CN117500886A - Resin composition, cured product, resin sheet, circuit board, and semiconductor chip package - Google Patents

Resin composition, cured product, resin sheet, circuit board, and semiconductor chip package Download PDF

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Publication number
CN117500886A
CN117500886A CN202280043646.0A CN202280043646A CN117500886A CN 117500886 A CN117500886 A CN 117500886A CN 202280043646 A CN202280043646 A CN 202280043646A CN 117500886 A CN117500886 A CN 117500886A
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China
Prior art keywords
resin composition
resin
mass
epoxy resin
inorganic filler
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CN202280043646.0A
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Chinese (zh)
Inventor
阪内启之
佐佐木成
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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Publication of CN117500886A publication Critical patent/CN117500886A/en
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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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a resin composition with stable viscosity life, a resin sheet, a circuit board and a semiconductor chip package using the resin composition. A resin composition comprising (A) a curable resin and (B) an inorganic filler, wherein the inorganic filler has an average particle diameter of 0.5-12 [ mu ] m and the crystalline silica content in the inorganic filler is in the range of 0-2.1 mass%.

Description

Resin composition, cured product, resin sheet, circuit board, and semiconductor chip package
Technical Field
The present invention relates to a resin composition. The present invention also relates to a cured product, a resin sheet, a circuit board, and a semiconductor chip package obtained by using the resin composition.
Background
In recent years, there has been an increasing demand for small-sized high-function electronic devices such as smartphones and tablet devices, and further improvement in functionality has been demanded for insulating materials (insulating layers) for packaging semiconductor chips used for these small-sized electronic devices. In order to form such an insulating layer, a resin composition is used (patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2006-037083
Disclosure of Invention
Technical problem to be solved by the invention
In addition, the resin composition is required to suppress warpage generated when forming an insulating layer. Here, in order to suppress warpage, it is conceivable to highly fill the inorganic filler. In order to make the inorganic filler highly filled, it is considered to define the particle size range of the inorganic filler. In addition to suppressing warpage, there are cases where the particle size range of the inorganic filler is limited.
However, as a result of the investigation by the inventors, it was found that a resin composition having a desired property, for example, a stable viscosity life may not be obtained by limiting the particle size range of the inorganic filler. The problem is not limited to the liquid resin composition (also referred to as "ink" or "resin paste"), but also occurs for the resin composition capable of forming a film (also referred to simply as "film product" or "sheet product"). Further, it is expected that a circuit board and a semiconductor chip package having a good yield can be provided by using a resin composition or a resin sheet having a stable viscosity life, and suppressing occurrence of flow marks or implantation defects.
The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a resin composition which is preferably a cured product in which occurrence of warpage is suppressed and which has at least a stable viscosity life, a resin sheet, a circuit board, and a semiconductor chip package each using the resin composition.
Technical proposal adopted for solving the technical problems
The present inventors have made intensive studies to solve the above-described problems. As a result, the present inventors have found that the above problems can be solved by setting the content of crystalline silica in the inorganic filler to be within a specific range when the average particle diameter of the inorganic filler is within a specific range as a resin composition containing (a) a curable resin and (B) an inorganic filler. Further, as a result of examining the cured product of the resin composition of the present invention, it was found that the adhesion to a substrate (for example, adhesion to a polyimide resin) was excellent.
Namely, the present invention includes the following.
[1] A resin composition comprising (A) a curable resin and (B) an inorganic filler, wherein the inorganic filler has an average particle diameter of 0.5-12 [ mu ] m and the crystalline silica content in the inorganic filler is 0-2.1 mass%.
[2] The resin composition according to [1], wherein the crystalline silica content is in a range of 0 mass% or more and 0.4 mass% or less.
[3] The resin composition according to [1] or [2], wherein the content of the inorganic filler (B) is 50% by volume or more, based on 100% by volume of the total resin composition.
[4] The resin composition according to any one of [1] to [3], wherein the resin composition comprises a curing agent (C), and the mass ratio of the component (C) to the component (A) is in the range of 1:0.01 to 1:10.
[5] The resin composition according to any one of [1] to [4], wherein the content of the crystalline silica is calculated based on an X-ray diffraction pattern obtained by X-ray diffraction measurement.
[6] The resin composition according to [5], wherein the content of the crystalline silica is calculated by performing a Ritewald analysis (Rietveld analysis) on an X-ray diffraction pattern.
[7] The resin composition according to any one of [1] to [6], wherein the resin composition is used for forming a resin composition layer having a thickness of 50 μm or more.
[8] The resin composition according to any one of [1] to [7], wherein it is used for sealing.
[9] A cured product of the resin composition according to any one of [1] to [8 ].
[10] A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of [1] to [8] provided on the support.
[11] The resin sheet according to [10], wherein it is a resin sheet for an insulating layer of a semiconductor chip package.
[12] A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [8 ].
[13] A semiconductor chip package comprising the circuit board of [12] and a semiconductor chip mounted on the circuit board.
[14] A semiconductor chip package comprising a semiconductor chip sealed with the resin composition according to any one of [1] to [8 ].
[15] A semiconductor chip package comprising a semiconductor chip sealed with the resin sheet of [10 ].
[16] A method for manufacturing a semiconductor chip package, comprising the step of curing a resin composition,
the resin composition comprises (A) a curable resin and (B) an inorganic filler, wherein the average particle diameter of the inorganic filler is in the range of 0.5-12 [ mu ] m, and the content of crystalline silica in the inorganic filler is in the range of 0-2.1 mass%.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides a resin composition having a stable viscosity life, a resin sheet, a circuit board, and a semiconductor chip package using the resin composition.
Drawings
Fig. 1 is a cross-sectional view schematically showing a configuration of a fan-out WLP as an example of a semiconductor chip package according to an embodiment of the present invention.
Detailed Description
Hereinafter, embodiments and examples of the present invention will be described in detail. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily modified within a range not departing from the scope of the claims and their equivalents.
[ resin composition ]
The resin composition of the present invention is a resin composition comprising (A) a curable resin and (B) an inorganic filler, wherein the inorganic filler has an average particle diameter of 0.5 to 12 [ mu ] m, and the crystalline silica content in the inorganic filler is in the range of 0 to less than 2.1 mass%. Further, as will be apparent from the following description, the present invention provides at least the effect of providing a resin composition having a stable viscosity life, a resin sheet, a circuit board and a semiconductor chip package using the resin composition. Other effects exhibited by the present invention can be understood by those skilled in the art by referring to the present specification and drawings.
[ composition of resin composition ]
The resin composition of the present invention contains (A) a curable resin and (B) an inorganic filler. The resin composition of the present invention may contain, for example, (C) a curing agent, (D) other additives, and a solvent, in addition to the component (a) and the component (B), as long as the above effects are not excessively impaired.
[ (A) curable resin ]
The resin composition of the present invention contains (A) a curable resin. As the curable resin (a), 1 or more resins selected from the group consisting of thermosetting resins, photocurable resins, and radical-polymerizable resins can be used. The radical polymerizable resin may be classified as a thermosetting resin or a photocurable resin according to the case where radical polymerization is performed by heat or light in the presence of a polymerization initiator. (A) The components may be used alone in 1 kind, or 2 or more kinds may be used in combination in any ratio.
Examples of the thermosetting resin include epoxy resin, epoxy acrylate resin, urethane resin, cyanate resin, polyimide resin, benzoxazine resin, unsaturated polyester resin, phenolic resin, melamine resin, silicone resin, and phenoxy resin. In one embodiment, the (a) curable resin comprises an epoxy resin. When the resin composition contains a thermosetting resin, it preferably contains (C) a curing agent, more preferably further contains a curing accelerator described later.
The epoxy resin means a resin having an epoxy group. Examples of the epoxy resin include a bisxylenol type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, a phenol novolac type epoxy resin, a glycidylamine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolac type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, a cycloaliphatic epoxy resin, an alicyclic epoxy resin having an ester skeleton, a heterocyclic type epoxy resin, a spiro ring-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, a naphthalene ether type epoxy resin, a tertiary butyl catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a naphthol novolac type epoxy resin, an isocyanurate type epoxy resin, an alkylene oxide skeleton and a butadiene skeleton-containing epoxy resin, a fluorene structure-containing epoxy resin, and the like. The epoxy resin may be used alone or in combination of 1 kind or 2 or more kinds.
From the viewpoint of obtaining a cured product excellent in heat resistance, the epoxy resin may include an epoxy resin containing an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatic and aromatic heterocyclic rings. Examples of the epoxy resin having 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, triphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butylcatechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, xylenol type epoxy resin, glycidylamine type epoxy resin having an aromatic structure, glycidylester type epoxy resin having an aromatic structure, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having an aromatic structure, butadiene type epoxy resin having an aromatic structure, alicyclic epoxy resin having an aromatic structure, heterocyclic type epoxy resin, spiro ring-containing epoxy resin having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, naphthalene ether type epoxy resin, trimethylol type epoxy resin having an aromatic structure, tetraphenyl ethane type epoxy resin having an aromatic structure, and the like.
Among the epoxy resins having an aromatic structure, epoxy resins having a condensed ring structure are preferable from the viewpoint of obtaining cured products having good heat resistance. Examples of condensed rings in the epoxy resin having a condensed ring structure include naphthalene rings, anthracene rings, phenanthrene rings, and the like, and naphthalene rings are particularly preferred. Therefore, the epoxy resin is preferably a naphthalene type epoxy resin comprising a naphthalene ring structure. The amount of the naphthalene-type epoxy resin is preferably 10 mass% or more, more preferably 15 mass% or more, particularly preferably 20 mass% or more, more preferably 50 mass% or less, more preferably 40 mass% or less, and still more preferably 30 mass% or less, based on 100 mass% of the total amount of the epoxy resin.
The epoxy resin may include a glycidylamine type epoxy resin from the viewpoint of improving heat resistance and metal adhesion of the cured product.
The epoxy resin may include an epoxy resin having a butadiene structure.
The resin composition preferably contains, as the epoxy resin, an epoxy resin having 2 or more epoxy groups in 1 molecule. The proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, relative to 100% by mass of the nonvolatile component of the epoxy resin.
Examples of the epoxy resin include an epoxy resin which is liquid at a temperature of 20 ℃ (hereinafter also referred to as "liquid epoxy resin") and an epoxy resin which is solid at a temperature of 20 ℃ (hereinafter also referred to as "solid epoxy resin"). The resin composition of the present embodiment may contain only a liquid epoxy resin, or may contain only a solid epoxy resin, or may contain a liquid epoxy resin and a solid epoxy resin in combination, but preferably contains at least a liquid epoxy resin. In one embodiment, the resin composition of the present invention contains only a liquid epoxy resin as a curable resin. In another embodiment, the resin composition of the present invention may contain a liquid epoxy resin and a solid epoxy resin in combination as the curable resin, or may contain only a liquid epoxy resin.
As the liquid epoxy resin, a liquid epoxy resin having 2 or more epoxy groups in 1 molecule is preferable.
As the liquid epoxy resin, 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, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, epoxy resin having a butadiene structure, epoxy resin having an alkylene oxide skeleton and butadiene skeleton, epoxy resin having a fluorene structure, dicyclopentadiene type epoxy resin are preferable. Among them, bisphenol a type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, alicyclic epoxy resin having an ester skeleton, epoxy resin having a butadiene structure, epoxy resin having an alkylene oxide skeleton and a butadiene skeleton, epoxy resin having a fluorene structure, dicyclopentadiene type epoxy resin are particularly preferable.
Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, "828US", "828EL", "jER828EL", "825", "EPIKOTE 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi chemical Co., ltd.), "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical Co., ltd., the "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi chemical Co., ltd., the "630", "630LSD" 604 "(glycidylamine type epoxy resin) manufactured by Mitsubishi chemical Co., ltd., the" ED-523T "(GLYCIROL type epoxy resin) manufactured by ADEKA, the" EP-3950L "and the" EP-3980S "manufactured by ADEKA (glycidylamine type epoxy resin), EP-4088S (dicyclopentadiene type epoxy resin) manufactured by ADEKA, ZX1059 (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nitro chemical Co., ltd., EX-721 (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., ltd., EX-991L (alkylene oxide skeleton-containing epoxy resin) manufactured by Dai chemical Co., ltd., EX-992L (polyether-containing epoxy resin) manufactured by Dai chemical Co., ltd., CELLOXIDE 2021P (alicyclic epoxy resin having an ester skeleton) manufactured by Dai chemical Co., ltd., PB-3600 manufactured by Dai chemical Co., ltd., JP-100 manufactured by Kai chemical Co., ltd., JP-100) manufactured by Kai chemical Co., ltd., CELLOXIDE 2021P (alicyclic epoxy resin having an ester skeleton-containing epoxy resin) manufactured by Dai chemical Co., ltd., JP-A "JP-200" (epoxy resin having butadiene structure), "ZX1658" manufactured by Nitro chemical materials Co., ltd., "ZX1658GS" (liquid 1, 4-glycidyl cyclohexane type epoxy resin), "EG-280" manufactured by Osaka gas chemical Co., ltd., "epoxy resin having fluorene structure), etc.
The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.
As the solid epoxy resin, there are preferable a bisxylenol type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthalene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, a tetraphenylethane type epoxy resin.
Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Co., ltd., "HP-4700" manufactured by DIC Co., ltd., and "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" manufactured by DIC Co., ltd., and "N-695" manufactured by DIC Co., ltd., and "cresol novolak type epoxy resin", and "HP-7200" manufactured by DIC Co., ltd., and "HP-7200" and "HP-7200H" (dicyclopentadiene type epoxy resin), and "EXA-7311" G3 "manufactured by DIC Co., ltd., and" EXA-7311-G4S "and" HP6000 "(naphthalene type epoxy resin), and" EPPN-502H "(triphenol type epoxy resin) manufactured by Japanese chemical Co., ltd.," NC7000L "(naphthol novolac type epoxy resin) manufactured by Nippon Kagaku Co., ltd.," NC3000"," NC3000L "," NC3100 "(biphenyl type epoxy resin) manufactured by Nippon Kagaku Co., ltd.," ESN475V "(naphthol type epoxy resin) manufactured by Nitro Kagaku Co., ltd.," ESN485 "(naphthol novolac type epoxy resin) manufactured by Nitro Kagaku Co., ltd.," YX4000H "," YX4000"," YL6121 "(biphenyl type epoxy resin) manufactured by Mitsubishi Kagaku Co., ltd.," YX4000HK "(bina xylenol type epoxy resin) manufactured by Mitsubishi Kagaku Co., ltd.," YX8800 "(anthracene type epoxy resin) manufactured by Mitsubishi Kagaku Co., ltd., "YX7700" of Mitsubishi chemical corporation (novolak type epoxy resin containing a xylene structure), "PG-100" of Osaka gas chemical corporation (CG-500), "YL7760" of Mitsubishi chemical corporation (bisphenol AF type epoxy resin), "YL7800" of Mitsubishi chemical corporation (fluorene type epoxy resin), "jER1010" of Mitsubishi chemical corporation (solid bisphenol A type epoxy resin), "jER1031S" of Mitsubishi chemical corporation, etc.
The amount of the liquid epoxy resin is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, particularly preferably 100% by mass, based on 100% by mass of the total amount of the epoxy resin.
The epoxy equivalent of the epoxy resin is preferably 50g/eq to 5000g/eq, more preferably 50g/eq to 3000g/eq, still more preferably 80g/eq to 2000g/eq, still more preferably 110g/eq to 1000g/eq. The epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy groups. The epoxy equivalent can be measured in accordance with JIS K7236.
The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 200 to 3000, still more preferably 400 to 1500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by Gel Permeation Chromatography (GPC).
The amount of the curable resin is not particularly limited, but is preferably 0.5 mass% or more, more preferably 1 mass% or more, particularly preferably 1.5 mass% or more, more preferably 45 mass% or less, more preferably 40 mass% or less, particularly preferably 35 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
[ (B) inorganic filler ]
The resin composition of the present invention contains (B) an inorganic filler. The cured product of the resin composition containing the inorganic filler (B) generally tends to be inhibited from warping. In addition, the cured product of the resin composition containing the inorganic filler (B) can generally reduce the thermal expansion coefficient.
As the inorganic filler, an inorganic compound is used. Examples of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate, and the like. Among them, silica and alumina are preferable, and silica is particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as the silica, spherical silica is preferable. (B) The inorganic filler may be used alone or in combination of 1 or more than 2.
From the viewpoint of improving moisture resistance and dispersibility, (B) the inorganic filler may be treated with a surface treating agent. Examples of the surface treating agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilane-nitrogen compounds, titanate coupling agents, and the like. In addition, 1 kind of the surface treating agent may be used alone, or 2 or more kinds may be used in any combination.
Examples of the commercial products of the surface treatment agent include "KBM403" manufactured by Shimadzu chemical Co., ltd. (3-glycidoxypropyl trimethoxysilane), "KBM803" manufactured by Shimadzu chemical Co., ltd. (3-mercaptopropyl trimethoxysilane), "KBE903" manufactured by Shimadzu chemical Co., ltd. (3-aminopropyl triethoxysilane), "KBE 573" manufactured by Shimadzu chemical Co., ltd. (N-phenyl-3-aminopropyl trimethoxysilane), "SZ-31" manufactured by Shimadzu chemical Co., ltd. (hexamethyldisilazane), "KBM103" manufactured by Shimadzu chemical Co., ltd. (phenyl trimethoxysilane), and "KBM-7103" manufactured by Shimadzu chemical Co., ltd. (long-chain epoxy silane coupling agent), and "KBM-7103" manufactured by Shimadzu chemical Co., ltd. (3, 3-trifluoropropyl trimethoxysilane).
The degree of the surface treatment with the surface treatment agent is preferably within a specific range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of the surface-treating agent, more preferably 0.2 to 3 parts by mass of the surface-treating agent, and still more preferably 0.3 to 2 parts by mass of the surface-treating agent.
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. From nothingThe carbon content per unit surface area of the inorganic filler is preferably 0.02mg/m from the viewpoint of improving dispersibility of the inorganic filler 2 The above is more preferably 0.1mg/m 2 The above is particularly preferably 0.2mg/m 2 The above. On the other hand, from the viewpoint of suppressing the rise in melt viscosity of the resin composition, it is preferably 1mg/m 2 Hereinafter, more preferably 0.8mg/m 2 The following is more preferable to be 0.5mg/m 2 The following is given.
The carbon amount per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is subjected to a washing treatment with a solvent such as Methyl Ethyl Ketone (MEK). Specifically, a sufficient amount of MEK was added as a solvent to the inorganic filler surface-treated with the surface treating agent, and the mixture was ultrasonically cleaned at 25 ℃ for 5 minutes. After the supernatant is removed and the solid component is dried, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, EMIA-320V manufactured by horiba, inc. can be used.
The inorganic filler (B) contained in the resin composition of the present invention is a specific inorganic filler (hereinafter also referred to as "high amorphous small-diameter inorganic filler") having an average particle diameter in the range of 0.5 to 12. Mu.m, and a crystalline silica content in the range of 0 mass% or more and less than 2.1 mass%. The resin composition of the present invention may contain 2 or more specific inorganic filler materials, but preferably at least 1 is silica. The resin composition of the present invention may contain an inorganic filler other than the high amorphous small-diameter inorganic filler, but preferably does not contain an inorganic filler other than the high amorphous small-diameter inorganic filler, as long as the desired effect of the present invention is not impaired.
The high amorphous small-diameter inorganic filler has an average particle diameter in the range of 0.5 μm to 12. Mu.m, as described above. Since the inorganic filler having a small diameter and a high amorphous state has a small average particle diameter, the degree of filling in the resin composition can be improved.
The lower limit of the average particle diameter of the inorganic filler may be set to be more than 0.5 μm, 0.6 μm or more, 0.7 μm or more, 0.8 μm or more, 0.9 μm or more, or 1.0 μm or more as long as the desired effect of the present invention is not impaired. The upper limit of the average particle diameter of the inorganic filler may be set to less than 12 μm, 10 μm or less, 8 μm or less, 6 μm or less, 5 μm or less, or 4.5 μm or less, as long as the desired effect of the present invention is not impaired, and the upper limit of the average particle diameter of the inorganic filler is preferably 10 μm or less, more preferably less than 10 μm, even more preferably 9 μm or less, particularly preferably 8 μm or less, from the viewpoint of reducing the content of crystalline silica to be described later.
(B) The average particle size of the components can be determined by laser diffraction scattering based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be produced by a laser diffraction scattering type particle size distribution measuring apparatus on a volume basis, and the median particle size can be measured as the average particle size. As a measurement sample, a sample obtained by weighing 100mg of an inorganic filler and 10g of methyl ethyl ketone into a vial and dispersing by ultrasonic waves for 10 minutes was used. For the measurement sample, a laser diffraction type particle size distribution measuring apparatus was used, blue and red were used as light source wavelengths, and the volume-based particle size distribution of the inorganic filler (B) was measured in a flow cell system, and the average particle size was calculated from the obtained particle size distribution as the median particle size. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, inc.
(B) The specific surface area of the inorganic filler is preferably 1m 2 Preferably 1.5m or more per gram 2 Preferably at least/g, more preferably at least 2m 2 Preferably at least 2.5m 2 And/g. The upper limit is not particularly limited, but is preferably 60m 2 Per gram of less than 50m 2 /g or less than 40m 2 And/g or less. The specific surface area can be obtained by adsorbing nitrogen gas onto the surface of a sample by a specific surface area measuring device (Macsorb HM-1210 manufactured by mountain Co., ltd.) according to the BET method, and calculating the specific surface area by the BET multipoint method.
As described above, the content of the crystalline silica in the high amorphous small-diameter inorganic filler is in the range of 0 mass% or more and less than 2.1 mass%. The high amorphous small-diameter inorganic filler has a low content of crystalline silica, and thus can exhibit the desired effects of the present invention. Further, as is clear from the examples in the columns of examples described later, the lower the content of crystalline silica, the closer to the detection limit, the better the stability of the viscosity life, and the more remarkable the desired effect of the present invention can be obtained. Further, although the higher the degree of filling of the inorganic filler, the lower the stability of the viscosity life tends to be in general, the higher the degree of filling of the inorganic filler can be than usual because the stability of the viscosity life is good if the present invention is employed.
From the viewpoint of better stability of viscosity life, the content of crystalline silica is preferably 2.0 mass% or less, 1.9 mass% or less, 1.8 mass% or less, 1.7 mass% or less, or 1.6 mass% or less, more preferably 1.5 mass% or less, 1.4 mass% or less, 1.3 mass% or less, 1.2 mass% or less, 1.1 mass% or less, or 1.0 mass% or less, and even more preferably 0.9 mass% or less, 0.8 mass% or less, 0.7 mass% or less, 0.6 mass% or less, 0.5 mass% or less, 0.4 mass% or less, 0.3 mass% or less, 0.2 mass% or less, or 0.1 mass% or less. The content of crystalline silica is particularly preferably not more than the detection limit amount and may be 0 mass%. On the other hand, from the viewpoint of obtaining an effect (for example, improvement in filling property or improvement in compatibility) due to the presence of crystalline silica, the content of crystalline silica is preferably more than 0 mass%, more preferably 0.01 mass% or more, 0.02 mass% or more, 0.03 mass% or more, 0.04 mass% or more, 0.05 mass% or more, 0.06 mass% or more, 0.07 mass% or more, or 0.08 mass% or more. Therefore, the content of crystalline silica is preferably within a range of more than 0 mass% and less than 2.1 mass%.
The content of crystalline silica is calculated based on an X-ray diffraction pattern obtained by X-ray diffraction measurement. The X-ray diffraction measurement can be performed using a commercially available X-ray diffraction analyzer, for example, an X-ray diffraction apparatus "SmartLab (registered trademark)" manufactured by Rigaku corporation. 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 power, measurement range of diffraction angle, scanning speed, and the like are appropriately set. Preferably, the content of crystalline silica is calculated by performing a Ritewald analysis on an X-ray diffraction pattern. The Ritewald analysis of the X-ray diffraction pattern is preferably performed using a dedicated software attached to an X-ray diffraction analyzer, for example, a qualitative analysis program PDXL attached to an X-ray diffraction apparatus "SmartLab (registered trademark)" manufactured by Rigaku corporation. The specialized software contains information on crystalline silica (usually α -quartz or cristobalite) and amorphous silica (amorphous silica). If the Ritewald analysis is used, the content of crystalline silica can be calculated even when the content of crystalline silica is 0.01 mass%, which is preferable.
The content of crystalline silica can be calculated by a method other than the above method. However, when the content of crystalline silica calculated by the above method is greatly different from the content of crystalline silica calculated by the above method (preferably, the method of the Litewald analysis), the above method should not be used. In the case of a method other than the above method, the content of crystalline silica may be calculated from the peak intensity of crystalline silica and the peak intensity (integrated value) of amorphous silica based on an X-ray diffraction pattern obtained by X-ray diffraction measurement, or the content of crystalline silica in an inorganic filler whose content of crystalline silica is unknown may be calculated using an X-ray diffraction pattern of a high amorphous small-diameter inorganic filler whose content of crystalline silica is known as a calibration curve.
As the high amorphous small-diameter inorganic filler, the inorganic filler A, B, C, D, E, F described in production examples 1 to 4 in columns of examples described later or a modification thereof (for example, a material in which the type of the surface treatment agent is changed, a material in which the surface treatment is not performed) can be used. The method for producing the high amorphous small-diameter inorganic filler is not limited. For a pair of As the high amorphous small diameter inorganic filler, a crystalline inorganic filler such as crystalline silica (for example, crystalline silica disclosed in Japanese patent application laid-open No. 2015-211086) can be used as a raw material, and for example, the heating temperature and heating time in the melting step in the melting method can be changed within the range of 500 to 1100℃for 1 to 12 hours, and it is preferable that the density of the obtained fused silica is 2.4g/cm 3 The heating temperature and heating time were adjusted under the following conditions (see japanese patent No. 6814906). From the viewpoint of obtaining an inorganic filler having a low crystalline silica content, it is preferable to perform the melting treatment in the melting method in a plurality of times (for example, 2 times). The high amorphous small-diameter inorganic filler may be amorphous inorganic filler such as amorphous silica containing no crystalline component.
As a result of the examination by the present inventors, it was found that when the inorganic filler is silica, if the melting treatment is performed a plurality of times, silica having a low content of crystalline silica (hereinafter also referred to as "high amorphous small diameter silica") tends to be obtained, and this is not changed depending on the type of silica. Further, whether or not the content of crystalline silica in the obtained inorganic filler is within the above-described range can be easily confirmed by calculating the content of crystalline silica by the above-described method, and if the content of crystalline silica is not within the above-described range, the operation such as increasing the number of melting steps may be performed to obtain the initial content of crystalline silica.
The amount of the high amorphous small-diameter inorganic filler is not particularly limited, but is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably more than 50% by mass, and may be 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, or 80% by mass, with respect to 100% by mass of the nonvolatile component in the resin composition, from the viewpoint of obtaining a cured product with suppressed warpage. The amount of the high amorphous small-diameter inorganic filler is not particularly limited, and may be 96 mass% or less, 95 mass% or less, 94 mass% or less, or 93 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The occurrence of warpage of the cured product of the resin composition containing the high amorphous small-diameter inorganic filler in the amount within the above range is suppressed. In addition, the cured product of the resin composition containing the high amorphous small-diameter inorganic filler in the amount within the above range can effectively reduce the thermal expansion coefficient.
The amount of the high amorphous small-diameter inorganic filler is not particularly limited, but is preferably 50% by volume or more, more preferably 55% by volume or more, still more preferably 60% by volume or more, still more preferably 65% by volume or more, and may be 66% by volume or more, 67% by volume or 68% by volume or more, with respect to 100% by volume of the nonvolatile component in the resin composition, from the viewpoint of obtaining a cured product with suppressed warpage. From the viewpoint of improving the desired effect of the present invention, the amount of the high amorphous small-diameter inorganic filler may be 95% by volume or less, 90% by volume or less, 85% by volume or less, or 83% by volume or less, relative to 100% by volume of the nonvolatile component in the resin composition. The cured product of the resin composition containing the high amorphous small-diameter inorganic filler in such an amount in the range can effectively reduce the thermal expansion coefficient.
[ (C) curing agent ]
The resin composition of the present invention preferably contains (C) a curing agent. (C) The curing agent generally has a function of reacting with the (a) curable resin to cure the resin composition. Examples of the (C) curing agent include an active ester curing agent, a phenol curing agent, a benzoxazine curing agent, an acid anhydride curing agent, an amine curing agent, and a cyanate curing agent. In one embodiment, at least 1 selected from the group consisting of acid anhydride-based curing agents, amine-based curing agents and phenol-based curing agents is used as the curing agent (C). When an acid anhydride-based curing agent, an amine-based curing agent or a phenol-based curing agent is used, warpage of the cured product can be generally suppressed. The curing agent may be used alone or in combination of 1 or more than 2.
As the curing agent (C), 1 or more selected from the group consisting of liquid curing agents and solid curing agents can be used, and liquid curing agents are preferable. In one embodiment, (C) the curing agent comprises a liquid curing agent. In another embodiment, (C) the curing agent comprises a solid curing agent.
"liquid curing agent" refers to a curing agent that is liquid at a temperature of 20 ℃, and "solid curing agent" refers to a curing agent that is solid at a temperature of 20 ℃.
Examples of the acid anhydride-based curing agent include curing agents having 1 or more acid anhydride groups in 1 molecule, and curing agents having 2 or more acid anhydride groups in 1 molecule are preferable. Specific examples of the acid anhydride-based curing agent include maleic anhydride-based polymers obtained by copolymerizing phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2, 5-dioxotetrahydro-3-furyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3'-4,4' -diphenyl sulfone tetracarboxylic dianhydride, 1, 3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (trimellitic anhydride), styrene and maleic acid. Examples of the commercial products of the acid anhydride-based curing agent include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Nippon chemical Co., ltd., and "YH306", "YH307" manufactured by Mitsubishi chemical Co., ltd., and "HN-2200", "HN-5500" manufactured by Hitachi chemical Co., ltd.
Examples of the amine curing agent include curing agents having 1 or more, preferably 2 or more amino groups in 1 molecule. Specific examples thereof include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like, and among these, aromatic amines are preferable. The amine curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine. As a specific example of the amine-based curing agent, examples thereof include 4,4' -methylenebis (2, 6-dimethylaniline), diphenyldiaminosulfone, 4' -diaminodiphenylmethane, 4' -diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyl toluenediamine, 4' -diaminodiphenyl ether, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dihydroxybenzidine, 2-bis (3-amino-4-hydroxyphenyl) propane 3, 3-dimethyl-5, 5-diethyl-4, 4-diphenyl methane diamine, 2-bis (4-aminophenoxy) phenyl) propane, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, and the like. As the amine curing agent, commercially available products can be used, and examples thereof include "SEIKACURE-S" manufactured by Seika, japan chemical Co., ltd. "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S", EPICURE W "manufactured by Mitsubishi chemical Co., ltd." DTDA "manufactured by Sumitomo chemical Co., ltd.).
Examples of the phenolic curing agent include curing agents having 1 or more, preferably 2 or more hydroxyl groups bonded to an aromatic ring such as a benzene ring or naphthalene ring in 1 molecule. Among them, a compound having a hydroxyl group bonded to a benzene ring is preferable. Further, from the viewpoints of heat resistance and water resistance, a phenolic curing agent having a phenolic structure is preferable. In addition, from the viewpoint of adhesion, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable. From the viewpoint of highly satisfying heat resistance, water resistance and adhesion, a novolac-type curing agent containing a triazine skeleton is particularly preferable.
Specific examples of the phenolic curing agent include "MEH-7700", "MEH-7810", "MEH-7851", "MEH-8000H" manufactured by Ming and Kagaku Co., ltd., "NHN", "CBN", "GPH" manufactured by Nippon Kagaku Co., ltd., "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165" manufactured by DIC, and "GDP-6115L", "GDP-6115H", "ELPC75" manufactured by Sigma Aldrich, inc., respectively.
(C) The reactive group equivalent of the curing agent is preferably 50g/eq to 3000g/eq, more preferably 100g/eq to 1000g/eq, still more preferably 100g/eq to 500g/eq, particularly preferably 100g/eq to 300g/eq. Reactive group equivalent means the mass of the curing agent per 1 equivalent of reactive group.
The amount of the curing agent (C) is preferably determined based on the number of reactive groups of the curable resin (A). For example, when the number of reactive groups of the curable resin (A) is 1, the number of reactive groups of the curing agent (C) is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.5 or more, preferably 5.0 or less, still more preferably 4.0 or less, still more preferably 3.0 or less. The "number of reactive groups of the curable resin" herein means a value obtained by dividing the mass of nonvolatile components of the curable resin present in the resin composition by the equivalent of reactive groups, and summing all the divided values. The "(number of reactive groups of (C) curing agent" means a value obtained by dividing the mass of the nonvolatile components of (C) curing agent present in the resin composition by the equivalent of reactive groups, and summing up the total.
In order to satisfy the above-mentioned range of the ratio of the number of active groups of the curing agent (C) to the number of reactive groups of the curable resin (A), the mass ratio of the component (C) to the component (A) ((A): (C)) is preferably in the range of 1:0.01 to 1:10. The mass ratio is more preferably in the range of 1:0.05 to 1:9, still more preferably in the range of 1:0.1 to 1:8.
The amount of the curing agent (C) is preferably 0.05 mass% or more, more preferably 0.1 mass% or more, particularly preferably 0.2 mass% or more, more preferably 25 mass% or less, more preferably 20 mass% or less, and still more preferably 15 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
[ (D) other additives ]
The resin composition of the present invention may further contain (D) other additives. Examples of the other additives in group 1 include 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.
(curing accelerator)
The resin composition of the present invention may further contain a curing accelerator as an optional component. If a curing accelerator is used, the curing time of the resin composition can be efficiently adjusted.
Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among them, imidazole-based curing accelerators are preferable. The curing accelerator may be used alone or in combination of 1 or more than 2.
Examples of the phosphorus curing accelerator include triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphine thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphine thiocyanate, and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.
Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-Dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, 1, 8-diazabicyclo [5.4.0] undecene-7, 4-dimethylaminopyridine, 2,4, 6-tris (dimethylaminomethyl) phenol, etc., preferably 4-dimethylaminopyridine and 1, 8-diazabicyclo [5.4.0] undecene.
Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-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-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2 '-methylimidazole- (1') ] -ethyl-s triazine, 2, 4-diamino-6- [2 '-undecylimidazole- (1') ] -ethyl-s triazine, 2, 4-diamino-6- [2 '-methyl-2' -undecylimidazole ] -2 '-ethyl-4-methylimidazole, 1' -cyanoethyl-2-cyanoethyl-phenylimidazole, 1 '-cyanoethyl-4-cyanoethyl-2-cyanoethyl-phenylimidazole and 1' -iminotriazine Imidazole compounds such as 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins. Preferably 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole.
As the imidazole curing accelerator, commercially available products may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi chemical corporation, and "Curezol 2MZ", "2E4MZ", "Cl1Z-CN", "Cl1Z-CNS", "Cl1Z-A", "2MZ-OK", "2MA-OK-PW", and "2PHZ" manufactured by Kabushiki Kaisha.
Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolylguanidine), dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] decen-5, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] decen-5, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolylguanide), and the like, and dicyandiamide and 1,5, 7-triazabicyclo [4.4.0] decen-5 are preferable.
Examples of the metal curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include an organocobalt complex such as cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, an organocopper complex such as copper (II) acetylacetonate, an organozinc complex such as zinc (II) acetylacetonate, an organoiron complex such as iron (III) acetylacetonate, an organonickel complex such as nickel (II) acetylacetonate, and an organomanganese complex such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
The amount of the curing accelerator is not less than 0% by mass, preferably not less than 0.01% by mass, more preferably not less than 0.05% by mass, particularly preferably not less than 0.1% by mass, more preferably not more than 5% by mass, more preferably not more than 4% by mass, and still more preferably not more than 3% by mass, based on 100% by mass of the nonvolatile component in the resin composition.
(silane coupling agent)
The resin composition of the present invention may further contain a silane coupling agent as an optional component. However, when a silane coupling agent is used as a surface treatment agent for an inorganic filler, the inorganic filler treated with the surface treatment agent is classified into the above-mentioned component (B). By including a silane coupling agent as an optional component, the combination of the resin component and the inorganic filler can be expected.
Examples of the silane coupling agent include an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, an alkoxysilane compound, an organosilane compound, and a titanate coupling agent. Among them, epoxy silane coupling agents containing an epoxy group and mercapto silane coupling agents containing a mercapto group are preferable, and epoxy silane coupling agents are particularly preferable. In addition, 1 kind of silane coupling agent may be used alone, or 2 or more kinds may be used in combination. In one embodiment, a single silane coupling agent is included as an optional component. In another embodiment, as an optional component, a plurality of, for example, 2 silane coupling agents are contained. The resin composition of the present invention preferably contains a plurality of silane coupling agents, and it is preferable that the silane coupling agent used as the surface treatment agent for the component (B) and the silane coupling agent used as the optional component contain a total of a plurality of silane coupling agents.
As the silane coupling agent, for example, commercially available ones can be used. Examples of the commercially available silane coupling agent include "KBM403" from Shimadzu chemical Co., ltd. (3-glycidoxypropyl trimethoxysilane), "KBM803" from Shimadzu chemical Co., ltd. (3-mercaptopropyl trimethoxysilane), "KBE903" from Shimadzu chemical Co., ltd. (3-aminopropyl triethoxysilane), "KBM573" from Shimadzu chemical Co., ltd. (N-phenyl-3-aminopropyl trimethoxysilane), "SZ-31" from Shimadzu chemical Co., ltd. (hexamethyldisilazane), "KBM103" from Shimadzu chemical Co., ltd. (phenyl trimethoxysilane), "KBM-4803" from Shimadzu chemical Co., ltd. (long-chain epoxy silane coupling agent), "KBM 7103" from Shimadzu chemical Co., ltd. (3, 3-trifluoropropyl trimethoxysilane), and "KBM5783" from Shimadzu chemical Co., ltd. ".
The amount of the silane coupling agent is 0 mass% or more, preferably 0.01 mass% or more, 0.05 mass% or more, or 0.1 mass% or more, preferably 10 mass% or less, 5 mass% or less, or 3 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
The amount of the silane coupling agent is 0 mass% or more, preferably 0.01 mass% or more, 0.1 mass% or more, or 0.2 mass% or more, preferably 15 mass% or less, 10 mass% or less, or 5 mass% or less, based on 100 mass% of the resin component in the resin composition.
(radical polymerizable Compound)
The resin composition of the present invention may further contain a radical polymerizable compound as an optional component. The radical polymerizable compound may be classified into the component (a).
As the radical polymerizable compound, a compound having an ethylenically unsaturated bond can be used. Examples of such a radically polymerizable compound include compounds having a radically polymerizable group such as vinyl, allyl, 1-butenyl, 2-butenyl, acryl, methacryl, fumaryl, maleimide, vinyl phenyl, styryl, cinnamoyl, and maleimide (2, 5-dihydro-2, 5-dioxo-1H-pyrrol-1-yl). The radical polymerizable compound may be used alone or in combination of at least 2 kinds.
Specific examples of the radical polymerizable compound include (meth) acrylic radical polymerizable compounds having 1 or 2 or more acryl groups and/or methacryl groups, styrene radical polymerizable compounds having 1 or 2 or more vinyl groups directly bonded to an aromatic carbon atom, allyl radical polymerizable compounds having 1 or 2 or more allyl groups, maleimide radical polymerizable compounds having 1 or 2 or more maleimide groups, and the like. Among them, a (meth) acrylic radical polymerizable compound is preferable.
The radical polymerizable compound preferably contains a polyoxyalkylene (polyalkylene oxide) structure. By using a radical polymerizable compound having a polyoxyalkylene structure, flexibility of a cured product of the resin composition can be improved.
The polyoxyalkylene structure may be of the formula (1): - (R) f O) n -a representation. In the formula (1), n generally 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 generally 101 or less, preferably 90 or less, more preferably 68 or less, still more preferably 65 or less. In the formula (1), R f Each independently represents an alkylene group which may have a substituent. The number of carbon atoms of the alkylene group is preferably 1 or more, more preferably 2 or more, still more preferably 6 or less, still more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, particularly preferably 2. Examples of the substituent which the alkylene group may have include a halogen atom, -OH, an alkoxy group, a primary or secondary amino group, an aryl group and, -NH 2 、-CN、-COOH、-C(O)H、-NO 2 Etc. Wherein the alkyl group preferably has no substituent. Specific examples of the polyoxyalkylene structure include a polyoxyethylene structure, a polyoxypropylene structure, a polyoxyn-butene structure, a poly (ethylene oxide-co-propylene oxide) structure, a poly (ethylene oxide-ran-propylene oxide) structure, and a poly (ethylene oxide) An alkene-alt-propylene oxide structure and a poly (ethylene oxide-block-propylene oxide) structure.
The number of polyoxyalkylene structures contained in 1 molecule of the radical polymerizable compound may be 1 or 2 or more. The number of the polyoxyalkylene structures contained in 1 molecule of the radical polymerizable compound is preferably 2 or more, more preferably 4 or more, further preferably 9 or more, particularly preferably 11 or more, more preferably 101 or less, more preferably 90 or less, further preferably 68 or less, particularly preferably 65 or less. When the radical polymerizable compound contains 2 or more polyoxyalkylene structures in 1 molecule, these polyoxyalkylene structures may be the same or different.
Examples of the commercially available products of the radical polymerizable compounds having a polyoxyalkylene structure include monofunctional acrylates "AM-90G", "AM-130G", "AMP-20GY", difunctional acrylates "A-1000", "A-B1206PE", "A-BPE-20", "A-BPE-30", monofunctional methacrylates "M-20G", "M-40G", "M-90G", "M-130G", "M-230G", and difunctional methacrylates "23G", "BPE-900", "BPE-1300N", "1206PE", which are manufactured by Xinzhou chemical Co. Further, examples of the "LIGHT ESTER BC", "LIGHT ESTER MA", "LIGHT ACRYLATE EC-A", "LIGHT ACRYLATE EHDG-AT" manufactured by Kyowa Kagaku Co., ltd., and "FA-023M" manufactured by Hitachi Kagaku Co., ltd., and "BLEMER (registered trademark) PME-4000", "BLEMER (registered trademark) 50POEO-800B", "BLEMER (registered trademark) PLE-200", "BLEMER (registered trademark) PLE-1300", "BLEMER (registered trademark) PSE-1300", "BLEMER (registered trademark) 43PAPE-600B", "BLEMER (registered trademark) ANP-300" manufactured by Hitachi Kagaku Co., ltd. In one embodiment, as the radical polymerizable compound containing a polyoxyalkylene structure, "M-130G" or "BPE-1300N" may be used.
The ethylenically unsaturated bond equivalent of the radical polymerizable compound is preferably 20g/eq to 3000g/eq, more preferably 50g/eq to 2500g/eq, still more preferably 70g/eq to 2000g/eq, particularly preferably 90g/eq to 1500g/eq. The ethylenically unsaturated bond equivalent means the mass of the radical polymerizable compound corresponding to each 1 equivalent of the ethylenically unsaturated bond.
The weight average molecular weight (Mw) of the radical polymerizable compound is preferably 150 or more, more preferably 250 or more, still more preferably 400 or more, more preferably 40000 or less, still more preferably 10000 or less, still more preferably 5000 or less, particularly preferably 3000 or less.
The amount of the radical polymerizable compound is 0 mass% or more, preferably 0.01 mass% or more, 0.05 mass% or more, or 0.1 mass% or more, preferably 15 mass% or less, 10 mass% or less, or 8 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
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 or more, preferably 25% by mass or less, 20% by mass or less, or 15% by mass, based on 100% by mass of the resin component in the resin composition.
(radical polymerization initiator)
The resin composition of the present invention may contain a radical polymerization initiator as an optional component. As the radical polymerization initiator, a thermal polymerization initiator which generates radicals upon heating is preferable. When the resin composition contains a radical polymerizable compound, the resin composition generally contains a radical polymerization initiator. The radical polymerization initiator may be used alone or in combination of 1 or more than 2.
Examples of the radical polymerization initiator include peroxide radical polymerization initiators and azo radical polymerization initiators. Among them, a peroxide-based radical polymerization initiator is preferable.
Examples of the peroxide radical polymerization initiator include hydrogen peroxide compounds such as 1, 3-tetramethylbutyl hydroperoxide; dialkyl compounds such as t-butylcumene peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, dicumyl peroxide, 1, 4-bis (1-t-butylperoxy-1-methylethyl) benzene, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) -3-hexyne; diacyl peroxide compounds such as dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, and the like; peroxy compounds such as t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyneodecanoate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxylaurate, 1-dimethylpropyl 2-ethylperoxyhexanoate, t-butyl 3, 5-trimethylperoxyhexanoate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxymaleate, and the like; etc.
Examples of the azo radical polymerization initiator include azonitrile compounds such as 2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobisisobutyronitrile, 2' -azobis (2-methylbutyronitrile), 1' -azobis (cyclohexane-1-carbonitrile), 1- [ (1-cyano-1-methylethyl) azo ] formamide, and 2-phenylazo-4-methoxy-2, 4-dimethyl-valeronitrile; 2,2 '-azobis [ 2-methyl-N- [1, 1-bis (hydroxymethyl) -2-hydroxyethyl ] propionamide ], 2' -azobis [ 2-methyl-N- [1, 1-bis (hydroxymethyl) ethyl ] propionamide ], 2 '-azobis [ 2-methyl-N- [2- (1-hydroxybutyl) ] -propionamide ], 2' -azobis [ 2-methyl-N- (2-hydroxyethyl) -propionamide ], azo amide compounds such as 2,2 '-azobis (2-methylpropionamide) dihydrate, 2' -azobis [ N- (2-propenyl) -2-methylpropionamide ], 2 '-azobis (N-butyl-2-methylpropionamide), and 2,2' -azobis (N-cyclohexyl-2-methylpropionamide); alkyl azo compounds such as 2,2 '-azobis (2, 4-trimethylpentane) and 2,2' -azobis (2-methylpropane); etc.
The radical polymerization initiator is preferably a substance having a medium temperature activity. Specifically, the radical polymerization initiator preferably has a 10-hour half-life temperature T10 (. Degree. C.) within a specific lower temperature range. The 10-hour half-life temperature T10 is preferably 50℃to 110℃and more preferably 50℃to 100℃and even more preferably 50℃to 80 ℃. Examples of such a radical polymerization initiator include "Luperox 531M80" manufactured by armema Fuji corporation, and "PERHEXYL (registered trademark) O" manufactured by solar oil corporation, and "MAIB" manufactured by fuji film and photoplethysmogram corporation.
The amount of the radical polymerization initiator is not particularly limited, but is preferably 0.01 mass% or more, more preferably 0.02 mass% or more, particularly preferably 0.05 mass% or more, more preferably 5 mass% or less, more preferably 2 mass% or less, and still more preferably 1 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
(polyether skeleton-containing Compound having reactive functional group)
The resin composition of the present invention may further contain a polyether skeleton-containing compound having a reactive functional group as an optional component. The polyether skeleton-containing compound having a reactive functional group can be classified as the (a) component.
The resin composition of the present invention may further contain a polyether skeleton-containing compound having a reactive functional group as an optional component. If a polyether skeleton-containing compound having a reactive functional group is used, warpage of a cured product of the resin composition can be suppressed. The polyether skeleton-containing compound having a reactive functional group may be used alone in an amount of 1 kind or in an amount of 2 or more kinds.
The polyether skeleton-containing compound having a reactive functional group means 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 1 or more monomer units selected from the group consisting of an ethylene oxide unit and a propylene oxide unit. Accordingly, the polyether skeleton-containing compound having a reactive functional group is preferably a polyether skeleton not including a monomer unit having 4 or more carbon atoms such as a butylene oxide unit or a phenylene oxide unit. In addition, the polyether skeleton-containing compound having a reactive functional group may contain a hydroxyl group as the reactive functional group.
The polyether backbone-containing compound having a reactive functional group may contain a silicone (silicone) backbone. Examples of the silicone skeleton include polydialkylsiloxane skeletons such as polydimethylsiloxane skeletons; polydiaryl siloxane skeletons such as polydiphenyl siloxane skeletons; a polyalkylaryl siloxane skeleton such as a polymethylphenyl siloxane skeleton; polydialkyl-diaryl siloxane backbones such as polydimethyl-diphenyl siloxane backbones; polydialkyl-alkylaryl siloxane backbones such as polydimethyl-methyl phenyl siloxane backbones; polydiaryl-alkylaryl siloxane skeletons such as polydiphenyl-methylphenyl siloxane skeletons are preferred, polydialkylsiloxane skeletons are more preferred, and polydimethyl siloxane skeletons are particularly preferred. The polyether skeleton-containing compound containing an organosilicon skeleton may be, for example, a polyoxyalkylene-modified organosilicon, an alkyl-etherified polyoxyalkylene-modified organosilicon (a polyoxyalkylene-modified organosilicon in which at least a part of the terminal of the polyether skeleton is an alkoxy group), or the like.
The polyether skeleton-containing compound having a reactive functional group may contain a polyester skeleton. The polyester skeleton is preferably an aliphatic polyester skeleton. The hydrocarbon chain contained in the aliphatic polyester skeleton may be linear or branched, but is preferably branched. The number of carbon atoms contained in the polyester skeleton may be, for example, 4 to 16. The polyester skeleton may be formed from polycarboxylic acid, lactone, or an anhydride thereof, and thus the polyether skeleton-containing compound having a reactive functional group containing a polyester skeleton may have a carboxyl group at a terminal of a molecule, but preferably has a hydroxyl group as a reactive functional group at a terminal of a molecule.
Examples of the polyether skeleton-containing compound having a reactive functional group include linear polyoxyalkylene glycols (linear polyalkylene glycols) such as polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene glycol, and the like; polyoxyalkylene glycols (polyalkylene glycols) such as polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene trimethylolpropane ether, polyoxypropylene trimethylolpropane ether, polyoxyethylene diglyceryl ether, polyoxypropylene diglyceryl ether, polyoxyethylene pentaerythritol ether, polyoxypropylene pentaerythritol ether, polyoxyethylene sorbitol (polyoxyethylene sorbit), polyoxypropylene sorbitol, polyoxyethylene polyoxypropylene sorbitol and the like; polyoxyalkylene alkyl ethers such as polyoxyethylene monoalkyl ether, polyoxyethylene dialkyl ether, polyoxypropylene monoalkyl ether, polyoxypropylene dialkyl ether, polyoxyethylene polyoxypropylene monoalkyl ether, and polyoxyethylene polyoxypropylene dialkyl ether; polyoxyalkylene esters (including acetate, propionate, butyrate, (meth) acrylate, etc.) such as polyoxyethylene monoester, polyoxyethylene diester, polypropylene glycol monoester, polypropylene glycol diester, polyoxyethylene polyoxypropylene monoester, polyoxyethylene polyoxypropylene diester, etc.; polyoxyalkylene alkyl ether esters (including acetate, propionate, butyrate, (meth) acrylate, etc.) such as polyoxyethylene monoester, polyoxyethylene diester, polyoxypropylene monoester, polyoxypropylene diester, polyoxyethylene alkyl ether ester, polyoxypropylene alkyl ether ester, polyoxyethylene polyoxypropylene alkyl ether ester, etc.; polyoxyalkylene alkylamines such as polyoxyethylene alkylamine, polyoxypropylene alkylamine and polyoxyethylene polyoxypropylene alkylamine; polyoxyalkylene alkylamides such as polyoxyethylene alkylamides, polyoxypropylene alkylamides and polyoxyethylene polyoxypropylene alkylamides; polyoxyalkylene modified silicones such as polyoxyethylene polydimethylsiloxane (polyoxyethylene dimeticone), polyoxypropylene polydimethylsiloxane, polyoxyethylene polydimethylsiloxane (siloxy) alkyl polydimethylsiloxane, polyoxypropylene polydimethylsiloxane alkyl polydimethylsiloxane, polyoxyethylene polyoxypropylene polydimethylsiloxane alkyl polydimethylsiloxane and polyoxyethylene polyoxypropylene polydimethylsiloxane alkyl polydimethylsiloxane; and alkyl etherified polyoxyalkylene modified silicone (polyoxyalkylene modified silicone in which at least a part of the end of the polyether skeleton is an alkoxy group) such as polyoxyethylene alkyl ether polydimethylsiloxane, polyoxypropylene alkyl ether polydimethylsiloxane, polyoxyethylene alkyl ether polydimethylsiloxane, polyoxypropylene alkyl ether polydimethylsiloxane, and polyoxyethylene polyoxypropylene alkyl ether polydimethylsiloxane.
The number average molecular weight of the polyether skeleton-containing compound having a reactive functional group is preferably 500 to 40000, more preferably 500 to 20000, still more preferably 500 to 10000. The weight average molecular weight of the polyether skeleton-containing compound is preferably 500 to 40000, more preferably 500 to 20000, still more preferably 500 to 10000. The number average molecular weight and the weight average molecular weight can be measured as values in terms of polystyrene by Gel Permeation Chromatography (GPC).
The polyether skeleton-containing compound having a reactive functional group is preferably in a liquid state at 25 ℃. The polyether skeleton-containing compound having a reactive functional group preferably has a viscosity of 100000 mPas or less, more preferably 50000 mPas or less, still more preferably 30000 mPas or less, 10000 mPas or less, 5000 mPas or less, 4000 mPas or less, 3000 mPas or less, 2000 mPas or less, or 1500 mPas or less at 25 ℃. The lower limit of the viscosity at 25℃of the polyether skeleton-containing compound having a reactive functional group is preferably 10 mPas or more, more preferably 20 mPas or more, still more preferably 30 mPas or more, 40 mPas or more or 50 mPas or more. The viscosity may be a viscosity (mpa·s) measured by a type B viscometer.
Examples of the commercial products of the polyether skeleton-containing compound having a reactive functional group include "PLONN#102", "PLONON#104", "PLONON#201", "PLONON#202B", "PLONON#204", "PLONON#208", "UNILUBE 70DP-600B", "UNILUBE 70DP-950B" (polyoxyethylene polyoxypropylene glycol), "Pluronic" L-23"," 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-84 "," Pluronic P-85"," Pluronic P-103"," Pluronic F-68"," Pluronic P-17 "," Pluronic R-17 "," Pluronic-25 "," Pluronic-17 "," Pluronic-2 ", and" PLONR-17 "of solar cell" of solar oil company, "KF-6011", "KF-6011P", "KF-6012", "KF-6013", "KF-6015", "KF-6017P", "KF-6043", "KF-6004", "KF351A", "KF352A", "KF353", "KF354L", "KF355A", "KF615A", "KF945", "KF-640", "KF-642", "KF-643", "KF-644", "KF-6020", and "KF-6020" manufactured by Xin Yuan organosilicon Co Ltd "KF-6204", "X22-4515", "KF-6028P", "KF-6038", "KF-6048", "KF-6025" (polyoxyalkylene modified silicone) and the like. As the polyether skeleton-containing compound having a reactive functional group, a polyester polyol synthesized by synthesis of "polyester polyol a" described later or a modification thereof can be used.
The amount of the polyether skeleton-containing compound having a reactive functional group is 0 mass% or more, preferably 0.01 mass% or more, 0.05 mass% or more, or 0.1 mass% or more, more preferably 15 mass% or less, 10 mass% or less, or 8 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
The amount of the polyether skeleton-containing compound having a reactive functional group is 0 mass% or more, preferably 0.01 mass% or more, 0.1 mass% or more, or 0.2 mass% or more, more preferably 25 mass% or less, 20 mass% or less, or 15 mass% or less, based on 100 mass% of the resin component in the resin composition.
(high molecular weight component)
The resin composition of the present invention may contain a high molecular weight component. The high molecular weight component may function as a plasticizer. As the commercial products of the high molecular weight component, there may be mentioned butadiene homopolymers "B-1000", "B-2000", "B-3000" manufactured by Kao corporation, japan, etc. The high molecular weight component may be used alone in an amount of 1 or in an amount of 2 or more.
The number average molecular weight of the high molecular weight component is preferably 500 to 40000, more preferably 500 to 20000, still more preferably 500 to 10000. The weight average molecular weight of the high molecular weight component is preferably 500 to 40000, more preferably 500 to 20000, still more preferably 500 to 10000. The number average molecular weight and the weight average molecular weight can be measured as values in terms of polystyrene by Gel Permeation Chromatography (GPC).
The high molecular weight component is in a liquid state at 25 ℃, or the viscosity of the high molecular weight component at 45 ℃ is preferably 100000 mPas or less, more preferably 50000 mPas or less, further preferably 30000 mPas or less, 10000 mPas or less, 5000 mPas or less, 4000 mPas or less, 3000 mPas or less, 2000 mPas or less, 1500 mPas or 500 mPas or less. The lower limit of the viscosity at 25℃of the polyether skeleton-containing compound having a reactive functional group is preferably 0.5 mPas or more, more preferably 1 mPas or more, still more preferably 2 mPas or more, 3 mPas or more, or 4 mPas or more. The viscosity may be a viscosity (mpa·s) measured by a type B viscometer.
The amount of the high molecular weight component is not limited to 100% by mass of the nonvolatile component in the resin composition, but is preferably 0% by mass or more, more preferably 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, and 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 preferably 0% by mass or more, more preferably 0.01% by mass or more, 0.1% by mass or more, or 0.2% by mass or more, and more preferably 15% by mass or less, 10% by mass or less, or 8% by mass or less.
Examples of group 2 of other additives include organic fillers such as rubber particles, polyamide particles, and silicone particles; thermoplastic resins such as polycarbonate resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, and polyester resins; a carbodiimide compound; organocopper compounds, organozinc compounds, organocobalt compounds, and other organometallic compounds; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine, etc.; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as Benton and montmorillonite; an antifoaming agent such as an organosilicon antifoaming agent, an acrylic antifoaming agent, a fluorine antifoaming agent, and a vinyl resin antifoaming agent; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; an adhesion improver such as urea silane; adhesion-imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents; antioxidants such as hindered phenol antioxidants and hindered amine antioxidants; fluorescent whitening agents such as stilbene derivatives; a surfactant such as a fluorine-based surfactant; and flame retardants such as phosphorus flame retardants (e.g., phosphate compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen flame retardants (e.g., melamine sulfate), halogen flame retardants, and inorganic flame retardants (e.g., antimony trioxide). The additive may be used alone in 1 kind, or may be used in combination of 2 or more kinds in any ratio.
[ solvent ]
The resin composition of the present invention may further contain any solvent as a volatile component. As the solvent, an organic solvent can be mentioned. The solvent may be used alone or in combination of 2 or more kinds at an arbitrary ratio. In one embodiment, the smaller the amount of solvent, the better. When the content of the solvent is set to 100% by mass, the content of the nonvolatile component in the resin composition is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less, still more preferably 0.01% by mass or less, and particularly preferably no content (0% by mass) of the volatile component. In another embodiment, a solvent is included. This improves the workability as a resin varnish.
[ method for producing resin composition ]
The resin composition of the present invention can be produced, for example, by mixing the above-described components. The above components may be mixed partially or completely at the same time or sequentially. The temperature may be set appropriately during the mixing of the components, so that heating and/or cooling may be performed for part of the time or throughout. In addition, stirring or shaking may be performed during mixing of the components.
[ Properties of the resin composition ]
The resin composition of the present invention comprises (A) a curable resin and (B) an inorganic filler, wherein the inorganic filler has an average particle diameter of 0.5-12 [ mu ] m, and the crystalline silica content in the inorganic filler is in the range of 0-2.1 mass%. Thus, the present invention provides a resin composition having a stable viscosity life, and a resin sheet, a circuit board and a semiconductor chip package using the resin composition. As will be exemplified in columns of examples described later, it has been found that the presence of crystalline silica in the case where the average particle diameter of the inorganic filler is controlled to be within a small range impairs the stability of viscosity life, and therefore the upper limit thereof should be limited, and the present invention has been completed based on this knowledge.
The stability of the viscosity life of the resin composition of the present invention can be evaluated by, for example, the method described in the column of examples described later. Specifically, when the initial melt viscosity MV0 and the 12-hour post-melt viscosity MV12 are measured and the tackifying ratio accompanying the lapse of 12 hours is obtained as the ratio of the 12-hour post-melt viscosity MV12 to the initial melt viscosity MV0 (i.e., MV12/MV 0), the tackifying ratio of the resin composition of the present invention is preferably less than 1.7, more preferably less than 1.6, even more preferably less than 1.5, particularly preferably less than 1.4, and usually more than 1.0.
In this case, the initial melt viscosity MV0 of the solvent-free resin composition (resin paste) according to an 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, and even more preferably in the range of 20 poise to 600 poise. The 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 from more than 20 poise to less than 1360 poise, more preferably in the range of from 21 poise to 1190 poise, and even more preferably in the range of from 21 poise to 1020 poise after 12 hours. In addition, when the resin paste according to one embodiment of the present invention is used, the inorganic filler can be highly filled, so that a cured product in which warpage is suppressed can be obtained. The amount of warpage can be measured by a method described later, for example, the amount of warpage is less than 1500. Mu.m, preferably less than 1300. Mu.m, more preferably less than 1100. Mu.m.
The initial melt viscosity MV0 of the resin composition layer formed using the solvent-containing resin composition (resin varnish) according to another embodiment of the present invention is preferably in the range of 20 poise to 20000 poise, more preferably in the range of 1000 poise to 19000 poise, and even more preferably in the range of 2000 poise to 18000 poise. Further, the melt viscosity MV12 after 12 hours of the resin composition layer formed by the solvent-containing resin composition (resin varnish) according to another embodiment of the present invention is preferably in the range of more than 20 poise to less than 34000 poise, more preferably in the range of 1100 poise to 30000 poise, still more preferably in the range of 2200 poise to 25000 poise. In addition, if the resin varnish according to one embodiment of the present invention is used, the inorganic filler can be highly filled, so that a cured product in which warpage is suppressed can be obtained. The amount of warpage can be measured by a method described later, for example, the amount of warpage is less than 2000. Mu.m, preferably less than 1800. Mu.m, more preferably less than 1600. Mu.m.
In one embodiment, the resin composition of the present invention is in the form of a paste. The resin composition (also referred to as "resin paste") in the form of a paste can be easily molded by compression molding. In another embodiment, 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, the operability can be improved. As described above, the thickening ratio is small in both the paste resin composition according to one embodiment and the resin composition (resin varnish) according to another embodiment, and therefore even if the thickness is increased, the occurrence of flow marks due to the non-uniformity of composition, the occurrence of embedding defects due to the non-uniformity of viscosity, and the like may be suppressed, and a circuit board and a semiconductor chip package having a good yield can be provided. Therefore, the resin composition of the present invention is also suitable for forming a resin composition layer having a thickness of 50 μm or more. Further, since the resin composition of the present invention can highly fill the inorganic filler, a circuit board and a semiconductor chip package in which warpage is suppressed can be provided.
[ use of resin composition ]
The resin composition of the present invention can be used favorably as a resin composition for sealing an electronic device such as an organic EL device or a semiconductor (sealing resin composition), and can be used particularly favorably as a resin composition for sealing a semiconductor (semiconductor sealing resin composition), preferably as a resin composition for sealing a semiconductor chip (semiconductor chip sealing resin composition). In addition, the resin composition may be used as a resin composition for insulation purposes for an insulation layer in addition to sealing purposes. For example, the resin composition can be suitably used as an insulating layer for forming a semiconductor chip package, for example, a resin composition for forming a rewiring forming layer (a resin composition for an insulating layer for a semiconductor chip package, a resin composition for a rewiring forming layer), or a resin composition for forming an insulating layer for a circuit board (including a printed wiring board) (a resin composition for an insulating layer for a circuit board).
As described above, the resin composition of the present invention can be used as a material for forming a sealing layer or an insulating layer of a semiconductor chip package. Examples of the semiconductor chip package include FC-CSP, MIS-BGA package, ETS-BGA package, fan-out WLP (wafer level package ), fan-in WLP, fan-out PLP (panel level package ), and fan-in PLP.
In addition, the resin composition can be used as an underfill, for example, as a material of MUF (molded underfill, molding Under Filling) used after the semiconductor chip is attached to a substrate.
The resin composition can be used in a wide range of applications using a resin composition such as a resin sheet, a sheet laminate such as a prepreg, a solder resist, a die bonding material, a hole filling resin, and a component embedding resin.
[ resin sheet ]
The resin sheet according to one embodiment of the present invention includes at least a support and a resin composition layer provided on the support, and optionally includes 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, by a known method, and the material used for the support can be arbitrarily selected.
The use of the resin sheet is the same as that of the resin composition of the present invention. Examples of applicable packages using a circuit board include FC-CSP, MIS-BGA, and ETS-BGA packages. Examples of applicable semiconductor chip packages include fan-out WLP, fan-in WLP, fan-out PLP, and fan-in PLP. In addition, a resin sheet may be used as a material of the MUF used after the semiconductor chip is connected to the substrate. In addition, the resin sheet can be used for other wide applications requiring high insulation reliability.
[ Circuit Board ]
The circuit board according to one embodiment of the present invention may contain a cured product of the resin composition of the present invention. The circuit board can be manufactured by a known method, for example, and the material used for the base material and the conductor layer that can be formed on the base material can be arbitrarily selected.
In the production of a circuit board, a substrate is prepared, and then, for example, a resin composition layer containing the resin composition of the present invention is formed on the substrate according to a known method. For example, the formation of the resin composition layer may be performed by a compression molding method. In the compression molding method, a base material and a resin composition are generally placed in a mold, and the resin composition is heated as needed by applying pressure to the resin composition in the mold, thereby forming a resin composition layer on the base material.
The specific operation of the compression molding method can be performed, for example, as follows. As a mold for compression molding, an upper mold and a lower mold were prepared. Further, a resin composition is coated on the substrate. The substrate coated with the resin composition was mounted on a lower die. Then, the upper mold and the lower mold are clamped, and the resin composition is heated and pressurized to perform compression molding.
The specific operation of the compression molding method may be performed as follows, for example. As a mold for compression molding, an upper mold and a lower mold were prepared. The resin composition is carried on the lower die. In addition, a base material and a release film which is used as needed are mounted on the upper die. Then, the upper mold and the lower mold are clamped so that the resin composition carried on the lower mold is brought into contact with the base material attached to the upper mold, and compression molding is performed by heating and pressurizing.
Molding conditions vary depending on the composition of the resin composition of the present invention, and appropriate conditions may be employed to achieve good sealing. For example, the temperature of the mold at the time of molding is preferably 70℃or higher, more preferably 80℃or higher, particularly preferably 90℃or higher, and still more preferably 200℃or lower. The pressure applied during molding is preferably 1MPa or more, more preferably 3MPa or more, particularly preferably 5MPa or more, more preferably 50MPa or less, more preferably 30MPa or less, particularly preferably 20MPa or less. The curing time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 3 minutes or more, more preferably 100 minutes or less, more preferably 90 minutes or less, and in one embodiment, 60 minutes or less, 30 minutes or less, or 20 minutes or less. Typically, after the resin composition layer is formed, the mold is removed. The removal of the mold may be performed before or after the heat curing of the resin composition layer.
After forming the resin composition layer on the substrate, the resin composition layer is thermally cured (post-cured) to form a cured layer. The heat curing conditions of the resin composition layer may be different depending on the kind of the resin composition, but the curing temperature is usually in the range of 120 to 240 ℃, preferably 150 to 220 ℃, more preferably 170 to 200 ℃, and the curing time is in the range of 5 to 120 minutes, preferably 10 to 100 minutes, more preferably 15 to 90 minutes.
The resin composition layer may be subjected to a preheating treatment of heating at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer may be preheated at a temperature of usually 50℃or higher and lower than 120℃or lower, preferably 60℃or higher and 110℃or lower, more preferably 70℃or higher and 100℃or lower, for usually 5 minutes or higher, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, before the resin composition layer is thermally cured.
In this way, a circuit board having a cured product layer formed from the cured product of the resin composition of the present invention can be produced. The method for manufacturing a circuit board may further include any steps.
[ semiconductor chip Package ]
The semiconductor chip package according to one embodiment of the present invention includes a cured product of the resin composition of the present invention. The semiconductor chip package may be, for example, as follows.
The semiconductor chip package according to the first example includes the above-described circuit board and a semiconductor chip mounted on the circuit board. The semiconductor chip package may be manufactured by bonding a semiconductor chip to a circuit substrate.
The bonding conditions between the circuit board and the semiconductor chip may be any conditions that can connect the terminal electrode of the semiconductor chip to the circuit wiring of the circuit board. For example, conditions used in flip-chip mounting of a semiconductor chip may be employed. For example, the semiconductor chip and the circuit board may be bonded to each other with an insulating adhesive interposed therebetween.
As an example of the bonding method, a method of crimping a semiconductor chip to a circuit board is given. The pressure conditions are such that the pressure temperature is usually in the range of 120 to 240 ℃, preferably 130 to 200 ℃, more preferably 140 to 180 ℃, and the pressure time is usually in the range of 1 to 60 seconds, preferably 5 to 30 seconds.
Further, as another example of the bonding method, a method of bonding a semiconductor chip to a circuit board by reflow soldering is given. The reflow conditions may be set in the range of 120℃to 300 ℃.
After the semiconductor chip is bonded to the circuit substrate, the semiconductor chip may be filled with a molding underfill material. As the molding underfill material, the above-mentioned resin composition can be used. Therefore, the method comprises a step of curing the resin composition of the present invention.
The semiconductor chip package according to the second example includes a semiconductor chip and a cured product of the resin composition of the present invention sealing the semiconductor chip. In such a semiconductor chip package, the cured product of the resin composition of the present invention generally functions as a sealing layer. As a semiconductor chip package according to the second example, for example, a fan-out WLP is given.
Fig. 1 is a cross-sectional view schematically showing a configuration of a fan-out WLP as an example of a semiconductor chip package according to the present embodiment. For example, as shown in fig. 1, a semiconductor chip package 100 as a fan-out WLP includes: the semiconductor chip 110, the sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110, the rewiring forming layer 130 as an insulating layer provided on the surface of the semiconductor chip 110 opposite to the sealing layer 120, the rewiring layer 140 as a conductor layer, the solder resist layer 150, and the bump 160.
The method for manufacturing the semiconductor chip package comprises the following steps:
(A) A step of laminating a temporary fixing film on a base material;
(B) A step of temporarily fixing the semiconductor chip to the temporary fixing film;
(C) Forming a sealing layer on the semiconductor chip;
(D) A step of peeling the base material and the temporary fixing film from the semiconductor chip;
(E) Forming a rewiring forming layer on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled off;
(F) Forming a rewiring layer as a conductor layer on the rewiring forming layer; and
(G) And forming a solder resist layer on the rewiring layer.
In addition, the method for manufacturing the semiconductor chip package may include:
(H) And dicing the plurality of semiconductor chip packages into individual semiconductor chip packages to form individual semiconductor chip packages.
(Process (A))
The step (a) is a step of laminating a temporary fixing film on a base material. The lamination conditions of the base material and the temporary fixing film may be the same as those of the base material and the resin sheet in the method for manufacturing a circuit board.
Examples of the base material include a silicon wafer, a glass substrate, a metal substrate such as copper, titanium, stainless steel, or a cold rolled steel Sheet (SPCC), a substrate obtained by impregnating glass fibers with an epoxy resin or the like and performing a heat curing treatment, a substrate formed of a bismaleimide-triazine resin such as BT resin, and the like.
The temporary fixing film may be made of any material that can be peeled off from the semiconductor chip and that can temporarily fix the semiconductor chip. As a commercial product, there may be mentioned "REVALPHA" manufactured by Nito electric Co., ltd.
(Process (B))
The step (B) is a step of temporarily fixing the semiconductor chip to the temporary fixing film. Temporary fixing of the semiconductor chip can be performed using, for example, a flip chip bonder, a chip mounter, or the like. The layout and the number of arrangement of the semiconductor chips may be appropriately set according to the shape, size, the number of production of the semiconductor chip packages as targets, and the like of the temporary fixing film. For example, the semiconductor chips may be temporarily fixed by being arranged in a matrix of a plurality of rows and a plurality of columns.
(Process (C))
The step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer can be formed by using a cured product of the resin composition of the present invention. The sealing layer is generally formed by a method including a step of forming a resin composition layer on a semiconductor chip and a step of forming a cured product layer as a sealing layer by thermally curing the resin composition layer. The formation of the resin composition layer on the semiconductor chip may be performed by the same method as the formation method of the resin composition layer on the base material described in the above [ circuit board ], except that, for example, a semiconductor chip is used instead of the substrate.
After forming a resin composition layer on a semiconductor chip, the resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor chip. Therefore, the method comprises a step of curing the resin composition of the present invention. Thus, the sealing of the semiconductor chip based on the cured product of the resin composition of the present invention is performed. The heat curing conditions of the resin composition layer may be the same as those of the resin composition layer in the method for producing a circuit board. Further, the resin composition layer may be subjected to a preheating treatment of heating at a temperature lower than the curing temperature before the resin composition layer is thermally cured. The pretreatment conditions for the preheating treatment may be the same as those for the preheating treatment in the method for producing a circuit board.
(Process (D))
The step (D) is a step of peeling the base material and the temporary fixing film from the semiconductor chip. The peeling method is preferably a method suitable for the material of the temporary fixing film. Examples of the peeling method include a method of peeling a temporary fixing film by heating, foaming, or swelling the temporary fixing film. Further, as a peeling method, for example, a method of peeling a temporary fixing film by irradiating the temporary fixing film with ultraviolet rays through a base material to reduce the adhesion of the temporary fixing film is exemplified.
In the method of peeling the temporary fixing film by heating, foaming or expanding, the heating condition is usually that the temporary fixing film is heated at 100 to 250℃for 1 to 90 seconds or 5 to 15 minutes. In the method of peeling the temporary fixing film by irradiating ultraviolet rays to reduce the adhesion of the temporary fixing film, the irradiation amount of ultraviolet rays is usually 10mJ/cm 2 ～1000mJ/cm 2 。
If the base material and the temporary fixing film are peeled off from the semiconductor chip as described above, the surface of the sealing layer is exposed. The method of manufacturing a semiconductor chip package may include a step of polishing a surface of the exposed sealing layer. The surface smoothness of the sealing layer can be improved by polishing. As the polishing method, the same method as described in the method for manufacturing a circuit board can be used.
(Process (E))
The step (E) is a step of forming a layer of rewiring as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled off. Generally, the rewiring forming layer is formed on the semiconductor chip and the sealing layer.
Any material having insulating properties can be used as the material of the rewiring forming layer. When the sealing layer is formed from a cured product of the resin composition of the present invention, the rewiring-forming layer formed on the sealing layer may be formed from a photosensitive resin composition.
After the formation of the rewiring formation layer, a via hole is usually formed in the rewiring formation layer in order to connect the semiconductor chip and the rewiring layer between layers. In the case where the rewiring-forming layer is formed of a photosensitive resin composition, the method of forming the via hole generally includes exposing the surface of the rewiring-forming layer through a mask. Examples of the active energy ray include ultraviolet rays, visible rays, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferred. Examples of the exposure method include a contact exposure method in which a mask is brought into close contact with the rewiring forming layer to expose the rewiring forming layer, and a non-contact exposure method in which exposure is performed using parallel light rays without bringing the mask into close contact with the rewiring forming layer.
Since the latent image can be formed on the rewiring formation layer by the exposure, a part of the rewiring formation layer is removed by development thereafter, and a via hole can be formed as an opening portion penetrating the rewiring formation layer. The development may be performed by either wet development or dry development. Examples of the developing method include a dipping method, a spin-coating immersing method, a spraying method, a brushing method, and a blade coating method, and the spin-coating immersing method is preferable from the viewpoint of resolution.
The shape of the through hole is not particularly limited, but generally circular (substantially circular) is employed. The top diameter of the through hole is, for example, 50 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less. Here, the top diameter of the via hole means the diameter of the via hole opening at the surface of the rewiring forming layer.
(Process (F))
The step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring layer. The method of forming the rewiring layer on the rewiring layer may be the same as the method of forming the conductor layer on the cured layer in the method of manufacturing the circuit board. Further, the step (E) and the step (F) may be repeated, and the rewiring layer and the rewiring forming layer may be alternately stacked (stacked).
(Process (G))
The step (G) is a step of forming a solder resist layer on the rewiring layer. As a material of the solder resist layer, any material having insulating properties can be used. Among them, from the viewpoint of ease of manufacturing the semiconductor chip package, a photosensitive resin and a thermosetting resin are preferable. Further, as the thermosetting resin, the resin composition of the present invention can be used. Accordingly, the resin composition of the present invention may be cured.
In the step (G), a bump process for forming a bump may be performed as needed. Bump processing may be performed using solder balls, solder plating, and the like. The formation of the through hole in the bump processing may be performed in the same manner as in the step (E).
(Process (H))
The method for manufacturing a semiconductor chip package may further include a step (H) in addition to the steps (a) to (G). The step (H) is a step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages and singulating the individual semiconductor chip packages. The method of dicing the semiconductor chip packages into individual semiconductor chip packages is not particularly limited.
As a semiconductor chip package according to a third example, there is a semiconductor chip package 100 as shown in an example in fig. 1, in which a rewiring forming layer 130 or a solder resist layer 150 is formed from a cured product of the resin composition of the present invention.
[ semiconductor device ]
The semiconductor device includes a semiconductor chip package. Examples of the semiconductor device include various semiconductor devices used for electric products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, televisions, and the like) and vehicles (for example, two-wheeled vehicles, automobiles, electric trains, ships, and aircraft, and the like).
Examples
Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to these examples. In the following, unless otherwise indicated, "part" and "%" indicating amounts refer to "part by mass" and "% by mass", respectively. The temperature conditions and pressure conditions in the case where the temperature is not specified are room temperature (25 ℃) and atmospheric pressure (1 atm).
First, the resin composition will be described.
Production example 1: manufacturing of inorganic filler A
The highly amorphous small-diameter silica B1 obtained by performing the melting step in the 2-time melting method using crystalline silica as a raw material was subjected to a surface treatment with a surface treatment agent "KBM573" (N-phenyl-3-aminopropyl trimethoxysilane) manufactured by shi chemical industry co.
The inorganic filler A had an average particle diameter of 3.1 μm and a specific surface area of 5.1m 2 And/g. The average particle diameter and specific surface area were measured by the methods described above.
The content of crystalline silica in the inorganic filler a was calculated based on an X-ray diffraction pattern obtained by X-ray diffraction measurement. For the X-ray diffraction measurement, an X-ray diffraction analyzer "SmartLab (registered trademark)" manufactured by Rigaku corporation was used. Specifically, as the content of crystalline silica, a value of 0.3% was used, which was calculated by performing a ritrewet analysis on an X-ray diffraction pattern using an X-ray derivative analyzer (and an attached qualitative analysis program PDXL).
Production examples 2 and 3: manufacturing of inorganic filler B, C
The high amorphous small diameter silica B2 obtained by performing the melting process in the 2-time melting method and the high amorphous small diameter silica B3 obtained by performing the melting process in the 1-time melting method using crystalline silica as a raw material were each subjected to surface treatment in the same manner as in production example 1, thereby obtaining an inorganic filler B, C.
The average particle diameter of the inorganic filler B was 10. Mu.m, and the specific surface area was 3.4m 2 The content of crystalline silica was 0.3%.
The average particle diameter of the inorganic filler C was 9.8. Mu.m, and the specific surface area was 3.5m 2 The content of crystalline silica was 0.09%.
Production example 4: manufacturing of inorganic filler D
Using amorphous silica as a raw material, the inorganic filler D was obtained by performing surface treatment in the same manner as in production example 1.
The inorganic filler D had an average particle diameter of 3.2 μm and a specific surface area of 3.8m 2 The content of crystalline silica is not more than the detection limit (the detection limit is about 0.01 mass%).
Production examples 5 and 6: manufacturing of inorganic filler E, F
The high amorphous small diameter silica B4 obtained by performing the melting process in the 1-time melting method and the high amorphous small diameter silica B5 obtained by performing the melting process in the 1-time melting method using crystalline silica as a raw material were each subjected to surface treatment in the same manner as in production example 1, thereby obtaining an inorganic filler E, F.
The inorganic filler E had an average particle diameter of 3.4 μm and a specific surface area of 5.0m 2 The content of crystalline silica was 2.1%.
The inorganic filler F had an average particle diameter of 9.5 μm and a specific surface area of 3.2m 2 The content of crystalline silica was 5%.
Example 1-1 >
8 parts of a curing agent (acid anhydride curing agent "MH-700", manufactured by Nippon chemical Co., ltd., acid anhydride group equivalent: 164G/eq.), 2 parts of an epoxy resin (liquid epoxy resin "ZX1059" manufactured by daily iron chemical Co., ltd., bisphenol a type epoxy resin and bisphenol F type epoxy resin in a 1:1 mixture (mass ratio), epoxy equivalent: 169G/eq.) and 2 parts of an epoxy resin (alicyclic epoxy resin "CELLOXIDE 2021P", manufactured by cellophane corporation, epoxy equivalent: 136G/eq.), 2 parts of an epoxy resin (naphthalene type epoxy resin "HP4032D" manufactured by DIC Co., ltd., epoxy equivalent: 143G/eq.), 0.4 part of a curing accelerator (imidazole type curing accelerator "2MA-OK-PW" manufactured by Kagaku Co., ltd.), 2 parts of an epoxy resin (glycidylamine type epoxy resin "EP-3950L" manufactured by ADEKA Co., ltd., epoxy equivalent: 95G/eq.), 2 parts of an epoxy resin (dicyclopentadiene dimethanol type epoxy resin "EP-4088S" manufactured by ADEKA Co., epoxy equivalent: 170G/eq.), 3 parts of a methacrylate (compound having a methacryloyl and polyoxyethylene structure "M-130G" manufactured by Xinzu Chemie Co., ltd.) as a component (D.), 0.1 part of a radical polymerization initiator (PERCEXYL (registered trademark) O, manufactured by Nikkin Co., ltd.) as the component (D), 110 parts of an inorganic filler A as the component (B) as the half-life temperature T10:69.9 ℃ C., and 0.2 part of a silane coupling agent (KBM 403 (3-glycidoxypropyl trimethoxysilane, manufactured by Xinyue chemical Co., ltd.) as the component (D) were uniformly dispersed by a mixer to prepare a paste-like resin composition (resin paste). When the total resin paste was 100% by volume, the content of the inorganic filler a was 71.7% by volume. The content of the inorganic filler in the resin composition paste is shown in table 1.
The resulting resin paste was rapidly subjected to measurement of initial melt viscosity MV0 described later.
Examples 1-2 >
In example 1-1, the following matters were changed.
Regarding the component (A), 2 parts of epoxy resin ("ZX 1059"), 2 parts of epoxy resin ("HP 4032D"), 2 parts of epoxy resin (polyether-containing epoxy resin "EX-992L" manufactured by Daiko chemical Co., ltd., epoxy equivalent: 680 g/eq.), 2 parts of epoxy resin (fluorene-containing epoxy resin "EG-280" manufactured by Osaka gas chemical Co., ltd., epoxy equivalent: 460 g/eq.), and 2 parts of epoxy resin (glycidylamine-type epoxy resin "EP-3980S" manufactured by ADEKA Co., ltd., epoxy equivalent: 115 g/eq.) were incorporated instead of 2 parts of epoxy resin ("ZX 1059", "CELLOXIDE 2021P", "HP4032D", "EP-3950L" and "EP-4088S"), respectively.
As for the component (D), 4 parts of a methacrylate (difunctional methacrylate "M-230G" manufactured by Xinzhou Chemicals Co., ltd.) was blended instead of 3 parts of a methacrylate ("M-130G"). Further, the blending amount of the curing accelerator ("2 MA-OK-PW") was changed from 0.4 parts to 0.5 parts.
The procedure of example 1-1 was repeated except for the above-mentioned matters, to prepare a resin paste according to example 1-2.
Examples 1 to 3 >
In example 1-1, the following matters were changed.
Regarding the component (A), the blending amounts of the epoxy resins ("ZX 1059", "CELLOXIDE2021P", "HP4032D", "EP-3950L" and "EP-4088S") were changed from 2 parts each to 3 parts each.
As to the component (C), 3 parts of a curing agent (an amine curing agent "KAYAHARD A-A" (4, 4 '-diamino-3, 3' -diethyldiphenylmethane) manufactured by Nippon Kagaku Co., ltd.) was incorporated instead of 8 parts of the curing agent ("MH-700").
For the component (D), 0.4 parts of a curing accelerator (imidazole-based curing accelerator "2E4MZ" manufactured by Kagaku Co., ltd.) was blended instead of 0.4 parts of a curing accelerator ("2 MA-OK-PW").
The procedure of example 1-1 was repeated except for the above-mentioned matters, to prepare resin pastes according to examples 1-3.
Examples 1 to 4 >
In example 1-1, the following matters were changed.
As to the component (A), 3 parts of an epoxy resin ("ZX 1059"), 2 parts of an epoxy resin ("HP 4032D"), and 1 part of an epoxy resin (epoxidized polybutadiene resin "JP-100" manufactured by Cato Corp.) were incorporated instead of 2 parts of an epoxy resin ("ZX 1059", "CELLOXDE 2021P", "HP4032D", "EP-3950L" and "EP-4088S"), respectively.
As for the component (B), 120 parts of the inorganic filler B was incorporated instead of 110 parts of the inorganic filler a.
The amount of the curing agent ("MH-700") was changed from 8 parts to 9 parts for the component (C).
Regarding component (D), the amount of the silane coupling agent ("KBM 403") was changed from 0.2 parts to 0.1 parts. The blending amount of the curing accelerator ("2 MA-OK-PW") was changed from 0.4 parts to 0.5 parts, and a radical polymerization initiator ("PERCEXYL (registered trademark) O") was not used.
The procedure of example 1-1 was repeated except for the above-mentioned matters, to prepare resin pastes according to examples 1-4.
Examples 1 to 5 >
In examples 1 to 4, the following matters were changed.
Regarding the (A) component, 3 parts of epoxy resin ("ZX 1059"), 1 part of epoxy resin ("HP 4032D") and 1 part of epoxy resin ("EG-280") were incorporated instead of 3 parts of epoxy resin ("ZX 1059"), 2 parts of epoxy resin ("HP 4032D") and 1 part of epoxy resin ("JP-100").
As to the component (D), instead of incorporating 0.1 part of the silane coupling agent ("KBM 403"), 0.1 part of the silane coupling agent ("KBM 803" (3-mercaptopropyl trimethoxysilane) manufactured by Xinyue chemical Co., ltd.) was incorporated. That is, in examples 1 to 5, various silane coupling agents were incorporated.
Further, 1 part of a silicone resin (KF-6012, a polyoxyalkylene-modified silicone resin "KF-6012", a viscosity (25 ℃ C.) of 1500mm, made by Xinyue silicone Co., ltd.) was blended as the component (D) 2 /s)。
The resin pastes according to examples 1 to 5 were produced in the same manner as in examples 1 to 4 except for the above-mentioned matters.
Examples 1 to 6 >
In examples 1 to 5, 1 part of a polyoxyethylene polyoxypropylene diol compound (polyoxyethylene polyoxypropylene diol "L-64" manufactured by ADEKA Co., ltd.) was incorporated in place of 1 part of a silicone resin ("KF-6012").
The resin pastes according to examples 1 to 6 were produced in the same manner as in examples 1 to 5 except for the above-mentioned matters.
Examples 1 to 7 >
In examples 1-5, with respect to component (A), 3 parts of epoxy resin ("ZX 1059"), 1 part of epoxy resin ("HP 4032D") and 2 parts of epoxy resin ("EP-3950L") were incorporated instead of 3 parts of epoxy resin ("ZX 1059"), 1 part of epoxy resin ("HP 4032D") and 1 part of epoxy resin ("EG-280").
In addition, in examples 1 to 5, regarding the component (D), 1 part of the polyester polyol A synthesized as described below was incorporated instead of 1 part of the silicone resin ("KF-6012").
Synthesis of "polyester polyol A
Into the reaction vessel, 22.6g of epsilon-caprolactone monomer (PLACCEL M, manufactured by Kagaku Kogyo Co., ltd.), 10g of polypropylene glycol (polypropylene glycol, 3000, manufactured by Fuji film and Wako pure chemical industries, ltd.), and 1.62g of tin 2-ethylhexanoate (manufactured by Fuji film and Wako pure chemical industries, ltd.) were added, and the mixture was heated to 130℃under a nitrogen atmosphere and stirred for about 16 hours to react. The product after the reaction was dissolved in chloroform, and the product was reprecipitated with methanol and dried. Thus, as the "polyester polyol A", a polyester polyol having a hydroxyl end of an aliphatic skeleton is obtained. Mn=9000 according to GPC analysis.
The resin pastes according to examples 1 to 7 were produced in the same manner as in examples 1 to 5 except for the above-mentioned matters.
Examples 1 to 8 >
In examples 1 to 3, the following matters were changed.
With respect to component (A), 3 parts of epoxy resin ("ZX 1059"), 3 parts of epoxy resin ("CELLOXIDE 2021P"), 3 parts of epoxy resin ("HP 4032D"), 2 parts of epoxy resin ("EP-3950L") and 1 part of epoxy resin ("EP-4088S") were incorporated instead of 3 parts of epoxy resin ("ZX 1059", "CELLOXIDE 2021P", "HP4032D", "EP-3950L" and "EP-4088S"), respectively.
As for the component (B), 120 parts of the inorganic filler B was incorporated instead of 110 parts of the inorganic filler a.
Regarding component (D), the amount of the silane coupling agent ("KBM 403") was changed from 0.2 parts to 0.3 parts. Furthermore, 1 part of polyester polyol A was incorporated instead of 3 parts of methacrylate ("M-130G"). Further, the blending amount of the radical polymerization initiator ("PERHEXYL (registered trademark) O") was changed from 0.1 part to 0 part. That is, in examples 1 to 8, a radical polymerization initiator was not used.
The resin pastes according to examples 1 to 8 were produced in the same manner as in examples 1 to 3 except for the above-mentioned matters.
Examples 1 to 9 >
In examples 1 to 8, the following matters were changed.
With respect to component (A), 3 parts of epoxy resin ("ZX 1059"), 3 parts of epoxy resin ("CELLOXIDE 2021P"), 3 parts of epoxy resin ("HP 4032D"), 2 parts of epoxy resin ("EP-3950L"), and 1 part of epoxy resin ("EX-992L") were incorporated in place of 3 parts of epoxy resin ("ZX 1059"), 3 parts of epoxy resin ("CELLOXIDE 2021P"), 3 parts of epoxy resin ("HP 4032D"), 2 parts of epoxy resin ("EP-3950L"), and 1 part of epoxy resin ("EP-4088S").
For the component (C), 3 parts of a curing agent (a phenolic curing agent "2, 2-diallyl bisphenol A" manufactured by Sigma Aldrich Co.) was incorporated instead of 3 parts of a curing agent ("KAYAHARD A-A").
The amount of the inorganic filler B to be added was changed from 120 parts to 100 parts for the component (B).
Regarding component (D), 2 parts of a silicone resin ("KF-6012") was incorporated instead of 1 part of polyester polyol A.
The resin pastes according to examples 1 to 9 were produced in the same manner as in examples 1 to 8 except for the above-mentioned matters.
Examples 1 to 10 >
In examples 1 to 7, 120 parts of the inorganic filler B as the component (B) was changed to 120 parts of the inorganic filler C.
The resin pastes according to examples 1 to 10 were produced in the same manner as in examples 1 to 7 except for the above-mentioned matters.
Examples 1 to 11 >
In examples 1 to 2, 110 parts of the inorganic filler A as the component (B) was changed to 110 parts of the inorganic filler D.
The resin pastes according to examples 1 to 11 were produced in the same manner as in examples 1 to 2 except for the above-mentioned matters.
Example 2-1 >
< preparation of resin varnish >
2 parts of a polyimide resin A solution synthesized as described below as the component (D), 2.4 parts of an epoxy resin (naphthalene type epoxy resin "ESN-475V" manufactured by Nitro chemical Co., ltd., epoxy equivalent: about 332 g/eq.), 6 parts of an epoxy resin ("HP 4032D") as the component (A), 7 parts of a curing agent (LA-3018-50P "manufactured by DIC Co., ltd., hydroxyl equivalent: 151g/eq., solid content 50% 2-methoxypropanol solution), 85 parts of an inorganic filler B as the component (B), 10 parts of Methyl Ethyl Ketone (MEK), and 8 parts of cyclohexanone were mixed and uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish.
Preparation of polyimide resin A solution
368.41g of diethylene glycol monoethyl ether acetate and 368.41g of an aromatic solvent "Solvesso 150 (registered trademark)" manufactured by Exxon Mobil corporation (aromatic solvent) were added as solvents to a flask equipped with a stirring device, a thermometer and a condenser. Further, 100.1g (0.4 mol) of diphenylmethane diisocyanate and 400g (0.2 mol) of polycarbonate diol (C-2015N, manufactured by Kagaku Kogyo Co., ltd., number average molecular weight: about 2000, hydroxyl equivalent: 1000g/eq., nonvolatile matter: 100% by mass) were charged into the flask, and the reaction was carried out at 70℃for 4 hours. Thereby, the 1 st reaction solution was obtained.
Next, 195.9g (0.2 mol) of a nonylphenol novolac resin (hydroxyl equivalent: 229.4g/eq, average 4.27 functions, average calculated molecular weight: 979.5 g/mol) and 41.0g (0.1 mol) of ethylene glycol bis (trimellitic anhydride) were further charged into the flask, and the temperature was raised to 150℃over 2 hours to react for 12 hours. Thereby, the 2 nd reaction solution was obtained. 2250cm by FT-IR -1 Is confirmed by the disappearance of the NCO peak of (a). The determination of the disappearance of the NCO peak was taken as the end point of the reaction, and the 2 nd reaction solution was cooled to room temperature. Subsequently, the reaction solution 2 was filtered through a 100-mesh filter cloth. Thus, as a filtrate, a polyimide resin a solution (nonvolatile component 50 mass%) containing a polyimide resin a having a polycarbonate structure as a nonvolatile component was obtained. The number average molecular weight of the polyimide resin a was 6100.
A part of the produced resin varnish was rapidly supplied to production of a resin sheet St0 described below.
The other part of the resin varnish was stored at 23℃under a humidity of 50% for 12 hours, and was used for producing a resin sheet St12 described below.
< production of resin sheet St0 >
As a support, a PET film (thickness: 38 μm, softening point: 130 ℃ C.) having been subjected to a mold release treatment with an alkyd resin-based mold release agent (AL-5, manufactured by Lindeke Co., ltd.) was prepared.
The resin varnish after preparation was uniformly applied to the support by a die coater in such a manner that the thickness of the dried resin composition layer became 200. Mu.m, and dried at 100℃for 6 minutes, thereby obtaining a resin composition layer on the support. Next, a rough surface of a polypropylene film (ALPHAN MA411, manufactured by Oji F-Tex) as a protective film was laminated on the surface of the resin composition layer which was not bonded to the support so as to be bonded to the resin composition layer (thickness 15 μm). Thereby, a resin sheet St0 formed of the support, the resin composition layer, and the protective film in this order is obtained.
When the resin composition layer of the resin sheet St0 was 100% by volume as a whole, the content of the inorganic filler B was 76.7% by volume. Further, as a result of heating and drying, when the resin composition layer of the resin sheet St0 is set to 100 mass% as a whole, the content of the solvent is estimated to be 5 mass% or less.
The resin composition layer of the produced resin sheet St0 was rapidly subjected to measurement of the initial melt viscosity MV0 described later.
< production of resin sheet St12 >
As a support, a PET film (thickness: 38 μm, softening point: 130 ℃ C.) having been subjected to a mold release treatment with an alkyd resin-based mold release agent (AL-5, manufactured by Lindeke Co., ltd.) was prepared.
The resin varnish stored for 12 hours was uniformly applied to a support by a die coater under the condition that the thickness of the dried resin composition layer became 200. Mu.m, and dried at 100℃for 6 minutes, whereby a resin composition layer was obtained on the support. Next, a rough surface of a polypropylene film (ALPHAN MA411, manufactured by prince Ai Fute corporation, thickness 15 μm) as a protective film was laminated on the surface of the resin composition layer which was not bonded to the support so as to be bonded to the resin composition layer. Thereby, a resin sheet St12 formed of the support, the resin composition layer, and the protective film in this order is obtained.
When the resin composition layer of the resin sheet St12 was set to 100% by volume as a whole, the content of the inorganic filler B was 76.7% by volume. Further, as a result of heating and drying, when the resin composition layer of the resin sheet St12 is set to 100 mass% as a whole, the content of the solvent is estimated to be 5 mass% or less.
The resin composition layer of the resin sheet St12 thus produced was rapidly subjected to measurement of the melt viscosity MV12 after 12 hours, which will be described later.
Example 2-2 >
2 parts of an epoxy resin (alicyclic epoxy resin "CELLOXIDE 2021P" manufactured by Dairy Kabushiki Kaisha), 4 parts of an epoxy resin (naphthalene ether epoxy resin "HP6000L" manufactured by DIC Kaisha), 2 parts of an epoxy resin (liquid 1, 4-glycidyl cyclohexane epoxy resin "ZX1658GS" (epoxy equivalent: 135 g/eq.), 10 parts of a curing agent (active ester resin "EXB-8150-60T" manufactured by DIC Kaisha), an active group equivalent: 230g/eq, 2 parts of a carbodiimide compound (toluene solution "manufactured by Nitro chemical Co., ltd.) as a component (solid content: 50% by mass), 85 parts of a filling agent (B) as a liquid 1, 4-glycidyl cyclohexane epoxy resin" ZX1658GS "(epoxy equivalent: 135 g/eq.), 10 parts of a curing agent (active ester resin" EXB-8150-60T "manufactured by DIC Kaisha reactive group: 230 g/eq), 2 parts of a carbodiimide compound (toluene solution" manufactured by Nitro chemical Co., ltd.), 85 parts of an inorganic filler (50 mass%) as a solid content 50% by Nitro), and 6 parts of a methyl ketone (methyl ketone) were uniformly mixed, and the mixture was prepared as a high-speed epoxy resin (MEK-type varnish).
Except for the above, the resin varnish, the resin sheet St0 and the resin sheet St12 according to example 2-2 were produced in the same manner as in example 2-1.
Examples 2 to 3 >
2 parts of an epoxy resin as component (A) ("EP-3950L" manufactured by ADEKA, epoxy equivalent: 95 g/eq.), 4 parts of an epoxy resin as component (A), 4 parts of a naphthalene-type epoxy resin as component (ESN-475V, manufactured by Nitro Chemicals, inc.), 4 parts of an epoxy resin as component (HP 4032D), 2 parts of an epoxy resin as component (liquid 1, 4-glycidyl cyclohexane-type epoxy resin as component (ZX 1658GS, manufactured by Nitro Chemicals, inc.), 135 parts of a curing agent as component (LA-3018-50P, manufactured by DIC, inc.), 151g/eq, a 2-methoxypropanol solution as solid component 50%, 85 parts of an inorganic filler as component (B), 10 parts of Methyl Ethyl Ketone (MEK), and 8 parts of cyclohexanone were mixed and uniformly by a high-speed spin mixer to prepare a varnish.
Except for the above, resin varnishes, resin sheets St0 and St12 according to examples 2 to 3 were produced in the same manner as in example 2 to 1.
Comparative example 1-1 >
In examples 1 to 3, 110 parts of the inorganic filler E as the component (B') was incorporated instead of 110 parts of the inorganic filler A as the component (B).
The procedure of example 1-3 was repeated except for the above-mentioned matters, to prepare a resin paste according to comparative example 1-1.
Comparative examples 1-2 >
In examples 1 to 7, 120 parts of the inorganic filler F as the component (B') was incorporated instead of 120 parts of the inorganic filler B as the component (B).
The resin pastes of comparative examples 1 to 2 were produced in the same manner as in examples 1 to 7 except for the above-mentioned matters.
Next, a method for measuring and evaluating the resin composition will be described.
Evaluation of stability of viscosity lifetime: determination of tackifying ratio
For stability of viscosity life, initial melt viscosity and melt viscosity after 12 hours were measured, and the viscosity-increasing ratio was determined and evaluated.
Determination of initial melt viscosity MV0
The dynamic viscoelasticity modulus of each resin composition layer of the resin pastes prepared in examples 1-1 to 1-11 and comparative examples 1-1 to 1-2 (resin pastes within 30 minutes after production) and the resin sheet St0 prepared in examples 2-1 to 2-3 (resin sheets within 30 minutes after production) was measured by using a dynamic viscoelasticity measuring apparatus (Rheosol-G3000 manufactured by UBM Co., ltd.). As measurement conditions, for 1g of the resin paste or resin composition layer, a parallel plate having a diameter of 18mm was used, and the temperature was raised from the initial temperature of 60℃to 200℃at a temperature raising rate of 5℃per minute, and the measurement temperature interval of 2.5℃and the frequency of 1Hz and the deformation of 1℃were employed. The lowest melt viscosity (poise) was determined from the dynamic viscoelasticity modulus obtained from the measurement results. The lowest melt viscosity thus obtained was defined as "initial melt viscosity MV0".
Determination of 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 at 23℃under a humidity of 50% for 12 hours. The dynamic viscoelasticity modulus of each resin composition layer of the resin paste after 12 hours and the resin sheet St12 (resin sheet within 30 minutes after production) produced in examples 2-1 to 2-3 was measured in the same manner as the measurement of the initial melt viscosity MV0, and the lowest melt viscosity (poise) was obtained. The lowest melt viscosity thus obtained was defined as "melt viscosity after 12 hours MV12".
Tackifying ratio
The ratio of the melt viscosity MV12 to the initial melt viscosity MV0 (i.e., MV12/MV 0) after 12 hours was used with a tackifying ratio of 12 hours. The tackifying ratio was evaluated according to the following criteria.
' good: the tackifying ratio is lower than 1.7
"×": the tackifying ratio is more than 1.7
The compositions and evaluation results of the resin compositions of examples 1-1 to 1-11 and comparative examples 1-1 to 1-2 are shown in Table 1. The compositions and evaluation results of the resin compositions of examples 2-1 to 2-3 are shown in Table 2.
TABLE 1
(Table 1)
<1> The volume ratio of the resin composition as a whole is 100% by volume
TABLE 2
(Table 2)
<1> The volume ratio of the resin composition as a whole is 100% by volume
Next, the evaluation results of the cured product of the resin composition according to examples will be described.
[ cured products of resin compositions according to examples 1-1 to 1-11 ]
< evaluation of the resistance to formation: determination of the presence of flow marks >
The resin compositions produced in examples 1-1 to 1-11 were compression molded on a 12-inch silicon wafer using a compression molding apparatus (mold temperature: 130 ℃, pressure: 6MPa, curing time: 10 minutes) to form a resin composition layer having a thickness of 300. Mu.m. After heating at 150℃for 60 minutes, flow marks were observed by visual inspection of the surface of the resin composition layer (cured product), and evaluation was performed according to the following criteria.
"good" is shown in the following description: no flow mark.
"×": there are flow marks.
< evaluation of adhesion: determination of shear Strength at interface with polyimide resin
(preparation of silicon wafer with polyimide resin formed on surface)
The first specific composition obtained in production example 3 described below was applied to a 4-inch silicon wafer (production examples 1 and 2 described below are production examples of materials of the first specific composition of production example 3). For the coating, spin coating was performed using a spin coater (MS-A150, manufactured by MIKASA Co., ltd.). The spin-coating speed is set in a range of a maximum spin-coating speed of 1000rpm to 3000rpm in accordance with conditions under which a test layer having a desired thickness is obtained after heat curing. Then, a preliminary baking treatment was performed on a heating plate at 120℃for 5 minutes to form a layer of the first specific composition having a thickness of 10 μm in the center on the polished surface. Then, the layer of the first specific composition was subjected to a complete curing treatment in which the layer was thermally cured at 250℃for 2 hours, to obtain a test layer having a central thickness of 8. Mu.m. Here, the cured product of the layer of the first specific composition obtained as a result of the complete curing contains a polyimide resin. In this way, a silicon wafer having a polyimide resin formed on the surface thereof was prepared. The silicon wafer was cut into a size of 1cm square (i.e., 1 cm. Times.1 cm).
(preparation of test piece)
A silicon wafer cut to 1cm square with polyimide formed on the surface thereof was provided with a cylindrical hollowed-out silicone rubber frame having a diameter of 4 mm. The cylindrical cavity of the silicone rubber frame was filled with the respective resin pastes prepared in examples 1-1 to 1-11 to a height of 5mm on the polyimide resin formed on the silicon wafer. After heating at 180℃for 90 minutes, the silicone rubber frame was removed, and a test piece formed of a cured product of a solid columnar resin composition formed on a polyimide resin formed on a silicon wafer was produced.
(measurement)
Shear strength [ kgf/mm ] of an interface between a polyimide resin and a cured product of the resin composition was measured by a bond tester (bond tester) (4000 series, manufactured by Dage Co.) under conditions that a test head position was 1mm from a silicon wafer and a test head speed was 700. Mu.m/s 2 ]The measurement was performed. The test was performed 5 times. The adhesion between the polyimide resin as a base material and the cured product of the resin paste was evaluated according to the following criteria using an average value of measured values obtained 5 times.
"verygood": shear strength of 2.5kgf/mm 2 The above.
"good" is shown in the following description: shear strength of 2.0kgf/mm 2 Above and below 2.5kgf/mm 2 。
"×": shear strength of less than 2.0kgf/mm 2 。
Production example 1 production of photosensitive polyimide precursor (Polymer A-1) as the first Polymer
155.1g of 4,4' -oxybisphthalic anhydride (ODPA) was charged into a 2 liter capacity, and 134.0g of 2-hydroxyethyl methacrylate (HEMA) and 400ml of gamma-butyrolactone were added. 79.1g of pyridine was added while stirring at room temperature, thereby obtaining a reaction mixture. After the heat generation by the reaction was completed, the reaction mixture was cooled to room temperature and allowed to stand for 16 hours.
A solution of 206.3g Dicyclohexylcarbodiimide (DCC) in 180ml of gamma-butyrolactone was prepared. The reaction mixture was stirred under ice-cooling, and the solution was added to the reaction mixture over 40 minutes.
Next, a suspension of 93.0g of 4,4' -diaminodiphenyl ether (DADPE) suspended in 350ml of gamma-butyrolactone was added to the reaction mixture for 60 minutes while stirring the reaction mixture.
After the reaction mixture was stirred at room temperature for 2 hours, 30ml of ethanol was added to the reaction mixture, followed by stirring for 1 hour.
Then, 400ml of gamma-butyrolactone was added to the reaction mixture. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.
The resulting reaction solution was added to 3 liters of ethanol to form a precipitate formed from the crude polymer. The crude polymer thus obtained 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 a polymer. The obtained precipitate was collected by filtration and then dried in vacuo to obtain polymer A-1 as a first polymer in the form of a powder.
The weight average molecular weight (Mw) of this polymer A-1 was measured and found to be 20000.
Production example 2 production of photosensitive polyimide precursor (Polymer A-2) as the second Polymer
Polymer A-2 was produced as a second polymer in the same manner as in production example 1 except that 147.1g of 3,3', 4' -biphenyltetracarboxylic dianhydride was used in place of 155.1g of 4,4' -oxydiphthalic dianhydride.
The weight average molecular weight (Mw) of this polymer A-2 was measured and found to be 22000.
Production example 3 production of negative photosensitive resin composition as first specific composition
50g of Polymer A-1, 50g of Polymer A-2, 2g of a compound represented by the formula (1), 8g of tetraethyleneglycol dimethacrylate, 0.05g of 2-nitroso-1-naphthol, 4g N-phenyldiethanolamine, 0.5g N- (3- (triethoxysilyl) propyl) anthranilic acid, and 0.5g of benzophenone-3, 3 '-bis (N- (3-triethoxysilyl) propylamide) -4,4' -dicarboxylic acid were dissolved in a mixed solvent formed of N-methylpyrrolidone and ethyl lactate (weight ratio N-methylpyrrolidone: ethyl lactate=8:2), to obtain a negative photosensitive resin composition as a first specific composition. The amount of the mixed solvent was adjusted so that the viscosity of the obtained negative photosensitive resin composition was 35 poise.
[ chemical formula 1]
< evaluation of Low warpage: measurement of warp >
Each of the resin pastes prepared in examples 1-1 to 1-11 (resin pastes within 30 minutes after the preparation) was compression molded on a 12-inch silicon wafer using a compression molding apparatus (mold temperature: 120 ℃, pressure: 6MPa, curing time: 12 minutes) to form a resin composition layer having a thickness of 250. Mu.m. Then, the resin composition layer was thermally cured by heating at 180℃for 90 minutes. Thus, a sample substrate including a silicon wafer and a cured layer of the resin composition was obtained. The warpage amount at 25℃was measured on the sample substrate using a shadow moire (shadow moire) measuring device (ThermoireAXP, manufactured by Akorometrix Co.). The measurement was performed in accordance with JEITA EDX-7311-24, a standard of the Japanese electronic information technology industry Association. Specifically, a fitting plane calculated by a least square method is used as a reference plane for all data on the substrate surface of the measurement region, and a difference between a minimum value and a maximum value in a vertical direction from the reference plane is obtained as a warpage [ μm ]. The warpage was evaluated according to the following criteria.
"good" is shown in the following description: the warpage is less than 1500 mu m
"×": the warpage is 1500 μm
The evaluation results of the cured products of the resin compositions according to examples 1-1 to 1-11 are shown in Table 3.
TABLE 3
(Table 3)
<2> Shear Strength [ kgf/mm ] of interface with polyimide resin 2 ]
[ cured products of the resin compositions according to examples 2-1 to 2-3 ]
The evaluation results of the cured products of the resin compositions according to examples 2-1 to 2-3 will be described.
< evaluation of adhesion: determination of shear Strength at interface with polyimide resin
(preparation of silicon wafer with polyimide resin formed on surface)
The first specific composition obtained in production example 3 was coated on a 4-inch silicon wafer. For the coating, spin coating was performed using a spin coater (MS-A150, manufactured by MIKASA Co., ltd.). The spin-coating speed is set in a range of a maximum spin-coating speed of 1000rpm to 3000rpm in accordance with conditions under which a test layer having a desired thickness is obtained after heat curing. Then, a preliminary baking treatment was performed on a heating plate at 120℃for 5 minutes to form a layer of the first specific composition having a thickness of 10 μm in the center on the polished surface. Then, the layer of the first specific composition was subjected to a complete curing treatment in which the layer was thermally cured at 250℃for 2 hours, to obtain a test layer having a central thickness of 8. Mu.m. Here, the cured product of the layer of the first specific composition obtained as a result of the complete curing contains a polyimide resin. In this way, a silicon wafer having a polyimide resin formed on the surface thereof was prepared.
(preparation of sample substrate)
The resin sheets St0 (thickness: 200 μm) produced in examples 2-1 to 2-3 were laminated on a 4-inch silicon wafer having a polyimide resin formed on the surface thereof using a batch vacuum press laminator (CVP 700, manufactured by Nikko-Materials Co., ltd., 2-stage lamination laminator). Each laminate was performed as follows: after the pressure was reduced to 13hPa or less for 30 seconds, the mixture was pressure-bonded at 100℃under a pressure of 0.74MPa for 30 seconds. Then, the peeling of the support and lamination of the resin composition layer (lamination under the same conditions) were repeated so that the total thickness of the laminate of the resin composition layer was 5mm. The silicon wafer was cut into a square 1cm size.
Then, the laminate of resin composition layers having a total thickness of 5mm on the silicon wafer was processed into a solid cylinder shape having a diameter of 4 mm. Thereby, a sample substrate including a cured product of a laminate of a silicon wafer and a resin composition layer was obtained. Next, the shear strength [ kgf/mm ] was measured in the same manner as described above 2 ]. The test was performed 5 times. The adhesion of the polyimide resin as a base material to the cured product of the laminate of the resin composition layer was evaluated according to the following criteria using an average value of measured values obtained 5 times.
"verygood": shear strength of 2.5kgf/mm 2 The above.
"good" is shown in the following description: shear strength of 2.0kgf/mm 2 Above and below 2.5kgf/mm 2 。
"×": shear strength of less than 2.0kgf/mm 2 。
< evaluation of Low warpage: measurement of warp >
The resin sheets St0 obtained in examples 2-1 to 2-3 were laminated on the entire surface of a 12-inch silicon wafer (thickness 775 μm) using a batch vacuum press laminator (CVP 700, manufactured by Nikko-Materials Co., ltd., 2-stage stack laminator), and the support was peeled off. Further, a resin sheet St0 was laminated on the resin composition layer laminated on a 12-inch silicon wafer, whereby 2 resin composition layers were laminated to form a resin composition layer having a thickness of 400 μm. The resulting silicon wafer with the resin composition layer was subjected to heat treatment in an oven at 180 ℃ and 90 minutes to form a silicon wafer with a cured resin composition layer (i.e., insulating layer). The warpage at 25℃was measured on the sample substrate using an image moire measuring device (ThermoireAXP, manufactured by Akorometrix Co.). The measurement was performed in accordance with JEITA EDX-7311-24, a standard of the Japanese electronic information technology industry Association. Specifically, a fitting plane calculated by a least square method is used as a reference plane for all data on the substrate surface of the measurement region, and a difference between a minimum value and a maximum value in a vertical direction from the reference plane is obtained as a warpage [ μm ]. The warpage was evaluated according to the following criteria.
"good" is shown in the following description: warpage of less than 2000 μm
"×": the warp amount is more than 2000 mu m
The evaluation results of the cured products of the resin compositions according to examples 2-1 to 2-3 are shown in Table 4.
TABLE 4
(Table 4)
<2> Shear Strength [ kgf/mm ] of interface with polyimide resin 2 ]
< investigation >
According to table 1, the resin compositions according to comparative examples have poor stability in viscosity life, and thus tend to have non-uniform compositions due to long-term storage. On the other hand, according to table 1, the stability of the viscosity life of the resin paste according to examples was good. Further, as is clear from table 3, the use of the resin paste resulted in a cured product having excellent properties. Thus, for example, a cured product having excellent adhesion to a substrate (for example, polyimide resin), a circuit board including the cured product, and a semiconductor chip package can be provided. As shown in table 2, the resin composition layer of the resin sheet according to the example had good stability in viscosity life. Further, it was confirmed from table 4 that the cured product having excellent properties was obtained by forming the resin varnish or resin composition layer. Thus, it is possible to provide, for example, a cured product having excellent adhesion to a substrate (for example, polyimide resin), a circuit board including the cured product, and a semiconductor chip package.
[ description of symbols ]
100. Semiconductor chip package
110. Semiconductor chip
120. Sealing layer
130. Rewiring forming layer
140. Rewiring layer
150. Solder mask
160. Bump block

Claims (16)

1. A resin composition comprising (A) a curable resin and (B) an inorganic filler,
wherein the inorganic filler (B) has an average particle diameter in the range of 0.5 to 12 μm,
the content of crystalline silica in the inorganic filler is in the range of 0 mass% or more and less than 2.1 mass%.
2. The resin composition according to claim 1, wherein the content of the crystalline silica is in a range of 0 mass% or more and 0.4 mass% or less.
3. The resin composition according to claim 1, wherein the content of the inorganic filler (B) is 50% by volume or more based on 100% by volume of the total resin composition.
4. The resin composition according to claim 1, wherein (C) a curing agent is contained,
(C) The mass ratio of the component (A) to the component (A) is in the range of 1:0.01 to 1:10.
5. The resin composition according to claim 1, wherein the content of the crystalline silica is calculated based on an X-ray diffraction pattern obtained by X-ray diffraction measurement.
6. The resin composition according to claim 5, wherein the content of the crystalline silica is calculated by performing a Rietveld analysis on an X-ray diffraction pattern.
7. The resin composition according to claim 1, which is used for forming a resin composition layer having a thickness of 50 μm or more.
8. The resin composition according to claim 1, which is used for sealing.
9. A cured product of the resin composition according to any one of claims 1 to 8.
10. A resin sheet, comprising: a support, and a resin composition layer comprising the resin composition according to any one of claims 1 to 8 provided on the support.
11. The resin sheet according to claim 10, which is a resin sheet for an insulating layer of a semiconductor chip package.
12. A circuit board comprising an insulating layer formed using the cured product of the resin composition according to any one of claims 1 to 8.
13. A semiconductor chip package, comprising: the circuit board according to claim 12, and a semiconductor chip mounted on the circuit board.
14. A semiconductor chip package comprising a semiconductor chip sealed with the resin composition according to any one of claims 1 to 8.
15. A semiconductor chip package comprising a semiconductor chip sealed with the resin sheet according to claim 10.
16. A method for manufacturing a semiconductor chip package, comprising the step of curing a resin composition,
the resin composition comprises (A) a curable resin and (B) an inorganic filler, wherein the average particle diameter of the inorganic filler is in the range of 0.5-12 [ mu ] m, and the content of crystalline silica in the inorganic filler is in the range of 0-2.1 mass%.
CN202280043646.0A 2021-06-22 2022-06-08 Resin composition, cured product, resin sheet, circuit board, and semiconductor chip package Pending CN117500886A (en)

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