JP2018150440A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which is capable of giving a cured product low in storage modulus, dielectric loss tangent, dielectric constant, and coefficient of linear thermal expansion (CTE) and is excellent in workability, and to provide a resin sheet, a circuit board, and a semiconductor chip package which are obtained by using the resin composition.SOLUTION: The resin composition contains: (A) an epoxy resin; (B) a polymer compound having one 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 the molecule; (C) a fluorine atom-containing alkoxysilane compound; and (D) an inorganic filler.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition. Furthermore, it is related with the resin sheet, circuit board, and semiconductor chip package which are obtained using the said resin composition.

  In recent years, the demand for small, high-performance electronic devices such as smartphones and tablet PCs has increased, and in response, the semiconductor package insulating material (insulating layer) used in these small electronic devices needs to have higher functionality. It has been.

  For example, an insulating layer used for a wafer level chip size package or a wiring board having an embedded wiring layer is required to suppress warpage generated when the insulating layer is formed and to have high adhesion to the conductor layer.

  Patent Document 1 discloses a thermosetting resin composition containing a specific linear modified polyimide resin and a thermosetting resin as a low elastic modulus thermosetting resin composition.

JP 2006-37083 A

  However, the design of the resin composition of the material described in Patent Document 1 is limited from the viewpoint of compatibility with other resins. Further, depending on the design of the resin composition, there are cases where the workability does not always show sufficient performance. Here, workability is a property indicating that since the resin composition becomes a uniform shape over time, it is not necessary to prepare the resin composition in a uniform shape, and the subsequent work is simplified.

  The present invention has been made to solve the above problems, and can provide a cured product having a low storage elastic modulus, dielectric loss tangent, relative dielectric constant, and linear thermal expansion coefficient (CTE), and further improves workability. An excellent resin composition; an object is to provide a resin sheet, a circuit board, and a semiconductor chip package obtained by using the resin composition.

  The present inventors have (A) epoxy resin, (B) in the molecule, polybutadiene structure, polysiloxane structure, poly (meth) acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure, And a polymer compound having at least one structure selected from polycarbonate structures, (C) a fluorine atom-containing alkoxysilane compound, and (D) an inorganic filler, so that storage elastic modulus, dielectric loss tangent, relative dielectric constant It has been found that a cured product having a low rate and coefficient of linear thermal expansion (CTE) can be obtained, and that a resin composition excellent in workability can be obtained, and the present invention has been completed.

That is, the present invention includes the following contents.
[1] (A) epoxy resin,
(B) One 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 the molecule A polymer compound having
A resin composition containing (C) a fluorine atom-containing alkoxysilane compound, and (D) an inorganic filler.
[2] The resin composition according to [1], wherein the component (B) is a polymer compound containing at least one structure selected from a polybutadiene structure, a polyisoprene structure, and a polycarbonate structure.
[3] The resin composition according to [1] or [2], wherein the average particle size of the component (D) is 0.5 μm or more and 20 μm or less.
[4] The resin composition according to any one of [1] to [3], wherein the component (D) is silica or alumina.
[5] Any of [1] to [4], wherein the content of the component (C) is 0.1% by mass or more and 2% by mass or less when the nonvolatile component in the resin composition is 100% by mass. The resin composition described in 1.
[6] The content of the component (B) is any one of [1] to [5], which is 3% by mass or more and 25% by mass or less when the nonvolatile component in the resin composition is 100% by mass. Resin composition.
[7] The content of the component (A) when the nonvolatile component in the resin composition is 100% by mass is A1, and the content of the component (B) when the nonvolatile component in the resin composition is 100% by mass The resin composition according to any one of [1] to [6], wherein (A1 / B1) × 100 is 30 or more and 250 or less when the amount is B1.
[8] The content of the component (D) is any one of [1] to [7], which is 70% by mass or more and 90% by mass or less when the nonvolatile component in the resin composition is 100% by mass. Resin composition.
[9] The resin composition according to any one of [1] to [8], further comprising (E) a curing agent.
[10] The resin composition according to [9], wherein the component (E) is a phenolic curing agent.
[11] The resin composition according to any one of [1] to [10], wherein the thixotropy index is 1 or less.
[12] The linear thermal expansion coefficient at 30 ° C. to 150 ° C. when the resin composition is thermally cured at 180 ° C. for 90 minutes is 3 ppm or more and 50 ppm or less, according to any one of [1] to [11]. Resin composition.
[13] The resin composition according to any one of [1] to [12], which is a resin composition for an insulating layer of a semiconductor chip package.
[14] A resin sheet comprising a support and a resin composition layer including the resin composition according to any one of [1] to [13] provided on the support.
[15] The resin sheet according to [14], which is a resin sheet for an insulating layer of a semiconductor chip package.
[16] A circuit board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [13].
[17] A semiconductor chip package comprising the circuit board according to [16] and a semiconductor chip mounted on the circuit board.
[18] A semiconductor chip package including a sealing layer and a semiconductor chip, wherein the sealing layer is a cured product of the resin composition according to any one of [1] to [13].

  According to the present invention, a cured product having a low storage elastic modulus, dielectric loss tangent, relative dielectric constant, and linear thermal expansion coefficient (CTE) can be obtained, and the resin composition excellent in workability; A resin sheet, a circuit board, and a semiconductor chip package obtained by use can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of a semiconductor chip package (Fan-out type WLP) of the present invention.

  Hereinafter, the resin composition, resin sheet, circuit board, and semiconductor chip package of the present invention will be described in detail.

[Resin composition]
The resin composition of the present invention comprises (A) an epoxy resin, (B) in the molecule, a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, and a polyisobutylene. A polymer compound having at least one structure selected from a structure and a polycarbonate structure; (C) a fluorine atom-containing alkoxysilane compound; and (D) an inorganic filler.

  By including the component (A), the component (B), the component (C), and the component (D) in the resin composition, a resin composition excellent in workability can be obtained. Further, a cured product having a low storage elastic modulus, dielectric loss tangent, relative dielectric constant, and linear thermal expansion coefficient (CTE) can be obtained from the resin composition. The resin composition may further contain (E) a curing agent, (F) a curing accelerator, and (G) a flame retardant, as necessary. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Epoxy resin>
The resin composition contains (A) an epoxy resin. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, Phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type Epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring Epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. The component (A) is preferably at least one selected from bisphenol A type epoxy resins, bisphenol F type epoxy resins, and biphenyl type epoxy resins.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. Moreover, it is preferable that an epoxy resin has an aromatic structure, and when using 2 or more types of epoxy resins, it is more preferable that at least 1 type has an aromatic structure. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it has two or more epoxy groups in one molecule, and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule, It is preferable to contain a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the cured product of the resin composition is also improved. The aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocycles.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. Preferred are cycloaliphatic epoxy resins, cyclohexanedimethanol type epoxy resins, glycidylamine type epoxy resins, and epoxy resins having a butadiene structure. Glycidylamine type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF Type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC, “828US”, “jER828EL” (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation. "JER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" (bisphenol A) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Type epoxy resin and bisphenol F type epoxy resin), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, “Celoxide 2021P” (manufactured by Daicel Corporation) (alicyclic epoxy having an ester skeleton) resin), "PB-3600" (epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd., "630LSD" (glycidylamine type epoxy manufactured by Mitsubishi Chemical Corporation) Resin), “EP-3980S” (glycidylamine type epoxy resin) manufactured by ADEKA, and the like. These may be used alone or in combination of two or more.

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” (manufactured by DIC) Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA-7311 ”,“ EXA-7311-G3 ”,“ EXA-7311-G4 ”,“ EXA-7311-G4S ”,“ HP6000 ”(naphthylene ether type epoxy resin),“ EPPN-502H ”(manufactured by Nippon Kayaku Co., Ltd.) Trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy) Fat), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthalene type epoxy resin), “ESN485” (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ), “YX4000H”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “PG” manufactured by Osaka Gas Chemical Co., Ltd. -100 "," CG-500 "," YL7760 "(bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation," YL7800 "(fluorene type epoxy resin)," jER1010 "(solid bisphenol A type manufactured by Mitsubishi Chemical Corporation) Epoxy resin)," ER1031S "(tetraphenyl ethane epoxy resin). These may be used alone or in combination of two or more.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1:15 in terms of mass ratio. preferable. By making the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a resin sheet, ii) when used in the form of a resin sheet Sufficient flexibility can be obtained, handling properties can be improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii), the quantitative ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.3 to 1:10 by mass ratio. Is more preferable, and the range of 1: 0.6 to 1: 8 is even more preferable.

  The content of the epoxy resin in the resin composition is preferably 1% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. More preferably, it is 2% by mass or more, and further preferably 5% by mass or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 20 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and it can bring about an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  The weight average molecular weight of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

  The number average molecular weight of the epoxy resin is preferably less than 5000, more preferably 4000 or less, and still more preferably 3000 or less. The lower limit is preferably 100 or more, more preferably 300 or more, and still more preferably 500 or more. The number average molecular weight (Mn) is a polystyrene equivalent number average molecular weight measured using GPC (gel permeation chromatography).

  The glass transition temperature (Tg) of the epoxy resin is preferably more than 25 ° C, more preferably 30 ° C or more, and further preferably 35 ° C or more. An upper limit becomes like this. Preferably it is 500 degrees C or less, More preferably, it is 400 degrees C or less, More preferably, it is 300 degrees C or less.

<(B) One or more kinds 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 the molecule Polymer compound having structure>
The resin composition is selected from (B) 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 the molecule. Contains a polymer compound having one or more structures. The workability of the resin composition is improved by including the polymer compound having such a structure in the resin composition, and further, the storage elastic modulus, dielectric loss tangent, relative dielectric constant of the cured product of the resin composition, And CTE is low. “(Meth) acrylate” refers to methacrylate and acrylate.

  More specifically, the component (B) includes polybutadiene structures such as polybutadiene and hydrogenated polybutadiene, polysiloxane structures such as silicone rubber, poly (meth) acrylate structures, and polyalkylene structures (polyalkylene having 2 to 15 carbon atoms). The structure is preferable, the polyalkylene structure having 3 to 10 carbon atoms is more preferable, the polyalkylene structure having 5 to 6 carbon atoms is more preferable, and the polyalkyleneoxy structure (the polyalkyleneoxy structure having 2 to 15 carbon atoms). Preferably, a polyalkyleneoxy structure having 3 to 10 carbon atoms is more preferable, and a polyalkyleneoxy structure having 5 to 6 carbon atoms is more preferable.), 1 selected from a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure Preferred to have a seed or two or more structures Preferably, it has one or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyisoprene structure, a polyisobutylene structure, or a polycarbonate structure. It is more preferable to have one or more structures selected from a structure and a polycarbonate structure.

  The component (B) preferably has a high molecular weight in order to exhibit flexibility, and the number average molecular weight (Mn) is preferably 1,000 to 1,000,000, more preferably 5,000 to 900,000. is there. The number average molecular weight (Mn) is a polystyrene equivalent number average molecular weight measured using GPC (gel permeation chromatography).

  In order to show flexibility, the component (B) is preferably at least one resin selected from a resin having a glass transition temperature (Tg) of 25 ° C. or lower and a resin that is liquid at 25 ° C.

  The glass transition temperature of the resin having a glass transition temperature (Tg) of 25 ° C. or lower is preferably 20 ° C. or lower, more preferably 15 ° C. or lower. Although the minimum of a glass transition temperature is not specifically limited, Usually, it can be set as -15 degreeC or more. The resin that is liquid at 25 ° C. is preferably a resin that is liquid at 20 ° C. or lower, more preferably a resin that is liquid at 15 ° C. or lower.

  The component (B) preferably has a functional group capable of reacting with the component (A) from the viewpoint of improving the mechanical strength of the cured product. In addition, as a functional group which can react with (A) component, the functional group which appears by heating shall also be included.

  In a preferred embodiment, the functional group capable of reacting with the component (A) is selected from the group consisting of a hydroxy group, a carboxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group. It is a functional group of more than species. Among these, the functional group is preferably a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, or a urethane group, more preferably a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, or an epoxy group. A functional hydroxyl group is particularly preferred.

  A preferred embodiment of the component (B) is a butadiene resin. As the butadiene resin, a butadiene resin which is liquid at 25 ° C. or has a glass transition temperature of 25 ° C. or less is preferable. Hydrogenated polybutadiene skeleton-containing resin, hydroxy group-containing butadiene resin, phenolic hydroxyl group-containing butadiene resin, carboxy group-containing butadiene resin, acid anhydride One or more resins selected from the group consisting of a physical group-containing butadiene resin, an epoxy group-containing butadiene resin, an isocyanate group-containing butadiene resin, and a urethane group-containing butadiene resin are more preferable, and a phenolic hydroxyl group-containing butadiene resin is more preferable. Examples of the hydrogenated polybutadiene skeleton-containing resin include a hydrogenated polybutadiene skeleton-containing epoxy resin. Examples of the phenolic hydroxyl group-containing butadiene resin include resins having a polybutadiene structure and having a phenolic hydroxyl group.

  Here, the “butadiene resin” refers to a resin containing a polybutadiene structure. In these resins, the polybutadiene structure may be contained in the main chain or in the side chain. A part or all of the butadiene structure may be hydrogenated. Here, the “hydrogenated polybutadiene skeleton-containing resin” refers to a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and is not necessarily a resin in which the polybutadiene skeleton is completely hydrogenated.

  The number average molecular weight (Mn) of the butadiene resin is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, more preferably 7,500 to 30,000, and still more preferably 10,000 to 10,000. 15,000. Here, the number average molecular weight (Mn) of the resin is a number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

  The functional group equivalent when the butadiene resin has a functional group is preferably 100 to 10,000, and more preferably 200 to 5000. The functional group equivalent is the number of grams of resin containing 1 gram equivalent of functional group. For example, the epoxy group equivalent can be measured according to JIS K7236. The hydroxyl equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

  Specific examples of the butadiene resin include “Ricon 657” (epoxy group-containing polybutadiene), “Ricon 130MA8”, “Ricon 130MA13”, “Ricon 130MA20”, “Ricon 131MA5”, “Ricon 131MA10”, “Ricon 131MA10” manufactured by Clay Valley. “Ricon 131MA17”, “Ricon 131MA20”, “Ricon 184MA6” (anhydride-containing polybutadiene), “JP-100”, “JP-200” (epoxidized polybutadiene), “GQ-1000” (manufactured by Nippon Soda Co., Ltd.) Hydroxyl group, carboxyl group-introduced polybutadiene), "G-1000", "G-2000", "G-3000" (both end hydroxyl group polybutadiene), "GI-1000", "GI-2000", "GI-3000" Hydroxylated polybutadiene at both ends), “PB3600”, “PB4700” (polybutadiene skeleton epoxy resin) manufactured by Daicel, “Epofriend A1005”, “Epofriend A1010”, “Epofriend A1020” (styrene, butadiene and styrene block) Copolymer epoxidized product), “FCA-061L” (hydrogenated polybutadiene skeleton epoxy resin), “R-45EPT” (polybutadiene skeleton epoxy resin) manufactured by Nagase ChemteX Corporation, and the like.

  A preferred embodiment of the component (B) is an isoprene resin. Specific examples of the isoprene resin include “KL-610” and “KL613” manufactured by Kuraray Co., Ltd. Here, the “isoprene resin” refers to a resin containing a polyisoprene structure. In these resins, the polyisoprene structure may be contained in the main chain or in the side chain.

  Moreover, suitable one Embodiment of (B) component is carbonate resin. As the carbonate resin, a carbonate resin having a glass transition temperature of 25 ° C. or lower is preferable, a hydroxy group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxy group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an epoxy group-containing carbonate resin, One or more resins selected from the group consisting of isocyanate group-containing carbonate resins and urethane group-containing carbonate resins are preferred. Here, the “carbonate resin” refers to a resin containing a polycarbonate structure. In these resins, the polycarbonate structure may be contained in the main chain or in the side chain.

  The number average molecular weight (Mn) and functional group equivalent of the carbonate resin are the same as those of the butadiene resin, and the preferred range is also the same.

  Specific examples of the carbonate resin include "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by Kuraray. Etc.

  A linear polyimide made from hydroxyl group-terminated polycarbonate, diisocyanate compound and tetrabasic acid anhydride can also be used. The content of the polycarbonate resin in the polycarbonate structure is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. Details of the polyimide resin can be referred to the description of International Publication No. 2016/129541, the contents of which are incorporated herein.

  As another preferred embodiment of the component (B), a resin having an imide structure can also be used. As such a component (B), a linear polyimide using a hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride as raw materials (Japanese Patent Laid-Open No. 2006-37083, polyimide described in International Publication No. 2008/153208) Etc. The content of the polybutadiene structure in the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. Details of the polyimide resin can be referred to the descriptions in JP-A-2006-37083 and International Publication No. 2008/153208, the contents of which are incorporated herein.

  Another suitable embodiment of the component (B) is an acrylic resin. As the acrylic resin, an acrylic resin having a glass transition temperature (Tg) of 25 ° C. or lower is preferable, and a hydroxy group-containing acrylic resin, a phenolic hydroxyl group-containing acrylic resin, a carboxy group-containing acrylic resin, an acid anhydride group-containing acrylic resin, an epoxy group. One or more resins selected from the group consisting of a containing acrylic resin, an isocyanate group-containing acrylic resin, and a urethane group-containing acrylic resin are more preferable. Here, “acrylic resin” means a resin containing a poly (meth) acrylate structure, and in these resins, the poly (meth) acrylate structure may be contained in the main chain or in the side chain. Good.

  The number average molecular weight (Mn) of the acrylic resin is preferably 10,000 to 1,000,000, more preferably 30,000 to 900,000. Here, the number average molecular weight (Mn) of the resin is a number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

  The functional group equivalent when the acrylic resin has a functional group is preferably 1000 to 50000, more preferably 2500 to 30000.

  Specific examples of acrylic resins include Teissan resin “SG-70L”, “SG-708-6”, “WS-023”, “SG-700AS”, “SG-280TEA” (carboxy group) manufactured by Nagase ChemteX Corporation. -Containing acrylic ester copolymer resin, acid value 5 to 34 mg KOH / g, weight average molecular weight 400,000 to 900,000, Tg-30 to 5 ° C), "SG-80H", "SG-80H-3", "SG -P3 "(epoxy group-containing acrylate copolymer resin, epoxy equivalent 4761-14285 g / eq, weight average molecular weight 350,000-850,000, Tg 11-12 ° C)," SG-600TEA "," SG-790 "" (Hydroxy group-containing acrylate copolymer resin, hydroxyl value 20 to 40 mgKOH / g, weight average molecular weight 500,000 to 1,200,000, Tg-37 to -32 ), “ME-2000”, “W-116.3” (carboxy group-containing acrylate copolymer resin), “W-197C” (hydroxyl group-containing acrylate copolymer resin) manufactured by Negami Kogyo Co., Ltd. “KG-25”, “KG-3000” (epoxy group-containing acrylic ester copolymer resin) and the like.

  Further, a preferred embodiment of the further component (B) is a siloxane resin, an alkylene resin, an alkyleneoxy resin, or an isobutylene resin.

  Specific examples of the siloxane resin include “SMP-2006”, “SMP-2003PGMEA”, “SMP-5005PGMEA” manufactured by Shin-Etsu Silicone Co., Ltd., linear polyimides made from amine group-terminated polysiloxane and tetrabasic acid anhydride (International Publication No. 2010/053185). Here, the “siloxane resin” refers to a resin containing a polysiloxane structure, and in these resins, the polysiloxane structure may be contained in the main chain or in the side chain.

  Specific examples of the alkylene resin include “PTXG-1000” and “PTXG-1800” manufactured by Asahi Kasei Fibers, “YX-7180” (resin containing an alkylene structure having an ether bond) manufactured by Mitsubishi Chemical Corporation, and the like. . Here, the “alkylene resin” refers to a resin containing a polyalkylene structure, and in these resins, the polyalkylene structure may be contained in the main chain or in the side chain.

  Specific examples of the alkyleneoxy resin include “EXA-4850-150”, “EXA-4816”, “EXA-4822” manufactured by DIC Corporation, “EP-4000”, “EP-4003”, “EP-4003” manufactured by ADEKA. 4010 "and" EP-4011 ", Shin Nippon Rika Co., Ltd." BEO-60E "," BPO-20E ", Mitsubishi Chemical Corporation" YL7175 ", and" YL7410 ". Here, the “alkyleneoxy resin” refers to a resin containing a polyalkyleneoxy structure, and in these resins, 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 Corporation. Here, the “isobutylene resin” means a resin containing a polyisobutylene structure, and in these resins, the polyisobutylene structure may be contained in the main chain or in the side chain.

  Further, preferred embodiments of the further component (B) include acrylic rubber particles, polyamide fine particles, silicone particles and the like. Specific examples of the acrylic rubber particles include resin fine particles obtained by subjecting a resin exhibiting rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber to a chemical crosslinking treatment, insoluble in an organic solvent and infusible, Specifically, XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (manufactured by Ganz Kasei Co., Ltd.), paraloid EXL2655, EXL2602 (manufactured by Kureha Chemical Industries, Ltd.) ) And the like. Specific examples of the polyamide fine particles include aliphatic polyamides such as nylon, and any flexible skeleton such as polyamideimide. Specifically, VESTOSINT 2070 (manufactured by Daicel Huls), SP500 (manufactured by Toray Industries, Inc.) and the like.

  The content of the component (B) in the resin composition is preferably 3% by mass or more, more preferably 5% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of imparting flexibility. More preferably, it is 7% by mass or more. The lower limit is preferably 25% by mass or less, more preferably 23% by mass or less, and still more preferably 20% by mass or less.

  The content of component (A) when the nonvolatile component in the resin composition is 100% by mass is A1, and the content of component (B) when the nonvolatile component in the resin composition is 100% by mass is B1. In this case, (A1 / B1) × 100 is preferably 30 or more, more preferably 45 or more, and still more preferably 60 or more. The upper limit is preferably 250 or less, more preferably 100 or less, and still more preferably 80 or less. By setting (A1 / B1) × 100 in such a range, an effect that a sufficient crosslinking density is formed and chemical resistance is obtained can be obtained.

<(C) Fluorine atom-containing alkoxysilane compound>
The resin composition contains (C) a fluorine atom-containing alkoxysilane compound. As a result of intensive studies by the present inventors, a resin composition excellent in workability can be obtained by containing the component (C), and by using the resin composition, the storage elastic modulus, dielectric loss tangent, relative dielectric constant can be obtained. And a cured product having a low CTE was found. Since the component (C) is chemically stable, the thixotropy index of the resin composition is lowered, which is considered to improve the workability. Moreover, since a thixotropy index | exponent falls, it can contain more (D) inorganic fillers mentioned later. As a result, a cured product having a low dielectric loss tangent, relative dielectric constant, and CTE can be obtained.

  From the viewpoint of reducing the thixotropy index, the component (C) preferably has 1 to 10 fluorine atoms, more preferably 1 to 5 fluorine atoms, and more preferably 1 to 3 fluorine atoms in one molecule of the component (C). Is more preferable.

The component (C) preferably has a fluorinated alkyl group from the viewpoint of lowering the thixotropy index, and the fluorinated alkyl group preferably has a fluorine atom at the terminal. The fluorinated alkyl group is preferably a fluorinated alkyl group having 1 to 20 carbon atoms, more preferably a fluorinated alkyl group having 1 to 10 carbon atoms, and further preferably a fluorinated alkyl group having 1 to 6 carbon atoms. Examples of such a fluorinated alkyl group include —CF ₃ , —CH ₂ CF ₃ , —CF ₂ CF ₃ , —CH ₂ CH ₂ CF ₃ , —CH (CF ₃ ) ₂ , —CH ₂ CH ₂ CH _2. Examples include CF ₃ , —CH ₂ CH (CF ₃ ) ₂ , —C (CF ₃ ) ₃ , and —CH ₂ CH ₂ CF ₃ is preferable.

  In addition, from the viewpoint of improving reactivity, the component (C) preferably has 1 to 5 alkoxy groups, more preferably 1 to 3 alkoxy groups in one molecule of the component (C), and the number of alkoxy groups. Is more preferably 2 to 3.

  The alkoxy group in component (C) is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms from the viewpoint of improving reactivity. More preferred are groups. Examples of such alkoxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, s-butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, and heptyloxy. Group, octyloxy group, nonyloxy group, and decyloxy group, and methoxy group is preferable.

The alkoxy group may have a substituent. The substituent is not particularly limited, for example, a halogen atom, -OH, _{-O-C 1-6} alkyl group, -N _{(C 1-6 alkyl) 2, C 1-6 alkyl, C 6- A 10} aryl group, —NH ₂ , —CN, —C (O) O—C _1-6 alkyl group, —COOH, —C (O) H, —NO _{2 and the} like.

Here, the term “C _pq ” (p and q are positive integers, satisfying p <q) means that the number of carbon atoms of the organic group described immediately after this term is p to q. Represents something. For example, the expression “C _1-6 alkyl group” refers to an alkyl group having 1 to 6 carbon atoms.

  The above-described substituent may further have a substituent (hereinafter sometimes referred to as “secondary substituent”). As the secondary substituent, the same substituents as described above may be used unless otherwise specified.

  The molecular weight of the component (C) is preferably 50 to 2000, more preferably 75 to 1000, and still more preferably 100 to 500 from the viewpoint of improving compatibility.

  Among these, examples of the component (C) include 3,3,3-trifluoropropyltrimethoxysilane, perfluoro (poly) ether group-containing alkoxysilane compounds, and the like. These may be used alone or in combination of two or more. Among these, 3,3,3-trifluoropropyltrimethoxysilane is preferable as the component (C). As the component (C), a commercially available product may be used, and examples thereof include “KBM-7103” and “OPTOOL DSX” manufactured by Shin-Etsu Chemical Co., Ltd.

Although the aspect of (C) component contained in a resin composition is not specifically limited, It is preferable to contain in the resin composition in the aspect of the following (i)-(iii), and the aspect of (i) or (iii) It is more preferable to contain in a resin composition, and it is still more preferable to contain in a resin composition in the aspect of (i). That is, the component (C) is preferably contained in the resin composition as a surface treatment agent for the component (D).
(I) The component (C) is contained as a surface treatment agent for the component (D) (ii) The component (C) is contained alone in the resin composition (iii) The component (C) is a surface treatment agent for the component (D) Contained and contained in resin composition by component (C) alone “(C) component is contained as a surface treatment agent for component (D)” means that (D) component is surface treated with component (C) It represents being done. In this case, the component (C) is usually on the surface of the component (D). In addition, “(C) component alone contained in resin composition” means that (C) component is not contained as a surface treatment agent for (D) component. In addition, when (C) component does not contain as a surface treating agent of (D) component, (C) component is free in the resin composition and is effective for low roughness of the insulating layer surface. .

  When the component (C) is contained alone in the resin composition, the content of the component (C) is preferably 0.01% by mass or more when the nonvolatile component in the resin composition is 100% by mass. 015% by mass or more is more preferable, and 0.1% by mass or more is more preferable. Although an upper limit is not specifically limited, 2 mass% or less is preferable, 1 mass% or less is more preferable, and 0.5 mass% or less is further more preferable. By making it within such a range, the thixotropy index can be lowered.

  When the component (C) is contained as the surface treatment agent for the component (D), the degree of surface treatment with the component (C) is 0. Surface treatment is preferably performed with 2 to 5 parts by weight of component (C), more preferably 0.3 to 3 parts by weight of component (C), and more preferably 0.5 to 0.5 parts by weight. It is more preferable that the surface treatment is performed with the component (C) in an amount of from mass parts to 2.5 mass parts.

<(D) Inorganic filler>
The resin composition contains (D) an inorganic filler. The material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica and alumina are particularly suitable. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 2 μm or less from the viewpoint of obtaining an insulating layer having a small surface roughness and improving the fine wiring formability. is there. Although the minimum of this average particle diameter is not specifically limited, Preferably it is 0.5 micrometer or more, More preferably, it is 1 micrometer or more, More preferably, it is 1.5 micrometers or more. Examples of commercially available inorganic fillers having such an average particle diameter include, for example, “FB-3SDX”, “FB-5SDX”, “FB-7SDX” manufactured by Denka Corporation, “manufactured by Nippon Steel & Sumikin Materials Co., Ltd.” SP60-05 "," SP60-10 "," SO-C4 "," SO-C2 "," SO-C5 ", etc. manufactured by Admatechs.

  The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring apparatus, “LA-500” manufactured by Horiba, Ltd. can be used.

  The inorganic filler is preferably surface-treated with a surface treatment agent. Examples of the surface treatment agent include the component (C) and a surface treatment agent other than the component (C) (hereinafter sometimes referred to as “other surface treatment agent”). The inorganic filler may be surface-treated with the component (C) or may be surface-treated with another surface treatment agent. From the viewpoint of lowering the thixotropy index, it is preferable that the surface treatment is performed with the component (C).

  Examples of other surface treatment agents include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. These may be used alone or in combination of two or more. Examples of such other commercially available surface treatment agents include “KBM-403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and “KBM-803” (3 -Mercaptopropyltrimethoxysilane), Shin-Etsu Chemical "KBE-903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane) ), “SZ-31” (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy manufactured by Shin-Etsu Chemical Co., Ltd.) Type silane coupling agent).

  The degree of surface treatment with the other surface treatment agent is the same as the degree of surface treatment with the component (C), and the preferred range is also the same.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.05 mg / m ² or more, more preferably 0.1 mg / m ² or more, and 0.2 mg / m ^2. The above is more preferable. On the other hand, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is more preferable from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the sheet form. preferable.

  The content of the inorganic filler in the resin composition is preferably 60% by mass or more, more preferably 65% by mass or more, and further preferably 70% by mass or more, from the viewpoint of lowering the dielectric loss tangent, relative dielectric constant, and CTE. It is. The upper limit of the content of the inorganic filler in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less, from the viewpoint of the mechanical strength of the insulating layer. When (D) component is surface-treated with (C) component, content of an inorganic filler is content including (C) component.

<(E) Curing agent>
The resin composition may contain (E) a curing agent. The curing agent is not particularly limited as long as it has a function of curing the resin such as component (A). For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, and a cyanate. Examples include ester-based curing agents. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together. The component (E) is preferably at least one selected from a phenolic curing agent, a naphthol curing agent, an active ester curing agent, and a cyanate ester curing agent, and is preferably a phenol curing agent.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | curing agent is more preferable. Among these, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer.

  Specific examples of the phenol-based curing agent and naphthol-based curing agent include “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., “NHN”, “CBN” manufactured by Nippon Kayaku Co., Ltd. ”,“ GPH ”,“ SN170 ”,“ SN180 ”,“ SN190 ”,“ SN475 ”,“ SN485 ”,“ SN495V ”,“ SN375 ”,“ SN395 ”manufactured by Nippon Steel & Sumitomo Metal,“ TD- ”manufactured by DIC 2090 "," LA-7052 "," LA-7054 "," LA-1356 "," LA-3018-50P "," EXB-9500 "," HPC-9500 "," KA-1160 "," KA- " 1163 "," KA-1165 "," GDP-6115L "," GDP-6115H "manufactured by Gunei Chemical Co., Ltd., and the like.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained 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, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, 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, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of a phenol novolac, and an active ester compound containing a benzoylated product of a phenol novolac are preferred, Of these, active ester compounds having a naphthalene structure and active ester compounds having a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structure composed of phenylene-dicyclopentylene-phenylene.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. 65TM "," EXB-8000L-65TM "(manufactured by DIC)," EXB9416-70BK "(manufactured by DIC) as an active ester compound containing a naphthalene structure, and" DC808 "as an active ester compound containing an acetylated product of phenol novolac ( Mitsubishi Chemical Co., Ltd.), “YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac, “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent which is an acetylated product of phenol novolac, "YLH1026" as an active ester-based curing agent is benzoyl product of E Nord novolac (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and the like.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd. and “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Novolac and K Polyfunctional cyanate resin derived from tetrazole novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolac polyfunctional cyanate ester resins), “BA230”, “BA230S75” (part of bisphenol A dicyanate) manufactured by Lonza Japan. Or a prepolymer which is all triazine-modified into a trimer).

  When the resin composition contains the component (E), the content of the curing agent is preferably 10% by mass or less, more preferably 8% by mass or less, when the nonvolatile component in the resin composition is 100% by mass. More preferably, it is 5 mass% or less. The lower limit is not particularly limited but is preferably 1% by mass or more.

<(F) Curing accelerator>
The resin composition 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, a metal-based curing accelerator, and the like. A curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

  Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo. (5,4,0) -undecene and the like are mentioned, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-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, 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-me Examples thereof include imidazole compounds such as ru-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2. -Phenylimidazole is preferred.

  Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine 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] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, 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 curing accelerator is preferably 0.01% by mass or more, more preferably 0 when the total amount of nonvolatile components in the resin composition is 100% by mass. 0.03 mass% or more, more preferably 0.05 mass% or more. An upper limit becomes like this. Preferably it is 3 mass% or less, More preferably, it is 1.5 mass% or less, More preferably, it is 1 mass% or less.

<(G) Flame retardant>
The resin composition may contain (G) a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

  Commercially available products may be used as the flame retardant, and examples thereof include “HCA-HQ” manufactured by Sanko Co., Ltd.

  When the resin composition contains a flame retardant, the content of the flame retardant is preferably 0.5% by mass to 20% by mass, more preferably 0.00% when the nonvolatile component in the resin composition is 100% by mass. 5 mass%-15 mass%, More preferably, 0.5 mass%-10 mass% are further more preferable.

<(H) Optional additive>
The resin composition may further contain other additives as necessary. Examples of such other additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, In addition, binders, thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, and resin additives such as colorants can be used.

<Physical properties of resin composition>
Since the resin composition contains the component (C), the resin composition exhibits a low thixotropy index. The thixotropy index is preferably 1 or less, more preferably 0.9 or less, and still more preferably 0.8 or less. The lower limit is not particularly limited, but may be 0.01 or more. The thixotropy index can be measured according to the method described in [Measurement of thixotropy index] described later.

  Since the resin composition has a low thixotropy index, the resin composition has a uniform shape as time passes. As a result, thickness unevenness and the like are eliminated, and there is no need to prepare a uniform shape, that is, excellent workability. For example, even when the resin composition is ejected from the cartridge, the surface of the resin composition has little unevenness. Therefore, it is possible to easily form the resin composition layer by the compression molding method. Workability can be measured according to the method described in [Evaluation of workability] described later.

  A cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 90 minutes exhibits a characteristic that the relative dielectric constant is low. The relative dielectric constant is preferably 6 or less, more preferably 5 or less, still more preferably 4 or less, and 3.5 or less. The lower limit is not particularly limited, but may be 0.1 or more. The relative dielectric constant can be measured according to the method described in [Measurement of relative dielectric constant and dielectric loss tangent] described later.

  A cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 90 minutes exhibits a characteristic that the dielectric loss tangent is low. The dielectric loss tangent is preferably 0.1 or less, more preferably 0.009 or less, and still more preferably 0.008 or less. The lower limit is not particularly limited, but may be 0.001 or more. The dielectric loss tangent can be measured according to the method described in [Measurement of relative dielectric constant and dielectric loss tangent] described later.

  The cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 90 minutes contains the component (B) and the component (C), and thus has a low storage elastic modulus. That is, an insulating layer in which warpage is suppressed is provided. The storage elastic modulus is preferably 10 GPa or less, more preferably 8 GPa or less, and further preferably 5 GPa or less. The lower limit is not particularly limited, but may be 0.1 GPa or more. The storage elastic modulus can be measured according to the method described in [Measurement of Storage Elastic Modulus] described later.

  A cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 90 minutes exhibits a characteristic that the coefficient of linear thermal expansion (CTE) at 30 ° C. to 150 ° C. is low. The linear thermal expansion coefficient is preferably 50 ppm or less, more preferably 30 ppm or less, and still more preferably 20 ppm or less. The lower limit is not particularly limited, but may be 3 ppm or more. The linear thermal expansion coefficient can be measured according to the method described in [Measurement of linear thermal expansion coefficient (CTE)] described later.

Since the resin composition of the present invention exhibits the property of being excellent in workability, it can be suitably used in a liquid form such as ink. Further, since the cured product of the resin composition of the present invention has low elasticity, the occurrence of warpage is suppressed, and an insulating layer having a low storage elastic modulus, dielectric loss tangent, relative dielectric constant, and linear thermal expansion coefficient (CTE) is provided. Can bring. Therefore, the resin composition of the present invention forms a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for an insulating layer of a semiconductor chip package) and an insulating layer of a circuit board (including a printed wiring board). Resin composition for forming an interlayer insulating layer that can be suitably used as a resin composition (resin composition for an insulating layer of a circuit board) and on which a conductor layer is formed by plating Can be more suitably used as a resin composition for an interlayer insulating layer of a circuit board on which a conductor layer is formed.
Also suitable as a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip) and a resin composition for forming wiring on a semiconductor chip (resin composition for forming a semiconductor chip wiring) Can be used.

[Resin sheet]
The resin sheet of the present invention includes a support and a resin composition layer formed on the support and formed of the resin composition of the present invention.

  The thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, further preferably 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less, or 40 μm or less from the viewpoint of thinning. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it may be 1 micrometer or more, 5 micrometers or more, 10 micrometers or more, etc.

  Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). It may be used.

  The support may be subjected to mat treatment or corona treatment on the surface to be bonded to the resin composition layer.

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1”, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. AL-5 ”,“ AL-7 ”,“ Lumirror T60 ”manufactured by Toray Industries, Inc.,“ Purex ”manufactured by Teijin Limited,“ Unipeel ”manufactured by Unitika Ltd., and the like.

  Although it does not specifically limit as thickness of a support body, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. In addition, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  The resin sheet is prepared by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater, a compression molding method, and the like, and further drying the resin varnish. It can be manufactured by forming a 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, cellosolve and butyl carbitol, etc. Carbitols, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  Drying may be performed by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. A physical layer can be formed.

  In the resin sheet, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The resin sheet can be stored in a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

  The resin sheet can be suitably used for forming an insulating layer in manufacturing a semiconductor chip package (insulating resin sheet for a semiconductor chip package). For example, a 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 an interlayer insulating layer on which a conductor layer is formed by plating is formed thereon Therefore, it can be more suitably used (for an interlayer insulating layer of a circuit board on which a conductor layer is formed by plating). Examples of a package using such a substrate include FC-CSP, MIS-BGA package, and ETS-BGA package.

  The resin sheet can be suitably used for sealing a semiconductor chip (resin sheet for sealing a semiconductor chip) or forming a wiring on a semiconductor chip (resin sheet for forming a semiconductor chip wiring). It can be suitably used for Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), Fan-in type PLP, and the like. Moreover, it can be used suitably also for the MUF (Molding Under Filling) material etc. which are used after connecting a semiconductor chip to a board | substrate. Further, the resin sheet can be suitably used for forming a wide range of other applications requiring high insulation reliability, for example, an insulating layer of a circuit board such as a printed wiring board.

  Instead of the resin sheet, a prepreg formed by impregnating the sheet-like fiber base material with the resin composition of the present invention may be used.

  The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of thinning, the thickness of the sheet-like fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and even more preferably 600 μm or less. Although the minimum of the thickness of a sheet-like fiber base material is not specifically limited, Usually, it may be 1 micrometer or more, 1.5 micrometers or more, 2 micrometers or more, etc.

  The prepreg can be produced by a known method such as a hot melt method or a solvent method.

  The thickness of the prepreg can be in the same range as the resin composition layer in the resin sheet described above.

[Circuit board]
The circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.
The method for manufacturing the circuit board of the present invention includes:
(1) preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate;
(2) The step of 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 to form an insulating layer;
(3) including a step of interconnecting the wiring layers. Moreover, the manufacturing method of a circuit board may include the process of (4) removing a base material.

  The step (3) is not particularly limited as long as the wiring layers can be connected to each other, but a step of forming a via hole in the insulating layer to form the wiring layer, and a step of polishing or grinding the insulating layer to expose the wiring layer It is preferable that it is at least one of these steps.

<Step (1)>
Step (1) is a step of preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate. Usually, a base material with a wiring layer has a first metal layer and a second metal layer, which are part of the base material, on both sides of the base material in this order, and is opposite to the base-side surface of the second metal layer. A wiring layer is formed on the side surface. In detail, a dry film (photosensitive resist film) is laminated on a substrate, and a pattern dry film is formed by exposing and developing under a predetermined condition using a photomask. A wiring layer is formed by electrolytic plating using the developed pattern dry film as a plating mask, and then the pattern dry film is peeled off. Note that the first metal layer and the second metal layer may not be provided.

  Examples of the base material include glass epoxy substrates, metal substrates (such as stainless steel and cold rolled steel plate (SPCC)), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. A metal layer such as a copper foil may be formed on the surface. Further, even if a metal layer such as a peelable first metal layer and a second metal layer (for example, an ultrathin copper foil with a carrier copper foil manufactured by Mitsui Kinzoku Co., Ltd., trade name “Micro Thin”) is formed on the surface. Good.

  The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition, and for example, a dry film such as a novolak resin or an acrylic resin can be used. A commercial product may be used as the dry film.

  The conditions for laminating the substrate and the dry film are the same as the conditions for laminating the resin sheet in step (2) described later so as to be embedded in the wiring layer, and the preferred range is also the same.

  After laminating the dry film on the substrate, exposure and development are performed under predetermined conditions using a photomask in order to form a desired pattern on the dry film.

  The line (circuit width) / space (inter-circuit width) ratio of the wiring layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 10/10 μm or less, and even more preferably 5 / It is 5 μm or less, 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 layer. The minimum pitch of the wiring layer may be 40 μm or less, 36 μm or less, or 30 μm or less.

  After forming the dry film pattern, a wiring layer is formed, and the dry film is peeled off. Here, the wiring layer can be formed by a plating method using a dry film having a desired pattern as a plating mask.

  The conductor material used for the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Contains metal. The wiring layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of wiring layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel-chromium alloy, copper An alloy layer of nickel alloy or copper / titanium alloy is preferable, and 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 layer of copper is preferable. A metal layer is more preferred.

  The thickness of the wiring layer is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 to 20 μm, or 15 to 20 μm, although it depends on the desired wiring board design. In the step (3), when the step of polishing or grinding the insulating layer and exposing the wiring layer to connect the wiring layers to each other is adopted, it is preferable that the wiring of the interlayer connection and the wiring not to be connected are different. . The thickness of the wiring layer can be adjusted by repeating the pattern formation described above. Of each wiring layer, the thickness of the thickest wiring layer (conductive pillar) depends on the design of the desired wiring board, but is preferably 2 μm or more and 100 μm or less. Further, the wiring for interlayer connection may be convex.

  After forming the wiring layer, the dry film is peeled off. Peeling of the dry film can be performed using, for example, an alkaline peeling solution such as a sodium hydroxide solution. If necessary, an unnecessary wiring pattern can be removed by etching or the like to form a desired wiring pattern. The pitch of the wiring layer to be formed is as described above.

<Step (2)>
Step (2) is a step of 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 thermosetting to form an insulating layer. For details, the wiring layer of the substrate with a wiring layer obtained in the above-mentioned 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 be insulated. Form a layer.

  Lamination | stacking of a wiring layer and a resin sheet can be performed by heat-pressing a resin sheet to a wiring layer from the support body side after removing the protective film of a resin sheet, for example. Examples of the member (hereinafter, also referred to as “thermocompression member”) for heat-pressing the resin sheet to the wiring layer include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll). It is preferable that the thermocompression bonding member is not pressed directly on the resin sheet, but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the wiring layer.

  Lamination of the wiring layer and the resin sheet may be performed by a vacuum laminating method after removing the protective film of the resin sheet. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 13 hPa or less.

  After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

  After laminating the resin composition layer on the substrate with the wiring layer so that the wiring layer is embedded, the resin composition layer is thermally cured to form an insulating layer. For example, although the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, the curing temperature can be in the range of 120 ° C. to 240 ° C., and the curing time can be in the range of 5 minutes to 120 minutes. Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature.

  The support for the resin sheet may be peeled after the resin sheet is laminated on the substrate with the wiring layer and thermally cured, or the support may be peeled off before the resin sheet is laminated on the substrate with the wiring layer. Good. Moreover, you may peel a support body before the roughening process process mentioned later.

  After the resin composition layer is thermally cured to form an insulating layer, the surface of the insulating layer may be polished. The polishing method is not particularly limited, and may be polished by a known method. For example, the surface of the insulating layer can be polished using a surface grinder.

<Step (3)>
Step (3) is a step of interconnecting the wiring layers. More specifically, this is a step of forming via holes in the insulating layer, forming a conductor layer, and interconnecting the wiring layers. Alternatively, the insulating layer is polished or ground, and the wiring layer is exposed to connect the wiring layers. The conductor layer is sometimes called a wiring layer.

  When adopting a process of forming a via hole in the insulating layer, forming a conductor layer and interconnecting the wiring layers, the formation of the via hole is not particularly limited, but laser irradiation, etching, mechanical drilling, etc. can be mentioned, but laser irradiation Is preferably carried out by This laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide gas laser, a YAG laser, an excimer laser or the like as a light source. Specifically, laser irradiation is performed from the surface side of the support of the resin sheet to form a via hole that exposes the wiring layer through the support and the insulating layer.

  The conditions for laser irradiation are not particularly limited, and laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.

  The shape of the via hole, that is, the shape of the outline of the opening when viewed in the extending direction is not particularly limited, but is generally circular (substantially circular).

  After forming the via hole, a so-called desmear process, which is a smear removing process in the via hole, may be performed. When the conductor layer described later is formed by a plating process, the via hole may be subjected to, for example, a wet desmear process, and when the conductor layer is formed by a sputtering process, for example, a plasma treatment process or the like. A dry desmear process may be performed. Moreover, the desmear process may serve as the roughening process.

  Before forming the conductor layer, the via hole and the insulating layer may be roughened. For the roughening treatment, known procedures and conditions that are usually performed can be employed. Examples of dry roughening treatment include plasma treatment, etc., and examples of wet roughening treatment include a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution in this order. Is mentioned.

  The surface roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 350 nm or more, more preferably 400 nm or more, and further preferably 450 nm or more. The upper limit is preferably 700 nm or less, more preferably 650 nm or less, and still more preferably 600 nm or less. The surface roughness (Ra) can be measured using, for example, a non-contact type surface roughness meter.

  After forming the via hole, a conductor layer is formed. The conductor material which comprises a conductor layer is not specifically limited, A conductor layer can be formed by arbitrary well-known methods, such as plating, a sputter | spatter, vapor deposition, and it is preferable to form by plating. In a preferred embodiment, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Of these, the semi-additive method is preferred. Moreover, when the support body in a resin sheet is metal foil, the conductor layer which has a desired wiring pattern can be formed by conventionally well-known techniques, such as a subtractive method. The conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated.

  In the case of forming by plating, specifically, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. An electrolytic plating layer is formed on the exposed plating seed layer by electrolytic plating. At that time, the filled via may be formed by filling the via hole by electrolytic plating together with the formation of the electrolytic plating layer. After the electrolytic plating layer is formed, the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern. In addition, when forming a conductor layer, the dry film used for formation of a mask pattern is the same as the said dry film.

  The conductor layer can include not only a linear wiring but also an electrode pad (land) on which an external terminal can be mounted, for example. The conductor layer may be composed only of electrode pads.

  The conductor layer may be formed by forming an electroplating layer and a filled via without using a mask pattern after the plating seed layer is formed, and then performing patterning by etching.

  When adopting a process of polishing or grinding the insulating layer and exposing the wiring layer to connect the wiring layers, the insulating layer polishing method or grinding method can be used to expose the wiring layer, polishing or grinding surface If it is horizontal, it will not specifically limit, A conventionally well-known grinding | polishing method or grinding method can be applied, for example, the chemical mechanical polishing method by a chemical mechanical polishing apparatus, the mechanical polishing methods, such as a buff, The surface grinding method by grindstone rotation Etc. Similar to the step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers to each other, a smear removing step and a roughening step may be performed, or a conductor layer may be formed. Further, it is not necessary to expose all the wiring layers, and a part of the wiring layers may be exposed.

<Process (4)>
Step (4) is a step of removing the base material and forming the circuit board of the present invention. The method for removing the substrate is not particularly limited. In a preferred embodiment, the substrate is peeled from the circuit board at the interface between the first and second metal layers, and the second metal layer is etched away with, for example, an aqueous copper chloride solution. As needed, you may peel a base material in the state which protected the conductor layer with the protective film.

  In other embodiments, the circuit board can be manufactured using the prepreg described above. The manufacturing method is basically the same as when using a resin sheet.

[Semiconductor chip package]
A first aspect of the semiconductor chip package of the present invention is a semiconductor chip package in which a semiconductor chip is mounted on the circuit board. A semiconductor chip package can be manufactured by bonding a semiconductor chip to the circuit board.

  As long as the terminal electrode of the semiconductor chip is conductively connected to the circuit wiring of the circuit board, the joining condition is not particularly limited, and a known condition used in flip chip mounting of the semiconductor chip may be used. Further, the semiconductor chip and the circuit board may be joined via an insulating adhesive.

  In a preferred embodiment, the semiconductor chip is pressure-bonded to the circuit board. As the crimping conditions, for example, the crimping temperature is in the range of 120 ° C. to 240 ° C. (preferably in the range of 130 ° C. to 200 ° C., more preferably in the range of 140 ° C. to 180 ° C.), and the crimping time is in the range of 1 second to 60 seconds. (Preferably 5 to 30 seconds).

  In another preferred embodiment, the semiconductor chip is reflowed and bonded to the circuit board. As reflow conditions, it can be set as the range of 120 to 300 degreeC, for example.

  After the semiconductor chip is bonded to the circuit board, for example, the semiconductor chip package can be obtained by filling the semiconductor chip with a mold underfill material. The method of filling with the mold underfill material can be performed by a known method. The resin composition or resin sheet of the present invention can also be used as a mold underfill material.

A second aspect of the semiconductor chip package of the present invention is, for example, a semiconductor chip package (Fan-out type WLP) as shown in FIG. A semiconductor chip package (Fan-out WLP) 100 as shown in FIG. 1 is a semiconductor chip package in which a sealing layer 120 is manufactured using the resin composition or resin sheet of the present invention. The semiconductor chip package 100 includes a semiconductor chip 110, a sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110, and a rewiring formed on a surface opposite to the side covered with the sealing layer of the semiconductor chip 110. A layer (insulating layer) 130, a conductor layer (redistribution layer) 140, a solder resist layer 150, and bumps 160 are provided. A manufacturing method of such a semiconductor chip package is as follows:
(A) Laminating a temporary fixing film on a substrate;
(B) a step of temporarily fixing the semiconductor chip on the temporary fixing film;
(C) The 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 thermosetting it to form a sealing layer;
(D) The process of peeling a base material and a temporary fixing film from a semiconductor chip,
(E) forming a rewiring forming layer (insulating layer) on the surface of the semiconductor chip substrate and the temporarily fixed film peeled off;
(F) forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer); and (G) forming a solder resist layer on the conductor layer. In addition, the method for manufacturing a semiconductor chip package may include (H) a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and dividing them into individual pieces.

<Process (A)>
Step (A) is a step of laminating a temporary fixing film on a base material. The lamination conditions of the base material and the temporary fixing film are the same as the lamination conditions of the wiring layer and the resin sheet in step (2) in the method for producing a circuit board, and the preferred range is also the same.

  The material used for the substrate is not particularly limited. As a base material, silicon wafer; glass wafer; glass substrate; metal substrate such as copper, titanium, stainless steel, cold rolled steel plate (SPCC); thermosetting treatment by impregnating glass fiber such as FR-4 substrate with epoxy resin. And a substrate made of bismaleimide triazine resin such as BT resin.

  The material for the temporarily 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. A commercially available product can be used as the temporary fixing film. Examples of commercially available products include Riva Alpha manufactured by Nitto Denko Corporation.

<Process (B)>
Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. The semiconductor chip can be temporarily fixed using a known apparatus such as a flip chip bonder or a die bonder. The layout and the number of semiconductor chips can be appropriately set according to the shape and size of the temporarily fixed film, the number of target semiconductor packages produced, and the like, for example, a matrix having a plurality of rows and a plurality of columns. Can be aligned and fixed temporarily.

<Process (C)>
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 to form a sealing layer. It is. In the step (C), it is preferable that the resin composition layer of the resin sheet is laminated on the semiconductor chip and thermally cured to form the sealing layer.

  Lamination | stacking of a semiconductor chip and a resin sheet can be performed by heat-pressing a resin sheet to a semiconductor chip from the support body side after removing the protective film of a resin sheet, for example. Examples of the member (hereinafter, also referred to as “heat-bonding member”) that heat-presses the resin sheet to the semiconductor chip include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll). Note that it is preferable that the thermocompression-bonding member is not pressed directly on the resin sheet, but is pressed via an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the semiconductor chip.

  Further, the lamination of the semiconductor chip and the resin sheet may be performed by a vacuum laminating method after removing the protective film of the resin sheet. The lamination conditions in the vacuum laminating method are the same as the lamination conditions of the wiring layer and the resin sheet in step (2) in the method for producing a circuit board, and the preferred range is 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 the support may be peeled off before the resin sheet is laminated on the semiconductor chip.

  The application conditions for the resin composition are the same as the application conditions for forming the resin composition layer in the resin sheet of the present invention, and the preferred ranges are also the same.

<Process (D)>
A process (D) is a process of peeling a base material and a temporary fixing film from a semiconductor chip. The method of peeling can be appropriately changed according to the material of the temporarily fixed film, for example, the method of heating, foaming (or expanding) the temporarily fixed film and peeling, and irradiating ultraviolet rays from the substrate side, Examples include a method of reducing the pressure-sensitive adhesive strength of the temporarily fixed film and peeling it off.

In the method of peeling by heating and foaming (or expanding) the temporarily fixed film, the heating condition is usually 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. Also, by irradiating ultraviolet rays from the substrate side, in the method for peeling to lower the adhesive strength of the temporary fixing film, dose of the ultraviolet rays is ^{usually, 10mJ / cm 2 ~1000mJ / cm} 2.

<Process (E)>
The step (E) is a step of forming a rewiring formation layer (insulating layer) on the surface from which the base material and the temporary fixing film of the semiconductor chip are peeled off.

  The material for forming the rewiring formation layer (insulating layer) is not particularly limited as long as it has insulating properties at the time of forming the rewiring forming layer (insulating layer). From the viewpoint of ease of manufacturing the semiconductor chip package, Photosensitive resins and thermosetting resins are preferred. As a thermosetting resin, you may use the resin composition of the same composition as the resin composition for forming the resin sheet of this invention.

  After forming the rewiring layer (insulating layer), via holes may be formed in the rewiring layer (insulating layer) in order to connect the semiconductor chip and a conductor layer described later.

  When forming the via hole, if the material for forming the rewiring layer (insulating layer) is a photosensitive resin, first, the surface of the rewiring layer (insulating layer) is irradiated with active energy rays through a mask pattern. The outermost wiring layer of the part is photocured.

  Examples of active energy rays include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable. The irradiation amount and irradiation time of ultraviolet rays can be appropriately changed according to the photosensitive resin. As the exposure method, a contact exposure method in which a mask pattern is brought into close contact with a rewiring formation layer (insulating layer) and exposure, and a mask pattern is exposed using parallel rays without being brought into close contact with the rewiring formation layer (insulating layer). Any non-contact exposure method may be used.

  Next, the rewiring formation layer (insulating layer) is developed, and the unexposed portion is removed to form a via hole. As the development, both wet development and dry development are suitable. A known developer can be used as the developer used in the wet development.

  Examples of the developing method include a dip method, a paddle method, a spray method, a brushing method, a scraping method, and the like, and the paddle method is preferable from the viewpoint of resolution.

  When the material for forming the rewiring layer (insulating layer) is a thermosetting resin, the formation of the via hole is not particularly limited, and examples thereof include laser irradiation, etching, mechanical drilling, and the like. preferable. Laser irradiation can be performed using any suitable laser processing machine that uses a carbon dioxide laser, UV-YAG laser, excimer laser, or the like as a light source.

  The conditions for laser irradiation are not particularly limited, and laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.

  The shape of the via hole, that is, the shape of the outline of the opening when viewed in the extending direction is not particularly limited, but is generally circular (substantially circular). The top diameter of the via hole (the diameter of the opening on the surface of the rewiring layer (insulating layer)) is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. Although a minimum is not specifically limited, Preferably it is 10 micrometers or more, More preferably, it is 15 micrometers or more, More preferably, it is 20 micrometers or more.

<Process (F)>
Step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer). The method for forming the conductor layer on the rewiring layer (insulating layer) is the same as the method for forming the conductor layer after forming the via hole in the insulating layer in the step (3) in the method for manufacturing a circuit board, and is preferable. The range is the same. Note that the step (E) and the step (F) may be repeated, and the conductor layer (redistribution layer) and the redistribution formation layer (insulating layer) may be alternately stacked (build-up).

<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 has insulating properties at the time of forming the solder resist layer. From the viewpoint of ease of manufacturing a semiconductor chip package, a photosensitive resin and a thermosetting resin are preferable. . As a thermosetting resin, you may use the resin composition of the same composition as the resin composition for forming the resin sheet of this invention.

  Further, in the step (G), a bumping process for forming bumps may be performed as necessary. The bumping process can be performed by a known method such as solder ball or solder plating. The via hole can be formed in the bumping process in the same manner as in the step (E).

<Process (H)>
The manufacturing method of the semiconductor chip package may include a step (H) in addition to the steps (A) to (G). Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and dividing them into individual pieces.

  A method for dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited, and a known method can be used.

  The third aspect of the semiconductor chip package of the present invention includes, for example, a rewiring formation layer (insulating layer) 130 and a solder resist layer 150 in a semiconductor chip package (Fan-out type WLP) as shown in FIG. It is the semiconductor chip package manufactured with the resin composition or resin sheet of invention.

[Semiconductor device]
Semiconductor devices to be mounted with the semiconductor chip package of the present invention include electrical products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles ( For example, various semiconductor devices used for motorcycles, automobiles, trains, ships, airplanes, and the like) can be given.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” representing amounts mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

[Synthesis Example 1: Synthesis of Component (B) in Synthesis Example 1]
In a reaction vessel, difunctional hydroxy group-terminated polybutadiene (G-3000, manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxy group equivalent = 1800 g / eq.) 69 g and ipsol 150 (aromatic hydrocarbon-based mixed solvent: Idemitsu) 40 g of petrochemicals) and 0.005 g of dibutyltin laurate were mixed and dissolved uniformly. When the temperature became uniform, the temperature was raised to 50 ° C., and 8 g of isophorone diisocyanate (manufactured by Evonik Degussa Japan, IPDI, isocyanate group equivalent = 113 g / eq.) Was added with further stirring, and the reaction was performed for about 3 hours. Next, after cooling the reaction product to room temperature, 23 g of cresol novolak resin (KA-1160, manufactured by DIC, hydroxyl equivalent = 117 g / eq.) And 60 g of ethyl diglycol acetate (manufactured by Daicel) were added. The temperature was raised to 80 ° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FT-IR. The confirmation of the disappearance of the NCO peak is regarded as the end point of the reaction, and the reaction product is cooled to room temperature and then filtered through a 100 mesh filter cloth to obtain the component (B) of Synthesis Example 1 having a butadiene structure and a phenolic hydroxyl group (nonvolatile content) 50% by mass) was obtained. The number average molecular weight was 5500.

[Synthesis Example 2: Synthesis of Component (B) in Synthesis Example 2]
A flask equipped with a stirrer, a thermometer and a condenser was charged with 292.09 g of ethyl diglycol acetate and 292.09 g of Solvesso 150 (aromatic solvent, manufactured by ExxonMobil) as a solvent, and 100.1 g of diphenylmethane diisocyanate ( 0.4 mol) and 500.0 g (0.2 mol) of polyisoprene diol (hydroxyl value 46.6 KOH-mg / g, molecular weight 2500) were charged and reacted at 70 ° C. for 4 hours. Subsequently, 195.9 g (0.2 mol) of nonylphenol novolac resin (hydroxyl equivalent 229.4 g / eq, average 4.27 functionality, average calculated molecular weight 979.5 g / mol) and ethylene glycol bisanhydro trimellitate 41.0 g ( 0.1 mol), heated to 150 ° C. over 2 hours, and allowed to react for 12 hours, whereby component (B) of Synthesis Example 2 having a butadiene structure and a phenolic hydroxyl group (nonvolatile content 55.2) Mass%).

[Synthesis Example 3: Synthesis of Component (B) in Synthesis Example 3]
In a reaction vessel, 80 g of polycarbonate diol (number average molecular weight: about 1,000, hydroxyl equivalent: 500, nonvolatile content: 100%, “C-1015N” manufactured by Kuraray Co., Ltd.) and 0.01 g of dibutyltin dilaurate were added to diethylene glycol monoethyl ether. It was uniformly dissolved in 37.6 g of acetate (“Ethyl Diglycol Acetate” manufactured by Daicel Corporation). Next, the mixture was heated to 50 ° C., and further stirred, 27.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent: 87.08) was added and reacted for about 3 hours. The reaction was then cooled to room temperature before 14.3 g benzophenone tetracarboxylic dianhydride (acid anhydride equivalent: 161.1), 0.12 g triethylenediamine, and diethylene glycol monoethyl ether acetate (Daicel). 84.0 g of “Ethyl Diglycol Acetate” manufactured by the company was added, the temperature was raised to 130 ° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FT-IR. After confirming the disappearance of the NCO peak, the reaction was considered to be the end point of the reaction, and the reaction product was cooled to room temperature and then filtered through a filter cloth having an opening of 100 μm to obtain an imide structure, a urethane skeleton, and a carbonate structure. B) The component (nonvolatile content 50 mass%) was obtained.

[Example 1]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 6 parts of 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), glycidylamine type epoxy Resin (“EP-3980S” manufactured by ADEKA, epoxy equivalent: 115 g / eq) 5 parts, curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole) 0.1 part, Synthesis Example 1 (B) component (solid content 50%, number average molecular weight: 5500) 30 parts, cresol novolak resin (“KA-1160” manufactured by DIC, phenolic hydroxyl group equivalent: 117 g / eq) 5 parts, spherical silica A (Fluorine-containing silane coupling agent (“KBM7103” manufactured by Shin-Etsu Chemical Co., Ltd., 100 parts by mass of inorganic filler) .66 parts by mass) surface-treated with spherical silica (specific surface area 5.7 m ² / g, average particle size 0.5 [mu] m)) were mixed 120 parts were uniformly dispersed in a planetary mixer, the resin composition 1 Was made.

[Example 2]
In Example 1, 30 parts of the component (B) synthesized in Synthesis Example 1 (solid content 50%, number average molecular weight: 5500) was changed to 27.2 parts of the component (B) synthesized in Synthesis Example 2. A resin composition 2 was produced in the same manner as in Example 1 except for the above items.

[Example 3]
In Example 1, 30 parts of the component (B) synthesized in Synthesis Example 1 (solid content 50%, number average molecular weight: 5500) was changed to 30 parts of the component (B) synthesized in Synthesis Example 3. A resin composition 3 was produced in the same manner as in Example 1 except for the above items.

[Example 4]
In Example 1, spherical silica (surface ratio treated with spherical silica A (fluorine containing silane coupling agent (“KBM7103” manufactured by Shin-Etsu Chemical Co., Ltd., 0.66 parts by mass with respect to 100 parts by mass of inorganic filler)) surface area 5.7 m ² / g, an average particle diameter of 0.5 [mu] m)) 120 parts of spherical silica B (fluorine-containing silane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM7103", the inorganic filler 100 parts by weight 0.33 parts by mass), and 120 parts of spherical silica (specific surface area 3.7 m ² / g, average particle size 8.5 μm). A resin composition 4 was produced in the same manner as in Example 1 except for the above items.

[Example 5]
In Example 2, spherical silica A (ratio silica (surface-treated with a fluorine-containing silane coupling agent (“KBM7103” manufactured by Shin-Etsu Chemical Co., Ltd., 0.66 parts by mass with respect to 100 parts by mass of inorganic filler)) 120 parts of spherical silica B (fluorine-containing silane coupling agent (“KBM7103” manufactured by Shin-Etsu Chemical Co., Ltd.), 100 parts by weight of an inorganic filler) 120 parts of a surface area of 5.7 m ² / g and an average particle size of 0.5 μm) 0.33 parts by mass), and 120 parts of spherical silica (specific surface area 3.7 m ² / g, average particle size 8.5 μm). A resin composition 5 was produced in the same manner as in Example 2 except for the above items.

[Example 6]
In Example 3, spherical silica A (ratio silica (surface-treated with a fluorine-containing silane coupling agent (“KBM7103” manufactured by Shin-Etsu Chemical Co., Ltd., 0.66 parts by mass with respect to 100 parts by mass of inorganic filler)) 120 parts of spherical silica B (fluorine-containing silane coupling agent (“KBM7103” manufactured by Shin-Etsu Chemical Co., Ltd.), 100 parts by weight of an inorganic filler) 120 parts of a surface area of 5.7 m ² / g and an average particle size of 0.5 μm) 0.33 parts by mass), and 120 parts of spherical silica (specific surface area 3.7 m ² / g, average particle size 8.5 μm). A resin composition 6 was produced in the same manner as in Example 3 except for the above items.

[Example 7]
In Example 1, spherical silica (surface ratio treated with spherical silica A (fluorine containing silane coupling agent (“KBM7103” manufactured by Shin-Etsu Chemical Co., Ltd., 0.66 parts by mass with respect to 100 parts by mass of inorganic filler)) 0 surface area 5.7 m ² / g, an average particle diameter of 0.5 [mu] m)) 120 parts of spherical silica C (aminosilane coupling agent (manufactured by Shin "KBM573", the inorganic filler 100 parts by weight. 33 parts), and spherical silica (specific surface area of 4.2 m) surface-treated with a fluorine-containing silane coupling agent (“KBM7103” manufactured by Shin-Etsu Chemical Co., Ltd., 0.33 parts by mass with respect to 100 parts by mass of the inorganic filler). ² / g, average particle diameter 3.7 μm))) 120 parts. A resin composition 7 was produced in the same manner as in Example 1 except for the above items.

[Example 8]
In Example 1, the amount of component (B) synthesized in Synthesis Example 1 was changed from 30 parts to 60 parts. A resin composition 8 was produced in the same manner as in Example 1 except for the above items.

[Example 9]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 8 parts, glycidylamine type epoxy Resin (ADEKA, “EP-3980S”, epoxy equivalent: 115 g / eq) 6 parts, curing accelerator (Shikoku Kasei “1B2PZ”, 1-benzyl-2-phenylimidazole) 0.1 part, Synthesis Example 1 (B) component (solid content 50%, number average molecular weight: 5500) 12 parts, cresol novolak resin (“KA-1160” manufactured by DIC, phenolic hydroxyl group equivalent: 117 g / eq) 5 parts, spherical silica A (Fluorine-containing silane coupling agent (“KBM7103” manufactured by Shin-Etsu Chemical Co., Ltd., 100 parts by mass of inorganic filler) .66 parts by mass) surface-treated with spherical silica (specific surface area 5.7 m ² / g, average particle size 0.5 [mu] m)) were mixed 120 parts were uniformly dispersed in a planetary mixer, the resin composition 9 Was made.

[Example 10]
In Example 1, spherical silica (surface ratio treated with spherical silica A (fluorine containing silane coupling agent (“KBM7103” manufactured by Shin-Etsu Chemical Co., Ltd., 0.66 parts by mass with respect to 100 parts by mass of inorganic filler)) 120 parts of surface area 5.7 m ² / g, average particle size 0.5 μm)) are changed to 120 parts of spherical silica F (specific surface area 2.1 m ² / g, average particle size 14 μm), and further fluorine atom-containing alkoxysilane compound 0.24 parts by mass (“KBM7103” manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed. A resin composition 10 was produced in the same manner as in Example 1 except for the above items.

[Example 11]
In Example 1, spherical silica (specific surface area 5.7 m ² / g, average particle size) surface-treated with spherical silica A (fluorine-containing silane coupling agent (“KBM7103” manufactured by Shin-Etsu Chemical Co., Ltd.) 0.66% by mass) 120 parts of diameter 0.5 μm) were changed to 150 parts of alumina A (specific surface area 0.8 m ² / g, average particle size 3 μm). A resin composition 11 was produced in the same manner as in Example 1 except for the above items.

[Comparative Example 1]
In Example 2, spherical silica A (specific surface area 5.7 m ² / g, average particle size) surface-treated with 0.66% by mass of spherical silica A (fluorine-containing silane coupling agent (“KBM7103” manufactured by Shin-Etsu Chemical Co., Ltd.)) Spherical silica (specific surface area 5.6 m ² / g, average particle size 0) whose surface was treated with spherical silica D (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) 0.5 μm))) to 120 parts. A resin composition 12 was produced in the same manner as in Example 2 except for the above items.

[Comparative Example 2]
In Example 2, spherical silica A (specific surface area 5.7 m ² / g, average particle size) surface-treated with 0.66% by mass of spherical silica A (fluorine-containing silane coupling agent (“KBM7103” manufactured by Shin-Etsu Chemical Co., Ltd.)) Spherical silica E (specific surface area 5.6 m ² / g, average particle size 0) whose surface was treated with 120 parts of spherical silica E (phenyltrimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.)) 0.5 μm))) to 120 parts. A resin composition 13 was produced in the same manner as in Example 2 except for the above items.

[Measurement of thixotropy index]
Using an E-type viscometer, the viscosity (Pa · s) at 25 ° C. of the resin compositions prepared in Examples and Comparative Examples was measured at a rotor rotation speed of 5 rpm. The thixotropy index was expressed as the ratio of the viscosity measured at a rotor speed of 5 rpm to the viscosity measured at 1 rpm (viscosity at 1 rpm / 5 viscosities at 5 rpm).

[Evaluation of workability]
The resin compositions prepared in the examples and comparative examples are filled into a 12 Oz cartridge (manufactured by Saneitec Co., Ltd., 5194C), 40 g of the resin composition is discharged from the cartridge, and a circle having a radius of about 4 cm toward the center on a 12 inch silicon wafer. It was used for the shape. After 1 minute, the appearance was observed and evaluated according to the following evaluation criteria. The workability is a property indicating that the resin composition becomes a uniform shape with the passage of time, so that it is not necessary to prepare the resin composition in a uniform shape, and the subsequent work becomes simple.
A: The resin composition on the silicon wafer has no ejection trace and the surface of the resin composition has few irregularities.
(Triangle | delta): There exists a discharge trace and there are some unevenness | corrugations on the resin composition surface.
X: There are ejection marks and the unevenness is large.

[Measurement of relative permittivity and loss tangent]
The resin compositions prepared in Examples and Comparative Examples were compression-molded on a release-treated SUS plate so as to have a thickness of 200 μm using a compression molding apparatus at 120 ° C., and then the resin composition was peeled off from the SUS plate. Heat curing was performed at 90 ° C. for 90 minutes. The cured product was cut out to have a length of 15 cm and a width of 15 cm to prepare an evaluation sample. This evaluation sample was measured for its relative dielectric constant and dielectric loss tangent at a measurement temperature of 24 ° C. and a frequency of 80 GHz by a Fabry-Perot method using a vector network analyzer N5227A manufactured by Keysight.

[Measurement of storage modulus]
The resin compositions prepared in Examples and Comparative Examples were heat-molded into a 2 mm thick sheet at 180 ° C. for 90 minutes, and the sheet was cut into a size of 60 mm × 10 mm × 2 mm to prepare an evaluation sample. The storage elastic modulus at 25 ° C. when this evaluation sample was measured by DMA (Dynamic mechanical analysis (dynamic viscoelasticity measuring device)) under the conditions of the three-point bending mode and the frequency of 1 Hz was determined.

[Measurement of linear thermal expansion coefficient (CTE)]
The resin compositions prepared in Examples and Comparative Examples were compression-molded on a release-treated SUS plate so as to have a thickness of 200 μm using a compression molding apparatus at 120 ° C., and then the resin composition was peeled off from the SUS plate. Heat curing was performed at 90 ° C. for 90 minutes.
The cured product was cut into test pieces having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer (Thermo Plus TMA8310) manufactured by Rigaku Corporation. After mounting the test piece on the apparatus, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. The average linear thermal expansion coefficient from 25 ° C. to 150 ° C. in the second measurement was determined.

The components used for the preparation of the resin compositions of Examples and Comparative Examples and their blending amounts (parts by mass) are shown in the following table. The abbreviations in the table below are as follows.
ZX1059: Liquid epoxy resin at 25 ° C., manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq
EP-3980S: Glycidylamine type epoxy resin, manufactured by ADEKA, epoxy equivalent: 115 g / eq
Synthesis Example 1: Component (B) synthesized in Synthesis Example 1: Compound Synthesis Example 2: Component (B) synthesized in Synthesis Example 2: Component Synthesis Example 3: Compound synthesized in Synthesis Example 3 (B) Component KBM-7103: Fluorine atom-containing alkoxy Silane compound, KA-1160 manufactured by Shin-Etsu Chemical Co., Ltd .: Cresol novolac resin, manufactured by DIC, phenolic hydroxyl group equivalent: 117 g / eq
1B2PZ: curing accelerator, manufactured by Shikoku Kasei Co., Ltd., content of 1-benzyl-2-phenylimidazole (C) component: content of component (C) when the nonvolatile component in the resin composition is 100% by mass ( B) Content of component: Content of (B) component when the non-volatile component in the resin composition is 100% by mass

  In the examples, even when the components (E) to (F) are not contained, it has been confirmed that the results are the same as those in the above examples although there is a difference in degree.

100 Semiconductor Chip Package 110 Semiconductor Chip 120 Sealing Layer 130 Rewiring Formation Layer (Insulating Layer)
140 Conductor layer (rewiring layer)
150 Solder resist layer 160 Bump

Claims (18)

(A) epoxy resin,
(B) One 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 the molecule A polymer compound having
A resin composition containing (C) a fluorine atom-containing alkoxysilane compound, and (D) an inorganic filler.   The resin composition according to claim 1, wherein the component (B) is a polymer compound containing at least one structure selected from a polybutadiene structure, a polyisoprene structure, and a polycarbonate structure.   (D) The resin composition of Claim 1 or 2 whose average particle diameter of a component is 0.5 micrometer or more and 20 micrometers or less.   The resin composition according to any one of claims 1 to 3, wherein the component (D) is silica or alumina.   (C) Content of a component is 0.1 mass% or more and 2 mass% or less of any one of Claims 1-4 when the non-volatile component in a resin composition is 100 mass%. Resin composition.   (B) Resin composition of any one of Claims 1-5 whose content of a component is 3 mass% or more and 25 mass% or less when the non-volatile component in a resin composition is 100 mass%. object.   The content of component (A) when the nonvolatile component in the resin composition is 100% by mass is A1, and the content of component (B) when the nonvolatile component in the resin composition is 100% by mass is B1. The resin composition according to any one of claims 1 to 6, wherein (A1 / B1) × 100 is 30 or more and 250 or less.   (D) Resin composition of any one of Claims 1-7 whose content of a component is 70 to 90 mass% when the non-volatile component in a resin composition is 100 mass%. object.   Furthermore, (E) The resin composition of any one of Claims 1-8 containing a hardening | curing agent.   (E) The resin composition of Claim 9 whose component is a phenol type hardening | curing agent.   The resin composition according to any one of claims 1 to 10, wherein the thixotropy index is 1 or less.   The resin composition according to any one of claims 1 to 11, wherein a linear thermal expansion coefficient at 30 ° C to 150 ° C when the resin composition is thermally cured at 180 ° C for 90 minutes is 3 ppm or more and 50 ppm or less. .   The resin composition according to claim 1, which is a resin composition for an insulating layer of a semiconductor chip package.   The resin sheet which has a support body and the resin composition layer provided on this support body containing the resin composition of any one of Claims 1-13.   The resin sheet according to claim 14, which is a resin sheet for an insulating layer of a semiconductor chip package.   The circuit board containing the insulating layer formed with the hardened | cured material of the resin composition of any one of Claims 1-13.   A semiconductor chip package comprising the circuit board according to claim 16 and a semiconductor chip mounted on the circuit board.   A semiconductor chip package including a sealing layer and a semiconductor chip, wherein the sealing layer is a cured product of the resin composition according to claim 1.

Images