide, di -tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy ) Dialkyl peroxide compounds such as hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne; dilauroyl peroxide, didecanoyl peroxide, dicyclohexylperoxydicarbonate, bis Diacyl peroxide compounds such as (4-tert-butylcyclohexyl) peroxydicarbonate; tert-butyl peroxy
  • azo radical polymerization initiators examples include 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2 '-Azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methyl Azonitrile compounds such as ethyl)azo]formamide, 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile; 2,2′-azobis[2-methyl-N-[1,1-bis(hydroxymethyl) -2-hydroxyethyl]propionamide], 2,2′-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide], 2,2′-azobis[2-methyl- N-[2-(1-hydroxybutyl)]-propionamide], 2,2′-azo
  • the radical polymerization initiator preferably has mesothermal activity. Specifically, the radical polymerization initiator preferably has a 10-hour half-life temperature T10 (°C) within a specific low temperature range.
  • the 10-hour half-life temperature T10 is preferably 50°C to 110°C, more preferably 50°C to 100°C, still more preferably 50°C to 80°C.
  • Commercial products of such radical polymerization initiators include, for example, “Luperox 531M80” manufactured by Arkema Fuji Co., Ltd., “Perhexyl (registered trademark) O” manufactured by NOF Corporation, and “MAIB” manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. mentioned.
  • the amount of the radical polymerization initiator is not particularly limited, it is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, based on 100% by mass of the non-volatile components in the resin composition. It is particularly preferably 0.05% by mass or more, preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.
  • the resin composition of the present invention may further contain a polyether skeleton-containing compound having a reactive functional group as an optional component.
  • a polyether skeleton-containing compound having a reactive functional group may be classified as component (A).
  • the resin composition of the present invention may further contain a polyether skeleton-containing compound having a reactive functional group as an optional component.
  • a polyether skeleton-containing compound having a reactive functional group can suppress warpage of a cured product of a resin composition.
  • the polyether skeleton-containing compound having a reactive functional group may be used alone or in combination of two or more.
  • a polyether skeleton-containing compound having a reactive functional group represents a polymer compound having a polyether skeleton.
  • the polyether skeleton contained in the polyether skeleton-containing compound having a reactive functional group is preferably a polyoxyalkylene skeleton composed of one or more monomer units selected from ethylene oxide units and propylene oxide units. Therefore, the polyether skeleton-containing compound having a reactive functional group preferably does not contain a polyether skeleton containing monomer units having 4 or more carbon atoms, such as butylene oxide units and phenylene oxide units. Moreover, the polyether skeleton-containing compound having a reactive functional group may contain a hydroxy group as a reactive functional group.
  • the polyether skeleton-containing compound having a reactive functional group may contain a silicone skeleton.
  • the silicone skeleton includes, for example, a polydialkylsiloxane skeleton such as a polydimethylsiloxane skeleton; a polydiarylsiloxane skeleton such as a polydiphenylsiloxane skeleton; a polyalkylarylsiloxane skeleton such as a polymethylphenylsiloxane skeleton; polydialkyl-diarylsiloxane skeleton; polydialkyl-alkylarylsiloxane skeleton such as polydimethyl-methylphenylsiloxane skeleton; polydiaryl-alkylarylsiloxane skeleton such as polydiphenyl-methylphenylsiloxane skeleton; A polydimethylsiloxane skeleton is preferred, and a polydimethylsiloxan
  • Polyether skeleton-containing compounds containing a silicone skeleton include, for example, polyoxyalkylene-modified silicones, alkyl-etherified polyoxyalkylene-modified silicones (polyoxyalkylene-modified silicones in which at least part of the polyether skeleton ends are alkoxy groups), and the like. sell.
  • the polyether skeleton-containing compound having a reactive functional group may contain a polyester skeleton.
  • This polyester skeleton is preferably an aliphatic polyester skeleton.
  • the hydrocarbon chain contained in the aliphatic polyester skeleton may be linear or branched, preferably branched.
  • the number of carbon atoms contained in the polyester backbone can be, for example, 4-16. Since the polyester skeleton can be formed from polycarboxylic acids, lactones, or anhydrides thereof, a polyether skeleton-containing compound having a reactive functional group containing a polyester skeleton has a carboxyl group at the end of the molecule. However, it is preferable to have a hydroxyl group as a reactive functional group at the end of the molecule.
  • Polyether skeleton-containing compounds having reactive functional groups include, for example, polyethylene glycol, polypropylene glycol, linear polyoxyalkylene glycol (linear polyalkylene glycol) such as polyoxyethylene polyoxypropylene glycol; polyoxyethylene Glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene glyceryl ether, polyoxyethylene trimethylolpropane ether, polyoxypropylene trimethylolpropane ether, polyoxyethylene polyoxypropylene trimethylolpropane ether, polyoxyethylene diglyceryl ether, polyoxypropylene diglyceryl ether, polyoxyethylene polyoxypropylene diglyceryl ether, polyoxyethylene polyoxypropylene diglyceryl ether, polyoxyethylene polyoxypropylene diglyceryl ether, polyoxyethylene topentaerythritol ether, polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene pent
  • the number average molecular weight of the polyether skeleton-containing compound having a reactive functional group is preferably 500-40,000, more preferably 500-20,000, and even more preferably 500-10,000.
  • the weight average molecular weight of the polyether skeleton-containing compound is preferably 500 to 40,000, more preferably 500 to 20,000, still more preferably 500 to 10,000.
  • the number average molecular weight and weight average molecular weight can be measured as polystyrene-equivalent values by gel permeation chromatography (GPC).
  • the polyether skeleton-containing compound having a reactive functional group is preferably liquid at 25°C.
  • the viscosity of the polyether skeleton-containing compound having a reactive functional group at 25° C. is preferably 100000 mPa ⁇ s or less, more preferably 50000 mPa ⁇ s or less, still more preferably 30000 mPa ⁇ s or less, 10000 mPa ⁇ s or less, or 5000 mPa ⁇ s or less. , 4000 mPa ⁇ s or less, 3000 mPa ⁇ s or less, 2000 mPa ⁇ s or less, or 1500 mPa ⁇ s or less.
  • the viscosity may be a viscosity (mPa ⁇ s) obtained by measuring with a Brookfield viscometer.
  • polyether skeleton-containing compounds having reactive functional groups include NOF Corporation's "Pronon #102", “Pronon #104", “Pronon #201", “Pronon #202B” and “Pronon #204”, “Pronon #208”, “Unilube 70DP-600B”, “Unilube 70DP-950B” (polyoxyethylene polyoxypropylene glycol); “Pluronic (registered trademark) L-23” manufactured by ADEKA, “Pluronic L-31", “Pluronic L-44”, “Pluronic L-61", “ADEKA Pluronic L-62", “Pluronic L-64", “Pluronic L-71”, “Pluronic L-72”, “Pluronic L-101”, “Pluronic L-121”, “Pluronic P-84”, “Pluronic P-85”, “Pluronic P-103”, “Pluronic F-68”, “Pluronic F-88”, “Pluronic
  • the amount of the polyether skeleton-containing compound having a reactive functional group is 0% by mass or more, preferably 0.01% by mass or more, and 0.05% by mass with respect to 100% by mass of non-volatile components in the resin composition. or 0.1% by mass or more, preferably 15% by mass or less, 10% by mass or less, or 8% by mass or less, and 15% by mass or less, 10% by mass or less, or 8% by mass or less.
  • the amount of the polyether skeleton-containing compound having a reactive functional group is 0% by mass or more, preferably 0.01% by mass or more, and 0.1% by mass with respect to 100% by mass of the resin component in the resin composition. or 0.2% by mass or more, preferably 25% by mass or less, 20% by mass or less, or 15% by mass or less.
  • the resin composition of the present invention may contain a high molecular weight component.
  • a high molecular weight component may function as a plasticizer.
  • Commercially available high molecular weight components include butadiene homopolymers “B-1000”, “B-2000” and “B-3000” manufactured by Nippon Soda Co., Ltd. The high molecular weight components may be used singly or in combination of two or more.
  • the number average molecular weight of the high molecular weight component is preferably 500 to 40,000, more preferably 500 to 20,000, still more preferably 500 to 10,000.
  • the weight average molecular weight of the high molecular weight component is preferably 500 to 40,000, more preferably 500 to 20,000, still more preferably 500 to 10,000.
  • the number average molecular weight and weight average molecular weight can be measured as polystyrene-equivalent values by gel permeation chromatography (GPC).
  • the high-molecular-weight component is liquid at 25°C, or the high-molecular-weight component has a viscosity at 45°C of preferably 100,000 mPa ⁇ s or less, more preferably 50,000 mPa ⁇ s or less, still more preferably 30,000 mPa ⁇ s or less, or 10,000 mPa. ⁇ s or less, 5000 mPa ⁇ s or less, 4000 mPa ⁇ s or less, 3000 mPa ⁇ s or less, 2000 mPa ⁇ s or less, 1500 mPa ⁇ s or less, or 500 mPa ⁇ s or less.
  • the viscosity of the polyether skeleton-containing compound having a reactive functional group is preferably 0.5 mPa ⁇ s or more, more preferably 1 mPa ⁇ s or more, still more preferably 2 mPa ⁇ s or more, 3 mPa ⁇ s or more, Or it is 4 mPa ⁇ s or more.
  • the viscosity may be a viscosity (mPa ⁇ s) obtained by measuring with a Brookfield viscometer.
  • the amount of the high molecular weight component is not limited to 100% by mass of the non-volatile components in the resin composition, but is 0% by mass or more, preferably 0.01% by mass or more, and 0.05% by mass. or 0.1% by mass or more, preferably 15% by mass or less, 10% by mass or less, or 8% by mass or less.
  • the amount of the high molecular weight component is not limited to 100% by mass of the resin component in the resin composition, but is 0% by mass or more, preferably 0.01% by mass or more, and 0.1% by mass. or 0.2% by mass or more, preferably 15% by mass or less, 10% by mass or less, or 8% by mass or less.
  • Second examples of other additives include, for example, organic fillers such as rubber particles, polyamide fine particles, and silicone particles; resin; carbodiimide compound; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; Polymerization inhibitors such as catechol, pyrogallol, and phenothiazine; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as bentone and montmorillonite; Antifoaming agents such as foaming agents and vinyl resin antifoaming agents; UV absorbers such as benzotriazole UV absorbers; Adhesion improvers such as urea silane; Adhesion-imparting agents such as triazine-based adhesion-imparting agents; antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; fluorescent brighten
  • phosphate ester compound phosphazene compound, phosphinic acid compound, red phosphorus
  • nitrogen flame retardant e.g. melamine sulfate
  • halogen flame retardant e.g. antimony trioxide
  • an additive may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
  • the resin composition of the present invention may further contain any solvent as a volatile component.
  • solvents include organic solvents.
  • a solvent may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios. In one embodiment, less solvent is preferred.
  • the content of the solvent is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less as a volatile component when the nonvolatile component in the resin composition is 100% by mass. It is more preferably 0.1% by mass or less, still more preferably 0.01% by mass or less, and is particularly preferably not contained (0% by mass).
  • Other embodiments include a solvent. Thereby, the handleability as a resin varnish can be improved.
  • the resin composition of the present invention can be produced, for example, by mixing the components described above. Some or all of the components described above may be mixed at the same time, or may be mixed in order. During the course of mixing each component, the temperature may be set accordingly, and thus may be temporarily or permanently heated and/or cooled. Moreover, you may perform stirring or shaking in the process of mixing each component.
  • the resin composition of the present invention is a resin composition containing (A) a curable resin and (B) an inorganic filler, wherein the average particle size of the (B) inorganic filler is in the range of 0.5 ⁇ m to 12 ⁇ m. and wherein the content of crystalline silica in the inorganic filler is in the range of 0% by mass or more and less than 2.1% by mass. Accordingly, the present invention has the effect of being able to provide a resin composition with a stable viscosity life; a resin sheet, a circuit board, and a semiconductor chip package using the resin composition.
  • the viscosity life stability of the resin composition of the present invention can be evaluated, for example, by the method described in the Examples section below. Specifically, the initial melt viscosity MV0 and the melt viscosity MV12 after 12 hours are measured, and the thickening ratio after 12 hours is calculated as the ratio of the melt viscosity MV12 after 12 hours to the initial melt viscosity MV0 (that is, MV12/ MV0), the thickening ratio of the resin composition of the present invention is preferably less than 1.7, more preferably 1.6 or less, still more preferably 1.5 or less, and particularly preferably is less than or equal to 1.4, and usually greater than 1.0.
  • the initial melt viscosity MV0 of the solvent-free resin composition (resin paste) according to one embodiment of the present invention is preferably in the range of 20 poise to 800 poise, more preferably in the range of 20 poise to 700 poise. preferably within the range of 20 poise to 600 poise.
  • the 12-hour melt viscosity MV12 of the solvent-free resin composition (resin paste) according to one embodiment of the present invention is preferably in the range of more than 20 poise to less than 1360 poise, more preferably 21 poise to 1190 poise. poise, more preferably 21 poise to 1020 poise.
  • the inorganic filler can be highly filled, it tends to be possible to obtain a cured product in which the occurrence of warping is suppressed.
  • the amount of warp can be measured by the method described later, and for example, the amount of warp is less than 1500 ⁇ m, preferably less than 1300 ⁇ m, more preferably less than 1100 ⁇ m.
  • the initial melt viscosity MV0 of the resin composition layer formed using the resin composition (resin varnish) containing a solvent according to another embodiment of the present invention is preferably in the range of 20 poise to 20000 poise, and more It is preferably in the range of 1000 poise to 19000 poise, more preferably in the range of 2000 poise to 18000 poise.
  • the 12-hour melt viscosity MV12 of the resin composition layer formed using the resin composition (resin varnish) containing a solvent according to another embodiment of the present invention is preferably more than 20 poise and less than 34000 poise. within the range, more preferably within the range of 1100 poise to 30000 poise, more preferably within the range of 2200 poise to 25000 poise.
  • the inorganic filler can be highly filled, it tends to be possible to obtain a cured product in which the occurrence of warping is suppressed.
  • the amount of warp can be measured by the method described later, and for example, the amount of warp is less than 2000 ⁇ m, preferably less than 1800 ⁇ m, more preferably less than 1600 ⁇ m.
  • the resin composition of the present invention is pasty.
  • a pasty resin composition also referred to as "resin paste”
  • the resin composition of the present invention is a resin varnish capable of forming a resin composition layer on a sheet-like substrate (for example, a support to be described later). Thereby, handleability can be improved.
  • the thickening ratio is small as described above, so even if the thickness is increased Also, it is possible to provide a circuit board and a semiconductor chip package with good yields by suppressing the occurrence of flow marks due to non-uniform composition and the occurrence of poor embedding due to non-uniform viscosity. Therefore, the resin composition of the present invention is also suitable for forming a resin composition layer having a thickness of 50 ⁇ m or more. In addition, since the resin composition of the present invention can be highly filled with an inorganic filler, it tends to be possible to provide a circuit board and a semiconductor chip package in which the occurrence of warping is suppressed.
  • the resin composition of the present invention can be suitably used as a resin composition (sealing resin composition) for sealing electronic devices such as organic EL devices and semiconductors. (semiconductor encapsulation resin composition), preferably as a resin composition for encapsulating a semiconductor chip (semiconductor chip encapsulation resin composition). Moreover, the resin composition can be used as an insulating resin composition for an insulating layer in addition to the sealing use.
  • the resin composition is a resin composition for forming an insulating layer of a semiconductor chip package, for example, a rewiring layer (a resin composition for an insulating layer of a semiconductor chip package, a resin for a rewiring layer). composition) and a resin composition for forming an insulating layer of a circuit board (including a printed wiring board) (a resin composition for an insulating layer of a circuit board).
  • the resin composition of the present invention can be used as a material for forming the sealing layer or insulating layer of semiconductor chip packages.
  • semiconductor chip packages include FC-CSP, MIS-BGA package, ETS-BGA package, Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), Fan-in type PLPs can be mentioned.
  • the resin composition may also be used as an underfill material, for example, as a material for MUF (Molding Under Filling) used after connecting a semiconductor chip to a substrate.
  • MUF Molding Under Filling
  • the resin composition can be used in a wide range of applications where resin compositions are used, such as resin sheets, sheet-like laminated materials such as prepreg, solder resists, die-bonding materials, hole-filling resins, and part-embedding resins.
  • a resin sheet according to one embodiment of the present invention has at least a support and a resin composition layer provided on the support, and optionally a protective film.
  • the resin composition layer is a layer containing the resin composition of the present invention.
  • the thickness of the resin composition layer and the thickness of the cured product layer obtained by curing the resin composition layer are arbitrary.
  • the resin sheet can be produced, for example, according to a known method, and the material used as the support is also selected arbitrarily.
  • the use of the resin sheet is the same as the use of the resin composition of the present invention described above.
  • packages using applicable circuit boards include FC-CSP, MIS-BGA packages, and ETS-BGA packages.
  • Applicable semiconductor chip packages include, for example, Fan-out type WLP, Fan-in type WLP, Fan-out type PLP, Fan-in type PLP and the like.
  • the resin sheet may be used as a material for the MUF that is used after connecting the semiconductor chip to the substrate. Furthermore, resin sheets can be used in a wide range of other applications that require high insulation reliability.
  • a circuit board according to an embodiment of the present invention may contain a cured product of the resin composition of the present invention.
  • the circuit board can be manufactured, for example, according to a known method, and the material used as the base material and the conductor layer that may be formed on the base material is also selected arbitrarily.
  • a resin composition layer for example, a resin composition layer containing the resin composition of the present invention is formed on the base material, for example, according to a known method.
  • the resin composition layer can be formed by compression molding.
  • a base material and a resin composition are usually placed in a mold, and pressure and, if necessary, heat are applied to the resin composition in the mold to form a resin composition layer on the base material.
  • the specific operation of the compression molding method can be, for example, as follows.
  • An upper mold and a lower mold are prepared as molds for compression molding.
  • the resin composition is applied onto the substrate.
  • the substrate coated with the resin composition is attached to the lower mold. After that, the upper mold and the lower mold are clamped, and heat and pressure are applied to the resin composition for compression molding.
  • the specific operation of the compression molding method may be, for example, as follows.
  • An upper mold and a lower mold are prepared as molds for compression molding.
  • a resin composition is placed on the lower mold.
  • a release film is attached to the upper mold as required for the base material.
  • the upper mold and the lower mold are clamped so that the resin composition placed on the lower mold is in contact with the base material attached to the upper mold, and heat and pressure are applied to perform compression molding.
  • the molding conditions differ depending on the composition of the resin composition of the present invention, and suitable conditions can be adopted so as to achieve good sealing.
  • the temperature of the mold during molding is preferably 70° C. or higher, more preferably 80° C. or higher, particularly preferably 90° C. or higher, and preferably 200° C. or lower.
  • the pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, particularly preferably 5 MPa or higher, and preferably 50 MPa or lower, more preferably 30 MPa or lower, and particularly preferably 20 MPa or lower.
  • Cure time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 3 minutes or more, preferably 100 minutes or less, more preferably 90 minutes or less, and in one embodiment, 60 minutes or less, 30 minutes or 20 minutes or less.
  • the mold is usually removed. The mold may be removed before or after heat curing of the resin composition layer.
  • the resin composition layer is thermally cured (post-cured) to form a cured product layer.
  • the thermosetting conditions for the resin composition layer may vary depending on the type of resin composition, but the curing temperature is usually in the range of 120° C. to 240° C. (preferably 150° C. to 220° C., more preferably 170° C. to 200° C.). ° C.), and the curing time is in the range of 5 minutes to 120 minutes (preferably in the range of 10 minutes to 100 minutes, more preferably in the range of 15 minutes to 90 minutes).
  • the resin composition layer Before thermally curing the resin composition layer, the resin composition layer may be subjected to a preliminary heating treatment of heating at a temperature lower than the curing temperature.
  • the resin composition layer prior to thermosetting the resin composition layer, the resin composition layer is usually heated at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). may be preheated for usually 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).
  • circuit board manufacturing method may further include an arbitrary step.
  • a semiconductor chip package according to one embodiment of the present invention includes a cured product of the resin composition of the present invention.
  • Examples of this semiconductor chip package include the following.
  • a semiconductor chip package according to the first example includes the circuit board described above and a semiconductor chip mounted on the circuit board.
  • This semiconductor chip package can be manufactured by bonding a semiconductor chip to a circuit board.
  • any condition that allows conductor connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board can be adopted as the bonding condition between the circuit board and the semiconductor chip.
  • the semiconductor chip and the circuit board may be bonded via an insulating adhesive.
  • the bonding method is the method of crimping the semiconductor chip to the circuit board.
  • the crimping temperature is usually in the range of 120° C. to 240° C. (preferably 130° C. to 200° C., more preferably 140° C. to 180° C.), and the crimping time is usually in the range of 1 second to 60 seconds. (preferably in the range of 5 seconds to 30 seconds).
  • the bonding method is a method of reflowing and bonding a semiconductor chip to a circuit board.
  • the reflow conditions may range from 120.degree. C. to 300.degree.
  • the semiconductor chip After bonding the semiconductor chip to the circuit board, the semiconductor chip may be filled with a mold underfill material.
  • a mold underfill material As this mold underfill material, the resin composition described above may be used. Therefore, a step of curing the resin composition of the present invention is included.
  • a semiconductor chip package according to the second example includes a semiconductor chip and a cured product of the resin composition of the present invention that seals the semiconductor chip.
  • the cured resin composition of the present invention usually functions as a sealing layer.
  • a semiconductor chip package according to the second example includes, for example, a fan-out type WLP.
  • FIG. 1 is a cross-sectional view schematically showing the configuration of a fan-out type WLP as an example of a semiconductor chip package according to this embodiment.
  • a semiconductor chip package 100 as a fan-out type WLP includes, for example, a semiconductor chip 110; a sealing layer 120 formed to cover the periphery of the semiconductor chip 110; and a sealing layer for the semiconductor chip 110, as shown in FIG.
  • a method for manufacturing such a semiconductor chip package includes: (A) a step of laminating a temporary fixing film on a substrate; (B) temporarily fixing the semiconductor chip on the temporary fixing film; (C) forming a sealing layer on the semiconductor chip; (D) a step of peeling the substrate and the temporary fixing film from the semiconductor chip; (E) forming a rewiring layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed; (F) forming a rewiring layer as a conductor layer on the rewiring forming layer; (G) forming a solder resist layer on the rewiring layer; including. Further, the method for manufacturing the semiconductor chip package includes: (H) A step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages to individualize them.
  • Step (A) is a step of laminating a temporary fixing film on a substrate.
  • the conditions for laminating the base material and the temporary fixing film may be the same as the conditions for laminating the base material and the resin sheet in the method for manufacturing a circuit board.
  • substrates examples include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel and cold-rolled steel plate (SPCC); FR-4 substrates and the like; A heat-cured substrate; a substrate made of bismaleimide triazine resin such as BT resin; and the like.
  • Any material that can be peeled off from the semiconductor chip and that can temporarily fix the semiconductor chip can be used for the temporary fixing film.
  • Commercially available products include "Riva Alpha” manufactured by Nitto Denko Corporation.
  • Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film.
  • Temporary fixing of the semiconductor chip can be performed using a device such as a flip chip bonder, a die bonder, or the like.
  • the layout and the number of semiconductor chips to be arranged can be appropriately set according to the shape and size of the temporary fixing film, the target production number of semiconductor chip packages, and the like.
  • the semiconductor chips may be arranged in a matrix of multiple rows and multiple columns and temporarily fixed.
  • Step (C) is a step of forming a sealing layer on the semiconductor chip.
  • the sealing layer can be formed from a cured product of the resin composition of the present invention.
  • the encapsulation layer is usually formed by a method including the steps of forming a resin composition layer on the semiconductor chip and thermosetting the resin composition layer to form a cured product layer as the encapsulation layer. .
  • the resin composition layer is formed on the semiconductor chip by the same method as the method for forming the resin composition layer on the substrate described in [Circuit board] above, except that the semiconductor chip is used instead of the substrate. can do
  • thermosetting conditions for the resin composition layer may be the same as the thermosetting conditions for the resin composition layer in the circuit board manufacturing method.
  • the resin composition layer may be subjected to a preheating treatment of heating at a temperature lower than the curing temperature. The processing conditions for this preheating treatment may be the same as those for the preheating treatment in the circuit board manufacturing method.
  • Step (D) is a step of peeling off the substrate and the temporary fixing film from the semiconductor chip.
  • the peeling method it is desirable to employ an appropriate method according to the material of the temporary fixing film.
  • the peeling method include a method of heating, foaming, or expanding the temporary fixing film to peel it.
  • a peeling method for example, a method of irradiating the temporary fixing film with ultraviolet rays through the base material to reduce the adhesive strength of the temporary fixing film and peel it off can be used.
  • the heating conditions are usually 100° C. to 250° C. for 1 second to 90 seconds or 5 minutes to 15 minutes.
  • the irradiation dose of ultraviolet rays is usually 10 mJ/cm 2 to 1000 mJ/cm 2 .
  • the method of manufacturing the semiconductor chip package may include polishing the exposed surface of the encapsulation layer. Polishing can improve the smoothness of the surface of the sealing layer. As the polishing method, the same method as described in the manufacturing method of the circuit board can be used.
  • Step (E) is a step of forming a rewiring forming layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed. Usually, this rewiring formation layer is formed on the semiconductor chip and the encapsulation layer.
  • the rewiring forming layer formed on the sealing layer may be formed from the photosensitive resin composition.
  • the method for forming via holes generally includes exposing the surface of the rewiring layer through a mask.
  • active energy rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferred.
  • the exposure method include a contact exposure method in which exposure is performed while a mask is brought into close contact with the rewiring formation layer, and a non-contact exposure method in which exposure is performed using parallel rays without making a mask in close contact with the rewiring formation layer. be done.
  • the development may be either wet development or dry development.
  • the development method includes, for example, a dipping method, a paddle method, a spray method, a brushing method, a scraping method, and the like, and the paddle method is preferable from the viewpoint of resolution.
  • the shape of the via hole is not particularly limited, but is generally circular (substantially circular).
  • the top diameter of the via hole is, for example, 50 ⁇ m or less, 30 ⁇ m or less, 20 ⁇ m or less, or 10 ⁇ m or less.
  • the top diameter of the via hole means the diameter of the opening of the via hole on the surface of the rewiring layer.
  • Step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring forming layer.
  • the method of forming the rewiring layer on the rewiring forming layer can be the same as the method of forming the conductor layer on the cured material layer in the method of manufacturing the circuit board.
  • the steps (E) and (F) may be repeated to alternately build up the rewiring layers and the rewiring formation layers (build-up).
  • Step (G) is a step of forming a solder resist layer on the rewiring layer.
  • Any insulating material can be used as the material of the solder resist layer.
  • photosensitive resins and thermosetting resins are preferable from the viewpoint of easiness in manufacturing semiconductor chip packages.
  • step (G) a bumping process for forming bumps may be performed as necessary. Bumping can be performed by a method such as solder balls or solder plating. Formation of via holes in the bumping process can be performed in the same manner as in step (E).
  • Step (H) The method for manufacturing a semiconductor chip package may include step (H) in addition to steps (A) to (G).
  • Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into pieces.
  • the method of dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited.
  • a semiconductor device includes a semiconductor chip package.
  • Semiconductor devices include, for example, electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, etc.) and aircraft, etc.).
  • ⁇ Production Example 1 Production of inorganic filler A> Using crystalline silica as a raw material, the highly amorphous small-diameter silica B1 obtained by performing the melting process twice in the melting method is treated with a surface treatment agent "KBM573" (N-phenyl-3 -aminopropyltrimethoxysilane) to obtain an inorganic filler A.
  • the inorganic filler A had an average particle size of 3.1 ⁇ m and a specific surface area of 5.1 m 2 /g. The average particle size and specific surface area were measured according to the methods described above.
  • the crystalline silica content of inorganic filler A was calculated based on the X-ray diffraction pattern obtained by X-ray diffraction measurement.
  • an X-ray diffraction analyzer "SmartLab (registered trademark)" manufactured by Rigaku was used for the X-ray diffraction measurement.
  • SmartLab registered trademark
  • Rigaku the X-ray diffraction analyzer
  • the value 0.3% obtained as a result of Rietveld analysis of the X-ray diffraction pattern by the X-ray diffraction analyzer (and the attached qualitative analysis program PDXL) is adopted. did.
  • inorganic fillers B and C Production of inorganic fillers B and C> Using crystalline silica as a raw material, highly amorphous small-diameter silica B2 obtained by performing the melting process twice in the melting method, highly amorphous obtained by performing the melting process once in the melting method Inorganic fillers B and C were obtained by surface-treating small-diameter silica B3 in the same manner as in Production Example 1, respectively.
  • the inorganic filler B had an average particle diameter of 10 ⁇ m, a specific surface area of 3.4 m 2 /g, and a crystalline silica content of 0.3%.
  • the inorganic filler C had an average particle size of 9.8 ⁇ m, a specific surface area of 3.5 m 2 /g, and a crystalline silica content of 0.09%.
  • Inorganic filler D was obtained by using amorphous silica as a raw material and subjecting it to surface treatment in the same manner as in Production Example 1.
  • the inorganic filler D had an average particle size of 3.2 ⁇ m, a specific surface area of 3.8 m 2 /g, and a crystalline silica content below the detection limit (the detection limit was about 0.01 mass%).
  • inorganic fillers E and F Production of inorganic fillers E and F> Using crystalline silica as a raw material, highly amorphous small-diameter silica B4 obtained by performing the melting process once in the melting method, highly amorphous obtained by performing the melting process once in the melting method Inorganic fillers E and F were obtained by surface-treating small-diameter silica B5 in the same manner as in Production Example 1, respectively.
  • the inorganic filler E had an average particle diameter of 3.4 ⁇ m, a specific surface area of 5.0 m 2 /g, and a crystalline silica content of 2.1%.
  • the inorganic filler F had an average particle size of 9.5 ⁇ m, a specific surface area of 3.2 m 2 /g, and a crystalline silica content of 5%.
  • Curing agent as component (C) (acid anhydride-based curing agent "MH-700" manufactured by Shin Nippon Rika Co., Ltd., acid anhydride group equivalent: 164 g / eq.) 8 parts, epoxy resin as component (A) ( Liquid epoxy resin "ZX1059” manufactured by Nippon Steel Chemical & Materials Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq.) 2 parts, ( A) 2 parts of epoxy resin as component (alicyclic epoxy resin "Celoxide 2021P” manufactured by Daicel Corporation, epoxy equivalent: 136 g/eq.), epoxy resin as component (A) (naphthalene type epoxy resin manufactured by DIC Corporation "HP4032D", epoxy equivalent: 143 g / eq.) 2 parts, curing accelerator as component (D) (imidazole curing accelerator manufactured by Shikoku Kasei Kog
  • KBM403 (3-glycidoxypropyltrimethoxysilane)) as a component (D) using a mixer.
  • a uniformly dispersed and pasty resin composition (resin paste) was prepared.
  • the content of the inorganic filler A was 71.7% by volume when the entire resin paste was taken as 100% by volume.
  • Table 1 shows the content of the inorganic filler in the resin composition paste.
  • the prepared resin paste was immediately subjected to the measurement of the initial melt viscosity MV0, which will be described later.
  • Example 1-1 In Example 1-1, the following items were changed.
  • component (A) instead of blending 2 parts each of epoxy resins ("ZX1059”, “Celoxide 2021P”, “HP4032D, “EP-3950L” and “EP-4088S"), epoxy resin ("ZX1059” ) 2 parts, epoxy resin ("HP4032D") 2 parts, epoxy resin (polyether-containing epoxy resin "EX-992L” manufactured by Nagase ChemteX Corporation, epoxy equivalent: 680 g / eq.) 2 parts, epoxy resin ( Fluorene structure-containing epoxy resin "EG-280” manufactured by Osaka Gas Chemicals Co., Ltd., epoxy equivalent: 460 g / eq.
  • Example 1-1 In Example 1-1, the following items were changed.
  • component (A) the amount of epoxy resin ("ZX1059”, “Celoxide 2021P”, “HP4032D, "EP-3950L” and “EP-4088S”) was changed from 2 parts to 3 parts.
  • component (C) instead of blending 8 parts of a curing agent ("MH-700"), a curing agent (Nippon Kayaku Co., Ltd. amine-based curing agent "Kayahard AA"(4,4'-Diamino-3,3'-diethyldiphenylmethane)) was added in 3 parts.
  • Example 1-3 For component (D), instead of adding 0.4 parts of a curing accelerator (“2MA-OK-PW”), a curing accelerator (imidazole-based curing accelerator “2E4MZ” manufactured by Shikoku Kasei Co., Ltd.) is added to 0. .4 parts were added.
  • a resin paste according to Example 1-3 was prepared in the same manner as in Example 1-1 except for the above items.
  • Example 1-1 In Example 1-1, the following items were changed.
  • component (A) instead of blending 2 parts each of epoxy resins ("ZX1059”, “Celoxide 2021P”, “HP4032D, “EP-3950L” and “EP-4088S"), epoxy resin ("ZX1059” ), 2 parts of an epoxy resin (“HP4032D”), and 1 part of an epoxy resin (epoxidized polybutadiene resin “JP-100” manufactured by Nippon Soda Co., Ltd.).
  • component (B) 120 parts of inorganic filler B was added in place of 110 parts of inorganic filler A.
  • component (C) the amount of curing agent (“MH-700”) was changed from 8 parts to 9 parts.
  • Example 1-4 A resin paste according to Example 1-4 was prepared in the same manner as in Example 1-1 except for the above items.
  • Example 1-5 In Examples 1-4, the following items were changed. Instead of blending 3 parts of epoxy resin (“ZX1059”), 2 parts of epoxy resin (“HP4032D”), and 1 part of epoxy resin (“JP-100”) for component (A), epoxy Three parts of resin (“ZX1059”), one part of epoxy resin (“HP4032D”), and one part of epoxy resin (“EG-280”) were blended.
  • component (D) instead of blending 0.1 part of silane coupling agent (“KBM403”), 0.1 part of silane coupling agent (“KBM403”) and 0.1 part of silane coupling agent (Shin-Etsu 0.1 part of "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Kagaku Kogyo Co., Ltd. was added. That is, in Examples 1-5, a plurality of types of silane coupling agents were blended.
  • Example 1-5 A resin paste according to Example 1-5 was prepared in the same manner as in Example 1-4 except for the above items.
  • Example 1-6 In Example 1-5, instead of blending 1 part of the silicone resin ("KF-6012") for the component (D), a polyoxyethylene polyoxypropylene glycol compound (manufactured by ADEKA) was added. 1 part of propylene glycol "L-64”) was added. A resin paste according to Example 1-6 was prepared in the same manner as in Example 1-5 except for the above items.
  • Example 1-7 In Example 1-5, 3 parts of epoxy resin ("ZX1059”), 1 part of epoxy resin (“HP4032D”), and 1 part of epoxy resin (“EG-280”) were added to component (A). Instead, 3 parts epoxy resin (“ZX1059”), 1 part epoxy resin (“HP4032D”), and 2 parts epoxy resin (“EP-3950L”) were blended. In addition, in Example 1-5, instead of blending 1 part of silicone resin ("KF-6012”) for component (D), 1 part of polyester polyol A synthesized as follows was blended.
  • polyester polyol A having an aliphatic skeleton and terminated with a hydroxyl group was obtained as "polyester polyol A”.
  • a resin paste according to Example 1-7 was prepared in the same manner as in Example 1-5 except for the above items.
  • Example 1-8> In Example 1-3, the following items were changed. Instead of blending 3 parts each of epoxy resins (“ZX1059”, “Celoxide 2021P”, “HP4032D, “EP-3950L” and “EP-4088S”) for component (A), epoxy resin (“ZX1059” ), 3 parts of epoxy resin (“Celoxide 2021P”), 3 parts of epoxy resin (“HP4032D”), 2 parts of epoxy resin (“EP-3950L”), and 2 parts of epoxy resin (“EP-4088S ”) was blended. For component (B), 120 parts of inorganic filler B was added in place of 110 parts of inorganic filler A.
  • Example 1D the amount of the silane coupling agent (“KBM403”) was changed from 0.2 parts to 0.3 parts. Also, instead of blending 3 parts of methacrylate (“M-130G”), 1 part of polyester polyol A was blended. Also, the blending amount of the radical polymerization initiator (“Perhexyl (registered trademark) O”) was changed from 0.1 part to 0 part. That is, in Example 1-8, no radical polymerization initiator was used. A resin paste according to Example 1-8 was prepared in the same manner as in Example 1-3 except for the above items.
  • Example 1-9 In Examples 1-8, the following items were changed.
  • component (A) 3 parts of epoxy resin (“ZX1059”), 3 parts of epoxy resin (“Celoxide 2021P”), 3 parts of epoxy resin (“HP4032D”), and 3 parts of epoxy resin (“EP-3950L”)
  • EP-4088S 3 parts of epoxy resin
  • ZX1059 3 parts of epoxy resin
  • HP4032D 3 parts of epoxy resin
  • EP-3950L 3 parts of epoxy resin
  • EX-992L 1 part of epoxy resin
  • component (C) instead of blending 3 parts of a curing agent ("Kayahard AA”), 3 parts of a curing agent (phenol-based curing agent "2,2-diallylbisphenol A” manufactured by Sigma-Aldrich) Partially mixed.
  • component (B) the amount of inorganic filler B was changed from 120 parts to 100 parts.
  • component (D) instead of blending 1 part of polyester polyol A, 2 parts of a silicone resin (“KF-6012”) was blended.
  • a resin paste according to Example 1-9 was prepared in the same manner as in Example 1-8 except for the above items.
  • Example 1-7 120 parts of the inorganic filler B as the component (B) was changed to 120 parts of the inorganic filler C.
  • a resin paste according to Example 1-10 was prepared in the same manner as in Example 1-7 except for the above items.
  • Example 1-11 In Example 1-2, 110 parts of the inorganic filler A as the component (B) was changed to 110 parts of the inorganic filler D. A resin paste according to Example 1-11 was prepared in the same manner as in Example 1-2 except for the above items.
  • Example 2-1 ⁇ Production of resin varnish>
  • component (D) 2 parts of polyimide resin A solution synthesized as follows, epoxy resin as component (A) (Nippon Steel Chemical & Material naphthalene type epoxy resin "ESN-475V", epoxy equivalent : about 332g/eq.) 2.4 parts, epoxy resin ("HP4032D") as component (A) 6 parts, curing agent as component (C) ("LA-3018-50P” manufactured by DIC Corporation, Hydroxy group equivalent: 151 g / eq., 2-methoxypropanol solution with a solid content of 50%) 7 parts, inorganic filler B 85 parts as component (B), methyl ethyl ketone (MEK) 10 parts, cyclohexanone 8 parts were mixed and rotated at high speed.
  • a resin varnish was prepared by uniformly dispersing the mixture with a mixer.
  • the second reaction solution was then filtered through a 100-mesh filter cloth.
  • a polyimide resin A solution (50% by mass of non-volatile components) containing polyimide resin A having a polycarbonate structure as a non-volatile component was obtained as a filtrate.
  • Polyimide resin A had a number average molecular weight of 6,100.
  • a portion of the prepared resin varnish was promptly used for production of a resin sheet St0 described below. Further, another part of the resin varnish was stored in an environment of 23° C. and 50% humidity for 12 hours, and used for the preparation of the resin sheet St12 described below.
  • a resin varnish that has just been prepared is evenly coated on the support with a die coater so that the thickness of the resin composition layer after drying is 200 ⁇ m, and dried at 100° C. for 6 minutes. to obtain a resin composition layer.
  • a rough surface of a polypropylene film (“Alphan MA411” manufactured by Oji F-Tex Co., Ltd., thickness 15 ⁇ m) as a protective film is attached to the resin composition layer. laminated to.
  • a resin sheet St0 consisting of the support, the resin composition layer, and the protective film in that order was obtained.
  • the content of the inorganic filler B was 76.7% by volume when the entire resin composition layer of the resin sheet St0 was taken as 100% by volume. Further, as a result of heating and drying, the content of the solvent was expected to be 5% by mass or less when the entire resin composition layer of the resin sheet St0 was taken as 100% by mass.
  • the resin composition layer of the produced resin sheet St0 was immediately subjected to the measurement of the initial melt viscosity MV0, which will be described later.
  • the resin varnish after storage for 12 hours was evenly coated on the support with a die coater so that the thickness of the resin composition layer after drying was 200 ⁇ m, and dried at 100° C. for 6 minutes. A resin composition layer was obtained.
  • a rough surface of a polypropylene film (“Alphan MA411” manufactured by Oji F-Tex Co., Ltd., thickness 15 ⁇ m) as a protective film is attached to the resin composition layer. laminated to.
  • a resin sheet St12 consisting of the support, the resin composition layer, and the protective film in that order was obtained.
  • the content of the inorganic filler B was 76.7% by volume.
  • the content of the solvent was expected to be 5% by mass or less when the entire resin composition layer of the resin sheet St12 was taken as 100% by mass.
  • the resin composition layer of the produced resin sheet St12 was immediately subjected to the measurement of the 12-hour melt viscosity MV12, which will be described later.
  • Example 2-2 2 parts of epoxy resin (alicyclic epoxy resin "Celoxide 2021P” manufactured by Daicel Corporation, epoxy equivalent: 136 g/eq.) as component (A), epoxy resin (naphthalene ether type manufactured by DIC Corporation) as component (A) Epoxy resin "HP6000L”, epoxy equivalent: 215 g / eq.) 4 parts, epoxy resin as component (A) (liquid 1,4-glycidylcyclohexane type epoxy resin "ZX1658GS” manufactured by Nippon Steel Chemical & Materials Co., Ltd.
  • V-03 solid content 50% by mass toluene solution
  • inorganic filler B85 parts as component (B)
  • component (D) 0.1 part of an amine-based curing accelerator (4-dimethylaminopyridine: DMAP), 9 parts of methyl ethyl ketone (MEK), and 6 parts of cyclohexanone were mixed and uniformly dispersed in a high-speed rotating mixer to prepare a resin varnish.
  • a resin varnish according to Example 2-2 was prepared and a resin sheet St0 and a resin sheet St12 were produced in the same manner as in Example 2-1 except for the above items.
  • Example 1-3 instead of blending 110 parts of inorganic filler A as component (B), 110 parts of inorganic filler E was blended as component (B').
  • a resin paste according to Comparative Example 1-1 was prepared in the same manner as in Example 1-3 except for the above items.
  • Example 1-7 instead of blending 120 parts of inorganic filler B as component (B), 120 parts of inorganic filler F was blended as component (B').
  • a resin paste according to Comparative Example 1-2 was prepared in the same manner as in Example 1-7 except for the above items.
  • ⁇ Evaluation of viscosity life stability Determination of thickening ratio> The viscosity life stability was evaluated by measuring the initial melt viscosity and the melt viscosity after 12 hours and determining the thickening ratio.
  • melt viscosity MV12 after 12 hours>>>
  • the resin pastes prepared in Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-2 were stored in an environment of 23° C. and 50% humidity for 12 hours.
  • the initial melt viscosity MV0 was measured and measured.
  • the dynamic viscoelastic modulus was measured to obtain the lowest melt viscosity (poise). The lowest melt viscosity obtained in this manner was defined as "12-hour melt viscosity MV12".
  • Table 1 shows the compositions and evaluation results of the resin compositions of Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-2.
  • Table 2 shows the compositions and evaluation results of the resin compositions of Examples 2-1 to 2-3.
  • the layer of the first specific composition was subjected to a full cure treatment of thermal curing at 250° C. for 2 hours to obtain a central test layer having a thickness of 8 ⁇ m.
  • the cured product of the layer of the first specific composition obtained as a result of full curing contains a polyimide resin.
  • a silicon wafer having a polyimide resin formed on its surface was prepared. Furthermore, this silicon wafer was cut into a size of 1 cm square (that is, 1 cm ⁇ 1 cm).
  • test piece A cylindrical silicon rubber frame with a diameter of 4 mm was placed on a silicon wafer cut into 1 cm squares with a polyimide resin formed on the surface. Each of the resin pastes prepared in Examples 1-1 to 1-11 was filled in the cylindrical cavity of the silicon rubber frame to a height of 5 mm on the polyimide resin formed on the silicon wafer. After heating at 180° C. for 90 minutes, the silicon rubber frame is removed to obtain a test piece consisting of a silicon wafer and a cured product of a solid cylindrical resin composition formed on a polyimide resin formed on the silicon wafer. was made.
  • the shear strength [kgf/mm 2 ] at the interface of the cured product of the polyimide resin and the resin composition was measured with a bond tester (Dage series 4000) under the conditions that the head position was 1 mm from the silicon wafer and the head speed was 700 ⁇ m/s. . The test was performed 5 times. Using the average value of five measurements, the adhesion between the polyimide resin as the substrate and the cured resin paste was evaluated according to the following criteria. "A”: Shear strength is 2.5 kgf/mm 2 or more. “ ⁇ ”: Shear strength of 2.0 kgf/mm 2 or more and less than 2.5 kgf/mm 2 . “ ⁇ ”: Shear strength is less than 2.0 kgf/mm 2 .
  • a solution was prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of ⁇ -butyrolactone. This solution was added to the above reaction mixture under ice cooling over 40 minutes while stirring the reaction mixture. Subsequently, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of ⁇ -butyrolactone was added to the above reaction mixture over 60 minutes while stirring the reaction mixture. Furthermore, after the reaction mixture was stirred at room temperature for 2 hours, 30 ml of ethyl alcohol was added to the reaction mixture, and the mixture was further stirred for 1 hour. 400 ml of ⁇ -butyrolactone was then added to the reaction mixture. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
  • DCC dicyclohexylcarbodiimide
  • DADPE 4,4'-diaminodiphenyl
  • the resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of crude polymer.
  • the resulting crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution.
  • the resulting crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer.
  • the obtained precipitate was collected by filtration and dried in a vacuum to obtain a powdery polymer A-1 as the first polymer.
  • Mw weight average molecular weight
  • the measurement was performed in accordance with JEITA EDX-7311-24 of the Japan Electronics and Information Technology Industries Association standard. Specifically, a virtual plane calculated by the method of least squares of all data of the substrate surface in the measurement area is used as a reference plane, and the difference between the minimum value and the maximum value in the vertical direction from the reference plane is obtained as the amount of warpage [ ⁇ m]. rice field.
  • the amount of warpage was evaluated according to the following criteria. “ ⁇ ”: Warp amount less than 1500 ⁇ m “ ⁇ ”: Warp amount 1500 ⁇ m or more
  • Table 3 shows the evaluation results of the cured products of the resin compositions according to Examples 1-1 to 1-11.
  • a pre-baking treatment was performed by heating on a hot plate at 120° C. for 5 minutes to form a layer of the first specific composition having a thickness of 10 ⁇ m in the center on the polished surface.
  • the layer of the first specific composition was subjected to a full cure treatment of thermal curing at 250° C. for 2 hours to obtain a central test layer having a thickness of 8 ⁇ m.
  • the cured product of the layer of the first specific composition obtained as a result of full curing contains a polyimide resin.
  • a silicon wafer having a polyimide resin formed on its surface was prepared.
  • the resin sheet St0 (thickness of 200 ⁇ m) prepared in Examples 2-1 to 2-3 was coated with a batch-type vacuum pressure laminator (2-stage build-up laminator “CVP700” manufactured by Nikko Materials Co., Ltd.) to obtain polyimide resin. It was laminated on a 4-inch silicon wafer formed on the surface. Each lamination was carried out by pressure bonding for 30 seconds at a temperature of 100° C. and a pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds. Subsequently, peeling of the support and lamination of the resin composition layer (lamination under the same conditions) were repeated until the total thickness of the laminate of the resin composition layers was 5 mm.
  • a batch-type vacuum pressure laminator (2-stage build-up laminator “CVP700” manufactured by Nikko Materials Co., Ltd.) to obtain polyimide resin. It was laminated on a 4-inch silicon wafer formed on the surface. Each lamination was carried out by pressure bonding for 30 seconds
  • this silicon wafer was cut into a size of 1 cm square.
  • the laminate of the resin composition layers on the silicon wafer with a total thickness of 5 mm was processed into a solid columnar shape with a diameter of 4 mm.
  • a sample substrate including a silicon wafer and a cured product of a laminate of resin composition layers was obtained.
  • the shear strength [kgf/mm 2 ] was measured in the same manner as described above. The test was performed 5 times. Using the average value of five measurements, the adhesion between the polyimide resin as the substrate and the cured product of the laminate of the resin composition layer was evaluated according to the following criteria.
  • ⁇ Shear strength of 2.0 kgf/mm 2 or more and less than 2.5 kgf/mm 2 .
  • ⁇ Shear strength is less than 2.0 kgf/mm 2 .
  • a silicon wafer with a cured resin composition layer that is, an insulating layer.
  • a shadow moire measuring device (“Thermoire AXP” manufactured by Akorometrics)
  • the amount of warpage at 25° C. was measured for the sample substrate.
  • the measurement was performed in accordance with JEITA EDX-7311-24 of the Japan Electronics and Information Technology Industries Association standard. Specifically, a virtual plane calculated by the method of least squares of all data of the substrate surface in the measurement area is used as a reference plane, and the difference between the minimum value and the maximum value in the vertical direction from the reference plane is obtained as the amount of warpage [ ⁇ m]. rice field.
  • the amount of warpage was evaluated according to the following criteria. " ⁇ ": Warp amount less than 2000 ⁇ m
  • ⁇ Warp amount 2000 ⁇ m or more
  • Table 4 shows the evaluation results of the cured products of the resin compositions according to Examples 2-1 to 2-3.
  • the resin composition according to the comparative example is inferior in viscosity life stability, and therefore tends to cause non-uniform composition during long-term storage.
  • the resin pastes according to the examples have good viscosity life stability.
  • the use of such a resin paste yields a cured product having excellent properties. This makes it possible to provide, for example, a cured product having excellent adhesion to a base material (eg, polyimide resin); a circuit board and a semiconductor chip package containing the cured product.
  • a base material eg, polyimide resin
  • the resin composition layers of the resin sheets according to the examples have good viscosity life stability.
  • REFERENCE SIGNS LIST 100 semiconductor chip package 110 semiconductor chip 120 sealing layer 130 rewiring forming layer 140 rewiring layer 150 solder resist layer 160 bump

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Abstract

L'invention concerne une composition de résine ayant une durée de vie stable ; une feuille de résine qui utilise ladite composition de résine ; un substrat de circuit ; et un boîtier de puce semi-conductrice.　Dans cette composition de résine, qui contient (A) une résine durcissable et (B) une charge inorganique, le diamètre moyen des particules de la charge inorganique (B) est compris entre 0,5 et 12 µm et la teneur en silice cristalline dans le matériau de charge inorganique est supérieure ou égale à 0 % en masse et inférieure à 2,1 % en masse.
PCT/JP2022/023158 2021-06-22 2022-06-08 Composition de résine, produit durci, feuille de résine, substrat de circuit et boîtier de puce semi-conductrice WO2022270316A1 (fr)

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JP2023529821A JPWO2022270316A1 (fr) 2021-06-22 2022-06-08
KR1020237044186A KR20240023049A (ko) 2021-06-22 2022-06-08 수지 조성물, 경화물, 수지 시트, 회로 기판 및 반도체 칩 패키지
CN202280043646.0A CN117500886A (zh) 2021-06-22 2022-06-08 树脂组合物、固化物、树脂片材、电路基板及半导体芯片封装

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011046782A (ja) * 2009-08-25 2011-03-10 Panasonic Electric Works Co Ltd プリント配線板用エポキシ樹脂組成物、樹脂フィルム、プリプレグ、樹脂付き金属箔、フレキシブルプリント配線板
JP2011246516A (ja) * 2010-05-24 2011-12-08 Panasonic Electric Works Co Ltd 樹脂組成物、樹脂ワニス、プリプレグ、金属張積層板、及びプリント配線板
JP2018044044A (ja) * 2016-09-13 2018-03-22 味の素株式会社 樹脂組成物
JP2021024994A (ja) * 2019-08-08 2021-02-22 株式会社スリーボンド 湿気硬化型樹脂組成物および硬化物

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JP4929623B2 (ja) 2004-06-21 2012-05-09 味の素株式会社 変性ポリイミド樹脂を含有する熱硬化性樹脂組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011046782A (ja) * 2009-08-25 2011-03-10 Panasonic Electric Works Co Ltd プリント配線板用エポキシ樹脂組成物、樹脂フィルム、プリプレグ、樹脂付き金属箔、フレキシブルプリント配線板
JP2011246516A (ja) * 2010-05-24 2011-12-08 Panasonic Electric Works Co Ltd 樹脂組成物、樹脂ワニス、プリプレグ、金属張積層板、及びプリント配線板
JP2018044044A (ja) * 2016-09-13 2018-03-22 味の素株式会社 樹脂組成物
JP2021024994A (ja) * 2019-08-08 2021-02-22 株式会社スリーボンド 湿気硬化型樹脂組成物および硬化物

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