CN108624218B - Resin composition - Google Patents

Resin composition Download PDF

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Publication number
CN108624218B
CN108624218B CN201810239264.0A CN201810239264A CN108624218B CN 108624218 B CN108624218 B CN 108624218B CN 201810239264 A CN201810239264 A CN 201810239264A CN 108624218 B CN108624218 B CN 108624218B
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resin composition
mass
component
resin
composition according
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CN108624218A (en
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奥山英惠
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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    • 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
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    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
    • H01L23/49894—Materials of the insulating layers or coatings
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
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Abstract

The invention provides a resin composition capable of obtaining an insulating layer with excellent thermal conductivity and peeling strength to a metal layer, a resin sheet using the resin composition, a circuit board and a semiconductor chip package. The solution of the present invention is a resin composition comprising: (A) a polymer compound having 1 or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule, (B) an epoxy resin, (C) a thermally conductive filler, and (D) an active ester curing agent.

Description

Resin composition
Technical Field
The present invention relates to a resin composition. Further, the present invention relates to a resin sheet, a circuit board, and a semiconductor chip package using the resin composition.
Background
In recent years, electronic devices have been reduced in size and improved in functionality, and the mounting density of semiconductor elements in printed wiring boards has been increasing. In connection with the high functionality of the mounted semiconductor device, a technique for effectively diffusing heat generated in the semiconductor device is required. When the resin composition containing the thermally conductive filler is cured to form the insulating layer, the thermal conductivity of the resulting insulating layer can be improved by increasing the content of the thermally conductive filler in the resin composition, but if the content of the thermally conductive filler is increased to such an extent that a sufficient thermal conductivity is exhibited, the adhesion strength of the resulting insulating layer to the metal layer for forming the wiring tends to deteriorate.
For example, patent document 1 discloses that by using an insulating layer obtained by curing a resin composition containing aluminum nitride or silicon nitride in a printed wiring board, heat diffusion is performed under conditions in which the surface roughness is low and the adhesion strength (peel strength) to a conductor layer is good, while exhibiting heat diffusion.
[ Prior art documents ]
[ patent document ]
Patent document 1: international publication No. 2014/208352.
Disclosure of Invention
Problems to be solved by the invention
In recent years, miniaturization and high functionality of electronic devices have been advanced, and thinning and coreless formation of substrates have been advanced, and materials are required to have heat diffusibility and adhesion strength (peel strength) and also to suppress warpage generated when an insulating layer is formed. These properties are in a trade-off relationship, and it is very difficult to design a resin that can achieve a balance.
The present invention has been made to solve the above problems, and provides a resin composition, a resin sheet, a circuit board, and a semiconductor chip package using the resin composition; the resin composition can obtain a cured product which is excellent in thermal conductivity and peeling strength to a metal layer and is balanced in the suppression of warpage generated when an insulating layer is formed.
Means for solving the problems
The present inventors have found that an insulating layer having excellent thermal conductivity, excellent peel strength to a metal layer (particularly, a metal layer formed by plating), and excellent suppression of warpage generated when forming the insulating layer can be obtained by containing (a) a polymer compound having 1 or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule, (B) an epoxy resin, (C) a thermally conductive filler, and (D) an active ester curing agent, and have completed the present invention.
That is, the present invention includes the following matters,
[1] a resin composition comprising:
(A) a polymer compound having 1 or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule,
(B) Epoxy resin,
(C) Thermally conductive filler, and
(D) an active ester curing agent;
[2] [1] the resin composition described in [1], wherein a peel strength between a cured product obtained by heat-curing the resin composition at 180 ℃ for 30 minutes and further at 180 ℃ for 60 minutes and a metal layer formed by plating is 0.4kgf/cm or more;
[3] the resin composition as described in [1] or [2], wherein the content of the component (C) is 85% by mass or more, assuming that the nonvolatile component in the resin composition is 100% by mass;
[4] the resin composition according to any one of [1] to [3], wherein the component (C) comprises alumina;
[5] the resin composition according to any one of [1] to [4], wherein the component (C) is surface-treated with an aminosilicone coupling agent;
[6] the resin composition according to any one of [1] to [5], wherein the component (C) is surface-treated with N-phenyl-3-aminoalkyltrimethoxysilane;
[7] the resin composition according to any one of [1] to [6], wherein a cured product obtained by thermally curing the resin composition at 180 ℃ for 90 minutes has a thermal conductivity of 1.5W/m and 5.0W/m inclusive;
[8] the resin composition according to any one of [1] to [7], wherein the component (A) is at least 1 selected from the group consisting of a resin having a glass transition temperature of 25 ℃ or less and a resin that is liquid at 25 ℃;
[9] the resin composition according to any one of [1] to [8], wherein the component (A) has a functional group reactive with the component (B);
[10] the resin composition according to any one of [1] to [9], wherein the component (A) has 1 or more functional groups selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a carbamate group;
[11] the resin composition according to any one of [1] to [10], wherein the component (A) has an imide structure;
[12] the resin composition according to any one of [1] to [11], wherein the component (A) has a phenolic hydroxyl group;
[13] the resin composition according to any one of [1] to [12], wherein the component (A) has a polybutadiene structure and a phenolic hydroxyl group;
[14] the resin composition according to any one of [1] to [13], which is a resin composition for an insulating layer for semiconductor chip encapsulation;
[15] the resin composition according to any one of [1] to [14], which is a resin composition for an insulating layer of a circuit board on which a circuit is formed by a semi-addition method;
[16] a resin sheet having: a support and a resin composition layer containing the resin composition according to any one of [1] to [15] provided on the support;
[17] a circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [15 ];
[18] a semiconductor chip package comprising the circuit board according to [17] and a semiconductor chip mounted on the circuit board;
[19] a semiconductor chip package comprising a semiconductor chip sealed with the resin composition as set forth in any one of [1] to [15] or the resin sheet as set forth in [16 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides a resin composition, a resin sheet, a circuit board, and a semiconductor chip package using the resin composition; among these, the resin composition can provide a cured product having a good balance among thermal conductivity, excellent adhesion strength to a metal layer (particularly, a metal layer formed by plating), and suppression of the amount of warpage generated when forming an insulating layer.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of a semiconductor chip package (Fan-out type WLP) of the present invention.
Detailed Description
The resin composition, resin sheet, circuit board, and semiconductor chip package of the present invention will be described in detail below.
[ resin composition ]
The resin composition of the present invention contains: (A) a polymer compound having 1 or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule, (B) an epoxy resin, (C) a thermally conductive filler, and (D) an active ester curing agent.
By containing the component (a), the component (B), the component (C), and the component (D) in the resin composition, an insulating layer excellent in thermal conductivity, peel strength to the metal layer, and suppression of warpage can be obtained. In addition, the aforementioned resin composition may generally have a low melt viscosity. The resin composition may further contain (E) a curing agent, (F) a curing accelerator, (G) an inorganic filler (excluding the material corresponding to the component (C)) and (H) a flame retardant, as required. The components contained in the resin composition will be described in detail below.
[ A ] A polymer compound having in the molecule at least 1 structure selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure ]
The resin composition contains (A) a polymer compound having 1 or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule. By including the polymer compound having the above structure in the resin composition, warpage of a cured product can be suppressed. In the present invention, "(meth) acrylate" means methacrylate and acrylate.
More specifically, it is preferable for the (a) component to have: 1 or 2 or more members selected from the group consisting of a polybutadiene structure such as polybutadiene or hydrogenated polybutadiene, a polysiloxane structure such as silica gel, a poly (meth) acrylate structure, a polyalkylene structure (preferably a polyalkylene structure having 2 to 15 carbon atoms, more preferably a polyalkylene structure having 3 to 10 carbon atoms, and still more preferably a polyalkylene structure having 5 to 6 carbon atoms), a polyalkyleneoxy structure (preferably a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, and still more preferably a polyalkyleneoxy structure having 5 to 6 carbon atoms), a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure; preferably, the method comprises: 1 or 2 or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure; more preferably, the resin composition has: 1 or more structures selected from a polybutadiene structure, a polyisoprene structure, and a polycarbonate structure.
In order to exhibit flexibility, the component (A) preferably has a high molecular weight, and the number average molecular weight (Mn) is preferably 1000 to 1000000, more preferably 5000 to 900000. The number average molecular weight (Mn) is a number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).
In order to exhibit flexibility, component (a) is preferably at least 1 resin selected from the group consisting of resins having a glass transition temperature (Tg) of 25 ℃ or lower and resins that are liquid at 25 ℃.
The glass transition temperature (Tg) of the resin is preferably 20 ℃ or lower, more preferably 15 ℃ or lower. The lower limit of the glass transition temperature is not particularly limited, and may be usually-15 ℃ or higher. The resin that is liquid at 25 ℃ is preferably a resin that is liquid at 20 ℃ or lower, and more preferably a resin that is liquid at 15 ℃ or lower.
The component (a) preferably has a functional group capable of reacting with the component (B) from the viewpoint of improving the mechanical strength of the cured product. The functional group reactive with the component (B) includes a functional group that appears by heating.
In one suitable embodiment, the functional group capable of reacting with component (B) is 1 or more functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a carbamate group. Among these, the functional group is preferably a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group, more preferably a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, and an epoxy group, and particularly preferably a phenolic hydroxyl group.
(A) One suitable embodiment of the component is a butadiene resin. The butadiene resin is preferably a butadiene resin which is liquid at 25 ℃ or has a glass transition temperature of 25 ℃ or lower, more preferably 1 or more resins selected from the group consisting of a resin having a hydrogenated polybutadiene skeleton, a butadiene resin having a hydroxyl group, a butadiene resin having a phenolic hydroxyl group, a butadiene resin having a carboxyl group, a butadiene resin having an acid anhydride group, a butadiene resin having an epoxy group, a butadiene resin having an isocyanate group, and a butadiene resin having a urethane group, and still more preferably a butadiene resin having a phenolic hydroxyl group. Examples of the resin having a hydrogenated polybutadiene skeleton include an epoxy resin having a hydrogenated polybutadiene skeleton. Examples of the phenolic hydroxyl group-containing butadiene resin include resins having a polybutadiene structure and a phenolic hydroxyl group.
Here, the "butadiene resin" refers to a resin containing a polybutadiene structure, and the polybutadiene structure may be contained in the main chain or in the side chain of these resins. The butadiene structure may be partially or fully hydrogenated. Here, the "resin having a hydrogenated polybutadiene skeleton" refers to a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and does not necessarily need to be a resin in which the polybutadiene skeleton is entirely hydrogenated.
The number average molecular weight (Mn) of the butadiene resin is preferably 1000 to 100000, more preferably 5000 to 50000, more preferably 7500 to 30000, and further preferably 10000 to 15000. Here, the number average molecular weight (Mn) of the resin is a number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).
The butadiene resin preferably has a functional group equivalent of 100 to 10000, more preferably 200 to 5000 when the butadiene resin has a functional group. The functional group equivalent means the number of grams of the resin containing 1 gram equivalent of the functional group. For example, the epoxy equivalent can be measured according to JIS K7236. The hydroxyl group equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl group value measured in accordance with JIS K1557-1.
Specific examples of the butadiene resin include: "Ricon 657" (polybutadiene containing epoxy group), "Ricon 130MA 8", "Ricon 130MA 13", "Ricon 130MA 20", "Ricon 131MA 5", "Ricon 131MA 10", "Ricon 131MA 17", "Ricon 131MA 20", "Ricon 184MA 6" (polybutadiene containing acid anhydride group), "JP-100", "JP-200" (epoxidized polybutadiene) manufactured by Nippon Kao corporation, "GQ-1000" (hydroxyl-and carboxyl-introduced polybutadiene), "G-1000", "G-2000", "G-3000" (both-terminal hydroxyl polybutadiene), "GI-1000", "GI-2000", "GI-3000" (both-terminal hydroxyl-hydrogenated polybutadiene), and "3600", "PB 4700" (polybutadiene skeleton epoxy compound), "FREEPEND 1005A", "FREIEND A1010", "FRIEND 1010", "RION-and" manufactured by Cray Valley, EPOFRIND A1020 (epoxy compound of styrene-butadiene-styrene block copolymer), FCA-061L (hydrogenated polybutadiene skeleton epoxy compound) manufactured by Nagase ChemteX, and R-45EPT (polybutadiene skeleton epoxy compound).
In another preferred embodiment of the component (a), a resin having an imide structure may be used. Examples of the resin having an imide structure include linear polyimides prepared from hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimides described in jp 2006-37083 a and international publication No. 2008/153208). The content of the polybutadiene structure in the polyimide resin is preferably 60 to 95 mass%, more preferably 75 to 85 mass%. The details of the polyimide resin can be found in Japanese patent application laid-open No. 2006-37083 and International publication No. 2008/153208, the contents of which are incorporated herein.
(A) One suitable embodiment of the ingredient is an isoprene resin. Specific examples of the isoprene resin include "KL-610" and "KL-613" manufactured by Colorado. Here, the "isoprene resin" refers to a resin having a polyisoprene structure, and the polyisoprene structure may be contained in the main chain or in the side chain of these resins.
In addition, one suitable embodiment of the component (a) is a carbonate resin. The carbonate resin is preferably a carbonate resin having a glass transition temperature of 25 ℃ or lower, and preferably 1 or more resins selected from a hydroxyl group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxyl group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an epoxy group-containing carbonate resin, an isocyanate group-containing carbonate resin, and a urethane group-containing carbonate resin. Here, the "carbonate resin" refers to a resin having a polycarbonate structure, and the polycarbonate structure may be contained in the main chain or in the side chain of these resins.
The number average molecular weight (Mn) of the carbonate resin and the equivalent weight of the functional group in the case of having the functional group are the same as those of the butadiene resin, and preferable ranges are also the same.
Specific examples of the carbonate resin include: "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi chemical Co., Ltd, "C-1090", "C-2090" and "C-3090" (polycarbonate diol) manufactured by Cola Co., Ltd.
Further, linear polyimides obtained from a hydroxyl-terminated polycarbonate, a diisocyanate compound and a tetrabasic acid anhydride as raw materials can also be used. The content of the polycarbonate structure in the polyimide resin is preferably 60 to 95 mass%, more preferably 75 to 85 mass%. The details of the polyimide resin can be found in International publication No. 2016/129541, and the contents thereof are incorporated herein.
(A) Yet another suitable embodiment of ingredient is an acrylic resin. The acrylic resin is preferably an acrylic resin having a glass transition temperature (Tg) of 25 ℃ or lower, and more preferably 1 or more resins selected from the group consisting of a hydroxyl group-containing acrylic resin, a phenolic hydroxyl group-containing acrylic resin, a carboxyl group-containing acrylic resin, an acid anhydride group-containing acrylic resin, an epoxy group-containing acrylic resin, an isocyanate group-containing acrylic resin, and a urethane group-containing acrylic resin. Here, the "acrylic resin" refers to a resin containing a poly (meth) acrylate structure, and the poly (meth) acrylate structure may be contained in the main chain or in the side chain in these resins.
The number average molecular weight (Mn) of the acrylic resin is preferably 10000 to 1000000, more preferably 30000 to 900000. Here, the number average molecular weight (Mn) of the resin is a number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).
The acrylic resin preferably has a functional group equivalent of 1000 to 50000, more preferably 2500 to 30000.
Specific examples of the acrylic resin include: TEISANRESIN 'SG-70L', 'SG-708-6', 'WS-023', 'SG-700 AS', 'SG-280 TEA' (acrylic ester copolymer resin containing carboxyl, acid value of 5-34 mgKOH/g, weight average molecular weight of 40-90 ten thousand, Tg-30-5 ℃) 'SG-80H', 'SG-80H-3', 'SG-P3' (acrylic ester copolymer resin containing epoxy group, epoxy equivalent of 4761-14285 g/eq, weight average molecular weight of 35-85 ten thousand, Tg of 11-12 ℃) 'SG-600 TEA' SG-790 '(acrylic ester copolymer resin containing hydroxyl group, hydroxyl value of 20-40 mgKOH/g, weight average molecular weight of 50-120 ten thousand, Tg-37- & gt-32 ℃), manufactured by Nagase ChemteX, ME-2000' manufactured by Shanghai industries, "W-116.3" (carboxyl group-containing acrylate copolymer resin), "W-197C" (hydroxyl group-containing acrylate copolymer resin), "KG-25" and "KG-3000" (epoxy group-containing acrylate copolymer resin) and the like.
Further, another suitable embodiment of the (a) component is a silicone resin, an alkylene (alkylene) resin, an alkyleneoxy (alkylene oxide) resin, or an isobutylene resin.
Specific examples of the Silicone resin include "SMP-2006", "SMP-2003 PGMEA", "SMP-5005 PGMEA", manufactured by Shin-Etsu Silicone company, and linear polyimides prepared from an amino-terminated polysiloxane and a tetrabasic acid anhydride (International publication No. 2010/053185). Here, the "silicone resin" refers to a resin containing a polysiloxane structure, and the polysiloxane structure may be contained in the main chain or in the side chain in these resins.
Specific examples of the alkylene resin and alkyleneoxy resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi chemical fibers, and "YX-7180" (a resin having an alkylene structure having an ether bond) manufactured by Mitsubishi chemical corporation. "EXA-4850-," EXA-4816-, "EXA-4822" manufactured by DIC Corporation, "EP-4000", "EP-4003", "EP-4010" and "EP-4011" manufactured by ADEKA Corporation, "BEO-60E", "BPO-20E" manufactured by Nisshinbo chemical Corporation and "YL 7175" and "YL 7410" manufactured by Mitsubishi chemical Corporation, and the like. Here, the "alkylene resin" refers to a resin containing a polyalkylene structure, and the "alkyleneoxy resin" refers to a resin containing a polyalkyleneoxy structure. In these resins, the polyalkylene structure and the polyalkyleneoxy structure may be contained in the main chain or in the side chain.
Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka. Here, the "isobutylene resin" refers to a resin having a polyisobutylene structure, and the polyisobutylene structure may be contained in the main chain or in the side chain of these resins.
Further preferable examples of the component (a) include acrylic rubber particles, polyamide fine particles, and silicone particles. Specific examples of the acrylate rubber particles include microparticles of a resin exhibiting rubber elasticity such as acrylonitrile butadiene rubber (nitrile rubber), butadiene rubber, or acrylate rubber, which is rendered insoluble and infusible in an organic solvent by chemical crosslinking treatment, and specifically include XER-91 (manufactured by Nippon rubber Co., Ltd.), StaphyLOID AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (manufactured by Gantsu Kasei Co., Ltd.), PARALOID EXL2655, and EXL2602 (manufactured by Wuhui chemical industries Co., Ltd.). Specific examples of the polyamide microparticles may be any polyamide microparticles as long as they are aliphatic polyamides such as nylon and soft skeletons such as polyamideimide, and specific examples thereof include VESTOSINT 2070 (manufactured by Daicel-Huels Co., Ltd.), SP500 (manufactured by Toray Co., Ltd.), and the like.
From the viewpoint of imparting flexibility, the content of the component (a) in the resin composition is preferably 65% by mass or less, more preferably 60% by mass or less, further preferably 55% by mass or less, and further more preferably 50% by mass or less, when the nonvolatile component (resin component) of the resin composition excluding the components (C) and (G) is 100% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and still more preferably 25% by mass or more.
< epoxy resin (B) >
The resin composition of the present invention contains an epoxy resin as the component (B). From the viewpoint of further improving the effect of the present invention, the component (B) is preferably an epoxy resin having an aromatic structure. Aromatic structures are chemical structures that are generally defined as aromatic and also include polycyclic aromatic and aromatic heterocycles.
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 glycidyl amine type epoxy resin having an aromatic structure, a glycidyl ester type epoxy resin having an aromatic structure, a cresol novolac (cresol novolac) type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin having an aromatic structure, an epoxy resin having a butadiene structure having an aromatic structure, an alicyclic epoxy resin having an aromatic structure, a heterocyclic type epoxy resin, an epoxy resin containing a spiro ring having an aromatic structure, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin having an aromatic structure, a naphthol novolac type epoxy resin having an aromatic structure, a naphthol type epoxy resin, a phenol type epoxy resin, a phenol, Cyclohexane dimethanol type epoxy resins having an aromatic structure, naphthylene ether type epoxy resins, trimethylol type epoxy resins having an aromatic structure, tetraphenylethane type epoxy resins, aminophenol type epoxy resins, and the like. The epoxy resin can be used alone in 1 kind, also can be used in combination of more than 2 kinds. (B) The component (B) is preferably at least 1 selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, aminophenol type epoxy resins and naphthalene type epoxy resins.
The epoxy resin preferably contains an epoxy resin having 2 or more epoxy groups in 1 molecule. When the nonvolatile content of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more of the epoxy resin is an epoxy resin having 2 or more epoxy groups in 1 molecule. Among them, an epoxy resin having 2 or more epoxy groups in 1 molecule and being liquid at a temperature of 20 ℃ (hereinafter referred to as "liquid epoxy resin") and an epoxy resin having 3 or more epoxy groups in 1 molecule and being solid at a temperature of 20 ℃ (hereinafter referred to as "solid epoxy resin") are preferably contained. As the epoxy resin, a resin composition having excellent flexibility can be obtained by using a liquid epoxy resin and a solid epoxy resin in combination. Further, the breaking strength of a cured product of the resin composition is improved.
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 having an aromatic structure, a glycidyl amine type epoxy resin having an aromatic structure, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an aromatic structure and an ester skeleton, a cyclohexane dimethanol type epoxy resin having an aromatic structure, an aminophenol type epoxy resin, and an epoxy resin having an aromatic structure and a butadiene structure, more preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, an aminophenol type epoxy resin, and a naphthalene type epoxy resin, and further preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, and an aminophenol type epoxy resin. Specific examples of the liquid epoxy resin include "HP 4032", "HP 4032D", "HP 4032 SS" (naphthalene-type epoxy resin), "828 US" and "jER 828 EL" (bisphenol A-type epoxy resin), "jER 806" and "jER 807" (bisphenol F-type epoxy resin), "jER 152" (phenol novolac-type epoxy resin), "630" (aminophenol-type epoxy resin), "630 LSD" (glycidyl amine-type epoxy resin), and "ZX 1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin), manufactured by Nagase ChemteX, "EX-721" (glycidyl ester-type epoxy resin), manufactured by Daicel, and "CELLOXIDE 2021P" (alicyclic epoxy resin having an ester skeleton), manufactured by Nissin iron chemical, and "ZX 1658", "ZX 1658 and 1658 GS" (liquid cyclohexane, 4-glycidyl ester, manufactured by DIC corporation, "YX 7400" (high resilience epoxy resin) manufactured by Mitsubishi chemical corporation. These can be used alone in 1 kind, also can be combined with more than 2 kinds.
The solid epoxy resin is preferably a biphenol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolac-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, or a tetraphenylethane-type epoxy resin, more preferably a biphenol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, or a naphthylene ether-type epoxy resin, and still more preferably a biphenol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a naphthylene ether-type epoxy resin, or a biphenyl-type epoxy resin. Specific examples of the solid epoxy resin include "HP 4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200L", "HP-7200 HH", "HP-7200H", "HP-7200 HHH" (dicyclopentadiene type epoxy resin), "EXA 7311", "EXA 7311-G3", "EXA 7311-G4", "EXA 7311-G4S", "HP 6000" (naphthalene ether type epoxy resin), "EPPN-502H" (trisphenol type epoxy resin), "NC 7000L" (NC novolac type epoxy resin), "3000H", "3000 NC 3100", "NC 3000L", "NC 85NC" (biphenyl type epoxy resin) manufactured by DIC, "ESN 475V" (naphthol type epoxy resin), "ESN 485" (naphthol novolac type epoxy resin), "YX 4000H" (YL 6121 "(biphenyl type epoxy resin)," YX4000HK "(biphenol type epoxy resin)," YL7760 "(bisphenol AF type epoxy resin)," YX8800 "(anthracene type epoxy resin)," PG-100 "(PG-100) (CG-500) (manufactured by Osaka gas chemical Co., Ltd.," YL7800 "(fluorene type epoxy resin) (manufactured by Mitsubishi chemical Co., Ltd.)" jER1010 "(solid bisphenol A type epoxy resin)," jER1031S "(tetraphenylethane type epoxy resin)," 157S70 "(bisphenol novolac type epoxy resin), and" YX4000HK "(biphenol type epoxy resin)," YX8800 "(anthracene type epoxy resin), and" PG-100 "(PG-100) (manufactured by Osaka chemical Co., Ltd.)," YX4000, "CG-500", "YL 7800 (fluorene type epoxy resin) manufactured by Mitsubishi chemical corporation and" JeR1031S (tetraphenylethane type epoxy resin) manufactured by Mitsubishi chemical corporation. These can be used alone in 1 kind, also can be combined with more than 2 kinds.
When the liquid epoxy resin and the solid epoxy resin are used in combination as the component (B), the amount ratio thereof (solid epoxy resin: liquid epoxy resin) is preferably 1: 0.1-1: 15, or more. By making the amount ratio of the liquid epoxy resin and the solid epoxy resin within the above range, the following effects can be obtained: i) appropriate tackiness can be obtained when used in the form of a resin sheet, ii) sufficient flexibility and improved handling properties can be obtained when used in the form of a resin sheet, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of the above i) to iii), the amount ratio of the liquid epoxy resin to the solid epoxy resin (solid epoxy resin: liquid epoxy resin) is more preferably 1: 0.3-1: 10, more preferably 1: 0.6-1: and 8, in the above range.
From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, the content of the epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, assuming that the nonvolatile component in the resin composition is 100% by mass. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exhibited, and is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 6% by mass or less.
In addition, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, the content of the epoxy resin in the resin composition is 20 mass% or more, more preferably 25 mass% or more, and still more preferably 30 mass% or more, assuming that the nonvolatile components of the resin composition excluding the component (C) and the component (G) are 100 mass%. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exhibited, and is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 55% by mass or less.
The epoxy resin preferably has an epoxy equivalent of 50 to 5000, more preferably 50 to 3000, even more preferably 80 to 2000, and even more preferably 110 to 1000. Within this range, an insulating layer having a sufficient crosslinking density and a small surface roughness of the cured product can be obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of epoxy group.
The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and 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 Gel Permeation Chromatography (GPC).
< C thermally conductive Filler >
The resin composition of the present invention contains (C) a thermally conductive filler. Here, in the present specification, the thermally conductive filler means an inorganic filler having a thermal conductivity of 20W/m, seed or K or more.
The material of the component (C) is not particularly limited as long as the thermal conductivity is within the above range. Examples of the material contained in component (C) include alumina, aluminum nitride, boron nitride, and silicon carbide. Among them, alumina is particularly suitable. (C) The components can be used alone in 1 kind, or in combination with 2 or more kinds. In addition, 2 or more kinds of the same material may be used in combination.
The average particle size of the component (C) is preferably 5 μm or less, more preferably 4 μm or less, even more preferably 3 μm or less, and preferably 0.1 μm or more, more preferably 1.0 μm or more, even more preferably 1.5 μm or more, from the viewpoint of obtaining an insulating layer excellent in both thermal conductivity and peel strength and from the viewpoint of improving filling properties. (C) The average particle diameter of the component 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 prepared on a volume basis by using a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size is determined as an average particle size. The measurement sample may be a sample obtained by dispersing the component (C) in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, there can be used "LA-500" manufactured by horiba, Inc., and "SALD 2200" manufactured by Shimadzu, Inc. Specifically, the measurement can be performed by the method described in < measurement of average particle diameter of thermally conductive filler > described later.
The specific surface area of the component (C) is preferably 0.5m from the viewpoint of obtaining an insulating layer excellent in both thermal conductivity and peel strength and from the viewpoint of improving filling property2More than g. (C) The specific surface area of the component is preferably 0.5m2/g~10m2A ratio of 0.5 m/g2/g~5m2(ii) in terms of/g. (C) The specific surface area of the component can be measured by the nitrogen BET method (BET nitrogen adsorption method). Specifically, the measurement can be performed by using an automatic specific surface area measuring apparatus, and as the automatic specific surface area measuring apparatus, "Macsorb HM-1210" manufactured by Mountech corporation or the like can be used. Specifically, the following may be mentioned<Determination of the specific surface area of the thermally conductive Filler>The method described in (1) for measurement.
From the viewpoint of improving moisture resistance and dispersibility, component (C) may be treated with 1 or more surface-treating agents such as an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane compound, an organosilazane compound, and a titanate-based coupling agent. Commercially available surface-treating agents include, for example, "KBM 403" (3-glycidoxypropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, "KBM 803" (3-mercaptopropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, "KBE 903" (3-aminopropyltriethoxysilane) manufactured by shin-Etsu chemical industries, "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, "KBM 5783" (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by shin-Etsu chemical industries, "SZ-31" (hexamethyldisilazane) manufactured by shin-Etsu chemical industries, "KBM 103" (phenyltrimethoxysilane) manufactured by shin-Etsu chemical industries, and "KBM-4803" (long-chain epoxy silane coupling agent) manufactured by shin-Etsu chemical industries. Among them, from the viewpoint of lowering the melt viscosity and improving the laminatability, the component (C) is preferably surface-treated with an aminosilane-based coupling agent, preferably N-phenyl-3-aminoalkyltrimethoxysilane typified by N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminooctyltrimethoxysilane, and more preferably N-phenyl-3-aminooctyltrimethoxysilane.
From the viewpoint of obtaining an insulating layer excellent in both thermal conductivity and peel strength, the content of the component (C) is preferably 85 mass% or more, more preferably 88 mass% or more, further preferably 89 mass% or more, or 90 mass% or more, assuming that the nonvolatile component in the resin composition is 100 mass%. The upper limit is preferably 95% by mass or less, more preferably 93% by mass or less, and still more preferably 92% by mass or less.
< D) active ester curing agent >
The resin composition of the present invention comprises (D) an active ester curing agent. The active ester curing agent is not particularly limited, and compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters (phenoxide ester), thiophenol esters (thiophenol ester), N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds, can be preferably used. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtainable from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester curing agent obtainable from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac (phenol novolac), and the like. The "dicyclopentadiene type diphenol compound" as used herein means a diphenol compound obtained by condensing 2 molecules of phenol on 1 molecule of dicyclopentadiene.
Specifically, preferred are an active ester compound having a dicyclopentadiene type diphenol structure, an active ester compound having a naphthalene structure, an active ester compound having an acetyl compound of a phenol novolac resin, and an active ester compound having a benzoyl compound of a phenol novolac resin, and more preferred are an active ester compound having a naphthalene structure and an active ester compound having a dicyclopentadiene type diphenol structure. The "dicyclopentadiene type diphenol structure" refers to a 2-valent structure formed from phenylene-dicyclopentylene-phenylene.
As the active ester compound, the active ester compounds disclosed in Japanese patent application laid-open Nos. 2004-277460 and 2013-40270 can be used, and commercially available active ester compounds can also be used. Commercially available active ester curing agents include, for example, "EXB 9451", "EXB 9460S", "HPC-8000-65T", "HPC-8000H-65 TM" and "EXB-8000L-65 TM" (manufactured by DIC), for example, "EXB 9416-70 BK" (manufactured by DIC), for example, "DC 808" (manufactured by Mitsubishi chemical corporation), for example, "YLH 1026" (manufactured by Mitsubishi chemical corporation), for example, "DC 808" (manufactured by Mitsubishi chemical corporation), and for example, "YLH 1026" (manufactured by Mitsubishi chemical corporation), for example, for the active ester curing agent of the acylate of phenol novolac "YLH 1030" (manufactured by Mitsubishi chemical corporation), "YLH 1048" (manufactured by Mitsubishi chemical corporation), and "EXB 9050L-62M" (active ester compound containing phosphorus atom) manufactured by DIC corporation.
The content of the component (D) is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 2% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass. The lower limit is not particularly limited, but is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. When the content of the component (D) is within the above range, the thermal conductivity and the peel strength can be improved.
< curing agent (E) >
The resin composition of the present invention may contain (E) a curing agent in addition to the component (D). However, the component (E) as referred to herein does not include (D) an active ester curing agent. The curing agent (E) is not particularly limited as long as it has a function of curing the resin such as the component (B), and examples thereof include phenol (phenol) curing agents, naphthol curing agents, benzoxazine curing agents, cyanate curing agents, and carbodiimide curing agents. The curing agent can be used singly or in combination of 2 or more. (D) The component (b) is preferably 1 or more selected from phenol-based curing agents, naphthol-based curing agents and cyanate-based curing agents, and preferably 1 or more selected from phenol-based curing agents.
As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a phenolic (novolak) structure or a naphthol-based curing agent having a phenolic structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to the wiring layer, a nitrogen-containing phenol curing agent is preferable, and a triazine skeleton-containing phenol curing agent is more preferable. Among them, a phenol novolac curing agent containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to a wiring layer.
Specific examples of the phenol curing agent and the naphthol curing agent include "MEH-7700", "MEH-7810", "MEH-7851", "NHN", "CBN", "GPH" manufactured by Nippon chemical Co., Ltd., "SN 170", "SN 180", "SN 190", "SN 475", "SN 485", "SN 495V", "SN 375", "SN 395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165", and "GDP-6115L" and "GDP-6115H" manufactured by Suzuo chemical Co., Ltd.
Specific examples of the benzoxazine-based curing agent include "HFB 2006M" manufactured by Showa Polymer Co., Ltd, "P-d" and "F-a" manufactured by Shikoku Industrial Co., Ltd.
Examples of the cyanate ester curing agent include 2-functional cyanate ester resins such as bisphenol a dicyanate, polyphenol cyanate ester, oligo (3-methylene-1, 5-phenylene cyanate ester), 4 '-methylenebis (2, 6-dimethylphenylcyanate), 4' -ethylenediphenyldicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanate ester) phenylpropane, 1-bis (4-cyanate ester phenylmethane), bis (4-cyanate ester-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate ester-1- (methylethylidene)) benzene, bis (4-cyanate ester phenyl) sulfide, and bis (4-cyanate ester phenyl) ether, and the like, Polyfunctional cyanate ester resins derived from phenol novolac resins, cresol novolac resins, and the like, prepolymers obtained by partially triazinating these cyanate ester resins, and the like. Specific examples of the cyanate ester-based curing agent include "PT 30" and "PT 60" (both phenol novolac type polyfunctional cyanate ester resins), "BA 230" and "BA 230S 75" (prepolymers in which a part or all of bisphenol a dicyanate is triazinized to form a trimer), which are manufactured by Lonza Japan.
Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.
When the resin composition contains the component (E), the content of the component (E) in the resin composition is not particularly limited, and is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less, assuming that the nonvolatile component in the resin composition is 100% by mass. The lower limit is not particularly limited, but is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more.
< curing accelerators (F) >
The resin composition of the present invention may contain (F) a curing accelerator. Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, and a metal-based curing accelerator, and the phosphorus-based curing accelerator, the amine-based curing accelerator, the imidazole-based curing accelerator, and the metal-based curing accelerator are preferable, and the amine-based curing accelerator, the imidazole-based curing accelerator, and the metal-based curing accelerator are more preferable. The curing accelerator may be used alone in 1 kind, or in combination of 2 or more kinds.
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, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo (5,4,0) -undecene, and preferably 4-dimethylaminopyridine and 1, 8-diazabicyclo (5,4,0) -undecene.
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, Imidazole compounds such as 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline 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 such as "P200-H50" manufactured by Mitsubishi chemical company 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, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene are preferred.
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) in the resin composition is not particularly limited, and is preferably 0.01 to 1% by mass, assuming that the nonvolatile component in the resin composition is 100% by mass.
< G inorganic Filler Material (except for Material corresponding to component (C) >
The resin composition of the present invention may contain (G) an inorganic filler. However, the inorganic filler (G) as used herein does not include a material corresponding to the thermally conductive filler (C). (G) The material of the component (a) is not particularly limited, and examples thereof include silica, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, zirconium phosphate, zirconium tungstate phosphate, and the like. Of these, silica is particularly preferable. Further, as the silica, spherical silica is preferable. The inorganic filler may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
From the viewpoint of improving the circuit embeddability and obtaining an insulating layer having low surface roughness, the average particle diameter of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, still more preferably 2.2 μm or less, and yet more preferably 2 μm or less. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.1 μm or more. The average particle diameter of the inorganic filler can be measured in the same manner as in the component (C). Examples of commercially available inorganic fillers having the above average particle size include "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C", manufactured by Electrical and chemical industries, "UFP-30", manufactured by Deshan (Tokuyama) Inc. "Silfil (シルフィル) NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N", manufactured by Admatech "SC 2500 SQ", "SO-C6", "SO-C4", "SO-C2" and SO-C1 ".
From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is preferably treated with 1 or more surface-treating agents selected from the group consisting of an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane compound, an organosilazane compound, a titanate-based coupling agent, and the like. The specific surface treatment agent is commercially available as described above.
When the resin composition contains the component (G), the content of the component (G) in the resin composition is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more, assuming that the nonvolatile component in the resin composition is 100% by mass. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.
< H flame retardant >
The resin composition may contain (H) a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, an organic silicon flame retardant, and a metal hydroxide. The flame retardant may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
As the flame retardant, commercially available products can be used, and examples thereof include "HCA-HQ" manufactured by Sanko corporation.
When the resin composition contains a flame retardant, the content of the component (H) is not particularly limited, and is preferably 0.5 to 10 mass%, more preferably 0.5 to 5 mass%, and further preferably 0.5 to 3 mass% with respect to 100 mass% of nonvolatile components in the resin composition.
< optional additive (I) >
The resin composition may contain other additives as needed, and examples of the other additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and resin additives such as binders, thickeners, defoaming agents, leveling agents, adhesion imparting agents, and coloring agents.
< Properties of resin composition >
A cured product obtained by heat-curing the resin composition of the present invention at 180 ℃ for 30 minutes and further at 180 ℃ for 60 minutes exhibits excellent peel strength with a metal layer, particularly a metal layer formed by plating. Namely, an insulating layer having excellent peel strength was obtained. In detail, the following characteristics are exhibited: the resin composition of the present invention is heat-treated at 180 ℃ for 30 minutes, and then a metal layer is formed by plating on the roughened surface obtained by roughening the surface of the cured product, and when heat-treated at 180 ℃ for 60 minutes, the peel strength between the cured product and the metal layer is excellent. The peel strength is preferably 0.4kgf/cm or more, more preferably 0.45kgf/cm or more, and still more preferably 0.5kgf/cm or more. On the other hand, the upper limit of the peel strength is not particularly limited, and may be 1.5kgf/cm or less, 1kgf/cm or less, or the like. The peel strength can be measured by the method described in < measurement and evaluation of peel strength (peel strength) of metal layer > described later. The metal layer is preferably a metal layer containing copper, and more preferably a metal layer formed by plating.
The cured product obtained by thermally curing the resin composition of the present invention at 180 ℃ for 90 minutes exhibits such a characteristic as excellent thermal conductivity. Namely, an insulating layer having excellent thermal conductivity was obtained. The thermal conductivity is preferably 1.5W/m, more preferably 1.8W/m, more preferably 2.0W/m, more preferably. The upper limit of the thermal conductivity may be 5.0W/m, or less than either a seed or seed. The thermal conductivity can be evaluated by the method described in < measurement of thermal conductivity of cured product > described below.
A cured product obtained by thermally curing the resin composition of the present invention at 180 ℃ for 90 minutes exhibits such a characteristic that the elastic modulus at 23 ℃ is low. Namely, an insulating layer having a low elastic modulus was obtained. The elastic modulus is preferably 25GPa or less, more preferably 20GPa or less, and still more preferably 15GPa or less. The lower limit may be 0.1GPa or more. The elastic modulus can be measured by the method described in < measurement of elastic modulus > described later.
The cured product obtained by heat-curing the resin composition of the present invention at 100 ℃ for 30 minutes and further at 180 ℃ for 30 minutes shows a low warpage. Namely, an insulating layer with a low warpage amount was obtained. The average value of the warpage amounts of the four corners is preferably less than 1 cm. The warpage amount can be measured by the method described in < evaluation of warpage amount > described later.
The resin composition of the present invention exhibits such a characteristic that the melt viscosity is low. This improves the lamination properties of the resin composition layer of the resin sheet described later, and a cured product of the resin composition having high peel strength can be obtained. The melt viscosity is preferably 500 poise or more, more preferably 1000 poise or more, further preferably 1500 poise or more, preferably 8500 poise or less, more preferably 8000 poise or less, further preferably 7500 poise or less, or 7000 poise or less. The melt viscosity can be measured by the method described in < measurement of melt viscosity > described later.
The resin composition of the present invention can provide an insulating layer having excellent thermal conductivity and peel strength. The resin composition of the present invention can be suitably used as: a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for an insulating layer of a semiconductor chip package), a resin composition for forming an insulating layer of a circuit board (including a printed wiring board) (resin composition for an insulating layer of a circuit board); and further can be suitably used as: a resin composition for forming an interlayer insulating layer on which a conductor layer is formed by plating (a resin composition for an interlayer insulating layer of a circuit substrate on which a conductor layer is formed by plating, that is, a circuit substrate on which a circuit is formed by a semi-addition method).
Further, it can also be suitably used as: a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip), and a resin composition for forming a wiring on a semiconductor chip (resin composition for forming a wiring on a semiconductor chip).
[ resin sheet ]
The resin sheet of the present invention comprises a support and a resin composition layer formed of the resin composition of the present invention provided on the support.
From the viewpoint of thinning, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, and still more preferably 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less, or 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be usually 1 μm or more, 5 μm or more, 10 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 preferably a film made of a plastic material and a metal foil.
When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter, sometimes simply referred to as "PET"), polyethylene naphthalate (hereinafter, sometimes simply referred to as "PEN"), acrylics such as polycarbonate (hereinafter, sometimes simply referred to as "PC"), polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. 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 a copper foil and an aluminum foil, and a copper foil is preferable. As the copper foil, a foil formed of metal copper alone 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 surface of the support to be bonded to the resin composition layer may be subjected to matting treatment or corona treatment.
In addition, 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 having a release layer include 1 or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. As the support having 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, "Miller T60" manufactured by Toray corporation, "Purex" manufactured by Ditika corporation, and "UNIPEEL" manufactured by UNITIKA corporation.
The thickness of the support is not particularly limited, but is preferably in the range of 5 to 75 μm, and more preferably in the range of 10 to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.
The resin sheet can be produced, for example, by: a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and the resin varnish is applied to a support using a die coater (die coater), a compression molding method, or the like, and is 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, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The drying can be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, and drying is performed so that the content of the organic solvent in the resin composition layer becomes 10 mass% or less, preferably 5 mass% or less. Although the boiling point of the organic solvent in the resin varnish varies, 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.
In the resin sheet, a protective film based on the support may be laminated on a surface of the resin composition layer not bonded to the support (i.e., a surface opposite to 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 dirt or the like to the surface of the resin composition layer and scratches can be prevented. The resin sheet may be stored in a roll form. In the case where the resin sheet has a protective film, the protective film can be used by peeling off the protective film.
The resin sheet can be suitably used for forming an insulating layer in the manufacture of a semiconductor chip package (insulating resin sheet for semiconductor chip package). For example, the resin sheet can be suitably used for forming an insulating layer of a circuit board (resin sheet for an insulating layer of a circuit board), and further can be suitably used for forming an interlayer insulating layer on which a conductor layer is formed by plating (for an interlayer insulating layer of a circuit board on which a conductor layer is formed by plating). Examples of the package using the substrate include FC-CSP, MIS-BGA package, and ETS-BGA package.
Further, the resin sheet can be suitably used for sealing a semiconductor chip (semiconductor chip sealing resin sheet) or for forming a wiring on a semiconductor chip (semiconductor chip wiring forming resin sheet), and can also be suitably used for, for example, a Fan-out type WLP (Wafer Level Package), a Fan-in type WLP, a Fan-out type PLP (Panel Level Package), a Fan-in type PLP, or the like. In addition, the present invention can be suitably used for a MUF (Molding Under Filling) material or the like used after connecting a semiconductor chip to a substrate. Further, the resin sheet can be suitably used for other wide-ranging uses requiring high insulation reliability, for example, for forming an insulating layer of a circuit substrate of a printed wiring board or the like.
Instead of the resin sheet, a prepreg obtained by impregnating a sheet-like fibrous base material with the resin composition of the present invention may be used.
The sheet-like fibrous base material used in the prepreg is not particularly limited, and a sheet-like fibrous base material commonly used as a base material for a prepreg, such as a glass cloth, an aramid nonwoven fabric, or a liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of thinning, the thickness of the sheet-like fibrous base material is preferably 900 μm or less, more preferably 800 μm or less, even more preferably 700 μm or less, and even more preferably 600 μm or less. The lower limit of the thickness of the sheet-like fibrous base material is not particularly limited, and may be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.
The prepreg can be produced by a known method such as a hot melt method or a solvent method.
The thickness of the prepreg may be in the same range as the resin composition layer in the resin sheet.
[ Circuit Board ]
The circuit board of the present invention includes an insulating layer formed from a cured product of the resin composition of the present invention.
The method for manufacturing a circuit board according to the present invention includes the steps of:
a step (1) of preparing a substrate with a wiring layer, the substrate having a substrate and a wiring layer provided on at least one surface of the substrate,
a step (2) of laminating the resin sheet of the present invention on a substrate with a wiring layer so as to embed the wiring layer in the resin composition layer, and heat-curing the laminate to form an insulating layer,
a step (3) of connecting the wiring layers between layers;
in addition, the method for manufacturing the circuit substrate may include: and (4) removing the base material.
The step (3) is not particularly limited as long as the wiring layers are connected to each other between layers, and is preferably a step of forming a wiring layer by forming a via hole in the insulating layer; and at least one of polishing and grinding the insulating layer to expose the wiring layer.
< step (1) >
The step (1) is a step of preparing a substrate with a wiring layer, which has a substrate and a wiring layer provided on at least one surface of the substrate. In general, a substrate with a wiring layer has a first metal layer and a second metal layer as a part of the substrate on both surfaces of the substrate in this order, and the wiring layer is provided on the surface of the second metal layer opposite to the surface on the substrate side. Specifically, a dry film (photosensitive resist film) is stacked on a substrate, and exposed and developed under a predetermined condition using a photomask to form a dry film pattern. Forming a wiring layer by an electrolytic plating method using the developed pattern dry film as a plating mask, and then peeling off the pattern dry film. The first metal layer and the second metal layer may not be provided.
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, a thermosetting polyphenylene ether substrate, etc., and a metal layer such as a copper foil can be formed on the surface of the substrate. In addition, a peelable metal layer such as a first metal layer and a second metal layer (for example, an extra Thin copper foil with carrier copper foil of a triple well metal, trade name "Micro Thin") may be formed on the surface.
The dry film is not particularly limited as long as it is a photosensitive dry film formed from the photoresist composition, and for example, dry films of phenol resin, acrylic resin, and the like can be used. The dry film may be a commercially available one.
The conditions for laminating the base material and the dry film are the same as those in the case of laminating the resin sheet so as to embed the resin sheet in the wiring layer in the step (2) described later, and the preferable range is also the same.
After laminating the dry film on a substrate, the dry film is exposed and developed under a predetermined condition using a photomask in order to form a desired pattern.
The ratio of the line width (line) to the space (space) of the wiring layers 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, even more preferably 5/5 μm or less, even more preferably 1/1 μm or less, and particularly preferably 0.5/0.5 μm or more. The pitch need not be the same throughout the wiring layers. The minimum pitch of the wiring layers may be 40 μm or less, 36 μm or less, or 30 μm or less.
After the dry film is patterned, a wiring layer is formed and the dry film is peeled off. Here, the formation of the wiring layer may be performed by a plating method using a dry film formed with a desired pattern as a plating mask.
The conductor material for the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer contains 1 or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The wiring layer may be a single metal layer or an alloy layer, and examples of the alloy layer include an alloy layer made of an alloy of 2 or more metals selected from the metals described above (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoint of versatility of wiring layer formation, cost, easiness of pattern formation, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferable, and a single metal layer of copper is even more preferable.
The thickness of the wiring layer depends on the design of the desired wiring board, and is preferably 3 to 35 μm, more preferably 5 to 30 μm, and further preferably 10 to 20 μm, or 15 to 20 μm. In the step (3), when a step of polishing or grinding the insulating layer to expose the wiring layer and interlayer-connecting the wiring layer is employed, it is preferable that the thickness of the wiring to be interlayer-connected is different from that of the wiring not to be connected. The thickness of the wiring layer can be adjusted by repeating the aforementioned pattern formation. The thickness of the thickest wiring layer (conductive pillar) among the wiring layers depends on the design of a desired wiring board, and is preferably 2 μm or more and 100 μm or less. In addition, the wiring for interlayer connection may be formed in a convex shape.
After the wiring layer is formed, the dry film is peeled off. The dry film can be peeled off using an alkaline peeling solution such as a sodium hydroxide solution. If necessary, unnecessary wiring patterns may be removed by etching or the like to form desired wiring patterns. As to the pitch of the wiring layer formed, as described above.
< step (2) >
The step (2) is a step of forming an insulating layer by laminating the resin sheet of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer and thermally curing the laminate. Specifically, the wiring layer of the base material with the wiring layer obtained in the step (1) is laminated so as to be embedded in the resin composition layer of the resin sheet, and the resin composition layer of the resin sheet is thermally cured to form the insulating layer.
The lamination of the wiring layer and the resin sheet may be performed by, for example, heat-crimping the resin sheet to the wiring layer from the support side after removing the protective film of the resin sheet. Examples of the member for heat-crimping the resin sheet to the wiring layer (hereinafter also referred to as "heat-crimping member") include a heated metal plate (SUS end plate (or other) plate) and a metal roll (SUS roll). It is preferable that the pressure is applied through an elastic material such as a heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the wiring layer, instead of directly applying pressure to the resin sheet.
The lamination of the wiring layer and the resin sheet may be performed by a vacuum lamination method after removing the protective film of the resin sheet. In the vacuum lamination method, the heating and crimping temperature is preferably 60-160 ℃, more preferably 80-140 ℃, the heating and crimping pressure is preferably 0.098-1.77 MPa, more preferably 0.29-1.47 MPa, and the heating and crimping time is preferably 20-400 seconds, more preferably 30-300 seconds. The lamination is preferably performed under a reduced pressure of 13hPa or less.
After lamination, the heat and pressure bonding member is pressurized at normal pressure (atmospheric pressure), for example, from the support side, whereby the smoothing treatment of the laminated resin sheet can be performed. The pressing conditions for the smoothing treatment may be set to the same conditions as the heating and pressure bonding conditions for the laminate. The lamination and smoothing processes can be continuously performed using the above-mentioned commercially available vacuum laminator.
The resin composition layer is laminated on the base material with the wiring layer in such a manner that the wiring layer is embedded, and then the resin composition layer is thermally cured to form the insulating layer. For example, although the conditions for heat curing the resin composition layer vary depending on the kind of the resin composition, the curing temperature may be set to a range of 120 to 240 ℃ and the curing time may be set to a range of 5 to 120 minutes. The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured.
The support of the resin sheet may be peeled off after the resin sheet is laminated on the substrate with the wiring layer and thermally cured, or may be peeled off before the resin sheet is laminated on the substrate with the wiring layer. The support may be peeled off before the roughening treatment step described later.
After the resin composition layer is thermally cured to form the insulating layer, the surface of the insulating layer may be polished. The polishing method is not particularly limited, and the surface of the insulating layer may be polished by a known method, for example, by using a flat grinding disk.
< step (3) >
The step (3) is a step of connecting the wiring layers between layers. Specifically, the method includes the steps of forming a via hole in an insulating layer, forming a conductor layer, and connecting wiring layers to each other. Or a step of polishing or grinding the insulating layer to expose the wiring layer and interlayer-connecting the wiring layer. The conductor layer is sometimes referred to as a wiring layer.
When the step of forming a via hole in the insulating layer, forming a conductive layer, and connecting wiring layers between layers is employed, the formation of the via hole is not particularly limited, and examples thereof include laser irradiation, etching, mechanical drilling, and the like, and it is preferable to perform laser irradiation. The laser irradiation can be performed by any suitable laser processing machine using a carbon dioxide laser, a YAG laser, an excimer laser, or the like as a light source. More specifically, laser light is irradiated from the front surface side of the support of the resin sheet, and a through hole for exposing the wiring layer is formed through the support and the insulating layer.
The conditions of laser irradiation are not particularly limited, and laser irradiation may be carried out by any suitable procedure according to a conventional method corresponding to the selected means.
The shape of the through-hole, i.e., the shape of the outline of the opening when viewed in the extending direction, is not particularly limited, and a circular shape (substantially circular shape) is generally employed.
After the through-hole is formed, a so-called desmear (desmear) process, which is a process of removing the smear in the through-hole, may be performed. In the case where a conductor layer is formed in a plating step, which will be described later, the through hole may be subjected to, for example, a wet desmearing process, and in the case where the conductor layer is formed in a sputtering step, the through hole may be subjected to, for example, a dry desmearing process such as a plasma processing step. In addition, the desmear step may be also used as the roughening treatment step.
The via hole and the insulating layer may be roughened prior to forming the conductive layer. The roughening treatment may be carried out by a known method and conditions. Examples of the dry roughening treatment include plasma treatment, and examples of the wet roughening treatment include a method in which swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralizing treatment with a neutralizing liquid are sequentially performed.
The surface roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 350nm or more, more preferably 400nm or more, and still more preferably 450nm or more. The upper limit is preferably 700nm or less, more preferably 650nm or less, and still more preferably 600nm or less. The surface roughness (Ra) can be measured, for example, using a non-contact surface roughness meter.
After the via hole is formed, a conductor layer is formed. The conductor material constituting the conductor layer is not particularly limited, and the conductor layer can be formed by any conventionally known suitable method such as plating, sputtering, vapor deposition, and the like, and is preferably formed by plating. In one preferred embodiment, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. Among them, the semi-addition method is preferable. When the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive (reactive) method. The conductor layer may have a single-layer structure, or may have a multilayer structure in which 2 or more kinds of single metal layers or alloy layers made of different kinds of metals or alloys are stacked.
In the case of the plating, specifically, the plating seed layers (めっきシード body regions) are formed on the surface of the insulating layer by electroless plating (electroless plating). Next, a mask pattern is formed on the plating seed layer so as to expose a part of the plating seed layer corresponding to a desired wiring pattern. An electrolytic plating layer is formed on the exposed plating seed layer by electrolytic plating. At this time, the electrolytic plating layer is formed and the through hole is filled by electrolytic plating to form a filled hole (filled via). After the electrolytic plating layer is formed, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern. In forming the conductor layer, a dry film used for forming a mask pattern is the same as the dry film.
The conductor layer may include not only a linear wiring but also an electrode pad (land) on which an external terminal can be mounted, for example. In addition, the conductor layer may be constituted only by the electrode pad.
In addition, the conductor layer may also be formed by: after the plating seed layer is formed, an electrolytic plating layer and filled holes are formed without using a mask pattern, and then pattern formation by etching is performed.
When the step of polishing or grinding the insulating layer to expose the wiring layer and interlayer-connecting the wiring layer is employed, the polishing method or grinding method of the insulating layer is not particularly limited as long as the wiring layer is exposed and the polished or ground surface is horizontal, and conventionally known polishing methods or grinding methods can be applied, and examples thereof include a chemical mechanical polishing method using a chemical mechanical polishing apparatus, a mechanical polishing method such as polishing (buff), and a plane grinding method using rotation of a grindstone. The steps of removing the smear and roughening the wiring layer may be performed in the same manner as the steps of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers between layers, or the conductor layer may be formed. In addition, it is not necessary to expose all the wiring layers, and a part of the wiring layers can be exposed.
< step (4) >
Step (4) is a step of removing the base material to form the circuit board of the present invention. The method for removing the base material is not particularly limited. In one suitable embodiment, the base material is peeled from the circuit substrate at the interface of the first metal layer and the second metal layer, and the second metal layer is etched away using, for example, an aqueous solution of copper chloride or the like. If necessary, the base material may be peeled off with the conductor layer protected by the protective film.
In other embodiments, a circuit substrate may be manufactured using the prepreg described above. The manufacturing method is basically the same as the case of using the resin sheet.
[ semiconductor chip Package ]
A first aspect of the semiconductor chip package according to the present invention is a semiconductor chip package in which a semiconductor chip is mounted on the circuit board. By bonding a semiconductor chip to the circuit board, a semiconductor chip package can be manufactured.
The bonding conditions are not particularly limited as long as the terminal electrodes of the semiconductor chip are conductively connected to the circuit wiring of the circuit board, and known conditions that can be used in flip-chip mounting of the semiconductor chip can be used. Further, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.
In one suitable embodiment, the semiconductor chip is crimped to the circuit substrate. The pressure bonding conditions may be, for example, a pressure bonding temperature in a range of 120 to 240 ℃ (preferably in a range of 130 to 200 ℃, and more preferably in a range of 140 to 180 ℃), and a pressure bonding time in a range of 1 to 60 seconds (preferably 5 to 30 seconds).
In another preferred embodiment, the semiconductor chip is bonded to the circuit board by reflow soldering. The reflow conditions may be set to a range of 120 to 300 ℃, for example.
After the semiconductor chip is bonded to the circuit substrate, the semiconductor chip may also be filled with a mold underfill material, for example, to obtain a semiconductor chip package. As for the method of filling with the mold underfill material, it can be carried out by a known method. The resin composition or the resin sheet of the present invention can also be used as a molding underfill material.
A second embodiment of the semiconductor chip package according to the present invention is, for example, a semiconductor chip package (Fan-out type WLP) as an example shown in fig. 1. A semiconductor chip package (Fan-out type WLP)100 as an example shown in fig. 1 is a semiconductor chip package in which an encapsulating layer 120 is formed using the resin composition or the resin sheet of the present invention. The semiconductor chip package 100 includes: the semiconductor device includes a semiconductor chip 110, a sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110, a rewiring formation layer (insulating layer) 130 on a surface of the semiconductor chip 110 opposite to the sealing layer covering side, a conductor layer (rewiring layer) 140, a solder resist (solder resist) layer 150, and a bump 160. The method for manufacturing the semiconductor chip package comprises the following steps:
a step (A) of laminating a temporary fixing film on a base material,
a step (B) of temporarily fixing the semiconductor chip to the temporary fixing film,
a step (C) of laminating the resin composition layer of the resin sheet of the present invention on a semiconductor chip, or applying the resin composition of the present invention on a semiconductor chip and heat-curing the resin composition to form a sealing layer,
a step (D) of peeling the base material and the temporary fixing film from the semiconductor chip,
a step (E) of forming a rewiring formation layer (insulating layer) on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off,
a step (F) of forming a conductor layer (rewiring layer) on the rewiring-forming layer (insulating layer), and
a step (G) of forming a solder resist layer on the conductor layer;
in addition, the method of manufacturing the semiconductor chip package may include: and (H) cutting the plurality of semiconductor chip packages into individual semiconductor chip packages for singulation.
< Process (A) >
The step (a) is a step of laminating a temporary fixing film on a substrate. The lamination condition of the base material and the temporary fixing film is the same as the lamination condition of the wiring layer and the resin sheet in the step (2) in the method for manufacturing the circuit board, and the preferable range is also the same.
The material for the base material is not particularly limited. 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; and substrates made of bismaleimide triazine resins such as BT resin.
The material of the temporary fixing film is not particularly limited as long as it can be peeled off from the semiconductor chip in the step (D) described later and the semiconductor chip can be temporarily fixed. Commercially available temporary fixing films can be used. Examples of commercially available products include REVALPHA manufactured by ritonary 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 by a known device such as a flip chip bonder (flip chip bonder) or a die bonder (die bonder). 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 package, and the like, and for example, the temporary fixing may be performed by arranging the temporary fixing films in a matrix of a plurality of rows and a plurality of columns.
< Process (C) >
The step (C) is a step of laminating the resin composition layer of the resin sheet of the present invention on a semiconductor chip, or applying the resin composition of the present invention on a semiconductor chip and thermally curing the applied resin composition to form a sealing layer. In the step (C), the sealing layer is preferably formed by laminating the resin composition layer of the resin sheet on the semiconductor chip and thermally curing the laminated layer.
The lamination of the semiconductor chip and the resin sheet may be performed by, for example, heat-crimping the resin sheet to the semiconductor chip from the support side after removing the protective film of the resin sheet. Examples of a member for heat-pressure bonding a resin sheet to a semiconductor chip (hereinafter also referred to as "heat-pressure bonding member") include a heated metal plate (such as SUS end plate) and a metal roll (SUS roll). It is preferable that the pressure is applied through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the semiconductor chip, instead of directly applying pressure to the resin sheet.
The lamination of the semiconductor chip and the resin sheet may be performed by a vacuum lamination method after removing the protective film of the resin sheet. The lamination conditions in the vacuum lamination method are the same as those in the step (2) of the method for producing a circuit board, and the lamination conditions of the wiring layer and the resin sheet are the same, and the preferable ranges are also the same.
The support for the resin sheet may be peeled off after the resin sheet is laminated on the semiconductor chip and thermally cured, or may be peeled off before the resin sheet is laminated on the semiconductor chip.
The coating conditions of the resin composition are the same as those in the case of forming the resin composition layer in the resin sheet of the present invention, and the preferable ranges are also the same.
< Process (D) >
The step (D) is a step of peeling the base material and the temporary securing film from the semiconductor chip. The method of peeling may be appropriately changed depending on the material of the temporary fixing film, and examples thereof include a method of peeling the temporary fixing film by heating and foaming (or expanding) the film, and a method of peeling the film by irradiating the temporary fixing film with ultraviolet light from the substrate side to lower the adhesive force of the film.
In the method of heating the temporary fixing film to foam (or expand) the film and then peeling the film, the heating condition is usually 1 second to 90 seconds or 5 minutes to 15 minutes at 100 ℃ to 250 ℃. In addition, in the method of irradiating ultraviolet rays from the substrate side to lower the adhesive force of the temporary fixing film and peeling it, the irradiation amount of the ultraviolet rays is usually 10mJ/cm2～1000mJ/cm2。
< Process (E) >
The step (E) is a step of forming a rewiring formation layer (insulating layer) on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled.
The material for forming the rewiring formation layer (insulating layer) is not particularly limited as long as it has insulation properties when forming the rewiring formation layer (insulating layer), and a photosensitive resin or a thermosetting resin is preferable from the viewpoint of ease of manufacturing the semiconductor chip package. As the thermosetting resin, a resin composition having the same composition as that of the resin composition used for forming the resin sheet of the present invention can be used.
After the rewiring formation layer (insulating layer) is formed, a through hole may be formed in the rewiring formation layer (insulating layer) in order to connect the semiconductor chip and a conductor layer to be described later between layers.
When the material forming the rewiring formation layer (insulating layer) is a photosensitive resin in forming the through hole, first, active energy rays are irradiated onto the surface of the rewiring formation layer (insulating layer) through a mask pattern to photocure the rewiring layer of the irradiation portion.
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 changed depending on the photosensitive resin. As the exposure method, there can be used: the contact exposure method of exposing the rewiring formation layer (insulating layer) with a mask pattern in a manner of being in close contact therewith, and the non-contact exposure method of exposing the rewiring formation layer (insulating layer) with parallel light rays so as not to make the mask pattern in close contact therewith.
Next, the rewiring formation layer (insulating layer) is developed to remove the unexposed portion, thereby forming a through hole. The development is preferably wet development or dry development. As the developer used in the wet development, a known developer can be used.
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 (squeegee) method, and the spin immersion method is preferable from the viewpoint of resolution.
When the material for forming the rewiring-forming layer (insulating layer) is a thermosetting resin, the formation of the through hole is not particularly limited, and examples thereof include laser irradiation, etching, mechanical drilling, and the like, and it is preferable to perform laser irradiation. The laser irradiation can be performed by any suitable laser processing machine using a carbon dioxide laser, a UV-YAG laser, an excimer laser, or the like as a light source.
The conditions of laser irradiation are not particularly limited, and laser irradiation may be carried out by any suitable procedure according to a conventional method corresponding to the selected means.
The shape of the through-hole, i.e., the shape of the outline of the opening when viewed in the extending direction, is not particularly limited, and a circular shape (substantially circular shape) is generally employed. The diameter of the top of the via hole (the diameter of the opening in the surface of the rewiring formation layer (insulating layer)) is preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 20 μm or less. The lower limit is not particularly limited, but is preferably 10 μm or more, more preferably 15 μm or more, and further preferably 20 μm or more.
< step (F) >
The step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer). The method of forming the conductor layer on the rewiring formation layer (insulating layer) is the same as the method of forming the conductor layer after forming the via hole in the insulating layer in step (3) of the method of manufacturing the circuit board, and the preferable range is also the same. The steps (E) and (F) may be repeated to alternately deposit (build-up) a conductor layer (rewiring layer) and a rewiring-forming layer (insulating layer).
< Process (G) >
Step (G) is a step of forming a solder resist layer on the conductor layer.
The material for forming the solder resist layer is not particularly limited as long as it is a material having insulation properties when forming the solder resist layer, and a photosensitive resin and a thermosetting resin are preferable from the viewpoint of easiness of manufacturing the semiconductor chip package. As the thermosetting resin, a resin composition having the same composition as that of the resin composition used for forming the resin sheet 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 bump processing may be performed by a known method such as solder ball or solder plating. 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 of 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 package into individual semiconductor chip packages is not particularly limited, and a known method can be used.
A third embodiment of the semiconductor chip package of the present invention is a semiconductor chip package in which a rewiring formation layer (insulating layer) 130 and a solder resist layer 150 in a semiconductor chip package (Fan-out type WLP) are manufactured using the resin composition or the resin sheet of the present invention, as shown in an example in fig. 1.
[ semiconductor device ]
Examples of the semiconductor device on which the semiconductor chip package of the present invention is mounted 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, aircraft, and the like), and the like.
[ examples ]
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. In the following description, "part" and "%" representing amounts refer to "part by mass" and "% by mass", respectively, unless otherwise specified.
< preparation of sample for measuring peeling Strength >
(1) Base treatment of inner layer circuit substrate
Both surfaces of a glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil 18 μm thick, substrate 0.3mm thick, R5715ES manufactured by panasonic corporation) on which an inner layer circuit was formed were immersed in CZ8100 manufactured by MEC corporation, and roughening treatment of the copper surface was performed.
(2) Lamination of resin sheets
The resin sheets prepared in examples and comparative examples were laminated on both surfaces of the inner layer circuit board using a batch vacuum press Laminator (2-Stage build-up Laminator "CVP 700" manufactured by Nikko-Materials), and the resin composition layer was bonded to the inner layer circuit board. The lamination was carried out as follows: after the pressure was reduced for 30 seconds to 13hPa or less, the resultant was pressure-bonded at 100 ℃ under a pressure of 0.74MPa for 30 seconds. Next, hot pressing was performed at 100 ℃ under a pressure of 0.5MPa for 60 seconds. The resulting laminate with the resin composition layer was heat-treated at 180 ℃ for 30 minutes to cure the resin composition layer, thereby obtaining a laminate with a cured product.
(3) Roughening treatment
The resulting laminate with the cured product was immersed in a spinning Dip securigrant P (Swelling solution) containing diethylene glycol monobutyl ether manufactured by ATOTECH JAPAN at 60 ℃ for 5 minutes, and then immersed in a centralized Compact P (KMnO) manufactured by ATOTECH JAPAN at 80 ℃ for 5 minutes4: 60g/L, NaOH: 40g/L aqueous Solution, an oxidizing agent (roughening Solution)) for 10 minutes, and finally immersed in Reduction Solution Securigiath P (neutralizing Solution) manufactured by ATOTECH JAPAN for 5 minutes at 40 ℃ to roughen the surface of the cured product. The laminate obtained by the roughening treatment was used as an evaluation substrate a.
(4) Forming metal layers by plating
The evaluation substrate A was immersed in a solution containing PdCl2The electroless copper plating solution of (1) is then immersed in an electroless copper plating solution. Next, copper sulfate electrolytic plating was performed to form a metal layer with a thickness of 30 μm on the roughened surface of the cured product. Followed by 60 minutes of annealing at 180 ℃. The annealed laminate was used as evaluation substrate B.
< measurement and evaluation of peeling Strength (peeling Strength) of Metal layer >
A10 mm wide and 100mm long portion was cut out of the metal layer of the evaluation substrate B, one end of the cut was peeled off and held by a jig (AUTO COM model testing machine "AC-50C-SL" manufactured by T.S. E), and the peel strength was measured by measuring the load (kgf/cm) at room temperature when the test piece was peeled off at a speed of 50 mm/min in the vertical direction by 20 mm.
< preparation of cured product for evaluation of elastic modulus >
The release PET film was placed on a double-sided copper-clad laminate of a glass cloth substrate epoxy resin (R5715 ES ", thickness 0.7mm, 255mm square manufactured by Panasonic corporation) so that the untreated surface of the release PET film (" 501010 ", manufactured by Leideke corporation, thickness 38 μm, 240mm square) was in contact with the double-sided copper-clad laminate of a glass cloth substrate epoxy resin, and the four sides of the release PET film were fixed with polyimide tapes (width 10 mm).
Each of the resin sheets (167 × 107mm square) produced in examples and comparative examples was laminated at the center using a batch vacuum press laminator (CVP 700, manufactured by Nikko-Materials) so that the resin composition layer was in contact with the release surface of the release PET film. The lamination process was carried out as follows: the pressure was reduced to 13hPa or less for 30 seconds, and then the pressure was reduced to 100 ℃ and 0.74MPa for 30 seconds.
Subsequently, the support was peeled off, and the resin composition layer was thermally cured under curing conditions of 180 ℃ for 90 minutes.
After thermosetting, the polyimide tape was peeled off, and the resin composition layer was removed from the glass cloth substrate epoxy resin double-sided copper-clad laminate. Further, the release PET film was peeled from the resin composition layer to obtain a sheet-like cured product (cured product for evaluation).
< measurement of elastic modulus >
The cured product for evaluation was cut into a dumbbell No. 1 to obtain a test piece. The tensile strength of the test piece was measured by using a tensile tester "RTC-1250A" manufactured by ORIENTEC corporation, and the elastic modulus at 23 ℃ was determined. The measurement was carried out according to JIS K7127. This operation was performed 3 times, and the average value thereof is shown in the table.
< evaluation of warpage amount >
The resin sheets prepared in examples and comparative examples were laminated on one side of a BT-resin double-sided copper-clad laminate (copper foil 18 μm thick, substrate 0.15mm thick, "HL 832NSF LCA" manufactured by mitsubishi gas chemical corporation, size 15cm × 18cm) as a glass cloth substrate using a batch vacuum press laminator (manufactured by Nikko-Materials, 2-stage stacked laminator, "CVP 700"), and after releasing the mold PET, the laminate was thermally cured at 100 ℃ for 30 minutes, further at 180 ℃ for 30 minutes, and placed on a plane to confirm the amount of warpage. The average value of the warpage amounts at the 4 corners was evaluated as "O" when the average value was less than 1cm, as "Delta" when the average value was 1 to 2cm, and as "X" when the average value was 2cm or more.
< measurement of thermal conductivity of cured product >
(1) Preparation of cured product sample
The resin varnishes prepared in examples and comparative examples were applied to a PET film (manufactured by Toray corporation, "Lu Miller R80", thickness 38 μm, softening point 130 ℃) which had been subjected to a releasing treatment with an alkyd resin-based releasing agent ("AL-5", manufactured by Lindcao corporation) so that the thickness of the dried resin composition layer became 100 μm using a die coater, and dried at 80 ℃ to 100 ℃ (average 90 ℃) for 7 minutes to obtain a resin composition layer.
The resin composition layer was laminated by 3 layers using a batch vacuum press laminator (2-stage lamination laminator "CVP 700" manufactured by Nikko-Materials), and then laminated, and the resin composition layer was cured at 180 ℃ for 90 minutes to obtain a cured product sample. The lamination was performed as follows: the pressure was reduced for 30 seconds to 13hPa or less, and then increased at 100 ℃ under 0.4MPa for 20 seconds.
(2) Determination of thermal diffusivity, alpha
For the cured product sample, using ai-Phase Mobile 1u, ai-Phase company, the thermal diffusivity alpha (m) in the thickness direction of the cured product sample was measured by the temperature wave analysis method2In s). The same sample was measured 3 times, and the average value was calculated.
(3) Determination of specific Heat Capacity Cp
The specific heat capacity Cp (J/kg. seed K) of the cured product sample at 25 ℃ was calculated by measuring the temperature of the cured product sample at a rate of 10 ℃/min from-40 ℃ to 80 ℃ using a differential scanning calorimeter ("DSC 7020" manufactured by SII Nano Technology Co.).
(4) Measurement of Density ρ
The density (kg/m) of the cured product sample was measured using an analytical balance XP105 (used for a specific gravity measuring device) manufactured by METTLER TOLEDO3)。
(5) Calculation of thermal conductivity λ
Obtained by the above (2) to (4)Thermal diffusivity of alpha (m)2Specific heat capacity Cp (J/kg. seed. K) and density rho (kg/m)3) Substituting the formula (I) below to calculate the thermal conductivity coefficient lambda (W/m & seed & K);
λ＝α×Cp×ρ (I)。
< measurement of melt viscosity >
The melt viscosity of the resin composition layer in the resin sheets produced in examples and comparative examples was measured. The melt viscosity was measured under the measurement conditions of a temperature rise rate of 5 ℃ per minute, a measurement temperature interval of 2.5 ℃ and a vibration of 1 Hz/deg.C from an initial temperature of 60 ℃ to 200 ℃ using a parallel plate having a diameter of 18mm and a resin amount of 1G and of the formula Rheosol-G3000 manufactured by UBM.
< synthetic example 1: synthesis of Polymer Compound 1>
In a reaction vessel, 69G of G-3000 (2-functional hydroxyl-terminated polybutadiene, number average molecular weight 5047(GPC method), hydroxyl equivalent 1798G/eq., 100% by mass of solid content manufactured by japan soh corporation), 40G of Ipsol (イプゾール) 150 (aromatic hydrocarbon-based mixed solvent manufactured by mitsunobu petrochemicals) and 0.005G of dibutyltin dilaurate were mixed and uniformly dissolved. After the mixture was homogenized, the temperature was raised to 50 ℃, and 8g of isophorone diisocyanate (IPDI, 113g/eq equivalent isocyanate group, manufactured by Evonik Degussa Japan) was added with stirring, and the reaction was carried out for about 3 hours. Subsequently, the reaction mixture was cooled to room temperature, and then 23g of cresol novolac (KA-1160, manufactured by DIC corporation, hydroxyl equivalent: 117g/eq.) and 60g of diethylene glycol ethyl ether acetate (manufactured by Daicel corporation) were added thereto, and the temperature was raised to 80 ℃ while stirring, and the reaction was carried out for about 4 hours. Confirmation of 2250cm by FT-IR-1Disappearance of NCO peak (b). When disappearance of NCO peak was recognized as the end point of the reaction, the reaction mixture was cooled to room temperature and then filtered through a filter cloth having a mesh size of 100. mu.m, to obtain polymer compound 1 having a polybutadiene structure and phenolic hydroxyl groups (nonvolatile content: 50 mass%).
< synthetic example 2: synthesis of Polymer Compound 2>
In a reaction vessel, a polycarbonate diol (number average molecular weight: about 1000, hydroxyl equivalent: 500, nonvolatile matter: 100%, product of Coly corporation)80g of "C-1015N") and 0.01g of dibutyltin dilaurate were uniformly dissolved in 37.6g of diethylene glycol monoethyl ether acetate ("diethylene glycol monoethyl ether acetate", manufactured by Daicel Co., Ltd.). Then, the mixture was heated to 50 ℃ and 27.8g of toluene-2, 4-diisocyanate (isocyanate group equivalent: 87.08) was added thereto with stirring to conduct a reaction for about 3 hours. Then, the reaction mixture was cooled to room temperature, and 14.3g of benzophenone tetracarboxylic dianhydride (acid anhydride equivalent: 161.1), 0.12g of triethylenediamine, and 84.0g of diethylene glycol monoethyl ether acetate ("diethylene glycol ethyl ether acetate" manufactured by Daicel corporation) were added thereto, and the temperature was raised to 130 ℃ with stirring, and the reaction was carried out for about 4 hours. Confirmation of 2250cm by FT-IR-1Disappearance of NCO peak (b). When disappearance of the NCO peak was recognized as the end point of the reaction, the temperature of the reaction mixture was lowered to room temperature, and then the reaction mixture was filtered through a filter cloth having a mesh size of 100. mu.m, whereby polymer compound 2 having a carbonate structure (nonvolatile content: 50 mass%) was obtained.
< measurement of average particle diameter of thermally conductive Filler >
A20 ml vial was charged with 0.01g of a thermally conductive filler, 0.2g of a nonionic dispersant ("T208.5" manufactured by NOF corporation) and 10g of pure water, and ultrasonically dispersed for 10 minutes by an ultrasonic cleaner to prepare a sample. Subsequently, the sample was put into a laser diffraction particle size distribution measuring apparatus ("SALD 2200" manufactured by Shimadzu corporation), and the sample was irradiated with ultrasonic waves for 10 minutes while being circulated. Then, the ultrasonic wave was stopped, and the particle size distribution was measured while maintaining the circulation of the sample, to determine the average particle size of the thermally conductive filler. The refractive index in the measurement is set to 1.45 to 0.001 i.
< measurement of specific surface area of thermally conductive Filler >
The specific surface area was determined by the nitrogen BET method using an automatic specific surface area measuring apparatus ("Macsorb HM-1210" manufactured by Mountech corporation).
< thermally conductive Filler used >
Alumina 1: alumina mixture with different average particle diameter and specific surface area, average particle diameter of 3 μm, and specific surface area of 1.5m2(iv)/g, KBM573 (N) manufactured by shin-Etsu chemical industries, LtdPhenyl-3-aminopropyltrimethoxysilane);
alumina 2: alumina mixture with different average particle diameter and specific surface area, average particle diameter of 3 μm, and specific surface area of 1.5m2Alumina surface-treated with KBM5783 (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by shin-Etsu chemical industries, Ltd;
alumina 3: alumina mixture with different average particle diameter and specific surface area, average particle diameter of 3 μm, and specific surface area of 1.5m2Aluminum oxide surface-treated with KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by shin-Etsu chemical Co., Ltd.;
alumina 4: alumina mixture with different average particle diameter and specific surface area, average particle diameter of 3 μm, and specific surface area of 1.5m2(iii)/g of alumina surface-treated with KBM903 (3-aminopropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, Ltd.
< example 1>
6 parts of an aminophenol type epoxy resin ("630" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 95g/eq), 5 parts of a liquid epoxy resin ("ZX 1059" manufactured by Nippon iron King chemical corporation, a 1: 1 mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169g/eq), 2 parts of a bixylenol type epoxy resin ("YX 4000H" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 185g/eq), 2 parts of a biphenyl type epoxy resin ("NC 3100" manufactured by Nippon chemical corporation, epoxy equivalent: 258g/eq) were dissolved in 10 parts of methyl ethyl ketone, and 1 part (270 parts) of alumina, 24 parts of a polymer compound 1 ("solid content" by mass, number average molecular weight 5500), an active ester curing agent ("HPC-8000-65T" manufactured by DIC corporation, active ester equivalent g/eq, and active ester curing agent ("HPC-8000-65T" manufactured by DIC corporation, active ester equivalent g/eq, A toluene solution having a solid content of 65%) 3 parts of a solid naphthol curing agent (SN 485, a hydroxyl equivalent of 215g/eq, manufactured by shin-chan-ku chemical company, used as a methyl ethyl ketone solution having a solid content of 50%), 1 part of a curing accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), an MEK solution having a solid content of 10 mass%) and 15 parts of methyl ethyl ketone were uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 1.
The resin varnish 1 was applied to a PET film (product of tommy corporation, "koumier R80", thickness 38 μm, softening point 130 ℃, and sometimes referred to as "release PET") subjected to a release treatment with an alkyd resin-based release agent ("AL-5", product of lindeko corporation) using a die coater so that the thickness of the dried resin composition layer became 50 μm, and was dried at 80 ℃ to 100 ℃ (average 90 ℃) for 5 minutes to obtain a resin sheet 1.
< example 2>
6 parts of an aminophenol type epoxy resin ("630" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 95g/eq), 5 parts of a liquid epoxy resin ("ZX 1059" manufactured by Nippon iron King chemical corporation, a 1: 1 mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169g/eq), 2 parts of a bixylenol type epoxy resin ("YX 4000H" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 185g/eq), 2 parts of a biphenyl type epoxy resin ("NC 3100" manufactured by Nippon chemical corporation, epoxy equivalent: 258g/eq) were dissolved in 10 parts of methyl ethyl ketone, and mixed with 24 parts of alumina 1 (270 parts), a polymer compound 1 ("solid content 50 mass%, number average molecular weight 0"), an active ester curing agent ("HPC-8000-65T" manufactured by Mitsubishi chemical corporation, active ester equivalent 223g/eq, and, A toluene solution having a solid content of 65%) 6 parts of a solid naphthol curing agent (SN 485, a hydroxyl equivalent of 215g/eq, manufactured by shin-chan-ku chemical company, used as a methyl ethyl ketone solution having a solid content of 50%), 1 part of a curing accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), an MEK solution having a solid content of 10 mass%) and 15 parts of methyl ethyl ketone were uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 2. A resin sheet 2 was obtained in the same manner as in example 1, except that the resin varnish 1 in example 1 was changed to the resin varnish 2.
< example 3>
6 parts of an aminophenol type epoxy resin ("630" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 95g/eq), 5 parts of a liquid epoxy resin ("ZX 1059" manufactured by Nippon iron King chemical corporation, a 1: 1 mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169g/eq), 2 parts of a bixylenol type epoxy resin ("YX 4000H" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 185g/eq), 2 parts of a biphenyl type epoxy resin ("NC 3100" manufactured by Nippon chemical corporation, epoxy equivalent: 258g/eq) were dissolved in 10 parts of methyl ethyl ketone, and mixed with 1 part (240 parts) of alumina, 24 parts of a polymer compound 1 ("solid content mass%, number average molecular weight: 5500"), an active ester curing agent ("HPC-8000-65T" manufactured by Mitsubishi chemical corporation, active ester equivalent 223g/eq, and, A toluene solution having a solid content of 65%) 3 parts, a solid naphthol curing agent (SN 485, a hydroxyl equivalent of 215g/eq, manufactured by shiniki chemical corporation, used as a methyl ethyl ketone solution having a solid content of 50%) 2 parts, a curing accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), an MEK solution having a solid content of 10% by mass) 1 part, and 15 parts of methyl ethyl ketone were uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 3. A resin sheet 3 was obtained in the same manner as in example 1, except that the resin varnish 1 was changed to the resin varnish 3 in example 1.
< example 4>
6 parts of an aminophenol type epoxy resin ("630" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 95g/eq), 5 parts of a liquid epoxy resin ("ZX 1059" manufactured by Nippon iron King chemical corporation, a 1: 1 mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169g/eq), 2 parts of a bixylenol type epoxy resin ("YX 4000H" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 185g/eq), 2 parts of a biphenyl type epoxy resin ("NC 3100" manufactured by Nippon chemical corporation, epoxy equivalent: 258g/eq) were dissolved in 10 parts of methyl ethyl ketone, and mixed with 24 parts of alumina 2 (270 parts), 24 parts of a polymer compound 1 ("solid content mass%, number average molecular weight: 5500"), an active ester curing agent ("HPC-8000-65T" manufactured by Mitsubishi chemical corporation, active ester equivalent 223g/eq, and, A toluene solution having a solid content of 65%) 3 parts of a solid naphthol curing agent (SN 485, a hydroxyl equivalent of 215g/eq, manufactured by shin-chan-ku chemical company, used as a methyl ethyl ketone solution having a solid content of 50%), 1 part of a curing accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), an MEK solution having a solid content of 10 mass%) and 15 parts of methyl ethyl ketone were uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 4. A resin sheet 4 was obtained in the same manner as in example 1, except that the resin varnish 1 was changed to the resin varnish 4 in example 1.
< example 5>
6 parts of an aminophenol type epoxy resin ("630" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 95g/eq), 5 parts of a liquid epoxy resin ("ZX 1059" manufactured by Nippon iron King chemical corporation, a 1: 1 mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169g/eq), 2 parts of a bisxylenol type epoxy resin ("YX 4000H" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 185g/eq), 2 parts of a biphenyl type epoxy resin ("NC 3100" manufactured by Nippon chemical corporation, epoxy equivalent: 258g/eq) were dissolved in 10 parts of methyl ethyl ketone, and 1 part (270 parts) of mixed alumina, 24 parts of a polymer compound 2 ("solid content, number average molecular weight 6000", number average molecular weight), an active ester curing agent ("HPC-8000-65T" manufactured by Mitsubishi chemical corporation, active ester equivalent 223g/eq, and, A toluene solution having a solid content of 65%) 3 parts of a solid naphthol curing agent (SN 485, a hydroxyl equivalent of 215g/eq, manufactured by shin-chan-ku chemical company, used as a methyl ethyl ketone solution having a solid content of 50%), 1 part of a curing accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), an MEK solution having a solid content of 10 mass%) and 15 parts of methyl ethyl ketone were uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 5. A resin sheet 5 was obtained in the same manner as in example 1, except that the resin varnish 1 was changed to the resin varnish 5 in example 1.
< comparative example 1>
6 parts of an aminophenol type epoxy resin ("630" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 95g/eq), 5 parts of a liquid epoxy resin ("ZX 1059" manufactured by Mitsubishi chemical corporation, a 1: 1 mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169g/eq), 2 parts of a bixylenol type epoxy resin ("YX 4000H" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 185g/eq), 2 parts of a biphenyl type epoxy resin ("NC 3100" manufactured by Nippon chemical corporation, epoxy equivalent: 258g/eq) were dissolved in 10 parts of methyl ethyl ketone, and 1 part (270 parts) of alumina, 24 parts of a polymer compound 1 ("solid content 50 mass%, number average molecular weight 5500"), 6 parts of a solid naphthol-based curing agent ("SN 485" manufactured by Nihon chemical corporation, hydroxyl equivalent 215g/eq, and 50% of the solid content were mixed with methyl ethyl ketone solution, 1 part of a curing accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution containing 10% by mass of solid content) and 15 parts of methyl ethyl ketone were uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 6. A resin sheet 6 was obtained in the same manner as in example 1, except that the resin varnish 1 in example 1 was changed to the resin varnish 6.
< comparative example 2>
6 parts of an aminophenol type epoxy resin ("630" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 95g/eq), 5 parts of a liquid epoxy resin ("ZX 1059" manufactured by Mitsubishi chemical corporation, a 1: 1 mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169g/eq), 2 parts of a bixylenol type epoxy resin ("YX 4000H" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 185g/eq), 2 parts of a biphenyl type epoxy resin ("NC 3100" manufactured by Nippon chemical corporation, epoxy equivalent: 258g/eq) were dissolved in 10 parts of methyl ethyl ketone, and 1 part (270 parts) of alumina, 26 parts of a polymer compound 1 ("solid content 50 mass%, number average molecular weight 5500"), 2 parts of a solid naphthol type curing agent ("SN 485" manufactured by Nihon chemical corporation, hydroxyl equivalent 215g/eq, and 50% of the solid content were mixed with 2 parts of methyl ethyl ketone solution, 1 part of a curing accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution containing 10% by mass of solid content) and 15 parts of methyl ethyl ketone were uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 7. A resin sheet 7 was obtained in the same manner as in example 1, except that the resin varnish 1 in example 1 was changed to the resin varnish 7.
< comparative example 3>
6 parts of an aminophenol type epoxy resin ("630" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 95g/eq), 5 parts of a liquid epoxy resin ("ZX 1059" manufactured by Mitsubishi chemical corporation, a 1: 1 mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169g/eq), 2 parts of a bixylenol type epoxy resin ("YX 4000H" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 185g/eq), 2 parts of a biphenyl type epoxy resin ("NC 3100" manufactured by Nippon chemical corporation, epoxy equivalent: 258g/eq) were dissolved in 10 parts of methyl ethyl ketone, and 3 parts of alumina (270 parts) were mixed, 24 parts of a polymer compound 1 ("solid content 50 mass%, number average molecular weight 5500"), 6 parts of a solid naphthol-based curing agent ("SN 485" manufactured by Nihon chemical corporation, hydroxyl equivalent 215g/eq, and a methyl ethyl ketone solution having a solid content of 50% were used, 1 part of a curing accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution containing 10% by mass of solid content) and 15 parts of methyl ethyl ketone were uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 8. A resin sheet 8 was obtained in the same manner as in example 1, except that the resin varnish 1 in example 1 was changed to the resin varnish 8.
< comparative example 4>
6 parts of an aminophenol type epoxy resin ("630" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 95g/eq), 5 parts of a liquid epoxy resin ("ZX 1059" manufactured by Mitsubishi chemical corporation, a 1: 1 mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169g/eq), 2 parts of a bixylenol type epoxy resin ("YX 4000H" manufactured by Mitsubishi chemical corporation, epoxy equivalent: 185g/eq), 2 parts of a biphenyl type epoxy resin ("NC 3100" manufactured by Nippon chemical corporation, epoxy equivalent: 258g/eq) were dissolved in 10 parts of methyl ethyl ketone, and mixed with alumina 4 (270 parts), a polymer compound 1 ("50 mass% in solid content, number average molecular weight 5500") 24 parts, a solid naphthol-based curing agent ("SN 485" manufactured by Nihon chemical corporation, 215g/eq in hydroxyl equivalent, and a methyl ethyl ketone solution having a solid content of 50% were used, 6 parts of the bisphenol A epoxy resin (epoxy equivalent: 169g/eq) was dissolved in 10 parts of methyl ethyl ketone solution, 1 part of a curing accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution containing 10% by mass of solid content) and 15 parts of methyl ethyl ketone were uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 9. A resin sheet 9 was obtained in the same manner as in example 1, except that the resin varnish 1 in example 1 was changed to the resin varnish 9.
The descriptions in the following tables and the like are as follows;
(A) the contents of the components are as follows: the content of the nonvolatile components of the resin components other than the component (C) being 100% by mass
(C) The contents of the components are as follows: the content of the nonvolatile component in the resin composition is set to 100 mass%
[ Table 1]
Figure DEST_PATH_IMAGE001
。
As shown in examples 1 to 5, it is understood that the insulating layer formed from the resin composition containing the components (A) to (D) is excellent in peel strength. On the other hand, it is found that the peel strength of comparative examples 1 to 4 containing no component (D) is inferior to that of examples 1 to 5. In addition, it is clear that comparative examples 3 to 4, in which component (C) was not treated with N-phenyl-3-aminoalkyltrimethoxysilane, had poor lamination properties and poor peel strength due to high melt viscosity.
In examples 1 to 5, the same results as those in the above examples were confirmed even though there was a difference in the degree between the components (E) and (F) that were not contained.
[ description of symbols ]
100 semiconductor chip package
110 semiconductor chip
120 sealing layer
130 rewiring forming layer (insulating layer)
140 conductor layer (rewiring layer)
150 solder resist layer
160 bumps.

Claims (50)

1. A resin composition comprising:
(A) a polymer compound having 1 or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule,
(B) Epoxy resin,
(C) Thermally conductive filler, and
(D) an active ester curing agent, a curing agent,
(C) the component (A) comprises aluminum oxide,
the content of the component (C) is 85% by mass or more based on 100% by mass of nonvolatile components in the resin composition,
(A) the component (B) is at least 1 selected from the group consisting of a resin having a glass transition temperature of 25 ℃ or lower and a resin which is liquid at 25 ℃,
(A) the number average molecular weight of the component (A) is 1000 to 1000000,
the content of the component (a) is 10 to 65 mass% based on 100 mass% of the resin component.
2. The resin composition according to claim 1, wherein a peel strength between a cured product obtained by heat-curing the resin composition at 180 ℃ for 30 minutes and further at 180 ℃ for 60 minutes and a metal layer formed by plating is 0.4kgf/cm or more.
3. The resin composition according to claim 1, wherein a peel strength between a cured product obtained by heat-curing the resin composition at 180 ℃ for 30 minutes and further at 180 ℃ for 60 minutes and a metal layer formed by plating is 0.45kgf/cm or more.
4. The resin composition according to claim 1, wherein a peel strength between a cured product obtained by heat-curing the resin composition at 180 ℃ for 30 minutes and further at 180 ℃ for 60 minutes and a metal layer formed by plating is 0.5kgf/cm or more.
5. The resin composition according to claim 1, wherein a peel strength between a cured product obtained by heat-curing the resin composition at 180 ℃ for 30 minutes and further at 180 ℃ for 60 minutes and a metal layer formed by plating is 1.5kgf/cm or less.
6. The resin composition according to claim 1, wherein a peel strength between a cured product obtained by heat-curing the resin composition at 180 ℃ for 30 minutes and further at 180 ℃ for 60 minutes and a metal layer formed by plating is 1kgf/cm or less.
7. The resin composition according to claim 1, wherein the content of the component (C) is 88% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.
8. The resin composition according to claim 1, wherein the content of the component (C) is 89% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.
9. The resin composition according to claim 1, wherein the content of the component (C) is 90% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.
10. The resin composition according to claim 1, wherein the content of the component (C) is 95% by mass or less, assuming that 100% by mass of nonvolatile components in the resin composition are contained.
11. The resin composition according to claim 1, wherein the content of the component (C) is 93% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.
12. The resin composition according to claim 1, wherein the content of the component (C) is 92% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.
13. The resin composition according to claim 1, wherein the component (C) is surface-treated with an aminosilicone-based coupling agent.
14. The resin composition according to claim 1, wherein component (C) is surface-treated with N-phenyl-3-aminoalkyltrimethoxysilane.
15. The resin composition according to claim 1, wherein a cured product obtained by heat curing the resin composition at 180 ℃ for 90 minutes has a thermal conductivity of 1.5W/m or more and 5.0W/m or less.
16. The resin composition according to claim 1, wherein a cured product obtained by thermally curing the resin composition at 180 ℃ for 90 minutes has a thermal conductivity of 1.8W/m, a seed, or K or more.
17. The resin composition according to claim 1, wherein a cured product obtained by thermally curing the resin composition at 180 ℃ for 90 minutes has a thermal conductivity of 2.0W/m, a seed K or more.
18. The resin composition according to claim 1, wherein a cured product obtained by thermally curing the resin composition at 180 ℃ for 90 minutes has a thermal conductivity of 4.0W/m or less.
19. The resin composition according to claim 1, wherein a cured product obtained by thermally curing the resin composition at 180 ℃ for 90 minutes has a thermal conductivity of 3.5W/m or less.
20. The resin composition according to claim 1, wherein component (A) has a functional group capable of reacting with component (B).
21. The resin composition according to claim 1, wherein the component (A) has 1 or more functional groups selected from the group consisting of a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group.
22. The resin composition according to claim 1, wherein the component (A) has an imide structure.
23. The resin composition according to claim 1, wherein the component (A) has a phenolic hydroxyl group.
24. The resin composition according to claim 1, wherein the component (A) has a polybutadiene structure and has a phenolic hydroxyl group.
25. The resin composition according to claim 1, wherein the component (A) is a polymer compound having 1 or more structures selected from a polybutadiene structure, a polyisoprene structure, and a polycarbonate structure in a molecule.
26. The resin composition according to claim 1, wherein the number average molecular weight of the component (A) is 5000 or more.
27. The resin composition according to claim 1, wherein the number average molecular weight of the component (A) is 900000 or less.
28. The resin composition according to claim 1, wherein the content of the component (A) is 60% by mass or less, when the resin component is 100% by mass.
29. The resin composition according to claim 1, wherein the content of the component (A) is 55% by mass or less, when the resin component is 100% by mass.
30. The resin composition according to claim 1, wherein the content of the component (A) is 50% by mass or less, when the resin component is 100% by mass.
31. The resin composition according to claim 1, wherein the content of the component (A) is 15% by mass or more, when the resin component is 100% by mass.
32. The resin composition according to claim 1, wherein the content of the component (A) is 20% by mass or more, based on 100% by mass of the resin component.
33. The resin composition according to claim 1, wherein the content of the component (A) is 25% by mass or more, based on 100% by mass of the resin component.
34. The resin composition according to claim 1, wherein the content of the component (B) is 1% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.
35. The resin composition according to claim 1, wherein the content of the component (B) is 2% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.
36. The resin composition according to claim 1, wherein the content of the component (B) is 3% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.
37. The resin composition according to claim 1, wherein the content of the component (B) is 10% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.
38. The resin composition according to claim 1, wherein the content of the component (B) is 8% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.
39. The resin composition according to claim 1, wherein the content of the component (B) is 6% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.
40. The resin composition according to claim 1, wherein the content of the component (D) is 5% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.
41. The resin composition according to claim 1, wherein the content of the component (D) is 3% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.
42. The resin composition according to claim 1, wherein the content of the component (D) is 2% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.
43. The resin composition according to claim 1, wherein the content of the component (D) is 0.1% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.
44. The resin composition according to claim 1, wherein the content of the component (D) is 0.5% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.
45. The resin composition according to claim 1, which is a resin composition for an insulating layer of a semiconductor chip package.
46. The resin composition according to claim 1, which is a resin composition for an insulating layer of a circuit board on which a circuit is formed by a semi-additive method.
47. A resin sheet comprising a support and, provided on the support, a resin composition layer comprising the resin composition according to any one of claims 1 to 46.
48. A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 46.
49. A semiconductor chip package comprising the circuit board according to claim 48 and a semiconductor chip mounted on the circuit board.
50. A semiconductor chip package comprising a semiconductor chip sealed with the resin composition according to any one of claims 1 to 46 or the resin sheet according to claim 47.
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