CN113801433A - Resin composition - Google Patents

Resin composition Download PDF

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Publication number
CN113801433A
CN113801433A CN202110643724.8A CN202110643724A CN113801433A CN 113801433 A CN113801433 A CN 113801433A CN 202110643724 A CN202110643724 A CN 202110643724A CN 113801433 A CN113801433 A CN 113801433A
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China
Prior art keywords
resin composition
component
group
resin
mass
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CN202110643724.8A
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Chinese (zh)
Inventor
佐佐木成
阪内启之
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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Priority claimed from JP2021085515A external-priority patent/JP2021195540A/en
Application filed by Ajinomoto Co Inc filed Critical Ajinomoto Co Inc
Publication of CN113801433A publication Critical patent/CN113801433A/en
Pending legal-status Critical Current

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    • 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
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • 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
    • 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
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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

Abstract

The subject of the invention is to provide: a resin composition or a resin paste which can give a cured product having a small warpage and a large elastic modulus and excellent adhesion to an inorganic material and which has excellent releasability from a film material; cured product, resin sheet, printed wiring board, semiconductor chip package, semiconductor device, method for manufacturing printed wiring board, and method for manufacturing semiconductor chip package. The present invention provides a resin composition comprising (a) an epoxy resin, (B) a compound having a radical polymerizable unsaturated group and a polyoxyalkylene structure and satisfying specific conditions, (C) an acid anhydride, (D) a radical generator, and (E) an inorganic filler, [ B ] indicating a mass ratio of the component (B) to the component (C): [c] at a speed of 0.2: 1-1.5: 1, in the above range.

Description

Resin composition
Technical Field
The present invention relates to a resin composition. Further, the present invention relates to a resin paste, a cured product, a resin sheet, a printed wiring board, a semiconductor chip package, a semiconductor device, a method for manufacturing a printed wiring board, and a method for manufacturing a semiconductor chip package.
Background
In order to seal a printed wiring board or a semiconductor chip included in a semiconductor device, a liquid resin composition may be used as a sealing material. Patent document 1 discloses a liquid epoxy resin composition containing (a) an epoxy resin, (b) a curing agent, (c) a latent catalyst, (d) a polymerizable monomer having 2 or more radically polymerizable double bonds, (e) a radical polymerization initiator, and (f) an inorganic filler as a sealing material (claim 2). Patent document 2 discloses a liquid epoxy resin composition containing an epoxy resin that is liquid at ordinary temperature, an amine curing agent, a thermosetting acrylic resin, a thermal polymerization initiator for the thermosetting acrylic resin, and an inorganic filler as a sealing material (claim 1).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 11-255864
Patent document 2: japanese patent laid-open No. 2014-094981.
Disclosure of Invention
Problems to be solved by the invention
Even when used as a resin composition for compression molding (compression molding), a cured product having a small warpage is generally required to be obtained. In addition, from the viewpoint of improving the handling properties of printed wiring boards and semiconductor chip packages, the resulting cured product is required to have a high elastic modulus. However, as a result of studies by the present inventors, a cured product having a small warpage tends to have a small elastic modulus. Further, a cured product having a large elastic modulus tends to be largely warped. Thus, there is a trade-off (1 st trade-off) relationship between the reduction of warpage and the increase of elastic modulus, and it is difficult to realize both of them.
In addition, from the viewpoint of reliability, a cured product of a resin composition as a sealing material is required to have high adhesion force (hereinafter, also referred to as "inorganic material adhesion") with an inorganic material (for example, silicon or copper) in contact with the cured product. On the other hand, a resin composition layer (compression-molded article) obtained by compression-molding a resin composition is required to have excellent releasability from a release film (hereinafter, also referred to as "film material releasability"). Here, the release film is a film material having releasability, which is generally used in compression molding. Since the resin composition layer can be prevented from directly contacting the mold by interposing the release film between the resin composition layer and the mold during compression molding, it is expected that the resin composition layer can be easily taken out after compression molding.
However, the results of the inventors' studies show that: when the cured product of the resin composition has high adhesion to the inorganic material, the adhesion between the resin composition layer (compression molded article) of the resin composition and the release film tends to be high (trade-off No. 2). Therefore, there are cases where: after the compression molding, it becomes not so easy to remove the resin composition layer from the mold as expected; alternatively, even if the resin composition layer can be removed from the mold, it is difficult to peel the release film from the resin composition layer.
In view of the above, it is required to eliminate the following from a resin composition for compression molding: the first trade-off between "reduction of warpage of a cured product" and "increase of elastic modulus of a cured product" and the second trade-off between "high adhesion between a cured product and an inorganic material" and "high peelability of a resin composition layer (compression molded article) from a film material" are both made. If these trade-offs are eliminated, it is expected that handling of the resin composition layer (compression-molded body) of the resin composition becomes easy, and handling of a sealed body in which a semiconductor chip is sealed with a cured product of the resin composition becomes easy, for example.
The subject of the invention is to provide: a resin composition or a resin paste which can give a cured product having a small warpage and a large elastic modulus and excellent adhesion to an inorganic material and which has excellent releasability from a film material; and a cured product, a resin sheet, a printed wiring board, a semiconductor chip package, a semiconductor device, a method for manufacturing a printed wiring board, and a method for manufacturing a semiconductor chip package, each obtained using the resin composition or the resin paste.
Means for solving the problems
The inventors of the present invention have made extensive studies and, as a result, have found that: the above problems can be solved by including specific components in a resin composition in specific amounts, and the present invention has been completed.
That is, the present invention includes the following;
[1] a resin composition comprising:
(A) epoxy resin,
(B) A compound having a radical polymerizable unsaturated group and a polyoxyalkylene (polyalkylene oxide) structure in a molecule, and satisfying the following formula (1):
E/N-(100×N)≥50···(1)
(in the formula (1), E represents the equivalent weight (g/eq.) of the radical polymerizable unsaturated group, and N represents the number of radical polymerizable unsaturated groups in the molecule, and is an integer of 1 or more),
(C) Acid anhydride, acid anhydride,
(D) A radical generator, and
(E) an inorganic filler material, which is a filler,
[ B ] representing the mass ratio of component (B) to component (C): [c] at a speed of 0.2: 1-1.5: 1 in the range of;
[2]according to [1]The resin composition, wherein the polyoxyalkylene structure of the component (B) is represented by the formula: - (R)BO)n-represents, in the above formula, n is an integer of 2 or more, RBEach independently is an alkylene group having 1 to 6 carbon atoms which may have a substituent;
[3]according to [ 2]]The resin composition, wherein at a plurality of groups RBIn (1), at least one group RBComprises an ethylene group;
[4] the resin composition according to any one of [1] to [3], wherein the radical polymerizable unsaturated group of the component (B) is at least one selected from the group consisting of a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, an acryloyl group, a methacryloyl group, a fumaryl group, a maleoyl group, a vinylphenyl group, a styryl group and a cinnamoyl group;
[5] the resin composition according to [4], wherein the radical polymerizable unsaturated group contained in the component (B) contains at least one member selected from the group consisting of a methacryloyl group and an acryloyl group;
[6] the resin composition according to [4] or [5], wherein the radical polymerizable unsaturated group contained in the component (B) contains a methacryloyl group;
[7] the resin composition according to any one of [1] to [6], wherein the component (B) comprises at least one compound selected from a compound in which N in the formula (1) is 1 and a compound in which N in the formula (1) is 2;
[8] the resin composition according to [7], wherein the molecular weight of the compound in which N in formula (1) is 1 is 150 or more;
[9] the resin composition according to [7] or [8], wherein the equivalent weight (g/eq.) of the radical polymerizable unsaturated group of the compound of formula (1) in which N is 2 is 500 or more;
[10] the resin composition according to any one of [1] to [9], wherein the equivalent weight of the radical polymerizable unsaturated group of the component (B) is 4500 g/eq.or less;
[11] the resin composition according to any one of [1] to [10], wherein the content of the component (B) is 10 mass% or more and 40 mass% or less, assuming that 100 mass% is a component other than the inorganic filler (E) in nonvolatile components in the resin composition;
[12] the resin composition according to any one of [1] to [11], wherein a value of an equivalence ratio (C)/(a) of a sum of a value obtained by dividing an amount (g) of the component (C) by an equivalent (g/eq.) of an acid anhydride group of the component (C) and a sum of a value obtained by dividing an amount (g) of the component (A) by an equivalent (g/eq.) of an epoxy group of the component (A) is 0.4 or more;
[13] the resin composition according to any one of [1] to [12], wherein the component (D) is at least one selected from radical generators having a 10-hour half-life temperature T10 (DEG C) in the range of 50 ℃ to 110 ℃;
[14] the resin composition according to any one of [1] to [13], wherein the content of the component (E) is 70% by mass or more, assuming that the content of nonvolatile components in the resin composition is 100% by mass;
[15] the resin composition according to any one of [1] to [14], which is used for compression molding;
[16] the resin composition according to [15], wherein the component (D) is at least one radical generator selected from the group consisting of radical generators, the difference Δ T (DEG C) between a mold temperature Tc (DEG C) at the time of compression molding and a 10-hour half-life temperature T10 (DEG C) of the component (D) being in the range of 20 ℃ to 80 ℃;
[17] the resin composition according to any one of [1] to [16], which is used for forming an insulating layer;
[18] a resin paste comprising the resin composition according to any one of [1] to [17 ];
[19] a cured product of the resin composition according to any one of [1] to [17] or the resin paste according to [18 ];
[20] a resin sheet having:
a support, and
a resin composition layer comprising the resin composition according to any one of [1] to [17] or the resin paste according to [18] provided on the support;
[21] a printed wiring board comprising an insulating layer formed using a cured product of the resin composition according to any one of [1] to [17] or the resin paste according to [18 ];
[22] a semiconductor chip package, comprising:
[21] the printed wiring board, and
a semiconductor chip mounted on the printed wiring board;
[23] a semiconductor chip package, comprising:
semiconductor chip, and
a cured product of the resin composition according to any one of [1] to [17] or the resin paste according to [18] encapsulating the semiconductor chip;
[24] a semiconductor device comprising the printed wiring board of [21] or the semiconductor chip package of [22] or [23 ];
[25] a method of manufacturing a printed wiring board, comprising:
a step of forming a resin composition layer containing the resin composition according to any one of [1] to [17] or a resin composition layer containing the resin paste according to [18] on a circuit board by a compression molding method, and
curing the resin composition layer;
[26] a method of manufacturing a semiconductor chip package, comprising:
a step of forming a resin composition layer containing the resin composition according to any one of [1] to [17] or a resin composition layer containing the resin paste according to [18] on a semiconductor chip by a compression molding method, and
and curing the resin composition layer.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a resin composition or a resin paste which can give a cured product having a small warpage and a large elastic modulus and excellent adhesion to an inorganic material and which has excellent releasability from a film material; and a cured product, a resin sheet, a printed wiring board, a semiconductor chip package, a semiconductor device, a method for manufacturing a printed wiring board, and a method for manufacturing a semiconductor chip package, each obtained using the resin composition or the resin paste.
Detailed Description
The resin composition, resin paste, cured product, resin sheet, printed wiring board, semiconductor chip package, semiconductor device, method for manufacturing printed wiring board, and method for manufacturing semiconductor chip package of the present invention will be described in detail below.
[ resin composition ]
The resin composition of the present invention comprises (a) an epoxy resin, (B) a compound having a radical polymerizable unsaturated group and an oxyalkylene structure and satisfying specific conditions, (C) an acid anhydride, (D) a radical generator, and (E) an inorganic filler, [ B ] indicating a mass ratio of the component (B) to the component (C): [c] at a speed of 0.2: 1-1.5: 1, in the above range. The resin composition exhibits the following effects: a cured product having a small warpage, a large elastic modulus, and excellent adhesion to an inorganic material can be obtained, and the cured product has excellent releasability from a film material. When such a resin composition is used, a resin paste, a cured product, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device which can exhibit the above-described effects can be provided.
The resin composition of the present invention may further contain an optional component in combination in addition to the components (a), (B), (C), (D) and (E). Examples of the optional component include (F) a curing accelerator, (G) a compound having a radical polymerizable unsaturated group (excluding a compound having a polyoxyalkylene structure), and (H) other additives. Hereinafter, each component contained in the resin composition will be described in detail. In the present invention, the content of each component in the resin composition is a value obtained when the nonvolatile content in the resin composition is 100 mass%, unless otherwise specified.
(A) epoxy resin
The resin composition of the present invention contains (a) an epoxy resin. The epoxy resin means a resin having 1 or more epoxy groups in a molecule. By containing (a) an epoxy resin in the resin composition, a cured product having a crosslinked structure can be obtained.
Examples of the epoxy resin include: a biscresol (bixylenol) 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 trisphenol type epoxy resin, a naphthol novolac (naphthol novolac) type epoxy resin, a phenol novolac (phenol novolac) type epoxy resin, a tert-butyl catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidylamine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolac (cresol novolac) type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol novolac type epoxy resin, a naphthol type epoxy resin, a styrene type epoxy resin, trimethylol epoxy resins, tetraphenylethane epoxy resins, oxyalkylene epoxy resins, etc. The epoxy resin may be used alone or in combination of two or more.
(A) The component (C) is preferably an epoxy resin having 2 or more epoxy groups in the molecule. It is preferable that the nonvolatile content of the component (A) is 100% by mass, and the content is usually 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, of the epoxy resin having 2 or more epoxy groups in the molecule.
The epoxy resin may be (A-1) a liquid epoxy resin or (A-2) a solid epoxy resin. The resin composition may contain, in combination, (A-1) a liquid epoxy resin and (A-2) a solid epoxy resin. The component (A) is preferably a liquid epoxy resin (A-1) from the viewpoint of obtaining a resin composition having excellent flowability at the time of molding. The component (A) may further contain (A-2) a solid epoxy resin, as required.
((A-1) liquid epoxy resin)
The liquid epoxy resin (A-1) means an epoxy resin which is liquid at a temperature of 20 ℃. The resin composition preferably contains (A-1) a liquid epoxy resin.
The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in the molecule, and more preferably an aromatic liquid epoxy resin having 2 or more epoxy groups in the molecule. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.
The liquid epoxy resin is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a glycidyl amine type epoxy resin, an oxyalkylene type epoxy resin, or an epoxy resin having a butadiene structure, more preferably a bisphenol a type epoxy resin, a naphthalene type epoxy resin, or a glycidyl amine type epoxy resin.
Specific examples of the liquid epoxy resin include: "YX 7400" manufactured by Mitsubishi chemical corporation; "HP 4032", "HP 4032D" and "HP-4032-SS" (naphthalene type epoxy resin) manufactured by DIC; 828US, jER828EL, 825 and 828EL (bisphenol A epoxy resin) manufactured by Mitsubishi chemical company; "jER 807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical corporation; "630" and "630 LSD" (glycidyl amine type epoxy resins) manufactured by mitsubishi chemical corporation; "EP 3950L" (glycidyl amine type epoxy resin) manufactured by ADEKA corporation; "ZX 1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nissian Ciki Kaisha; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "CELLOXIDE 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Dailuo corporation; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Dailuo corporation; "ZX 1658" and "ZX 1658 GS" (liquid 1, 4-glycidylcyclohexane-type epoxy resins) manufactured by Nippon iron and Japan chemical Co., Ltd. These epoxy resins may be used alone or in combination of two or more. As will be exemplified in examples described later, it is one of preferable modes to use one or more liquid epoxy resins selected from "ZX 1059" manufactured by Nippon Tekken chemical Co., Ltd, "HP-4032-SS" manufactured by DIC Co., Ltd and "630 LSD" manufactured by Mitsubishi chemical Co., Ltd. From the viewpoint of reducing warpage of the cured product, it is more preferable to use 2 or more kinds of liquid epoxy resins selected from "ZX 1059" manufactured by Nippon Tekken chemical Co., Ltd, "HP-4032-SS" manufactured by DIC Co., Ltd, "630 LSD" manufactured by Mitsubishi chemical Co., Ltd. Further, from the viewpoint of reducing warpage of a cured product, it is more preferable to use 2 or more kinds of liquid epoxy resins selected from "ZX 1059" manufactured by Nippon Tekken chemical Co., Ltd, "HP-4032-SS" manufactured by DIC Co., Ltd and "630 LSD" manufactured by Mitsubishi chemical Co., Ltd.
From the viewpoint of obtaining the effects (for example, improvement in handling properties (fluidity during molding) and improvement in compatibility) of the resin composition and the like due to the inclusion of the component (a-1), and from the viewpoint of obtaining a cured product with little warpage, the content of the component (a-1) in the resin composition is preferably 1 mass% or more, more preferably 2 mass% or more, further preferably 3 mass% or more, and particularly preferably 5 mass% or more, with the nonvolatile content in the resin composition being 100 mass%. The upper limit of the content of the component (A-1) is not particularly limited as long as the effect of the present invention is not impaired, and may be, for example, 30 mass% or less or 25 mass% or less, and 20 mass% or less or 15 mass% or less from the viewpoint of obtaining a cured product having a high elastic modulus.
((A-2) solid epoxy resin)
By solid epoxy resin is meant an epoxy resin that is solid at a temperature of 20 ℃. The resin composition may contain only (A-1) a liquid epoxy resin as the component (A), but from the viewpoint of increasing the crosslinking density, it is preferable to contain (A-1) a liquid epoxy resin and (A-2) a solid epoxy resin in combination. The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in the molecule.
The solid epoxy resin is preferably a biphenol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene 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, and more preferably a naphthol-type epoxy resin, a bisphenol AF-type epoxy resin, a naphthalene-type epoxy resin, and a biphenyl-type epoxy resin.
Specific examples of the solid epoxy resin include: HP4032H (naphthalene epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP 7200L", "HP-7200 HH" and "HP-7200H" (dicyclopentadiene type epoxy resins) manufactured by DIC; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP 6000" and "HP 6000L" manufactured by DIC corporation (naphthylene ether type epoxy resins); EPPN-502H (trisphenol type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "NC 7000L" (naphthol novolac type epoxy resin) manufactured by japan chemicals); "NC 3000H", "NC 3000L" and "NC 3100" (biphenyl type epoxy resin) manufactured by japan chemical company; ESN475V (naphthol type epoxy resin) manufactured by Nippon iron and gold Chemicals; ESN485 (naphthol novolac type epoxy resin) manufactured by Nippon iron and gold Chemicals, Ltd; "YX 4000H", "YX 4000", "YL 6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical company; "YX 4000 HK" (bisphenol type epoxy resin) manufactured by Mitsubishi chemical corporation; YX8800 (anthracene-based epoxy resin) available from Mitsubishi chemical corporation; PG-100 and CG-500 manufactured by Osaka gas chemical company; "157S 70" (bisphenol A novolac type epoxy resin) manufactured by Mitsubishi chemical company; "YL 7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL 7800" (fluorene-based epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 1010" (bisphenol a type epoxy resin) manufactured by mitsubishi chemical corporation; "jER 1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi chemical corporation, and the like. These may be used alone or in combination of two or more.
The content of the component (A-2) in the resin composition may be 0% by mass (that is, not contained) when the nonvolatile content in the resin composition is 100% by mass, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, particularly preferably 0.2% by mass or more, from the viewpoint of obtaining the effects (for example, lowering the average linear thermal expansion coefficient, improving the heat resistance, or improving the crosslink density) by containing the component (A-2). The upper limit of the content of the component (A-2) is preferably smaller than the content of the component (A-1). From the viewpoint of appropriately suppressing the crosslinking density, the upper limit of the content of the component (a-2) may be 10 mass% or less, 5 mass% or less, 3 mass% or less, or 1 mass% or less, when the nonvolatile component in the resin composition is 100 mass%.
When the (A-1) liquid epoxy resin and the (A-2) solid epoxy resin are used in combination as the component (A), the amount ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.01-1: a range of 0.8. By setting the amount ratio of the (a-1) liquid epoxy resin to the (a-2) solid epoxy resin to the above range, effects such as i) providing appropriate fluidity during molding, ii) improving handling properties when used in the form of a resin composition molded body, and iii) obtaining a cured product having sufficient breaking strength can be obtained. From the viewpoint of obtaining the effects of the above-described i) to iii) and from the viewpoint of appropriately suppressing the crosslinking density, the amount ratio of (a-1) the liquid epoxy resin to (a-2) the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.01-1: a range of 0.5, more preferably 1: 0.01-1: a range of 0.1.
(A) The epoxy equivalent of the component (A) is preferably 50 to 5000g/eq, more preferably 50 to 3000g/eq, still more preferably 70 to 2000g/eq, and still more preferably 70 to 1000g/eq. When the amount is within this range, the crosslinking density of the cured product becomes sufficient, and a cured product having excellent strength and heat resistance can be obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.
(A) The weight average molecular weight of the component (B) is preferably 100 to 5000, more preferably 250 to 3000, further preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method.
From the viewpoint of improving the desired effect of the present invention, the content of the component (a) in the resin composition is preferably 1 mass% or more, more preferably 2 mass% or more, further preferably 3 mass% or more, particularly preferably 5 mass% or more, when the nonvolatile content in the resin composition is 100 mass%. The upper limit of the content of the component (a) is not particularly limited as long as the effect of the present invention is not impaired, and may be, for example, 30 mass% or less or 25 mass% or less, and 20 mass% or less or 15 mass% or less from the viewpoint of obtaining a cured product having a high elastic modulus.
From the viewpoint of enhancing the desired effect of the present invention, the content of the component (a) is preferably 10 mass% or more, more preferably 15 mass% or more, further preferably 20 mass% or more, particularly preferably 25 mass% or more, based on 100 mass% of the components other than the inorganic filler (E) in the nonvolatile components in the resin composition. The upper limit of the content of the component (a) is not particularly limited as long as the effect of the present invention is not impaired, and is, for example, 70 mass% or less or 65 mass% or less, and may be 50 mass% or less, 48 mass% or less or 45 mass% or less from the viewpoint of obtaining a cured product with little warpage.
The content (mass) of the component (a) in the resin composition is preferably at least one fifth, more preferably at least one fourth, and further preferably at least three tenths of the total (mass) of the content of the component (B) and the content of the component (C), from the viewpoint of improving the desired effect of the present invention. The percentage of the value [ a ]/([ B ] + [ C ]) of the mass ratio of the content of the component (A) to the total of the content of the component (B) and the content of the component (C) in the resin composition is preferably 20 mass% or more, more preferably 25 mass% or more, and still more preferably 30 mass% or more. The upper limit of the percentage of the value [ a ]/([ b ] + [ c ]) of the mass ratio may be 100 mass% or less, 90 mass% or less, or 80 mass% or less, from the viewpoint of further improving the desired effect of the present invention.
< (B) A compound having a radically polymerizable unsaturated group and a polyoxyalkylene structure and satisfying specific conditions
The resin composition of the present invention contains: (B) a compound having a radical polymerizable unsaturated group and a polyoxyalkylene structure and satisfying specific conditions (hereinafter also referred to as "radical reactive poly RO compound of the present invention"). The radical-reactive poly-RO compound of the present invention may be used in 2 or more species. It is considered that, by including the component (B) in combination with the components (a) and (C) in the resin composition, the component (B) contributes to the exertion of at least part of the effects (warpage, inorganic material adhesion, elastic modulus, and film peeling property) desired by the present invention, and in particular, the flexibility due to the polyoxyalkylene structure greatly contributes to the reduction of warpage of the cured product and the improvement of inorganic material adhesion.
(B) Examples of the radical polymerizable unsaturated group contained in the component (a) include groups containing an ethylenic carbon-carbon double bond. Specific examples thereof include at least one selected from the group consisting of vinyl, allyl, 1-butenyl, 2-butenyl, acryloyl, methacryloyl, fumaryl, maleoyl, vinylphenyl, styryl and cinnamoyl. (B) The component (B) may contain 2 or more radical polymerizable unsaturated groups in 1 molecule. (B) The radical polymerizable unsaturated group contained in the component (a) preferably contains at least one selected from the group consisting of a methacryloyl group and an acryloyl group from the viewpoint of improving reactivity, and more preferably contains a methacryloyl group from the viewpoint of controlling reactivity. In addition, from the viewpoint of obtaining a cured product with little warpage, component (B) preferably has a radical polymerizable unsaturated group at the molecular terminal.
(B) Specific conditions to be satisfied by the components are the following formula (1):
E/N-(100×N)≥50···(1)
(in the formula (1), E represents the equivalent weight (g/eq.) of the radical polymerizable unsaturated group, and N represents the number of radical polymerizable unsaturated groups in the molecule, and is an integer of 1 or more). The equivalent of the radical polymerizable unsaturated group means the mass of the resin containing 1 equivalent of the radical polymerizable unsaturated group. By satisfying this condition, the desired effects of the present invention can be exhibited. N is, for example, 5 or less, 4 or less, or 3 or less.
The above formula (1) means that the molecular weight per 1 equivalent (corresponding to the term "E/N" in formula (1)) needs to be sufficiently large depending on the number N of radical polymerizable unsaturated groups. Specifically, when N is 1, the above formula (1) means that the molecular weight of the compound needs to be 150 or more; when N is 2, the equivalent weight (g/eq.) of the radical polymerizable unsaturated group of the compound needs to be 500 or more (that is, the molecular weight is 1000 or more). Thus, it is considered that: the molecular weight of component (B) per 1 equivalent is large depending on the number of radical polymerizable unsaturated groups, and thus there is a tendency that the increase in warpage due to the influence of curing shrinkage of the resin composition can be suppressed.
(B) The components include, for example: at least one compound selected from the group consisting of a compound represented by formula (1) wherein N is 1 and a compound represented by formula (1) wherein N is 2. Here, as described above, the compound in which N in formula (1) is 1 is a compound whose molecular weight is 150 or more. Similarly, the compound of formula (1) in which N is 2 is a compound having an equivalent weight (g/eq.) of the radical polymerizable unsaturated group of 500 or more.
(B) When the component (C) is a compound represented by the formula (1) wherein N is 1, the equivalent weight of the radical polymerizable unsaturated group is 150 g/eq.or more, and the lower limit thereof may be 250 g/eq.or more or 400 g/eq.or more. (B) When the component (C) is a compound represented by the formula (1) wherein N is 2, the equivalent weight of the radical polymerizable unsaturated group is 500g/eq or more, and the lower limit thereof may be 510g/eq or more or 600g/eq or more. The upper limit of the equivalent weight of the radical polymerizable unsaturated group in the radical reactive polyro compound of the present invention is 4500g/eq. From the viewpoint of improving the fluidity of the resin composition (the viscosity of the resin composition or the filling property of the inorganic filler), the upper limit of the equivalent weight of the radical polymerizable unsaturated group is preferably 3000 g/eq.or less, more preferably 2000 g/eq.or less, and still more preferably 1500 g/eq.or less. When the resin composition contains a plurality of the radically reactive polyro compounds of the present invention as the component (B), it is preferable that the equivalent of the radically polymerizable unsaturated group of each compound satisfies the above range.
In the present embodiment, the polyoxyalkylene structure possessed by the (B) component is represented by the formula (2): - (R)BO)n-represents, here, in formula (2), n is an integer of 2 or more, RBEach independently is an alkylene group having 1 to 6 carbon atoms which may have a substituent. (B) The component (C) contains at least 1 polyoxyalkylene structure in 1 molecule, and from the viewpoint of obtaining a cured product excellent in inorganic material adhesion, it is preferable that 1 molecule contains 2 or more polyoxyalkylene structures, and in this case, a plurality of polyoxyalkylene structures may be the same to each otherAnd may be different. When the radical-reactive poly-RO compound of the present invention contains a plurality of polyoxyalkylene structures which are the same as or different from each other, the number of repetitions of the oxyalkylene structure per 1 molecule (hereinafter also referred to as "RO number") is represented by the total number of the numerical values represented by n in formula (2) representing each oxyalkylene structure. That is, the RO number means a divalent group R in the above formula (2) contained in 1 molecule of the radical-reactive polyrO compound of the present inventionBThe amount of O.
In the above formula (2), n is an integer of 2 or more, preferably 4 or more, more preferably more than 9, or 9 or more, further preferably 11 or more, from the viewpoint of obtaining a cured product excellent in adhesion. From the viewpoint of improving the fluidity of the resin composition (the viscosity of the resin composition or the filling property of the inorganic filler), n is an integer of usually not more than 101, preferably not more than 90, more preferably not more than 68, further preferably not more than 65.
In the above formula (2), RBThe number of carbon atoms of the alkylene group contained in (A) is usually 1 to 6, and from the viewpoint of increasing the content of oxygen atoms as polar sites contained in the polyoxyalkylene structure to obtain a cured product excellent in adhesion to inorganic materials, it is preferably 1 to 5, more preferably 1 to 4, further preferably 1 to 3, particularly preferably 1 to 2, and from the viewpoint of obtaining a cured product reduced in warpage due to the influence of curing shrinkage, it is preferably 2 to 5, further preferably 2 to 4, further preferably 2 to 3. In the above formula (2), R is R from the viewpoint of obtaining a cured product excellent in adhesion to an inorganic material and from the viewpoint of obtaining a cured product reduced in warpage due to the influence of curing shrinkageBThe number of carbon atoms of the alkylene group contained in (1) is typically 2. Thus, in formula (2) above, at a plurality of radicals RBIn (1), at least one group RBThe inclusion of ethylene is a particularly preferred example.
In the above formula (2), RBThe alkylene group contained in (1) usually has no substituent, but optionally has a substituent. Examples of such a substituent include: alkyl with 1-3 carbon atoms, halogen atom, -OH, -O-C1-5Alkyl, -N (C)1-5Alkyl radical)2、C1-5Alkyl radical, C6-10Aryl, -NH2、-CN、-C(O)O-C1-5Alkyl, -COOH, -C (O) H, epoxy, -NO2And the like. From the viewpoint of improving the reactivity with the component (A) and/or the component (C), such a substituent is preferably an epoxy group, -OH, -NH2and-COOH. Even when the radical-reactive polyro compound of the present invention has an epoxy group in the molecule, the compound is classified as the component (B) as long as it has a radical-polymerizable unsaturated group and a polyoxyalkylene structure and satisfies the above-mentioned specific conditions. As described above, the radical-reactive polyro compound of the present invention preferably contains a group reactive with the component (a) and/or the component (C), preferably a group reactive with the component (a), and can form a crosslinked structure, and a cured product having a high elastic modulus and excellent handling properties can be obtained. In this case, the "one or more kinds of radical-reactive poly-RO compounds containing a group reactive with the component (a) and/or the component (C)" and the "one or more kinds of radical-reactive poly-RO compounds containing no group reactive with the component (a) and/or the component (C)" may be used in combination. Further, from the viewpoint of obtaining a cured product having a low dielectric loss tangent, it is preferred that the halogen atom is selected from RBExcept for the substituents contained in the alkylene group. The substituents may be contained alone or in combination of 2 or more.
Specific examples of the polyoxyalkylene structure contained in the component (B) include: polyethylene oxide Structure (- (C)2H4O)n-; here, n is the same as n in the formula (2), and a polyoxypropylene structure (- (C)3H6O)n-; here, n is the same as n in the formula (2), and a polyoxy-n-butene structure (- (C)4H8O)n-; here, n is the same as n in formula (2), a poly (ethylene oxide-co-propylene oxide) structure, a poly (ethylene oxide-ran-propylene oxide) structure, a poly (ethylene oxide-alt-propylene oxide) structure, and a poly (ethylene oxide-block-propylene oxide) structure. Among them, from the viewpoint of obtaining a cured product excellent in the adhesion of inorganic materials, the polyoxyalkylene structure of the component (B) is preferably the polyoxyethylene structure or the polyoxypropylene structureAny of the alkylene structures, more preferably the above polyoxyethylene structure. However, the epoxy resin having an oxyalkylene structure is excluded from the component (B).
When 1 molecule or more of the polyoxyethylene structures is contained in 1 molecule of the radical reactive poly RO compound of the present invention, the number of repetition of the ethylene oxide structure (hereinafter also referred to as "EO number") per 1 molecule is 2 or more, and from the viewpoint of obtaining a cured product excellent in adhesion, it is preferably an integer of 4 or more, more preferably 9 or more, further preferably 11 or more, and usually 101 or less, and from the viewpoint of improving the fluidity of the resin composition (the viscosity of the resin composition or the filling property of the inorganic filler), it is preferably 90 or less, more preferably 68 or less, further preferably 65 or less. The EO number means a divalent group R in the above formula 1 contained in 1 molecule of the radical-reactive polyrO compound of the present inventionBO is composed of- (C)2H4O) -represents the number thereof. The PO number means a divalent group R in the above formula 1 contained in 1 molecule of the radical-reactive polyrO compound of the present inventionBO is composed of- (C)3H6O) -represents the number thereof.
Specific examples of the component (B) include compounds containing the following radical polymerizable unsaturated group and the following polyoxyalkylene structure and satisfying the above formula (1); the radical polymerization unsaturated group is more than one selected from vinyl, allyl, 1-butenyl, 2-butenyl, acryloyl, methacryloyl, fumaryl, maleoyl, vinylphenyl, styryl and cinnamoyl; the polyoxyalkylene structure is selected from the group consisting of polyoxyethylene structures (- (C)2H4O)n-; here, n is the same as n in the formula (2), and a polyoxypropylene structure (- (C)3H6O)n-; here, n is the same as n in the formula (2), and a polyoxy-n-butene structure (- (C)4H8O)n-; here, n is the same as n in formula (2), a poly (ethylene oxide-co-propylene oxide) structure, a poly (ethylene oxide-ran-propylene oxide) structure, a poly (ethylene oxide-alt-propylene oxide) structure, and a poly (ethylene oxide-block-propylene oxide) structure. From the viewpoint of obtaining a cured product excellent in heat resistanceThe component (B) preferably contains 1 or more monovalent or divalent aromatic hydrocarbon groups in the molecule, more preferably 2 or more monovalent or divalent aromatic hydrocarbon groups in the molecule. Examples of the monovalent or divalent aromatic hydrocarbon group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenylene group, a 1-naphthylene group, and a 2-naphthylene group. The 2 or more monovalent or divalent aromatic hydrocarbon groups may be bonded to each other directly or via a linking group, and by the bonding, for example, a bisphenol structure, preferably a bisphenol A structure, may be formed.
As the component (B), commercially available products can be used. Examples of commercially available products include: monofunctional acrylates "AM-90G" (EO number: 9), "AM-130G" (EO number: 13), "AMP-20 GY" (EO number: 2) manufactured by Xinzhongcun chemical industry Co., Ltd; difunctional acrylates "A-1000" (EO number: 23), "A-B1206 PE" (EO number: 6, PO number: 12, RO number: 18), "A-BPE-20" (EO number: 17), "A-BPE-30" (EO number: 30); monofunctional methacrylates "M-20G" (EO number: 2), "M-40G" (EO number: 4), "M-90G" (EO number: 9), "M-130G" (EO number: 13), "M-230G" (EO number: 23); and di-functional methacrylate "23G" (EO number: 23), "BPE-900" (EO number: 17), "BPE-1300N" (EO number: 30), "1206 PE" (EO number: 6, RO number: 18), and "LIGHT ESTER BC" (EO number: 2) manufactured by Kyoho chemical company, "LIGHT ESTER 041 MA" (EO number: 30), "LIGHT ACRYLATE EC-A" (EO number: 2), "LIGHT ACRYLATE EHDG-AT" (EO number: 18), "FA-023M" manufactured by Kyoho chemical company, "BLEMER (registered trademark) PME-4000 (EO number: 90)," BLEMER (registered trademark) 50POEO-800B "(EO number: 8, PO number: 7)," BLEMER (registered trademark) PLE-200 "(EO number: 4)," MMBLER (registered trademark) PLE-1300 "(EO number: 30)," PSE (registered trademark) PLE-1300 "(PSE number: 30)," PSE-1300 (MMER number: 1300) (registered trademark), "BLEMMER (registered trademark) 43 PAPE-600B" (EO number: 6, PO number: 6), "BLEMMER (registered trademark) ANP-300" (PO number: 5), and the like. Among them, from the viewpoint of improving the desired effect of the present invention, for example, one or more commercially available products selected from the group consisting of "M-230G", "M-130G", "23G", "M-40G", "M-90G" and "BPE-1300N" can be used.
The molecular weight of the radical reactive polyro compound of the present invention is 150 or more, and may be 250 or more or 400 or more, with respect to the compound of the formula (1) in which N is 1. (B) The molecular weight of the radical reactive poly-RO compound of the present invention is 1000 or more, and may be 1020 or more or 1200 or more, with respect to the compound of formula (1) in which N is 2. From the viewpoint of improving the fluidity of the resin composition (the viscosity of the resin composition or the filling property of the inorganic filler), the upper limit of the molecular weight of the radical reactive polyro compound of the present invention is, for example, 5000 or less, preferably 3000 or less, more preferably 2500 or less, further preferably 2000 or less, further preferably 1500 or less. (B) When the component (C) is a commercially available product, the molecular weight as a nominal value thereof is preferably within the above range. (B) When the component (C) is a polymer, the weight average molecular weight or the number average molecular weight is preferably in the above range. When the component (B) is a polymer, the weight average molecular weight or the number average molecular weight thereof is a weight average molecular weight or a number average molecular weight in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method.
The content of the component (B) is not limited as long as the mass ratio of the component (B) to the component (C) is within the range described later, and the content of the component (B) is 0.1 mass% or more, 0.2 mass% or more, or 0.3 mass% or more from the viewpoint of improving the desired effect of the present invention when the nonvolatile component in the resin composition is 100 mass%, and is preferably 1 mass% or more, more preferably 1.5 mass% or more, further preferably 2 mass% or more from the viewpoint of further improving the desired effect of the present invention. The upper limit is not particularly limited, but is, for example, 20 mass% or less and 15 mass% or less, and is preferably less than the content of the component (A) when the nonvolatile content in the resin composition is 100 mass%.
The content of the component (B) is not limited as long as the mass ratio of the component (B) to the component (C) is within the range described later, and when 100 mass% is taken as a component other than the inorganic filler (E) in the nonvolatile components in the resin composition, it is preferably 10 mass% or more, more preferably 13 mass% or more, further preferably 15 mass% or more, particularly preferably 16 mass% or more, from the viewpoint of improving the desired effect of the present invention. The upper limit is not particularly limited, but is preferably 40% by mass or less, more preferably 39% by mass or less, further preferably 38% by mass or less, from the viewpoint of enhancing the desired effect of the present invention, and may be 35% by mass or less or 30% by mass or less from the viewpoint of obtaining a cured product having a higher elastic modulus.
(C) acid anhydride
The resin composition contains (C) an acid anhydride. The acid anhydride refers to a compound having an acid anhydride group. (C) The component (b) may be an acid anhydride which is liquid at a temperature of 20 ℃ (hereinafter also referred to as "liquid acid anhydride"), or may be an acid anhydride which is solid at a temperature of 20 ℃ (hereinafter also referred to as "solid acid anhydride"), or may be a combination thereof. From the viewpoint of improving the fluidity of the resin composition (the viscosity of the resin composition or the filling property of the inorganic filler), the component (C) is preferably a liquid acid anhydride. The component (C) may further contain a solid acid anhydride, if necessary. By including the component (C) in combination with the components (a) and (B) in the resin composition, the component (C) contributes to at least part of the effects (warpage, inorganic material adhesion, elastic modulus, and film peeling property) desired by the present invention, and particularly, as exemplified in the column of examples, the resin composition including the component (C) tends to have excellent film releasability.
(C) The acid anhydride may react with the component (A) to cure the resin composition. Specific examples of the acid anhydride include: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4' -diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-C furan-1, 3-dione, ethylene glycol bis (trimellitic anhydride ester), styrene-maleic acid resin obtained by copolymerizing styrene with maleic acid, and other polymer type acid anhydrides.
Commercially available acid anhydrides include: HNA-100, MH-700, MTA-15, DDSA, OSA, YH-306, YH-307, manufactured by Mitsubishi chemical corporation, HN-2200, and HN-5500, manufactured by Hitachi chemical corporation, manufactured by New Japan chemical and physical Co., Ltd.
In the present invention, [ B ] indicating the mass ratio of the component (B) to the component (C): [c] from the viewpoint of exhibiting the desired effects of the present invention, the ratio of 0.2: 1-1.5: 1, preferably in the range of 0.25: 1-1.35: 1, more preferably in the range of 0.3: 1-1.3: 1, in the above range.
The value of the ratio (equivalent ratio) (C)/(a) of "the sum of the values obtained by dividing the amount (g) of the component (C) by the equivalent (g/eq.) of the acid anhydride group contained in the component (C)" and "the sum of the values obtained by dividing the amount (g) of the component (a) by the equivalent (g/eq.) of the epoxy group contained in the component (a)" is preferably 0.4 or more, more preferably 0.5 or more, further preferably 0.6 or more, from the viewpoint of exerting the desired effect of the present invention, and is preferably 1.6 or less, more preferably 1.5 or less, further preferably 1.4 or less, from the viewpoint of obtaining a cured product with little warpage.
The content of the component (C) is not limited as long as the mass ratio of the component (B) to the component (C) is within the above range, and the content of the component (C) may be 10 mass% or more or 15 mass% or more from the viewpoint of improving the desired effect of the present invention, when the component other than the inorganic filler (E) in the nonvolatile component in the resin composition is 100 mass%. From the viewpoint of obtaining a resin composition layer (compression-molded article) excellent in film releasability, the content of the component (C) is preferably 17 mass% or more, more preferably 20 mass% or more, and further preferably 23 mass% or more, assuming that the components other than the inorganic filler (E) in the nonvolatile components in the resin composition are 100 mass%. The upper limit is not particularly limited, but is, for example, 60 mass% or less, preferably 58 mass% or less, more preferably 55 mass% or less, from the viewpoint of improving the desired effect of the present invention, and may be 49 mass% or less or 48 mass% or less from the viewpoint of obtaining a cured product with less warpage.
The content of the component (C) is not limited as long as the mass ratio of the component (B) to the component (C) is within the above range, and when the nonvolatile component in the resin composition is 100 mass%, the content of the component (C) is preferably 0.5 mass% or more, more preferably 1 mass% or more, further preferably 2 mass% or more, or 3 mass% or more, from the viewpoint of improving the desired effect of the present invention. The upper limit is not particularly limited, and is, for example, 40 mass% or less, 30 mass% or less, or 20 mass% or less, preferably less than 2 times the content of the component (a) when the nonvolatile component in the resin composition is 100 mass%.
< D radical Generator
The resin composition of the present invention contains (D) a radical generator. As the component (D), a thermal radical generator is preferably used. Thermal radical generators typically generate radicals by imparting thermal energy.
Examples of the thermal radical generator include: dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, and tert-hexyl peroxy-2-ethylhexanoate; diacyl peroxides such as lauroyl peroxide, benzoyl toluoyl peroxide, and toluoyl peroxide; peroxy esters such as t-butyl peracetate, t-butyl peroxooctanoate and t-butyl peroxobenzoate; ketone peroxides; peroxycarbonates; peroxy ketals such as 1, 1-di (t-amylperoxy) cyclohexane; azonitrile compounds such as 2,2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobis (isobutyronitrile), 2' -azobis (2-methylbutyronitrile) and 2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), and azoamide compounds such as 2,2' -azobis { 2-methyl-N- [1, 1-bis (hydroxymethyl) -2-hydroxyethyl ] propionamide }; azoamidine compounds such as 2,2 '-azobis (2-amidinopropane) dihydrochloride and 2,2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride; azoalkane compounds such as 2,2 '-azobis (2,4, 4-trimethylpentane) and 4,4' -azobis (4-cyanopentanoic acid); azo compounds having an oxime skeleton such as 2,2 '-azobis (2-methylpropionamidoxime), and azo compounds such as dimethyl 2,2' -azobis (isobutyrate). The thermal radical generator may be used alone, or two or more of them may be used in combination at an arbitrary ratio. The azo-based compound generally generates nitrogen upon decomposition, and thus voids tend to be easily generated in a cured product of the resin composition, but it can be preferably used in the present invention. Among the above-described examples of the peroxide-based thermal radical generating agent and the azo compound-based thermal radical generating agent, the peroxide-based thermal radical generating agent is more preferably used from the viewpoint of suppressing the generation of voids.
As the thermal radical generator, a substance having a mesophilic activity is preferred. Specifically, the component (D) is preferably at least one selected from thermal radical generators having a 10-hour half-life temperature T10 (DEG C) in the range of 50 to 110 ℃, more preferably at least one selected from thermal radical generators having a 10-hour half-life temperature T10 (DEG C) in the range of 50 to 100 ℃, and further preferably at least one selected from thermal radical generators having a 10-hour half-life temperature T10 (DEG C) in the range of 50 to 80 ℃ from the viewpoint of obtaining a cured product with less warpage. Examples of such commercially available products include "LUPEROX 531M 80" manufactured by Arkema Fuji corporation, "PERHEXYL (registered trademark) O" manufactured by Nichikuwa Fuji corporation, and "MAIB" manufactured by Fuji film and Wako pure chemical industries.
The component (D) is preferably at least one radical generator selected from the group consisting of radical generators having a difference Δ T (DEG C) between a mold temperature Tc (DEG C) at the time of compression molding and a 10-hour half-life temperature T10 (DEG C) of the component (D) within a range of 20 ℃ to 80 ℃, more preferably 30 ℃ to 80 ℃. That is, when the mold temperature Tc (. degree. C.) used in compression molding is clear, it is preferable to select a thermal radical generator having the above difference Δ T (. degree. C.) within the above range as the component (D) to be contained in the resin composition of the present invention. This makes it possible to obtain a cured product with less warpage.
The content of the component (D) is not limited as long as the desired effects of the present invention are exhibited, and may be, for example, 0.02 mass% or more and 5 mass% or less, 0.03 mass% or more and 4 mass% or less, or 0.04 mass% or more and 3 mass% or less, when the nonvolatile component in the resin composition is 100 mass%. The content of the component (D) is not limited as long as the desired effects of the present invention are exhibited, and when the content of the component (E) other than the inorganic filler is 100 mass% in the nonvolatile components in the resin composition, it may be, for example, 0.02 mass% or more and 5 mass% or less, 0.1 mass% or more and 4 mass% or less, or 0.2 mass% or more and 3 mass% or less.
(E) inorganic filler
The resin composition of the present invention contains (E) an inorganic filler. By containing the component (E) in the resin composition, a cured product with less warpage can be obtained.
The material of the inorganic filler is not particularly limited as long as it is an inorganic compound, and examples thereof 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 zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like, with silica being particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as the silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more. Commercially available products of silica include "SO-C2", "SO-C1" manufactured by Yadmax, and "UFP-30" and "UFP-40" manufactured by DENKA.
The average particle size of the inorganic filler is usually 30 μm or less, and from the viewpoint of enhancing the desired effect of the present invention, it is preferably 25 μm or less, more preferably 20 μm or less, and still more preferably 18 μm or less. The lower limit of the average particle diameter may be 1nm (0.001 μm) or more, 5nm or more, or 10nm or more, and from the viewpoint of improving the desired effect of the present invention, it is preferably 1.0 μm or more, more preferably 1.2 μm or more, and still more preferably 1.4 μm or more.
The average particle diameter of the inorganic filler can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size is measured as an average particle size. As the measurement sample, a sample obtained by weighing 100mg of the inorganic filler and 10g of methyl ethyl ketone in a vial and dispersing them by ultrasonic waves for 10 minutes can be used. For the measurement sample, the volume-based particle size distribution of the inorganic filler was measured by a flow cell method using a laser diffraction type particle size distribution measuring apparatus with the wavelengths of the light source used being blue and red. Then, the average particle diameter was calculated from the obtained particle diameter distribution as a median particle diameter. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, Ltd.
From the viewpoint of improving embeddability, the inorganic filler is preferably treated with a surface treatment agent, more preferably with one or more surface treatment agents selected from fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilicon nitrogen alkane compounds, acryl silane compounds, methacryl silane compounds, titanate coupling agents, and the like, and still more preferably with an aminosilane silane coupling agent. The surface treatment agent preferably has a functional group reactive with other components such as a resin, for example, an epoxy group, an amino group or a mercapto group, and more preferably the functional group is bonded to a terminal group. Examples of commercially available surface treatment agents include: silane coupling agent "KBM 403" (3-glycidoxypropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, silane coupling agent "KBM 803" (3-mercaptopropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, silane coupling agent "KBE 903" (3-aminopropyltriethoxysilane) manufactured by shin-Etsu chemical industries, silane coupling agent "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, silane coupling agent "SZ-31" (hexamethyldisilazane) manufactured by shin-Etsu chemical industries, alkoxysilane compound "KBM 103" (phenyltrimethoxysilane) manufactured by shin-Etsu chemical industries, silane coupling agent "KBM-4803" (glycidoxypropyltrimethoxysilane; long-chain epoxy silane coupling agent), Silane coupling agent "KBM-7103" (3,3, 3-trifluoropropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, Ltd. Among them, silane coupling agents "KBM 573", "KBM-4803" and "KBM 403" manufactured by shin-Etsu chemical industries, Inc. are preferably used as the surface treatment agent. Further, from the viewpoint of obtaining a cured product with less warpage, a long-chain type silane coupling agent is preferable, and a long-chain epoxy type silane coupling agent as a long-chain type silane coupling agent having an epoxy group is particularly preferable.
The degree of surface treatment with the surface treatment agent is preferably 0.2 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, and still more preferably 0.3 to 3 parts by mass, based on 100 parts by mass of the component (E), from the viewpoint of improving embeddability.
The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the embeddability, etc., the carbon content per unit surface area of the inorganic filler is preferably 0.02mg/m2Above, preferably 0.1mg/m2Above, more preferably 0.2mg/m2The above. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, it is preferably 1mg/m2The concentration is preferably 0.8mg/m or less2The concentration is preferably 0.5mg/m or less2The following.
The amount of carbon per unit surface area of the inorganic filler can be measured after the inorganic filler after surface treatment is subjected to a cleaning 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 treatment agent, and ultrasonic cleaning was performed at 25 ℃ for 5 minutes. After removing the supernatant liquid and drying the nonvolatile components, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by horiba, Ltd., can be used.
The specific surface area of the component (E) is preferably 0.3m2More than g, preferably 0.5m2More than g, particularly preferably 0.7m2More than g. The upper limit is not particularly limited, but is preferably 60m2Less than 50 m/g2Less than or equal to 40 m/g2The ratio of the carbon atoms to the carbon atoms is less than g. The specific surface area can be obtained by adsorbing nitrogen gas onto the surface of a sample by the BET method using a BET full-automatic specific surface area measuring apparatus ("Macsorb HM-1210" manufactured by Mountech corporation) and calculating the specific surface area by the BET multipoint method.
The content of the component (E) is preferably 70 mass% or more, more preferably 71 mass% or more, and further preferably 72 mass% or more, from the viewpoint of obtaining a cured product with less warpage, when the content is high in the resin composition and the nonvolatile content in the resin composition is 100 mass%; the upper limit is naturally determined depending on the content of other components, and may be, for example, 95 mass% or less, 93 mass% or less, or 90 mass% or less.
(F) curing Accelerator
The resin composition may contain (F) a curing accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators, and phosphorus-based curing accelerators and imidazole-based curing accelerators are preferred, and imidazole-based curing accelerators are more preferred. The curing accelerator may be used alone or in combination of two or more.
Examples of the phosphorus-based curing accelerator include triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.
Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-Dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo [5.4.0] undecene, with 4-dimethylaminopyridine and 1, 8-diazabicyclo [5.4.0] undecene being preferred. As a commercially available product of the amine-based curing accelerator, for example, "DMP-30" manufactured by Fuji film and Wako pure chemical industries, Ltd.) can be used.
Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like, dicyandiamide and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene are preferable. As a commercial guanidine-based curing accelerator, for example, at least one member selected from pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, and 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene can be used.
Examples of the imidazole-based 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, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-cyanoethyl-2-methylimidazole, 2-decylimidazole, 2-ethylimidazole, 2-decylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-dodecylimidazole, 2-methylimidazole, and mixtures thereof, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1') ] -ethyl-s-triazine isocyanuric acid adduct, and mixtures thereof, 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, imidazole compounds such as 2-methylimidazoline and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.
As the imidazole-based curing accelerator, commercially available products can be used, and examples thereof include imidazole compounds "1B 2 PZ" and "2E 4 MZ" manufactured by Sichuan chemical company, "P200-H50" manufactured by Mitsubishi chemical company, and "2 MA-OK-PW" manufactured by Sichuan chemical company.
Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
When the resin composition contains the component (F), the content of the component (F) may be, for example, 0.01 to 5 mass%, 0.05 to 4 mass%, or 0.08 to 3 mass% when the nonvolatile content in the resin composition is 100 mass%. The content of the component (F) may be, for example, 0.05 to 10 mass%, 0.1 to 5 mass%, or 0.2 to 3 mass% when the components other than the inorganic filler (E) in the nonvolatile components in the resin composition are 100 mass%.
< (G) A compound having a radically polymerizable unsaturated group (excluding a compound having a polyoxyalkylene structure) >)
The resin composition of the present invention preferably further contains (G) a compound having a radical polymerizable unsaturated group (excluding a compound having a polyoxyalkylene structure). As the component (G), 2 or more species can be used. It is considered that the desired effect of the present invention can be improved by including the component (B) in the resin composition and further including the component (G) so that the radical polymerization reaction proceeds in an accelerated or competitive manner, and the component (G) exerts a part of the function of the component (B).
(G) Examples of the radical polymerizable unsaturated group contained in the component (a) include groups containing an ethylenic carbon-carbon double bond. Specific examples thereof include one or more groups selected from the group consisting of vinyl, allyl, 1-butenyl, 2-butenyl, acryloyl, methacryloyl, fumaryl, maleoyl, vinylphenyl, styryl, cinnamoyl, and maleimido. (G) Component (c) may contain 2 or more radical polymerizable unsaturated groups in 1 molecule. (G) The radical polymerizable unsaturated group contained in the component (a) preferably contains at least one selected from the group consisting of a methacryloyl group and an acryloyl group from the viewpoint of improving reactivity, and more preferably contains a methacryloyl group from the viewpoint of controlling reactivity.
Specific examples of the component (G) include compounds containing at least one radical polymerizable unsaturated group selected from the group consisting of a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, an acryloyl group, a methacryloyl group, a fumaroyl group, a maleoyl group, a vinylphenyl group, a styryl group, a cinnamoyl group, and a maleimido group. From the viewpoint of obtaining a cured product having excellent heat resistance, the component (G) preferably contains 1 or more monovalent or divalent aromatic hydrocarbon groups in the molecule, and more preferably 2 or more monovalent or divalent aromatic hydrocarbon groups in the molecule. Examples of the monovalent or divalent aromatic hydrocarbon group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenylene group, a 1-naphthylene group, and a 2-naphthylene group. The 2 or more monovalent or divalent aromatic hydrocarbon groups may be bonded to each other directly or via a linking group, and by the bonding, for example, a bisphenol structure, preferably a bisphenol A structure, may be formed.
(G) The components are also preferredIs a compound further containing a group reactive with the component (A) in the molecule. This enables the formation of a crosslinked structure, and further reduces warpage in the cured product. Examples of the group reactive with the component (A) include epoxy group, -OH, -NH2and-COOH. Even when the component (G) is a compound having an epoxy group in the molecule, the component (G) is classified as the component (G) as long as it is a compound having a radical polymerizable unsaturated group (except a compound having a polyoxyalkylene structure). As the component (G), one or more compounds "containing a group reactive with the component (a) in a molecule" and one or more compounds "containing no group reactive with the component (a) in a molecule" may be used in combination.
The component (G) may be a compound having an oxyalkylene structure in the molecule. (G) The oxyalkylene structure of the component (a) is represented by the formula (3): - (R)CO)n-represents, wherein, in formula (3), n is an integer of 1, RCIs an alkylene group having 1 to 6 carbon atoms which may have a substituent.
The content of the component (G) is arbitrary as long as it does not impair radical polymerization of the component (B), and may be, for example, 20 mass% or less, 19.5 mass% or less, or 19 mass% or less, when the content of the component other than the inorganic filler (E) in the nonvolatile components in the resin composition is 100 mass%. From the viewpoint of improving the desired effect of the present invention, the lower limit is preferably 1% by mass or more, more preferably 1.3% by mass or more, further preferably 1.5% by mass or more, particularly preferably 1.6% by mass or more.
(H) optional additives
In one embodiment, the resin composition may further contain (H) other additives as needed, and examples of the other additives include: curing agents other than component (C), thermoplastic resins, organic fillers, organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds, and resin additives such as thickeners, defoamers, leveling agents, adhesion imparting agents, and colorants, and solvents. The content of the component (H) is arbitrary as long as the desired effects of the present invention are not impaired, and is, for example, 0.1 mass% or more, 0.3 mass% or more, or 0.5 mass% or more, and may be, for example, 15 mass% or less, 13 mass% or less, or 10 mass% or less, when the nonvolatile component in the resin composition is 100 mass%.
Examples of the curing agent other than the component (C) include at least one curing agent selected from the group consisting of an active ester-based curing agent, a phenol-based curing agent (phenol-based curing agent), a naphthol-based curing agent, a carbodiimide-based curing agent, a benzoxazine-based curing agent, an amine-based curing agent, a guanidine-based curing agent, and a cyanate-based curing agent, and commercially available products can be used, for example. From the viewpoint of obtaining a resin composition layer (compression molded article) excellent in film releasability, as the curing agent other than the component (C), it is preferable to use one or more curing agents selected from the group consisting of an active ester-based curing agent, a phenol-based curing agent, a naphthol-based curing agent, a carbodiimide-based curing agent, a benzoxazine-based curing agent and a cyanate-based curing agent. One or more curing agents selected from amine-based curing agents (for example, "KAYAHARD A-A" manufactured by Nippon chemical Co., Ltd.) and guanidine-based curing accelerators (for example, dicyandiamide (DICY 7 "manufactured by Mitsubishi chemical Co., Ltd.) can be used as long as the desired effects of the present invention are not impaired.
Examples of the thermoplastic resin include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetheretherketone resins, and polyester resins. The thermoplastic resin preferably contains a reactive functional group, and thus can be incorporated into the crosslinked structure formed from the component (A). The reactive functional group may be a group that exhibits reactivity by heating or light irradiation. The content of the thermoplastic resin is arbitrary as long as the desired effect of the present invention is not impaired, and is, for example, 0.1 mass% or more, 0.2 mass% or more, or 0.3 mass% or more, when the nonvolatile content in the resin composition is 100 mass%, or 5 mass% or less, 3 mass% or less, or 1 mass% or less, from the viewpoint of improving the crosslinking density.
As the organic filler, any organic filler that can be used in forming an insulating layer of a printed wiring board can be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles. As the rubber particles, commercially available products can be used, and examples thereof include "EXL 2655" manufactured by Touchi chemical Japan, "AC 3401N" manufactured by AIKA industries, and "AC 3816N". The content of the organic filler is arbitrary as long as the desired effects of the present invention are not impaired, and may be, for example, 0.1 mass% or more, 0.3 mass% or more, or 0.5 mass% or more, and may be, for example, 10 mass% or less, 7 mass% or less, or 5 mass% or less, when the nonvolatile content in the resin composition is 100 mass%.
When the resin composition contains a solvent, it is preferable that the amount of the solvent is small. The content of the solvent is more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less, particularly preferably 0% by mass (not contained), when the nonvolatile content of the resin composition is set to 100% by mass. In order to reduce the amount of the solvent, it is preferable to use a liquid component as at least one component selected from the group consisting of the component (a), the component (C), the component (D), the component (F) and the component (G).
< Property of resin composition >
(warpage and modulus of elasticity)
The resin composition of the present invention is cured at 150 ℃ for 60 minutes to obtain a cured product having less warpage. Specifically, as evaluated in the column of examples, the warpage amount measured for a laminate comprising a silicon wafer and a cured product formed on the silicon wafer is, for example, less than 2300 μm, more preferably less than 2000 μm, and still more preferably less than 1500 μm. In addition, the resin composition of the present invention cured at 150 ℃ for 60 minutes to obtain a cured product with high elastic modulus. Specifically, as evaluated in the column of examples, the elastic modulus at 25 ℃ of the cured product is, for example, 7GPa or more, more preferably 9GPa or more. Therefore, the resin composition of the present invention can obtain a cured product without the 1 st tradeoff.
(adhesion to inorganic Material and releasability of film Material)
The cured product obtained by curing the resin composition of the present invention at 150 ℃ for 60 minutes has excellent adhesion to inorganic materials. Specifically, as evaluated in the column of examples, the adhesion strength (copper foil peel strength) of a laminate comprising a copper foil and a cured product formed on the copper foil was, for example, 100kgf/cm2The above. Further, the resin composition layer (compression-molded article) obtained by curing the resin composition of the present invention at 130 ℃ for 10 minutes is excellent in film releasability. Specifically, as evaluated in the column of examples, after the resin composition layer (compression-molded body) was compression-molded, the mold was opened with a normal driving force, and it was observed that the resin composition layer was peeled from the release film and was on the silicon wafer. Therefore, the resin composition of the present invention can obtain a resin composition layer (compression molded article) and a cured article without the 2 nd trade-off.
As described above, the resin composition of the present invention can provide a cured product having small warpage, a large elastic modulus, and excellent adhesion to an inorganic material, and exhibits an effect of excellent releasability from a film material. The reason for the effect is not completely clear, but it is clear that: the resin composition of the present invention contains the components (a) to (E), and the mass ratio of the component (B) to the component (C) is within a predetermined range, so that the above-mentioned 1 st and 2 nd trade-offs tend to be unexpectedly eliminated. Further, the resin composition of the present invention has a large elastic modulus of a cured product thereof, specifically, an elastic modulus at 25 ℃, and therefore, for example, the handling property of a sealed body including a semiconductor chip and a cured product in which the semiconductor chip is embedded can be improved. Further, the resin composition of the present invention has excellent inorganic material adhesion of a cured product thereof, and thus has high reliability as, for example, a sealing material for sealing a semiconductor chip. In addition, the resin composition of the present invention has excellent film releasability of the resin composition layer (compression-molded article), and therefore can be easily removed from the mold after compression molding.
The resin composition of the present invention can provide an insulating layer formed from a cured product having a small warpage, excellent inorganic material adhesion, and a high elastic modulus. Therefore, the resin composition of the present invention can be preferably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board), and can be more preferably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board). The resin composition of the present invention brings about an insulating layer having a small warpage, excellent adhesion to inorganic materials, and a large elastic modulus, and therefore, the resin composition can be preferably used even when a printed wiring board is a component-embedded circuit board. Further, the resin composition of the present invention brings about an insulating layer formed of a cured product having a small warpage, excellent adhesion to an inorganic material, and a large elastic modulus, and therefore, can be more preferably used as a resin composition for forming a solder resist layer (a resin composition for forming a solder resist layer of a printed wiring board). The resin composition of the present invention is a resin composition for forming a sealing layer for sealing a semiconductor chip for semiconductor chip encapsulation (a resin composition for forming a sealing layer for semiconductor chip encapsulation), since it provides an insulating layer formed of a cured product having a small warpage, excellent inorganic material adhesion, and a large elastic modulus. Further, the resin composition of the present invention can be preferably used as a resin composition for forming a rewiring-forming layer of a semiconductor chip package (resin composition for forming a rewiring-forming layer for semiconductor chip package).
The semiconductor chip package including the rewiring formation layer can be manufactured by the following manufacturing method, for example. Further, in manufacturing the semiconductor chip package including the sealing layer, a rewiring layer may be further formed on the sealing layer.
< method for producing resin composition >
The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the compounding ingredients are mixed with a solvent as necessary, and dispersed using a rotary mixer or the like.
The resin composition can be obtained as a resin varnish by containing, for example, a solvent. In one embodiment, the amount of the solvent is preferably small, and the amount of the solvent is more preferably 0.5% by mass or less, further preferably 0.1% by mass or less, when the nonvolatile content of the resin composition is 100% by mass.
< Properties and uses of resin composition layer or cured product of resin composition >
(warpage and modulus of elasticity)
A cured product obtained by thermally curing the resin composition of the present invention generally has a small warpage. For example, in the case of a cured product of a resin composition having a thickness of 100 μm, the amount of warpage measured in a laminate comprising a silicon wafer and a cured product formed on the silicon wafer is, for example, less than 2300 μm, more preferably less than 2000 μm, and still more preferably less than 1500 μm. In addition, a cured product obtained by thermally curing the resin composition of the present invention generally has a large elastic modulus. For example, the cured product of the resin composition has an elastic modulus at 25 ℃ of usually 7GPa or more, preferably 9GPa or more. Therefore, the 1 st tradeoff can be generally eliminated for the cured product of the resin composition of the present invention.
(sealing property of inorganic Material)
The cured product obtained by thermally curing the resin composition of the present invention is generally excellent in adhesion to inorganic materials. For example, in the case of a cured product of a resin composition having a thickness of 300 μm, the adhesion strength (copper foil peel strength) measured in a laminate comprising a copper foil and a cured product formed on the copper foil is usually 100kgf/cm2The above. Further, since the resin composition layer (compression-molded article) of the resin composition of the present invention is excellent in film releasability as described above, a cured article obtained by thermally curing the resin composition of the present invention can be easily taken out from a mold used in compression molding in general. Therefore, the 2 nd trade-off is usually eliminated for the cured product of the present invention.
The cured product of the resin composition of the present invention has a small warpage, excellent inorganic material adhesion, and a large elastic modulus. Therefore, the cured product of the resin composition of the present invention can be preferably used as an insulating layer of a printed wiring board, and can be more preferably used as an interlayer insulating layer of a printed wiring board. Further, the cured product of the resin composition of the present invention can provide an insulating layer having a small warpage, excellent inorganic material adhesion, and a large elastic modulus, and therefore, it can be preferably used even when the printed wiring board is a component-embedded circuit board. Further, the cured product of the resin composition of the present invention can provide an insulating layer formed from a cured product having a small warpage, excellent adhesion to an inorganic material, and a large elastic modulus, and therefore can be more preferably used as a solder resist. Further, the cured product of the resin composition of the present invention can provide an insulating layer having a small warpage, excellent inorganic material adhesion, and a large elastic modulus, and therefore, can be suitably used as a sealing layer for sealing a semiconductor chip for semiconductor chip encapsulation. Further, the cured product of the resin composition of the present invention can be preferably used as a rewiring-forming layer (insulating layer) for forming a rewiring layer of a semiconductor chip package.
[ resin paste ]
The resin paste of the present invention contains the aforementioned resin composition. The resin paste of the present invention generally contains only the aforementioned resin composition. The viscosity of the resin paste at 25 ℃ is preferably in the range of 20 pas to 1000 pas. In order to suppress the generation of voids, the weight loss of the resin paste upon heating is preferably 5% or less.
[ molded article of resin composition ]
The resin composition of the present invention can be formed into a resin composition molded body by compression molding or the like. The shape of the resin composition molded body is not limited to a sheet (sheet), and the resin composition can be processed into any shape. Further, by compression molding or a method other than compression molding, a resin composition molded body in a powder form, a pellet form, or a pellet form (these may be referred to as a resin powder, a resin pellet, or a resin pellet, respectively) can be formed from the resin composition of the present invention.
[ resin sheet ]
The resin sheet of the present invention comprises a support and a resin composition layer comprising the resin composition of the present invention provided on the support.
The thickness of the resin composition layer of the resin sheet is usually 600 μm or less, preferably 500 μm or less, and may be 400 μm or less or 300 μm or less from the viewpoint of thinning of the printed wiring board. The thickness can be further reduced. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be usually 1 μm or more, 10 μm or more, 50 μm or more, or the like.
Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.
When a film made of a plastic material is used as the support, examples of the plastic material include: polyester such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), acrylic polymer such as polycarbonate (hereinafter sometimes abbreviated as "PC") and polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and particularly, inexpensive polyethylene terephthalate is preferable.
When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. As the copper foil, a foil formed of a single metal of copper may be used, and a foil formed of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, or the like) may also be used.
The support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface bonded to the resin composition layer.
Further, as the support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. Examples of the release agent used for the release layer of the support with a release layer include 1 or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. As the support with a release layer, commercially available products can be used, and examples thereof include a PET film having a release layer containing an alkyd resin-based release agent as a main component, "SK-1", "AL-5" and "AL-7" manufactured by Lindedaceae, "LUMIRROR T60" manufactured by Toray, and "Purex" manufactured by Ditika, and "Unipel" manufactured by Unitika.
The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably within the above range.
In one embodiment, the resin sheet may further contain other layers as necessary. Examples of the other layer include a protective film provided on a surface of the resin composition layer not bonded to the support (i.e., a surface opposite to the support) and selected for the support. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust or the like to the surface of the resin composition layer and formation of scratches can be prevented.
The resin sheet can be produced, for example, as follows: a resin varnish obtained by dissolving a resin composition in an organic solvent is prepared, and the resin varnish is applied to a support by a die coater or the like, and dried to form a resin composition layer.
Examples of the organic solvent include: ketones such as acetone, Methyl Ethyl Ketone (MEK) and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. One kind of the organic solvent may be used alone, or two or more kinds may be used in combination. In one embodiment, the smaller the amount of the organic solvent, the better (for example, 0.5% by mass or less, 0.1% by mass or less, 0.01% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass), and it is particularly preferable that the organic solvent is not contained.
The drying can be carried out by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, and the drying is performed under conditions such that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30 to 60 mass% of the organic solvent is used, the resin composition layer can be formed by drying at 50 to 150 ℃ for 3 to 10 minutes.
The resin sheet can be stored in a roll form. When the resin sheet has a protective film, the protective film can be peeled off and used.
The resin sheet of the present invention has an insulating layer formed of a cured product having a small warpage, excellent inorganic material adhesion, and a large elastic modulus. Therefore, the resin sheet of the present invention can be preferably used as a resin sheet for forming an insulating layer of a printed wiring board (resin sheet for forming an insulating layer of a printed wiring board), and can be more preferably used as a resin sheet for forming an interlayer insulating layer of a printed wiring board (resin sheet for an interlayer insulating layer of a printed wiring board). Further, the resin sheet of the present invention can be preferably used as a resin sheet for forming a solder resist layer of a printed wiring board (a solder resist layer-forming resin sheet of a printed wiring board). The resin sheet of the present invention is preferably used as a resin composition for forming a sealing layer for sealing a semiconductor chip for semiconductor chip encapsulation (a sealing layer-forming resin sheet for semiconductor chip encapsulation), since it provides an insulating layer formed of a cured product having a small warpage, excellent inorganic material adhesion, and a large elastic modulus. Further, the resin sheet of the present invention can be preferably used as a resin sheet for forming a rewiring forming layer (insulating layer) of a semiconductor chip package (a rewiring forming layer forming resin sheet for semiconductor chip package).
< printed wiring board >
The printed wiring board of the present invention comprises an insulating layer comprising a cured product of the resin composition of the present invention. The printed wiring board can be manufactured, for example, by a manufacturing method including the following steps (1) and (2):
(1) a step of forming a resin composition layer containing a resin composition on a substrate by using the resin composition of the present invention;
(2) a step of forming an insulating layer by thermally curing the resin composition layer,
for example, the method for manufacturing a printed wiring board of the present invention includes: a step of forming a resin composition layer containing the resin composition of the present invention or a resin composition layer containing the resin paste of the present invention on a circuit board by a compression molding method, and a step of curing the resin composition layer.
In step (1), a substrate is prepared. Examples of the base material include substrates such as a glass epoxy substrate, a metal substrate (stainless steel, cold-rolled steel Sheet (SPCC), etc.), a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The substrate may have a metal layer such as a copper foil as a part of the substrate on the surface. For example, a substrate having a first metal layer and a second metal layer which can be peeled off on both surfaces may be used. When such a base material is used, a conductor layer serving as a wiring layer functioning as a circuit wiring is usually formed on the surface of the second metal layer opposite to the first metal layer. Examples of the substrate having such a metal layer include an extra Thin copper foil "Micro Thin" with a carrier copper foil manufactured by mitsui metal mining corporation.
In addition, a conductive layer may be formed on one or both surfaces of the substrate. In the following description, a member including a base material and a conductor layer formed on the surface of the base material is sometimes referred to as a "base material with a wiring layer" as appropriate. Examples of the conductor material contained in the conductor layer include materials containing 1 or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. As the conductor material, a single metal may be used, and an alloy may be used. Examples of the alloy include alloys of 2 or more metals selected from the above metals (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as a single metal is preferable from the viewpoint of versatility of forming a conductor layer, cost, and easiness of pattern formation; and alloys such as nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy as alloys. Among them, preferable are monometallics of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper; and nickel-chromium alloys, particularly preferably copper.
The conductor layer may be patterned to function as a wiring layer, for example. In this case, the ratio of the line width (circuit width)/the pitch (width between circuits) of the conductor layer is not particularly limited, but is preferably 20/20 μm or less (i.e., the pitch is 40 μm or less), more preferably 10/10 μm or less, still more preferably 5/5 μm or less, still more preferably 1/1 μm or less, and particularly preferably 0.5/0.5 μm or more. The pitch need not be the same in the entirety of the conductor layer. The minimum pitch of the conductor layers may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.
The thickness of the conductor layer depends on the design of the printed wiring board, and is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, further preferably 10 μm to 20 μm, particularly preferably 15 μm to 20 μm.
The conductor layer can be formed, for example, by a method including the steps of: a step of laminating a dry film (photosensitive resist film) on a substrate; a step of obtaining a dry film pattern by exposing and developing the dry film under a predetermined condition using a photomask to form a pattern; forming a conductor layer by a plating method such as electrolytic plating using the developed pattern dry film as a plating mask; and a step of peeling off the pattern dry film. As the dry film, a photosensitive dry film formed of a photoresist composition can be used, and for example, a dry film formed of a resin such as novolac resin (novolak resin) or acrylic resin can be used. The lamination conditions of the base material and the dry film may be the same as those of the base material and the resin sheet described later. The dry film can be peeled off by using an alkaline peeling liquid such as a sodium hydroxide solution.
After the base material is prepared, a resin composition layer is formed on the base material. When the conductive layer is formed on the surface of the base material, the resin composition layer is preferably formed so that the conductive layer is embedded in the resin composition layer.
The resin composition layer is formed by, for example, laminating a resin sheet and a base material. The lamination can be performed, for example, by: the resin sheet is heat-pressure bonded to the base material from the support side, whereby the resin composition layer is bonded to the base material. Examples of the member for heat-pressure bonding the resin sheet to the base material (hereinafter, sometimes referred to as "heat-pressure bonded member") include a heated metal plate (e.g., SUS end plate) and a metal roll (e.g., SUS roll). It is preferable that the heat-pressure bonding member is not directly pressed against the resin sheet, but is pressed via an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the base material.
The lamination of the substrate and the resin sheet can be performed by, for example, a vacuum lamination method. In the vacuum lamination method, the heating and press-bonding temperature is preferably in the range of 60 to 160 ℃, more preferably 80 to 140 ℃. The pressure of the heat-pressure bonding is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47 MPa. The heat-pressure bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably performed under a reduced pressure of 13hPa or less.
After the lamination, the smoothing treatment of the laminated resin sheets may be performed under normal pressure (atmospheric pressure), for example, by pressing the heat crimping member from the support side. The pressing conditions for the smoothing treatment may be the same as the above-described conditions for the heat and pressure bonding of the laminate. The lamination and smoothing processes may be continuously performed using a vacuum laminator.
The resin composition layer can be formed by, for example, compression molding. The molding conditions may be the same as those of the method for forming the resin composition layer in the step of forming the sealing layer of the semiconductor chip package, which will be described later.
After the resin composition layer is formed on the base material, the resin composition layer is thermally cured to form the insulating layer. Although the conditions for heat-curing the resin composition layer vary depending on the kind of the resin composition, the curing temperature is usually in the range of 120 to 240 ℃ (preferably in the range of 130 to 220 ℃, more preferably in the range of 140 to 200 ℃), and the curing time is usually 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 preliminary heat 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 for usually 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes) at a temperature of usually 50 ℃ or more and less than 120 ℃ (preferably 60 ℃ or more and 110 ℃ or less, more preferably 70 ℃ or more and 100 ℃ or less) before the resin composition layer is thermally cured.
As described above, the printed wiring board having the insulating layer can be manufactured. The method for manufacturing a printed wiring board may further include any step. For example, when a printed wiring board is manufactured using a resin sheet, the method for manufacturing a printed wiring board may include a step of peeling off the support body of the resin sheet. The support may be peeled off before the resin composition layer is thermally cured, or may be peeled off after the resin composition layer is thermally cured.
The method for manufacturing a printed wiring board may include, for example, a step of polishing a surface of an insulating layer after the insulating layer is formed. The polishing method is not particularly limited. For example, the surface of the insulating layer may be polished using a surface grinder.
The method for manufacturing a printed wiring board may include, for example, a step (3) of connecting the conductor layers between layers, for example, a step of forming a hole in the insulating layer. Thus, a via hole, a through hole, or the like can be formed in the insulating layer. Examples of the method for forming the through hole include laser irradiation, etching, and mechanical drilling. The size and shape of the through hole may be determined as appropriate according to the design of the printed wiring board. In the step (3), the interlayer connection may be performed by polishing or grinding of the insulating layer.
After the formation of the through-hole, a step of removing the contamination (smear) in the through-hole is preferably performed. This process is sometimes referred to as a desmear process. For example, in the case where the formation of the conductor layer on the insulating layer is performed by the plating process, the through-hole may be subjected to a wet desmear treatment. In the case where the conductive layer is formed on the insulating layer by a sputtering process, a dry contamination removal process such as a plasma treatment process may be performed. Further, the insulating layer may be roughened by a desmear process.
Further, the insulating layer may be subjected to roughening treatment before forming the conductor layer on the insulating layer. By this roughening treatment, the surface of the insulating layer including the inside of the through hole can be roughened in general. As the roughening treatment, any of dry and wet roughening treatments can be performed. Examples of the dry roughening treatment include plasma treatment. Further, as an example of the wet roughening treatment, there is a method of sequentially performing an expansion treatment with an expansion liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid.
After the via hole is formed, a conductor layer is formed on the insulating layer. By forming a conductor layer at the position where the via hole is formed, the newly formed conductor layer is electrically connected to the conductor layer on the surface of the base material, thereby performing interlayer connection. Examples of the method for forming the conductor layer include plating, sputtering, and vapor deposition, and among them, plating is preferred. In a preferred embodiment, plating is performed on the surface of the insulating layer by an appropriate method such as a semi-additive method or a full-additive method, thereby forming a conductor layer having a desired wiring pattern. When the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a subtractive method. The material of the formed conductor layer may be a single metal or an alloy. In addition, the conductor layer may have a single-layer structure or a multilayer structure including 2 or more layers of different kinds of materials.
Here, an example of an embodiment in which a conductor layer is formed over an insulating layer will be described in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern for exposing a part of the plating seed layer is formed on the formed plating seed layer corresponding to a desired wiring pattern. An electrolytic plating layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed. In the formation of the conductor layer, the dry film used for the formation of the mask pattern is the same as the dry film described above.
The method for manufacturing a printed wiring board may include a step (4) of removing the base material. By removing the base material, a printed wiring board having an insulating layer and a conductor layer embedded in the insulating layer can be obtained. For example, when a substrate having a peelable metal layer is used, the step (4) can be performed.
< semiconductor chip Package >
A semiconductor chip package according to a first embodiment of the present invention includes: the printed wiring board and the semiconductor chip mounted on the printed wiring board. The semiconductor chip package can be manufactured by bonding a semiconductor chip to a printed wiring board. The method of manufacturing a semiconductor chip package of the present invention may include: a step of forming a resin composition layer containing the resin composition of the present invention or a resin composition layer containing the resin paste of the present invention on a semiconductor chip by a compression molding method, and a step of curing the resin composition layer.
As for the bonding condition between the printed wiring board and the semiconductor chip, any condition that the terminal electrode of the semiconductor chip and the circuit wiring of the printed wiring board can be conductively connected can be adopted. For example, conditions used in flip-chip mounting of a semiconductor chip may be employed. Further, for example, the semiconductor chip and the printed wiring board may be bonded to each other via an insulating adhesive.
As an example of the bonding method, a method of bonding a semiconductor chip to a printed wiring board by pressure bonding is given. The pressure bonding temperature is usually in the range of 120 to 240 ℃ (preferably 130 to 200 ℃, more preferably 140 to 180 ℃) and the pressure bonding time is usually in the range of 1 to 60 seconds (preferably 5 to 30 seconds) as the pressure bonding conditions.
In addition, as another example of the bonding method, a method of bonding a semiconductor chip to a printed wiring board by reflow soldering is given. The reflow soldering conditions may be in the range of 120 ℃ to 300 ℃.
After the semiconductor chip is bonded to the printed wiring board, the semiconductor chip may be filled with a mold underfill material. The resin composition described above can be used as the molding underfill material, and the resin sheet described above can also be used.
A semiconductor chip package according to a second embodiment of the present invention includes: a semiconductor chip and a cured product of the resin composition for sealing the semiconductor chip. In such a semiconductor chip package, a cured product of the resin composition generally functions as a sealing layer. For example, the method of manufacturing a semiconductor chip package of the present invention may include: a step of forming a resin composition layer containing the resin composition of the present invention or a resin composition layer containing the resin paste of the present invention on a semiconductor chip by a compression molding method, and a step of curing the resin composition layer.
The method for manufacturing the semiconductor chip package may include the steps of:
(A) a step of laminating a temporary fixing film on the base material,
(B) a step of temporarily fixing the semiconductor chip to the temporary fixing film,
(C) a step of 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) a step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled,
(F) a step of forming a rewiring layer as a conductor layer on the rewiring formation 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 the steps of:
(H) and a step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages and singulating the 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 securing film may be the same as those of the base material and the resin sheet in the manufacturing method of the printed wiring board.
Examples of the substrate include: a silicon wafer; a glass wafer; a glass substrate; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel Sheet (SPCC); a substrate such as an FR-4 substrate obtained by impregnating glass fibers with an epoxy resin or the like and thermally curing the resin; a substrate made of bismaleimide triazine resin such as BT resin; and the like.
As the temporary securing film, any material that can be peeled off from the semiconductor chip and can temporarily secure the semiconductor chip can be used. Examples of commercially available products include "REVALPHA" manufactured by ritonary electric corporation.
(Process (B))
The step (B) is a step of temporarily fixing the semiconductor chip to the temporary fixing film. The temporary fixing of the semiconductor chip can be performed using a device such as a flip chip bonder (flip chip bonder), a die bonder (die bonder) or the like. The layout (layout) and the number of semiconductor chips to be arranged may be appropriately set according to the shape and size of the temporary fixing film, the number of production processes of the target semiconductor chip package, and the like, and for example, the semiconductor chips may be arranged in a matrix of a plurality of rows and a plurality of columns to be temporarily fixed.
(Process (C))
The step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer is formed from a cured product of the resin composition. The sealing layer is generally formed by a method including the following steps: the method includes a step of forming a resin composition layer on a semiconductor chip, and a step of forming a sealing layer by thermally curing the resin composition layer.
The formation of the resin composition layer is preferably performed by compression molding. In the compression molding method, generally, a semiconductor chip and a resin composition are placed in a mold, and a resin composition layer covering the semiconductor chip is formed in the mold by applying pressure and heating as necessary to the resin composition.
The specific operation of the compression molding method can be performed, for example, in the following manner. As a mold for compression molding, an upper mold (cope) and a lower mold (drag) were prepared. Further, the semiconductor chip temporarily fixed to the temporary fixing film as described above is coated with a resin composition. The semiconductor chip coated with the resin composition is mounted on a lower mold together with a base material and a temporary fixing film. Then, the upper mold and the lower mold are closed, and heat and pressure are applied to the resin composition to perform compression molding.
Further, the specific operation of the compression molding method can be performed, for example, as follows. An upper mold and a lower mold were prepared as a mold for compression molding. A resin composition is placed on the lower mold. The semiconductor chip is mounted on the upper mold together with the base material and the temporary fixing film. Then, the upper mold and the lower mold are closed so that the resin composition placed on the lower mold contacts the semiconductor chip mounted on the upper mold, and heat and pressure are applied to the mold to perform compression molding. In general, in the compression molding method, a mold release film is provided on the surface of a mold. Therefore, the resin composition can be molded in a state of being in contact with the release film. The resin composition containing the components (a) to (E) combined as described above has excellent releasability from a release film, and therefore, the molded resin composition layer or cured product can be smoothly taken out from a mold.
The molding conditions vary depending on the composition of the resin composition, and suitable conditions can be adopted to achieve good sealing. For example, the temperature of the mold (mold temperature Tc) at the time of molding is preferably 70 ℃ or higher, more preferably 80 ℃ or higher, particularly preferably 90 ℃ or higher, preferably 200 ℃ or lower, more preferably 170 ℃ or lower, particularly preferably 150 ℃ or lower. The pressure applied during molding is preferably 1MPa or more, more preferably 2MPa or more, particularly preferably 3MPa or 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, preferably 60 minutes or less, further preferably 30 minutes or less, particularly preferably 20 minutes or less. Generally, after the resin composition layer is formed, the mold is removed. The removal of the mold may be performed before or after the thermosetting of the resin composition layer.
The resin composition layer can be formed by laminating a resin sheet and a semiconductor chip. For example, the resin composition layer of the resin sheet is thermally and pressure-bonded to the semiconductor chip, whereby the resin composition layer can be formed on the semiconductor chip. The resin sheet and the semiconductor chip are generally laminated using a semiconductor chip instead of the base material, in the same manner as the resin sheet and the base material are laminated in the method for manufacturing a printed wiring board.
After a resin composition layer is formed on a semiconductor chip, the resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor chip. Thus, the semiconductor chip is sealed with the cured product of the resin composition. The conditions for heat curing of the resin composition layer may be the same as those for heat curing of the resin composition layer in the method for manufacturing a printed wiring board. Further, before the resin composition layer is thermally cured, a preliminary heat treatment of heating the resin composition layer at a temperature lower than the curing temperature may be performed. The same conditions as the preliminary heating process in the method for manufacturing a printed wiring board can be adopted as the process conditions for the preliminary heating process.
(Process (D))
The step (D) is a step of peeling the base material and the temporary securing film from the semiconductor chip. The peeling method is preferably an appropriate method in accordance with the material of the temporary fixing film. Examples of the peeling method include a method in which the temporary fixing film is heated, foamed, or expanded to be peeled. In addition, as a peeling method, for example, a method of irradiating ultraviolet rays to the temporary fixing film through the base material to lower the adhesion of the temporary fixing film and peeling the film can be given.
In the method of peeling the temporary fixing film by heating, foaming or expanding, the heating condition is usually from 1 second to 90 seconds or from 5 minutes to 15 minutes at 100 ℃ to 250 ℃. In the method of peeling the temporary fixing film by irradiating ultraviolet rays to decrease the adhesive force of the temporary fixing film, the irradiation amount of ultraviolet rays is usually 10mJ/cm2～1000mJ/cm2。
(Process (E))
The step (E) is a step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled.
Any insulating material can be used as the material of the rewiring formation layer. Among them, a photosensitive resin and a thermosetting resin are preferable from the viewpoint of easiness of manufacturing the semiconductor chip package. Further, as the thermosetting resin, the resin composition of the present invention can be used.
After the rewiring layer is formed, a through hole may be formed in the rewiring layer in order to connect the semiconductor chip and the rewiring layer between layers.
In a method for forming a through hole in the case where the material of the rewiring formation layer is a photosensitive resin, generally, the surface of the rewiring formation layer is irradiated with an active energy ray through a mask pattern, and the irradiated portion of the rewiring formation layer is photocured. Examples of the active energy ray include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. The amount and time of ultraviolet irradiation can be appropriately set according to the photosensitive resin. Examples of the exposure method include a contact exposure method in which a mask pattern is brought into close contact with the rewiring formation layer to perform exposure, a non-contact exposure method in which exposure is performed using parallel light rays without bringing the mask pattern into close contact with the rewiring formation layer, and the like.
After photocuring the rewiring formation layer, the rewiring formation layer is developed to remove the unexposed portion, thereby forming a through hole. The development may be any of wet development and dry development. Examples of the developing method include a dipping method, a spin immersion (paddle) method, a spraying method, a brush coating method, and a doctor blade (spraying) method, and the spin immersion method is preferable from the viewpoint of resolution.
Examples of a method for forming a through hole in the case where the material of the rewiring formation layer is a thermosetting resin include laser irradiation, etching, and mechanical drilling. Among them, laser irradiation is preferable. The laser irradiation can be performed using an appropriate laser processing machine using a light source such as a carbon dioxide laser, a UV-YAG laser, or an excimer laser.
The shape of the through-hole is not particularly limited, but a circular shape (substantially circular shape) is generally used. The diameter of the top of the through-hole is preferably 50 μm or less, more preferably 30 μm or less, and further preferably 20 μm or less. Here, the top diameter of the via hole means the opening diameter of the via hole on the surface of the rewiring formation layer.
(Process (F))
The step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring formation layer. The method of forming the rewiring layer on the rewiring-forming layer may be the same as the method of forming the conductor layer on the insulating layer in the method of manufacturing the printed wiring board. Further, the step (E) and the step (F) may be repeated to alternately stack (stack) the rewiring layer and the rewiring-forming layer.
(Process (G))
The step (G) is a step of forming a solder resist layer on the rewiring layer. Any material having insulating properties can be used as the material of the solder resist layer. Among them, a photosensitive resin and a thermosetting resin are preferable from the viewpoint of easiness of manufacturing the semiconductor chip package. Further, as the thermosetting resin, the resin composition of the present invention can be used.
In the step (G), a bump process for forming a bump (bump) may be performed as necessary. The bumping process may be performed by solder ball, solder plating (solder plating), and the like. The formation of the through hole in the bump processing can be performed in the same manner as in the step (E).
(Process (H))
The method for manufacturing a semiconductor chip package may include the 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 cutting the semiconductor chip packages into the semiconductor chip packages one by one is not particularly limited.
< semiconductor device >
The semiconductor device includes a semiconductor chip package. Examples of the semiconductor device include a printed wiring board, a semiconductor chip Package, a multi-chip Package, a Package-on-Package (Package), a wafer level Package (Fan-out) WLP), a panel level Package, and a system level Package. Examples of the semiconductor device include various semiconductor devices used in electric products (for example, computers, mobile phones, smartphones, tablet-type devices, wearable devices, digital cameras, medical devices, televisions, and the like), vehicles (for example, motorcycles, automobiles, electric trains, ships, airplanes, and the like), and the like.
Examples
The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples. In the following description, "part" and "%" representing amounts mean "part by mass" and "% by mass", respectively, unless otherwise specified. The following operations are performed under an ambient temperature and pressure atmosphere unless otherwise stated.
[ example 1]
< preparation of resin paste A >
10 parts of an epoxy resin (ZX-1059, epoxy equivalent: 165G/eq., manufactured by Nippon iron Chemicals Co., Ltd.) as component (A), 5 parts of a compound having a methacryloyl group and a polyoxyethylene structure (M-130G, methacryl equivalent: 628G/eq., manufactured by Nippon village chemical industry Co., Ltd.) as component (B), 8 parts of an acid anhydride curing agent (MH-700, acid anhydride equivalent: 163G/eq., manufactured by Nippon Japan chemical Co., Ltd.) as component (C), 0.1 part of a thermal radical generator (LUPEROX 531M80, manufactured by Arkema Fuji Co., Ltd., "LUPEROX 531M 8932, 10-hour half-life temperature T10: 93.0 ℃ C., a hydrocarbon solution having a peroxide content of 80%) as component (D), 0.15 part of an imidazole curing accelerator (1B 2PZ, manufactured by Nippon chemical Co., Ltd.) as component (F), and 0.15 parts of an imidazole curing accelerator (1B 2PZ, manufactured by Nippon chemical Co., Ltd.) as component (F) were mixed by a mixer, And an inorganic filler A (average particle diameter: 1.8 μm, specific surface area: 3.6 m) as the component (E)2(iv)/g, maximum cut diameter (cut diameter): 5 μm, 85 parts of spherical silica treated with KBM573 (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by shin-Etsu chemical Co., Ltd.) was uniformly dispersed. Thus, a liquid resin composition was prepared. Hereinafter, the liquid resin composition thus prepared is also referred to as "resin paste a".
< evaluation of cured product of resin paste A >
Using the obtained resin paste a, a compression molded body (resin composition layer) or a cured product or an evaluation substrate comprising a cured product was obtained, and the obtained compression molded body (resin composition layer) or cured product or evaluation substrate was subjected to evaluation from the viewpoints of warpage, elastic modulus, adhesion to an inorganic material, and peeling property from a film material, which will be described later.
[ examples 2 to 6]
In examples 2 to 6, 5 parts of the compound having a methacryloyl group and a polyoxyethylene structure (M-130G, manufactured by Ninghamura chemical industries, Ltd.) as the component (B) in example 1 were changed to: 5 parts of a compound having a methacryloyl group and a polyoxyethylene structure as component (B) (M-230G, equivalent methacryloyl group: 1068G/eq., manufactured by Nippon Memura chemical industries Co., Ltd.), 5 parts of a compound having a methacryloyl group and a polyoxyethylene structure as component (B) (M-23G, equivalent methacryloyl group: 568G/eq., manufactured by Nippon Memura chemical industries Co., Ltd.), 5 parts of a compound having a methacryloyl group and a polyoxyethylene structure as component (B) (M-90G, equivalent methacryloyl group: 468G/eq., manufactured by Nippon Memura chemical industries Co., Ltd.), 5 parts of a compound having a methacryloyl group and a polyoxyethylene structure as component (B) (M-40G, equivalent methacryloyl group: 276G/eq., manufactured by Nippon Memura chemical industries Co., Ltd.), 5 parts of a compound having a methacryloyl group and a polyoxyethylene structure (BPE-1300N, methacryloyl equivalent: 842g/eq, manufactured by Ninghamu chemical industries, Ltd.) as a component (B).
In the same manner as in example 1 except for the above, resin paste a was prepared. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 1, and these were subjected to evaluation in the same manner as in example 1.
[ example 7]
In example 6, 85 parts of the inorganic filler A as the component (E) was changed to the inorganic filler B as the component (E) (average particle diameter: 2.6 μm, specific surface area: 1.4 m)2(iv)/g, maximum cut particle diameter: 10 μm, 140 parts of spherical alumina treated with KBM573 (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by shin-Etsu chemical Co., Ltd.).
In the same manner as in example 6 except for the above, resin paste a was prepared. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 6, and these were subjected to evaluation in the same manner as in example 6.
[ examples 8 and 9]
In example 8, 0.1 part of the thermal radical generating agent (LUPEROX 531M80 manufactured by Arkema Fuji Co., Ltd., hydrocarbon solution having a peroxide content of 80%) as the component (D) in example 6 was changed to 0.1 part of the thermal radical generating agent (PERHEXYL (registered trademark) O manufactured by Nichigan Co., Ltd., 10-hour half-life temperature T10: 69.9 ℃) as the component (D), and in example 9, 0.1 part of the thermal radical generating agent (LUPEROX 531M80 manufactured by Arkema Fuji Co., Ltd., hydrocarbon solution having a peroxide content of 80%) as the component (D) in example 6 was changed to 0.1 part of the thermal radical generating agent (MAIB manufactured by Fuji film and Wako pure chemical Co., Ltd.) (dimethyl 2,2' -azobisisobutyrate) as the component (D), 10-hour half-life temperature T10: 67.0 ℃).
In the same manner as in example 6 except for the above, resin paste a was prepared. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 6, and these were subjected to evaluation in the same manner as in example 6.
[ example 10]
In example 6, 8 parts of the acid anhydride-based curing agent (MH-700, manufactured by Nippon chemical Co., Ltd.) as the component (C) was changed to 8 parts of the acid anhydride-based curing agent (HNA-100, manufactured by Nippon chemical Co., Ltd.; acid anhydride group equivalent: 179g/eq.) as the component (C).
In the same manner as in example 6 except for the above, resin paste a was prepared. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 6, and these were subjected to evaluation in the same manner as in example 6.
[ example 11]
In example 6, 8 parts of the acid anhydride curing agent (MH-700, manufactured by Nissian chemical Co., Ltd.) as the component (C) was changed to 15 parts of the acid anhydride curing agent (MH-700, manufactured by Nissian chemical Co., Ltd.) as the component (C), and 85 parts of the inorganic filler A as the component (E) was changed to 100 parts of the inorganic filler A as the component (E).
In the same manner as in example 6 except for the above, resin paste a was prepared. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 6, and these were subjected to evaluation in the same manner as in example 6.
[ example 12]
In example 6, 5 parts of the compound having a methacryloyl group and a polyoxyethylene structure (BPE-1300N, manufactured by Ningmura chemical industries, Ltd.) as the component (B) was changed to 10 parts of the compound having a methacryloyl group and a polyoxyethylene structure (BPE-1300N, manufactured by Ningmura chemical industries, Ltd.) as the component (B), and 85 parts of the inorganic filler A as the component (E) was changed to 95 parts of the inorganic filler A as the component (E).
In the same manner as in example 6 except for the above, resin paste a was prepared. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 6, and these were subjected to evaluation in the same manner as in example 6.
[ example 13]
In example 6, 10 parts of an epoxy resin ("ZX-1059" manufactured by Nippon iron Chemicals) and 5 parts of an epoxy resin ("HP-4032 SS" manufactured by DIC) were changed to 5 parts of an epoxy resin ("ZX-1059" manufactured by Nippon iron Chemicals) and 8 parts of an acid anhydride curing agent ("MH-700" manufactured by Nippon iron Chemicals) were changed to 9 parts of an acid anhydride curing agent ("MH-700" manufactured by Nippon iron Chemicals) and 85 parts of an inorganic filler A as a component (E) were changed to 90 parts of an inorganic filler A as a component (E).
In the same manner as in example 6 except for the above, resin paste a was prepared. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 6, and these were subjected to evaluation in the same manner as in example 6.
[ example 14]
In example 6, 10 parts of an epoxy resin ("ZX-1059" manufactured by Nippon iron Chemicals) and 5 parts of an epoxy resin ("630 LSD" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 98g/eq.) were changed to 5 parts of an epoxy resin ("ZX-1059" manufactured by Nippon iron Chemicals) and 8 parts of an acid anhydride-based curing agent ("MH-700" manufactured by Nippon iron Chemicals) and 11 parts of an acid anhydride-based curing agent ("MH-700" manufactured by Nippon iron Chemicals) were changed to 11 parts of component (A) and 85 parts of an inorganic filler (A) was changed to 95 parts of an inorganic filler (A) was changed to component (E).
In the same manner as in example 6 except for the above, resin paste a was prepared. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 6, and these were subjected to evaluation in the same manner as in example 6.
[ example 15]
In example 6, 85 parts of the inorganic filler A as the component (E) was changed to the inorganic filler C as the component (E) (average particle diameter: 1.8 μm, specific surface area: 3.6 m)2(iv)/g, maximum cut particle diameter: 5 μm, spherical silica treated with KBM-4803 (glycidooctyltrimethoxysilane) manufactured by shin-Etsu chemical Co., Ltd.) in 95 parts.
In the same manner as in example 6 except for the above, resin paste a was prepared. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 6, and these were subjected to evaluation in the same manner as in example 6.
[ example 16]
In example 6, 85 parts of the inorganic filler A as the component (E) was changed to the inorganic filler D as the component (E) (average particle diameter: 1.8 μm, specific surface area: 3.6 m)2(iv)/g, maximum cut particle diameter: 5 μm, KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by shin Etsu chemical Co., LtdAlkane) treated spherical silica) 85 parts.
In the same manner as in example 6 except for the above, resin paste a was prepared. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 6, and these were subjected to evaluation in the same manner as in example 6.
Comparative example 1
In example 1,5 parts of a compound having a methacryloyl group and a polyoxyethylene structure (manufactured by Ningmura chemical industries, Ltd. "M-130G") as a component (B) was changed to 5 parts of a compound having a methacryloyl group and a polyoxyethylene structure (manufactured by Ningmura chemical industries, Ltd. "BPE-500", methacryloyl group equivalent: 402G/eq.) as a component (B'). That is, in comparative example 1, the component (B) was not used.
In the same manner as in example 1 except for the above, resin paste a was prepared. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 1, and these were subjected to evaluation in the same manner as in example 1.
Comparative example 2
In example 6, 8 parts of an acid anhydride-based curing agent (MH-700, manufactured by Nippon chemical Co., Ltd.) as the component (C) was changed to 0.5 part of an amine-based curing agent (KAYAHARD A-A, manufactured by Nippon chemical Co., Ltd.) as the component (H). That is, in comparative example 2, component (C) was not used. In example 6, 0.15 parts of the imidazole-based curing accelerator (1B 2PZ, manufactured by four chemical industries, Ltd.) as the component (F) was changed to 0.2 parts of the imidazole-based curing accelerator (2E 4MZ, manufactured by four chemical industries, Ltd.) as the component (F), and 85 parts of the inorganic filler a as the component (E) was changed to 60 parts of the inorganic filler a as the component (E).
In the same manner as in example 6 except for the above, resin paste a was prepared. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 6, and these were subjected to evaluation in the same manner as in example 6.
Comparative example 3
In comparative example 2, 0.5 part of an amine-based curing agent (KAYAHARD A-A, manufactured by Nippon chemical Co., Ltd.) as the component (H) was changed to 1 part of dicyandiamide (DICY 7, manufactured by Mitsubishi chemical Co., Ltd.). That is, in comparative example 3, the component (C) was not used as in comparative example 2.
Except for the above, resin paste a was prepared in the same manner as in comparative example 2. Then, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained using the resin paste a in the same manner as in comparative example 2, and these were subjected to evaluation in the same manner as in comparative example 2.
Comparative example 4
In comparative example 2, 0.5 part of an amine-based curing agent (KAYAHARD A-A, manufactured by Nippon chemical Co., Ltd.) was not used as the component (H). That is, in comparative example 4, the component (C) was not used as in comparative example 2.
Except for the above, resin paste a was prepared in the same manner as in comparative example 2. Then, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained using the resin paste a in the same manner as in comparative example 2, and these were subjected to evaluation in the same manner as in comparative example 2.
Comparative example 5
In example 1,5 parts of a compound having a methacryloyl group and a polyoxyethylene structure (M-130G, manufactured by Ninghamu chemical industries, Ltd.) was not used as the component (B). That is, in comparative example 5, the component (B) was not used. In example 1, 85 parts of the inorganic filler a as the component (E) was changed to 65 parts of the inorganic filler a as the component (E).
In the same manner as in example 1 except for the above, resin paste a was prepared. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 1, and these were subjected to evaluation in the same manner as in example 1.
Comparative example 6
In example 6, 8 parts of the acid anhydride-based curing agent (MH-700, manufactured by Nissian chemical Co., Ltd.) as the component (C) was changed to 3 parts of the acid anhydride-based curing agent (MH-700, manufactured by Nissian chemical Co., Ltd.). In example 6, 85 parts of the inorganic filler a as the component (E) was changed to 65 parts of the inorganic filler a as the component (E).
Except for the above, resin paste a was prepared in the same manner as in example 6. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 6, and these were subjected to evaluation in the same manner as in example 6.
Comparative example 7
In example 6, 5 parts of the compound having a methacryloyl group and a polyoxyethylene structure (BPE-1300N, manufactured by Ningmura chemical industries, Ltd.) as the component (B) was changed to 1 part of the compound having a methacryloyl group and a polyoxyethylene structure (BPE-1300N, manufactured by Ningmura chemical industries, Ltd.) as the component (B). In example 6, 85 parts of the inorganic filler a as the component (E) was changed to 70 parts of the inorganic filler a as the component (E).
In the same manner as in example 6 except for the above, resin paste a was prepared. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 6, and these were subjected to evaluation in the same manner as in example 6.
Comparative example 8
In example 6, 5 parts of the compound having a methacryloyl group and a polyoxyethylene structure (BPE-1300N, manufactured by Ningmura chemical industries, Ltd.) as the component (B) was changed to 13 parts of the compound having a methacryloyl group and a polyoxyethylene structure (BPE-1300N, manufactured by Ningmura chemical industries, Ltd.) as the component (B). In example 6, 85 parts of the inorganic filler a as the component (E) was changed to 110 parts of the inorganic filler a as the component (E).
In the same manner as in example 6 except for the above, resin paste a was prepared. Then, using the resin paste a, a compression molded body (resin composition layer), a cured product, or an evaluation substrate including a cured product was obtained in the same manner as in example 6, and these were subjected to evaluation in the same manner as in example 6.
[ evaluation method ]
A compression molded body (resin composition layer) or a cured product of the resin paste a obtained in the above examples and comparative examples, or a substrate for evaluation including a cured product were obtained, and evaluation was performed by the following method from the viewpoint of warpage, elastic modulus, adhesion to an inorganic material, and peeling property from a film material. The evaluation results are shown in tables 1 and 2.
< evaluation of peelability from film >
The resin paste a was subjected to compression molding (resin composition layer) to evaluate the releasability from the film material as follows.
(production of substrate for evaluation Bb containing resin composition layer Ba)
First, a compression molding apparatus provided with a mold is prepared. A mold release film (double-faced pear skin processing film "AFREX (アフレックス) (registered trademark) 50 MW", manufactured by AGC Co., Ltd.) was attached to the surface of the mold. Using this compression molding apparatus, the mold temperature Tc: 130 ℃ and pressure: 6MPa, curing time: the resin paste A was compression-molded on a 12-inch silicon wafer (substrate) under a condition of 10 minutes. Thus, an evaluation substrate comprising a "silicon wafer" and a resin composition layer having a thickness of 150 μm as a compression-molded product of the resin paste A formed on the silicon wafer "was prepared in a mold. Hereinafter, the resin composition layer and the evaluation substrate thus produced are also referred to as a "resin composition layer Ba" and an "evaluation substrate Bb", respectively.
(evaluation of resin composition layer Ba)
After the compression molding was completed, it was confirmed whether or not the molds were opened (i.e., whether or not the pair of opposing molds were separated by a normal driving force set in the compression molding apparatus). Further, with the mold opened, it was observed whether the resin composition layer Ba was peeled off from the release film and was on the silicon wafer. The results of these confirmations and observations were evaluated according to the following criteria:
". o": as a result of the test, it was observed that the mold was opened with a normal driving force and the resin composition layer B was peeled from the release film and was on the silicon wafer, and therefore, it was evaluated that the releasability of the resin composition layer B from the film material was excellent;
"×": as a result of the test, the mold was not opened with a normal driving force. Alternatively, since the resin composition layer B was not peeled from the release film, (i) a state in which the entire evaluation substrate Bb was adhered to the release film or (ii) a part or all of the resin composition layer Ba was peeled from the silicon wafer was observed. Therefore, the resin composition layer Ba was evaluated to be not excellent in releasability from the film material.
< evaluation of warpage >
The resin composition layer Ba contained in the evaluation substrate Bb prepared at the time of evaluation of the peeling property from the film material was cured to obtain an evaluation substrate including a cured product, and the warpage of the cured product was evaluated by measuring the warpage amount of the evaluation substrate as described in detail below.
(preparation of substrate Cb for evaluation of cured product Ca comprising resin composition layer Ba)
The resin composition layer Ba contained in the evaluation substrate Bb prepared at the time of evaluation of the peeling property from the film material was heated together with the silicon wafer at 150 ℃ for 60 minutes. Thereby, the resin composition layer Ba is thermally cured on the silicon wafer to form a cured product. Hereinafter, the cured product of the resin composition layer and the evaluation substrate thus produced are also referred to as "cured product Ca" and "evaluation substrate Cb", respectively. In comparative examples 2 to 4 and 6, since the mold was not opened by a normal driving force as a result of evaluation of the releasability from the film material, the evaluation substrate Bb was obtained by first removing the release film from the compression molding apparatus, then removing the evaluation substrate Bb with the release film adhered thereto from one of the molds, and further peeling the release film from the resin composition layer Ba. In comparative examples 2 to 4 and 6, no interfacial peeling was observed between the resin composition layer Ba and the silicon wafer and between the resin composition layer Ba and the release film. Therefore, in comparative examples 2 to 4 and 6, as described above, the substrate Cb for evaluation of the cured product Ca including the resin composition layer Ba was obtained.
(measurement and evaluation of the amount of warpage)
The warpage amount of each evaluation substrate Cb was measured in a room at 25 ℃ using a video moir e (shadow moir) measuring apparatus ("thermoureaxp" manufactured by Akorometrix corporation). The assay was performed according to JEITA EDX-7311-24, a standard of the electronic information technology industry Association. Specifically, a fitting plane calculated by a least square method of all data on the substrate surface of the measurement region is used as a reference plane, and a difference between a minimum value and a maximum value in a vertical direction from the reference plane is obtained as a warp amount.
The obtained warpage amount was evaluated according to the following criteria;
"verygood": the warpage amount is less than 1500 μm, and the warpage amount is evaluated to be particularly small;
good for: the warpage amount is more than 1500 μm and less than 2000 μm, and the warpage amount is evaluated to be sufficiently small;
". DELTA": the warpage amount is more than 2000 μm and less than 2300 μm, and the warpage amount is evaluated to be small;
"×": the warpage amount was 2300 μm or more, and the warpage amount was evaluated to be large.
< evaluation of adhesion to inorganic Material >
The cured product obtained using the resin paste a was obtained, and adhesion to an inorganic material was evaluated by measuring the adhesive strength with a copper foil as described in detail below.
(preparation of laminate Db of resin composition layer Da containing resin paste A)
First, a compression molding apparatus provided with a mold is prepared. Using this compression molding apparatus, the mold temperature Tc: 130 ℃ and pressure: 6MPa, curing time: the resin paste A was placed on a SUS plate (12 inches) coated with a release agent under a condition of 10 minutes, and was compression-molded in a state of being placed on a glossy surface (bright surface) of a copper foil having a thickness of 18 μm. After the compression molding, the resin composition layer was peeled off from the SUS plate. Thus, a laminate comprising "a resin composition layer having a thickness of 300 μm as a compression-molded product of the resin paste A" and "a copper foil provided on the resin composition layer" was obtained. In this laminate, the copper foil has its non-glossy surface (matte surface) exposed. Hereinafter, the resin composition layer and the laminate produced in this manner are also referred to as a "resin composition layer Da" and a "laminate Db", respectively.
(preparation of laminate Eb of cured product Ea comprising resin composition layer Da)
Subsequently, the laminate Db was heated at 150 ℃ for 60 minutes. In this way, the resin composition layer Da is thermally cured while holding the copper foil, and a cured product is formed. Hereinafter, the cured product and the laminate of the resin composition layer thus produced are also referred to as "cured product Ea" and "laminate Eb", respectively.
(preparation of test piece F)
Next, the laminate Eb was cut into 1cm square. Thus, a plurality of test pieces having a thickness of 318 μm were obtained in a square of 1 cm.
Further, 1 stud pin (stud pin) (5.8 mm) with an adhesive was vertically provided on the matte surface of the copper foil of each test piece. Then, a backing plate (backing plate) with an adhesive was placed on the surface of the cured product (cured product Ea) of the resin composition layer of the test piece material. This gave a laminate comprising a backing plate, a test piece material, and a stud pin in this order. Then, the laminate was heated at 150 ℃ for 60 minutes. As a result, the adhesive was cured, the copper foil and the stud pin were fixed, and a laminated body in which the test piece material and the backing plate were fixed was obtained. Next, a cutting line was cut only in the copper foil along the circumferential surface (5.8 mm) of the stud pin by using a cutter at the portion of the copper foil bonded to the stud pin. Hereinafter, the laminate thus obtained is also referred to as "test piece F".
(measurement and evaluation of adhesive Strength between cured article Ea and inorganic Material)
A vertical tensile test was carried out at a test speed of 0.1kg/sec on each of the obtained test pieces F using a vertical tensile tester "ROMULUS" manufactured by QUAD GROUP corporation, and a measured value indicating the peel strength (hereinafter, also referred to simply as "adhesive strength") of the copper foil was obtained. Specifically, the measured value generally indicates the bonding strength between the cured product Ea and the copper foil as the inorganic material. The test piece F at 5 was measured, and the average value of the measured values of the adhesive strength was calculated. Then, the average value of the measured values of the calculated adhesive strength was evaluated according to the following criteria;
". o": the average value of the measured values of the adhesive strength was 100kgf/cm2The evaluation above shows that the cured product Ea has excellent adhesion to the inorganic material;
"×": the average value of the measured values of the adhesive strength is less than 100kgf/cm2The evaluation results show that the cured product Ea has poor adhesion to the inorganic material.
< evaluation of elastic modulus >
The elastic modulus of a cured product obtained using resin paste a was evaluated as described in detail below.
(preparation of laminate Gb of resin composition layer Ga containing resin paste A)
The resin paste A in a state of being placed on an SUS plate of which surface was subjected to a mold release treatment was compression-molded in a mold using a compression molding apparatus (mold temperature Tc: 130 ℃, pressure: 6MPa, curing time: 10 minutes). Thus, a laminate was obtained which was composed of "a SUS plate" and "a resin composition layer having a thickness of 300 μm as a compression-molded product of the resin paste a" provided on the SUS plate ". Hereinafter, the resin composition layer and the laminate produced in this manner are also referred to as a "resin composition layer Ga" and a "laminate Gb", respectively.
(preparation of cured product H of resin composition layer Ga)
Next, the laminate Gb was heated at 150 ℃ for 60 minutes. Thereby, the resin composition layer Ga is thermally cured on the SUS plate to form a cured product. Then, the cured product was peeled from the SUS plate. Hereinafter, the cured product of the resin composition layer thus produced is also referred to as "cured product H".
(preparation of test piece I and measurement and evaluation of modulus of elasticity at 25 ℃ C.)
Then, 3 dumbbell-shaped test pieces No. 1 in plan view were cut out from the cured product H. Each of the test pieces thus obtained is hereinafter also referred to as "test piece I". Next, for each test piece I, a tensile test was carried out in a room at 25 ℃ using a tensile tester "RTC-1250A" manufactured by Orientec corporation, whereby the elastic modulus (GPa) at 25 ℃ was measured. Measurement was carried out according to JIS K7127: 1999. The average value of the measured values of the elastic modulus at 25 ℃ of 3 test pieces I was calculated. The average value of the measured values of the elastic modulus at 25 ℃ calculated was evaluated according to the following criteria;
". o": the average value of the measured values of the elastic modulus at 25 ℃ is 9GPa or more, and the elastic modulus is evaluated to be high;
". DELTA": the average value of the measured values of the elastic modulus at 25 ℃ is 7GPa or more and less than 9GPa, and the elastic modulus is evaluated to be sufficiently high;
"×": the average value of the measured values of the elastic modulus at 25 ℃ was less than 7GPa, and the elastic modulus was evaluated to be low.
[ results ]
The results of the above examples and comparative examples are shown in tables 1 and 2 below.
In tables 1 and 2 below, the amounts of the respective components are expressed in terms of nonvolatile components. The "resin component" shown in tables 1 and 2 means a component other than (E) the inorganic filler among nonvolatile components in the resin composition. "mass ratio [ b ]: [c] "represents the mass ratio of the component (B) to the component (C). The "content ratio of the component (B) in the resin component" represents the content of the component (C) when the resin component in the nonvolatile component in the resin composition is 100 mass%. The "equivalent ratio (C)/(a)" represents the value of the equivalent ratio (C)/(a) of the sum of the value obtained by dividing the amount (g) of the component (C) by the equivalent (g/eq.) of the acid anhydride group contained in the component (C) and the sum of the value obtained by dividing the amount (g) of the component (a) by the equivalent (g/eq.) of the epoxy group contained in the component (a). "the content ratio of the component (E) in the resin composition" means the content of the component (E) assuming that the content of the nonvolatile component in the resin composition is 100 mass%. ". DELTA.T" of component (D) "represents the difference (. degree. C.) between the mold temperature Tc (130 ℃ C.) at the time of compression molding and the 10-hour half-life temperature T10 (. degree. C.) of the component (D).
[ Table 1]
Figure BDA0003108160730000451
[ Table 2]
Figure BDA0003108160730000461
< discussion >
As is clear from tables 1 and 2, the resin compositions in the examples include, as compared with the comparative examples: (A) an epoxy resin, (B) a compound having a radical polymerizable unsaturated group and an oxyalkylene structure and satisfying the following formula (1), (C) an acid anhydride, (D) a radical generator, and (E) an inorganic filler,
E/N-(100×N)≥50···(1)
(in the formula (1), E represents the equivalent weight (g/eq.) of the radical polymerizable unsaturated group, N represents the number of radical polymerizable unsaturated groups in the molecule, and is an integer of 1 or more),
[ B ] representing the mass ratio of component (B) to component (C): [c] at a speed of 0.2: 1-1.5: 1, whereby it is possible to provide: a resin composition or a resin paste which has a small warpage, a large elastic modulus, and excellent adhesion to an inorganic material and which has excellent releasability from a film material can be obtained.
Further, it is also found that a cured product, a resin sheet, a printed wiring board, a semiconductor chip package and a semiconductor device obtained by using the resin composition or the resin paste according to the examples are also provided.

Claims (26)

1. A resin composition comprising:
(A) an epoxy resin;
(B) a compound having a radical polymerizable unsaturated group and a polyoxyalkylene structure in a molecule, and satisfying the following formula (1):
E/N-(100×N)≥50　　　・・・(1)
in formula (1), E represents the equivalent weight (g/eq.) of the radical polymerizable unsaturated group, N represents the number of radical polymerizable unsaturated groups in the molecule, and is an integer of 1 or more;
(C) an acid anhydride;
(D) a free radical generator; and
(E) an inorganic filler material, which is a filler,
and [ B ]: C ] representing the mass ratio of the component (B) to the component (C) is in the range of 0.2: 1 to 1.5: 1.
2. The resin composition according to claim 1, wherein the component (B) has a polyoxyalkylene structure represented by the formula: - (R)BO)n-represents, in the above formula, n is an integer of 2 or more, RBEach independently is an alkylene group having 1 to 6 carbon atoms which may have a substituent.
3. The resin composition of claim 2, wherein at a plurality of groups RBIn (1), at least one group RBComprising an ethylene group.
4. The resin composition according to claim 1, wherein the radical polymerizable unsaturated group contained in the component (B) is at least one selected from the group consisting of a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, an acryloyl group, a methacryloyl group, a fumaryl group, a maleyl group, a vinylphenyl group, a styryl group and a cinnamoyl group.
5. The resin composition according to claim 4, wherein the radical polymerizable unsaturated group contained in the component (B) contains at least one member selected from the group consisting of a methacryloyl group and an acryloyl group.
6. The resin composition according to claim 4, wherein the radical polymerizable unsaturated group contained in the component (B) contains a methacryloyl group.
7. The resin composition according to claim 1, wherein the component (B) comprises at least one compound selected from the group consisting of a compound in which N in the formula (1) is 1 and a compound in which N in the formula (1) is 2.
8. The resin composition according to claim 7, wherein the molecular weight of the compound in which N in formula (1) is 1 is 150 or more.
9. The resin composition according to claim 7, wherein the equivalent (g/eq.) of the radical polymerizable unsaturated group of the compound represented by formula (1) wherein N is 2 is 500 or more.
10. The resin composition according to claim 1, wherein the equivalent weight of the radical polymerizable unsaturated group of component (B) is 4500g/eq.
11. The resin composition according to claim 1, wherein the content of the component (B) is 10% by mass or more and 40% by mass or less, assuming that the components other than the inorganic filler (E) in the nonvolatile components in the resin composition are 100% by mass.
12. The resin composition according to claim 1, wherein the equivalent ratio (C)/(a) is 0.4 or more, which is the sum of the value obtained by dividing the amount (g) of the component (C) by the equivalent (g/eq.) of the acid anhydride group contained in the component (C) and the sum of the value obtained by dividing the amount (g) of the component (A) by the equivalent (g/eq.) of the epoxy group contained in the component (A).
13. The resin composition according to claim 1, wherein the component (D) is at least one radical generator selected from the group consisting of radical generators having a 10-hour half-life temperature T10 (DEG C) in the range of 50 ℃ or higher and 110 ℃ or lower.
14. The resin composition according to claim 1, wherein the content of the component (E) is 70% by mass or more, assuming that the content of nonvolatile components in the resin composition is 100% by mass.
15. The resin composition according to claim 1, which is used for compression molding.
16. The resin composition according to claim 15, wherein the component (D) is at least one radical generator selected from the group consisting of radical generators, the difference Δ T (DEG C) between a mold temperature Tc (DEG C) at the time of compression molding and a 10-hour half-life temperature T10 (DEG C) of the component (D) being in the range of 20 ℃ to 80 ℃.
17. The resin composition according to claim 1, which is used for forming an insulating layer.
18. A resin paste comprising the resin composition according to any one of claims 1 to 17.
19. A cured product of the resin composition according to any one of claims 1 to 17 or the resin paste according to claim 18.
20. A resin sheet having:
a support, and
a resin composition layer comprising the resin composition according to any one of claims 1 to 17 or the resin paste according to claim 18, provided on the support.
21. A printed wiring board comprising an insulating layer formed using a cured product of the resin composition according to any one of claims 1 to 17 or the resin paste according to claim 18.
22. A semiconductor chip package, comprising:
the printed wiring board of claim 21, and
and a semiconductor chip mounted on the printed wiring board.
23. A semiconductor chip package, comprising:
semiconductor chip, and
a cured product of the resin composition according to any one of claims 1 to 17 or the resin paste according to claim 18, which encapsulates the semiconductor chip.
24. A semiconductor device comprising the printed wiring board of claim 21 or the semiconductor chip package of claim 22 or 23.
25. A method of manufacturing a printed wiring board, comprising:
forming a resin composition layer containing the resin composition according to any one of claims 1 to 17 or a resin composition layer containing the resin paste according to claim 18 on a circuit board by a compression molding method; and
and curing the resin composition layer.
26. A method of manufacturing a semiconductor chip package, comprising:
forming a resin composition layer containing the resin composition according to any one of claims 1 to 17 or a resin composition layer containing the resin paste according to claim 18 on a semiconductor chip by a compression molding method; and
and curing the resin composition layer.
CN202110643724.8A 2020-06-12 2021-06-09 Resin composition Pending CN113801433A (en)

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JP2021-085515 2021-05-20

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JPH11255864A (en) 1998-03-09 1999-09-21 Toshiba Corp Liquid epoxy rein composition and resin-sealed type semiconductor apparatus
JP2014094981A (en) 2012-11-07 2014-05-22 Panasonic Corp Liquid epoxy resin composition for encapsulating semiconductor and semiconductor device using the same

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